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ABSTRACT

HOLBERT, JR., RICHARD MOORE. Empirical and Theoretical Indigo Dye Models Derived from
Observational Studies of Production Scale Chain Rope Indigo Dye Ranges. (Under the direction of
Peter Hauser, Warren Jasper, Jon Rust, and Richard Gould.)

An observational study of production scale chain rope indigo dye ranges was conducted
using 100% cotton open end spun yarns to confirm previously published dye trends, investigate the
effects of dye range speed, and develop dye prediction models. To achieve these objectives, several
milestones were identified and systematically addressed. A comprehensive laboratory preparation
method was developed to ensure consistent yarn preparation. Equilibrium sorption experiments
were conducted to determine the functional relationship between dye bath concentration and pH to
indigo dye uptake in the cotton yarn. Additionally, the resulting shade from equilibrium sorption
data was expanded to create an innovative method of quantitatively characterizing indigo
penetration level of non-uniformly dyed yarns.
The following dye range set-up conditions were recorded for each observational point: yarn
count, number of dips, dye range speed, dwell length, nip pressure, dye bath indigo concentration,
dye bath pH, dye bath reduction potential, and oxidation time. All observations were conducted
after the dye range had been running for several hours and no feed rate adjustments were required.
Later the following measurements were taken to determine each response variable state: total
percent chemical on weight of yarn, percent of fixed indigo on weight of yarn, and Integ shade
value.
Analysis of data from the observational study confirmed most previously published dye
trends relating to dye uptake, shade, and penetration level. Notably, the percent indigo on weight
of yarn as a function of dye bath pH was not confirmed. Although it was noted this relationship may
be dependent on the pH range evaluated during the observational study and not the broader
general trend. All other general trends were confirmed. Additionally several new dye range set-up
conditions were determined to significantly affect dye uptake, shade, and/or penetration level. Yarn
count, speed, and dwell time were deemed significant in affecting dye uptake behavior. Increasing
yarn count to finer yarns resulted in greater percent indigo on weight of yarn, Integ, and penetration
level. Increasing dye range speed resulted in less percent indigo on weight of yarn, lighter Integ
shade, and lower penetration level or more ring dyeing. And, increasing dwell time resulted in
lighter Integ shade.
Using the dye range set-up conditions and measured response variables from the
observational study data, empirical and dye theory models were constructed to predict percent
indigo on weight of yarn, Integ shade, and the resulting penetration level. An independent
production scale indigo dye range, which was not included in dye model creation, was used to
validate of each model for accurate prediction of percent indigo on weight of yarn, Integ shade, and
corresponding penetration level. The dye model predictions were compared to actual production
scale indigo dyed cotton yarns. By making adjustments in yarn porosity values the dye theory model
outperformed the empirical model in predicting final Integ shade although both models accurately
predicted the total percent indigo on weight of yarn.



















Copyright 2011 by Richard Moore Holbert, Jr.
All Rights Reserved

Empirical and Theoretical Indigo Dye Models Derived from Observational Studies of Production Scale
Chain Rope Indigo Dye Ranges


by
Richard Moore Holbert, Jr.


A dissertation submitted to the Graduate Faculty of
North Carolina State University
in partial fulfillment of the
requirements for the Degree of
Doctor of Philosophy

Fiber and Polymer Science

Raleigh, North Carolina
2011



APPROVED BY:




Warren Jasper






Richard Gould

Jon Rust

Peter Hauser
Chair of Advisory Committee

ii

BIOGRAPHY
Richard Moore Holbert, Jr. was born on March 18, 1971 in Charlotte, NC. He graduated with a high
school diploma from North Mecklenburg High School in 1989. He received a Bachelor of Science
degree in Mechanical Engineering and Master of Science in Textile Engineering and Mechanical
Engineering from North Carolina State University in 1994 and 1997 respectively.
In 1997 he married Avian Kay and began working at Swift Denim in Erwin, NC denim facility. He
started working as a process engineer in the finishing and indigo dye house departments. After 8
years with the company he transferred to the Society Hill, SC piece dye plant in 2005. There he
assumed the role of director of global product development. In December 2010, Avian and he were
blessed with the arrival of Aleaha Louise Holbert.



iii

ACKNOWLEDGEMENTS
I would like to whole heartily thank my loving wife. After so many years of missed family weekends,
outings, birthdays, and occasional holiday gatherings; it is a wonder she has stayed by my side.
Without my laboratory assistant I doubt I would have ever finished this research.
To Geoff Gettilife and all the technicians at Swift Denim's Boland plant, I would like to thank you.
I'd like to thank my research committee. I know this process has taken longer than I (or you)
envisioned, but I believe this work is a perfect example of the "ends justifying the means".



iv

TABLE OF CONTENTS
List of Tables vi
List of Figures ix
List of Equations xv
1. Indigo Dyeing Principles: Review of Current Knowledge 1
1.1 Commercial Indigo Dyeing 2
1.2 Indigo Chemistry 7
1.2.1 Indigo Reduction or Vatting 7
1.2.2 Classification of Indigo Dye Species 10
1.2.3 Indigo dyeing Measurement Methods 14
1.3 Characteristics of Indigo Dyed Yarns 19
1.4 Dye Theory 32
1.4.1. Fundamental Sequence of Events during Dyeing 32
1.4.2 Fick's Law of Diffusion 34
1.4.3. Diffusional boundary Layer 41
1.4.4. Empirical Simplifications of Diffusion 44
1.5 Indigo Dyeing Experiments 49
1.5.1. Previous Investigations and Methods on Indigo Dyeing 49
1.5.2. Discussion of Previously Published Experimental Results 58
1.6 Summary of Key Developments and Identification of Deficiencies 83
2. Objectives of the Present Investigation 86
3. Experimental Methods and Procedures 89
3.1 Response Variables Definition, Collection Methods, and Evaluation Methods 89
3.1.1 Yarn Skein Definition and Creation 89
3.1.2 Running Yarn Skeins on Production Indigo Dye Range Equipment 89
3.1.3 Yarn Skein Evaluations 90
3.2 Determining Optimum Method for Laboratory Preparation 97
3.2.1 Analysis of Laboratory Preparation Time, Temperature, and Sodium Hydroxide
Concentration Affect on %Boil-off Loss 101
3.2.2 Analysis of Laboratory Preparation Time, Temperature, and Sodium Hydroxide
Concentration Affect on %IOWY after One and Six Dip Indigo Dyeing Conditions 106
3.2.3 Analysis of Laboratory Preparation Time, Temperature, and Sodium Hydroxide
Concentration Affect on Integ Shade Value after One and Six Dip Indigo Dyeing
Conditions 114
3.2.4 Analysis of Laboratory Preparation Time, Temperature, and Sodium Hydroxide
Concentration Affect on Penetration Factor after One and Six Dip Indigo Dyeing
Conditions 119
3.2.5 Determine Optimum Settings for Laboratory Preparation Procedure 126
v

3.3 Equilibrium Sorption Experiment to Determine %IOWY and Shade Relationship for
Uniformly Dyed Skeins 130
3.4 Observational Indigo Study: Establishing Breadth of Dye Conditions and
Convergence Test to Determine Conclusion of Study 141
4. Data Analysis from the Observational Study 146
4.1 Review of Main Parameter Affects on Response Variables Obtained from
Observational Study 146
4.2 Empirical Dye Models Based on Dye Range Parameters and the Resulting
Affect on Indigo Dye Response Variables 170
4.2.1 %COWY Empirical Model Generation 170
4.2.2 %IOWY Empirical Model Generation 176
4.2.3 Integ Empirical Model Generation 183
4.2.4 Penetration Level Empirical Model Generation 188
4.3 Theoretical Model for Indigo Dye Process 196
4.3.1 Derivation of Theoretical Dye Model 196
4.3.2 Algorithm to Calculate the Dye Coefficients 218
4.3.3 Spatial and Time Step Optimization 219
4.3.4 Determination of Indigo Dyeing Coefficient Models 219
4.3.5 Algorithm to Calculate the %COWY, %IOWY, and Integ Shade 237
5. Empirical and Theoretical Dye Model simulation and validation 239
5.1 Simulation of Empirical and Dye Theory models on Third Independent Dye Range 239
5.1.1 Actual Versus Predicted %COWY 240
5.1.2 Actual Versus Predicted %IOWY 243
5.1.3 Actual Versus Predicted Integ Shade Value 246
5.1.4 Actual Versus Predicted Penetration Level 249
5.1.5 Summary of Dye Theory Model Compared with Empirical Model 252
5.2 Simulation of Empirical and Dye Theory Models to Actual Production Yarn 256
6. Summary of Results, Discussions, and Recommendations 267
References 274
Appendix 279

vi

LIST OF TABLES
1. Indigo Dyeing Principles: Review of Current Knowledge
Table 1-1: Typical Stock Mix. 9
Table 1-2: A typical indigo stock mix formula. 9
Table 1-3: Additional indigo stock mix recipes. 10
Table 1-4: Estimated diffusion coefficients for disperse Red 11 (D, cm
2
/sec x 10
-10
). 43
Table 1-5: Regression values for three parameter emphirical solution. 48
Table 1-6: Concentration of alkali system. 49
Table 1-7: Etters 1989 data set. 51
Table 1-8: Annis and Etters 1991 data set. 52
Table 1-9: Etters 1991 Equilibrium sorption of indigo on cotton obtained from different
pHs in grams of dye per 100 grams of water(bath) or fiber. 54
Table 1-10: Dye concentrations required to yield equivalent shade at different pHs. 55
Table 1-11: % reflectance and corrected K/S values for different dyebath concentrations
and pH. 56

2. Objectives of the Present Investigation
3. Experimental Methods and Procedures
Table 3-1: Target dyed yarn sample weight for Methyl Pyrrolidinone extraction. 93
Table 3-2: Time, temperature, and sodium hydroxide concentration levels plus
response variable for one dip of indigo. 99
Table 3-3: Time, temperature, and sodium hydroxide concentration levels plus
response variable for six dips of indigo. 100
Table 3-4: ANOVA analysis results for laboratory preparation parameters on %Boil-off loss. 105
Table 3-5: ANOVA analysis results for laboratory preparation parameters on
%IOWY for one dip of indigo. 111
Table 3-6: ANOVA analysis results for laboratory preparation parameters on
%IOWY for six dips of indigo. 113
Table 3-7: ANOVA analysis results for laboratory preparation parameters on
Integ for one dip of indigo. 118
Table 3-8: ANOVA analysis results for laboratory preparation parameters on
Integ for six dips of indigo. 119
Table 3-9: ANOVA analysis results for laboratory preparation parameters on
penetration factor from one dip of indigo. 123
Table 3-10: ANOVA analysis results for laboratory preparation parameters on
penetration factor from six dips of indigo. 125
Table 3-11: %IOWY and Integ shade data from equilibrium sorption experiment. 132
Table 3-12: Observational study parameters and potential range of values. 141
Table 3-13: Prime data set in the observational study. 142


vii

4. Data Analysis from the Observational Study
Table 4-1: ANOVA analysis results from the prime data set on %COWY. 171
Table 4-2: ANOVA analysis for %COWY from the entire data set. 173
Table 4-3: ANOVA analysis from the prime data set on %IOWY. 177
Table 4-4: Effects test from %IOWY ANOVA analysis for the entire data set
with pH component. 179
Table 4-5: ANOVA analysis for the %IOWY from the entire data set. 180
Table 4-6: ANOVA analysis of Integ shade from the prime data set. 183
Table 4-7: ANOVA analysis for Integ from the entire data set. 185
Table 4-8: ANOVA analysis results from the prime data set and penetration level. 189
Table 4-9: Effect tests for all data points with speed and pH interaction. 191
Table 4-10: Final empirical model ANOVA analysis for all data sets. 192
Table 4-11: ANOVA analysis results for fiber diffusion coefficient. 221
Table 4-12: ANOVA analysis results for yarn diffusion coefficient. 225
Table 4-13: ANOVA analysis for wet pick-up coefficient. 229
Table 4-14: ANOVA analysis results for wash reduction coefficient. 232
Table 4-15: ANOVA analysis results for oxidation rate coefficient. 235
5. Empirical and Theoretical Dye Model simulation and validation
Table 5-1: Canadian dye range set-up conditions used for simulation. 239
Table 5-2: ANOVA analysis results of empirical model to actual measured %COWY. 241
Table 5-3: ANOVA analysis results of dye theory model to actual measured %COWY. 242
Table 5-4: ANOVA analysis results of empirical model to actual measured %IOWY. 244
Table 5-5: ANOVA analysis results of dye theory model to actual measured %IOWY. 245
Table 5-6: ANOVA analysis results of empirical model to actual measured Integ. 247
Table 5-7: ANOVA analysis results of dye theory model to actual measured Integ. 248
Table 5-8: ANOVA analysis results of empirical model to actual measured
penetration level. 250
Table 5-9: ANOVA analysis results of dye theory model to actual measured
penetration level. 251
Table 5-10: ANOVA analysis results of empirical model indirect penetration
level to actual measured penetration level. 256
Table 5-11: Production Yarn Dye Range Set-up Conditions. 257
Table 5-12: Measured, Empirical Model, and Dye Theory Model %IOWY and Integ values. 257
Table 5-13: ANOVA analysis results of empirical model to actual measured
production yarn %IOWY. 259
Table 5-14: Calculated porosity value to fit Dye theory model %IOWY to
production yarn results. 259
Table 5-15: ANOVA analysis results of dye theory model to actual measured
production yarn %IOWY. 261
Table 5-16: ANOVA analysis results of empirical model to actual measured
production yarn Integ. 262

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Table 5-17: ANOVA analysis results of dye theory model to actual measured
production yarn Integ. 264
Table 5-18: ANOVA analysis results of dye theory model calculated porosity
value to dye range speed. 265
6. Summary of Results, Discussions, and Recommendations
Table 6-1: Empirical model performance review. 271
Table 6-2: Dye theory model performance review. 271

Appendix
Table A-3-1: % Reflectance of mock dyed 100% cotton yarns used to calculate K/S. 282
Table A-3-3: %IOWY and Integ shade data from equilibrium sorption experiment. 283
Table A-4-1: Prime and replica raw data set. 284
Table A-4-2a: Convergence test - standard errors from empirical model %COWY parameter. 370
Table A-4-2b: Convergence test - standard errors from empirical model %IOWY parameter. 370
Table A-4-2c: Convergence test - standard errors from empirical model Integ parameter. 371
Table A-4-2d: Convergence test - standard errors from empirical model penetration level
parameter. 371
Table A-5-1: Independent dye range raw data set. 396


ix

LIST OF FIGURES
1. Indigo Dyeing Principles: Review of Current Knowledge
Figure 1-1: Typical dye range equipment to apply indigo dye. 2
Figure 1-2: Pre-scour section on long chain indigo dye range. 3
Figure 1-3: Indigo dye boxes on long chain dye range. 4
Figure 1-4: Wash and dry section of long chain indigo dye range. 5
Figure 1-5: Re-circulation system on long chain indigo dye range to maintain dye
box uniformity. 6
Figure 1-6: Oxidized and reduced form of indigo dye. 8
Figure 1-7: Various forms of indigo: I - Oxidized, II - Reduced acid leuco,
III - Monophenolate, and IV - Biphenolate. 11
Figure 1-8: Fraction of leuco reduced indigo as a function of pH. 14
Figure 1-9: Specific Absorptivity of oxidized and reduced indigo as a function of wavelength. 15
Figure 1-10: Redox potential curve of reduced indigo undergoing oxidation
by sodium hypochlorite. 16
Figure 1-11: Calibration curve of Sahin laser diode spectrometer. 17
Figure 1-12: Kubelka-Munk analysis of downward and upward components of light flux. 19
Figure 1-13: Calculated R-square values for blue, red, and yellow dyes at various
surface reflectances. 24
Figure 1-14: Calculated y intercepts for blue, red, and yellow dyes. 25
Figure 1-15: Comparison of original K/S and corrected K/S for blue, red, and yellow dyes. 26
Figure 1-16: Examples of limited ring dyeing on the left, medium in the middle,
and high degree of ring dyeing on the right picture. 27
Figure 1-17: Pre-scour caustic concentration effect of dye uptake. 28
Figure 1-18: Typical reflectance values for indigo dyed denim yarn - 6.3/1 open end
yarn at 31 m/min, 2.3 g/l, 11.9 pH, and 6 dips. 29
Figure 1-19: Typical corrected K/S values for indigo dyed denim yarn - 6.3/1 open end
yarn at 31 m/min, 2.3 g/l, 11.9 pH, and 6 dips. 29
Figure 1-20: Distribution of indigo dye and penetration level in denim yarn. 30
Figure 1-21: Basic sequence of events in dyeing fibers. 33
Figure 1-22: Graphical solution of Fick's 2nd Law for Diffusion in long cylinders. 38
Figure 1-23: Predicted fractional dye uptake as a functin of dimensionless time at
various flow rates. 42
Figure 1-24: Red 11 dye desorption at various oscillating speeds. 44
Figure 1-25: M
t
/ M

as a function of Dt/r
2
for various values of E

. 47
Figure 1-26: Effect of oxidation time on color. 58
Figure 1-27: Effect of reduction agent concentration on shade. 59
Figure 1-28: Effect of immersion time on shade. 60
Figure 1-29: Chong's effect of immersion time on uncorrected K/S. 61
Figure 1-30: Relationship between number of dips and shade. 62
Figure 1-31: Chong's relationship between number of dips and uncorrected K/S. 63
Figure 1-32: Relationship between dye bath concentration and shade. 64
Figure 1-33: Chong's relationship between dye bath concentration and uncorrected K/S. 65
x

Figure 1-34: pH effect of shade with other parameters held constant. 66
Figure 1-35: K/S shade vs % indigo on weight of yarn at various pHs. 67
Figure 1-36: Non-equilibrium Concentration of dye in fiber (g/100g) vs concentration
of dye in bath (g/100g). 68
Figure 1-37: Equilibrium isotherm for dye concentration in dye bath and fiber (g/100g). 69
Figure 1-38: Logarithmic plot of equilibrium isotherms for dye concentration. 70
Figure 1-39: Mean technical distribution as a function of dyebath pH. 71
Figure 1-40: Apparent reflectance absorptivity coefficient vs pH. 72
Figure 1-41: Reflectance absorptivity coefficient as a function of mean technical
distribution coefficient. 73
Figure 1-42: Relationship of Mono-ionic species of indigo and pH. 74
Figure 1-43: Relationship between mean technical distribution coefficient and
fraction of indigo existing as mono-ionic form. 75
Figure 1-44: Correlation of fractional distribution of apparent absorptivity
coefficient and mono-ionic form of indigo as a function of pH. 76
Figure 1-45: Indigo concentration in dye bath required to produce a given shade
depth at various pHs from a 5 dip laboratory dyeing. 77
Figure 1-46: Effect of dye bath concentration and pH on dye uptake. 78
Figure 1-47: Yarn dye uptake as a function of dye bath concentration and pH. 79
Figure 1-48: Corrected depth of shade as a linear function of indigo concentration
in yarn and dyebath pH. 80
Figure 1-49: Estimated concentration of unfixed indigo on yarn at corresponding
dye bath concentration and pH. 81

2. Objectives of the Present Investigation
3. Experimental Methods and Procedures
Figure 3-1: Relationship of maximum K/S shade shift as depth increases. 95
Figure 3-2: Relationship of K/S by wavelength as a function of %IOWY. 96
Figure 3-3: Relationship of time on %boil-off loss during laboratory preparation. 101
Figure 3-4: Relationship of sodium hydroxide concentration on %Boil-off loss
during laboratory preparation. 102
Figure 3-5: Relationship of temperature on %Boil-off loss during the laboratory preparation. 103
Figure 3-6: Interaction profile for time, temperature, and sodium hydroxide concentration
on %boil-off loss during laboratory preparation process. 104
Figure 3-7: %Boil-off loss model as a function of time (seconds), temperature (C),
and sodium hydroxide concentration (g/l) in laboratory preparation process. 106
Figure 3-8: Relationship of laboratory preparation time on %IOWY after one
and six dips of indigo dye. 107
Figure 3-9: Relationship of sodium hydroxide concentration during laboratory
preparation on %IOWY from one and six dips of indigo dye. 108
Figure 3-10: Relationship of temperature during laboratory preparation on %IOWY
from one and six dips of indigo dye. 109
Figure 3-11: Interaction profile for time, temperature, and sodium hydroxide concentration
on %IOWY after one and six dips of indigo dye. 110
xi

Figure 3-12: %IOWY for one dip of indigo model as a function of time, temperature,
and sodium hydroxide concentration in laboratory preparation process. 112
Figure 3-13: %IOWY for six dips of indigo model as a function of time, temperature,
and sodium hydroxide concentration in laboratory preparation process. 114
Figure 3-14: Relationship of laboratory preparation time on Integ shade value from
one and six dips of indigo dye. 115
Figure 3-15: Relationship of sodium hydroxide concentration during laboratory preparation
on Integ shade value after one and six dips of indigo dye. 116
Figure 3-16: Relationship of temperature during laboratory preparation on Integ shade
value after one and six dips of indigo dye. 117
Figure 3-17: Relationship of time during laboratory preparation on penetration factor
after one and six dips of indigo dye. 120
Figure 3-18: Relationship of sodium hydroxide concentration during laboratory preparation
on penetration factor after one and six dips of indigo dye. 121
Figure 3-19: Relationship of temperature during laboratory preparation on penetration
factor after one and six dips of indigo dye. 122
Figure 3-20: Interaction profile for time, temperature, and sodium hydroxide concentration
on penetration factor after one and six dips of indigo dye. 123
Figure 3-21: Penetration factor for one dip of indigo model as a function of time, temperature,
and sodium hydroxide concentration in laboratory preparation process. 124
Figure 3-22: Penetration factor for six dips of indigo model as a function of time, temperature,
and sodium hydroxide concentration in laboratory preparation process. 126
Figure 3-23: Optimized laboratory preparation parameters incorporating prediction profiles
from %Boil-off loss and %IOWY from one dip of indigo dye. 128
Figure 3-24: Optimized laboratory preparation parameters incorporating prediction profiles
from %Boil-off loss and %IOWY from six dips of indigo dye. 129
Figure 3-25: %IOWY from 6.3/1, 7.1/1, 8.0/1, and 12.0/1 OE yarns compared to Etters
20
data
under equilibrium sorption at pH 13 range. 133
Figure 3-26: %IOWY on 6.3/1, 7.1/1, 8.0/1, and 12.0/1 OE yarns compared to Etters
20
data
under equilibrium sorption at pH 11 range. 134
Figure 3-27: Power function coefficients A and B as a function of dye bath pH. 135
Figure 3-28: Equilibrium sorption power function coefficients as a function of
monophenolate ionic form of indigo. 136
Figure 3-29: Comparison of calculated and measured %IOWY under equilibrium sorption
laboratory dyeing conditions as the dye bath concentration and pH were varied. 137
Figure 3-30: Relationship of Integ shade value for various yarn counts as %IOWY from
equilibrium sorption. 138
Figure 3-31: Relationship of %IOWY on the outside surface for various yarn counts as Integ
from equilibrium sorption. 139
Figure 3-32: Shape of K/S at 660 nm as a function of %IOWY from equilibrium sorption
experiments. 140
Figure 3-33: Range of observational study dye range set-up conditions and interactions. 143
Figure 3-34: Affect of additional replicated data sets on standard error of indigo dye bath
concentration parameter and four response variables after one dip of indigo. 145

xii

4. Data Analysis from the Observational Study
Figure 4-1: Number of dips affect on %COWY and %IOWY for all data points. 146
Figure 4-2: Build curve relationship for %COWY as a function of number of dips on
6.3/1 yarn count at similar speed, pH, and reduction potential. 147
Figure 4-3: Build curve relationship for %IOWY as a function of number of dips on
6.3/1 yarn count at similar speed, pH, and reduction potential. 148
Figure 4-4: Integ shade value as a function of number of indigo dye box dips for
all data points. 149
Figure 4-5: Integ shade value as a function of number of dips on 6.3/1 yarn count at
similar speed, pH, and reduction potential. 150
Figure 4-6: Penetration level for all data points as a function of the number of dips. 151
Figure 4-7: Penetration level as a function of number of dips on 6.3/1 yarn count at
similar speed, pH, and reduction potential. 152
Figure 4-8: %COWY for all data points as a function of dye bath concentration after
one, three, and six dips. 153
Figure 4-9: %IOWY for all data points as a function of dye bath concentration after
one, three, and six dips. 154
Figure 4-10: Integ shade value as a function of dye bath concentration at various
numbers of dips. 155
Figure 4-11: Penetration level for all data points as a function of dye bath concentration
within each dip. 156
Figure 4-12: Illustrates %COWY, %IOWY, Integ, and penetration level varies with
yarn count and dye concentration after six dips. 158
Figure 4-13: Speed affect on %COWY, %IOWY, Integ, penetration level at various
dye bath concentrations after six dips of indigo on 6.3/1 yarn. 160
Figure 4-14: pH affect on %COWY, %IOWY, Integ, penetration level at various
dye bath concentrations after six dips of indigo on 6.3/1 yarn. 162
Figure 4-15: Reduction potential affect on %COWY, %IOWY, Integ, and penetration level
at various dye bath concentrations after six dips of indigo on 6.3/1 yarn. 164
Figure 4-16: Dwell length affect on %COWY, %IOWY, Integ, and penetration level at
various dye bath concentrations after six dips of indigo on 6.3/1 yarn. 166
Figure 4-17: Dwell time affect on %COWY, %IOWY, Integ, and penetration level at
various dye bath concentrations after six dips of indigo on 6.3/1 yarn. 168
Figure 4-18: Nip pressure affect on %COWY, %IOWY, Integ, and penetration level at
various dye bath concentrations after six dips of indigo on 6.3/1 yarn. 169
Figure 4-19: Convergence test for empirical %COWY model. 172
Figure 4-20: Comparison of actual versus predicted %COWY for the entire data set. 175
Figure 4-21: %COWY prediction profile for dye range set-up condition affect on %COWY
from the empirical model. 176
Figure 4-22: Convergence test for the empirical %IOWY model. 178
Figure 4-23: Comparison of actual and predicted %IOWY from the final empirical model. 181
Figure 4-24: Prediction profile for %IOWY and dye range set-up parameters. 182
Figure 4-25: Convergence test for empirical model Integ. 184
Figure 4-26: Comparison of actual and empirical model predicted Integ shade values. 186

xiii

Figure 4-27: Prediction profile for Integ shade values as a function of each dye
range set-up conditions. 187
Figure 4-28: Convergence test for empirical model penetration level. 190
Figure 4-29: Comparison between actual and predicted penetration level. 194
Figure 4-30: Prediction profile of empirical model penetration level as a function of
dye range set-up parameters. 195
Figure 4-31: Nodal mesh arrangement and nomenclature for finite difference
method implementation. 205
Figure 4-32: Fiber diffusion coefficients for each yarn count as the oxidation rate changes. 215
Figure 4-33: Yarn diffusion coefficients for each yarn count as a function of oxidation rate. 216
Figure 4-34: Wet pick-up variation within yarn counts as a function of oxidation rate. 217
Figure 4-35: Standard deviations as a function of oxidation rate. 218
Figure 4-36: Comparison of model predicted and actual fiber diffusion coefficient. 222
Figure 4-37: Effective fiber diffusion functional relationship to dye range set-up conditions. 223
Figure 4-38: Comparison of model predicted and actual yarn diffusion coefficient. 226
Figure 4-39: Effective yarn diffusion functional relationship to dye range set-up conditions. 227
Figure 4-40: Comparison of model predicted and actual wet pick-up coefficient. 230
Figure 4-41: Dye theory model wet pick-up functional relationship to dye range
set-up conditions. 231
Figure 4-42: Comparison of model predicted and actual wash reduction. 233
Figure 4-43: Dye theory model wash reduction functional relationship to dye range
set-up conditions. 234
Figure 4-44: Comparison of model predicted and actual oxidation rate. 236
Figure 4-45: Dye theory model oxidation rate functional relationship to dye range
set-up conditions. 237
5. Empirical and Theoretical Dye Model simulation and validation
Figure 5-1: Empirical model predicted %COWY compared to actual measured values. 240
Figure 5-2: Dye theory model predicted %COWY compared to actual measured values. 242
Figure 5-3: Empirical model predicted %IOWY compared to actual measured values. 243
Figure 5-4: Dye theory model predicted %IOWY compared to actual measured values. 245
Figure 5-5: Empirical model predicted Integ compared to actual measured values. 246
Figure 5-6: Dye theory model predicted Integ compared to actual measured values. 248
Figure 5-7: Empirical model predicted penetration level compared to actual measured values. 249
Figure 5-8: Dye theory model predicted penetration level compared to actual measured
values. 251
Figure 5-9: Indigo build profile for Canadian dye range set-up on 443 shade
with 29 m/min, 1.26 g/l dye bath concentration and 12.2 pH. 253
Figure 5-10: Indigo build profile for Canadian dye range set-up on 418 shade with
32 m/min, 1.66 g/l dye bath concentration and 11.8 pH. 254
Figure 5-11: Indigo build profile for Canadian dye range set-up on 471 shade with
32 m/min, 2.09 g/l dye bath concentration and 12.1 pH. 254
Figure 5-12: Empirical model predicted indirect penetration level compared to
actual measured values. 255

xiv

Figure 5-13: Empirical model predicted %IOWY compared to actual measured values
from production yarns. 258
Figure 5-14: Dye theory model predicted %IOWY compared to actual measured values
from production yarns. 260
Figure 5-15: Empirical model predicted Integ compared to actual measured values
from production yarns. 262
Figure 5-16: Dye theory model predicted Integ compared to actual measured values
from production yarns. 263
Figure 5-17: Functional relationship between theoretical porosity value and
dye range speed. 265
6. Summary of Results, Discussions, and Recommendations

xv

LIST OF EQUATIONS
1. Indigo Dyeing Principles: Review of Current Knowledge
Equation 1-1: First law of thermodynamics. 6
Equation 1-2: Example calculation of percent indigo shade. 7
Equation 1-3: Reaction of sodium dithionite and sodium hydroxide. 8
Equation 1-4: First ionization of indigo dye. 11
Equation 1-5: First associated equilibrium ionization constant. 12
Equation 1-6: Second ionization of indigo dye. 12
Equation 1-7: Second associated equilibrium ionization constant. 12
Equation 1-8: Indigo fractional form calculation based on pH and respective pka values. 13
Equation 1-9: Change in downward flux by Kubelka-Munk. 20
Equation 1-10: Change in upward flux by Kubelka-Munk. 20
Equation 1-11: Kubelka-Munk reflectance equation. 20
Equation 1-12: Kubelka-Munk equation for light absorbance and scattering. 21
Equation 1-13: Correction to Kubelka-Munk for light reflectance properties of mock dyed
substrate. 21
Equation 1-14: Corrected Kubelka-Munk to account for surface reflectance. 22
Equation 1-15: Relationship of K/S corrected to dye bath concentration. 22
Equation 1-16: L*, a*, and b* equations based on the tristimulus values as defined by CIELAB. 23
Equation 1-17: Calculation of Integ as a function of K/S values, average observer, and
standard light source. 23
Equation 1-18: Adjusting K/Scorr for non-uniformly distributed dye. 31
Equation 1-19: Fick's first law of diffusion. 35
Equation 1-20: Fick's second law of diffusion. 36
Equation 1-21: Expansion of Fick's second law of diffusion into cylindrical coordinate system. 36
Equation 1-22: Reduction of Fick's second law of diffusion to radial component only. 36
Equation 1-23: Non-steady state solution to equation 1-21. 37
Equation 1-24: Solution of diffusion from constant initial concentration. 37
Equation 1-25: Hill's solution of dye concentration under infinite dye bath conditions. 39
Equation 1-26: Newman's solution of dye concentration under infinite dye bath conditions that
contain surface barrier effects. 40
Equation 1-27: Definition of L term utilized in Newman's dye concentration solution. 40
Equation 1-28: Othmer-Thakar relationship for diffusion coefficient in dilute aqueous solutions. 41
Equation 1-29: Vickerstaff one parameter approximate solution for dye distribution. 44
Equation 1-30: Urbanik two parameter approximate solution for dye distribution. 45
Equation 1-31: Etters three parameter approximate solution for dye distribution. 45
Equation 1-32: Etters empirical fit equation to calculate parameters in three parameter
approximate solution of dye distribution when L is 20 to infinity. 46
Equation 1-33: Etters empirical fit equation to calculate parameters a in three parameter
approximate solution of dye distribution when L is 1 to 20. 46
Equation 1-34: Etters empirical fit equation to calculate parameters b in three parameter
approximate solution of dye distribution when L is 1 to 20. 46

xvi

Equation 1-35: Etters empirical fit equation to calculate parameters c in three parameter
approximate solution of dye distribution when L is 1 to 20. 47
Equation 1-36: Etters relationship for apparent diffusion coefficient and three parameter
estimates. 48
Equation 1-37: Calculation of Integ as a function of K/S values, average observer, and
standard light source. 57
Equation 1-38: Mono-ionic fraction form of indigo dye as function of pH. 73
Equation 1-39: Definition of technical distribution coefficient. 82
Equation 1-40: Approximation for technical distribution coefficient as a function of dye bath pH. 82
Equation 1-41: Empirical model of apparent reflectance absorptivity coefficient. 82
2. Objectives of the Present Investigation
3. Experimental Methods and Procedures
Equation 3-1: Calculation of %Boil off loss. 91
Equation 3-2: Calculation of %COWY. 91
Equation 3-3: Calculation of %IOWYwash. 91
Equation 3-4: Calculation of %IOWY by Methyl Pyrrolidinone extraction. 92
Equation 3-5: Calculation of %IOWY in terms of 100% indigo paste from Methyl Pyrrolidinone
extracts. 93
Equation 3-6: Calculation of K/S from Kubelka-Munk. 94
Equation 3-7: Calculation of Integ shade value from K/S values. 94
Equation 3-8: Calculation of penetration factor from Integ and %IOWY. 97
Equation 3-9: %Boil-off loss as a function of time, temperature, and sodium hydroxide
concentration. 105
Equation 3-10: %IOWY as a function of time, temperature, and sodium hydroxide
concentration after one dip of indigo. 111
Equation 3-11: %IOWY as a function of time, temperature, and sodium hydroxide
concentration after six dips of indigo. 113
Equation 3-12: Calculation of penetration level as a function of measured %IOWY and
converted surface %IOWY from Integ shade reading. 130
Equation 3-13: Power function relationship of indigo dye bath concentration to %IOWY under
equilibrium sorption. 134
Equation 3-14: General relationships between indigo dye bath concentration and pH to
resulting %IOWY under equilibrium sorption. 136
Equation 3-15: Calculation of Integ shade based on %IOWY under equilibrium sorption. 139
Equation 3-16: Calculation of surface %IOWY from Integ shade values. 139
4. Data Analysis from the Observational Study
Equation 4-1: Empirical model %COWY as a function of dye range set-up conditions. 174
Equation 4-2: Empirical model %IOWY as a function of dye range set-up conditions. 181
Equation 4-3: Empirical model Integ as a function of dye range set-up conditions. 186
Equation 4-4: Empirical model penetration level as a function of dye range set-up conditions. 193
Equation 4-5: Ozisik diffusion coefficient calculation in external medium. 197
Equation 4-6: Fick's first and second law of diffusion. 200
Equation 4-7: Transient second order partial differential of mass diffusion in radial direction. 200
xvii

Equation 4-8: Crank-Nicholson explicit finite difference model for mass diffusion. 201
Equation 4-9: Actual %IOWY based on maximum possible %IOWY and fractional relationship. 202
Equation 4-10: Crank's expression for the fractional relationship of dye pick-up. 202
Equation 4-11: Maximum %IOWY from equilibrium sorption experiments. 202
Equation 4-12: Fractional relationship between indigo leaving the dye bath stream and dye
diffused into the cotton fiber. 203
Equation 4-13: Initial dye distribution at t<0. 203
Equation 4-14: Dye bath concentration at the outside surface node. 203
Equation 4-15: Boundary condition at the center of the yarn due to symmetry. 204
Equation 4-16: Functional relationship of %IOWY at the surface related to Integ shade. 204
Equation 4-17: Relationship of surface %IOWY by Integ shade. 204
Equation 4-18: Nodal equation for center node. 206
Equation 4-19: Nodal equation for interior nodes. 206
Equation 4-20: Nodal equation for exterior node. 206
Equation 4-21: Expression for lambda and beta coefficients in the nodal equations. 206
Equation 4-22: Matrix example of all nodal equations in finite difference model. 207
Equation 4-23: Mogahzy's relationship for open end yarn radius as a function of yarn count. 207
Equation 4-24: Calculation of oxidized boundary layer as a function of wash reduction
coefficient, and %COWY and %IOWY from the previous dip. 208
Equation 4-25: Determining the reduced boundary layer concentration and quantity after the
nip process. 209
Equation 4-26: Explicit finite difference equation for oxygen distribution in the nodal mesh. 209
Equation 4-27: Rate of oxygen removal from the air stream. 209
Equation 4-28: Fraction of oxygen removed from the air stream as a function of total reduced
dye present. 210
Equation 4-29: Boundary conditions for solving finite difference equations. 210
Equation 4-30: Equations used to track the convergence of reduced indigo dye into oxidized
state. 211
Equation 4-31: Chemical reactions and intermediaries during the oxidation process. 212
Equation 4-32: Relationship for the grams of auxiliary chemicals per gram of indigo present. 212
Equation 4-33: Calculation of the %COWY based on total indigo amounts. 213
Equation 4-34: Dye theory model effective fiber diffusion coefficient. 222
Equation 4-35: Dye theory model prediction equation of effective yarn diffusion coefficient. 226
Equation 4-36: Dye theory model prediction equation wet pick-up. 230
Equation 4-37: Dye theory model prediction equation of wash reduction. 233
Equation 4-38: Dye theory model prediction equation of oxidation rate. 236
5. Empirical and Theoretical Dye Model simulation and validation
6. Summary of Results, Discussions, and Recommendations
Equation 6-1: Equations to calculate %IOWY as a function of dye bath concentration and pH
under equilibrium sorption conditions. 267
Equation 6-2: Expressions to relate penetration level of non-uniformly dyed yarns. 268

xviii

Appendix
Equation A-1-1: oz/gal of 20% indigo related by %T by spectrophotometric method. 280
Equation A-1-2: Calculation of total alkalinity by titration method. 281

1

1 Indigo Dyeing Principles: Review of Current Knowledge

Indigo is a vat dye which was probably one of the oldest known coloring agents and has
been used to dye fabric for thousands of years. In fact, it is thought that this ancient dye was the
first naturally occurring blue colorant discovered by primitive man. The origin of the name indigo
can be traced back to the word Indic which means of India. Indigo has also been greatly valued by
the Chinese. Egyptian Mummy cloths have been discovered that were dyed with the ntinkon, a
blue dye having all the properties of indigo.
Today, the indigo used in commercial dyeing of denim yarn is no longer of natural origin.
After 12 years of research by Adolf von Baeyer, a method of laboratory synthesis of indigo was
discovered in 1880. By 1897 the first commercial form of indigo based on Baeyers method
appeared on the market. After the turn of the 20
th
century, synthetic indigo gradually replaced
natural dye worldwide. Over the last hundred plus years more indigo dye has been produced than
any other single dye.
Even though indigo is classified as a vat dye, it does not perform like other vat dyes because
it has little affinity for cotton. Compared to other vat dyes, indigo has inferior fastness properties.
But these poor performance properties are indeed the very nature of the dye which makes it so
popular. Due to the poor fastness properties, a desirable blue shade develops when indigo dyed
denim is laundered repeatedly.
If indigo was introduced today, not many dyers or chemists would be interested. In fact, it
might not even leave the lab compared to todays requirements for commercializing a new dye.
Zollinger noted in 1988
19
, Were it not for the persistence of the denim fashion, indigo would hardly
be produced or used at all today. This statement still rings true today. Given the extensive use of
indigo in commercial dyeing applications, one would speculate the literature would be filled with
fundamental experiments and knowledge of the use and driving properties of this important dye. At
last, until recently this is not the case. It wasnt until the end of the 1980s when the Southeastern
Section of the AATCC committee lead by investigations of J.N. Etters that significant research
revealed the physico-chemical mechanisms of the sorption of indigo by cellulosic materials.
2

1.1 Commercial Indigo Dyeing
Indigo dye (C.I. Vat Blue 1) is insoluble in water. In order to effectively be used it must be
reduced to the leuco-soluble form using a suitable reducing agent with an alkali such as sodium
hydroxide. There are three main types of dye ranges used in traditional indigo dyeing which are
summarized below and shown in figure 1-1.
1. The long chain or rope type dye range which is characterized by multiple dye boxes that
allows great production rate and flexibility.
2. The sheet or slasher dye range which can have multiple boxes but with reduced
production capability.
3. The looptex dye range which has a common dye box. This machine has limited number of
dip capability. Figure 1-1 graphically illustrates the three types of machines.



Figure 1-1: Typical dye range equipment to apply indigo dye.
1

3

The majority of denim yarns dyed with indigo utilizes the 6-dip (or more) continuous rope
dye range. A typical rope dye range will process 20 to 40 ropes of yarns at a time. The exact
number will be predetermined by machine layout and subsequent slasher restrictions. 300-400
individual yarns make up a single rope. The final number of ropes will equate to 2 to 4 slasher sets.
This characteristic allows the continuous rope dye range to produce uniformly dyed yarn at great
production rates in a variety of shades.
Before the cotton yarns can be dyed with indigo, the cotton must be prepared. The pre-
scouring process shown in figure 1-2 involves two main objectives. First the cotton is chemically
cleaned with a penetrant, sequestering agent, and sodium hydroxide solution. Typical sodium
hydroxide concentrations range from 10-25 g/l although higher levels (mercerization strength) are
used to create unique dye characteristics. The main purpose is to remove natural waxes and oils
from the cotton fibers. During this stage sulfur dyes are commonly added to enhance the final
indigo dye shade. Multiple wash boxes follow the scour box to rinse contaminants from the yarns.
The last benefit of the pre-scour section is to remove all excess air trapped in the yarns. Excess air in
the yarns will prematurely oxidize the reducing agent and possibly indigo in the dye boxes causing
the entire system to fall out of reduction.


Figure 1-2: Pre-scour section on long chain indigo dye range.
1


4

After the last wash box in the pre-scouring section, the yarns are immediately immersed
into the first indigo dye box. There are two main ways to build the amount of indigo on weight of
yarn. 1. Indigo concentration in the dye boxes. 2. The total number of dips. Each dip is
characterized by submerging the yarn into the dye liquor for 15-60 seconds with a W type thread-
up. Then excess dye liquor is squeezed from the yarns by using 4-5 ton nip which typically produces
70 90% wet pick-up. Skying after each nip allows natural air oxidation of the leuco indigo.
Typical sky times are 1+ minute. By chaining multiple dips together as shown in figure 1-3, the
indigo shade can be built to the final desired depth. Most commercial dye ranges have 4 to 8
successive dye boxes although some extreme new machines are being manufactured with 12 indigo
dye boxes. The maximum amount of indigo applied in any one dye box is approximately 2% of 20%
indigo paste. Therefore, approximately 6 dips are required to produce a 12% indigo shade.


Figure 1-3: Indigo dye boxes on long chain dye range.
1


Following the dye boxes, the yarns are washed to remove excess alkali and any unfixed
surface dye. During this stage sulfur dye tops can be applied to further enhance the indigo shade.
Figure 1-4 shows washing begins with cool water around 80F in the first wash box and the
temperature is gradually increased by 20 degrees in each subsequent box. The final wash box is
5

usually around 140F. Just before drying begins, typically a beaming aid is applied to improve
beaming efficiency.


Figure 1-4: Wash and dry section of long chain indigo dye range.
1


Of course the main purpose of indigo dyeing is to apply indigo to the yarn. Indigo dyeing
occurs in an infinite bath condition because uniform dye concentration is maintained throughout
the dyeing process by the addition of make-up dye. Uniform dye concentration throughout all the
dye boxes is therefore paramount. Uniformity is achieved by re-circulating the dye liquor while
additional dye is metered into the range. Typical circulation system is shown in figure 1-5. Each dye
box is cross connected by 4 inch pipes located at the bottom of each box. Dye liquor is pulled from
the bottom of the vats by a circulation pump. The circulated liquor plus indigo and chemical feed
make-up is returned to each box near the top. Dye overflow is typically on the top of the first dye
box. This overflow is typically captured and re-used later.

Figure


indigo
contro


Equatio

1-5: Re-circulat
Since dye l
o dye boxes c
ol volume un

on 1-1: First law
ion system on lo
liquor is circu
can be modele
dergoing a pr

w of thermodyna
ong chain indigo
ulated throug
ed as one gia
rocess can be
=
amics
o dye range to m
h the dye box
nt dye box. T
e expressed a

maintain dye bo
xes to mainta
The conservat
s equation 1-

ox uniformity.
1

ain uniform co
tion of mass
-1.

oncentrations
principle for a

6

s, the
a
7

The purpose of measuring the indigo concentration in the dye liquor is to maintain a
constant dye concentration so the net change in mass within the control volume equals zero.
Therefore the total mass entering equals total mass leaving the dye box. Total mass entering the
dye box is generally known. The concentration of indigo stock mix is predetermined and the feed
rate is measured by flow meters. The total mass leaving the system is divided into two components.
1. Indigo pick-up in the cotton yarns. 2. Indigo in the overflow from indigo dye box. Typical indigo
shades are expressed in terms of % indigo shades. This is calculated by dividing the pounds of indigo
per hour by the pounds of cotton per hour. For example:

3.75 pound/gallon indigo stock mix
78.3 gallons/hour indigo stock mix feed rate
293.6 pounds of indigo/hour feed rate
3673 pounds cotton/hour
293.6/3673=8.0% indigo shade
Equation 1-2: Example calculation of % indigo shade

The approach shown in equation 1-2 neglects the indigo mass component in the overflow.
For a more accurate % indigo shade calculation, the mass of the discharged indigo must be
considered. Additionally, unfixed indigo removed from the dye bath on the yarn but later removed
during the washing process must be accounted for. Due to the complexity of measuring these
discrepancies, many indigo dyers refer to equation 1-2 for its simplicity.

1.2 Indigo Chemistry
1.2.1 Indigo Reduction or Vatting
Reduced indigo is called leuco indigo and is yellow in color. Leuco indigo can dye cellulose
materials and will later be oxidized back to blue color. The traditional reducing agent is sodium
dithionite also called sodium hydrosulphite or simply hydro. Other reducing agents fill special
demands and have not gained large practical acceptance. Hydro is extremely sensitive to
8

atmospheric oxygen. Oxidation of hydro is accompanied by consuming sodium hydroxide, NaOH,
when atmospheric oxygen is present in the alkaline medium.
The reduction of indigo dye requires two chemical processes as shown in equation 1-3 and
figure 1-6. Caustic and sodium hydrosulfite react to liberate two hydrogen atoms which react with
the two carbonyl groups (C = O) on the indigo molecule. Additional sodium hydroxide reacts with C
OH group to form C ONa group which solubilizes the dye into leuco indigo.

4
+2
cIds
--2
-
+ 2
2

3

Equation 1-3: Reaction of sodium dithionite and sodium hydroxide


Figure 1-6: Oxidized and reduced form of indigo dye.
1


The theoretical calculations of caustic and hydro in indigo stock mix are as follows. The
molecular weight of indigo, hydro, and caustic are 262.26, 174.11, and 40.01 respectively. From the
above two reactions 4 moles of 100% NaOH and 1 mole of 100% Na
2
S
2
O
4
(Hydro) are required to
completely reduce 1 mole of 100% indigo. In commercial operations, excess sodium hydroxide and
9

hydrosulphite are used to reduce indigo. An example of a typical indigo stock mix formula is given in
table 1-1.

Table 1-1: Typical Stock Mix.
As is
#/Gal
As is
g/l
% OWI 100%
g/l
Total
Moles
Theory
Moles
Excess
Moles
Excess
g/l
Indigo 3.75 450 -- 90 0.343 0.343 -- --
Caustic 1.50 180 40 112.5* 2.813 1.372 1.441 57.6
Hydro 0.60 72 16 64.8 0.372 0.343 0.029 5.1
* Includes the caustic present in the Indigo paste (5.2%).

The excess caustic and hydro are present to ensure complete reduction is reached and
maintained for the life of the mix. Additionally the excess chemicals will reduce the required
auxiliary chemical feed rates to maintain the desired pH during the dyeing process. In order to
maintain proper reduction of the indigo in the dye boxes, a total hydro consumption factor based on
the weight of the Indigo (OWI) would be approximately 32%.
Other typical indigo stock mixes follow formulas in table 1-2 and 1-3. Table 1-2 formula will
produce a 3.75 lb/gal or 450 g/l indigo concentration. Vatting or reducing the indigo usually occurs
at 50 C in approximately 30 minutes. Properly vatted indigo is yellow or amber in color. The liquor
turns green in 12-15 seconds on clean glass as air oxidation begins.

Table 1-2: A typical indigo stock mix formula.
1

Stock Mix concentration
Gallons Lbs Lbs/Gal oz/gal g/l
Indigo 20% Paste 320 3000 3.75 60 450
Sodium Hydroxide 50% 94 1200 1.50 24 180
Liq. Hydro 170g/l 340 3250 4.06 65 490
Water 46 382 - - -
Total Volume 800

10

Table 1-3: Additional indigo stock mix recipes.
13

Plant 20% Indigo
Paste (g/l)
50% Caustic
Soda (g/l)
Hydro (g/l) 50% Caustic
Soda (%I)
Hydro (%I)
1 450 143 68 31.77 15.11
2 414 140 54 33.77 13.09
3 382 140 71 36.79 18.55
4 400 118 60 29.5 15
5 450 136 69 30.02 15.33
6 420 121 64 28.17 15.33
7 450 150 75 33.33 16.67
8 381 120 63 31.49 16.54
9 400 270 64 67.5 16.5

1.2.2 Classification of Indigo Dye Species
Indigo dye can exist as four species as shown in figure 1-7:
I. oxidized or keto indigo.
II. Reduced nonionic acid leuco indigo.
III. Monophenolate ion of reduced indigo.
IV. Biphenolate ion of reduced indigo.

Both forms I and II are highly insoluble compounds of unknown solubility and virtually no
substantivity for cotton. The solubility of the other species III and IV can be calculated when given
the pKas of the reduced forms. These two ionic forms vary greatly with di-ionic form having the
higher solubility but lower substantivity. The mono-ionic form of indigo predominates in the lower
pH ranges of 11.
11


Figure 1-7: Various forms of indigo: I - Oxidized, II - Reduced acid leuco, III - Monophenolate, and IV - Biphenolate.
17


Indigo can undergo a two-step ionization to produce the two ionic species: mono-ionic and
di-ionic or the monophenolate and biphenolate forms respectively. The relative amount of each
species is governed by the pH of the dye bath. The poorly water-soluble nonionic or acid leuco
form of reduced indigo can be abbreviated as H
2
I where H is hydrogen and I represents indigo. The
first ionization step produces the more soluble mono-ionic form of indigo, HI
-
as shown in equation
1-4.

2

+
+
-

Equation 1-4: First ionization of indigo dye


12

The associated equilibrium ionization constant k
1
is given by equation 1-5.

1
=
|H
+
]|HI
-
]
|H
2
I]

Equation 1-5: First associated equilibrium ionization constant

The second ionization step produces the even more soluble di-ionic form of indigo, I
2-
by equation 1-
6.

-

+
+
2-

Equation 1-6: Second ionization of indigo dye

The associated equilibrium ionization constant k
2
is given equation 1-7.

2
=
|H
+
]|I
2-
]
|HI
-
]

Equation 1-7: Second associated equilibrium ionization constant

The fractional distribution of each indigo dye form in figure 1-7 is governed by the pH and respective
pKa values. The functional relationship for each form is given in equations 1-8.


13

=
1
|1+10
A
+10
B
]
, = (
1
) = (2
1

2
)
=
1
|1+10
C
+10
D
]
, = (
1
) = (
2
)
=
1
|1+10
E
+10
F
]
, = (
1
+
1
2) = (
2
)
Equation 1-8: Indigo Fractional form calculation based on pH and respective pK values

A higher pKa value indictates weaker ionization. In fact, the autoprotolysis equilibrium of water has
a pKa = 14.00. The relatively high value of 14 indicates only a few water molecules are ionized.
8

In 1993 the actual pK
1
and pK
2
values for reduced indigo were unknown. Etters used the
values found for tetra-, tri-, di-, and mono- sulphonic acid forms of indigo. He states when these
data are extrapolated to the zero sulponic acid form, i.e. conventional reduced indigo, reasonable
estimates for pK
1
and pK
2
with 95% confidence limits are made.
25
Etters' reported pKa estimates
are: pK
1
mean value is 7.97 (limits 7.19, 8.74) and pK
2
mean value is 12.68 (limits 12.23, 13.08).
The pKas of the first and second ionization steps of the acid leuco of indigo were later
measured to be pK
1
= 9.5 and pK
2
= 12.7.
19
By using these values it is possible to calculate the
fractional amount of each reduced species of indigo in the dye bath for a given pH. Figure 1-8
illustrates the mono-ionic form dominates at pH of 11.0 while the di-ionic form reins superior at pH
of 14.0. At traditional indigo pH dye ranges of 12.0 13.0, the mono-ionic to di-ionic form ratio is
basically 50/50.
14



Figure 1-8: Fraction of leuco reduced indigo as a function of pH.
15


1.2.3 Indigo dyeing Measurement Methods
Indigo concentrations in the dye box are measured by three different methods: visual versus
standard, Spectrophotometric analysis, or gravimetric analysis. All of the above methods are
affected to some degree by sulfur contamination in the indigo boxes when a sulfur bottom is
applied. However, results should be relative to previous measurements, therefore comparative.
By far the most widely accepted indigo measurement system in commercial operations is
the %T measurement. This technique is based on the transmittance values of a spectrophotometer
reading a diluted and oxidized dye sample. A known aliquot of dye is diluted to a fixed volume with
water and allowed to oxidize. Usually the resulting measurement is compared to a predetermined
standard. By using Beers Law: A=ebc; where A is absorbance, c is concentration g/l, b is cell
thickness cm, and e is specific absorptivity L/gcm; the indigo dye concentration can be calculated.
15

The specific procedure is outlined in appendix A-1-2a. Since oxidized indigo is not water soluable,
the mixature must be constantly stirred to maintain uniform distribution.
Figure 1-9 graphically depicts the specific absorptivity of oxidized and reduced indigo. The
specific absorptivity is independent of concentration and cell thickness.


Figure 1-9: Specific Absorptivity of oxidized and reduced indigo as a function of wavelength.
53


Caustic is necessary to dissolve the reduced indigo into the leuco-indigo form. Caustic is also
the regulator of the dyeing process. Excess caustic results in increase penetration making the shade
appear weaker. Not enough caustic results in poor crocking properties, increased ring dyeing,
streaked dyeing, and/or a precipitation in the vat. The total alkalinity caustic level can be measured
by titration method. The specific method is given in appendix A-1-2b.
Sodium hydrosulfite is required to reduce the indigo and keep the indigo dye boxes in the
proper dyeing condition. Excess hydro results in increased penetration, greener and brighter
shades, weaker dyeing, potential streaking, higher cost, and slower wash down. Too little hydro
results in increased surface dyeing, redder and duller shades, color of the dye liquor changing from
16

amber to green, and/or dyeings which are not fast to washing. Sodium hydrosulfite concentrations
can be determined by volumetric titration with iodine or with K
3
[Fe(CN)
6
]. The end point is
determined either visually or potentiometrically.
The hydro level can be measured by four different methods: 1. Iodine titration. 2.
Potassium Ferricyanide titration. 3. Vatometer. 4. MV measurement of the oxidation reduction
potential (ORP) which is a composite value based on indigo, caustic and hydro concentrations.
Reduced indigo dye bath can be titrated with sodium hypochlorite to produce the following
potential curve, figure 1-10. Starting from -890 mV to point A on the curve (-850 mV), the potential
depends on the concentration of sodium hydrosulphite in the dye bath. When all the hydro is
consumed, the potential undergoes a sudden increase to point B which is about -695 mV. As indigo
is insoluble in the aqueous dye bath, the potential of the solution is therefore the potential of leuco
indigo. At point C the leuco indigo molecules are oxidized and the potential quickly rises.
Electrochemical titration methods to measure Indigo and hydro use potassium hexacyanoferrate (III)
as the titrant.


Figure 1-10: Redox potential curve of reduced indigo undergoing oxidation by sodium hypochlorite.
46

17

Several alternative methods have been developed over the years to measure and monitor
indigo and sodium hydrosulfite concentrations. Westbroek
51
used an electrochemical method using
multistep chronoamperometry. Photometric and spectrophotometric reflectance can be used to
determine indigo concentrations by potentiometric titration. However the system doesnt
differentiate between unreduced indigo and leuco indigo in the dye bath. This is due to the
oscillation of potential used to remove indigo particles from the electrode. By applying a -0.90 mV
potential across the electrode, all indigo in the sample vessel is completely reduced to leuco indigo.
Sahin
53
describes a laser diode spectrometer for monitoring indigo concentrations. A laser
diode absorption spectrometer with monochromatic radiaton emmited at 635 nm to measure
oxidized indigo absorption at the shoulder of a broad absorption peak. A linear calibration curve
between 10 and 150 mg/l is shown in figure 1-11 which corresponds to indigo concentrations in the
dye bath from 0.8 to 12 g/l (diluted with aerated water by a factor of 80). Typical dye bath indigo
concentrations ranges are 1 to 3 g/l. Sahin claims no interference due to sulfur compounds present
in dye bath which is a problem with electrochemical titration methods but no supporting evidence is
provided.


Figure 1-11: Calibration curve of Sahin laser diode spectrometer.
53

18

Another method for monitoring indigo is the Flow Injection analysis (FIA)
61
. FIA is a Real-
time analytical technique for determining leuco indigo dye concentration in batch dye bath. 20 uL
sample was introduced in FIA and diluted with 5 different reducing agents. Absorbance
measurements are made at 406 nm (maximum absorption of leuco indigo) by fiber optic coupled
spectrometer. To prevent premature oxidation, nitrogen gas was continuously bubbled in.
While many automatic systems have been developed over the years, few have gained wide
acceptance. Most automatic methods have limited success due to poisoning of the system, either
build-up on potentiometric electrodes, blocking of valves, and/or peristaltic pumps failures.
Extraction of indigo on yarns and fabrics was historically carried out by pyridine reflux. A
given dyed sample of approximately 0.5 grams would have the indigo dye removed until the solution
siphoning from the fabric was colorless. The pyridine solution extract was then brought up to 250
ml in a volumetric flask. Absorbance of the solutions at 608 nm is measured on either a single beam
spectrophotometer or a dual-beam diode array spectrophotometer. This particular method of
indigo on weight of yarn measurement is no longer utilized.
Recently Hauser and Merritt
29
demonstrated the effective use of ferrous
sulfate/triethanolamine/sodium hydroxide or Fe/TEA/OH as the extraction solvent. Approximately
0.5 gram dyed sample is placed in flask then 100 ml of pre-prepared Fe/TEA/OH solution is added.
(Fe/TEA/OH is prepared by adding 5 g/l ferrous sulfate, 50 g/l triethanolamine, and 10 g/l sodium
hydroxide (pellets) to distilled water.) The extraction is carried out at 45 C for 90 minutes on a
stirring hot plate. After 90 minutes the solution is cooled to room temperature, volume topped off
to 100 ml, and absorbance measured at 406 nm. The solutions once again follow Beers law with
dilutions made by additional reducing solution if needed.


19

1.3 Characteristics of Indigo Dyed Yarns

To accurately describe and discuss the characteristics of indigo dyed yarn, a back ground
understanding of color measurement, shade, and ring dyeing is required. Color measurement and
shade are physical measurements one can make to qualify the amount of dye on a textile substrate.
1.3.1 Color Measurement and Representation
1.3.1.a Kubelka-Munk Color Evaluation
Most opaque colored objects illuminated by white light produce diffusely reflected colored
radiation by light absorption and scattering. A function based on this fact was developed by Kubelka
and Munk in 1931. These researchers theorized that the ratio of the coefficient of light absorption,
K, to the coefficient of light scattering, S, is related to the fractional reflectance of light R
d
of a given
wavelength from the opaque substrate.
Consider the simple case of a light beam passing vertically through a very thin pigmented
layer of thickness dx in a paint film, figure 1-12. The downward (incident) and upward (reflected)
components can be considered separately by the absorption coefficient K and the scattering
coefficient S.



Figure 1-12: Kubelka-Munk analysis of downward and upward components of light flux.
9
Surface of paint film
X dx
Substrate
I J
20

The downward flux (intensity I) is:
- decreased by absorption = -KIdx
- decreased by scattering = -SIdx
- increased by backscatter = +SJdx
To yield the change in downward flux, equation 1-9 is utilized.
9


= + = ( +) +
Equation 1-9: Change in downward flux by Kubelka-Munk

The upward flux (intensity J) is:
- decreased by absorption = -KJdx
- decreased by scattering = -SJdx
- increased by backscatter = +SIdx
To yield the change in upward flux, equation 1-10 is utliized.
9


= + = ( + ) +
Equation 1-10: Change in upward flux by Kubelka-Munk

Solution of these differential equations for an isotropically absorbing and scattering layer of infinite
thickness leads to the widely used Kubelka-Munk equation, equation 1-11.
9

d
= 1 + [
K
S
_[
K
S

2
+2 [
K
S
_
12

Equation 1-11: Kubelka-Munk reflectance equation

21

This equation can be solved for K/S and the widely used form of K/S results in equation 1-12.
9

K
S
=
(1-R
d
)
2
2R
d

Equation 1-12: Kubelka-Munk equation for light absorbance and scattering

This is the most widely known form of the equation and most used by textile professionals
directly or indirectly through specialty software programs. For the equation to be of practical value
it is necessary for the equation to be corrected to take into account light reflectance properties of
the textile substrate. One correction to this equation accounts for the light reflectance (R
m
) from a
mock-dyed substrate, i.e., a substrate that has been subjected to a dyeing process containing all the
chemicals other then dye.
9

K
S
= j
(1-R
d
)
2
2R
d
[ j
(1-R
m
)
2
2R
m
[
Equation 1-13: Correction to Kubelka-Munk for light reflectance properties of mock dyed substrate

The range of applicability of the mock dyed corrected formula can be extended by
accounting for surface reflectance of the fabric. It is easily shown that as the dye content of a textile
substrate increases, less and less light is reflected from the substrate. However zero reflectance is
never achieved. Instead a low limiting value of reflectance is encountered that is insensitive to
further increases in concentration of dye in the substrate. This limiting value of reflectance is the
surface reflectance, R
s
. By including R
s
, the range of linearity is extended to higher concentrations
of dye. The final corrected K/S formula is given in equation 1-14.
9
22


K
S
co
= j
(1-R
d
-R
s
)
2
2(R
d
-R
s
)
[ j
(1-R
m
-R
s
)
2
2(R
m
-R
s
)
[
Equation 1-14: Corrected Kubelka-Munk to account for surface reflectance.

Where R
d
is the reflectance of light from the substrate containing a given concentration of dye, R
m
is
the light reflectance from a mock-dyed substrate, and R
s
is the so-called surface reflectance.
It is found that the resulting corrected K/S can be shown to be a linear function of dye
concentration in the textile substrate.
9
In equation 1-15, "C" is the concentration of dye in the
substrate and a is the reflectance absorptivity coefficient. Since the reflectance absorptivity
coefficient is equal to the value of K/S that is obtained per unit concentration of dye in the
substrate, the reflectance absorptivity coefficient is a measure of the color yield that is obtained
for a given system
25
. As the value of a increases, the greater the depth of shade for a given unit of
fixed dye.

K
S
co
=
Equation 1-15: Relationship of K/S corrected to dye bath concentration.

The definition of reflectance absorptivity coefficient requires uniform dye distribution in the
cross section of the yarn. There is only one true reflectance absorptivity coefficient, a
t
, for a given
dye/fiber system. Etters has estimated that the value of a
t
for dyeings in which indigo is uniformly
distributed in the cross-section of the substrate is approximately 40 when the dye concentration is
expressed as grams of indigo per 100 g of fiber.
33

A useful description to represent an object's color was defined by the Committee of the
Society of Dyers and Colourists in 1976 as the CIELAB system. This system defined three parameters
that related the color value of an object. The L* represents the light to dark aspect, a* describes the
23

red to green color shift, and the b* term describes the yellow to blue relationship. These values are
calculated using the equations in 1-16 that involve the tristimulus values which relate the measured
reflectance wavelength values, average observer, and the standard light source. All calculations
presented in this paper use a 10 observer and D65 standard light source. For more detailed review
please reference book 9 in the bibliography section: Colour Physics for Industry.

= 116 [

1
3
16

= Suu|[
X
X
n

1
3
[

1
3
]

= 2uu|[

1
3
[
z
z
n

1
3
]
Equation 1-16: L*, a*, and b* equations based on the tristimulus values as defined by CIELAB.

where =
L
Z
x
Z
R
Z
L
Z

Z
, =
L
Z

Z
R
Z
L
Z

Z
, and =
L
Z
z
Z
R
Z
L
Z

Z


Another method of expressing the overall color value from a sample is the Integ shade
value, equation 1-17. In this calculation the K/S at each wavelength is scaled by the average
observer and standard light source. The resulting Integ value increases in value as the overall color
depth increases.

=
K
S
x
700 nm
400 nm
E
\
(
x
+
x
+
x
)
Equation 1-17: Calculation of Integ as a function of K/S values, average observer, and standard light source.
46




24

1.3.1.b Determination of Surface Reflectance, R
s

Etters summarized a method for the determination of R
s
in 1991.
18
To determine the R
s

value, make successive linear regression analyses of K/S
corr
versus concentration for various values
of R
s
until both a high value of R
2
and a statistically optimum zero value for the intercept are found.
Etters plotted the R
2
versus R
s
values for blue, red, and yellow reactive dye on velour cotton in figure
1-13. It is revealed the R
2
value for the blue dye is insensitive to surface reflectance with all the
values being greater than 0.99. On the other hand, R
2
for the red dye exhibits much greater
sensitivity to surface reflectance, with the maximum R
2
occurring at an R
s
of about 0.01. R
2
for the
yellow dye has only limited sensitivity to surface reflectance, with the R
2
value reaching a maximum
between 0.020 and 0.025. The most important point made in figure 1-13 is that, for the present
series of dyes on the given velour substrate, the R
2
value that results from the use of an optimum
value of R
s
is only slightly improved over that which is obtained with an R
s
of zero.


Figure 1-13: Calculated R-square values for blue, red, and yellow dyes at various surface reflectances.
18

25

The intercepts of the linear regression lines obtained in the analysis of K/S
corr
versus
concentration are given as a function of surface reflectance in figure 1-14. The zero intercept for
the red and yellow dyes occur at about the same value of surface reflectance: 0.0166 and 0.0163.
However the zero intercept for the blue dye occurs at a surface reflectance of 0.0128. Yellow dye is
most sensitive to surface reflectance while the blue dye is the least.


Figure 1-14: Calculated y intercepts for blue, red, and yellow dyes.
18


From the R
2
and intercept analysis, Etters determined he could use a surface reflectance of
1.5% for each dye. Plots of K/S
corr
versus concentration in which both zero surface reflectance and
the common value of 0.015 are given in figure 1-15. In each case the linearity is significantly
improved by accounting for surface reflectance. The reflectance absorptivity coefficient (line slope)
is increased in each case. Recall the R
2
analysis indicated only small improvement by accounting for
R
s
would be expected. Yet, the surface reflectance had a dramatic visual impact on the correlation
of K/S versus concentration.
26


Figure 1-15: Comparison of original K/S and corrected K/S for blue, red, and yellow dyes.
18

Corrected
Original
Original
Original
Corrected
Corrected
27

1.3.1.c Investigating the Ring Dyeing Property of Indigo Dyed Yarn
Ring dyeing is characterized by the inner layer of fibers containing little to no dye while the
outer layer is highly pigmented. During indigo dyeing, the degree of ring dyeing can be regulated by
pH of the dye bath or pretreatments used during pre-scour section. Typically pH 11 displays better
ring dyeing, while pH 13 exhibits much greater penetration. Figure 1-16 illustrates the difference in
degree of ring dyeing between normal pre-scour and causticization as well as pH 13.3 vs pH 12.3.
Adsorption and absorption of dyestuff by textiles is strongly dependent on the nature, source, and
properties of the fibers and their surface activity.


Figure 1-16: Examples of limited ring dyeing on the left, medium in the middle, and high degree of ring dyeing on the
right picture.
19


Indigo dyeing naturally produces a ring dyed effect where the dye concentration is greater
on the surface of the yarn then the interior or core of the yarn. This characteristic is a desirable part
of the indigo dyeing and produces the aesthetic high and low or uneven shade on the final product
after garment wet processing. As mentioned earlier, the ring dye effect can be further enhanced by
causticizing or even mercerization during the pre-scouring process. The figure 1-16 illustrates the
ring dye effect from a pre-scour and causticized warp yarn. The amount of caustic used during pre-
scouring also affects the %indigo pick-up on the cotton yarns. Figure 1-17 documents the change in
indigo pick-up or uptake given constant dye range parameters with only changes in the scour box.


28


Figure 1-17: Pre-scour caustic concentration effect of dye uptake.
1


Typical % reflectance values for a 6 dip indigo shade are shown in figure 1-18. These were
measured from production dyeing on 6.3/1 open end 100% cotton yarn dyed at 31 m/min, 2.3 g/l,
11.9 pH, and 6 dips of indigo. When these % reflectance values are corrected for the mock
substrate, the K/S values as a function of wavelength can be calculated as demonstrated in figure 1-
19. Typically the wavelength of the minimum reflectance or the corresponding maximum K/S is
used for calculations. Color yield can be expressed as the depth of shade obtained for a given
amount of fixed dye. Color depth is usually expressed as K/S at the wavelength of minimum
reflectance.

Indigo Pick-up vs. Caustic Concentration in the Scour Box
0
2
4
6
8
10
12
14
1.5 5 10 20 30 45.5 61.2 80 88.2
50%NaOH Concentration (opg)
%

I
n
d
i
g
o

P
i
c
k
-
u
p
Mild Alkali Causticizing Mercerizing
29


Figure 1-18: Typical reflectance values for indigo dyed denim yarn - 6.3/1 open end yarn at 31 m/min, 2.3 g/l, 11.9 pH,
and 6 dips.



Figure 1-19: Typical corrected K/S values for indigo dyed denim yarn - 6.3/1 open end yarn at 31 m/min, 2.3 g/l, 11.9 pH,
and 6 dips.

% Reflectance Values of Typical 6 Dip Indigo Dye Shade
0
0.5
1
1.5
2
2.5
3
3.5
400 450 500 550 600 650 700
Wavelength (nm)
%

R
e
f
l
e
c
t
a
n
c
e
K/S Corrected Values of Typical 6 Dip Indigo Dye Shade
0
10
20
30
40
50
60
400 450 500 550 600 650 700
Wavelength (nm)
K
/
S

C
o
r
r
e
c
t
e
d
30

As previously illustrated in figure 1-16, microscopy has revealed that for indigo dye baths
having the same level of alkalinity, but buffered to different pHs; the resulting distribution of dye
exhibits more or less ring dyeing. When the buffered dye bath pH decreases from 13.0 to 11.0 the
denim yarn progressively becomes more and more ring dyed. Associated with the increased ring
dyeing is more color yield. When a given concentration of dye (expressed as percent on the weight
of the yarn) is located in progressively fewer and fewer fibers, the concentration of dye in each dyed
fiber increases. Reflected light from the surface of the dyed yarn is therefore lower. Etters
proposed the relationship between depth of shade (K/S) and ring dyeing for a given concentration of
dye may be approximated by accounting for dye distribution within the yarn.
22






r
p
Figure 1-20: Distribution of indigo dye and penetration level in denim yarn.
22

31

The volume of a yarn can be defined as V
m
=r
2
1, where the r is the yarn radius and using 1
as a unit length. The volume of yarn not occurred by dye when penetration is not complete (indigo
dyeing) can be expressed as V
i
= (r pr)
2
1, where p is the penetration of the yarn expressed as a
fraction of the yarn radius, r. The volume of yarn that is occupied by dye then becomes V
d
= V
m
- V
i
.
For a yarn of unit radius and length this equation reduces to V
d
= p (2 p) and the fractional
volume of yarn occupied by dye can be expressed as V
f
= p(2 p).
The effective concentration of dye in the yarn is related to the actual concentration from a
shade stand point by C
e
= C
a
/ V
f
, where C
e
is the effective concentration of dye in the yarn and C
a
is
the actual concentration of dye in the yarn. When the fractional penetration of the yarn is 1.0, i.e.
uniform dye distribution in the cross section, C
e
= C
a
. But as penetration becomes less the effective
concentration of dye becomes greater.
When dealing with indigo dyed yarn the shade values or K/S are related to the effective dye
concentration not the actual, the previously discussed K/S
corr
= a C can be adjusted for non-
uniformly distributed dye concentrations by substituting C
e
.

K
S
co
=
c

K
S
co
=
t
j
C
c
p(2-p)
[
K
S
co
=
t
j
C
c
(2p-p
2
)
[
Equation 1-18: Adjusting K/Scorr for non-uniformly distributed dye

Where a
t
in equation 1-18 is the true reflectance absorptivity coefficient for indigo that is
distributed uniformly in the cross section of the yarn (p=1). C
a
is the actual concentration of dye in
the yarn cross section, and p is the fractional penetration of the yarn by the fixed dye.


32

1.4 Dye Theory

Numerous books and articles have been published on the topic of dye theory. This review is
intended to provide a fundamental background on key topics that are relevant to indigo-cotton dye
system. This discussion will start with basic sequence of events during dyeing, then Ficks laws of
diffusion, next diffusional boundary layer, and ending with empirical simplifications. More in-depth
discussion can be found in Weisz
3
and McGregor
4
.
1.4.1. Fundamental Sequence of Events during Dyeing
Etters
28
defined four fundamental steps which outline the path of dye molecules from the
bath to the fiber as illustrated in figure 1-21.

1. Diffusion of the dye in the external medium (usually water) toward the diffusional boundary
layer at the fiber surface.
2. Diffusion of dye through the diffusional boundary layer that exists at the fiber surface.
3. Adsorption of the dye onto the fiber surface.
4. Diffusion of dye into the fiber interior by absorption.


Figure

chem
1
2
3
4
5
6

denie
1-21: Basic sequ
The rate o
ical paramete
. Denier of f
. Liquor rati
. Distributio
application
. Diffusion c
. Fundamen
. Thickness
Rate of dy
er of a given fi
uence of events
f sorption of
ers.
fiber, which is
o, the ratio o
on coefficient
n medium an
coefficient of
ntal nature of
of the diffusi
eing for a giv
iber increases
s in dyeing fibers
dye by textile
s proportiona
of volume of d
or ratio of th
d the fiber.
the dye in bo
f the dyeing sy
onal boundar
en system is
s, the surface
s.
28

e materials is
al to radius of
dye bath to th
he equilibrium
oth the applic
ystem: infinit
ry layer at the
inversely pro
e area decrea
controlled by
f the cylinder
he volume of
m concentrati
cation medium
te or finite ba
e fiber surface
portional to t
ses for a give

y several fund
fiber.
fiber mass.
on of dye in b
m and the fib
ath condition.
e.
the denier of
en mass of fib
damental phy
both the
ber.
.
the fiber. As
er available f
33
ysico-
s the
for
34

dye sorption. Accompanying the increased surface area that is associated with decreasing fiber
radius is a decreased distance that the dye on the exterior fiber surface must diffuse to fill the
fiber to an equilibrium fixation level. Lengths to diameter ratios for useful fibers are usually greater
then 1000, so the surface area contributions from the ends of the individual fibers are relatively
small and usually ignored.
Since dyeing on a continuous rope dye range is conducted under constant dye bath
concentrations, the process is defined as an infinite dye bath. Since the liquor ratio is infinitely high,
the exhaustion is zero.
28
Under infinite dye bath conditions, since dye that is absorbed at the fiber
surface is in equilibrium with dye in the dye bath, diffusion of dye into the fiber interior will occur
from a constant surface concentration.
28
From a mathematical standpoint, Etters has stated
Sorption of dye from a constant surface concentration is a much simpler system from an
experimental and analytical point of view.
31
Some argue diffusion coefficient of dye in a fiber is
really the same as it is in the surrounding aqueous medium.
28

Rate of dyeing is controlled by the rate of diffusion of dye in fiber unless a significantly
thick diffusional boundary layer exists at the fiber surface. If a diffusional boundary layer exists,
then rate of dyeing is influenced by rate of diffusion of dye in dyeing medium and fiber which may
possess different diffusion coefficients.
28

One problem related to indigo dyeing is when dye becomes immobilized as diffusion
proceeds. When diffusion is accompanied by absorption, conventional equation of diffusion in one
dimension has to be modified to allow for immobilization.
48

1.4.2 Fick's Law of Diffusion
Any discussion involving diffusion should begin with the some basic definitions.
1. Absorption: the process of absorbing. Absorb: to take up and make part of an existent whole.
2. Adsorption: the adhesion in extremely thin layer of molecules to the surface of solid bodies or
liquids with which they are in contact.
3. Desorption: the reverse of absorption or adsorption.
4. Sorption: the process of sorbing. Sorb: to take up and hold by either absorption or adsorption.
35

During the the indigo-cotton dyeing process, the following steps are assumed to occur. The
indigo dye molecules form a thin layer surrounding each cotton fiber. This process is adsorption of
dye to the fiber surface. Once the indigo dye molecules adhere to the fiber surface, indigo dye can
absorb into the fiber interior by absorption. This entire process can also be referred to as sorption
of indigo dye into the cotton fibers. If indigo dye is removed from the cotton fiber either from the
interior to the surface or from the surface to the surrounding bath, the process is referred to as
desorption.
Crank defines diffusion as the process by which matter is transported from one part of a
system to another as a result of random molecular motions.
2
Etters defines the diffusion coefficient
as a measure of the rapidity of movement of a molecule through a given medium. As the value of
diffusion coefficient increases, the speed of movement of a molecule through the medium also
increases.
28

The complicated process of dyeing is modeled on the diffusion principles outlined by Fick.
Fick recognized the relationship between diffusion and heat transfer by conduction. He adopted the
mathematical equations derived by Fourier to quantify diffusion. Ficks first law of diffusion for one
dimensional isotropic medium is written in equation 1-19.

=
C
x

Equation 1-19: Fick's first law of diffusion.
2


Here F is the rate of transfer per unit area of section, C the concentration of diffusing substance, D is
the diffusion coefficient, and x the space coordinate measured normal to the section.

36

Using Ficks first law, Ficks second law for diffusion in one dimension can be derived as
equation 1-20.

C
t
=

2
C
x
2

Equation 1-20: Fick's second law of diffusion.
2


Furthermore, the equations can be expanded to multi-dimensions in cylindrical coordinate system
to describe diffusion in cylinders.

C
t
=
1

[
C

+

0
[

C
0
+

z
[
C
z
[
Equation 1-21: Expansion of Fick's second law of diffusion into cylindrical coordinate system.
2


Here x = r cos and y = r sin , where r, , and z are cylindrical coordinates. Equation 1-21 can be
solved by the method of separation of variables, method of Laplace transformation, or numerical
solutions when the diffusion coefficient can be assumed constant.
Modeling the dye process by considering diffusion in long circular cylinders reduces the 3-
dimensional equation to the following diffusion equation 1-22.

C
t
=
1

[
C

[
Equation 1-22: Reduction of Fick's second law of diffusion to radial component only.
2



37

This equation is one dimensional since diffusion progresses radially into the yarn and is constant
around the yarn. No diffusion occurs along the axis of the yarn. The non-steady state solution for
solid cylinder with constant surface concentration and uniform initial internal concentration that
possesses the boundary conditions: C=f(r), at 0<r<a and t=0; and C=C
o
at r=a and t0, produces
equation 1-23.

=
0
|1
2
u

1
u
n

0
(
n
)
1
(
n
)
-u
n
2nt
] +
2
u
2

-u
n
2nt

0
(
n
)
1
2
(
n
)
()
0
(
n
)
Equation 1-23: Non-steady state solution to equation 1-21.
2


Here
n
s are the positive roots of J
o
which are the Bessel function of the first kind of order zero.
If the concentration is initially uniform throughout the cylinder than equation 1-23 reduces
to equation 1-24 and is graphically depicted in figure 1-22.

C-C
1
C
0
-C
1
= 1
2
u

]
0
(u
n
)c
-Do
n
2nt
u
n
]
1
(uu
n
)

Equation 1-24: Solution of diffusion from constant initial concentration.
2


Here the C is the concentration within the cylinder, C
1
is the initial uniform concentration within the
cylinder, and C
0
is the constant surface concentration on the cylinder.

38


Figure 1-22: Graphical solution of Fick's 2nd Law for Diffusion in long cylinders.
2





39

The sorption curves on figure 1-22 are defined by the dimensionless parameter Dt/a
2
.
Other formal solutions to the partial differential equation have been developed. However
there are certain limiting assumptions that must exist for the mathematical solutions to be valid.
1. It is assumed the diffusion coefficient is constant and not dependent on concentrations.
2. Equilibrium distribution coefficient of dye between fiber and dye bath is linear for a wide
range of concentrations, i.e. linear sorption isotherms.
3. All fibers are morphologically stable, homogenous, and uniformly accessible endless
cylinders.
4. No diffusional boundary layer exists in the dye bath and no skin-core effect exists in the
fiber. This results in instantaneous equilibrium between dye on fiber surface and dye in the
bath.

Given these assumptions Hill
31
has developed a solution for infinite dye bath conditions in the
absence of surface barrier effects, equation 1-25.

M
t
M

= 1
4
[
n
2

-[
n
2
[
Dt
r
2


Equation 1-25: Hill's solution of dye concentration under infinite dye bath conditions.
31


Here the
n
s are the positive transcendental Bessel roots given by J
0

n
= 0 and
M
t
M

is the fractional
equilibrium uptake of dye at a given time M
t
and at equilibrium

. An unfortunate limitation of
Hills infinite bath equation is that all of the four assumptions previously mentioned must be
present.
Newman
31
developed an alternative solution for infinite dye bath conditions that does not
require assumption #4. Namely, Newmans solution is applicable in the presence of surface barrier
effects. Due to this fact, Newmans equation (equation 1-26) is particularly useful for diagnostic or
analytical work.
40

M
t
M

= 1
4c
-
n
2
[
Dt
r
2

[
n
2
(1+

n
2
L
2
)

Equation 1-26: Newman's solution of dye concentration under infinite dye bath conditions that contain surface barrier
effects.
31


Here the
n
s are the roots of the transcendental equation:
n
J
1
(
n
) - LJ
0
(
n
) = 0 in which J
0
and J
1

again are zero and first order Bessel functions, and the dimensionless parameter, L is defined by
equation 1-27.

=

m

s
K6
D

Equation 1-27: Definition of L term utilized in Newman's dye concentration solution.

Here D
m
and D
s
are the diffusion coefficients of the diffusant in the external medium and polymer
respectively, K is the equilibrium distribution coefficient of the diffusant between the external
medium and the polymer, r is the radius of the cylinder, and
D
is the thickness of the diffusional
boundary layer.
The diffusional boundary layer is a mechanical characteristic that impedes sorption or
desorption and is inversely proportional to the rate of flow of the external medium past the surface
of the cylinder. When the rate of flow of the external medium is very high, the thickness of the
diffusional boundary layer approaches zero and the value of L approaches infinity. As the value of
L approaches infinity, the
n
2
/L
2
drops out from Newmans equation (equation 1-26) which then
becomes equivalent to Hills equation (equation 1-25).
These solutions may not directly apply to indigo dyed cotton yarn due to several underlying
assumptions. Namely the constant initial uniform concentration within the cylinder only applies
before the first dip where C
1
=0. Also the diffusion coefficient may not remain constant through
41

every dip of indigo. In fact it may be a function of the dye concentration within the yarn.
Furthermore, the skin of oxidized indigo dye on each yarn after the first dip may have a different
diffusion coefficient then the partially dyed cotton yarn.
In the absence of experimental data, the Othmer-Thakar
31
correlation can be used to
estimate the diffusion coefficient, D
s
, of various substances in dilute aqueous solutions. The
Othmer-Thakar correlation was defined in equation 1-28.

s
1u
5
=
14
0
w
1.1
v
m
0.6

Equation 1-28: Othmer-Thakar relationship for diffusion coefficient in dilute aqueous solutions.

Here U
w
is the viscosity of water in centipoises and V
m
is the molal volume of the diffusing substance
in ml per gram-mole. With the D
s
value the apparent diffusional boundary layer,
D
, can be
determined.
1.4.3. Diffusional boundary Layer
The diffusional boundary layer,
D
, potentially impedes dye uptake by the fiber. The
thickness of diffusional boundary layer is proportional to the thickness of the hydrodynamic
boundary layer and the thickness of the hydrodynamic boundary layer is inversely proportional to
velocity of flow of the bath past the fiber surface. Figure 1-23 illustrates the effect of dye bath
movement on fractional dye uptake. In case #4 of E=0 (infinite dye bath conditions), at low flow
rate 50% uptake occurs at 0.4 dimensionless time units. Whereas 50% dye uptake occurs almost at
0.2 dimensionless time units at the higher flow rate.
42


Figure 1-23: Predicted fractional dye uptake as a function of dimensionless time at various flow rates.
28


Etters evaluated Newmans equation on Disperse Red 11 in stabilized, 40 denier, 13 filament
nylon 66 tricot using desorption experiments. The results are presented in table 1-4. There was
variation in the desorption data leading to uncertainty in the computation of not only the diffusion
coefficient but also the L value. In response, the approximate L values and apparent diffusion
coefficients were determined by utilizing the % CV minimization technique.

43


Table 1-4: Estimated diffusion coefficients for disperse Red 11 (D, cm
2
/sec x 10
-10
).
31

Time (min) 15 opm (L=2) 30 opm (L=80) 90 opm (L=)
0.50 4.72 5.38 4.81
1.00 4.17 4.89 4.38
2.00 5.06 3.84 5.03
3.00 4.29 4.11 4.56
4.00 3.04 4.75 4.50
5.00 5.31 4.39 4.89
10.0 5.06 4.63 4.34
15.0 5.14 5.08 4.20
Mean 4.60 4.63 4.59
%CV 16.33 10.94 6.38


The experimental data was plotted according to Newmans equation using the mean value
of the diffusion coefficient for each value of L. When 1-
M
t
M

was plotted versus the square root of


time, an intercept on the root time axis was detected for lowest value of L, see figure 1-24. This
behavior is typical for systems in which a surface barrier exists in either the bath or the fiber. It is
also important to note, since an L value of infinity is found for the highest oscillation rate, no skin-
core effect is detected for the nylon fiber. If the value of L had not increased very much as the
oscillation rate of the bath increased, an argument could be made that the effect was caused by a
barrier that existed in the fiber surface rather than in the bath itself.

44


Figure 1-24: Red 11 dye desorption at various oscillating speeds.

1.4.4. Empirical Simplifications of Diffusion
The formal solution to Ficks 2
nd
law of diffusion is a grueling task even for a superior
mathematician. To simply the equations many empirical equations have been proposed over the
years. Three such exponential equations were compared for the efficacy in simulating the
functional relationship between
M
t
M

, Dt/r
2
, and L that is found by formal use of Newmans equation
1-26.
31
The equations that were examined are one, two, and three parameter exponential
equations. Vickerstaff suggested an empirical approximation using one parameter as shown in
equation 1-29.
31


M
t
M

= 1
-cDt
r
2

Equation 1-29: Vickerstaff one parameter approximate solution for dye distribution.
45

Urbanik was the among the first to use the two parameter equation to describe dye uptake which is
provided in equation 1-30.
31

M
t
M

= 1
(
-cDt
r
2
)
b

Equation 1-30: Urbanik two parameter approximate solution for dye distribution.

Etters developed a three parameter equation to express the functional relationship as shown in
equation 1-31.
31

M
t
M

= |1
[
-cDt
r
2

b
]
c

Equation 1-31: Etters three parameter approximate solution for dye distribution.

Each of the three equations were fitted to data obtained by the use of formal solutions to
Newmans equation for the
M
t
M

range of 0.05 to 0.95 at 0.05 intervals and associated values of Dt/r


2

for values of L ranging from infinity to 1.0. The goodness of fit is expressed as adjusted R
2
. Etters
three parameter equation provides the best fit of the three empirical exponential equations over a
very wide range of L. Only at very low values of L does the two parameter equation perform as well.
For the three parameter equation to have empirical utility for a wide range of L values, it is
necessary to express the parameters a, b, and c as a function of L. Etters derived the following
expression for L at a range of 20 to infinity.
46


=
q
0
+
q
1
L
+
q
2
L
2
1+
q
3
L
+
q
4
L
2

Equation 1-32: Etters empirical fit equation to calculate parameters in three parameter approximate solution for dye
distribution when L is 20 to infinity.
31


Here PV equals a, b, or c in his three parameter equation for L range of 20 to infinity.
parameter a: q
0
=5.530554, q
1
=160.58898, q
2
=-1750.616, q
3
=37.494042, q
4
=-374.48753
parameter b: q
0
=1.2479036, q
1
=27.400938, q
2
=88.43848, q
3
=33.90477, q
4
=52.505626
parameter c: q
0
=0.3798136, q
1
=12.004462, q
2
=-6.8204581, q
3
=11.003091, q
4
=5.3552691
For L range from 20 to 1, the three equations shown in equations 1-33, 1-34, and 1-35
accurately express the parameter values of a, b, and c which are utilized in equation 1-30.

=
0
+
q
1
L
ln
1
L
+
2
_
1
L
+
3
_
1
L

Equation 1-33: Etters empirical fit equation to calculate parameter a in three parameter approximate solution for dye
distribution when L is 1 to 20.
31


Here: q
0
=4.098044891, q
1
=3.024653177, q
2
=-2.49630292, q
3
=2.59232464

=
0
+
q
1
L
+
2
ln
1
L
+
q
3
1
L
_
1
L

Equation 1-34: Etters empirical fit equation to calculate parameter b in three parameter approximate solution for dye
distribution when L is 1 to 20.
31


Here: q
0
=1.179748591, q
1
=-0.14496394, q
2
=0.094386506, q
3
=0.001282442
47

=
0
+
q
1
L
2
+
q
2
L
2
_
1
L
+
q
3
_
1
L

Equation 1-35: Etters empirical fit equation to calculate parameter c in three parameter approximate solution for dye
distribution when L is 1 to 20.
31


Here: q
0
=0.916905399, q
1
=0.146475883, q
2
=-0.08873859, q
3
=-0.06737345

Etters supplied supporting evidence that the strength of the relationship is nearly as
accurate as the formal equation of Newman and can be used with confidence as an analytical tool.
31

Regression analysis is made according to the following equation for various values of c until,
simply through trial and error, a value of c is found which results in the highest degree of
linearization in a graphical plot of ln {-ln[1 (
M
t
M

)
1/c
]} versus ln(Dt/r
2
) as shown in figure 1-25.


Figure 1-25: M
t
/ M

as a function of Dt/r
2
for various values of E

.
10

48


As shown in Figure 1-25, the above technique results in a series of nearly straight lines
corresponding to various values of equilibrium bath exhaustion, E

. The slope of each line defines


the parameter b and the line intercept I (at Dt/r
2
=1) gives the parameter a, a=e
I
. Table 1-5
summarizes the regression values for a, b, and c for various E

. For infinite dye bath conditions,


E

= 0, table 1-5 gives the following values: a=5.3454, b=1.1299, and 1/c=2.3.


Table 1-5: Regression values for three parameter emphirical solution.
10

E

a b 1/c
0.995 13.4067 0.1150 0.0625
0.98 10.6394 0.1619 0.17
0.95 9.0635 0.2177 0.32
0.90 8.1074 0.2904 0.52
0.75 7.2074 0.4742 1.00
0.50 6.5849 0.7373 1.60
0.30 6.1410 0.9319 2.00
0.00 5.3454 1.1299 2.30

Rearranging Etters three parameter equation permits the direct calculation of the apparent
diffusion coefficient D as shown in equation 1-36.

= [

2
t
|
-In( 1-[
M
t
M

1
c
)
u
)]
1
b

Equation 1-36: Etters relationship for apparent diffusion coefficient and three parameter estimates.
31




49

1.5 Indigo Dyeing Experiments

The methods and procedures used by various experimenters will be presented in one
section for direct comparison. The cotton yarn and fabric substrate from each experiment should be
noted as well as the dye procedure. Later the actual results from all experiments have been
grouped together. This will facilitate discussion of a particular topic based on all available analysis.
1.5.1. Previous Investigations and Methods on Indigo Dyeing
Southeastern Section of AATCC 1989 Experiment
15

The Southeastern Section Research Committee published a paper in 1989 investigating the
effect of dye bath pH on color yield. This study used 8/1s yarn knitted into tube form having a
flattened width of about 2 inches. The dye baths used 20% indigo paste, sodium hydrosulfite power,
sodium hydroxide pellets, and potassium phosphate buffered alkalis.
The dye baths were prepared by mixing the required amount of dye, 150 ml of the selected
type of stock alkali solution, and 15 grams of sodium hydrosulfite with 500 ml of water at 90 C for 2
minutes. The dye baths were then diluted to a volume of 3 liters with room temperature water and
cooled to room temperature of 25 C.
For each group of dyeings made at a measured dye bath pH, the indigo dye bath
concentrations consisted of 2.0, 1.5, 1.0, 0.5, and 0.2 g/l (based on 100% indigo). The concentration
of alkali (hydrated form) in stock solution is outlined in table 1-6.

Table 1-6: Concentration of alkali system.
Group A 60.1% Sodium hydroxide
Group B 37.0% Sodium hydroxide
Group C 37.5% Potassium Phosphate Buffer 1
Group D 36.0% Potassium Phosphate Buffer 2
Group E 39.3% Potassium Phosphate Buffer 3
Group F 39.2% Potassium Phosphate Buffer 4
Group G 37.7% Potassium Phosphate Buffer 5
50

Lengths of tubing weighing 7.5 grams each were wet out in room temperature baths
containing 5 g/l of wetting agent and squeezed to 71% wet pick-up. These were then placed into a
three liter dye bath containing a specified dye concentration at a given pH. The dwell time in the
dye bath was 15 seconds, followed by a squeeze and skying time of 45 seconds. Each dyeing
consisted of five, 15 second dips in the dye bath followed by squeezing and 45 second aeration.
After all dyeings had been completed, the knitted tubes were rinsed together three times in a 90 C
water bath, squeezed by a padder after each rinse, and finally air dried. Since the liquor ratio from
which the dyeings were made was 400/1, dye uptake can be considered to be occurring from
essentially an infinite bath. Following this assumption, the concentration of dye at the fiber surface
does not change during the course of dyeing.
The dye on the knitted tubes was determined by hot pyridine extractions. The pyridine
extractions were diluted to 25 ml in a volumetric flask. The absorbance was measured on a
spectrophotometer at a wavelength of 612 nm. Using known absorbance versus concentration
data, the calculated dye content on the denim yarn was determined.
Reflectance values from 400 to 700 nm at 20 nm intervals were measured on all dyeings and
a mock dyed sample by a spectrophotometer with ultraviolet and specular reflectance contributions
using C2 illuminant.
The following was assumed for the analysis and results summarized in table 1-7.
1. There was sufficient reducing agent in the dye bath at all times to completely reduce all of the
indigo.
2. Ionic strength is approximately constant over all dye bath conditions.
3. Solubility does not limit the concentration of any salt in the bath.

51

Table 1-7: Etters 1989 data set.
15

Group pH
Dyebath
(g/L)
Dye in Fiber
(g/100g) Reflectance Crock
A 13.3 0.2 0.03 17.79 4
A 13.3 0.5 0.06 12.73 3
A 13.3 1 0.15 8.81 4
A 13.3 1.5 0.26 6.04 3
A 13.2 2 0.42 3.94 3
B 13.2 0.2 0.02 17.69 4
B 13.1 0.5 0.1 9.34 4
B 13.1 1 0.28 4.76 3
B 13.1 1.5 0.39 3.63 3
B 13.1 2 0.61 2.97 3
C 12.3 0.2 0.06 7.37 4
C 12.3 0.5 0.24 3.39 3
C 12.3 1 0.51 2.33 3
C 12.2 1.5 0.66 2.11 2
C 12.1 2 0.81 2.02 2
D 11.4 0.2 0.09 4.68 4
D 11.4 0.5 0.28 2.46 3
D 11.3 1 0.53 1.98 2
D 11.3 1.5 0.77 1.88 2
D 11.2 2 1.01 1.95 2
E 11.2 0.2 0.08 4.67 4
E 11.2 0.5 0.26 2.47 2
E 11.1 1 0.54 1.96 2
E 11 1.5 0.77 1.89 2
E 10.9 2 1.1 2.01 2
F 10.4 0.2 0.13 4.09 4
F 10.3 0.5 0.34 2.24 3
F 10 1 0.62 2.1 2
F 9.8 1.5 0.92 1.89 1
F 9.4 2 1.15 2.32 1
G 7.7 0.2 0.04 11.87 4
G 7.7 0.5 0.08 9.84 3
G 7.7 1 0.13 9.04 3
G 7.8 1.5 0.15 7.75 2
G 7.8 2 0.22 6.61 2


52

Annis and Etter 1991 Experiment
19

In May 1991 Annis and Etters published results from an experiment designed to investigate
dye uptake and resulting color yield as influenced by dye bath pH. The same material, laboratory
simulations of indigo dyeing, and analytical techniques used by the Southeastern Section of AATCC
were used in this experiment except 0.25 g/l indigo concentration was used instead of 0.20 g/l. The
experimental results are summarized in table 1-8.

Table 1-8: Annis and Etters 1991 data set.
19

pH C
b
C
f
R
d


pH C
b
C
f
R
d

9.3 1 0.63 0.02 12.8 1.5 0.27 0.034
8.5 0.25 0.05 0.12 9 0.5 0.15 0.04
12.1 0.25 0.08 0.063 11.9 2 0.6 0.022
13.1 2 0.62 0.03 11.2 2 1.06 0.017
10.5 2 1.18 0.017 13 2 0.52 0.028
11 1 0.53 0.021 12.5 0.5 0.13 0.056
11.2 0.25 0.11 0.038 13.3 1.5 0.285 0.044
13.1 1.5 0.405 0.036 13.3 1 0.15 0.088
11.3 0.5 0.265 0.026 7.8 1.5 0.18 0.076
11.8 2 0.8 0.019 7.8 2 0.22 0.06
12.3 2 0.84 0.02 12.2 0.5 0.24 0.031
12.3 1 0.47 0.024 13.3 2 0.44 0.031
12.8 1 0.2 0.046 11.1 1.5 0.78 0.018
7.7 0.25 0.048 0.18 9.8 2 1.18 0.018
10.3 1 0.64 0.02 10 0.25 0.165 0.037
10.8 0.5 0.27 0.025 11.4 1.5 0.76 0.019
10.8 0.25 0.108 0.04 10.4 1.5 0.885 0.019
7.7 1 0.15 0.048 12.3 1.5 0.63 0.022
13.1 0.5 0.09 0.1 11.3 1 0.52 0.02
7.7 0.5 0.08 0.099 10.3 0.5 0.335 0.023
13.3 0.5 0.065 0.159 9.5 1.5 0.9 0.019
13.1 1 0.26 0.046 7.7 0.25 0.044 0.191


53

Etters 1991 Experiment
20

In December 1991, Etters published results from an experiment investigating the effect of
pH and dye concentrations on fiber dye uptake under equilibrium conditions. 8/1s cotton yarn
knitted into tubes was dyed with indigo, sodium hydrosulfite, and sodium hydroxide or proprietary
buffered alkali solution. Dye baths were prepared by mixing the required amount of dye with either
20 grams of NaOH to obtain dye bath pH of 13.1-13.3 or with 100 ml of buffered alkali solution to
obtain dye bath pH of 11.1-11.3. 10 grams of sodium hydrosulfite and 600 ml of de-ionized water at
80 C were then added to each mixture and stirred for 30 seconds to facilitate dye reduction to
leuco form. The total volume was then increased to 2 liters with de-ionized water at room
temperature. The following indigo dye concentrations were prepared (expressed as 100% pure
indigo): 0.05, 0.10, 0.175, 0.25, 0.375, 0.50, 0.625, 0.75, 1.00, 1.125, 1.25, 1.5, 2.00, and 2.50 g/l.
To perform the dyeings, the knitted tubes were wet out at room temperature in baths
containing 5 g/l wetting agent. The tubes were then rinsed three times in warm de-ionized water
and squeezed to 71% pick-up. A 1 g sample of the rinsed knit tube was attached to the sample
holder of the dyeing machine and placed into an 850 ml dye bath which contained the specified dye
amount and pH. Since the liquor ratio was 850/1, infinite dye bath conditions were in effect.
Preliminary experiments revealed that the mean relative dye uptakes for 0.1 and 1.0 g/l dye bath
concentrations at dyeing times of 2, 4, and 8 hours at 25 C were 0.978, 0.933, and 0.930
respectively. Eight hours appeared to be more than sufficient to achieve a close approximation to
equilibrium. Cross sections of yarn and fibers were examined to confirm complete penetration after
8 hours. So all dyeing was conducted over 8 hours with agitation at 25 C in covered cylinders. After
dyeing, the samples were exposed to air for 30 seconds to promote dye oxidation, rinsed with warm
de-ionized water, and squeezed to about 71% pickup. The samples were then dried overnight at 65
C in an oven.
Fiber dye content was determined by using pyridine extraction technique. 20 to 60 mg
dried sample from each dye condition was weighed, stored in a desiccator with anhydrous CaSO
4
for
24 hours, and weighed again. Dye was extracted using pyridine at about 80 C. The resulting dye
solutions were built to 25 ml in a volumetric flask and the absorbance of each solution was
measured at a wavelength of 610 nm using a spectronic colorimeter. Using known absorbance
54

versus concentration data, the dye content was calculated. The results of the equilibrium sorption
experiment were summarized in table 1-9.

Table 1-9: Etters 1991 Equilibrium sorption of indigo on cotton obtained from different pHs in grams of dye per 100
grams of water(bath) or fiber.
20

C
b
C
f
(pH=13.2) C
f
(pH=11.2) C
b
C
f
(pH=13.2) C
f
(pH=11.2)
0.005 0.075 0.316 0.075 0.635 1.557
0.005 0.077 0.314 0.0875 0.649 1.679
0.01 0.139 0.553 0.0875 0.652 1.727
0.01 0.14 0.561 0.1 0.753 1.742
0.0175 0.195 0.69 0.1 0.729 1.837
0.0175 0.189 0.7 0.1125 0.81 2.098
0.025 0.296 0.933 0.1125 0.767 1.971
0.025 0.3 0.917 0.125 0.872 2.111
0.0375 0.361 1.047 0.125 0.838 2.147
0.0375 0.342 0.999 0.15 0.907 2.34
0.05 0.472 1.239 0.15 0.927 2.517
0.05 0.444 1.296 0.2 1.251 3.181
0.0625 0.513 1.409 0.2 1.191 3.024
0.0625 0.525 1.459 0.25 1.44 3.518
0.075 0.547 1.535 0.25 1.465 3.418


Etters 1994 Experiment
27

To investigate shade sensitivity as a function of pH, Etters designed an experiment at two
different pH levels and small permutations of pH were introduced. The experiment utilized 8/1s
denim yarn knitted into tubes with a flattened width of 4.5 cm and weight of 7.2 grams per 30 cm
length.
The dye baths were three liters in total volume to ensure infinite dye bath conditions. Table
1-10 outlines the dye concentrations utilized in the experiment.
55


Table 1-10: Dye concentrations required to yield equivalent shade at different pHs.
27

K/S pH 11.0 pH 12.5
50 0.5 g/l 1.7 g/l
100 1.0 g/l 3.2 g/l
200 2.1 g/l 6.5 g/l

In addition to the indigo dye concentration, 2.0 g/l of sodium hydrosulfite was maintained in all dye
baths. pH of 11.0 was obtained by using 50 g/l of commercial buffered alkali, Virco Buffer ID. A
nearly equivalent total alkalinity amount of sodium hydroxide was used to obtain 12.5 pH. The dye
bath pH was then adjusted downward with the addition of sodium bisulfite and upward with sodium
hydroxide.
The knitted tubes were wet out at room temperature in a solution containing 1.5 g/l sodium
dioctyl sulfosuccinate, wetting agent, and passed through a pad. The tubes were then rinsed with
de-ionized water and squeezed again. Finally the tubes placed into a fresh bath of de-ionized water
until needed.
To dye each tube, the excess de-ionized water was squeezed from the tube prior to
immersion into the dye bath at room temperature for 15 seconds. The excess dye liquor was then
squeezed from the tube to 70% pick-up and air oxidized for 45 seconds. This process was repeated
4 times on each tube to simulate a 5 dip dye range. After all dyeings were completed, the tubes
were rinsed together with warm water until the rinse water appeared to be colorless. After drying
all the tubes, reflectance measurements were collected using a LabScan 6000 spectrophotometer.
Corrected K/S values were calculated based on the 660 nm wavelength reflectance. The results are
summarized in table 1-11.


56

Table 1-11: % reflectance and corrected K/S values for different dyebath concentrations and pH.
27

C
b
(g/l) pH %R
c
K/S C
b
(g/l) pH %R
c
K/S
0.5 10.6 2.52 48 1.7 12.1 2.29 62.2
0.5 10.8 2.5 48.9 1.7 12.3 2.38 55.8
0.5 11 2.48 50 1.7 12.5 2.47 50.5
0.5 11.2 2.51 48.4 1.7 12.7 2.59 44.8
0.5 11.4 2.53 47.5 1.7 12.9 2.74 39.3
1 10.6 2.01 97 3.2 12.1 1.9 123.9
1 10.8 2 98.9 3.2 12.3 1.95 110.1
1 11 1.99 101 3.2 12.5 1.99 101
1 11.2 2 98.9 3.2 12.7 2.05 89.8
1 11.4 2.01 97 3.2 12.9 2.12 79.6
2.1 10.6 1.77 184.1 6.5 12.1 1.7 248.9
2.1 10.8 1.75 198.9 6.5 12.3 1.72 226.2
2.1 11 1.75 198.9 6.5 12.5 1.75 198.9
2.1 11.2 1.76 191.2 6.5 12.7 1.78 177.5
2.1 11.4 1.77 184.1 6.5 12.9 1.81 160.2

Chong 1995 Experiment
29

The material used in the experiment was 16/1s yarn woven in a 2x1 twill with 78x50
construction. One standard dipping consisted of immersing the material into a leuco indigo dye
bath for 1 minute followed by immediate air oxidation for 3 minutes. 5 successive dips were chosen
as the standard procedure. After dyeing, the material was thoroughly rinsed and soaped at boil for
10 minutes in a soaping bath containing 1.5 g/l of Lissapol NX. The standard dye bath consisted of
the following formula.
Indigo dye 2 g/l
Sodium dithionite 6 g/l
Caustic soda 5 g/l
Sandozin NI 0.2 g/l
The reduction of indigo dye was carried out at 80 C for 10 minutes.
After each dyeing the color yield as expressed by Kubelka-Munk K/S at 660 nm was
calculated.

57

Xin 2000 Experiment
46

In 2000 Xin, Chong, and Tu studied the effects of indigo, caustic, and hydro concentrations,
immersion time, and number of indigo dips on the depth of shade. They used a 100% cotton 7/1s
open end yarn loosely knitted into fabric as the dyeing substrate. The fabric was boiled for 30
minutes in a solution of Sandopan DTC (1 g/l, wetting agent) and caustic soda (1.5 g/l) with a liquor
ratio of 30:1. The fabric was then air dried.
The basic dye bath formula utilized 2 g/l of 100% indigo, 4 g/l of sodium hydrosulphite
(85%), and 4 g/l sodium hydroxide. The fabric was dyed at room temperature with each dip
immersed for 30 seconds. The excess liquor was removed by squeezing to 80% wet pick-up and air
oxidized for 2 minutes. Five dips were simulated for all experiments except on the effect of dips.
After dyeing each fabric was thoroughly rinsed with warm water.
To evaluate the dyed samples spectrophotometric analysis was conducted. The K/S value at
660 nm and an Integ value, expressed in equation 1-37, were used.

=
K
S
x
700 nm
400 nm
E
\
(
x
+
x
+
x
)
Equation 1-37: Calculation of Integ as a function of K/S values, average observer, and standard light source.
46


Here: E

spectral power distribution of illuminant and (x

+ y

+ z

) is the standard observer


function. As the maximum absorption wavelength shifts to less than 660 nm for samples with high
shade depth, the Integ value was used instead of the traditional K/S values.

58

1.5.2. Discussion of Previously Published Experimental Results
1.5.2.a Oxidation Time Effect on Indigo Dye Uptake
To achieve the progressive build-up of indigo dye it is important to ensure adequate
oxidation time after each immersion. If complete oxidation is not allowed to occur, desorption of
indigo dye from the cotton yarn will result in weaker dye build-up. As part of Chongs 1995
experiment the effect of oxidation time was evaluated. While the K/S values have not been
corrected, the results are still relative. Figure 1-26 shows the effect of oxidation time on the color
depth. Complete oxidation is achieved after 60 seconds. Oxidation times in excess of 60 seconds
are not required to completely develop the indigo shade.


Figure 1-26: Effect of oxidation time on color.
29



Effect of Oxidization Time on Depth of Shade
10
15
20
25
30
30 60 90 120 150 180
Oxidization Time (sec)
K
/
S
59

1.5.2.b Amount of Reduction Agent Effect of Indigo Dye Uptake
The effect of excess hydro was investigated by Xin and the results displayed in figure 1-27.
Only a minor change in dye yield was observed between 0 g/l to 0.25 g/l (excess). Greater excess
hydro concentrations beyond 0.25 g/l had no appreciable impact on dye yield. There is of course
the limiting case, when excessive hydro actually doesnt permit complete oxidation during the
skying phase. In this case, reduced indigo can be stripped from the yarn and the depth of shade
reduced.


Figure 1-27: Effect of reduction agent concentration on shade.
46



60

1.5.2.c Immersion Time Effect of Indigo Dye Uptake
Xin's investigation into immersion time effects on indigo dye uptake is shown in figure 1-28.
Any immersion time greater than 20 seconds does not affect the dye yield significantly. Dye yield
had slight changes between 0 to 20 seconds. Typical indigo dye ranges have 20 to 30 seconds of
immersion time.


Figure 1-28: Effect of immersion time on shade.
46


Chong
29
also investigated the effect of increasing immersion time on color depth. In figure
1-29, an immersion time of 30 seconds appears to be adequate. Prolonged immersion time does
not increase the color depth because the oxidized indigo on the material may be re-reduced by the
reducing agents present and causes desorption of the indigo. These two separate experiments
support each others conclusions.
61



Figure 1-29: Chong's effect of immersion time on uncorrected K/S.
29


1.5.2.d Number of Dips Effect of Indigo Dye Uptake
As previously stated indigo dye has a low affinity for cotton. To increase the depth of shade
multiple dips are widely utilized. Xin explored the impact of multiple dips on the resulting shade
with results shown in figure 1-30. The effect of number of dye dips produced results as expected.
As the number of dips increased, the shade darkened. After the 8
th
dip the change in depth of shade
significantly decreases but does continue to darken. Also notice the cast shifts from greenish dark
blue to redder less blue shade as the number of dips increase.
Effect of Immersion Time on Depth of Shade
10
15
20
25
30
15 30 45 60 75 90
Immersion Time (sec)
K
/
S
62


Figure 1-30: Relationship between number of dips and shade.
46


Since the color depth of indigo dyed yarns relies on the progressive build-up of color
through successive dipping and oxidation, the number of dips is the prime factor determining the
final color yield. As shown in figure 1-31, the optimum color yield is achieved after about 10 dips.
Chong
29
and Xin
46
independently confirm the results.

63


Figure 1-31: Chong's relationship between number of dips and uncorrected K/S.
29


1.5.2.e Dye Bath Concentration Effect of Indigo Dye Uptake
The effect of dye concentration was studied by immersing knitted fabric into the simulated 5
dip method with varying dye bath concentrations by Xin
46
. The first graph in figure 1-32 illustrates a
rapidly decreasing L* value with increasing dye concentrations until ~2 g/l, after which the level of
decrease lightness slows down and tends to level off. The cast shift is displayed in the second graph
of figure 1-32 with the shade shifting more red and yellow as dye concentration was increased. The
final graph in figure 1-32 confirms the increasing depth of shade trend as indigo dye bath
concentration was increased.

64



Figure 1-32: Relationship between dye bath concentration and shade.
46


Chong
29
examined the effect of indigo dye bath concentration on color yield as shown in
figure 1-33. The affinity of indigo dye is very low, as is its build-up property. Hence increased color
depth cannot be achieved solely by increasing the dye concentration. In fact the color yield remains
fairly flat after 3 g/l.

65


Figure 1-33: Chong's relationship between dye bath concentration and uncorrected K/S.
29


1.5.2.f The Affect of pH on Indigo Dye Uptake
Since leuco indigo is a weak acid, the pH of the dye liquor will have a significant effect on
dye yield. This can be explained by ionization which changes the substantivity of the dye to cotton
fiber. The highest substantivity of dye for the cotton fiber can be achieved at about pH 10.0. Thus
the degree of ring dyeing would be higher at pH 11.0 then more conventional pH region of 12.0-
13.0. The effect of pH on depth of shade and the corresponding cast shift is illustrated in figure 1-
34.

66


Figure 1-34: pH effect of shade with other parameters held constant.
46


Although the maximum Integ shade in graph 3 of figure 1-34 reveal that color yield is much
greater for a dyeing conducted at pH 11 then it is for a dyeing conducted at pH 13, a more detailed
picture is given in figure 1-35. At a given indigo on weight of yarn concentration, the color yield will
be greater at lower pH. Maximum color yield occurs in pH range of 10.5 to 11.5 and decreases as
the dye bath pH is increased. It was suggested that it is owing to the higher affinity and lower
solubility of the monophenolate form of indigo present at this pH range.


Figure
dye fo
zones
diffus
by the
by the
distrib
equili
affinit
infinit
value
condi
steep
1-35: K/S shade

Etters & H
or the cotton
s of the yarn a
sion rate cann
e affinity of th
e fiber is that
Affinity or
bution coeffic
brium. Relat
ty of the dye
te indigo dye
s may be rega
tions. Both p
er. This data
e vs % indigo on
ou have note
fiber in the y
at the expens
not indicate th
he dye. If two
having the h
substantivity
cient or K, the
tively high val
for the fiber.
bath as given
arded as tech
pH ranges exh
suggest that
weight of yarn
ed ring dyeing
yarn surface,
se of fibers in
he actual pro
o dyes are pr
igher affinity
y of a dye for
e ratio of con
ues of distrib
Figure 1-36
n from 5 dip l
hnical quantit
hibit a linear r
t either the a
at various pHs
3
g of cotton ya
i.e. the dye e
the yarn inte
ogress of dyei
esent in a bin
y, irrespective
a fiber can be
centrations o
bution coeffic
illustrates the
aboratory dy
ties since they
relationship,
affinity of th

30
.
arn can be cau
xhausts rapid
erior. Vickers
ng in the initi
nary mixture,
e of their relat
e expressed i
of dye in fiber
ient indicate
e ratio of dye
eings conduc
y were not ob
but the slope
e dye for the
used by a hig
dly onto the f
staff has obse
ial stages, as t
the dye whic
tive diffusion
n terms of an
r to dye in dye
relatively hig
e in denim yar
cted at pH 11
btained unde
e of the lower
fiber is much
h strike rate o
ibers in the o
erved that "
this is determ
ch is first adso
rates."
n equilibrium
e bath at
gh substantivi
rn to dye in a
and 13. Thes
r equilibrium
r pH line is mu
h higher at th
67
of the
outer
the
mined
orbed
ity or
n
se

uch
e

lower
the di

Figure

range
techn
equili
dyein
isothe
limitin
effect
r pH or the dif
istribution co
1-36: Non-equi

Equilibrium
es (11.1-11.3)
nical paramete
brium sorptio
gs at the low
erms given in
ng fiber satur
t on dye upta
ffusion of the
oefficients are
librium Concent
m sorption iso
and (13.1-13
ers such as dy
on data are p
er pH. Furthe
figure 1-36.
ration value is
ke appears to
e dye into the
e much highe
tration of dye in
otherms for in
3.3) from 8 ho
ye uptake, ya
lotted in figu
ermore, the i
For the expe
s evident for d
o be caused b
e fiber is much
r at lower pH
n fiber (g/100g) v
ndigo on cott
our dyeings. T
arn penetratio
re 1-37. The
sotherms are
erimental con
dyeings at eit
by a real diffe
h more rapid
values than
vs concentratio
ton fiber were
These isother
on, and color
indigo uptak
e not linear as
ditions used,
ther pH range
rence in appa
at the lower
at higher pH
n of dye in bath
e obtained at
rms show a la
yield. To cla
ke is significan
s were the no
no obvious a
e. The previo
arent affinity
pH. Either w
values.
h (g/100g).
20

t two dye bat
arge differenc
rify this point
ntly higher for
on-equilibrium
approach to a
ously observe
.
68
way

h pH
ce in
t, the
r the
m
a
d pH

Figure

betwe
in figu
Freun
relatio
1-37: Equilibriu

When figu
een equilibriu
ure 1-38. This
ndlich isother
onship on log
m isotherm for
re 1-37 is rec
um concentra
s indicates th
m
20
. A Freun
g by log scale.
dye concentrat
configured on
ation of dye in
hat equilibrium
dlich isotherm
.
ion in dye bath
n a logarithmi
n the fiber an
m sorption in
m is characte
and fiber (g/100
c scale, an ex
nd dye in the d
both pHs ar
erized by the p
0g).
20

xcellent linear
dye bath is ob
re effectively
power functio
r correlation
btained as sh
described by
on or linear
69

own
the

Figure
in yar
and te
techn
subst
Altho
comm
dye b
1-38: Logarithm

The mean
rn by indigo c
echnical distr
nical distributi
antivity assoc
ugh this infor
mercial dyeing
ath pH is mai

mic plot of equili
technical dist
oncentration
ribution coeff
ion coefficien
ciated with ri
rmation is bas
gs tend to con
intained with
ibrium isotherm
tribution coe
in dye bath.
ficient, K, and
nt decreases w
ng dyeing and
sed on labora
nfirm the con
in the range
ms for dye conce
fficient is calc
In figure 1-3
d the coefficie
with increasin
d color yield b
atory dyeings
nstancy of sub
of 10.8 to 11
entration.
20

culated by div
9 the relation
ent of variatio
ng pH and the
become more
according to
bstantivity of
.2.
viding the ind
nship betwee
on of %CV are
e %CV increas
e variable wit
o Etters
30
, the
indigo for de
digo concentr
en dye bath p
e given. The
ses. This mea
th increasing
results from
enim yarn whe
70

ration
H
ans
pH.
en
71


Figure 1-39: Mean technical distribution as a function of dyebath pH.
30


Ring dyeing of yarns can be increased by dyeing conditions that promote a very fast initial
strike of the dye for the fiber surface. The rapid exhaustion of the dye onto the fibers in the exterior
regions of the yarn will lead to decreased dyeing of the fibers in the yarn interior. Recall the
expression derived by Etters, K/S = a
t
[C
f
/(2p p
2
)]; where a
t
is the true value of the reflectance
absorptivity coefficient, i.e., the value for uniform distribution of dye in the yarn cross-section, C
f
is
the concentration of dye in the yarn, and p is the fractional penetration of fixed dye in the yarn
cross-section. This equation will hold approximately unless a severe concentration gradient exists
within the dyed ring or colorant layer becomes translucent. The values of p have been roughly
estimated by microscopy to be 0.65, 0.33, 0.20, and 0.20 for pH ranges 13, 12, 11, and 10
respectively
33
.

practi
appar
dye b
ring d
betwe

Figure

plotte
from
may b
increa
baths
Etters' equ
ical indigo dy
rent coefficie
ath pH is illus
dyeing and an
een pH 10.8 a
1-40: Apparent
Figure 1-4
ed as a functio
other dye bat
be concluded
asing substan
s. The fact tha
uation makes
eing processe
nts. The rela
strated in figu
increasing ap
and 11.2, the
reflectance abs
1 illustrates t
on of the tech
th pHs. As th
from figure 1
ntivity and str
at the appare
use of the tr
es true reflec
tionship betw
ure 1-40. As t
pparent refle
greatest colo
sorptivity coeffic
he apparent
hnical distrib
he distributio
1-41 that the
ike of indigo
ent reflectanc
ue reflectanc
tance absorp
ween apparen
the dye bath
ectance absor
or yield is ach
cient vs pH.
30

reflectance a
ution coeffici
on coefficient
yarn ring dye
for cotton fib
ce absorptivit
ce absorptivit
ptivity coeffici
nt reflectance
pH decreases
rptivity coeffic
ieved.
absorptivity co
ents with add
increases, th
eing phenome
ber that is ass
ty coefficients
y coefficient.
ients must be
e absorptivity
s from 13 to 1
cient. It has b
oefficients of
ditional data
he color yield
enon is highly
sociated with
s found in the
However in
e replaced by
y coefficient a
11 there is mo
been found th

f figure 1-40
points added
also increase
y correlated w
lower pH dye
ese experime
72
and
ore
hat
d
es. It
with
e
nts
73

are pH dependent can be explained by the effect of pH on the distribution of dye in the cross-
section of yarn. As the degree of ring dyeing increases so does the apparent absorptivity coefficient.


Figure 1-41: Reflectance absorptivity coefficient as a function of mean technical distribution coefficient.
30


Etters
15
proposed the effect of pH on distribution coefficient and apparent absorptivity
coefficient is due to the ionized form of the dye molecule in the dye bath. The fraction of reduced
indigo that exists as the mono-ionic form is given by equation 1-38.

=
1
1+10
pK
1
-pH
+10
pH-pK
2

Equation 1-38: Mono-ionic fraction form of indigo dye as a function of pH.
15


Here
Mean
above
and c
furthe
exists

Figure

reduc
excep
fractio
indigo
pK
1
and pK
2
a
n values of mo
e pH 11.5 the
ontinues to d
er to produce
s as mono-ion
1-42: Relations

The mean
ce indigo that
ptionally high
on of indigo t
o has a much
are the pKa va
ono-ionic form
fraction of in
decrease as p
e the more so
nic and half ha
hip of Mono-ion
technical dist
t exists as a m
linear correla
that exists in
higher substa
alues associa
m are plotted
ndigo that exi
H increases.
oluble di-ionic
as di-ionic for
nic species of ind
tribution coe
mono-ionic for
ation betwee
mono-ionic fo
antivity for co
ted with the
d in figure 1-4
ists as a mono
This is due to
c form. At dye
rm.
digo and pH.
30
fficients are p
rm at various
en the substan
orm. Etters
15
otton fiber th
two step ioni
42 as a functio
o-anion begin
o more of the
e bath pH of

plotted as a f
dye bath pH
ntivity of indi
5
concluded t
hen does the d
ization of red
on of dye bat
ns to drop off
e mono-ionic f
12.7 about ha
unction of th
s, figure 1-43
go for cotton
hat the mono
di-ionic form.
uced indigo
15
h pH. It is no
f rather sever
form ionizing
alf of the indi
e mean fracti
3. There is an
n fiber and the
o-ionic form o
.
74
5
.
oted
rely
g
igo
ion of
n
e
of

Figure
form.
30

depth
indigo
appar
yarn s
region
into a
functi
1-43: Relations
0


Recall redu
h for a given a
o that exists a
rent affinity o
surfaces incre
It is readily
n of maximum
a fractional fo
ion of pH, the
hip between me
uced indigo c
amount of fix
as a monophe
of the mono a
eases, leading
y seen that th
m reflectance
orm and supe
e relationship
ean technical di
an exist in tw
ed dye is sho
enolate ion in
anion form. A
g to a more ri
he fractional a
e absorptivity
rimposing on
p becomes cle
stribution coeff
wo forms: mo
wn to be high
n dye bath. Th
As the affinity
ng dyed yarn
amount of th
. By converti
top of the fr
earer, figure 1
ficient and fract
nophenolate
hly correlated
he correlation
y increases, th
n.
e mono-ionic
ng the appar
actional amo
1-44. Only at
ion of indigo ex
ion or biphen
d with the fra
n is explained
he strike rate
c form is maxi
ent reflectan
ount of mono-
low pH value
isting as mono-
nolate ion. S
ctional amou
d as an increa
of the dye fo
imum near th
ce absorptivi
-ionic form as
es does this
75

ionic
hade
unt of
ased
or the
he
ty
s a
76

relationship break down. This can be explained by the superficial staining of the yarn by the acid
leuco form (II). Based on these results, it is reasonable to postulate that the mono-ionic form is the
principal species absorbed by the cotton. Or at least mono-ionic form has the highest apparent
affinity for cotton.


Figure 1-44: Correlation of fractional distribution of apparent absorptivity coefficient and mono-ionic form of indigo as a
function of pH.
15



1.5.2.
dye u
demo
depth
produ
is req
the cr

Figure
laborat
figure
dye in
in the
specif
g Interrelatio
Given the
ptake, penet
onstrates the
h (K/S) at vari
uce a rather d
uired to prod
ross section o
1-45: Indigo con
tory dyeing
30
.

When the
e 1-46. It is sh
n the dye bath
e dye bath inc
fied range. It
onship of Dye
strong effect
ration, and sh
mean indigo
ous dye bath
dark shade (K/
duce the same
of yarn.
ncentration in d
dye uptake d
hown the max
h. Maximum
creases the m
t could be tha
Concentratio
dye bath con
hade; a more
concentratio
pH values. F
/S = 100) is a
e shade dept
dye bath require
data is plotted
ximum uptak
uptake occu
maximum upta
at all of the dy
on and pH on
ncentration a
in-depth disc
on in the dye b
For example t
bout 3 g/l at
h at pH 11.0.
ed to produce a
d vs. dye bath
ke at a particu
rs between p
ake occurs at
ye extracted f
Shade
nd pH indepe
cussion is wa
bath needed
the indigo con
pH 12.5. But
This is the re

given shade dep
h pH, the follo
ular pH depen
pH 9.25 10.5
lower and lo
from the knit
endently have
rranted. Figu
to produce a
ncentration re
only 1 g/l of
esult of dye d
pth at various p
owing relation
nds on the co
5. As the con
wer pH value
ted yarn tube
e on the resu
ure 1-45
given shade
equired to
indigo in dye
distribution w
Hs from a 5 dip
nship develop
ncentration o
centration of
es within the
e was not in f
77
lting
e bath
within
p
ps,
of
f dye
fact
78

taken up by the fiber. Some of the dye may have been merely precipitated within the knitted yarn
bundle.


Figure 1-46: Effect of dye bath concentration and pH on dye uptake.
15


In figure 1-47 dye uptake is shown to increase linearly with increasing concentration of dye
in the dye bath. The linear relationship holds for all dye bath pH values but the slopes of the lines
are shown to increase as dye bath pH decreases from 13.3 to ~10 range. As pH continues to
decrease to the 7.7 range, the dye uptake slopes drop sharply.
79


Figure 1-47: Yarn dye uptake as a function of dye bath concentration and pH.
15


The linear relationship between K/S and concentration of dye in the substrate is illustrated
in figure 1-48. The slope of each pH range corresponds to the various apparent reflectance
absorptivity coefficients. The apparent absorptivity coefficients increase as the pH is decreased
from 13.3 to ~ 11.0 pH. As the pH is further decreased to 10.0 the absorptivity coefficients
decrease. And as the pH is reduced to 7.7 the line slope decreases to the extent that is
superimposed on the line slope obtained at pH 13.3.
80


Figure 1-48: Corrected depth of shade as a linear function of indigo concentration in yarn and dyebath pH.
15


Since less indigo dye bath concentration is required at lower pH values to achieve a desired
shade, less indigo is washed off of the yarn at the conclusion of dyeing. In figure 1-49 the
concentration of unfixed indigo has been estimated by Etters
30
as a function of both concentrations
of dye in the dye bath and dye bath pH. As the dye bath pH decreases, the amount of oxidized
indigo that is trapped between the fibers in the denim yarn is decreased. Therefore, less dye is
available to be washed off of the yarn.

Figure

1.5.2.

yarn a
derive
Etters
coeffi

obtain
tubes
mathe

conce
conce
1-49: Estimated
h Empirical in
The Holy G
and shade to
ed. But an em
s
21
. In this mo
icient, indigo
The empir
ned from bot
s as previously
ematical mod
The techni
entration of d
entrations are
d concentration
ndigo dye mo
Grail for indig
various contr
mpirical mode
odel the dye
on weight of
ical model is
th investigatio
y outlined. B
del.
ical distributi
dye in the fibe
e expressed in
of unfixed indig
odel
o dyers world
rollable dye r
el based on a
bath indigo c
f yarn, and su
based on the
ons is based o
y analyzing th
on coefficien
er, C
f
, divided
n terms of gra
go on yarn at co
dwide would
range parame
5 dip laborat
oncentration
bsequently th
e Southeaster
on 5 dip, 15 se
hese two data
t, K, is define
by the conce
ams of dye pe

orresponding dy
be a dye mod
eters. This on
tory experime
and pH is us
he final yarn s
rn Section
15
a
econd immer
a sets, Etters
2
d in equation
entration of d
er 100 grams
e bath concentr
del relating in
ne equation h
ent has been
ed to predict
shade.
nd Annis rese
rsions of knitt
21
developed
n 1-39 to equa
dye in the dye
of fiber or w
ration and pH.
30
ndigo on weig
has not yet be
proposed by
the distribut
earch
19
. The d
ted denim ya
the following
al the
e bath, C
b
. Th
ater.
81
0

ght of
een
y
tion
data
rn
g
he
82

=
C
]
C
b

Equation 1-39: Definition of technical distribution coefficient.
21


A regression analysis explains 86% of the variability of K in terms of the variability of pH and the
relationship was defined in equation 1-40.

= +(
3
)
Equation 1-40: Approximation for the technical distribution coefficient as a function of dye bath pH.
21


Here the components are defined: a = 0.9623 and b = -0.000331.
Given the pH and dye concentration of the dye bath, one can calculate the technical distribution
coefficient, K, and subsequently the dye concentration in the fiber, C
f
.
The second part of the empirical model is based on the relationship between pH and the
apparent reflectance absorptivity coefficient, a. Recall K/S
corr
= a C
f
. A regression analysis explains
94% of the variability of apparent reflectance absorptivity in terms of variability around pH. The
empirical model for apparent reflectance absorptivity coefficient was defined by Etters in equation
1-41.

=
+bpH+c(pH
2
)+d(pH
3
)+c(pH
4
)

Equation 1-41: Empirical model of apparent reflectance absorptivity coefficient.
21


Here i=-46.3280, b=6.4373, c=0.4733, d=-0.0905, and e=0.0030.
Given the dye bath pH one can calculate the apparent absorptivity coefficient, a. Using the
calculated value for a and C
f
, one can estimate the shade of the dyed fabric in terms of K/S
corr
.
83

1.6 Summary of Key Developments and Identification of Deficiencies

The head indigo dyer responsible for daily production quality is always relentlessly searching
for new methods, procedures, and technology to reduce variability in the indigo dyeing process.
Their shade control war chest includes some basic qualitative rules of thumb for indigo dyeing.
1. If the shade drifts green and light, reduce the hydrosulfite.
2. If shade drifts red, reduce caustic and/or slightly increase hydro.
3. If changing green and dull, increase caustic.
4. If drifting red and dull, increase hydro.
5. A gradual increase or decrease in depth, if on cast, is corrected by changing the indigo feed rate.
6. If increase in depth is accompanied by bronzing, increase hydro and/or decrease dye feed rate.
While these qualitative measures can not be forgotten, further improvements in shade control and
prediction can only be made with definitive quantitative measures.
To the aim of reducing the art of dyeing and increasing the science of dyeing, much
improvement has been made over the last 20+ years. Through many laboratory experiments we
now have a much greater understanding of indigo dye uptake, penetration distribution, and
corresponding shade as it relates to dye bath concentration, pH, and number of dips. Finally an
empirical model has been proposed to relate the desired dye outcome to measurable and
controllable dyeing parameters. Unfortunately the head indigo dyer cannot take these relationships
directly to production environment due to the key underlying assumptions.
Lets begin the discussion with where all the indigo dye goes from a macroscopic scale. It
may sound elementary, yet no model has been published to accurately account for all the indigo
dye. We know how much indigo is fed to the range. But how much is removed during washing? At
the overflow? Current indigo dye terminology expresses % indigo on weight of yarn as a function of
pounds per minute of indigo and pounds per minute of cotton. This relationship does not account
for either. Attempts have been made to explain the amount of dye removed during washing yet
these have not been substantiated with actual production data.
84

No attempt has been made to relate classical diffusion theory to the experimental data for
dyeing denim yarn with indigo. Many of the expressions and terms have been employed but not the
actual diffusion solutions. In as such, the diffusion coefficient for the indigo-cotton dye system has
not been completely explored or expressed. More specifically the potential dependence on dye
bath pH, dye concentration in the dye bath, dye concentration in the yarn, boundary layer, and/or
other yet unknown parameters is not fully understood.
All of the experimental data presented in the literature are based on laboratory dyeings.
While this research certainly explains the relationship of variable effects on measurable responses, it
does not directly provide quantitative relationships on production dye equipment. There are four
fundamental issues that may affect the results.
The substrates used in the experiments have been some form of fabric either knitted tubes
or woven twills. In either case, the interlacing or interloping of yarns may affect the amount of dye
uptake. This is due to where the two yarns cross; dye is not allowed to contact the yarn surface. As
a result, the measured dye concentration in fiber will probably be less than the results on actual
production yarns. Furthermore, the fabric structure makes any measured shade values (K/S)
depend on the substrate. While these are probably relative to each other, the shade values will not
directly correlate to production dyed denim yarns.
In all of Etters non-equilibrium experiments, a 15 second immersion time was used. While
this is a viable dwell time for indigo dyeing, not every dye range matches this time exactly. Chong
29

and Xin
46
have demonstrated the significant effect immersion times less than 30 seconds have on
the resulting shade. Any indigo dyer with immersion times different than 15 seconds must proceed
cautiously when applying Etters relationships.
The vast majority of indigo dyed cotton experiments have been conducted with simulated 5
dip dye range set-up. While 5 dip dyeing may represent a significant amount of the denim yarn
dyed, it is certainly not the only set-up. In fact the majority of denim shade spectrum produced falls
within the 2 to 8 dip range. Once again, Chong
29
and Xin
46
have demonstrated the significant affect
number of dyes has on the resulting shade. Since indigo dye uptake and/or degree of penetration
85

may be affected by previous dye applications (i.e. previous dip), relationships derived from 5 dip
simulations may not translate to more or fewer dips.
The movement of dye bath during the simulated laboratory experiments may affect the final
dye uptake and penetration. More specifically, no discussion of agitation during dyeing experiments
was mentioned. Dye bath agitation has been well documented to have a significant effect on
disperse dye uptake on polyester. While the same relationship may not hold true for indigo-cotton
system, the contrary has not be demonstrated. Furthermore, it may not be possible to recreate real
world boundary layer development in the laboratory.
Etters empirical indigo dye model appears to accurately predict yarn shade and dye uptake
given certain dye range parameters, specifically dye bath concentration and pH. However this
model is derived from very specific laboratory conditions involving: substrate, number of dips,
immersion time, and agitation (boundary layer development). Furthermore, the indigo penetration
is modeled as a step function. All of these issues may have some affect on Etters empirical indigo
dye model. More importantly since no actual production data was given for comparison or
compared to classical diffusion theory, at the very least it raises some doubt.
86

2 Objectives of the Present Investigation

Although there is a long history of dyeing denim yarn with indigo, the process of dyeing with indigo
still remains largely an art and not a science. - Zhou
48


In an ideal world to investigate the effect of yarn count, number of dips, immersion time,
dye bath pH, speed, and dye bath concentration on yarn uptake of dye and the resulting shade; a
systematic design of experiment would be conducted. At last, this researcher has yet to find a
denim manufacture willing to blindly produce a million+ yards of denim fabric that would be
required for such an experiment. As a result, an indigo-cotton dye observational study is proposed
that would gather key processing parameters and yarn samples during "actual indigo dyeing
process. It is hoped the resulting data and relationships provide more refined insight into the
indigo-cotton dye system.
By processing yarn skeins through an actual indigo dye range it is put forth many of the
issues surrounding laboratory experiments will be avoided. While certain dye parameters cannot be
controlled by the experimenter, others can actually be more easily manipulated. Furthermore,
careful selection of various production shades should yield adequate variation in the dyeing
parameters to produce reliable results.
For each set of skeins processed, the following dye range set-up conditions were monitored.
1. Date and time skeins were processed.
2. Production shade number, dye range, and location.
3. Production yarn count and total number of ends per ball
4. Production indigo, caustic, and hydro feed rates to the dye range.
5. Dye range speed
6. Immersion time (dye dwell time)
7. Sky time (oxidation time)
8. Chemical checks made by the technician (g/l of indigo, mV potential, vatometer, pH, and %
alkalinity.
9. Yarn count of skeins and the sequence of dye boxes that they were processed through.

87

The following response variables were measured.
1. Greige weight of skein and shade
2. Laboratory prepared weight of skein and shade
3. Dyed but unwashed weight of skein and shade
4. Dyed and laboratory washed weight of skein and shade
- All weight measurements will be conducted according to AATCC methods.
5. Shade readings will include the CIELAB L*, a*, b* values using 10 observer and D65
illuminant; and % reflectance from 400 to 700 nm at 20 nm intervals.
6. %IOWY determination by 1-Methyl-2-Pyrrolidinone extraction

Data analysis involved comparing chemical on weight of yarn measurements to actual
production parameters. Determination of fixed versus unfixed indigo dye on yarn was calculated
from before and after washed skeins.
An empirical model based on analysis of indigo on weight of yarn and shade values was
developed. This model was based on two different indigo dye ranges. This should yield a more
reliable and transferable indigo-cotton dye model. Next the diffusion coefficients were calculated
for various dyeing set-ups and analysis identified key influential parameters. To validate the
empirical dye model, comparisons were evaluated to classical diffusion theory and previously
published laboratory experiments.
A reliable indigo model would improve quality control by removing the art of indigo
dyeing and replacing with the science of indigo dyeing. At the very least a better understanding of
the indigo dye process would allow the production dyer to better control the process. Most
optimistically an accurate indigo-cotton dye model would allow product development to design dye
range set-ups to produce new and unique dye shades possessing shade and penetration
characteristics never before imagined.
While much research has been conducted in the field of chain rope indigo dyeing, many
questions still remain unanswered. Specifically a rigorous math and science based model to explain
dye pick-up, final shade, and dye penetration. Previous research has indicated dye bath
concentration, immersion time, number of dips, pH, and reduction potential have a significant effect
on the dye on weight of yarn and the resulting shade. Furthermore little research actually specifies
88

quantitative changes and instead focuses on general trends and qualitative relationships. This
researcher submits that dye range speed would also have a significant contribution to dye pick-up
and shade. Furthermore, the specific quantity of indigo on weight of yarn and resulting shade was
predicted given fundamental dye range parameters.
Ideally, a design of experiment would be evaluated to determine the effect of each listed
variable. Alas, laboratory dye equipment has restrictions on dwell length and immersion time over a
range of typical dye range speeds. Not to mention limitations on dye bath volume and maintaining
chemical equilibrium. Furthermore, such an experiment cannot be conducted on production dye
equipment since strict and specific dye conditions must be maintained in order to ensure proper
shade on bulk production orders. However, an observational study of indigo dyeing may be
conducted on production bulk equipment without adversely affecting bulk orders. Specifically, dye
pick-up or percent indigo on weight of yarn and shade can be measured on skeins while noting the
various dye range parameters. While the researcher cannot change the dye range parameters to a
specific value in a study, multiple evaluations over a range of production dyeings will allow
determination of parameter affects on response variables.
At the conclusion of the study, mechanical dye range parameters: speed, immersion thread-
up length, oxidation time, and number of dips coupled with dye bath conditions: indigo dye bath
concentration, pH, and reduction potential effects will be evaluated on response variables % indigo
on weight of yarn, shade, and dye penetration. Insight will be gained regarding equilibrium sorption
of indigo dyed cotton yarns by maximum dye up take and resulting shade. This information was
presented to quantify the level of indigo penetration when ring dyeing conditions exist. Last the
relationships will be viewed under Fick's laws of diffusion. The extension to diffusion equations will
explain the cause and effect and allow a rigorous mathematical model to be developed. Specifically
the diffusion coefficients for the cotton-indigo interface will be determined.
89

3 Experimental Methods and Procedures

To evaluate production indigo dyeing without influencing actual production orders, skeins of
cotton yarns were tied onto the production yarns during the dyeing process. By running skeins
instead of looking at actual production yarns, effects of boil off efficiency, washing after boil off,
washing after indigo dyeing, and sulfur dye bottom or top were eliminated. Additionally, yarn skeins
were prepared in a laboratory to ensure consistent base for dyeing from skein to skein.
Additionally, skeins were made from the same yarn package to remove inconsistencies from yarn
package to package. These precautions provided consistent base from dye set-up to set-up since
bulk production yarns will most certainly vary over the observational time frame.
3.1 Response Variables Definition, Collection Methods, and Evaluation Methods

3.1.1 Yarn Skein Definition and Creation
A yarn skein consists of evenly wound yarns from the same yarn count to produce a uniform
loop. The loop can then be tied at the top to maintain integrity while being handled. A yarn skein
was made by winding a specific yarn count into a loop of approximately 80 centimeters in length,
100 loops, and weighing roughly 4 to 8 grams. The specific length, number of loops and weight
wasn't critical. The weight for each skein was later measured and documented. The specific yarn
counts used for this study were 6.3/1, 7.1/1, 8.0/1, and 12.0/1 English cotton count formed on an
open end Schlafhorst spinning frame.
3.1.2 Running Yarn Skeins on Production Indigo Dye Range Equipment
Laboratory prepared yarn skeins were tied onto a production dye range in multiple locations
by the use of a 100% polyester spun thread. The polyester thread was strong enough to ensure the
skein remained tied to the production rope while easily broken when pulled off later. Also note the
100% polyester thread will not be dyed by indigo and therefore will not interfere during the dyeing
process. A simple loop knot was tied around the yarn skein with 8 inches extra thread on both sides
of the knot. While the dye range was running, a simple, loose double knot was formed around the
production rope. With one swift motion starting above the head, tighten the first knot followed by
90

the second knot to secure the skein to the production rope. With practice, the procedure becomes
effortless.
Most indigo dye ranges have walkways and platforms around the wash boxes, after the boil-
off box, as well as the indigo dye boxes. These allow operators to access the production cotton
ropes to repair lost or broken ends while the dye range remains operational. This researcher used
these access points to tie on the yarn skeins. Following standard production procedures the skeins
would be immersed in at least one wash box before entering the indigo dye boxes. The wash box
would remove trapped air in and around the cotton fibers as well as provide uniform water pick up.
To pull off the yarn skeins a simple good grip and quick pull breaks the polyester thread.
Ideally this process should be conducted while the polyester thread and production rope interface
was in direct contact with a steel roller in the sky or oxidation section after each indigo box. The
contact point provides stability to the production yarn thereby resisting the pulling motion. To avoid
a dye range stop, pull down (perpendicular to the roller axis of rotation), never across (parallel to
the roller axis)! Any parallel motion can pull the production rope out of track.
3.1.3 Yarn Skein Evaluations
Once the yarn skeins were processed, critical information was measured and recorded.
These measured values will later be the response variables used to evaluate dye range parameter
effects. The first group of response variables was dry weight measurements which were conducted
on the yarn skeins in accordance to AATCC 20A section 8 (Moisture Content) method. All weights
were measured on a Mettler AE100 scale. The weight was recorded before laboratory preparation
and noted as "greige" weight. After the skeins had been laboratory prepared the weight was
recorded as "boil-off" weight. The weight was measured after processing through the dye range.
This last weight measurement was recorded as "dyed" weight. Finally, the dyed yarn skeins were
washed in the laboratory and identified as "washed" weight.
The %Boil-Off Loss was defined as the difference in Greige weight and Boil-off weight
divided by the Greige weight as shown in equation 3-1.
91


% =
ucgc wcght-BoI o]] wcght
ucgc wcght

Equation 3-1: Calculation of %Boil off Loss.

Given the boil-off and dyed weight, the total percent chemical on weight of yarn (%COWY)
was calculated according to equation 3-2. Note this was the total chemical amount on weight of
yarn after dyeing. This number has fixed and unfixed indigo dye as well as residual sodium
hydroxide and other salts resulting from oxidation.

% =
cd wcght-BoI o]] wcght
BoI o]] wcght

Equation 3-2: Calculation of %COWY.

The skeins were washed in the laboratory using warm water of ~40C. Washing of the yarn
skeins was necessary to simulate dye range set-up and remove unfixed dye and chemical residuals
from the yarn. Each skein was passed under running water until the water was clear of color. The
final washed percent indigo on weight of yarn (%IOWY
wash
) was calculated by dividing the difference
between Washed weight and Boil-off weight by the Boil-off weight, equation 3-3.

%
wush
=
wushcd wcght-BoI o]] wcght
BoI o]] wcght

Equation 3-3: Calculation of %IOWYwash.

The final method used to determine %IOWY after the yarn skeins had been washed was
Spectrophotometric Methyl Pyrrolidinone extraction. This method was ultimately chosen for later
92

data analysis due to greater acceptance and use in literature. The following Methyl Pyrrolidinone
method to measure the %IOWY was provided by Clariant Inc.
1. Prepare the solvent solution as follows: (sufficient for one sample)
To a 400 ml beaker, add:
200 ml of distilled water
7.2 grams of sodium hydroxide (50%)
4.0 grams of sodium hydrosulfite (90%)
After the sodium hydrosulfite was dissolved, add 120 ml of 1-Methyl-2-Pyrrolidinone

Cool to ambient temperature and pour into a graduated cylinder. Then fill to the 400 ml mark with
distilled water and mix well before use.

2. Weigh out yarn per Table 3-1 and place in a 250 ml volumetric flask. Add the solvent solution
prepared in step #1 to the mark. Add a 1.5 inch magnabar and stir for 15 minutes.
Note: At the end of this time, the indigo on the yarn should be completely reduced. The yarn
should be devoid of color unless sulfur dye was present on the yarn.

3. Recheck the volume in the flask by removing the magnabar. If necessary, add solvent solution
prepared in step #1 to bring back up to the 250 ml mark in the flask and mix well.

4. To a 100 ml volumetric flask, add 80 - 90 mls of the solvent solution prepared from step #1.
Pipette 5.0ml of the solution from step #3, being careful to wipe off any excess from the outside of
the pipette.
Note: Dip the point of the pipette into the solvent solution to prevent oxidation of the reduced
indigo.

5. Dilute to the 100 ml mark with the solvent solution prepared in step #1.

6. On a suitable spectrophotometer, record the absorbance of the solvent solution prepared in step
#1 at 406 nm using a 1cm cell. [Current study used a Thermo Spectronic 20D+.]

7. Measure the maximum absorbance of the sample solution prepared in step #5 at 406nm. Adjust
the sample absorbance by adding or subtracting the absorbance of the blank solution measure in
step #6.

8. Calculation by equation 3-4:


%
20% Pustc
=
Absobuncc
406nm
27.74
SumpIc wcght

Equation 3-4: Calculation of %IOWY by Methyl Pyrrolidinone extraction.

93

Table 3-1: Target dyed yarn sample weight for Methyl Pyrrolidinone extraction
Anticipated Indigo Concentration Amount of Yarn to Weigh
5 - 7% 1.5 - 2.0 grams
8 - 12% 1.0 - 1.5 grams
13 - 17% 0.5 - 1.0 grams
18 - 30% 0.4 - 0.7 grams

The resulting %IOWY calculated from the Spectrophotometric Methyl Pyrrolidinone
extractions were expressed in terms of 20% paste. This convention has its roots from the days when
20% indigo paste was the only commercially available concentration. Today 20%, 40% and even
42% indigo paste is commercially available. To express the indigo dye concentration more
generically the above value was divided by 5 to make the units %IOWY in terms of 100% indigo as
outlined in equation 3-5. This final form was used in all subsequent analysis and will here forth be
known simply as %IOWY.

% =
%I0w
cs 20% pcstc
5

Equation 3-5: Calculation of %IOWY in terms of 100% Indigo paste from Methyl Pyrrolidinone extracts.

The next response variable was a calculation based on the actual shade of the dyed and
washed yarn skein. The relationship K/S shade was expressed as a function of the % reflectance of
the dyed sample minus the % reflectance of a mock sample at various wavelengths. The mock
sample was the same yarns as the dyed sample processed the same way except without any actual
indigo dye involved. Of course all mock dyed samples were created in the laboratory by padding
dye bath chemicals minus the indigo on the yarn skeins. The mock dyed yarn % reflectance values
are referenced in appendix section A-3-1. Higher values indicate a darker shade or in this case
greater transfer of indigo during the dyeing process. Lower K/S values correspond to lighter shades
with less dyed on weight of yarn and/or more penetration into the yarn structure. The equation for
94

K/S was given in equation 3-6. The %reflectance values were measured on a Hunterlab ColorQuest
XE running on Gretag-Macbeth SLI-Form software.

K
S
x
=
(1 - %Rc]Icctuncc
Djcd
)
2
2 %Rc]Icctuncc
Djcd

(1 - %Rc]Icctuncc
Mcck
)
2
2 %Rc]Icctuncc
Mcck

Equation 3-6: Calculation of K/S from Kubelka-Munk.

To ensure accurate and repeatable shade measurements the yarn skeins were wrapped
around a white plastic board 6 centimeters wide. By pulling the yarns tight during the wrapping
process, the individual yarns were straight without any knots or twists and parallel to one another.
The shade was measured with a 1 inch port on the spectrophotometer. The shade software
automatically averages three individual readings. By moving the yarn skein between individual
readings the average % reflectance was calculated. Furthermore each dyed yarn skein was
measured on three separate occasions. The three separate readings were later averaged in
Microsoft's Excel spreadsheet which resulted in the % reflectance values at each wavelength
representing nine different readings.
To represent the total shade over many wavelengths in one number, the value of Integ has
been developed. As pointed out by Xin
46
the Integ value has greater importance when evaluating
shade over a wide range of depths as the maximum absorption wavelength tends to shift at greater
depths of shade. In equation 3-7, E

equals the spectral power distribution of the illuminant. The x


+ y

+ z

function was the standard observer function. All shade evaluations were conducted using
D65 illuminant with a 10 observer.

=
K
S
x
700 nm
400 nm
E
\
(
x
+
x
+
x
)
Equation 3-7: Calculation of Integ shade value from K/S values.

95

Graphical representation of the K/S by wavelengths further illustrates the shift Xin was
referring. Figure 3-1 shows the K/S by wavelength from multiple dips of 6.3/1 OE yarn in 3.0 g/l
indigo dye set-up at 31 meters per minute and 12.0 pH. The maximum K/S value shifts from 660 nm
at one dip to 640 nm at 3 dips. By the time dip 6 and 7 occur, the maximum K/S value occurs at 580
nm. Since the wavelength of maximum K/S shade shifts, no single wavelength will accurately
describe the change in shade as a function of dye concentration or location. For reference the Integ
shade value for the same dips of figure 3-1 was 24.2, 64.8, 95.1, and 103.9 respectively.


Figure 3-1: Relationship of maximum K/S shade shift as depth increases

In addition to the shifting maximum wavelength, the K/S shade value was non-linear as a
function of %IOWY. In the past this had been corrected by Etters and others by adjusting the K/S
value for higher %IOWY. This approach worked for relatively low %IOWY values. However as the
%IOWY or degree of ring dyeing was increased the K/S value not only was non-linear but non-
unique. In figure 3-2 at 580 nm the K/S shade becomes non-linear at approximately 1.25% IOWY. At
0.0
5.0
10.0
15.0
20.0
25.0
30.0
35.0
40.0
45.0
50.0
400 450 500 550 600 650 700
K
/
S

s
h
a
d
e

v
a
l
u
e
Wavelength (nm)
K/S Shade Values by Wavelength for Typical 3.0
gm/lit Indigo Dye Set-up
1 dip 3 dip 6 dip 7 dip
96

660 nm the K/S shade value becomes non-linear at 0.75 %IOWY. Furthermore K/S
660nm
reached a
maximum value at 1.25 %IOWY. With continued increase in %IOWY the K/S
660nm
shade value
actually decreased in value. No amount of mathematical correction could compensate for this
relationship. Figure 3-2 illustrates the relationship of Integ to %IOWY. While this function was
certainly not linear, at least the values are unique over the entire %IOWY range and possessed
greater change in value at higher %IOWY measurements. Therefore Integ shade value was used for
all future calculations related to shade.


Figure 3-2: Relationship of K/S by wavelength as a function of %IOWY

The final response variable was a calculation based on the shade of the yarn and %IOWY,
equation 3-8. This response variable qualifies the location of the indigo in the cross section of the
yarn. A relatively lower penetration factor value indicates more indigo penetration into the cross
section of the yarn, while a higher value indicates less penetration. Of course this value is relative to
other skeins dyed under similar conditions.
0.0
20.0
40.0
60.0
80.0
100.0
120.0
0.000% 0.500% 1.000% 1.500% 2.000% 2.500% 3.000% 3.500%
I
n
t
e
g

o
r

K
/
S

S
h
a
d
e

V
a
l
u
e
%IOWY
Integ and K/S Shade at 580nm and 660nm vs %IOWY
580nm 660nm Integ
97

Penetiation Factoi =
Intcg
%I0w

Equation 3-8: Calculation of penetration factor from Integ and %IOWY.

3.2 Determining Optimum Method for Laboratory Preparation
During the indigo dyeing process, 100% cotton yarn was run through the dye range to
produce a specific desired shade. The cotton yarn was first exposed to the Boil-Off box, which
contained chelate, wetter, sodium hydroxide, and water (and sometimes sulfurs dyes). The purpose
of this box was to prepare the yarn for the subsequent indigo dye boxes. The experimenter wished
to conduct an observational study of the various parameters that affect the indigo dye process. But
one key parameter was the boil-off box, which was not a desired part of the study. To overcome
this obstacle, skeins were prepared in a laboratory thereby bypassing the boil off box on the dye
range. This would allow other factors of interest to be studied without the negative impact of boil-
off box variation and/or sulfur dye from regular production.
Previously published articles on indigo dyeing have used a variety of preparation methods.
Some researchers have used room temperature distilled water. Some have used water and wetters.
Finally, a few have used water, wetters, and sodium hydroxide. What was the best laboratory
preparation process? What characteristics does a good laboratory procedure possess?
Some initial trials run and intuition from this experimenter indicated: the dwell time,
temperature, and amount of sodium hydroxide played a major role in the laboratory preparation
process. The use of chelates was ultimately only important in bulk production equipment designed
to run continuously for hours. The experimenter wished to develop a laboratory preparation
procedure, which was robust in design. Ideally, reasonably small changes in time, temperature,
and/or sodium hydroxide concentration have little to no effect on the degree of dyeing. Or at the
very least the experimenter needs to understand the amount of error the lab preparation procedure
can impart on the research to be conducted.
To understand the laboratory preparation procedure better, the experimenter conducted a
design of experiment based on central composite design with axial components that were
98

orthogonal and inscribed with 4 replicated center points under two blocks. The three factors of
interest were time the skeins were allowed to cook, temperature the skeins were cooked, and
sodium hydroxide concentration of the bath used for "cooking". Time was measured with a
stopwatch in minutes with a range of 20 to 40 minutes. Temperature was measured with a
thermometer with a range of 76 C to 100 C. The sodium hydroxide concentration was measured
on weight basis with a range from 0 to 15 grams per liter where a measured weight of sodium
hydroxide was added to a measured volume of water. The sodium hydroxide used in this
experiment was a 50% solution not dry weight and the units were actually X g/l of 50% sodium
hydroxide.
The two blocks of the design of experiment consisted of the actual indigo dyeing process.
Block #1 was the skeins run through only one dip of indigo. Block #2 was the skeins run through six
dips of indigo. While six dips of indigo represents typical indigo dyeing set-up, one dip of indigo
produced the most extreme case with the yarn skein exposed to the least amount of indigo. This
should accentuate any variation in the yarn skeins from the laboratory preparation procedure.
Using SAS's JMP 8.0 statistical software package, the central composite experimental design
was laid out and the package automatically created a randomized run order. Following this run
order each laboratory preparation recipe was mixed with 3.785 liters of water, brought to the
correct temperature, and yarn skein added for the desired amount of time. After the required time,
the yarn skein was removed from the boil-off mixture and washed under hot water at 40C for 5
minutes. The washing process again mirrors actual indigo dye range set-up, which was to remove
residual boil-off mixture from the cotton yarn.
Table 3-2 details the level of each variable and the order in which it was conducted in the
laboratory. This run order list was used for block #1, one dip of indigo. There were 4 response
variables that were measured at each level of the laboratory preparation procedure. These
consisted of the %Boil-Off Loss, %IOWY, Integ shade, and penetration factor as defined in section
3.1.


99

Table 3-2: Time, temperature, and sodium hydroxide concentration levels plus response variable for one dip of indigo
Pattern Time
(min)
Temperature
(C)
NaOH
(g/l)
%Boil-Off
Loss
%IOWY Integ Penetration
Factor
Run
Order
a00 20 88 7.5 2.00% 0.307% 23.0 75.01 1
+-- 37 79 2.25 1.34% 0.115% 23.3 201.47 2
000 30 88 7.5 2.11% 0.270% 22.4 82.86 3
A00 40 88 7.5 2.62% 0.283% 27.2 96.23 4
+++ 37 96 12.7 2.62% 0.306% 23.3 75.98 5
0A0 30 100 7.5 2.77% 0.310% 26.4 85.26 6
000 30 88 7.5 2.34% 0.336% 23.2 69.10 7
++- 37 96 2.25 2.26% 0.341% 25.4 74.54 8
00A 30 88 15 2.26% 0.348% 21.6 62.07 9
00a 30 88 0 1.46% 0.202% 23.4 115.78 10
000 30 88 7.5 2.21% 0.312% 25.3 81.05 11
-+- 23 96 2.25 2.37% 0.240% 23.1 96.06 12
0a0 30 76 7.5 1.32% 0.155% 23.3 150.37 13
+-+ 37 79 12.7 1.43% 0.085% 23.3 272.92 14
--+ 23 79 12.7 1.71% 0.104% 23.3 223.49 15
--- 23 79 2.25 1.27% 0.019% 23.2 1232.46 16
-++ 23 96 12.7 2.94% 0.261% 22.7 86.77 17
000 30 88 7.5 2.20% 0.296% 22.2 75.09 18


Table 3-3 details the run order in the laboratory for block #2, six dips of indigo. This list was also
randomized and the corresponding measured response variables were included.
100

Table 3-3: Time, temperature, and sodium hydroxide concentration levels plus response variable for six dips of indigo
Pattern Time
(min)
Temperature
(C)
NaOH
(g/l)
%Boil-Off
Loss
%IOWY Integ Penetration
Factor
Run
Order
+-+ 37 79 12.7 1.47% 1.818% 98.4 54.13 1
-++ 23 96 12.7 2.89% 2.190% 96.5 44.08 2
a00 20 88 7.5 2.02% 2.043% 97.3 47.62 3
-+- 23 96 2.25 2.19% 2.109% 96.0 45.50 4
++- 37 96 2.25 2.63% 2.059% 93.9 45.60 5
0A0 30 100 7.5 2.68% 2.158% 95.6 44.30 6
--- 23 79 2.25 1.09% 1.869% 100.1 53.56 7
+-- 37 79 2.25 1.30% 1.902% 91.0 47.86 8
000 30 88 7.5 2.19% 2.224% 93.4 41.99 9
000 30 88 7.5 2.41% 2.159% 100.9 46.73 10
00a 30 88 0 1.26% 1.940% 93.5 48.21 11
A00 40 88 7.5 2.79% 2.073% 97.0 46.80 12
000 30 88 7.5 2.28% 2.250% 94.3 41.94 13
0a0 30 76 7.5 1.02% 1.719% 100.3 58.33 14
+++ 37 96 12.7 3.52% 2.208% 99.4 45.02 15
000 30 88 7.5 2.11% 2.034% 100.5 49.43 16
--+ 23 79 12.7 1.18% 1.637% 95.1 58.06 17
00A 30 88 15 2.22% 2.167% 98.9 45.65 18

The data analysis was broken into five parts. Part 1 involved the boil-off loss during the
laboratory preparation process. This does not involve the indigo dyeing process and does not
require separating one dip of indigo versus six dips of indigo. In other words, the experimenter had
a completely replicated central composite design with axial components. The remaining parts
involved analyzing the data after the indigo dyeing process and therefore must take into
consideration the amount of indigo applied from either one or six dips. Part 2 involved %IOWY after
one and six dips of indigo. Part 3 involved Integ shade value after one and six dips of indigo. Part 4
involved penetration factor after one and six dips of indigo. Finally, the optimum laboratory set-up
was determined from the results in previous parts. While the exact indigo dye conditions were not
of major importance in determining preparation parameter affects, for the record the production
shade consisted of 3 g/l indigo dye bath concentration, 12.5 pH, 31 m/sec, and 8.6 meter dwell
length. The skeins were prepared as outlined in section 3.2 (table 3-2 and 3-3), processed through
the range as discussed in section 3.1.2, and all yarn evaluations were conducted as detailed in
section 3.1.3.
101

3.2.1 Analysis of Laboratory Preparation Time, Temperature, and Sodium Hydroxide Concentration
Affect on %Boil-off Loss
Figure 3-3 illustrates the affect of time on the %Boil-off loss for all data points. The general
trend was slightly greater %Boil-off loss as dwell time increased. However the effect was minimal as
the average value shifts from 2.0% at 20 minutes to 2.25% at 40 minutes. Furthermore the
correlation of %Boil-off loss and time was extremely low as indicated by the R
2
value of 0.025. This
low correlation was due to the high variability around the average value at each evaluated time and
the relative low time dependence. This does not necessarily mean time doesn't play a significant
role in %Boil-off loss but instead the affect of time could be over shadowed by other parameters.


Figure 3-3: Relationship of time on %boil-off loss during laboratory preparation

The effect of sodium hydroxide concentration in the boil off box is illustrated in figure 3-4.
As with time, sodium hydroxide concentration causes a slight increase in %Boil-off loss as the
concentration was increased. Unlike time, sodium hydroxide appears to reach a plateau at ~11 g/l.
R = 0.025
0.00%
0.50%
1.00%
1.50%
2.00%
2.50%
3.00%
3.50%
4.00%
20 25 30 35 40
%
B
o
i
l
-
o
f
f

L
o
s
s
Time (minutes)
Relationship of Time on %Boil-off Loss during
Laboratory Preparation
102

Further increases in concentration appear to have a little effect on average. Also as with time, the
correlation of the effect was minimal with a R
2
value of 0.148. Again the low correlation was due
the high variability of %Boil-off loss at various levels of sodium hydroxide concentration.


Figure 3-4: Relationship of sodium hydroxide concentration on %Boil-off loss during laboratory preparation

With very low correlations of time and sodium hydroxide concentration to %Boil-off loss,
one would expect the temperature to play a major role during the laboratory preparation process.
Based on all %boil-off loss values as a function of temperature, it does play a significant role. As
temperature was increased the %Boil-off loss also increased in a non-linear fashion as seen in figure
3-5. The R
2
value was 0.687 which indicates a fairly strong single parameter correlation.
Furthermore, the degree of change was rather large with 1.25% at 76C and increasing to 2.75% at
100C. This means the %Boil-off loss more than doubles over the range of temperatures evaluated.
R = 0.148
0.00%
0.50%
1.00%
1.50%
2.00%
2.50%
3.00%
3.50%
4.00%
0 2 4 6 8 10 12 14 16
%
B
o
i
l
-
o
f
f

L
o
s
s
Caustic Concentration (g/l)
Relationship of Sodium Hydroxide Concentration on
%Boil-off Loss during Laboratory Preparation
103


Figure 3-5: Relationship of temperature on %Boil-off loss during the laboratory preparation

Before a mathematical model of %Boil-off loss can be constructed, possible parameter
interactions must be evaluated. Interactions were easy to identify graphically as two curves will
cross when each is held constant by one parameter while a second parameter is varied. Figure 3-6
shows the interactions of all parameters on %Boil-off loss. The left column of graphs show the
interaction of time with temperature (middle graph) then sodium hydroxide concentration (bottom
graph). The middle column of graphs show the interaction of temperature with time (top graph)
and sodium hydroxide concentration (bottom graph). The right column of graphs shows the
interaction of sodium hydroxide concentration with time (top graph) and temperature (middle
graph). Since none of the curves on any graph cross each other, there were no significant
interaction effects on %Boil-off loss.
R = 0.687
0.00%
0.50%
1.00%
1.50%
2.00%
2.50%
3.00%
3.50%
4.00%
70 75 80 85 90 95 100
%
B
o
i
l
-
o
f
f

L
o
s
s
Temperature (C)
Relationship of Temperature on %Boil-off Loss during
Laboratory Preparation
104


Figure 3-6: Interaction profile for time, temperature, and sodium hydroxide concentration on %boil-off loss during
laboratory preparation process

The interaction profile does however illustrate that time and sodium hydroxide
concentration independently can play a major role in %Boil-off loss even though the R
2
values from
figures 3-3 and 3-4 were very low. For example, the lower left hand graph of %Boil-of loss as a
function of time and sodium hydroxide concentration shows a change in time and sodium hydroxide
concentration causes a linear change in %Boil-off loss. Specifically, as the sodium hydroxide
concentration was held constant at 0 g/l, the increase in time causes a linear increase in %Boil-off
loss. The upper right hand graph shows that as time was held constant an increase in sodium
hydroxide concentration causes a non-linear increase in %Boil-off loss. Graphical depictions of
single parameter affects on %Boil-off loss highlight these detailed changes in the overall variation of
the experiment. A more rigorous analysis was needed to determine the significance of each
parameters affect on %Boil-loss.
An ANOVA analysis of time, temperature, and sodium hydroxide concentration on %boil-off
revealed the statistically significant parameters as well as created a model to predict %Boil-off loss
as a function of those parameters. Table 3-4 summarizes the ANOVA analysis results after removing
0.01
0.02
0.03
0.04
%

B
o
i
l
-
o
f
f

L
o
s
s
0.01
0.02
0.03
0.04
%

B
o
i
l
-
o
f
f

L
o
s
s
0.01
0.02
0.03
0.04
%

B
o
i
l
-
o
f
f

L
o
s
s
Time
76
100
0
15
2
0
2
5
3
0
3
5
4
0
20
40
Temperature
0
15
8
0
8
5
9
0
9
5
1
0
0
20
40
76
100
NaOH
05
1
0
1
5
T
i
m
e
T
e
m
p
e
r
a
t
u
r
e
N
a
O
H
Interaction Profiles
(min)
(C)
(g/l)
%Boil-off Loss Interaction Profile
105

insignificant interaction effects. The parameter estimates indicate time, temperature, and sodium
hydroxide concentrations each have a statistically significant affect as the P-value for each was less
the 0.0059. Furthermore the analysis indicates the second order effect of temperature was
statistically significant with a P-value of 0.0411. This finding was graphically supported in figure 3-5
since the R
2
value for second order trend curve was higher than a linear trend line. The summary of
fit produces a R
2
of 0.89 for this model compared to the actual data points. Furthermore the
analysis of variance calculates a P-value less than 0.0001 for this model. Both values indicate high
correlation and significance for the model compared to actual data points.

Table 3-4: ANOVA analysis results for laboratory preparation parameters on %Boil-off loss


The model was constructed using the estimates from the parameter estimates section in
table 3-4, equation 3-9.

% = 1.6S4
-5
( 88.uS)
2
+ 7.41
-4
+
6.68S
-5
( 7.64)
2
+ 4.69
-4
+ 1.942
-4
u.uS178
Equation 3-9: %Boil-off loss as a function of time, temperature, and sodium hydroxide concentration.
106

This equation was represented in the prediction profiler graph shown in figure 3-7. Now the
main effects were more easily identified. The time increased the %Boil-off loss linearly while sodium
hydroxide concentration and temperature increase have a non-linear increasing affect. Importantly,
the maximum effect of sodium hydroxide on %Boil-off loss occurs at 11 g/l regardless of time or
temperature. The true relationship could be a plateau was reached at 11 g/l were further increases
in concentration have little affect on %Boil-off loss. Recall the average effect illustrated in figure 3-
4. These results will later be coupled with effects of time, temperature, and sodium hydroxide
concentration affects on %IOWY, Integ, and penetration factor to determine the optimum
laboratory values.


Figure 3-7: %Boil-off loss model as a function of time (minutes), temperature (C), and sodium hydroxide concentration
(g/l) in laboratory preparation process

3.2.2 Analysis of Laboratory Preparation Time, Temperature, and Sodium Hydroxide Concentration
Affect on %IOWY after One and Six Dip Indigo Dyeing Conditions
The %IOWY after one and six dips of indigo as a function of time was illustrated in figure 3-8.
Inspection of one dip dyeing represented by X's and solid trend line, showed poor correlation which
is statistically supported by the low second order polynomial R
2
value of 0.046. While the
correlation coefficient was obviously very low the general trend was an increasing %IOWY value
%

B
o
i
l
-
o
f
f

L
o
s
s
0
.
0
3
0
2
1
1

0
.
0
0
2
3
3
2
0
2
5
3
0
3
5
4
0
7
5
8
0
8
5
9
0
9
5
1
0
005
1
0
1
5
Time (min) Temperature (C) NaOH (g/l)
%Boil-off Loss Prediction Profile for Laboratory Preparation Process
107

until approximately 32 minutes. After 32 minutes the amount of %IOWY decreases with further
increase in time. The %IOWY after six dips of indigo as represented by O's and dotted trend line
likewise showed poor correlation which is supported by the second order polynomial with a R
2
value
of 0.034. As with one dip, the %IOWY after six dips as a function of time appears to reach a critical
value at 32 minutes. Further increases in time result in slightly lower %IOWY. While the effect of
time appears to have more importance at one dip, the same effect can be seen after six dips. The
time affect was highly variable, particularly after one dip, and thus difficult to draw immediate
conclusions on the role time plays in the laboratory preparation procedure.


Figure 3-8: Relationship of laboratory preparation time on %IOWY after one and six dips of indigo dye

Unfortunately the effect of laboratory preparation sodium hydroxide concentration on
%IOWY was similar to the effect of time. The best curve fit after one dip was by second order
polynomial with a R
2
value of 0.086. Increasing sodium hydroxide concentration resulted in
increasing %IOWY until 9 g/l. Further increases in concentration resulted in decreased %IOWY as
R = 0.046
R = 0.034
0.000%
0.500%
1.000%
1.500%
2.000%
2.500%
0.000%
0.050%
0.100%
0.150%
0.200%
0.250%
0.300%
0.350%
0.400%
20 25 30 35 40
%
I
O
W
Y

(
s
i
x

d
i
p
s
)
%
I
O
W
Y

(
o
n
e

d
i
p
)
Time (minutes)
Effect of Time on %IOWY from One and Six Dips of Indigo
One Dip Six Dips
108

illustrated in figure 3-9. For six dips the best curve fit was described as essentially constant with a R
2

value of 0.037. Again, the poor correlation was due to high variability in the data points and limited
effect sodium hydroxide concentration during the laboratory preparation process played in %IOWY.


Figure 3-9: Relationship of sodium hydroxide concentration during laboratory preparation on %IOWY from one and six
dips of indigo dye

The effect of temperature during laboratory preparation had a major impact on %IOWY.
After one dip of indigo the best curve fit was by a second order polynomial with a R
2
value of 0.708.
After six dips of indigo the second order polynomial R
2
value was 0.743. The same general trend
was seen after one and six dips of indigo. Under both dyeing conditions as the temperature was
increased from 76C, the %IOWY increased. The maximum %IOWY occurred at 94C as shown in
figure 3-10. Furthermore, the change in %IOWY appears to flatten out at 94C. The data points
indicate temperatures higher then 95C do not produce a true change in %IOWY. Also notice the
R = 0.086
R = 0.037
0.000%
0.500%
1.000%
1.500%
2.000%
2.500%
0.000%
0.050%
0.100%
0.150%
0.200%
0.250%
0.300%
0.350%
0.400%
0 2 4 6 8 10 12 14 16
%
I
O
W
Y

(
s
i
x

d
i
p
s
)
%
I
O
W
Y

(
o
n
e

d
i
p
)
Sodium Hydroxide Concentration (g/l)
Effect of Sodium Hydroxide Concentration on %IOWY from
One and Six Dips of Indigo
One Dip Six Dips
109

variability around the curve fit appeared to reduce at higher temperatures for both one and six dip
dyeings.


Figure 3-10: Relationship of temperature during laboratory preparation on %IOWY from one and six dips of indigo dye

The interaction of the parameters on %IOWY were also evaluated to determine if
any significant effect was attributed. Figure 3-11 shows the interaction profiles for time,
temperature, and sodium hydroxide concentration on %IOWY after one and six dips of indigo.
Inspection of all graphs in figure 3-11 revealed no interactions exist as no curves cross. Temperature
appears to be the only major influence on the %IOWY after one and six dips of indigo.



R = 0.708
R = 0.743
0.000%
0.500%
1.000%
1.500%
2.000%
2.500%
0.000%
0.050%
0.100%
0.150%
0.200%
0.250%
0.300%
0.350%
0.400%
70 75 80 85 90 95 100
%
I
O
W
Y

(
s
i
x

d
i
p
s
)
%
I
O
W
Y

(
o
n
e

d
i
p
)
Temperature (C)
Effect of Temperture on %IOWY from One and Six Dips of
Indigo
One Dip Six Dips
110



Figure 3-11: Interaction profile for time, temperature, and sodium hydroxide concentration on %IOWY after one and six
dips of indigo dye

A full ANOVA analysis was conducted on %IOWY after one dip of indigo by time, sodium
hydroxide concentration, and temperature during laboratory preparation. The analysis revealed the
second order effect of time and sodium hydroxide concentration to be insignificant. Furthermore,
the first order effect was actually determined to be insignificant as illustrated by the high P-values in
the parameter estimates from table 3-5. Time had a P-value of 0.6761 while sodium hydroxide
concentration was 0.4675. In fact, the only statistically significant parameter effect was the first and
second order temperature along with intercept (P-value 0.0010, 0.0176, and 0.0259 respectively).
Even though time and sodium hydroxide concentration parameters were determined to be
insignificant, it is customary to leave the first order parameters in model calculations especially since
the equation will be later joined with other models that may have all three parameters. The
summary of fit for the resulting model was 0.71 with a P-value of 0.0029. Both indicate the model
produced a reasonable fit that was statistically significant compared to the data points.


%IOWY Interaction Profile for One Dip %IOWY Interaction Profile for Six Dips
(min) (min)
(C) (C)
(g/l) (g/l)
111

Table 3-5: ANOVA analysis results for laboratory preparation parameters on %IOWY for one dip of indigo


The exact model was constructed by pulling the parameter estimates from table 3-5 and
equation 3-10 was created.

% = 7.S12
-6
( 88.29)
2
+ 8.42S
-5
+
1.u
-5
+ 2.S4S
-5
u.uSu7S
Equation 3-10: %IOWY as a function of time, temperature, and sodium hydroxide concentration after one dip of indigo.

This equation was used to build the prediction profiler graphs shown in figure 3-12. These curves
finally illustrate the significance of temperature during laboratory preparation on %IOWY. They also
show the low dependence of %IOWY on time and sodium hydroxide concentration. The 95%
confidence intervals were also calculated and plotted as blue dotted curves. The best overall
combination yields confidence intervals of 0.0896% with a mean value of 0.2946% indigo on weight
of yarn.


112


Figure 3-12: %IOWY for one dip of indigo model as a function of time, temperature, and sodium hydroxide
concentration in laboratory preparation process

A full ANOVA analysis was conducted on %IOWY after six dips of indigo by time, sodium
hydroxide concentration, and temperature during laboratory preparation. The results are presented
in table 3-6. Just like one dip of indigo the parameter estimates indicate the first and second order
term of temperature were statistically significant with P-values of 0.0001 and 0.0148 respectively
for six dips of indigo. Time and sodium hydroxide concentration were left in the model calculations
even though each was determined to be insignificant. The summary of fit for the model was
calculated to be R
2
of 0.76 and the analysis of variance had a P-value of 0.0006. Both indicate the
model was a good fit and statistically significant compared to the data used to create the model.


%
I
O
W
Y
0
.
0
0
2
9
4
6

0
.
0
0
0
8
9
5
2
0
2
5
3
0
3
5
4
0
7
5
8
0
8
5
9
0
9
5
1
0
005
1
0
1
5
%IOWY Prediction Profile on One Dip of Indigo for Laboratory Preparation Process
Time (min) Temperature (C) NaOH (g/l)
113

Table 3-6: ANOVA analysis results for laboratory preparation parameters on %IOWY for six dips of indigo


Using the parameter estimates from table 3-6, equation 3-11 for 6 dips of indigo was
created.

% = 1.S86
-5
( 87.78)
2
+ 1.9u1
-4
+
2.64
-5
+ S.u81
-5
+ u.uuS2114
Equation 3-11: %IOWY as a function of time, temperature, and sodium hydroxide concentration after six dips of indigo.

This equation was also graphically represented in figure 3-13. These curves finally illustrate
the significance of temperature on %IOWY. They also show the low dependence of %IOWY on time
and sodium hydroxide concentration. The 95% confidence intervals are at minimum value when
time equals 30 minutes based on the blue dotted confidence curves. The best overall combination
yields confidence intervals of 0.1654% with a mean value of 2.143% IOWY. While the magnitude of
confidence intervals for six dips of indigo is two times greater than one dip, the mean %IOWY at six
dips is almost ten times greater than one dip. Therefore, the overall confidence after six dips of
indigo is actually greater than after one dip of indigo.
114



Figure 3-13: %IOWY for six dips of indigo model as a function of time, temperature, and sodium hydroxide
concentration in laboratory preparation process

3.2.3 Analysis of Laboratory Preparation Time, Temperature, and Sodium Hydroxide Concentration
Affect on Integ Shade Value after One and Six Dip Indigo Dyeing Conditions
The general trend for time's effect on Integ shade value from both one and six dip dyeings is
shown in figure 3-14. After one dip of indigo, increasing boil-off time caused the Integ shade value
to increase which indicates the indigo color became darker. The trend has an overall R
2
value of
0.245 which indicated a poor overall correlation. The general trend is for constant Integ shade value
from 20 minutes till 30 minutes. At 30 minutes a high degree of variability exists in Integ shade
value. Further increases in time result in increased Integ shade values.
During six dips of indigo dyeing, time had the opposite effect on Integ shade value as
reflected in figure 3-14. As the time increased the Integ shade value decreased indicating the indigo
color becomes lighter. The trend has an overall R
2
value of 0.021 which indicates a very poor overall
correlation. Over the entire time span the Integ shade value ranged from 91 at 37 minutes to 101 at
30 minutes. This is a change of 10 Integ shade value units or less than 10%. The general trend for
Integ as a function of time after six dips of indigo dyeing is that of constant value. Neither the one
%
I
O
W
Y
0
.
0
2
1
4
2
9

0
.
0
0
1
6
5
4
2
0
2
5
3
0
3
5
4
0
7
5
8
0
8
5
9
0
9
5
1
0
005
1
0
1
5
%IOWY Prediction Profile on Six Dips of Indigo for Laboratory Preparation Process
Time (min) Temperature (C) NaOH (g/l)
115

dip nor the six dip indigo dyeing condition exhibited a major contribution to Integ shade value due
to time.


Figure 3-14: Relationship of laboratory preparation time on Integ shade value from one and six dips of indigo dye

Next sodium hydroxide concentration during laboratory preparation was evaluated after
one and six dips of indigo. Both dyeing conditions exhibited a plateau as the sodium hydroxide
concentration was increased. Figure 3-15 shows the apex is approximately 6 g/l for one dip and 11
g/l for six dips. Continued increasing concentration levels beyond these values resulted in
decreasing Integ values for both dip conditions. However, both dyeing conditions exhibited poor
correlation as reflected in the R
2
values of 0.187 and 0.182 for one and six dips respectively. The
poor correlation can be explained by the relatively small change in Integ values over a wide range of
concentrations coupled with the high variability associated with each concentration. At 7.5 g/l
concentration the variability of Integ shade value dramatically increased compared to lower
R = 0.245
R = 0.021
75.0
80.0
85.0
90.0
95.0
100.0
105.0
20.0
22.0
24.0
26.0
28.0
30.0
32.0
34.0
20 25 30 35 40
I
n
t
e
g

(
s
i
x

d
i
p
s
)
I
n
t
e
g

(
o
n
e

d
i
p
)
Time (minutes)
Effect of Time on Integ from One and Six Dips of Indigo
One Dip Six Dips
116

concentrations. As the concentration is further increased the variability appears to reduce while the
overall Integ shade value also decreased.


Figure 3-15: Relationship of sodium hydroxide concentration during laboratory preparation on Integ shade value after
one and six dips of indigo dye

Unlike previous %IOWY analysis, temperature doesn't play a major role in Integ shade value
variation. After one dip of indigo, the general trend was increased Integ shade as the temperature
was increased from 88C to 100C. However the changes in Integ shade values were small and the
overall R
2
correlation was low at 0.122 as shown in figure 3-16. After six dips of indigo the general
trend was decreased Integ shade as the temperature was increased from 88C to 100C. However,
the changes in Integ shade values were small and the overall R
2
correlation was low at 0.015 as
shown in figure 3-16. At 88C the variability increased considerably under both one and six dip
dyeing conditions and appears to decrease as the temperature is increased. Like the other two
parameters, temperature has a high degree of variability so a detailed ANOVA analysis was needed
to confirm insignificance.
R = 0.187
R = 0.182
75.0
80.0
85.0
90.0
95.0
100.0
105.0
20.0
22.0
24.0
26.0
28.0
30.0
32.0
34.0
0 2 4 6 8 10 12 14 16
I
n
t
e
g

(
s
i
x

d
i
p
s
)
I
n
t
e
g

(
o
n
e

d
i
p
)
Sodium Hydroxide Concentration (g/l)
Effect of Sodium Hydroxide Concentration on Integ from One
and Six Dips of Indigo
One Dip Six Dips
117


Figure 3-16: Relationship of temperature during laboratory preparation on Integ shade value after one and six dips of
indigo dye

The full ANOVA analysis involving first and second order plus interactions of parameters was
shown in table 3-7 for one dip indigo dyeing condition. The P-values calculated in parameter
estimates shown no statistically significant effect for all values except the intercept which of course
was meaningless. This conclusion was further supported by relatively low R
2
in the summary of fit
and high P-value in analysis of variance results. As a result, the Integ shade value from one dip of
indigo was not used to optimize the laboratory preparation procedure.

R = 0.122
R = 0.015
75.0
80.0
85.0
90.0
95.0
100.0
105.0
20.0
22.0
24.0
26.0
28.0
30.0
32.0
34.0
70 75 80 85 90 95 100
I
n
t
e
g

(
s
i
x

d
i
p
s
)
I
n
t
e
g

(
o
n
e

d
i
p
)
Temperature (C)
Effect of Temperture on Integ from One and Six Dips of
Indigo
One Dip Six Dips
118

Table 3-7: ANOVA analysis results for laboratory preparation parameters on Integ for one dip of indigo


The full ANOVA analysis involving first and second order plus interactions of parameters was
shown in table 3-8 for six dip indigo dyeing condition. The P-values calculated in parameter
estimates showed no statistically significant effect on all values except the intercept which of course
was meaningless. This conclusion was further supported by relatively low R
2
in the summary of fit
and high P-value in analysis of variance results. No statistically significant effect from time,
temperature, or sodium hydroxide concentration on Integ shade value for six dips of indigo existed.
This is the same results as seen in one dip of indigo dye. As a result, the Integ shade value from six
dips of indigo was not used to optimize the laboratory preparation procedure.

119

Table 3-8: ANOVA analysis results for laboratory preparation parameters on Integ for six dips of indigo


3.2.4 Analysis of Laboratory Preparation Time, Temperature, and Sodium Hydroxide Concentration
Affect on Penetration Factor after One and Six Dip Indigo Dyeing Conditions
Since time, temperature, and sodium hydroxide concentration were determined to have
insignificant effect on Integ shade value and penetration factor is a function of Integ shade value
and %IOWY, this researcher expects the penetration factor to have the same relationship as the
inverse of %IOWY. For completeness, the full analysis was presented. First, notice a high degree of
variability in the penetration factor presented in figure 3-17 after one dip of indigo. The extremely
low levels of %IOWY at shorter times produced high penetration factor values. With all data points
the R
2
correlation was very low at 0.088. If the single point at 1200+ penetration factor was
removed, the function was flat with R
2
of 0.057. Time doesn't appear to affect penetration factor
after one dip of indigo.

120

A similar relationship exists for six dips of indigo on penetration factor as a function of time.
The high degree of variability in the penetration factor presented in figure 3-17 continues for six
dips. While the range of penetration factors from six dips is smaller than one dip, the overall
variation is high. With all data points the R
2
correlation was very low at 0.03 and is basically
constant over all times.


Figure 3-17: Relationship of time during laboratory preparation on penetration factor after one and six dips of indigo
dye

The same observations can be made in regards to sodium hydroxide concentration influence
on penetration factor after one and six dips of indigo. Very poor correlation exists as illustrated in
figure 3-18 with R
2
values of 0.094 and 0.011 for one and six dips respectively. If the 1200+
penetration factor value was removed, the resulting trend after one dip of indigo was flat with a R
2

value of 0.049. Sodium hydroxide concentration doesn't have a major affect on penetration factor.

R = 0.088
R = 0.03
0.00
10.00
20.00
30.00
40.00
50.00
60.00
70.00
0.00
200.00
400.00
600.00
800.00
1000.00
1200.00
1400.00
20 25 30 35 40
P
e
n
e
t
r
a
t
i
o
n

F
a
c
t
o
r

(
s
e
x

d
i
p
s
)
P
e
n
e
t
r
a
t
i
o
n

F
a
c
t
o
r

(
o
n
e

d
i
p
)
Time (minutes)
Effect of Time on Penetration Factor from One and Six Dips
of Indigo
One Dip Six Dips
121


Figure 3-18: Relationship of sodium hydroxide concentration during laboratory preparation on penetration factor after
one and six dips of indigo dye

The temperature effect on penetration factor after one and six dips of indigo was discussed.
Under both indigo dyeing conditions the penetration factor decreased as the temperature was
increased, figure 3-19. This was the opposite trend as shown for %IOWY as a function of
temperature, refer back to figure 3-10. After one dip the general trend in figure 3-19 isn't as
pronounced due to the greater variation in penetration factor values which was reflected in the R
2

value of 0.246. However, after six dips the general trend has a much stronger correlation as
reflected in the R
2
value of 0.729. Both dyeing conditions exhibit reduce variation as the
temperature is increased. The penetration factor reaches the minimum value at approximately 95C
and does not vary further as temperature continues to increase.
R = 0.094
R = 0.011
0.00
10.00
20.00
30.00
40.00
50.00
60.00
70.00
0.00
200.00
400.00
600.00
800.00
1000.00
1200.00
1400.00
0 2 4 6 8 10 12 14 16
P
e
n
e
t
r
a
t
i
o
n

F
a
c
t
o
r

(
s
i
x

d
i
p
s
)
P
e
n
e
t
r
a
t
i
o
n

F
a
c
t
o
r

(
o
n
e

d
i
p
)
Sodium Hydroxide Concentration (g/l)
Effect of Sodium Hydroxide Concentration on Penetration
Factor from One and Six Dips of Indigo
One Dip Six Dips
122


Figure 3-19: Relationship of temperature during laboratory preparation on penetration factor after one and six dips of
indigo dye

Evaluation of parameter interaction was shown in figure 3-20 for both one and six dip indigo
conditions. As with %IOWY, no actual parameter interactions were detected. Furthermore, the only
major change in penetration factor occurs as a result of temperature as evident in large change from
76C to 100C in the second row of graphs for both one and six dip conditions.


R = 0.246
R = 0.729
0.00
10.00
20.00
30.00
40.00
50.00
60.00
70.00
0.00
200.00
400.00
600.00
800.00
1000.00
1200.00
1400.00
70 75 80 85 90 95 100
P
e
n
e
t
r
a
t
i
o
n

F
a
c
t
o
r

(
s
i
x

d
i
p
s
)
P
e
n
e
t
r
a
t
i
o
n

F
a
c
t
o
r

(
o
n
e

d
i
p
)
Temperature (C)
Effect of Temperture on Penetration Factor from One and Six
Dips of Indigo
One Dip Six Dips
123


Figure 3-20: Interaction profile for time, temperature, and sodium hydroxide concentration on penetration factor after
one and six dips of indigo dye

The full ANOVA analysis results after one dip of indigo were shown in table 3-9. The
parameter estimates with statistical significance was determined to be first and second order
temperature represented by P-values of 0.0021 and 0.0293 respectively. The R
2
of 0.68 and P-value
of 0.0050 for the complete model indicate reasonable agreement that was statistically significant to
the actual data points. While the overall agreement was lower than for %IOWY, this was somewhat
expected given the greater degree of variability especially with the 1200+ penetration value.

Table 3-9: ANOVA analysis results for laboratory preparation parameters on penetration factor from one dip of indigo

50
100
150
200
250
P
.
F
.
50
100
150
200
250
P
.
F
.
50
100
150
200
250
P
.
F
.
Time
76
100
0
15
2
0
2
5
3
0
3
5
4
0
20
40
Temperature
0
15
8
0
8
5
9
0
9
5
1
0
0
20
40
76
100
NaOH
05
1
0
1
5
T
i
m
e
T
e
m
p
e
r
a
t
u
r
e
N
a
O
H
Interaction Profiles
40
45
50
55
60
P
.
F
.
40
45
50
55
60
P
.
F
.
40
45
50
55
60
P
.
F
.
Time
75
102.5
0
15
2
0
2
5
3
0
3
5
4
0
20
40
Temperature
0
15
7
5
8
5
9
5
1
0
5
20
40
75
102.5
NaOH
05
1
0
1
5
T
i
m
e
T
e
m
p
e
r
a
t
u
r
e
N
a
O
H
Interaction Profiles
P.F. Interaction Profile for One Dip P.F. Interaction Profile for Six Dips
(min) (min)
(C) (C)
(g/l) (g/l)
124

The prediction profiler, figure 3-21, further agrees with the inverse of %IOWY. Time and
sodium hydroxide concentration have little influence on penetration factor regardless of
temperature. While an increasing temperature causes a decrease in penetration factor. This trend
was governed by the %IOWY at each temperature level. At low temperatures, the %IOWY was low
while at higher temperatures the amount of %IOWY increased. Therefore dividing a relatively
constant Integ shade value by low %IOWY at low temperatures produces a high penetration factor
and low penetration factor at high temperatures since the %IOWY was higher. Since no new
information regarding laboratory preparation process was gleamed, this relationship will not be
used to determine the optimum laboratory preparation procedure.


Figure 3-21: Penetration factor for one dip of indigo model as a function of time, temperature, and sodium hydroxide
concentration in laboratory preparation process

The full ANOVA analysis results after six dips of indigo were shown in table 3-10. The
parameter estimates with statistical significance was determined to be first and second order
temperature represented by P-values of 0.0001 and 0.0171 respectively. The R
2
of 0.75 and P-value
of 0.0007 for the complete model indicated reasonable agreement that was statistically significant
to the actual data points. However, the overall agreement was less than previous %IOWY analysis.

Penetration Factor Prediction Profile on One Dip of Indigo for Laboratory Preparation
Time (min) Temperature (C) NaOH (g/l)
125

Table 3-10: ANOVA analysis results for laboratory preparation parameters on penetration factor from six dips of indigo


The prediction profiler, figure 3-22, further agrees with the inverse of %IOWY. Time and
sodium hydroxide concentration have little influence on penetration factor regardless of
temperature. While increasing temperature causes a decrease in penetration factor. Just like one
dip of indigo, this trend was governed by the %IOWY at each temperature level. At low
temperatures, the %IOWY was low while at higher temperatures the amount of %IOWY increased.
Therefore, dividing a relatively constant Integ shade value by low %IOWY at low temperatures
produces a high penetration factor and low penetration factor at high temperatures since the
%IOWY was higher. This relationship will not be used to determine the optimum laboratory
preparation procedure.
126


Figure 3-22: Penetration factor for six dips of indigo model as a function of time, temperature, and sodium hydroxide
concentration in laboratory preparation process

3.2.5 Determine Optimum Settings for Laboratory Preparation Procedure
By joining the prediction formulas of %Boil-off loss and %IOWY at one dip, the prediction
profile illustrated in figure 3-23 was generated. The desired outcome was flat or very little change in
%Boil-off loss and %IOWY at specific values of time, temperature, and sodium hydroxide
concentration. The first row of graphs in figure 3-23 illustrated the relationship between %Boil-off
loss as a function of time, temperature, and sodium hydroxide concentration. The second row of
graphs illustrated the relationship between %IOWY as a function of time, temperature, and sodium
hydroxide concentration. Again, these were the same relationships previously determined in the
ANOVA analysis. The third row of graphs represents the combined response by placing equal
importance to %Boil-off loss and %IOWY. This sequence of graphs was used to determine the
optimum setting for each parameter.
The first column of graphs shows the total effect of time on each response variable and the
corresponding desire function. As one can see increasing time caused increase in %Boil-off loss and
no affect on %IOWY which resulted in very little overall affect on the total desire function.
Therefore, any value of time greater than 20 minutes will produce consistent and repeatable %Boil-
off loss and more importantly %IOWY. Given 30 minutes was the center point of the design of
Penetration Factor Prediction Profile on Six Dips of Indigo for Laboratory Preparation
Time (min) Temperature (C) NaOH (g/l)
127

experiment and therefore has the greatest replicated data points, this researcher selected 30
minutes for time value under one dip of indigo.
The second column of graphs illustrated the total effect of temperature on each response
variable and the corresponding desire function. According to %Boil-off loss the ideal temperature
value lays greater than 100 C. However, the %IOWY function indicated temperature values greater
than ~95 C have no additional impact. Therefore the combined desire function of %Boil-off loss
and %IOWY actually flattens out at 95 C. As a result, temperatures greater than 95 C had lower
sensitivity to changes which of course was desired, therefore temperature values greater than 95 C
were preferred.
The third column in figure 3-23 corresponds to sodium hydroxide concentration effect on
%Boil-off loss and %IOWY. Here 11 g/l was determined to have the greatest %Boil-off loss while no
concentration level significantly impacts %IOWY. The combined desire function indicates
concentration levels greater than 11 g/l had no additional impact. Therefore, any level greater the
11 g/l was preferred.


128


Figure 3-23: Optimized laboratory preparation parameters incorporating prediction profiles from %Boil-off loss and
%IOWY from one dip of indigo dye

Similar prediction profile graphs were created for six dips of indigo, figure 3-24. Following
the same logic as discussed with one dip of indigo produced the following results. The first column
shows time levels greater the 30 minutes yields little to no impact on the overall desire function.
The second column illustrated the highest level of desire function to occur at 100 C and doesn't
flatten out. However, more detailed review shows temperature levels greater the 95 C has little
additional impact on the %IOWY. The third column for sodium hydroxide concentration mirrors the
results for one dip of indigo. Concentrations greater than 11 g/l have little or no additional effect on
%Boil-off loss or %IOWY.
0.015
0.02
0.025
0.03
P
r
e
d

F
o
r
m
u
l
a

%
B
o
i
l
-
o
f
f

L
o
s
s
0
.
0
3
0
2
1
1
0
0.005
0.01
0.015
0.02
P
r
e
d

F
o
r
m
u
l
a
%
I
O
W
Y

B
y

D
i
p

#
0
.
0
0
2
8
2
3
0
0
.
2
5
0
.
7
5
1
D
e
s
i
r
a
b
i
l
i
t
y
0
.
3
6
3
6
6
7
2
0
2
5
3
0
3
5
4
0
30
Time
7
5
8
0
8
5
9
0
9
5
1
0
0
100
Temperature
05
1
0
1
5
11
NaOH
16
1
Dip #
0
0
.
2
5
0
.
5
0
.
7
51
Desirability
Prediction Profiler Optimized Prediction Profile on One Dip of Indigo for Laboratory Preparation Process
Time (min) Temperature (C) NaOH (g/l)
129



Figure 3-24: Optimized laboratory preparation parameters incorporating prediction profiles from %Boil-off loss and
%IOWY from six dips of indigo dye

Additional observations made during the experiment were controlling the temperature of
the solution was the most difficult of the three factors. The time and sodium hydroxide
concentration were the easiest. Temperature levels of 100C were easily maintained at atmospheric
conditions by just maintaining a slow boil in the preparation bath. Combining the above comments
with the results from the analysis of one and six dip indigo dyed skeins yields the following optimum
laboratory preparation procedure. These specific laboratory preparation parameters were used on
all following trials.
Time: 30 minutes
Temperature: 100C
Sodium hydroxide concentration: 12.7 g/l of 50% caustic soda

0.015
0.02
0.025
0.03
P
r
e
d

F
o
r
m
u
l
a

%
B
o
i
l
-
o
f
f

L
o
s
s
0
.
0
3
0
2
1
1
0
0.005
0.01
0.015
0.02
P
r
e
d

F
o
r
m
u
l
a
%
I
O
W
Y

B
y

D
i
p

#
0
.
0
2
1
2
3
1
0
0
.
2
5
0
.
7
5
1
D
e
s
i
r
a
b
i
l
i
t
y
0
.
9
6
4
2
8
6
2
0
2
5
3
0
3
5
4
0
30
Time
7
5
8
0
8
5
9
0
9
5
1
0
0
100
Temperature
05
1
0
1
5
11
NaOH
16
6
Dip #
0
0
.
2
5
0
.
5
0
.
7
51
Desirability
Prediction Profiler
Optimized Prediction Profile on Six Dips of Indigo for Laboratory Preparation Process
Time (min) Temperature (C) NaOH (g/l)
130

3.3 Equilibrium Sorption Experiment to Determine %IOWY and Shade Relationship for Uniformly
Dyed Skeins
In 1991 Etters
20
published equilibrium sorption curves for %IOWY as a function of dye bath
concentration and pH. Unfortunately this data did not contain shade information. With the shade
information from uniformly dyed yarns, the shade of ring dyed yarns could be converted into
equivalent %IOWY on the "visible" surface of yarn. This value compared to actual %IOWY would
give a measurement of dye penetration into the yarn structure. This method would give a more
quantitative measurement of dye penetration as opposed to qualitative such as penetration factor
discussed in section 3.1.3. Specifically penetration level was defined by equation 3-12.

Penetiation Level =
%I0w
Measued
%I0w
Integ

Equation 3-12: Calculation of penetration level as a function of measured %IOWY and converted surface %IOWY from
Integ shade readings.

Here the %IOWY in the numerator was measured by Pyrrolidinone extract as discussed in
section 3.1. The %IOWY converted from Integ shade value in the denominator was the %IOWY that
corresponds to the measured Integ shade value if the dying had been conducted under uniform
dyeing conditions, i.e. uniform dye concentration distribution in the cross section of the yarn. The
penetration level values will vary from 1.0 to 0.0 with 1.0 corresponding to uniformly dyed cross
sections of yarn and 0.0 representing ideal ring dyed yarn with all dye located on the very outer
perimeter of the yarn.
To collect the shade information a series of laboratory dyeings were conducted. Eight
different stock mixes were made up and diluted to specific dye bath concentrations. Each dye bath
contained 3 liters of volume and at most 4 yarn skeins were dyed in each bath. Approximately 30
grams of cotton (4 times 7 grams/skein) to 3000 grams of dye bath followed 100:1 liquor: cotton
ratio. The initial dye bath pH was also measured. Then up to 4 skeins that had been pre-wet out
and nipped to 70% wet pick-up were submerged into the dye bath suspended by plastic hooks to
131

keep the skeins from lying on top of each other. The top of each dye mix was covered with plastic
film to prevent air oxidation of the dye. After 14 hours of dyeing time, each skein was pulled from
the dye bath and run through a laboratory pad nip to squeeze excess dye from the yarn to
approximately 70% wet pick-up. The skeins were then allowed to air oxidize for 3 minutes prior to
laboratory washing at 40C. The washing process was deemed completed when the wash water was
void of color. Once the skeins were dried, the shade was measured as previously discussed and
finally the %IOWY was measured by Pyrrolidinone extraction. Table 3-11 listed the specific dye bath
concentration, pH, and resulting %IOWY and Integ shade for 6.3/1 yarn counts. The remaining yarn
counts and measured values are provided in appendix section A-3-3.


132

Table 3-11: %IOWY and Integ shade data from equilibrium sorption experiment
Yarn Count Dye Bath g/l Dye Bath pH %IOWY Integ Shade Stock Mix #
6.3 0.308 11.1 1.19% 27.9 2
6.3 2.548 11.2 2.97% 63.5 8
6.3 0.641 12.25 1.09% 31.3 1
6.3 0.17663 12.8 0.30% 7.6 4
6.3 1.2287 12.8 1.14% 30.6 6
6.3 1.602 12.72 1.65% 42.4 1
6.3 1.602 12.72 1.66% 43.7 7
6.3 2.564 12.9 2.07% 47.9 7
6.3 8.413 12.8 4.59% 75.1 2
6.3 0.01577 13.17 0.02% 1.2 3
6.3 0.03494 13.3 0.04% 2.3 6
6.3 0.49612 13.19 0.52% 13.4 5
6.3 1.99985 13.21 1.50% 35.3 3
6.3 3.8843 13.24 2.21% 49.9 5
6.3 4.487 13.14 2.70% 58.1 7
6.3 4.487 13.14 2.68% 57.1 1
6.3 6.3355 13.1 3.32% 63.3 4
6.3 9.61464 13.31 4.05% 69.4 3
6.3 14.0149 13.2 4.94% 75.6 6
6.3 14.422 13.2 5.65% 77.2 8
6.3 19.2293 13.43 6.20% 77.7 5
6.3 20.191 13.3 6.68% 81.8 8
6.3 24.037 13.2 8.10% 89.5 2
6.3 29.95 13.2 8.38% 91.3 4

Graphical representation of the equilibrium sorption data revealed the same correlation
previously published by Etters
20
. Namely the %IOWY follows a Freundlich isotherm or power
relationship between %IOWY and dye bath concentration at different dye bath pH values. Also
note the %IOWY was independent of the yarn count. In figure 3-25 the equilibrium sorption data at
pH ranges 13.1 to 13.3 were illustrated. The "X" marks were Etter's 1991 data points. The other
points were 6.3/1, 7.1/1, 8.0/1, and 12.0/1 yarn count data from current equilibrium sorption
experiment. The curve fit was Etter's 1991 data points extended above and below the original data
range to encompass the range of current values.
133


Figure 3-25: %IOWY from 6.3/1, 7.1/1, 8.0/1, and 12.0/1 OE yarns compared to Etters
20
data under equilibrium sorption
at pH 13 range.

The same relationship was illustrated in figure 3-26 for pH ranges of 11.0 to 11.2. Once
again the current experimental results mirror Etter's 1991 data. Both sets of data are almost
perfectly modeled by a power function.
y = 0.007303x
0.734588
R = 0.996
0.01%
0.10%
1.00%
10.00%
100.00%
0.01 0.1 1 10
%
I
O
W
Y

(
g
m

I
n
d
i
g
o
/
1
0
0

g
m

c
o
t
t
o
n
)
Dye Concentration (g/l)
Equilibrium Sorption Relationship at 13.1 to 13.3 pH
6.3 7.1 8 12 Etters 1991
134


Figure 3-26: %IOWY on 6.3/1, 7.1/1, 8.0/1, and 12.0/1 OE yarns compared to Etters
20
data under equilibrium sorption at
pH 11 range.

By combining all current equilibrium sorption data with Etter's 1991 data, a general
relationship between dye bath concentration and pH affect on total %IOWY was revealed. The
power functions at various pH values were summarized in equation 3-13 in the general form.

At each pH: % =
ComponcntB

11.2 pH: % = u.u191S6
0.583135

12.8 pH: % = u.u1u7S4
0.710523

13.2 pH: % = u.uu7448
0.755688

Equation 3-13: Power function relationship of indigo dye bath concentration to %IOWY under equilibrium sorption.


y = 0.019156x
0.583135
R = 0.992
0.10%
1.00%
10.00%
100.00%
0.01 0.1 1 10
%
I
O
W
Y

(
g
m

I
n
d
i
g
o
/
1
0
0

g
m

c
o
t
t
o
n
)
Dye Concentration (g/l)
Equilibrium Sorption Relationship at 11.0 to 11.2 pH
6.3 8 Etters 1991
135

When the component values of the power functions were graphed as a function of pH, the A
component increased with decreasing pH and the B component increased with increasing pH. The
trend for each was shown in figure 3-27. Furthermore the shape of the component A was very
reminiscent of the monophenolate ionic form of indigo dye as a function of pH.


Figure 3-27: Power function coefficients A and B as a function of dye bath pH.

By converting figure 3-27 into a function of monophenolate ionic indigo dye as it varies with
pH, the regression between all three points becomes linear as shown in figure 3-28. Component A
now increased as the monophenolate fraction increased which occurs as pH decreased. Component
B now decreased with an increase in the monophenolate fraction which occurs as the pH decreased.
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0
0.005
0.01
0.015
0.02
0.025
11 11.5 12 12.5 13 13.5
V
a
l
u
e

o
f

C
o
m
p
o
n
e
n
t

B
V
a
l
u
e

o
f

C
o
m
p
o
n
e
t

A
pH
Coefficients of Equilibrium Sorption %IOWY Power
Function
Component A Component B
136


Figure 3-28: Equilibrium sorption power function coefficients as a function of monophenolate ionic form of indigo.

These linear equations for component A and B as a function of monophenolate ionic indigo
dye fraction which were actually a function of pH were used in the general power function to relate
%IOWY to dye bath concentration under equilibrium sorption. The specific results were given in
equation 3-14.

=
1
1+10
9.S-pH
+10
pH-12.

= u.u16492 + u.uuS46S
= u.244296 +u.8161S8
% =
ComponcntB

Equation 3-14: General relationships between indigo dye bath concentration and pH to resulting %IOWY under
equilibrium sorption.

y = 0.016492x + 0.003465
R = 0.999981
y = -0.244296x + 0.816158
R = 0.999384
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0
0.005
0.01
0.015
0.02
0.025
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
V
a
l
u
e

o
f

C
o
m
p
o
n
e
n
t

B
V
a
l
u
e

o
f

C
o
m
p
o
n
e
t

A
Value of Monophenolate Indigo Dye Fraction as a Function of pH
Coefficients of Equilibrium Sorption %IOWY Power
Function
Component A Component B
137

Figure 3-29 shows the results of theoretical %IOWY at 11.2, 12.2, 12.8, and 13.2 pH. The
curves at various pH levels were the theoretical values based on equation 3-14. The individual data
points were all available points of equilibrium sorption as a function of dye bath pH and
concentration. While equation 3-14 was certainly not the only possible solution from regression to
fit the data available, it possesses certain elegance by combining the characteristic nature of
Freundlich isotherm and monophenolate ionic fraction into one equation. This represents the
maximum amount of dye pick-up under equilibrium sorption (M

) that can be achieved given these


two important chemical dye range parameters.


Figure 3-29: Comparison of calculated and measured %IOWY under equilibrium sorption laboratory dyeing conditions as
the dye bath concentration and pH were varied.

0.01%
0.10%
1.00%
10.00%
100.00%
0.01 0.1 1 10
C
a
l
c
u
l
a
t
e
d

%
I
O
W
Y

(
g
m

I
n
d
i
g
o
/
1
0
0

g
m

c
o
t
t
o
n
)
Dye Concentration (g/l)
Calculated Equilibrium Sorption Relationship at
Various pH's
11.2 pH 12.8 pH 13.2 pH Power (11.2 pH)
Power (13.2 pH) Power (12.2 pH) Power (12.8 pH)
138

The shade of the yarns as a function of %IOWY can now be investigated. The relationships
were later used to determine the penetration level for each dye range set-up observation. The
Integ shade value of a particular yarn was converted into the corresponding %IOWY from
equilibrium sorption. Then the penetration level was calculated when compared to the actual
%IOWY. The specific Integ shade values from each yarn count as a function of %IOWY from
equilibrium sorption is featured in figure 3-30. The %IOWY and Integ relationship starts off linear at
low %IOWY values. As the %IOWY increased the resulting change in Integ shade value had less
effect. Therefore the %IOWY and Integ relationship is non-linear but does possess unique values
over the entire range of %IOWY. The best model fit resulted in equation 3-15 that would allow Integ
shade calculations based on the %IOWY under equilibrium sorption.


Figure 3-30: Relationship of Integ shade value for various yarn counts as %IOWY from equilibrium sorption.

I
n
t
e
g
139

= 4S.6u9S7 + (S92.19421 %) (9928.SSS9 (% u.u4S77S)
2
) +
(1.8SSS8
5
(% u.u4S77S)
3
) (1.S224S
6
(% u.u4S77S)
4
) + (4.27u8u
6

(% u.u4S77S)
5
)
Equation 3-15: Calculation of Integ shade based on %IOWY under equilibrium sorption conditions.

The inverse relationship was actually required in order to calculate the penetration level.
Switching the independent and dependent variables produced the relationship for calculating the
%IOWY on the outside surface as a function of Integ shade value. The relationship is displayed in
figure 3-31 and resulting equation listed as equation 3-16.


Figure 3-31: Relationship of %IOWY on the outside surface for various yarn counts as Integ from equilibrium sorption.

%
su]ucc
= u.u2646 +(9.SS86
-4
) + (1.SS9S
-5
( SS.2u88)
2
) +
(S.9u9
-8
( SS.2u88)
3
) + (2.4244
-9
( SS.2u88)
4
) + (6.4SuS
-11

( SS.2u88)
5
)
Equation 3-16: Calculation of surface %IOWY from Integ shade values.
%
I
O
W
Y

o
n

O
u
t
s
i
d
e

S
u
r
f
a
c
e
140

As previously discussed K/S
660nm
cannot be used for %IOWY conversion involving equilibrium
sorption data. The relationship was not only non-linear but it was non-unique as shown in figure 3-
32. In fact most researchers who have used K/S
660nm
have adjusted or "corrected" the curve to
create a linear relationship. However, the correction was based on slope at very low dye
concentrations and projected to about 3.0 %IOWY. While this correction was certainly an
acceptable manner to handle the non-linearity at low %IOWY values, it was apparent at much higher
%IOWY values the correction loses all meaning. For this reason the researcher has decided to use
Integ shade value instead of K/S
660nm
.


Figure 3-32: Shape of K/S at 660 nm as a function of %IOWY from equilibrium sorption experiments.


0.0
5.0
10.0
15.0
20.0
25.0
30.0
35.0
40.0
0.00 5.00 10.00 15.00 20.00 25.00 30.00 35.00 40.00 45.00
K
/
S

a
t

6
6
0

n
m
%IOWY from Equilibrium Sorption
K/S at 660nm as a Function of %IOWY
6.3 7.1 8 12
Poly. (6.3) Poly. (7.1) Poly. (8) Poly. (12)
141

3.4 Observational Indigo Study: Establishing Breadth of Dye Conditions and Convergence Test to
Determine Conclusion of Study
The dye range conditions consist of two different attributes: mechanical parameters and
chemical parameters. Mechanical parameters were the yarn count, dye range speed, immersion
dye bath thread-up length, oxidation thread-up length, nip pressure, and number of dye bath dips.
The chemical parameters were the indigo dye bath concentration, pH, and reduction potential.
When a set of yarn skeins was processed in the dye range, each parameter was measured and
recorded. As previously discussed, the response variables were %COWY, %IOWY, Integ shade, and
penetration level. The range of each parameter must be understood prior to beginning the study
and a game plan developed to justify ending the study. Table 3-12 lists the specific parameters
available from all bulk production dye range conditions at this researcher's disposal.

Table 3-12: Observational study parameters and potential range of values
Parameter Minimum Value Maximum Value
Yarn Count 6.3/1 12.0/1
Speed (m/sec) 26.5 36.6
Immersion Length (meter) 8.6 11.4
Oxidation Length (meter) 36.0 37.0
Number of dips 1 7
Dye concentration (g/l) 0.75 3.25
pH 11.0 13.0
Reduction potential (mV) 720 900
Nip Pressure (psi) 40 75

The dye range speed was set to match the specific dye range set-up sheet by the operator.
The magnitude was controlled and maintained by ABB digital drive control system. The immersion
length was determined by multiplying speed and immersion time. The immersion time of each yarn
skein was measured with a stop watch. Immersion time was defined to be from liquor surface to nip
point at the squeeze rolls and was averaged from 10 different measurements each time data was
collected. The dye concentration was measured according to accepted industry methods. The %T
was measured and converted into g/l concentrations by using calibration equations. The %T
142

method is given in Appendix A-1-2a. The reduction potential and pH were measured by respective
probes.
If a traditional 3 level full factorial design of experiment was planned, this would result in 3
9

or 19683 trials to cover 3 levels on 9 parameters. As previously discussed, such an experiment isn't
possible. But if it were possible, the levels would look like table 3-13. Here the yarn count, number
of dips, and nip pressure were removed. Also oxidation thread-up length was assumed to be
sufficient to result in complete oxidation and therefore inconsequential. The first values in table 3-
13 for each parameter were the target value and the numbers in ()'s were the acceptable ranges to
fall within that group. These were grouped for each yarn count and each dip for analysis.
Because every possible combination of parameters were not processed in production, a
certain prime data set was defined which covers an acceptable range of parameters. Specifically
yarn skeins were processed targeting the following parameters and response variables measured
accordingly. The percent range of span from minimum to maximum value was calculated. Dye bath
concentration appears to vary over a large range. Likewise, the immersion length and speed change
by 30%. The pH does not appear to vary a great deal. This was not unexpected given this particular
dye house does not utilize dye bath pH buffering systems like those discussed by Etters and others.

Table 3-13: Prime data set in the observational study
Parameter Low Value Middle Value High Value Range in Percent
Immersion Length (m) 8.6 11.4 33%
Speed (m/min) 29 (26.5-31) 32 (31-34.5) 35 (34.5-36.6) 37%
Dye Conc. (g/l) 1.1 (0.7-1.5) 1.9 (1.5-2.3) 2.7 (2.3-3.1) 342%
pH 11.3 (11-11.6) 11.8 (11.7-12) 12.3 (12-12.6) 18%
mV 740 (700-780) 820 (780-850) 880 (850-900) 27%


143

The prime data set was created by assigning all possible production variations to one of the
groups in table 3-13. Once all possible production variations had been assigned, it was time to
collect data from the observational study. The actual value for each parameter in the prime data set
was illustrated in figure 3-33. Across each parameter the three ranges were demarcated.


Figure 3-33: Range of observational study dye range set-up conditions and interactions.


26
28
30
32
34
36
38
S
p
e
e
d

m
/
m
i
n
1
2
3
I
n
d
i
g
o
g
m
/
l
i
t
11
12
13
B
o
x

p
H
700
800
900
B
o
x

m
V
8.63 11.37
Dwell
length m
26 2931333537
Speed m/min
1 2 3
Indigo
gm/lit
11 12 13
Box pH
Scatterplot Matrix
High value
Middle value
Low value
High value
Middle value
High value
High value
Middle value
Low value
Middle value
Low value
Low value
Scatterplot of Observational Study Dye Range Set-up Conditions and Interactions
g/l
144

Once all data was collected for the prime data set, ANOVA analysis was conducted to
determine significance of each parameter. Unlike traditional design of experiments, analysis of
observational studies incorporate the actual parameter value measured during the study instead of
the target value. An effects screening test was conducted and the standard error recorded for the
parameters at each response variable for 6.3/1 yarns after one dip of indigo. Then more data,
defined to be the replicated data set, was collected at the same dye range set-up conditions.
Although the dye range set-up conditions were replica of the prime data set, the actual measured
dye range variables were not the same. As each new data set was collected, the data was fed into
the effect screening test and ANOVA analysis was repeated. The new standard error was recorded.
This process was repeated for each replicated dye range condition until the standard error reached
a point of diminishing return. At this point, the addition of more data would not further improve
the model and the observational study was concluded.
Figure 3-34 demonstrates the diminishing improvement of standard error for dye bath
concentration parameter with the addition of replicates. "0" replicates on the x axis represents the
original prime data set. As each replicate data set was added, the new standard error was
calculated. In figure 3-34 the standard error of indigo dye bath concentration parameter affect on
%COWY, %IOWY, Integ, and Penetration level was monitored. Dye bath concentration was chosen
since it was the most statistically significant parameter on all response variables. The curves for
each response variable were a second order polynomial fit with projected trajectory of 5 imaginary
replicates. After 11 replicates the standard error of %IOWY, Integ, and Penetration Level appear to
reach their minimum value. In fact the last additional 6 data sets have a standard error average of
1.56e-4, 9.8e-1, and 1.66e-2 for %IOWY, Integ, and Penetration level respectively. The last four
replicate data sets had an average standard error of 2.82e-3 for %COWY with the last data set
having a value higher than the previous three data sets. Since the standard error was no longer
improving, the observational study was concluded. For completeness, this convergence test based
on parameter standard error was repeated after the official dye model was constructed and
redisplayed later.
145



Figure 3-34: Affect of additional replicated data sets on standard error of indigo dye bath concentration parameter and
four response variables after one dip of indigo.

Data analysis was conducted on all available data sets. After all data had been collected, the
data was then compared to Fick's law of diffusion to calculate the diffusion coefficients.
Additionally, cause and effect and the mechanism for dye pick-up were determined.
The final step in traditional design of experiments is simulation. Since true simulation isn't
possible, model predicted dye responses were compared to data sets from an independent dye
range. The simulation data sets were collected from a third indigo dye range from a different dye
house in a different country. Use of the third dye house guaranteed zero affect in developing the
model. The %COWY, %IOWY, penetration level, and final indigo shade from the third dye range
were compared to calculated values from the indigo dye models. The final simulation and validation
are shown in Chapter 5.
0
0.5
1
1.5
2
2.5
3
3.5
4
4.5
0 5 10 15 20 25
S
t
a
n
d
a
r
d

E
r
r
o
r

o
f

I
n
d
i
g
o

(
g
/
l
)
Number of Additional Replicates Added
Additional Replicates Affect on Standard Error
%COWY e-3 %IOWY e-4 Integ PL e-2
146

4 Data Analysis from the Observational Study
Yarn skeins were run and dye range set-up conditions were recorded as discussed in chapter
3. Also, response variables were measured and expressions calculated as detailed in chapter 3. The
entire data set is presented in Appendix section A-4-1 for reference. Data analysis consisted of
graphical and statistical techniques to evaluate and discuss general trends and specific relationships
between dye range set-up conditions and response variables. Once the effects of each parameter
were understood, empirical models were constructed to calculate %COWY, %IOWY, penetration
level, and Integ shade value. Last, dye theory model was constructed based on general dye and
diffusion theory.
4.1 Review of Main Parameter Affects on Response Variables Obtained from Observational Study
To determine the significance of each dye range set-up condition on the response variables,
first a graphical approach was employed. The left graph in figure 4-1 illustrates the impact number
of dips had on the %COWY. Clearly, by increasing the number of dips, the total %COWY was
increased. The variability within each individual dip was due to other parameter effects. The right
graph in figure 4-1 illustrates the effect of successive dips on %IOWY. While there is still a good deal
of variability in the %IOWY at each dip, the trend from dip to dip appears to be more linear in nature
when compared to %COWY relationship to dips.


Figure 4-1: Number of dips affect on %COWY and %IOWY for all data points.
%IOWY vs. Dip
Dip
1 2 3 4 5 6 7
0.000%
1.000%
2.000%
3.000%
4.000%
Graph Builder


specif
conce
meter
and 2
in %C
a slow
bath c
%COW


Figure
and red


%IOW
relatio
To further
fic data sets a
entrations wit
rs/minute. T
.3 g/l at 11.9
OWY from 1
wer rate. Last
concentration
WY.
4-2: Build curve
duction potenti
Using the s
WY build curve
onship for %I
explore the %
are presented
th approxima
he 3.0 g/l dye
pH and 805 m
to 2 dips. Ad
t, the spacing
n resulting in
e relationship fo
al.
same data se
e as a functio
OWY to num
%COWY and %
d. In figure 4-
ately constant
eing was 12.0
mV. All three
dditional dips
g between dye
higher %COW
or %COWY as a f
ets a similar re
n of number
ber of dips. T
%IOWY as the
-2, 6.3/1 yarn
t speed, pH, a
0 pH and 789
e follow the s
beyond 2 con
e bath conce
WY while low
function of num
elationship ex
of dips based
These curves
e number of
n was dyed in
and mV. All t
mV with the
same general
ntinued to inc
ntrations was
er concentrat
mber of dips on 6
xist for %IOW
d on the same
illustrate wit
dips increase
three differe
hree were 31
2.7 g/l at 11.8
build curve w
crease the %C
s as expected
tions resulted
6.3/1 yarn count
WY. Figure 4-3
e data points.
th increasing
ed, a couple o
ent indigo dye
1.1
8 pH and 800
with large inc
COWY althou
d with higher
d in the lower
t at similar spee
3 illustrates th
. Notice the l
number of di
147
of
e bath
0 mV,
crease
ugh at
dye
r

ed, pH,
he
linear
ps

the %
This s
previo
exam
dips.


Figure
and red



depth
4-4 ill
points
versu
Integ
penet
%IOWY lineary
ame linear be
ous data has
ples have bee
Refer to Xin
4
4-3: Build curve
duction potenti
Since the %
h of shade to
ustrates the
s. Even thoug
s the number
and %IOWY u
tration levels
y increases. A
ehavior is exh
been publish
en discussed
46
Integ vs dip
e relationship fo
al.
%IOWY increa
increase as w
realationship
gh the %IOW
r of dips is jus
under equilib
from one dip
Also the highe
hibited by all
ed comparing
relating shad
ps curve in sec
or %IOWY as a fu
ased with eac
well. Howeve
p between Int
WY builds in a l
stified when c
brium sorption
p to the next.
er the dye bat
data sets from
g %IOWY and
de of the yarn
ction 1-1.
unction of numb
ch additional
r, the relation
eg shade valu
linear nature,
consideration
n dye conditio
It should be
th concentrat
m all dye rang
d the effects o
n (K/S or Integ
ber of dips on 6
dip of indigo
nship does no
ue and numb
, the non-line
n is given to n
ons as well as
noted the in
tion, the high
ge set-up con
of increasing
g) to increasin
.3/1 yarn count
dye, one wo
ot appear to b
er of indigo d
ear nature of
non-linear rela
s the possibil
crease in dips
her the %IOW
nditions. Whi
dips, number
ng numbers o
at similar speed
uld expect th
be linear. Fig
dips from all d
Integ shade
ationship bet
ity for variabl
s does not ac
148
WY.
ile no
rous
of

d, pH,
e
gure
data
ween
le
ctually
149

cause the change in Integ shade. Instead, the change in Integ is caused by the increase in %IOWY
and it's distribution which is a result of the additional indigo box dip.


Figure 4-4: Integ shade value as a function of number of indigo dye box dips for all data points.

To further investigate Integ variation as it relates to number of dips, once again three
specific dye conditions were used. These specific dye conditions are graphed in figure 4-5. Clearly,
the Integ shade value builds in a non-linear fashion as the number of dips is increased. The depth of
shade also maintains the effect of indigo dye box concentration: the higher the dye concentration,
the darker the shade while lighter indigo dye bath concentrations resulted in lighter shades.
Integ vs. Dip
Dip
1 2 3 4 5 6 7
I
n
t
e
g
0
20
40
60
80
100
120
Graph Builder

Figure
potent


be no
non-li
curve
of dip
previo
dips w
decre
uncha
relatio
with e
4-5: Integ shade
tial.
Since %IOW
on-linear func
inear relation
s in figure 4-5
ps. The penet
ous relationsh
was increased
ease with redu
anged. The d
onship betwe
each addition
e value as a fun
WY caused th
ction of numb
nship to %IOW
5. The other
tration level a
hips, the pene
d. As the num
ucing severity
ecreased ave
een Integ and
nal dip due to
ction of number
he Integ shade
ber of dips? A
WY during equ
possibility wa
as a function
etration leve
mber of dips w
y. From dip 5
erage penetra
d dip as demo
additive proc
r of dips on 6.3/
e and %IOWY
As previously
uilibrium sorp
as changes in
of all data po
l has a unique
was increased
5 through 7 th
ation level wit
ostrated in fig
cess of layeri
/1 yarn count at
Y by dips was
shown in cha
ption. This co
penetration
oints is shown
e and unexpe
d the penetra
he penetratio
th each dip, c
ure 4-5. The
ng dye not by
t similar speed,
linear, what
apter 3, the In
ould explain t
level as a fun
n in figure 4-6
ected shape a
tion level con
on level remai
could explain
penetration
y the dip proc
pH, and reducti
caused Integ
nteg shade ha
the shape of
nction of num
6. Unlike the
s the numbe
ntinued to
ins relatively
the non-linea
level decreas
cess itself.
150

on
to
as a
mber
r of
ar
sed
151


Figure 4-6: Penetration level for all data points as a function of the number of dips.

When reviewing the penetration level as a function of the number of dips under the three
specific dye conditions, a similar relationship as shown in figure 4-6 exists. Figure 4-7 shows the
specific relationships. At dip #1 all three dye box concentrations have approximately the same
penetration level. After dip 2, the penetration level becomes separated by the dye box
concentration with higher concentration resulting in a lower penetration level. The decreased
penetration level signifies increased ring dyeing or decreased dye penetration into the yarn. This
effect is actually expected when consideration is given to how dye is added at each dip. The indigo
dye added at dip 4 is layered on top of the existing dye from dip 1, 2, and 3. And as additional dye is
added by more dips, the dye continues to be layered on. Thus the Integ shade value becomes
darker with each additional dip because the dye is applied in a ring dyed fashion by each dip. Notice
the greater the dye bath concentration, the lower the penetration level or more ring dyed the yarn.
Penetration level vs. Dip
Dip
1 2 3 4 5 6 7
P
e
n
e
t
r
a
t
i
o
n

l
e
v
e
l
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
Graph Builder


Figure
potent


have
indigo
the nu
by on
Also a
%COW
4-7: Penetratio
tial.
Besides th
a strong impa
o dye bath co
umber of dips
e, three, and
as in figure 4-
WY build is fa
n level as a func
e number of
act on the res
oncentration o
s. Figure 4-8
six dips. As i
2, as the indi
irly linear by
ction of number
dips, the indi
sponse variab
on %COWY, %
shows the ef
in figure 4-1,
go dye bath c
indigo dye ba
r of dips on 6.3/
igo dye conce
bles. The nex
%IOWY, Integ
ffect of indigo
as the numbe
concentration
ath concentra
/1 yarn count at
entration in th
xt series of gra
g, and penetra
o concentratio
er of dips inc
n increased, t
ation within e
similar speed, p
he dye bath o
aphs investiga
ation level wh
on on %COW
reased so did
the %COWY in
each individua
pH, and reductio
of each dip sh
ates the effec
hile consideri
WY when sepa
d the %COWY
ncreased. Th
al dip.
152

on
hould
ct of
ng
rated
Y.
he
153


Figure 4-8: %COWY for all data points as a function of dye bath concentration after one, three, and six dips.

As expected the %IOWY had a strong relationship to the dye bath concentration. Figure 4-9
illustrates the build curve of %IOWY as a function of dye concentration when separated by one,
three, and six dips. As shown in figure 4-3, as the number of dips increased the total amount of
%IOWY also increased. Additionally, the general trend was increased %IOWY as the dye bath
concentration was increased. However, this relationship wasn't linear over the entire range of dye
bath concentrations. The %IOWY build curve was fairly linear from low concentrations till
approximate 1.75 g/l. But increasing concentration from 1.75 g/l to 2.5 g/l does not result in
substantial change in %IOWY. Then, at 2.5 g/l continued increases in dye concentration does result
in increased %IOWY. This relationship was repeated for each number of dips although it is
accentuated by the higher number of dips. This relationship is best described as an indigo dye bath
concentration build plateau spanning 1.75 to 2.5 g/l.
%COWY vs. Average Indigo (gm/lit) by Dip
Average Indigo (gm/lit)
0.5 1 1.5 2 2.5 3 3.5 4
%
C
O
W
Y
0.00%
2.00%
4.00%
6.00%
8.00%
10.00%
12.00%
14.00%
Legend
1
3
6
1
3
6
Graph Builder
(g/l)
%COWY vs Average Indigo (g/l) by Dip
154


Figure 4-9: %IOWY for all data points as a function of dye bath concentration after one, three, and six dips.

Since there is a strong relationship between %IOWY and Integ shade value as well as %IOWY
and dye bath concentration, Integ versus dye bath concentration at various number of dips should
have a similar shape as discussed from %IOWY versus dye bath concentration in figure 4-9. This is
confirmed in figure 4-10. The Integ shade value has a fairly linear relationship to dye bath
concentration until 1.75 g/l. At 1.75 g/l a plateau is reached where further increases in dye
concentration does not produce substantial increased depth of shade. Once the dye concentration
reaches 2.5 g/l, the Integ shade value resumes increasing in value with increased dye concentration.
While there was variation in data points on both figures 4-9 and 4-10, the plateau relationship is
graphically evident.
Measured %IOWY vs. Average Indigo (gm/lit) by
Dip
Average Indigo (gm/lit)
0.5 1 1.5 2 2.5 3 3.5 4
M
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%
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0.000%
0.500%
1.000%
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2.000%
2.500%
3.000%
3.500%
4.000%
4.500%
Legend
1
3
6
1
3
6
Graph Builder
(g/l)
Measured %IOWY vs Average Indigo (g/l) by Dip
155


Figure 4-10: Integ shade value as a function of dye bath concentration at various numbers of dips.

To investigate penetration level as a function of dye bath concentration, figure 4-6 was
expanded to include the variation in dye bath concentration within each dip to produce figure 4-11.
In this graph, the penetration level is shown to vary by dye bath concentration after 1, 3, and 6 dips.
The mean value within each dip forms the same relationship with increasing dips as previously
discussed: increasing dips resulted in decreased penetration level. Additionally, the variation due to
dye concentration within each dip illustrates penetration level is dependent on dye concentration
and the number of dips. Notice a great deal of random variation in penetration level at any specific
dip and/or dye bath concentration indicates other parameters have an effect on penetration level.
Measured Integ vs. Average Indigo (gm/lit) by Dip
Average Indigo (gm/lit)
0.5 1 1.5 2 2.5 3 3.5 4
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20
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100
120
Legend
1
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1
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6
Graph Builder
(g/l)
Measured Integ vs Average Indigo (g/l) by Dip
156




Figure 4-11: Penetration level for all data points as a function of dye bath concentration within each dip.

With the obvious main parameter effects accounted for, further investigation of secondary
parameters such as yarn count, speed, pH, mV, dwell length, and nip pressure become difficult to
visualize if the entire data set was incorporated in graphical form. To reduce the complexity, all of
the remaining parameter screenings and graphical analysis will be discussed after six dips of indigo.
Also, all graphs are generated with arrows that insect at 2.0 g/l dye bath concentrations and a single
figure incorporates all four response variables graphs to facilitate trend illustration and discussion.
Before reducing yarn count to a single value, the effect of yarn count on the response
variables was evaluated. To illustrate the effect of yarn count on %COWY, %IOWY, Integ, and
penetration level; figure 4-12 was constructed after six dips of indigo with various dye bath
concentrations. The overall general trend was increasing %COWY as the dye bath concentration
Penetration level vs. Average Indigo (gm/lit) by Dip
Average Indigo (gm/lit)
0.5 1 1.5 2 2.5 3 3.5 4
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Legend
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Graph Builder
(g/l)
Penetration Level vs Average Indigo (g/l) by Dip
157

was increased. Furthermore, increasing the yarn count resulted in greater %COWY values at any
given dye bath concentration. The general relationship across all dye conditions is greater yarn
counts (ie finer yarns) have greater %COWY then lower yarn counts (ie courser yarns).
Given the %COWY dependence on yarn count, a similar relationship is expected for %IOWY.
The second row of graphs in figure 4-12 illustrates the relationship of %IOWY as a function of dye
bath concentration after six dips for each yarn count. As expected, the general %IOWY curve had a
plateau from 1.75 g/l to 2.5 g/l within each yarn count. Furthermore, the higher yarn counts (finer
yarns) had greater %IOWY than the lower yarn counts (coarser yarns). More specifically the same
relationship for yarn count exists at every dip of indigo.
If the %COWY and %IOWY varies with different yarn counts, how does the resulting Integ
shade value vary? Well, in fact the Integ shade value doesn't vary at least not as much as one might
expect. The third row of graphs in figure 4-12 shows the Integ values as the indigo dye bath
concentration was increased after six dips across all four yarn counts. The biggest trend was the
increased Integ as the dye bath concentration was increased within each yarn count. Although a
slight increase in Integ is exhibited as the yarn count is increased. Any significance with increasing
yarn count will need to be determined from a full ANOVA analysis.
If the %IOWY increased by yarn count and the Integ shade is relatively constant by yarn
count than the penetration level as the yarn count was increased is expected to increase. The
bottom row of graphs in figure 4-12 illustrates that very relationship for six dips as a function of dye
bath concentration. The penetration level clearly decreased as the dye bath concentration was
increased at a constant yarn count. The penetration level increased as the yarn count was increased
regardless of the dye bath concentration.

158


Figure 4-12: Illustrates %COWY, %IOWY, Integ, and penetration level varies with yarn count and dye concentration after
six dips.
Yarn Count Affect on %COWY, %IOWY, Integ, and
Penetration Level
6.3 7.1 8 12
Yarn Count
Indigo gm/lit
0.51 1.5 2 2.5 3 3.5
%
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2.00%
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8.00%
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0.5 1 1.5 2 2.5 3 3.5 0.51 1.5 2 2.5 3 3.5 0.5 1 1.5 2 2.5 3 3.5
Graph Builder
(g/l)
159

Now that yarn count effects had been investigated and to further reduce the complexity, all
of the remaining parameter screenings and graphical analysis were reduced to 6.3/1's yarn count
after six dips of indigo. All graphs will continue to be generated with arrows that insect at 2.0 g/l
dye bath concentrations and a single figure incorporates all four response variables graphs to
facilitate trend illustration and discussion.
This researcher hypothesized speed would have an impact in overall indigo dyeing process.
However, the top graphs in figure 4-13 indicates speed has very little affect on %COWY. Within each
speed range, the %COWY builds in a similar fashion as previously discussed with changes in dye bath
indigo concentration. Alas, there are no obvious curve shifts as the speed range is increased from
26.5-31 m/min to 31-34.75 m/min or to 34.75-36.6 m/min. The 2.0 g/l indigo dye bath
concentration arrow remains mostly flat as the speed was increased from the left most graph to
center graph and ending with the right most graph.
However, it is clear from graphs on second row in figure 4-13 that speed does have an
impact on %IOWY. The %IOWY build curves maintain characteristic shape as a function of indigo
dye bath concentration including the 1.75 g/l plateau. The 2.0 g/l concentration arrow shows a
decrease in %IOWY as the speed was increased. In fact, the average %IOWY shift is from ~2.25 % to
~1.5% IOWY when the speed was increased from 26.5 m/min to 36.5 m/min. Whether the
reduction is due to lower wet pick-up or less time for diffusion to occur, the trend is apparent.
The increasing speed also affected the Integ shade value. As the speed increased, the Integ
value decreased as seen by following the 2.0 g/l concentration arrow in third row of graphs of figure
4-13. At lower speed ranges the Integ value for 2.0 g/l is approximately 85. However, at the higher
speed levels the Integ value had dropped to below 70 given the same dye bath concentration.
Given speed affects on %IOWY and Integ, it is expected to have an impact on the
penetration level. The last row of graphs in figure 4-13 showed an increased speed causing an
increase in penetration level. This was due to the greater rate of drop in Integ value compared to
the drop in %IOWY as speed was increased. The Integ value was lower than expected given the
amount of indigo on weight of yarn. Therefore, the penetration level increased indicating more
penetration of the dye into the yarn structure at greater speeds.
160



Figure 4-13: Speed affect on %COWY, %IOWY, Integ, penetration level at various dye bath concentrations after six dips
of indigo on 6.3/1 yarn.
Speed Affect on %COWY, %IOWY, Integ, and Penetration Level
26.52 - 31.09 31.09 - 34.75 34.75 - 36.58
Speed
Indigo gm/lit
0.5 1 1.5 2 2.5 3 3.5
%
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2.00%
3.00%
4.00%
5.00%
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8.00%
9.00%
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11.00%
12.00%
%
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Graph Builder
(g/l)
(m/min)
161

Next the effect of pH was investigated. As previous research by Etters and others, pH
should play a major role in the %IOWY, Integ, and penetration level. Figure 4-14 was created based
on 6.3/1 yarn count after six dips of indigo dyeing. Four rows of graphs represent each of the
response variables. The pH range is broken down into three groups: Low with pH from 10.96 to
11.6, Middle range with pH from 11.61 to 11.86, and High with pH from 11.9 to 12.6. Across each
response variable graphs a 2.0 g/l constant dye bath concentration arrow was drawn.
Across the first row of graphs, as the pH of the dye bath was increased the %COWY actually
decreased. This relationship is a little surprising considering, with everything else constant, higher
pH should have more sodium hydroxide in the bath which should result in more sodium hydroxide
on weight of yarn and therefore higher %COWY. Perhaps other parameters or interactions are
causing this unexpected trend. Unlike pH's effect on %COWY, the %IOWY actually increased at
higher pH levels. While the increase in %IOWY was not overwhelming, the second row of graphs
gives a good indication that increased pH causes higher %IOWY. Furthermore, given the reduced
%COWY and the increased %IOWY, the fixation rate appears greater at higher pH levels.
The Integ shade value remained constant as the pH was increased as shown in third row of
graphs of figure 4-14. A constant Integ value coupled with increasing %IOWY should have a major
impact on penetration level. As expected, increasing pH caused a major shift toward increased
penetration level. The relationship is clearly illustrated in final row of graphs in figure 4-14. This
was caused by the increase in %IOWY while the Integ shade remained constant or actually become
lighter in shade. There the Integ value is not as great as one would expect given the %IOWY because
the dye is more penetrated into the yarn structure. This relationship was also supported by
research of Etters and others.

162


Figure 4-14: pH affect on %COWY, %IOWY, Integ, penetration level at various dye bath concentrations after six dips of
indigo on 6.3/1 yarn.
pH Affect on %COWY, %IOWY, Integ, and Penetration Level
10.96 - 11.6 11.6 - 11.86 11.86 - 12.588
Box pH
Indigo gm/lit
0.5 1 1.5 2 2.5 3 3.5
%
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2.00%
3.00%
4.00%
5.00%
6.00%
7.00%
8.00%
9.00%
10.00%
11.00%
12.00%
%
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2.50%
3.00%
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Graph Builder
(g/l)
163

The effects reduction potential had on response variables were far less pronounced
compare to any previous parameter. In fact, any effect may not be significant and must be validated
by a complete ANOVA analysis. Figure 4-15 indicates mV may have a non-linear effect on %COWY.
There are shifts to higher %COWY at the middle mV range compared to the lower and upper ranges.
The exact extent and significance of the effect can only be determined during complete ANOVA
analysis.
Increased reduction potential does appear to have a major and consistent role in the
%IOWY after six dips of indigo at various dye bath concentration levels. The line of constant dye
concentration is clearly trending lower as the reduction potential is increased as evident in second
of graphs in figure 4-15. This relationship is contradictory to traditional indigo dyeing theory since
lower mV means greater reduction potential. One would think greater reduction potential would
result in more indigo on weight of yarn not less. There are of course other potential causes for this
relationship such as effects from speed, pH, etc.
Reduction potential also has a slight non-linear effect on Integ shade values. The third row
of graphs in figure 4-15 indicates the shade becomes slightly darker as the reduction potential is
increased from low mV to mid-range mV along constant dye bath concentrations. Yet the Integ
shifts slightly lower as the reduction potential is further increased to the high mV range. Once again
the overall change in Integ values isn't great but the general trend does appear to exist.
Coupling %IOWY and Integ shade values to calculate penetration level reveals the overall
trend of decreasing penetration level as the reduction potential is increased. This trend is
demonstrated in the fourth row of figure 4-15. This is not surprising given the general trend of
increasing Integ and decreasing %IOWY as the reduction potential is increased. A darker shade with
less dye can only exist when a greater percentage of the dye is located at the outer surface, i.e.
more ring dyed.
164



Figure 4-15: Reduction potential affect on %COWY, %IOWY, Integ, and penetration level at various dye bath
concentrations after six dips of indigo on 6.3/1 yarn.
Reduction Potential Affect on %COWY, %IOWY, Integ, and
Penetration Level
726 - 786 786 - 851 851 - 891
Box mV
Indigo gm/lit
0.5 1 1.5 2 2.5 3 3.5
%
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2.00%
4.00%
6.00%
8.00%
10.00%
12.00%
%
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Graph Builder
(g/l)
165

The effect of dwell length on each response variable is displayed in figure 4-16 for the
relationship on 6.3/1 yarn after 6 dips of indigo. Increasing the dwell length from 8.6 meters to 11.4
meters causes the %COWY, %IOWY, and Integ shade values to decrease as demonstrated by arrows
of constant dye bath concentration in graphical rows 1, 2, and 3. This relationship is also
contradictory to traditional thinking. If the dwell length increased and everything else is constant,
the yarn would be exposed to the dye bath for a greater time. One would think greater time should
result in more pick-up or exchange of dye and other chemicals from the bath to the yarn. As rows 1,
2, and 3 from figure 4-16 demonstrates, this did not happen. Therefore another parameter or
interaction of parameters must be affecting the results.
The penetration level has a slight increase in value as the dwell length is increased in figure
4-16. This trend would be expected since everything else held constant greater dwell length would
result in greater time for the dye to penetrate into the yarn structure.


166


Figure 4-16: Dwell length affect on %COWY, %IOWY, Integ, and penetration level at various dye bath concentrations
after six dips of indigo on 6.3/1 yarn.
Dwell Length Affect on %COWY, %IOWY, Integ, and
Penetration Level
8.63 11.37
Dwell length
Indigo gm/lit
0.5 1 1.5 2 2.5 3 3.5
%
C
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Y
2.00%
4.00%
6.00%
8.00%
10.00%
12.00%
%
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0.50%
1.00%
1.50%
2.00%
2.50%
3.00%
3.50%
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Graph Builder
(g/l)
(m)
167

Given the odd relationships uncovered while investigating dwell length, a detailed review of
dwell time is presented. Dwell time is a factor of speed and dwell length and presented in terms of
seconds. The dwell time was measured from dye liquor surface to entry nip point on the dye range.
The dwell time was summarized into three groups: 14 to 16.7 seconds, 16.7 to 19.6 seconds, and
19.6 to 25.7 seconds. Each group and corresponding response variables on 6.3/1 after 6 dips of
indigo are presented in figure 4-17.
Unfortunately, the effect of dwell time presents more surprising results. The first row of
graphs in figure 4-17 indicates %COWY decreases with increasing dwell time. This is unexpected
since typically increased dwell time allows for greater dye pick-up and therefore greater %COWY.
Likewise, the second row of graphs show %IOWY doesn't change with dwell time. This is also
surprising following the same logic as %COWY. Third row of graphs show Integ values generally
decrease with increasing dwell time. The behavior of these response variables is contradictory to
conventional thinking under the influence of changing dwell time. There must be an underlying
effect from another parameter or interaction of parameters which should be revealed by a detailed
ANOVA analysis.
The last row of figure 4-17 indicates increasing penetration level with increasing dwell time.
This is expected. By increasing submerge time in the dye, the dye is expected to penetrate deeper
into the yarn structure. This causes great dye penetration or less ring dyeing as reflected in higher
penetration level values.


168


Figure 4-17: Dwell time affect on %COWY, %IOWY, Integ, and penetration level at various dye bath concentrations after
six dips of indigo on 6.3/1 yarn.
Dwell Time Affect on %COWY, %IOWY, Integ, and
Penetration Level
14.03 - 16.7 16.7 - 19.6 19.6 - 25.7
Dwell time
Indigo gm/lit
0.5 1 1.5 2 2.5 3 3.5
%
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2.00%
4.00%
6.00%
8.00%
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12.00%
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Graph Builder
(g/l)
(sec)
169

The effect of nip pressure on %COWY, %IOWY, Integ, and penetration level is examined in
figure 4-18. As the nip pressure is increased from the 40/45 psi range to the 50/75 psi range,
virtually no impact is detected on the %COWY, %IOWY, Integ, and penetration level.


Figure 4-18: Nip pressure affect on %COWY, %IOWY, Integ, and penetration level at various dye bath concentrations
after six dips of indigo on 6.3/1 yarn.
(g/l)
170

4.2 Empirical Dye Models Based on Dye Range Parameters and the Resulting Affect on Indigo Dye
Response Variables
Clearly manual calculation of the ANOVA analysis for all nine dye range set-up condition
affects and interactions on four response variables is mathematically daunting and more
importantly unnecessary. Thanks to the advances of modern technology, the observational data
was analyzed using SAS JMP 8.0 statistical software package. As discussed in chapter 3.4, the initial
or "prime data" sets were analyzed using the statistical package on all four response variables. Once
a base line model was established, additional data points or "replicas" were added to each model.
Then the analysis was repeated to confirm statistically significant parameters remained important
and no new parameters became important. Also, the standard error after the addition of each
replica was recorded. The standard errors were tracked to determine convergence. The
observational study was concluded. The final response model generated. Following this procedure
the initial model, convergence check, and final model are presented next for dye range set-up
condition affects on %COWY, %IOWY, Integ shade, and penetration level.
4.2.1 %COWY Empirical Model Generation
Using the prime data set and SAS JMP 8.0 statistical software package the %COWY empirical
model was generated using the dye range set-up conditions as the input values. The overall
correlation of fit was determined to 0.91 with an F ratio of 374.2 as shown in table 4-1. The best
model fit was determined to involve the dye bath concentration and pH. Also, the second order
term of speed and interaction of speed and pH were also determined to be statistically significant as
indicated by the P-values. Because the second order term of speed was significant the first order
term was left in the model even though the P-value warrants removal. Also listed in table 4-1 are
the standard errors for each significant parameter.
171

Table 4-1: ANOVA analysis results from the prime data set on %COWY.




With the initial model for %COWY generated and the standard errors recorded, additional
replica data set were added one at a time. The actual parameter standard errors are listed in
appendix section A-4-2a for reference. To facilitate communication of convergence, the standard
errors for each parameter were normalized by the initial standard error from the prime data set.
Then the normalized parameter standard errors were averaged at each replica point to create a
single value. Figure 4-19 demonstrates the convergence test for the empirical model of %COWY as
each new averaged normalized standard error is added. At the 0 x-axis point the value is 1.0 since
172

this is the average normalized value to itself. All additional points are based on this starting point.
With the addition of the first three replica points the average normalized standard error
actually increased. However after 5 replica points were added to the model, the average
normalized standard error dropped below 1.0 and continued to decrease with each additional
replica set. After 11 replica data sets were added, the average normalized standard error was
approximately 0.90 or 10% less than the prime data set and remained virtually unchanged for the
balance of replica data sets. This signifies the observational study could have been concluded after
11 replica data sets based on %COWY analysis.


Figure 4-19: Convergence test for empirical %COWY model.

Now the final empirical %COWY model was generated based on all available data points.
The final R
2
correlation coefficient was 0.88 with an F ratio of 380 as shown in table 4-2. For
completeness the final parameter estimates and standard errors are also shown. The final model
maintained the same statistically significant parameters as the prime data set model as
demonstrated in the effect tests. No new statistically significant terms surfaced.
0.8
0.85
0.9
0.95
1
1.05
1.1
1.15
1.2
0 5 10 15 20 25
A
v
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r
a
g
e

N
o
r
m
a
l
i
z
e
d

S
t
a
n
d
a
r
d

E
r
r
o
r

f
o
r

a
l
l

S
i
g
n
i
f
i
c
a
n
t

P
a
r
a
m
e
t
e
r
s
Number of Additional Replicates Added
Convergence Test for Empirical %COWY Model
173

Table 4-2: ANOVA analysis for %COWY from the entire data set.





174

Using the parameter estimates from table 4-2, the final empirical model for %COWY was
created. The official equation is listed below as equation 4-1.

% =

u.6S9u +(u.uS819 ) + ()

1: u.u
2: u.1642
S: u.S126
4: u.42uS
S: u.4862
6: u.S41u
7: u.S8Su

+ (2.8S76
-3

) + [u.8S76 log (
gm
It
) (u.2874 ) (6.Su4u
-3
( SS.1)
2
)
[2.Su18
-2
(( 11.8S) ( SS.1))


Equation 4-1: Empirical model %COWY as a function of dye range set-up conditions.

To better illustrate the relationship between actual %COWY and the predicted value from
the empirical model the two values were plotted against each other in figure 4-20. There is
obviously a strong relationship with the predicted versus actual following a linear 1 to 1 relationship.
There are however a few points were the predicted %COWY is in the range of 4% to 6% but the
actual values are in the 8% to 12% range. However, overall the %COWY model performed well.



175


Figure 4-20: Comparison of actual versus predicted %COWY for the entire data set.

To investigate the effects of each parameter on %COWY and compare the results to
previous graphical analysis, the prediction profile was created. Figure 4-21 illustrates the calculated
%COWY as it varies by each dye range set-up condition. The graph in the first column shows an
increasing %COWY value as the yarn count is increased. This confirms the significance graphically
displayed in figure 4-12. Additionally, the influence of yarn count on %COWY has not been observed
in previously published experiments.


A
c
t
u
a
l

%
C
O
W
Y
176


Figure 4-21: %COWY prediction profile for dye range set-up condition affect on %COWY from the empirical model.

The graph in the second column from figure 4-21 confirms the number of dips has a non-
linear impact on the %COWY. The shape of this curve is very similar to the curve in figure 4-1 when
the %COWY versus dips was discussed. Also, the dye range speed was determined to be statistically
significant but by the second order term. As the middle column graph illustrates, as the speed is
increased the %COWY increases until a limit is reached at approximately 33 m/min. The original
graphical analysis did not detect this relationship. The graph in the fourth column identifies a strong
relationship between the dye bath indigo concentration and the %COWY. Logically, as the dye bath
concentration is increased the %COWY also increases. In the final coumn graph of figure 4-21, as
the pH of the dye bath is increased the %COWY decreases. Recall this same relationship was
detected in figure 4-14.
4.2.2 %IOWY Empirical Model Generation
The same process was repeated for the %IOWY using the prime data set as the initial
starting point for the ANOVA analysis. The R
2
correlation coefficient was determined to be 0.97 with
an F ratio of 1585 as shown in table 4-3. This was determined to be the best possible model fit using
all dye range set-up conditions, second order terms, and interactions. The parameter estimates
listed in table 4-3 produce the initial standard errors for each significant parameter. Note the dye
bath pH was determined to be statistically insignificant with a P-value of 0.1449. However, this
%
C
O
W
Y
0
.
0
8
6
3
7
1
[
0
.
0
8
2
7
2
,

0
.
0
9
0
1
8
]
68
1
0
1
2
1
41357
2
6
2
9
3
2
3
5123
1
1
1
2
(g/l)
%COWY Prediction Profile for Dye Range Set-up Conditions
177

parameter was left in the model due to strong evidence in the graphical analysis section and
previously published material that pH should play a strong role in %IOWY.

Table 4-3: ANOVA analysis from the prime data set on %IOWY.




Next, each replica data set was introduced to the empirical model for %IOWY. After each
introduction, the new parameter standard errors were recorded. As with %COWY, the average
normalized standard error after introduction of each replica set was calculated. The convergence
trend is illustrated in figure 4-22 with the individual data posted in appendix section A-4-2b. As each
178

new replica data set is introduced, the average normalized standard error continues to decrease.
After 14 replica sets were included, the average normalized standard error remains fairly flat with
no major change in the values. After 16 replica sets the average normalized standard error is 0.85 or
15% less than the prime data set and point of diminishing returns indicated the observational study
was concluded.


Figure 4-22: Convergence test for the empirical %IOWY model.

The final empirical model for %IOWY as a function of dye range set-up conditions was
calculated based on the entire data set. During this analysis, no new single order, second order, or
interaction parameter effects were deemed statistically significant. Additionally, the effect of pH
was determined not to have become significant. The P-value of 0.3704 in table 4-4 indicates the
variation due to another parameter is just as likely as the affect of pH. For this reason, the pH
parameter was removed from the model and the ANOVA analysis repeated.
0.8
0.85
0.9
0.95
1
1.05
1.1
1.15
1.2
0 5 10 15 20 25 A
v
e
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a
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e

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t
a
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a
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d

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o
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a
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a
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m
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t
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r
s
Number of Additional Replicates Added
Convergence Test for Empirical %IOWY Model
179

Table 4-4: Effects test from %IOWY ANOVA analysis for the entire data set with pH component.


After removing the pH parameter from the ANOVA analysis the R
2
correlation coefficient
was determined to be 0.97 with an F ratio of 2597 from table 4-5. These two coefficients indicate
the model is a very strong fit to the data. Also listed under the parameter estimate section is the
final standard error for each parameter.
180

Table 4-5: ANOVA analysis for the %IOWY from the entire data set






Using the parameter estimates from table 4-5, the final %IOWY empirical model equation
was determined and listed as equation 4-2.


181

% = exp|6.u772 + ()

1: u.u
2: u.6uS7
S: 1.uS41
4: 1.SuS1
S: 1.S2S7
6: 1.7u62
7: 1.8717

+ 4.482Se
-2
1.S847e
-2

+ u.871S log _ [
g
I
]]
Equation 4-2: Empirical model %IOWY as a function of dye range set-up conditions.

To better illustrate the relationship between actual %IOWY and the predicted value from
the empirical model the two values were plotted against each other in figure 4-23. There is
obviously a strong relationship with the predicted versus actual following a linear 1 to 1 relationship.


Figure 4-23: Comparison of actual and predicted %IOWY from the final empirical model.


A
c
t
u
a
l

%
I
O
W
Y
182

A prediction profile graph was created for the empirical model %IOWY as a function of each
dye range set-up condition. As shown in figure 4-24, increasing yarn count causes the %IOWY to
increase. This relationship was observed during the graphical analysis section and hasn't been
documented by others. Just as demonstrated by other experiments (Xin
46
) and illustrated in the
graphical analysis section, increasing the number of dips causes the %IOWY to increase in a nearly
linear fashion. This relationship is highlighted in the second column graph of figure 4-24. The third
column graph shows increasing speed was determined to cause the %IOWY to decrease. This was
originally observed in the graphical analysis section and hasn't been documented by others. In the
final column of figure 4-24, increasing the indigo concentration in the dye bath causes the %IOWY to
increase. This relationship has been well documented in previous experiments.


Figure 4-24: Prediction profile for %IOWY and dye range set-up parameters.


M
e
a
s
u
r
e
d
%
I
O
W
Y
0
.
0
1
9
9
3
[
0
.
0
1
9
3
4
,

0
.
0
2
0
5
4
]
789
1
0
1
1
1
21357
2
6
2
8
3
0
3
2
3
4
3
6123
(g/l)
%IOWY Prediction Profile for Dye Range Set-up Conditions
183

4.2.3 Integ Empirical Model Generation
ANOVA analysis of the prime data set for dye range set-up conditions affect on Integ shade
are presented in table 4-6. The overall correlation coefficient R
2
was 0.96 with an F ratio of 1049.
This was determined to be statistically significant. The initial parameter standard errors are listed in
parameter estimates section of table 4-6. The P-value for each dye range set-up parameter is listed
in effect tests section. No other first or second order condition or interaction of conditions was
determined to be statistically significant.

Table 4-6: ANOVA analysis of Integ shade from the prime data set.




184

The convergence test for dye range set-up parameter affects on Integ shade value are
illustrated in figure 4-25. The individual parameter standard error for each replica set is
documented in the appendix section A-4-2c. Each additional replica set caused the average
normalized standard error to decrease. After 17 replica sets the average normalized standard error
reached the point of diminishing return at 0.816 or 18.4% less than the prime data set average
normalized standard error. As indicated by the overall trend line, additional replica sets would not
greatly reduce the standard error and the observational study was concluded.


Figure 4-25: Convergence test for empirical model Integ.

The final empirical Integ model based on dye range set-up parameters was generated. The
correlation coefficient R
2
value of 0.96 and F ratio of 1610 from table 4-7 indicated the overall model
improved from the prime data set. The final parameter standard errors are displayed in the
parameter estimates section of table 4-7. During the ANOVA analysis other dye range set-up
condition first order, second order, and interaction effects were evaluated and determined to not
0.8
0.85
0.9
0.95
1
1.05
1.1
1.15
1.2
0 5 10 15 20 25
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P
a
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r
s
Number of Additional Replicates Added
Convergence Test for Empirical Integ Model
185

become statistically significant. The final P-value for each parameter is listed in effect tests section
of table 4-7.

Table 4-7: ANOVA analysis for Integ from the entire data set.




The final Integ equation was determined based on the parameter estimates from table 4-7.
The empirical model Integ prediction equation based on dye range set-up conditions is listed in
equation 4-3.
186

Integ = exp|4.u128 + ()

1: u.u
2: u.676S
S: 1.uS11
4: 1.2771
S: 1.4299
6: 1.SS44
7: 1.6S67

+ 1.uS8Se
-2
8.6794e
-3

+ u.7791 log _ [
gm
It
] u.1271 ]
Equation 4-3: Empirical model Integ as a function of dye range set-up conditions.

The comparison between actual Integ shade values and empirical model predicted are
shown in figure 4-26. Overall the model fit is fairly uniform. However, notice at the higher
predicted Integ values the relationship falls off the 1 to 1 line. Second, there is a group of data
points at 40, 80, 110, and 140 predicted Integ units completely off line with the actual values.


Figure 4-26: Comparison of actual and empirical model predicted Integ shade values.

A
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I
n
t
e
g
187

The prediction profile for each dye range set-up condition effect on predicted Integ shade
value from the empirical model is shown in figure 4-27. Just as seen in the graphical analysis section
as the yarn count is increased the Integ value increased. Increasing depth of shade as a function of
yarn count has not been previously published. Just as Xin
46
and Chong
29
have demonstrated, as the
number of dips was increased the resulting Integ shade value also increased. As previously
discussed in the graphical section, increases in speed caused the Integ values to decrease. Again,
this hasn't been previously discussed in the literature. As the dye bath concentration was increased
the predicted Integ shade value also increased. This again is a well established relationship in
published literature and confirmed here. In the last column of figure 4-27, as the dye bath pH values
increase the Integ shade values decrease. This mirrors Etter's detailed experiments on pH sensitivity
of the resulting shade of the yarn.


Figure 4-27: Prediction profile for Integ shade values as a function of each dye range set-up conditions.

M
e
a
s
u
r
e
d
I
n
t
e
g
8
4
.
1
9
7
9
8
[
8
1
.
3
5
1
8
,

8
7
.
1
4
3
7
]
79
1
11357
2
6
2
8
3
0
3
2
3
4
3
6123
1
1
1
2
(g/l)
Integ Prediction Profile for Dye Range Set-up Conditions
188

4.2.4 Penetration Level Empirical Model Generation
The penetration level from the ANOVA analysis will be discussed. The empirical model from
the prime data set doesn't exhibit a strong correlation to the data as demonstrated by the R
2

correlation coefficient of 0.48 but deemed significant due to F ratio of 32.6 and P-value for the
model less than 0.0001 as shown in table 4-8. Also, the parameter standard errors are shown in the
parameter estimate section. The effect tests determined the yarn count, dip, dye bath
concentration, pH, speed/pH interaction, and second order speed terms to be significant. Notice
the first order speed term has been left in the model due to interaction and second order effects.
No other dye range set-up parameter was determined to be significant.
189

Table 4-8: ANOVA analysis results from the prime data set and penetration level.




Following the previously discussed convergence test, the average normalized standard error
for each parameter and interaction was recorded after each replica data set was introduced. The
complete standard error values are recorded in appendix section A-4-2d. As shown in figure 4-28, as
each new replica set was introduced, the average normalized standard error decreased in value.
After 15 replica data sets were introduced, the average normalized standard error remains fairly
190

consistent and the point of diminishing return was determined to have been reached. The value of
the last three replica sets was 0.73 or 27% less than the prime data set average normalized standard
error. At this point the observational study was concluded.


Figure 4-28: Convergence test for empirical model penetration level.

The ANOVA analysis on all data sets for penetration level determined the speed and pH
interaction term to no longer be statistically significant as indicated by the P-value of 0.3853 in table
4-9. Therefore, this parameter interaction was removed from the final empirical model for
penetration level as a function of dye range set-up parameters and the analysis was repeated.
0.6
0.7
0.8
0.9
1
1.1
1.2
0 5 10 15 20 25
A
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i
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t

P
a
r
a
m
e
t
e
r
s
Number of Additional Replicates Added
Convergence Test for Empirical Penetration Level
Model
191

Table 4-9: Effect tests for all data points with speed and pH interaction


The final ANOVA analysis of penetration level as a function of all dye range set-up conditions
did not reveal any new first order, second order, or interaction terms. The final model correlation
coefficient was 0.51 with an F ratio of 62.5 as shown in table 4-10. While this isn't a strong
relationship it is deemed significant due to medium strength F ratio and model P-value much less
than 0.0001. The individual parameter final standard error is listed in parameter estimate section.
Note the speed first order term was determined to remain unimportant in the effect tests section
however the term was left in the model due to the significance of the second order speed term.
192



Table 4-10: Final empirical model ANOVA analysis for all data sets




The final penetration level prediction equation was determined based on the parameter
estimates from table 4-10. The empirical model prediction equation for penetration level as a
function of dye range set-up conditions is provided as equation 4-4.

193

Penetiation Level = u.4789 + ()

1: u.u
2: u.u4SS
S: u.uu98
4: u.uS98
S: u.u7S6
6: u.1u44
7: u.1214

+ 1.4u97e
-2

8.6uS4e
-4
S.S66Se
-2
Bye Bath [
gm
IIt
+ 7.6S9S
-2
+ 9.S778
4
(
SS.1)
2

Equation 4-4: Empirical model penetration level as a function of dye range set-up conditions.

The comparison between actual and predicted penetration level for all data points is
illustrated in figure 4-29. The poor correlation highlighted in the ANOVA analysis is graphically
apparent. However, the overall trend does follow the general 1 to 1 line. One possible reason for
this error lies in using the ANOVA analysis to calculate and model the penetration level directly. An
alternative method would be to use the calculated %IOWY and Integ shade values from the
prediction models. The Integ would be converted into %IOWY from equilibrium sorption then the
penetration level directly calculated. This may yield a better correlation and will be investigated
shortly.
194



Figure 4-29: Comparison between actual and predicted penetration level.

The dye range set-up parameter effects on the predicted penetration level will be discussed.
Figure 4-30 shows the prediction profile. As discussed and highlighted in the graphical analysis
section, increasing yarn count caused the penetration level to increase. This indicates finer yarns
are more penetrated than courser counts given everything else as a constant. This is an interesting
observation that hasn't been discussed by others. The same relationship for increasing dip is
exhibited in the empirical model for penetration level. Speed does affect the penetration level but
not in a linear fashion as discussed in the graphical analysis section. Instead, increasing the speed
from 26 m/min to 32 m/min caused the penetration level to decrease. After 32 m/min further
increases in speed have little effect on the penetration level. As discussed numerous times,
increasing the dye bath concentration caused the penetration level to decrease. In the last graph on
figure 4-30, the dye box pH has the same relationship as documented by many others in the
published experiments. Increasing the box pH caused the penetration level to increase or the yarns
become less ring dyed.
A
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P
e
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a
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L
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195


Figure 4-30: Prediction profile of empirical model penetration level as a function of dye range set-up parameters.



A
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P
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i
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L
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0
.
3
1
0
2
5
3

0
.
0
1
7
6
2
5
79
1
11357
2
6
2
9
3
2
3
5123
1
1
1
2
(g/l)
Penetration Level Prediction Profile for Dye Range Set-up Conditions
196

4.3 Theoretical Model for Indigo Dye Process
A theoretical dye model was constructed based on general dye theory summarized by Etters
and discussed in section 1.4.1 coupled with diffusional theory developed by Ficks. The primary
purpose for this investigation was to gain an understanding of the mechanisms that influence the
general trends discussed in section 4.1 and 4.2. Additionally, develop a rigorous mathematical
model of the indigo dye process that would be quantitatively extendable to all long chain rope
indigo dye ranges.
4.3.1 Derivation of Theoretical Dye Model
Following Etters's dye theory model, the approach is broken into two different components.
1. Dye movement and propagation on a macro scale into the yarn structure from the dye bath. 2.
Dye attraction and movement into the fibers on a micro scale. Both processes occur simultaneously
during the dipping process. After the yarns have been squeezed by the nip rollers, macro movement
within the yarn stops. However, dye attraction for the individual fibers may continue until all the
dye is oxidized. Using this approach, the theoretical model was broken down into three main
sections: the dip process where the yarns are actually submerged in the indigo dye bath, the nip
process where the excess dye liquor is squeezed from the yarns, and last the oxidation process
where the final fixed indigo (%IOWY) was determined.
Etters described four main paths that occur in the dip process. These are summarized
below. This dye model did incorporate these four dye paths in the dipping process. However, the
model was expanded to allow path 4 to continue beyond the nip process.
1. Diffusion of the dye in the external medium (usually water) toward the diffusional boundary layer
at the fiber surface.
2. Diffusion of dye through the diffusional boundary layer that exists at the fiber surface.
3. Adsorption of the dye onto the fiber surface.
4. Diffusion of dye into the fiber surface.

In addition to these four paths, the theoretical model compensated for wet pick-up from the
nip process, wash reduction of chemicals on weight of yarn, and the rate of oxidation. All combined
this would result in eight unknown coefficients to completing describe the indigo dyeing process:
the four previously discussed paths each with an unknown coefficient, the wet pick-up, wash
197

reduction, diffusion of oxygen through the yarn structure, and oxidation rate. The observational
study produced three known values for each yarn, dip, and dye range set-up. Specifically the three
known values were %COWY, %IOWY, and Integ shade. To overcome the deficiency in number of
known values, several assumptions were made.
First the diffusion of dye in the external medium and diffusion of dye through the boundary
layer were grouped together as one unknown coefficient called the effective yarn diffusion
coefficient, D
y
. This coefficient controlled the dye bath concentration within the yarn structure that
was available to dye into the fiber. It was not the actual diffusion coefficient of indigo dye through
the dye bath. The influence of this parameter determined the effective dye bath concentration
within the yarn structure which affected the %COWY, %IOWY, and indigo distribution within the
yarn.
The diffusion coefficient for indigo dye in the water solution is not directly known.
However, a value can be assumed based on other equations and theoretical work. Ozisik
59

presented a method that calculates the diffusion coefficient by use of equation 4-5.

= 7.4
-8

(s
B
M
B
)
12
1
v
A
0.6

Equation 4-5: Ozisik diffusion coefficient calculation in external medium.

= Association factor for solvent, H
2
0, = 2.6.
M = Molecular weight of solvent, H
2
0, = 18.02.
T = Temperature in Kelvin = 293K.
= Viscosity of solvent = 1 cP (centipoise).
V = Molal volume of solute A as liquid at its normal boiling point = 165 cm
3
/g mol.

After performing the calculations the indigo dye diffusion coefficient in dye bath was determined to
be 6.934e-6 cm
2
/sec. While this value is not exact, it does provide a starting point for optimization
calculations that iteratively seek the effective yarn diffusion coefficient final value.
Second, the adsorption of dye onto the fiber surface and the diffusion of dye into the fiber
surface were grouped together to created the effective fiber diffusion coefficient, D
f
. The coefficient
198

controlled the total movement of dye into the fiber surface. It was not the actual fiber diffusion
coefficient. This coefficient regulated the amount of dye into the fiber which resulted in the final
%IOWY value.
Now the theoretical model had six unknown values and one more unknown value can be
approximated. The diffusion of oxygen, DO
y
, through air follows known classical diffusion process.
The mass percentage composition of dry air at sea level is approximately 75.5% nitrogen, 23.2%
oxygen, and 1.3% argon
8
. The corresponding mole fractions are 0.78 N
2
, 0.21 O
2
, and 0.0096 Ar at
one atmosphere pressure. The density of air at room temperature (20 C) and one atmosphere
pressure is 1.21 kg/m
3
or g/l
8
. Therefore the initial concentration of oxygen in the air is 0.21 * 1.21
g/l = 0.2541 g/l. Since air is mostly composed of oxygen and nitrogen, the mixture can be modeled
as a binary system. The diffusion of oxygen through nitrogen at room temperature (20 C) and one
atmosphere pressure has been determined to be 0.219 cm
2
/sec
60
. This value was used during the
oxidation process.
In order to manipulate the remaining five unknown coefficients, calculations were expanded
to incorporate several dips of indigo across multiple yarn counts. The following relationships were
utilized to construct an iterative process to goal seek the optimum value for each unknown
coefficient.
1. The effective fiber diffusion coefficient, D
f
, was assumed constant regardless of yarn count and
only dependent on the specific dye range set-up and indigo dip analyzed.
2. The effective yarn diffusion coefficient, D
y
, was assumed constant regardless of yarn count and
only dependent on the specific dye range set-up and indigo dip analyzed.
3. The wash reduction coefficient was constant regardless of yarn count and dips. The dip
assumption applied only to the interior dips not first or last dip since these nip pressures were
higher than the interior dips. This coefficient only depended on dye range set-up.
4. The wet pick-up coefficient was constant regardless of yarn count and dips. Constant wet pick-up
only applied to the interior dips for the same reason as wash reduction.
5. The oxidation rate was assumed constant for each yarn count and dip process. It only depended
on the dye range set-up parameters.

Using the above assumptions the following relationships were identified. The effective fiber
diffusion coefficient was governed by the final Integ shade of the yarn. By converting the Integ
shade into %IOWY from equilibrium sorption, the outside or visible surface indigo concentration was
199

determined. The concentration was fiber diffusion dependent. Therefore the goal seek algorithm
adjusted the fiber diffusion coefficient until the calculated %IOWY on the outside surface matched
the target value from the Integ conversion.
With the fiber diffusion coefficient identified the effective yarn diffusion coefficient was
regulated by the final calculated total %IOWY. The algorithm adjusted the yarn diffusion coefficient
while applying the appropriate fiber diffusion coefficient until the total calculated %IOWY matched
the target value from Pyrrolidinone extractions.
The wet pick-up coefficient controlled the final %COWY. Given the yarn diffusion
coefficient, the dye concentration distribution within the yarn was calculated. The wet pick-up
coefficient regulated the percentage of dye bath concentration that was allowed to move on to the
oxidation process. Excess dye bath concentration would either continue to diffuse into the fiber or
was oxidized by oxygen and formed the oxidized boundary layer. By calculating the oxidized
boundary layer the wet pick-up coefficient was determined by the algorithm by matching the value
to the targeted measured %COWY.
Once the fiber diffusion coefficient, yarn diffusion coefficient, and wet pick-up were
determined that matched the targeted %COWY, %IOWY, and Integ shade for each yarn count and
dip; the wash reduction value was adjusted until the wet pick-up coefficient was constant across all
interior dye baths. Then the oxidation rate was adjusted until the minimum standard deviation was
determined for fiber diffusion coefficient, yarn diffusion coefficient, and wet pick-up across all the
yarn counts. This method resulted in one fiber diffusion coefficient per dip, one yarn diffusion
coefficient per dip, one wash reduction value, one wet pick-up value, and one oxidation rate per
indigo dye range set-up across all yarn counts.
Once the individual dye theory coefficients are determined, a model for each coefficient was
constructed using the nine dye range set-up conditions. Using the dye theory coefficient equations,
the resulting %COWY, %IOWY, and Integ values would emerge from the model. Then the
penetration level was calculated based on the predicted %IOWY and Integ values. At the conclusion
the theoretical and empirical models will be compared to one another to identify agreements and
conflicts.
200

4.3.1.a The Dip Process
The dye theory model will incorporate dye bath concentration variation as it moves through
the yarn structure, effective diffusion coefficient encompassing the affinity of reduced indigo dye
molecules for the surface of cotton fibers and diffusion of indigo dye into the fiber surface, wet pick-
up caused by the nip rollers, and last oxidation. Of course any discussion on diffusion will involve
Fick's first and second laws of diffusion which are presented in one dimensional form in equation 4-
6. The parameter D is referred as the diffusion coefficient and is written in terms of distance
squared per second (cm
2
/sec). The coefficient describes the rate at which a material diffuses
through a unit area.

=
C
x

C
t
=

2
C
x
2

Equation 4-6: Fick's first and second law of diffusion.

When expanding Fick's laws to cylinders it is customary to neglect material transport along
the yarn length or z axis and assumes no differential material transport occurs around the
circumference of the yarn. The remaining direction is radial or along the yarn's radius. This was
considered the primary route for material transport and Fick's laws are rewritten into equation 4-7.

C
t
=
1

(, )
Equation 4-7: Transient second order partial differential of mass diffusion in radial direction.

Here C is defined to represent the dye bath concentration in grams/liter, t is the time in seconds, r is
the radius in centimeters, D
y
is the yarn diffusion coefficient in cm
2
/sec, and F(C,r) is the grams per
liter of indigo in the dye bath removed per time into the cotton fibers. This last term behaves
201

similar to heat generation term in classical heat transfer theory and is dependent on the dye bath
concentration and location within the yarn.
One of the simpler methods to solve classic transient second order partial diffusion
equations is to approximate the solution through finite difference methods. The introduction of
F(C,r) term to represent the rate of dye removal adds a twist but finite difference remains the
simplest method. First, the partial differential equation is transformed into a series of linear
algebraic equations by Crank-Nicholson's explicit finite difference method by assuming constant Dy.
The resulting expression is listed in equation 4-8.

C
i
]+1
- C
i
]
t
=

_
1
2
_
C
i+1
]+1
-C
i-1
]+1
2
+
C
i+1
]
-C
i-1
]
2
]_ +

j
1
2
2
(
+1
]+1
2

]+1
+
-1
]+1
+
+1
]
2

]
+

-1
]
)[ |(, )]
Equation 4-8: Crank-Nicholson explicit finite difference model for mass diffusion.

The superscript j was used to represent the current time while j+1 equals next time step. The
subscript i represents the current node while i-1 and i+1 represents the previous and next
node respectively.
The dye removal term, F(C,r), was defined by the amount of dye that leaves the dye stream
and transfers to the cotton fiber per time. The amount of dye in grams leaving the dye bath at each
node is defined by the affinity of the dye molecule for cotton fiber surface. This dye will form a
boundary layer around the fibers as long as the affinity is faster than the diffusion of dye from the
surface into the fiber interior. Since the exact boundary layer thickness is unknown, the affinity of
dye for cotton fiber and subsequent diffusion from boundary layer into fiber was grouped together.
The resulting expression was the relative or effective fiber diffusion coefficient, D
f
.
By setting the amount of dye leaving the dye stream at each node equal to the amount of
dye transferred to the fiber, the F(C,r) term was defined. This relationship was modeled by
incorporating two different aspects. First, the maximum possible %IOWY was calculated based on
202

the equilibrium sorption experiments discussed in chapter 3.3, equation 4-11. Second, the fraction
of the maximum possible %IOWY was calculated based on Cranks
2
theoretical analysis solution for
infinite dye bath conditions, equation 4-10. Incorporating these two expressions together in
equation 4-9 resulted in the final relationship of %IOWY at each node.

%

= %
mux

M
t
M


Equation 4-9: Actual %IOWY based on maximum possible %IOWY and fractional relationship.

M
t
M

= 1
4
u
2
6
n
2

n=1

-
]
6
n
2
t

4
n
12
[

]
t
u
2

12

]
t
u
2

1
3n
12
[

]
t
u
2

32

Equation 4-10: Crank's expression for the fractional relationship of dye pick-up.
2


Where
n
's are the positive roots of
0
(
n
) = u and introduced D
f
to represent the fiber
diffusion coefficient, units of cm
2
/sec, into the fibers where is the cotton fiber radius in
centimeters. The effective fiber radius of 0.0009 cm was used from Hudson
56
.

%
mux
= (

]
)
Comp B

Equation 4-11: Maximum %IOWY from equilibrium sorption experiments.

It follows that the grams of indigo removed from the dye stream were related to the %IOWY
at each node by converting the %IOWY into grams. Recognizing the %IOWY was actually grams of
indigo per gram of cotton, the grams of indigo was calculated by multiplying the %IOWY by the
number of grams of cotton at each node. Now the results from equation 4-9 was linked with the
F(C,r) term by equation 4-12. Since the fraction of maximum possible %IOWY was non-linearly
dependent on the step time, t, the solution for dye stream concentration is no longer explicit in
nature. Therefore, the greatest time step that ensured stability must be deteremined.
203


(, ) =
uums o] Cotton
i
%I0w
i
Ltcs bctwccn ]bcs
i

Equation 4-12: Functional relationship between indigo leaving the dye bath stream and dye diffused into the cotton
fiber.

The boundary conditions needed to solve the finite difference model consists of initial time
conditions, dye concentration conditions at the interior node, and dye conditions at the exterior
node. The initial boundary conditions at t<0 are listed in equation 4-13.

() = u < u
Equation 4-13: Initial dye distribution at t<0.

Obviously the dye concentration within the yarn is zero prior to the first indigo dye box. During
multiple dip applications, this assumes all indigo dye has been either extracted by the nip or fully
oxidized and therefore immobile for continued yarn or fiber diffusion.
Next the dye bath concentration at the outside node was defined by boundary condition in
equation 4-14.

() = = u
Equation 4-14: Dye bath concentration at the outside surface node.

This condition assumes dye stream concentration at the outside node is equal to dye bath
concentration and all other chemical additives as soon as yarn enters the dye bath and maintained
during the entire dip process. Given the relatively rough yarn surface, due to irregular shape from
uneven yarn thickness and wrapper fibers, micro turbulent flow develops instead of conventional
204

laminar flow. The micro vortices produce localized mixing of the dye bath. This was assumed to
result in constant concentration of the dye bath at the outside or surface node.
Equation 4-15 exists due to symmetry about the center of the yarn where r = 0.

C

= u = u > u
Equation 4-15: Boundary condition at the center of the yarn due to symmetry.
Prior to indigo dye box #1, the yarns are free of any indigo dye. Also the calculated %IOWY
distribution from a dip was used in additive nature for each subsequent dip. This will simulate the
additive nature of multiple dip indigo dyeing and expressed in equation 4-16.

% = ( )
Equation 4-16 Functional relationship of %IOWY at the surface related to Integ shade.

To determine the distribution of indigo dye within the yarn, the amount of indigo on the
surface was assumed to equal the corresponding amount of dye from uniformly dyed yarns. The
relationship developed in chapter 3.3 for Integ shade value will be utilized. Given the Integ shade
value, the corresponding %IOWY on the surface of the yarn was calculated by relationship in
equation 4-16 and utilizing expression in equation 4-17.

%
Su]ucc
= 2.646S
-2
+9.SS86
-4
+ 1.SS9S
-5
( SS.2u88)
2
+
S.9u9u
-8
( SS.2u88)
3
+2.4244
-9
( SS.2u88)
4
+6.4SuS
-11

( SS.2u88)
5

%
Su]ucc
= %
mux

M
t
M


Equation 4-17: Relationship of surface %IOWY by Integ shade.

205

A finite difference nodal mesh was then constructed starting at the center of the yarn
(node=0) and progressing toward the exterior surface of the yarn (node=M) as shown in figure 4-31.
By applying the appropriate finite difference equations and/or boundary conditions, M numbers of
linear algebraic equations were developed. The experimenter has assumed uniform dye bath
conditions exist surrounding the individual fibers in each node during the time step under
consideration.



Each nodal equation was rearranged with all dye concentrations at time step j+1 on the left
hand side and j time steps on the right hand side and making substitutions for beta and lambda.
This resulted in the following equations for the center (equation 4-18), interior (equation 4-19), and
exterior (equation 4-20) nodes.
Node = 0, center where
+1
]+1
=
-1
]+1
and
+1
]
=
-1
]
:
0 1 2 m-1 m m+1 M-1 M
r
r
r
r/2
nodes
C
0

C
1

C
2

C
m

C
M

Figure 4-31: Nodal mesh arrangement and nomenclature for finite difference method implementation.
206

+1
]+1
( ) +

]+1
(1 +2) =
+1
]
( + ) +

]
(1 2) (

]
,

]+1
(1 +2) =

]
(1 2) (

]
,

)
Equation 4-18: Nodal equation for the center node.

+1
]+1
( ) +

]+1
(1 +2) +
-1
]+1
( ) =
+1
]
( +) +

]
(1 2) +
-1
]
( +)
(

]
,

)
Equation 4-19: Nodal equation for the interior nodes.

Node = M - 1 where
M
]+1
and
M
]
= dye bath concentration:

M-1
]+1
(1 +2) +
M-2
]+1
( ) =
M-1
]
(1 2) +
M-2
]
( + ) +2
M
( +) (

]
,

)
Equation 4-20: Nodal equation for the exterior node.

All three nodal equations utilized a simplified expression for lambda and beta as detailed in equation
4-21.

=

j
t
2
2
, =

j
t
4rr

Equation 4-21: Expression for lambda and beta coefficients in the nodal equations.

Here the D
y
coefficient is assumed to be a constant value, cm
2
/sec. Re-arranging and grouping the
following M simultaneous equations were written in matrix form, equation 4-22.
207

1 +2 2 u u
1 + 2 u
u u
u 1 + 2
u u 1 + 2

0
]+1

1
]+1

M-2
]+1

M-1
]+1

1 2 2 u u
+ 1 2 + u
u u
u + 1 2 +
u u + 1 2


0
]

1
]

M-2
]

M-1
]

(
0
]
,
0
)
(
1
]
,
1
)

(
M-2
]
,
M-2
)
(
M-1
]
,
M-1
) + 2
M
( +)


Equation 4-22: Matrix example of all nodal equations in finite difference model.

To utilize the lambda and beta equations from equation 4-21, the effective yarn radius was
determined from Mogahzy's relationship for yarn count (English cotton count)
57
. Equation 4-22 was
the equation to calculate the effective yarn radius at a given open end spun yarn count. With the
effective yarn radius, the r value was calculated by dividing the radius by the number of nodes
minus one.

() =
-0.16155+[
1.9S1
Nc

20

Equation 4-23: Mogahzy's relationship for open end yarn radius as a function of yarn count.
57


Additionally the yarn porosity value was determined. This property was defined to be the
area of the fiber in a nodal shell per total area of yarn at that nodal shell. Nabovati
58
reported
typical yarn porosity values in the range of 0.69 to 0.95. Given the 100% cotton yarns are dyed in a
zero tension state, the porosity value of 0.65 was assumed for all calculations since this was the
absolute low end of published values.
Solution for the future dye concentration within the yarn from the algebraic equations in 4-
22 was conducted by Guess-Jordan elimination method executed in purpose written software
208

program. The concentration gradient is in units of grams per liter and was governed by the diffusion
of dye through the yarn through coefficient D
y
.
4.3.1.b The Nip Process
Before defining the parameters and equations in the oxidation process two more
parameters must be defined. The wash reduction is defined as the percent of unfixed oxidized dye
and other chemicals removed from the fiber surface resulting from previous dip of indigo. These
remaining chemicals were called the Oxidized Boundary Layer or OBL. It was calculated as shown in
equation 4-24 by subtracting the fixed indigo on weight of yarn from the unfixed chemicals after the
previous dip, converting the percent chemical on weight of yarn into grams of chemical, and
multiplying by the wash reduction coefficient. The wash reduction value will be zero during the first
dip of indigo since no previous dye exists.

() = (% %)
pcous dp
(
gms
nodc
)
Equation 4-24: Calculation of oxidized boundary layer as a function of wash reduction coefficient, and %COWY and
%IOWY from the previous dip.

Next, the wet pick-up caused by the squeeze of nip rolls after the dip process was
investigated. Wet pick-up is defined to cause a fraction of excess reduced dye bath liquor between
the fibers to be extracted. The excess reduced dye was called the Reduced Boundary Layer or RBL
and two forms must be tracked. The concentration of the RBL so future %IOWY calculations could
be determined and the number of grams of reduced dye for oxidation tracking. The concentration
of the RBL is simply the concentration of the dye bath at each node after the nip process, since
squeezing the yarns and reducing the quantity of excess dye doesn't change the concentration. This
is summarized in equation 4-25. Second, the quantity of reduced dye must be tracked. Here the
grams were calculated by multiplying the dye bath concentration by the available liter space
between the fibers at each node and then multiplying by the wet pick-up coefficient.
209


[
gm
It
= (
gm
It
)
() = [
gm
It
[
spucc
nodc

Equation 4-25: Determining the reduced boundary layer concentration and quantity after the nip process.

4.3.1.c The Oxidation Process
The movement and concentration of oxygen in the yarn structure was modeled exactly the
same as the dye bath liquor. The same nodal mesh was utilized. The difference was oxygen
concentration was determined at each time step instead of dye bath concentration. This was
expressed in grams of oxygen (O
2
) per liter. The equations and boundary conditions are listed in
equations 4-26 to 4-28.

0
i
]+1
- 0
i
]
t
=
0
j

_
1
2
_
0
i+1
]+1
-0
i-1
]+1
2
+
0
i+1
]
-0
i-1
]
2
]_ +

j
1
2
2
(
+1
]+1
2

]+1
+
-1
]+1
+
+1
]
2

]
+

-1
]
)[ |(, )]
Equation 4-26: Explicit finite difference equation for oxygen distribution in the nodal mesh.

Here DO
y
was the oxygen diffusion coefficient.

(, ) = |

]
]
Equation 4-27: Rate of oxygen removal from the air stream.
Here X
i
was defined to be the fraction of oxygen removed from the air stream.
210

=
(RBLgm+%I0w
i
Cotton(
gms
ncdc
))
0xdzuton Rutc0
i
]
Ltc[
spccc
ncdc
t

Equation 4-28: Fraction of oxygen removed from the air stream as a function of total reduced dye present.

The initial oxygen concentration is assumed zero at the start of the oxidation process. The
outside node oxygen concentration was set equal to the air concentration and maintained during
the entire oxidation process. Also like the dye bath concentration, oxygen concentration was
symmetrical about the center or core of the yarn.

() = u < u
() = = u
0

= u = u > u
Equation 4-29: Boundary conditions for solving finite difference equations.

The oxidation rate, O
R
, is an unknown coefficient defined to be the grams of reduced indigo
per gram of oxygen per second consumed during the oxidation process and has units of 1/sec. The
values of X
i
can range from zero to one. A value greater than one means either the oxidation rate,
grams of reduced indigo, and/or time step were high compared to the grams of available oxygen. In
this situation all of the available oxygen was consumed by the reduced indigo but more wasn't
consumed than available. This assumption now makes the total finite difference model implicit
instead of full explicit since the X
i
value was dependent on the t value. Therefore, many more time
steps were used in the calculations to produce a stable solution.
After each oxidation rate time step the grams of oxygen and impact on reduced indigo are
tracked. First the grams of oxygen removed from the air stream were calculated based on reduced
boundary layer and the %IOWY that required oxidizing. Then the total change in grams per liter of
211

oxygen was calculated so the next time step calculation would impact air stream concentration
within the yarn structure. Next the quantity of reduced boundary layer components RBLgm (grams)
and RBL (g/l) were reduced by indigo diffused into the cotton fiber and the dye in the boundary
layer oxidized by oxygen. The diffusion of dye into the fiber utilized the same equations as
previously discussed during the dip process. This property allowed fiber diffusion which impacts
Integ shade and total %IOWY to continue beyond the dip process. The oxidized boundary layer was
increased by the addition of oxidized dye from the reduced boundary layer. Of course oxidation at
each node was complete after RBLgm equals zero and all dye in the %IOWY was oxidized. Equation
4-30 summarizes the expressions used to track the converting of reduce dye into oxidized state.

= %

[
gms
nodc

]
[
spucc
nodc


=
RBLgm
Ltc[
spccc
ncdc

]
[
spucc
nodc


%

= %
mux

M
t
M


Equation 4-30: Equations used to track the convergence of reduced indigo dye into oxidized state.

Last the %COWY calculation must be defined. This value represents the unfixed indigo and
residual sodium hydroxide and sodium sulfate from the dyeing process that has not been washed off
the fiber surface. The measured value of this parameter will depend on three main constitutes.
1. The indigo dye, sodium hydroxide, and sodium dithionite concentration in the dye bath.
2. The net pick-up of chemicals during the dip and nip process.
3. The fixation rate of the dye.

The indigo dye concentration is a measured value based on empirical correlations discussed
during the %T measurements. On the other hand, the total alkalinity measurement doesn't directly
relate to just the sodium hydroxide concentration. Likewise, the mV reduction potential doesn't
212

directly measure only sodium dithionite concentration. As a result, only one component of item #1
is a direct measurement of concentration in the dye bath. Additionally, the actual wet pick-up of
chemicals during the dip and nip process was an unknown property which was approximated by the
wet pick-up coefficient. The fixation rate of indigo dye was unknown and the main property under
investigation. Due to these shortcomings an approximation was developed. The amount of residual
chemicals on weight of yarn will be a direct function of the amount of indigo on weight of yarn. This
functional relationship was developed by analyzing the indigo reduction/oxidation process.
The oxidation of reduced indigo, I
R
, produces the following chemical reactions.

R
+
2
+
2
u
cIds
--
0
+2 +2
2

3

2
2

3
+
2
cIds
--2
2

4

Equation 4-31: Chemical reactions and intermediaries during the oxidation process.

From equation 4-31, for every mole of reduced indigo that is oxidized, 2 moles of sodium hydroxide
and 2 moles of sodium sulfate or Glauber salt were produced. By converting the mole fractions by
the molecular weight a relationship of grams of each chemical per gram of indigo was generated a
shown in equation 4-32.

2moIcs Nu0H
moIc Indgo
= 2
40.01
262.26
=
0.305117 gums o] Nu0H
gum o] Indgo


2moIcs Nu
2
S0
4
moIc Indgo
= 2
142.05
262.26
=
1.083276 gums o] Nu
2
S0
4
gum o] Indgo

Equation 4-32: Relationship for the grams of auxiliary chemicals per gram of indigo present.

Adding these two together and 1.0 for the grams of indigo itself resulted in a value of 2.3884 grams
of total chemicals per gram of indigo. The total %COWY at each node was calculated based on the
213

total indigo on weight of yarn from yarn diffusion, fiber diffusion, and wet pick-up reduction effect
during the nip process plus residual oxidized indigo dye in the oxidized boundary layer . This
expression is summarized in equation 4-33.

%

= 2.S884 |(%

[
gms
nodc
) +

]
Equation 4-33: Calculation for the %COWY based on total indigo amounts.

Equation 4-33 assumes the only residual chemicals on weight of yarn were derived from the
oxidation of reduced indigo and no other residual chemicals exist. This obviously isn't the situation
under real world dyeing conditions where excess sodium hydroxide and sodium dithionite are feed
to the dye range. However, it was directly related to the amount of indigo on weight of yarn and
varies linearly with indigo amount. Due to this assumption calculated values for the wet pick-up and
wash reduction will not be absolute numbers. Instead, the wet pick-up and/or wash reduction
coefficient may scale greater or less than reality to make the calculated %COWY match the
measured value. How these scale will depend on the actual concentration of sodium hydroxide and
sodium sulfate in the dye bath. Since the amount of these components is usually related to the
indigo concentration, it is expected wet pick-up and wash reduction coefficients will depend on
indigo dye bath concentration.


214

4.3.1.d Optimization of Wet Pick-up and Wash Reduction

Once the fiber diffusion, yarn diffusion, and wet pick-up coefficients were determined for
the individual yarn counts after each dip, nip, and oxidation process; the slope of the wet pick-up as
it changed across each dip of indigo was calculated. The wash reduction value, which was constant
across all dips, was adjusted until the slope of wet pick-up equaled zero. This resulted in a constant
wash reduction and wet pick-up coefficient value for each yarn count across the interior indigo dye
boxes.
4.3.1.e Optimization of Oxidation Rate
The oxidation rate was determined for all yarn counts at each indigo dye box and individual
dye range set-up. This was carried out by following the original dye coefficient assumptions.
Specifically, constant fiber diffusion, yarn diffusion, and wet pick-up regardless of yarn count. The
standard deviation for the fiber diffusion, yarn diffusion, and wet pick-up was calculated for a
specific indigo dip across the yarn counts. The goal was to determine the oxidation rate that
minimized the standard deviation for these coefficients. To facilitate the optimization the variation
in standard deviation as the oxidation rate changes was incorporated.
To establish an algorithm to goal seek the optimum oxidation rate, the behavior of oxidation
was investigated. All of the following calculations and relationships pertain to a 36.5 m/min, 2.5 g/l
dye bath concentration, 11.7 pH, 800 mV reduction potential, and 8.6 meter dwell length dye range
set-up and one indigo dip but the same relationships exists under all set-up conditions. The
optimum fiber diffusion coefficient was calculated for each yarn count at a given oxidation rate. The
results are illustrated in figure 4-32. At extremely fast oxidation rates the variation in fiber diffusion
coefficient across the yarn counts was great. As the oxidation rate decreased, the variation in fiber
diffusion decreased. Also note the overall fiber diffusion coefficient value decreased. At low
oxidation rates the fiber diffusion coefficients became approximately equal and independent of yarn
count. There are two properties of oxidation rate worth noting. At extremely high oxidation rates
the reduced indigo on the yarn after the nip process was flash oxidized. This means the indigo was
instantaneously oxidized. While at extremely low oxidation rates, the indigo was never oxidized in
the time allotted. Recall oxidation time was determined by oxidation thread-up length and dye

range
oxidat

Figure


figure
decre
acros
was a
to dec
e speed. Both
tion rate occu
4-32: Fiber diffu
The same
e 4-33. Here
eased. As the
s the yarn co
at a maximum
crease and th
h of these cas
urred betwee
usion coefficient
graph was cre
e the yarn diff
oxidation rat
unts became
m. Further red
he magnitude
ses do not act
en 1.0 e-3 and
ts for each yarn
eated for yar
fusion coeffic
te was decrea
greater. At 1
ductions in ox
e of the yarn d
tually exist in
d 1.0 oxidatio
n count as the ox
n diffusion co
cients have a
ased from hig
1.0 e-2 oxidat
xidation rate
diffusion coef
real world. F
on rate units.
xidation rate ch
oefficients as
different beh
gh values, the
tion rate unit
caused the va
fficient shifte
For this exam
anges.
a function of
havior as the o
e variation in
s the variatio
ariation betw
d lower.
ple the real
f oxidation ra
oxidation rate
yarn diffusion
on in yarn diff
ween yarn cou
215

te in
e was
n
fusion
unts

Figure


invest
variat
value
up at
Again
4-33: Yarn diffu
The variati
tigated. As ill
tion between
of wet pick-u
low oxidation
this phenom
usion coefficient
ion in calcula
lustrated in fi
yarn counts
up shifts high
n rates were
menon doesn'
ts for each yarn
ted wet pick-
igure 4-34, as
increased. A
er regardless
caused by lac
t occur in the
count as a func
-up values as
s the oxidatio
At approximat
s of yarn coun
ck of indigo o
e real world.
tion of oxidatio
a function of
on rate was de
tely 1.0 e-2 ox
nt. The shifts
xidation duri
n rate.
f oxidation rat
ecreased from
xidation rate
in yarn diffus
ng the allotte
te was
m high values
units the mea
sion and wet
ed oxidation t
216

s the
an
pick-
time.

Figure


error
deviat
Next,
coeffi
meas
been
relatio
comb
comb
optim
the co
result
4-34: Wet pick-
By incorpo
in fiber diffus
tion for fiber
these standa
icient. Then,
urement rela
determined.
onship are di
bined normali
bined normali
mum oxidation
ombined norm
ting in consta
-up variation wit
orating these
sion, yarn diff
diffusion, yar
ard deviations
the normaliz
tionship. Wh
The normali
splayed in fig
zed standard
zed standard
n rate was 0.0
malized stand
nt combined
thin yarn counts
properties to
fusion, and w
rn diffusion, a
s were norma
ed standard d
hen this value
zed standard
gure 4-35. Sta
deviations w
deviations b
064 oxidation
dard deviatio
normalized s
s as a function o
ogether the o
wet pick-up w
and wet pick-
alized by the
deviations we
e reached a m
deviations fo
arting with an
were high. As
egan to decre
n rate units. F
n to increase
standard devi
of oxidation rate
ptimum oxid
as determine
-up at each ox
average stand
ere combined
minimum the
or each dye c
n extremely lo
the oxidation
ease. In this
Further increa
slightly in va
iations due to
e.
ation rate tha
ed. First, the
xidation rate
dard deviatio
d to produce
optimum oxid
oefficient and
ow oxidation
n rate was inc
particular exa
ases in oxidat
lue with furth
o instantaneo
at minimizes
standard
was calculate
on for each
a single error
dation rate h
d the combin
rate the
creased the
ample, the
tion rate caus
her increases
ously fast indi
217

the
ed.
r
ad
ed
sed

go

oxidat
end o
stand


Figure

4.3.2


bath c
count
calcul
rate.
value
comb
tion. Due to
of the spectru
ard deviation
4-35: Standard
Algorithm to
The operat
concentration
t and dip. Firs
lated based o
Then the wa
s across all dy
bined normali
the nature of
m with increa
n was reached
deviations as a
Calculate the
tor would inp
n, etc and the
st the fiber di
on the yarn co
sh reduction
ye dips and ya
zed standard
f the oxidatio
asing oxidatio
d.
function of oxid
e Dye Coeffic
put the specif
e final target v
iffusion coeff
ount and assu
coefficient an
arn counts. T
deviation oc
on profile all o
on rate until t
dation rate.
ients
fic dye range
values for %C
ficient, yarn d
umed initial w
nd wet pick-u
Then the oxid
ccurred at eac
oxidation rate
the minimum
set-up condit
COWY, %IOW
diffusion coeff
wash reductio
up were optim
dation rate wa
ch dip. After
e optimization
m combined n
tions such as
WY, and Integ s
ficient, and w
on, wet pick-u
mized to main
as adjusted u
all calculation
n began at th
ormalized
speed, indigo
shade by yarn
wet pick-up w
up, and oxidat
ntain constan
ntil the minim
ns and
218
e low

o dye
n
as
tion
t
mum
219

convergence were satisfied, the program would output the average fiber diffusion coefficient,
average yarn diffusion coefficient, and average oxidation rate by indigo dip and the overall wash
reduction and wet pick-up coefficient values. The actual c++ computer program is provided in
appendix section A-4-3a.
4.3.3 Spatial and Time Step Optimization
Before the program can be used to determine the indigo dyeing coefficient from the
experimental data, the stability of the program was ensured. With the introduction of time
dependent components in the dye bath and air stream calculation, the model was no longer explicit
in nature. Additionally, the nodal spacing would influence the dye coefficient values. An iterative
process was utilized to determine the optimum nodal mesh size and time step to ensure stability of
the dye and air stream and convergence for the dye coefficients. The initial value was 5 nodes and 1
second time step. These two values were increased until both stability and convergence was
guarantee across both the lowest and highest yarn counts and several dye range set-up conditions.
The final optimum values were 21 nodes and 0.01 second time step.

4.3.4 Determination of Indigo Dyeing Coefficient Models
After the computer program was utilized to calculate the optimum fiber diffusion
coefficient, yarn diffusion coefficient, wash reduction, wet pick-up, and oxidation rate for each yarn
count processed through each dye range set-up; each dye coefficient was profiled to determine
relationship to the dye range set-up values. Since convergence of the observational study was
already established during the empirical model phase, all available data from the two separate
indigo dye ranges were utilized in the analysis. When evaluating each dye coefficient all first and
second order dye range step-up parameters and the respective interactions were considered. The
following models for fiber diffusion coefficient, yarn diffusion coefficient, wash reduction, wet pick-
up, and oxidation rate were based on only the dye range set-up parameters that were statistically
significant.

220

4.3.4.a Functional Relationship of Effective Fiber Diffusion Coefficient
A statistical analysis of all dye range set-up parameters and the effect on effective fiber
diffusion coefficient was conducted to develop the functional relationship. It was determined the
dye bath concentration and pH at each dip was statistically significant. This was not surprising and
in fact desirable. Likewise, no significant effect was contributed by dye range speed, dwell time,
dwell length, or yarn count. As shown in table 4-11, the adjusted R
2
value was 0.68 for the
relationship between individual fiber diffusion coefficients and the calculated values from the
model. While this is not a perfect fit the F ratio of 100.5 and P value much less than 0.0001 does
support a statistically significant correlation. The influence and significance of dye bath
concentration and pH at each dip was re-enforced by evaluating the parameter estimates and effect
tests of each. Table 4-11 shows the P value for the dip number, dye bath concentration and pH was
much less than 0.0001.
221


Table 4-11: ANOVA analysis results for fiber diffusion coefficient.



Graphically, the relationship between calculated fiber diffusion and the individual points is
shown in figure 4-36. The wide variation at higher values contributed to the relatively poor
correlation. However, a large cluster of relatively similar values existed at lower values. This
grouping caused the correlation to improve.
222


Figure 4-36: Comparison of model predicted and actual fiber diffusion coefficient.


The statistical analysis also produced the working equation for fiber diffusion coefficient.
Equation 4-34 allows the fiber diffusion coefficient to be calculated based on the dye bath
concentration, pH, and specific dip.

]
= exp (27.S48u + ()

1: u.u
2: u.S9uS
S: u.2868
4: u.uS78S
S: u.918u
6: 1.u88u
7: u.9494

+ u.77664 [
gm
It
+ u.4uS16 )
Equation 4-34: Dye Theory model effective fiber diffusion equation.

The prediction profile was produced and presented in figure 4-37. In the predication profile
the calculated value of fiber diffusion is shown as each dye range parameter varies with the 95%
confidence intervals shown in dotted blue lines. The general trend was increasing fiber diffusion as
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the dye bath pH was increased. This relationship supports the concept of increased dye affinity at
higher pH values. The effect of increased dye bath concentration was not completely unexpected as
many substances diffusion rate is concentration dependent. Under these conditions, faster diffusion
occurred at higher dye bath concentrations.
The fiber diffusion coefficient was effectively constant for dip one and two. Clearly, as the
yarns process through increasing numbers of dye dips, the fiber diffusion coefficient increased.
After dip two, the effective fiber diffusion coefficient increased from greater affinity of dye for the
fiber surface or actual diffusion into the fiber interior. This effect was also seen in the general trend
analysis and the empirical model discussion sections. This effect results in the yarn not only getting
darker due to more indigo on the outside surface with increasing dips but in fact gets darker than
simply multiplying the first dip times 2, 3, or say 6. Etters has already discussed increasing fiber
diffusion as the number of dips increased could be related to ionic charging of the cotton fiber by
excess sodium hydroxide thus increasing the affinity. The ionization after each dip causes the dye to
be more attracted to the fiber in the subsequent dip.


Figure 4-37: Effective fiber diffusion functional relationship to dye range set-up conditions.


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1234567123
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2
(g/l)
Effective Fiber Diffusion Coefficient Prediction Profile for Dye Range Set-up
224

4.3.4.b Functional Relationship of Yarn Diffusion Coefficient
The yarn diffusion coefficient was evaluated against all dye range set-up values. The dye
bath concentration, pH, and dwell time at each dip was determined to have the greatest statistical
effect. Once again this was not surprising. Concentration and pH effect on diffusional coefficients
was expected. As shown in table 4-12 the adjusted R
2
value was 0.72 for the relationship between
individual yarn diffusion coefficients and the calculated values from the model. While this was not a
perfect fit the F ratio of 106.6 does support a statistically significant correlation. The influence and
significance of dye bath concentration, pH, and dwell time at each dip was re-enforced by evaluating
the parameter estimates and effect tests of each. Table 4-12 shows the P value for the dip number,
dye bath concentration, pH, and dwell time was much less than 0.0001. A strong correlation
coefficient, reasonable F ratio for the model, and extremely low P values indicated the model was
more likely to cause the variation in yarn diffusion coefficient values than happenstance.
225

Table 4-12: ANOVA analysis results for yarn diffusion coefficient.


Using the parameter estimates from table 4-12, the functional relationship between yarn
diffusion coefficient and dye range set-up parameters was determined. The specific mathematical
equation is given as equation 4-35 and the distribution of actual versus calculated yarn diffusion
coefficients is shown in figure 4-39. Like the fiber diffusion coefficient distribution, the separation
between the model and actual values becomes greater at higher values. Similarly, the large cluster
of values at lower actual yarn diffusion coefficients influenced the overall model correlation.
226



Figure 4-38: Comparison of model predicted and actual yarn diffusion coefficient.

= exp (17.S7uu + ()

1: u.u
2: u.uS16
S: u.4S49
4: 1.uS27
S: 1.S927
6: 1.48Su
7: 1.4SS8

u.SuSS [
gm
It
+ u.S889
u.u7S67 )
Equation 4-35: Dye theory model prediction equation of effective yarn diffusion coefficient.

The prediction profile was created and presented in figure 4-39. As the number of dips
increased the yarn diffusion coefficient decreased. This could be due to increasing amounts of
residual chemicals (oxidized dye, sodium hydroxide, and/or gluber salt) from the previous dip
impeding the path of the dye bath stream. Strangely, as the dye bath concentration increased the
yarn diffusion decreased. This is opposite the traditional behavior for concentration dependent
diffusion. However, taken in context with residual chemicals impeding the path, this relationship
0
0.000001
0.000002
0.000003
0.000004
0.000005
0.000006
0.000007
0.000008
0.000009
0.00001
0.000011
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0 0.000001 0.000003 0.000005 0.000007 0.000009 0.000011
Predicted Yarn Diffusion Coefficient
Comparison of Actual Yarn Diffusion by Dye Theory Model
227

becomes understandable. As the dye bath concentration increases, the amount of residual
chemicals from the previous dip increases. Thus the dye stream path was further hindered resulting
in a slower diffusion process at greater numbers of dip.


Figure 4-39: Effective yarn diffusion functional relationship to dye range set-up conditions.

The effect of pH on yarn diffusion coefficient is also shown in figure 4-39. As the pH was
increased the diffusion coefficient also increased. A higher diffusion value means a greater dye bath
concentration was penetrating into the structure of the yarn. This resulted in more dye being
available for fiber transfer in the yarn interior. This coupled with a higher fiber diffusion coefficient
at higher pH values as demonstrated in section 4.3.4.a produced a more penetrated (or less ring
dyed) yarn cross section. This supports the concept of ring dyed yarns as a function of pH previously
discussed by numerous authors and summarized in chapter 1.
The effect of dwell time on yarn diffusion coefficient must be discussed. As the dwell time
was increased, the yarn diffusion coefficient actually decreased. At first glance this seemed counter-
intuitive. However, one must realize to increase the dwell time on a fixed dwell length dye range,
the speed must be reduced. As the speed was reduced the turbulent forces acting to push the dye
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1
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2
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1
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2
0
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2
(g/l)
Effective Yarn Diffusion Coefficient Prediction Profile for Dye Range Set-up Conditions
228

bath into the yarn structure were reduced. Whether this was an actual phenomenon or the result of
assuming constant dye bath concentration at the outside node surface, it was reasonable for this
effect to be present.
4.3.4.c Functional Relationship of Wet Pick-up
In contrast to the fiber and yarn diffusion coefficient analysis, the wet pick-up relationship
to individual dye range set-up parameters was not very strong. This was primarily due to the fact
that wet pick-up was dye range specific and highly dependent on chemical exchange. The calculated
wet pick-up numbers were indirectly measurements of the individual dye range under certain
dyeing conditions. Also, it was influenced by the diffusion of dye into the yarn and fiber structure
since this was a wet on wet application. Technically speaking the pick-up would be 0% if the yarns
were squeezed at the same pressure by the entrance and exit nip running through water only dye
bath. Any pick-up on the yarn in actual dyeing process was the result of dye and other chemicals
replacing the water in the yarn. With this in mind, the nip pressure, dye bath concentration, and
yarn diffusion coefficient were expected to have the greatest impact on wet pick-up. After detailed
statistical analysis these dye range set-up parameters were the only significant influences. The best
possible model resulted in an R
2
correlation coefficient of 0.26 and F ratio of 43.0 as shown in table
4-13. While this certainly wasn't a great model fit to the data, the significance of dye bath
concentration and yarn diffusion coefficients were deemed statistically significant due to P values
much less than 0.0001 and 0.0061 for nip pressure as shown in the effect test section of table 4-13.
The lack of correlation was certainly due the error or variation surrounding each wet pick-up value.

229

Table 4-13: ANOVA analysis for wet pick-up coefficient.



The poor correlation was further demonstrated by plotting the actual versus calculated wet
pick-up values as shown in figure 4-40. While a general trend following the 1 to 1 center line was
apparent, much variation occurred off line. The overall average wet pick-up was 4.1% and no
significant difference was determined between the two dye ranges in the investigation. Using the
parameter estimates from table 4-13, the analysis produced the following mathematical expression
for the wet pick-up coefficient as a function of dye range set-up parameters, equation 4-36. This
researcher proposed the unexplained variation in wet pick-up could be due to errors in the yarn dye
measurement properties such as %COWY. These errors would certainly influence the wet pick-up
values as well as other coefficients. Hopefully, the error in calculated coefficients would later off set
each other and the final model would still produce reliable %COWY, %IOWY, and Integ values
compared to measured performance.
230


Figure 4-40: Comparison of model predicted and actual wet pick-up coefficient.

= 7.9S9S
-2
1.S981
-4
1.11S4
-2
[
gm
It

S96u.69
Pcdctcd

Equation 4-36: Dye theory model prediction equation of wet pick-up.

Figure 4-41 demonstrates the predicted wet pick-up as a function of dye range set-up
parameters. As the nip pressure was increased the resulting wet pick-up decreased. This is typical
of most textile processes involving squeeze rolls. As the dye bath concentration or yarn diffusion
coefficient increased, the wet pick-up decreased. As discussed during the definition of %COWY
calculation, wet pick-up was expected to vary as the dye bath concentration varied. One would
expect the resulting %COWY to increase if exposed to greater concentration or if the diffusion of
chemicals into the yarn structure increased. However, the wet pick-up decreased in order to
maintain the correct %COWY value as the dye concentration increased. In any case, the relationship
of dye bath concentration and yarn diffusion coefficient was determined to be significant.
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Figure 4-41: Dye theory model wet pick-up functional relationship to dye range set-up conditions.

4.3.4.d Functional Relationship of Wash Reduction
The wash reduction or amount of chemical on weight of yarn from a previous dip removed
during a subsequent dip was determined to be related to the dye bath concentration, speed, dwell
time, and dye bath reduction potential. The correlation between actual and calculated was 0.45
with an F ratio of 60.0 as displayed in table 4-14. While the correlation wasn't great it was deemed
significant due to a P value much less than 0.0001. The overall average wash reduction value was
13.1%. Evaluation of the individual parameter effects is shown in table 4-14. Speed had a P value of
0.0015 while all other parameters were much less than 0.0001. This indicated all were statistically
significant.
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0
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(g/l)
Wet Pick-up Coefficient Prediction Profile for Dye Range Set-up Conditions
232

Table 4-14: ANOVA analysis results for wash reduction coefficient


The plot of actual versus calculated wash reduction coefficient is shown in figure 4-42. The
values vary in order of magnitude from 0.01 to 0.3 with a mean value of 0.13. The overall trend
followed a 1 to 1 relationship. However, there are obvious issues with the correlation. When the
model predicted the wash reduction value to be 0.15, the actual value varied from 0.02 to 0.26. As
with wet pick-up this variation could be explained by error in measurements of yarn properties
which resulted in other dye coefficients skewing to match the results. It is hoped the averages will
balance out in the final model. The parameter estimates from table 4-14 produced the following
mathematical expression for the wash reduction coefficient as a function of dye range set-up
parameters, equation 4-37.
233


Figure 4-42: Comparison of model predicted and actual wash reduction.

= u.1u4S +4.S698
-3
1.7414
-2
+ 6.4822
-4

6.8279
-2
(
g
I
)
Equation 4-37: Dye theory model prediction equation of wash reduction.

The effect of each parameter on wash reduction is shown in figure 4-43. As the speed
increased the wash reduction increased. This seems straight forward as greater speed should
facilitate more chemical removal. As the dwell time increased the wash reduction decreased. As
with yarn diffusion this seemed counter-intuitive but on fixed length dye ranges an increase in time
results from a decrease in speed. As the dye box reduction potential increased the wash reduction
also increased. This was possibly due to actual reduction of the oxidized dye thereby increasing the
mobility of the dye molecule. In the last column of figure 4-43, as dye bath concentration increased
the wash reduction decreased. This probably has more to do with an increase in chemicals to be
removed and less with the influence of the concentration on washing. However, dye bath
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concentration effect on wash reduction maybe related to the definition of %COWY as previously
discussed.


Figure 4-43: Dye theory model wash reduction functional relationship to dye range set-up conditions.

4.3.4.e Functional Relationship of Oxidation Rate
The last dye theory coefficient evaluated was oxidation rate. It was determined the speed,
oxidation time, and reduction potential at each dip were statistically significant. The other dye
parameters did not have a significant impact. The best correlation established was 0.51 with an F
ratio of 45.3 and P value much less than 0.0001 as shown in table 4-15. The parameter estimates
and effect tests are also displayed in table 4-15. While only dip had a P value much less than 0.0001,
the other parameters were statistically significant since P values were below 0.0272. While the
model fit did not possess an extremely strong correlation to the data, it was deemed the best model
possible.

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0
0123
(g/l)
Wash Reduction Coefficient Prediction Profile for Dye Range Set-up Conditions
235


Table 4-15: ANOVA analysis results for oxidation rate coefficient.


The plot of actual versus calculated oxidation rate is presented in figure 4-44. The values
ranged from 0.01 to 0.2 grams of reduced indigo that were oxidized per gram of oxygen per second.
Of course this wasn't necessarily the true or absolute oxidation rate; it was relative to other dye
range set-up conditions in this observational study under the current dye theory model. As the
actual oxidation rate increased in most cases the predicted values did not increase as rapidly.
However, the correlation at lower oxidation rates appears to be quite well. The analysis produced
the following mathematical expression for the oxidation rate coefficient as a function of dye range
set-up parameters, equation 4-38.
236


Figure 4-44: Comparison of model predicted and actual oxidation rate.

= exp (1u.46S4 + ()

1: u.u
2: u.4686
S: u.69S2
4: u.9826
S: u.688S
6: 1.S462
7: 1.S17u

+ u.126S +
6.8SSu
-2
1.u179
-3
)
Equation 4-38: Dye theory model prediction equation of oxidation rate.

The prediction profile which relates the calculated oxidation rate to the input variables is
shown in figure 4-45. As the dip number increased the oxidation rate decreased. This was probably
related to the increase of residual chemicals on weight of yarn as the number of dips increased. As
the speed increased the oxidation rate increased. This was probably due to increase air circulation
into and through the yarn structure thereby increasing the amount of available oxygen. Likewise, as
the oxidation time increased due to either slower speeds or increased thread-up length, the rate
increased. Interestingly as the reduction potential increased, the oxidation rate decreased. This of
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course makes sense. The interestingly part was that reduction potential wasn't used in any dye
theory model calculation and yet the effect surfaced here.


Figure 4-45: Dye theory model oxidation rate functional relationship to dye range set-up conditions.

4.3.5 Algorithm to Calculate the %COWY, %IOWY, and Integ Shade
The final program enters in the appropriate dye range set-up conditions: yarn count, dip
number, speed, dyeing dwell time, pH, dye bath concentration, nip pressure, and oxidation dwell
time. Then the corresponding values for indigo dyeing coefficients: fiber diffusion, yarn diffusion,
wet pick-up, wash reduction, and oxidation rate were calculated. The following logic was used to
calculate the %IOWY, %COWY, and Integ shade value. The actual computer program is referenced
in appendix section A-4-3b.
Enter dye range parameters
Calculate dyeing coefficients and initialize all parameters
Start time loop for the dip process equal to total dwell time
Calculations:
Dye bath concentration within the yarn
Diffusion of dye into the fiber
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0
Oxidation Rate Coefficient Prediction Profile for Dye Range Set-up Conditions
238

Close dip time loop
Adjust boundary layers due to wet pick-up and removal of previous oxidized dye
Start oxidation time loop equal to total oxidation time
Calculations:
Oxygen concentration within the yarn
Adjust reduced indigo available in yarn
1. Dye in boundary layer by amount of dye oxidized
2. Dye diffused into fiber
3. If no reduced boundary exists start to oxidize dye in the fiber
Increase oxidized boundary layer
Close oxidation time loop
Calculate total %IOWY by summing all %IOWY at each node
Calculate total %COWY by adding total %IOWY and summing oxidized boundary layer at each node
Convert %IOWY at the surface of the yarn into Integ shade value
Repeat for each additional dip


239

5 Empirical and Dye theory model simulation and validation

The final step in traditional experimental design is model simulation and validation. Under
this observational study, simulation was conducted by comparing calculated and measured %COWY,
%IOWY, and Integ shade values, from sources of data independent from the respective data sets
used to create the models. First the models were compared to a third dye range located in Canada.
Again, none of the Canadian data was used in the creation of the empirical or dye theory models.
Second, the empirical and dye theory models were compared to actual production yarns. This will
validate the effectiveness of model results to actually predict production dye properties.
5.1 Simulation of Empirical and Dye Theory models on Third Independent Dye Range
Yarn skeins were processed on a third indigo long chain rope dye range following the same
methods and procedures previously discussed in Chapter 3. Due to curtailment of this production
facility all indigo shades were transferred to US operations so customers would have a seamless
transition. To make the transition as smooth as possible, US technicians with US laboratory
equipment went to the Canadian operation. By having the same person and the same equipment
perform indigo dye box testing, conditions such as grams of indigo per liter and reduction potential,
as much testing error was removed as possible. This effort resulted in five different dye range set-
ups with yarn skeins to be compared to empirical and dye theory models. The specific dye range
conditions for each dye range set-up are listed in table 5-1. The complete set of observational data
is listed in appendix section A-5-1 for detailed review.

Table 5-1: Canadian dye range set-up conditions used for simulation
Reference
Shade #
# of
Dips
Speed
(m/min)
Dwell
Time (sec)
Oxidation
Time (sec)
Dye Bath
(g/l)
Dye
pH
Dye
mV
Dye NaOH
(g/l)
443 1 to 6 29 20.1 73.6 1.26 12.2 813 2.58
418 1 to 6 32 18.2 66.7 1.66 11.8 814 3.29
402 1 to 6 28 20.8 76.3 1.99 12.2 841 3.53
471 1 to 6 32 18.2 66.7 2.09 12.1 838 3.42
401 1 to 6 28 20.8 76.3 2.21 12.1 820 3.72


240

5.1.1 Actual Versus Predicted %COWY
The individual dye range parameters were used to calculate %COWY from the empirical dye
model. The empirical model performed beautifully with a great correlation of R
2
= 0.91 and deemed
highly significant with F ratio of 651 as shown in table 5-2. The predicted versus actual graph, figure
5-1, does however show a slight issue. The slope of curve fit wasnt 1.0. With a slope of 1.014, the
model over predicts the true %COWY by 1.4%. This isnt a huge difference but it was real.


Figure 5-1: Empirical model predicted %COWY compared to actual measured values.


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Table 5-2: ANOVA analysis results of empirical model to actual measured %COWY



Following the same analysis method the dye theory model %COWY was compared to actual
measured values. The results weren't as well correlated as the empirical model. The resulting R
2
correlation coefficient is 0.74 with an F ratio of 179 as shown in table 5-3. Furthermore, the slope
was 0.76 with an intercept of 0.72%. This indicates the dye theory model over predicts the true
%COWY at high values. This is graphically represented in figure 5-2 where a 10% predicted %COWY
corresponds to an 8% actual value.
242



Figure 5-2: Dye theory model predicted %COWY compared to actual measured values.

Table 5-3: ANOVA analysis results of dye theory model to actual measured %COWY


The empirical model obviously out performs the dye theory model in predicting the
%COWY. Not only does the empirical model predict the true value better but the error associated
with the prediction was about half that of the dye theory model. The flaw in the dye theory model
%
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was traced back to the basic assumptions used to generate the solution algorithm. By assuming
total chemical on weight of yarn was directly related to amount of indigo on weight yarn, the dye
theory model doesn't accurately predict the true %COWY. This wasn't a good start for the dye
theory model but there are many more comparisons to evaluate.
5.1.2 Actual Versus Predicted %IOWY
At the end of the day the most important property any model should predict well is %IOWY
and the resulting shade. The comparison of calculated %IOWY to actual measured %IOWY is
presented in figure 5-3 and table 5-4 for the empirical model. The empirical model matched up with
the actual values very well as indicated by the R
2
of 0.94. Furthermore the model results were
deemed statistically significant following the overall model F ratio of 1077. However, like %COWY,
the predicted %IOWY over estimated the actual %IOWY by 1.2% since the slope is 1.012.


Figure 5-3: Empirical model predicted %IOWY compared to actual measured values.

%
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Table 5-4: ANOVA analysis results of empirical model to actual measured %IOWY



After a rough start in predicting %COWY, hopefully the dye model theory will redeem itself
in predicting the %IOWY. In fact, the dye theory model actually has a slightly better correlation
coefficient than the empirical model at 0.95 and an F ratio of 1112, see table 5-5. Both of these
indicate extremely good fit to the measured values. However, the slope of the fit is 0.94 which
indicates approximately 6% over estimation. While this was an extremely accurate data fit, the
overall performance wasn't as good as the empirical model but certainly redeemed itself from the
misstep on %COWY predication.
245



Figure 5-4: Dye theory model predicted %IOWY compared to actual measured values.

Table 5-5: ANOVA analysis results of dye theory model to actual measured %IOWY





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5.1.3 Actual Versus Predicted Integ Shade Value
The Integ shade values for the empirical model prediction versus actual are presented in
figure 5-5 and table 5-6. The overall correlation coefficient for the fit was R
2
of 0.97 with an F ratio
of 2108. Both of these calculations indicate extremely strong empirical model fit to the actual
measured values. The slope of the model fit was 1.084 which means the model underestimates the
actual Integ shade values by 8.4%.


Figure 5-5: Empirical model predicted Integ compared to actual measured values.


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Table 5-6: ANOVA analysis results of empirical model to actual measured Integ





The dye theory model fit to actual measured Integ shade values is shown in figure 5-6. The
overall model fit correlation coefficient was R
2
of 0.97 with an F ratio of 1823 as shown in table 5-7.
These values indicate an extremely strong correlation to the actual values and perform as well as
the empirical model. Unfortunately, the slope of the fit is 1.097 with an intercept of -5.8. These are
the result of the dye theory model over predicting the Integ shade at low values and slightly under
predicting at high values. However, the general trend is for comparable Integ prediction
performance to the empirical model.
248


Figure 5-6: Dye theory model predicted Integ compared to actual measured values.

Table 5-7: ANOVA analysis results of dye theory model to actual measured Integ







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5.1.4 Actual Versus Predicted Penetration Level
By converting the measured Integ shade values into %IOWY on the surface of the yarn, the
actual penetration level was calculated. Comparison of the empirical model predicted penetration
level to actual penetration levels are presented in figure 5-7 and table 5-8. The overall model
correlation coefficient was R
2
of 0.63 which isnt extremely strong but deemed statistically
significant by the F ratio of 109 and P-value < 0.0001. The reason for poor correlation is due to the
great variation as evident by the wider range of the confidence intervals in figure 5-7. The mean
penetration level is 0.38 units. The slope of the data fit is 0.97 which is very close to a 1 to 1 ratio as
visibly evident. However, the intercept is -0.05 penetration units which is 1/8 of the mean value.
This causes the empirical model to over predict the level of penetration in the yarns. In other words
the empirical model predicts the yarns are less ring dyed or more penetrated than what actually
occurred.


Figure 5-7: Empirical model predicted penetration level compared to actual measured values.

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Table 5-8: ANOVA analysis results of empirical model to actual measured penetration level



The dye theory model has a similar issue with the predicted penetration level on the
Canadian dye range. Comparison of the dye theory model predicted penetration level to actual
values were summarized in the table 5-9 and figure 5-8. The overall model fit was slightly better
than the empirical model as indicated by R
2
correlation coefficient of 0.67 and F ratio of 129.
However, the slope wasn't close 1 to 1. A slope of 0.81 coupled with an intercept of 0.04 indicates
the dye theory model also over estimates the level of penetration.
251



Figure 5-8: Dye theory model predicted penetration level compared to actual measured values.

Table 5-9: ANOVA analysis results of dye theory model to actual measured penetration level



0.2
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0.4
0.5
0.6
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0.2 0.25 0.3 0.35 0.4 0.45 0.5 0.55 0.6
Dye Theory Model Penetration Level Predicted
Linear Fit
Dye Theory Model Compared to Canadian Dye Range Actual Penetration Level
252

5.1.5 Summary of Dye Theory Model Compared with Empirical Model
It was expected that the empirical model would provide the best possible prediction of
%COWY, %IOWY, Integ, and penetration level. This was the purpose of the calculation, to provide a
baseline for comparing the dye theory model performance. Taken in this context, the dye theory
model preformed reasonably well. While the dye theory model did not perform well in predicting
the %COWY, this property in fact has little to do with actual dyeing of yarns with indigo dye as all
residual chemicals are washed off during the final wash stage in the dye range. The most important
properties are %IOWY, Integ shade, and the resulting penetration level.
As shown, the dye theory model preformed very well compared to the empirical model in
predicting the %IOWY and Integ shade. The difference between the two models is approximately
5% in %IOWY prediction while the Integ shade predictions were almost identical. The relatively poor
performance of the dye theory model in penetration level prediction compared to empirical model
is disappointing but understandable. The empirical model directly calculates the penetration level
while the dye theory model penetration level was calculated based on predicted %IOWY and
converted Integ shade values. The difference between direct and indirect penetration level
calculations can certainly explain the difference in performance of the two models. This discrepancy
warrants further investigation.
Indigo build profiles were constructed for each Canadian dye range set-up for detailed
comparison of measured %IOWY and Integ shade versus the predicted values from both models.
Figure 5-9 shows the build profile of Integ shade as a function of %IOWY for the measured
observational skeins, empirical model, and dye theory model. Each individual point represents the
%IOWY and Integ shade after a particular dip of indigo. Clearly on this dye range set-up, both
models over predict the amount of %IOWY. The empirical model predicts the Integ shade values
fairly well while the dye theory model over predicts the Integ.
The really interesting observation is the location of the prediction profiles relative to the
observational skein data. Curves falling below the measured build profile indicate more penetration
or less ring dyeing. While any curves above the measured profile would indicate less penetration or
more ring dyeing. On this particular dye range set-up, the dye theory model prediction build curve

is actu
penet

Figure
concen


simila
dye se
under
profil
penet
and In
the In
same

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tration level t
5-9: Indigo build
ntration and 12.
By constru
ar relationship
et-up and figu
r predict the %
e better matc
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nteg values w
nteg. In this d
degree.
o the observa
than the emp
d profile for Can
2 pH.
ucting similar
p developed.
ure 5-11 from
%IOWY and t
ches the obse
measured. In
while the dye t
dye range set-
ational curve.
pirical model.
nadian dye rang
build profile
Figure 5-10
m 32 m/min, 2
the resulting I
ervational me
n figure 5-11,
theory mode
-up, both mo
This indicate

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curves for th
was construc
2.09 g/l, and 1
Integ shade.
easured profil
the empirica
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3 shade with 29
e other Cana
cted from 32 m
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However, the
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m/min, 1.26 g/
dian dye rang
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igure 5-10 bo
e dye theory
gh both mode
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he %IOWY bu
ration level by
better predict
l dye bath
ge set-ups a
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models build
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mates the %I
t underestim
y basically the
253
s the

pH
ghtly
d
ore
OWY
mates
e

Figure
concen

Figure
concen

5-10: Indigo bu
ntration and 11.
5-11: Indigo bu
ntration and 12.
ild profile for Ca
8 pH.
ild profile for Ca
1 pH.
anadian dye ran
anadian dye ran
nge set-up on 41
nge set-up on 47
18 shade with 32
71 shade with 32
2 m/min, 1.66 g
2 m/min, 2.09 g
g/l dye bath
g/l dye bath
254


255

The superior performance of empirical model prediction of penetration level compared to
dye theory model results from the model's ability to calculate the penetration level independent of
the %IOWY and Integ shade values. The dye theory model penetration level is indirectly converted
from the predicted %IOWY and Integ values. This ability gives the empirical model a false sense of
conformity. The analysis of empirical model penetration level prediction is repeated but this time
the penetration level is calculated from the predicted %IOWY and Integ values. Figure 5-12 and
table 5-10 compares the empirical model predicted indirect penetration level to the actual
penetration level calculated from the measured %IOWY and Integ. Now the correlation coefficient
is R
2
of 0.59 with an F ratio of 92.7. This is actually a slightly inferior fit to the data than the dye
theory model. More importantly, with a slope of 0.70 and intercept of 0.066 the shape of the fit
was worse than the dye theory model. Recall dye theory had a slope of 0.80 and intercept of 0.04.


Figure 5-12: Empirical model predicted indirect penetration level compared to actual measured values.

0.2
0.3
0.4
0.5
0.6
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Empirical Model Indirect
Penetration Level Predicted
Linear Fit
Empirical Model Indirect Penetration Level Comparison on Canadian Dye Range
256

Table 5-10: ANOVA analysis results of empirical model indirect penetration level to actual measured penetration level



Considering the overall performance of the dye theory model compared to empirical model,
an acceptable level of performance was obtained. The dye theory model predicts the %IOWY and
Integ shade as well as the empirical model. While the empirical model direct penetration level does
perform better than the dye theory model, the calculated indirect penetration level of the empirical
model was actually worse than the dye theory model.


5.2 Simulation of Empirical and Dye Theory Models to Actual Production Yarn

The real measure of any indigo dye model is how well it predicts %IOWY and Integ shade
from actual production dyed yarns. To perform this comparison, actual production dyed yarns were
measured for %IOWY and Integ shade after processing through production scale indigo chain rope
dye ranges. Six production shades were selected and the particular dye range set-up conditions are
summarized in table 5-11. Five of the shades were pure indigo so %IOWY and Integ values were
measured. The 1169 shade was a black sulfur top so only the %IOWY was applicable. Three samples
were collected from each of the two prime USA production ranges to provide variation in dwell
length.
257


Table 5-11: Production Yarn Dye Range Set-up Conditions
Reference
Shade #
# of
Dips
Speed
(m/min)
Dwell
Time (sec)
Oxidation
Time (sec)
Dye Bath
(g/l)
Dye
pH
Dye
mV
Dwell
Length, m
1134 1 to 7 31.1 16.7 69.5 2.994 11.98 789 8.63
1157 1 to 6 32.9 15.9 65.7 2.497 12.41 847 8.63
1169 1 to 7 31.1 16.7 69.5 2.34 11.6 888 8.63
4223 1 to 2 32.9 20.7 67.5 2.07 12.49 907 11.37
1134 1 to 6 29.3 23.5 75.9 3.497 11.62 897 11.37
1110 1 to 2 32.9 20.7 69.5 0.733 12.23 813 11.37

The resulting %IOWY and Integ values are detailed in table 5-12. The actual %IOWY and
Integ values correspond to the actual production yarn count were measured. Columns five and six
list the results predicted by the empirical model. Columns seven and eight list the predicted results
from the dye theory model.

Table 5-12: Measured, Empirical Model, and Dye Theory Model %IOWY and Integ values
Reference
Shade #
Production
Yarn Count
Actual
%IOWY
Actual
Integ
Empirical
%IOWY
Empirical
Integ
Dye Theory
%IOWY
Dye Theory
Integ
1134 7.75 3.01% 85.4 3.21% 112.7 3.02% 92.2
1157 6.55 1.89% 77.3 2.34% 91.3 1.88% 76.2
1169 9.75 2.56% N/A 2.79% N/A 2.55% N/A
4223 6.3 0.55% 33 0.64% 32.37 0.55% 33.2
1134 7.75 3.39% 101.1 3.28% 128.7 3.39% 107.7
1110 12 0.30% 12.1 0.33% 15.53 0.31% 14.2

One will notice the dye theory %IOWY in column seven of table 5-12 matches the measured
actual %IOWY from column three. This was an intentional result due to adjustments in the yarn
porosity value during the prediction model calculation phase. Unlike the empirical model, the dye
theory model was porosity dependent. The original value of 0.65 was selected as discussed in
section 4.3.1.a since observational yarn skeins were in non-tension state. But what value should be
used for yarns under tension when submerged in a dye bath? Instead of guessing at a value, this
258

researched decided to find the porosity value that would match the target %IOWY. This would allow
the predicted Integ values to be calculated and the final porosity value would be analyzed. Given
this assumption the dye theory model predicted %IOWY will match the production yarn actual
value.
The results of the empirical model predicted %IOWY are presented in figure 5-13 and table
5-13. The model predicts the %IOWY extremely well as the correlation coefficient of 0.97 and F
ratio of 180 indicates. This is visually evident in the graph of predicted versus actual with all points
falling extremely close to the center line and well within the 95% confidence intervals demarcated
by the dotted lines. Furthermore, the slope of 0.98 and intercept of -0.10% confirms the empirical
model performed exceptional well at predicting the %IOWY on actual production scale dyed yarns.


Figure 5-13: Empirical model predicted %IOWY compared to actual measured values from production yarns.

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Table 5-13: ANOVA analysis results of empirical model to actual measured production yarn %IOWY


As previously discussed the dye theory model %IOWY value was calculated by adjusting the
porosity value used in the model. These results are listed in table 5-14. To match the actual %IOWY
from production yarns the porosity value ranged from 0.92 to 0.995. Two interesting points to
make: the porosity values weren't constant and the porosity values were much higher than
expected. One possible cause for porosity variation will be presented shortly. For the higher values,
this could be explained by the high tension of the yarns in a wet state during the dyeing process or
the need for lower porosity value than 0.65 during the model construction phase. Either way the
porosity values were below the theoretical limit of 1.0.

Table 5-14: Calculated porosity value to fit Dye theory model %IOWY to production yarn results
Reference
Shade #
Production
Yarn Count
Actual
%IOWY
Actual
Integ
Dye Theory
%IOWY
Dye Theory
Integ
Porosity
Value
1134 7.75 3.01% 85.4 3.02% 92.2 0.964
1157 6.55 1.89% 77.3 1.88% 76.2 0.98
1169 9.75 2.56% N/A 2.55% N/A 0.968
4223 6.3 0.55% 33 0.55% 33.2 0.9925
1134 7.75 3.39% 101.1 3.39% 107.7 0.92
1110 12 0.30% 12.1 0.31% 14.2 0.995

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For completeness, the resulting model fit of dye theory model %IOWY to actual measured
production yarns is presented in figure 5-14 and table 5-15. Of course there were no surprises.
Basically there was a perfect model fit to the data.


Figure 5-14: Dye theory model predicted %IOWY compared to actual measured values from production yarns.

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Table 5-15: ANOVA analysis results of dye theory model to actual measured production yarn %IOWY


Next the empirical model predicted Integ values were compared to the measured values
from production yarns. The ANOVA analysis results are presented in table 5-16 and than graphically
displayed in figure 5-15. The empirical model had an extremely strong model fit to the measured
data as indicated by a correlation coefficient of 0.98 and F ratio of 254. Graphically, the model fit
demonstrates the strong correlation with most points falling near the center line and well within the
95% confidence intervals.
Unfortunately, the parameter estimates tell a different story. The slope of the fit is 0.75
with an intercept of 4.7 Integ units. As a result, the empirical model performs reasonably well at
predicting Integ values at lower depths of shade. But as the actual depth increases (higher Integ),
the predicted values over estimate the real values. As a result, at 85.4 measured Integ the empirical
model predicts 112.7 Integ and at 101.1 measured units the model predicts 128.7 units. These two
points average to 30% over estimate of Integ at darker shades by the empirical model.
262



Figure 5-15: Empirical model predicted Integ compared to actual measured values from production yarns.

Table 5-16: ANOVA analysis results of empirical model to actual measured production yarn Integ


In contrast, the dye theory model performed much better at predicting the Integ shade of
production dyed yarns. The model fit analysis results are presented in table 5-17 and figure 5-16.
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The correlation coefficient is 0.99 with an F ratio of 498. This indicated an extremely strong
correlation that was statistically significant. Even better, the slope of the fit was 0.94 and intercept
was 0.64. As a result, the dye theory model predicted Integ virtually falls on the 1 to 1 curve to
actual Integ values and the 95% confidence intervals are extremely tight with the root mean square
error of the fit at 3.36 compared to 4.69 for the empirical model.


Figure 5-16: Dye theory model predicted Integ compared to actual measured values from production yarns.

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Table 5-17: ANOVA analysis results of dye theory model to actual measured production yarn Integ


The superior performance of the dye theory model compared to empirical model resulted
from the ability to compensate for yarn porosity. While this may seem like an unfair advantage for
the dye theory model, it illustrates the importance of building models based on theory instead of
pure statistical analysis. Simply by adjusting the space between fibers in the yarn cross section, the
dye theory model could accurately predict the %IOWY and Integ shade while maintaining the
established relationships of the underlying dye coefficients such as fiber and yarn diffusion.
So what is the actual production yarn porosity value? After a complete ANOVA statistical
analysis only one parameter showed correlation to changes in required porosity value: dye range
speed. Regardless of yarn count, dwell length, dye concentration, and/or pH; only the dye range
speed correlated well with the changes in required porosity value. The ANOVA analysis results are
shown in table 5-18 and graphically displayed in figure 5-17. The correlation coefficient R
2
was 0.90
and F ratio was 47.4. While this isn't the strongest correlation it was deemed to be statistically
significant due to P values of 0.0023.

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Figure 5-17: Functional relationship between theoretical porosity value and dye range speed.

Table 5-18: ANOVA analysis results of dye theory model calculated porosity value to dye range speed


The relationship between yarn porosity and dye range speed makes sense under the context
of tension. Production yarn under tension will have a high porosity value than observerational
skeins under no tension. Additionally, as the dye range speed was increased, the tension the yarn
was exposed to would increase as well. The higher tension at faster speeds would result in slightly
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higher porosity values as the individual fibers are packed closer together. While care should be
exercised not to base definitive conclusions from 6 data points, the evidence and rational behind the
relationship was compelling.
267

6 Summary of Results, Discussions, and Recommendations

During this endeavor several important learning's have been detailed and this researcher
will present each item with highlights and discussions on key components. Before any observational
data was gathered, a rigorous experimental design was conducted to determine the optimum
method for preparing 100% cotton yarn skeins in the laboratory. The optimum laboratory
procedure involved cooking the yarn skeins at 100 C temperature with 12.7 g/l of 50% sodium
hydroxide for 30 minutes. Following this method ensured the most consistent yarn preparation
from day to day. While this research was conducted on 100% cotton open end spun yarns, similar
methods more than likely applies to knitted or woven substrates. Hopefully, future studies will
repeat the analysis on several substrates so a common preparation method can be established.
Today, most published articles provide a detailed description of the preparation method utilized but
there are too many variations, study to study. Variations in preparation potentially can skew
measured results and absolute values do not translate from one experiment to another. If industry
adopted a common preparation method, research from many experiments could be grouped
together for greater understanding instead of each being treated as a standalone data set.
Following the practice of Etters, laboratory experiments were conducted under equilibrium
sorption conditions. There were two primary reasons for conducting these experiments. Under
equilibrium sorption conditions, a mathematical expression was developed that relates indigo dye
bath concentration to the maximum %IOWY. A relationship was developed that expressed %IOWY
in terms of indigo dye bath concentration at specific dye bath pH levels. It was determined the
profile of pH dependence followed the monophenolate ionic form of the indigo dye molecule as
purposed by Etters and summarized in equation 6-1.

=
1
1+10
9.S-pH
+10
pH-12.

= u.u16492 + u.uuS46S
= u.244296 +u.8161S8
% =
ComponcntB

Equation 6-1: Equations to calculate %IOWY as a function of dye bath concentration and pH under equilibrium sorption
conditions.
268

Second, equilibrium sorption conditions were used to develop a mathematical expression
for %IOWY located at the surface of the yarn to the Integ shade value. The reverse expression was
also developed. With these two equations the approximate %IOWY at the surface from non-
uniformly dyed yarns were calculated based on the measured Integ shade value as summarized in
equation 6-2. This resulted in the ability to quantitatively express the penetration level of non-
uniformly dyed yarns. Combining the two primary conclusions from the equilibrium sorption
experiments provided the base relationships needed to develop a theoretical dye model.

%
su]ucc
= u.u2646 +(9.SS86
-4
) + (1.SS9S
-5
( SS.2u88)
2
) +
(S.9u9
-8
( SS.2u88)
3
) + (2.4244
-9
( SS.2u88)
4
) + (6.4SuS
-11

( SS.2u88)
5
)
Penetiation Level =
%I0w
Measued
%I0w
suIace

Equation 6-2: Expressions to relate penetration level of non-uniformly dyed yarns.

An extensive observational study was conducted on production scale indigo chain rope dye
ranges. During this study various dye range set-up parameters were recorded: yarn count, dip,
speed, dwell length, dwell time, oxidation time, nip pressure, dye bath indigo concentration, dye
bath pH, dye bath reduction potential, and dye bath total alkalinity. After processing each yarn
skein the %COWY, %IOWY, and Integ shade values were measured. The results from the
observational study provided the basis for general trend analysis, empirical dye modeling, and
theoretical dye modeling.
The general trends confirm many previously published conclusions but also indentified
several new relationships never before discussed. Measurement and analysis has never been
conducted on the %COWY after each dip of indigo. At first glance this value may seem trivial since
the property never shows up at the doff end of the indigo dye range. However, the residual
chemicals washed off during the wash section have monetary value. A better understanding of the
dye range set-up parameters that cause %COWY to increased while not improving either the %IOWY
269

or the Integ shade value; may result in reducing variable cost associated with each yard of fabric and
reduce effluent chemicals that require processing before releasing to the environment.
It was determined that finer yarns have a greater %COWY and the relationship is fairly linear
in nature. Likewise, adding more dips of indigo increased the %COWY but the relationship wasn't
linear as each additional dip resulted in a smaller change in %COWY. Increasing the speed from 26
m/min to 33 m/min resulted in an increase in %COWY. At approximately 33 m/min the relationship
peaked and %COWY deceased at higher speeds. Unsurprisingly, increasing the dye bath indigo
concentration resulted in greater %COWY. Last, increasing pH actually decreased the %COWY. It
would appear that operating the indigo dye range with high number of dips, relatively fast speeds,
high pH values, and coarse yarns would reduce the residual %COWY. Of course these changes may
change the %IOWY and Integ shade values on established production shades but when developing a
new production shade with new dye range set-up conditions these trends should be kept in mind.
Many results have been published relating %IOWY to various parameters. Results from the
graphical and ANOVA analysis for %IOWY confirm many of these relationships. Specifically,
increased number of dips and increased dye bath concentration both resulted in increased %IOWY.
However, contrary to previously published results, dye bath pH was determined to be statistically
insignificant. This, of course, could be related to the limited dye bath pH range over which the
observational study was conducted. Also, the graphical analysis indicated an increase in pH caused
an increase in %IOWY. Both of these conclusions contradict conventional wisdom and should be
confirmed with additional production scale indigo dye range analysis preferably at far lower pH
ranges. In addition to previously published dye range set-up parameters this observational study
included many parameters never investigated before. It was determined that finer yarns have
increased %IOWY compared to courser counts. Also, the dye range speed was determined to have a
significant impact and increased speeds resulted in decreased %IOWY.
Besides %IOWY many published experiments discuss the relationship of indigo shade to dye
range set-up conditions. In most cases, the discussions are based on corrected K/S values at a
specific wavelength. In this study, shade was expressed in terms of Integ values which proved to be
continuous and unique, although not linear, over a wide range of %IOWY values. The general trend
and ANOVA analysis results from the observational study confirms all published trends. Specifically,
270

increased %IOWY, increased number of dips, increased dye bath concentration, and decreased dye
bath pH caused the Integ shade values to increase. Additionally, new relationships were uncovered
from the analysis of observational data. Finer yarns produced higher Integ values than courser
counts. Increasing the dye range speed resulted in a decreased Integ value; and increasing the dwell
time caused the Integ values to slightly decrease.
The last response variable evaluated from the observational study was penetration level. As
mentioned before, penetration level was a calculated parameter dependent on the Integ shade,
%IOWY, and derived expression relating Integ and %IOWY from equilibrium sorption. Finer yarn
counts were observed to have higher penetration levels than courser counts. This relationship
mirrors real world experiences since finer yarn counts are more penetrated or less ring dyed than
coarser counts. While finer yarns do have slightly higher Integ values at a given dye range set-up,
the change in %IOWY was much greater at finer counts. As the number of dips of indigo increased
the penetration level decreased. This was due to the additive nature of indigo dyeing with each
additional dip layered on top of the previous dip. As speed was increased, the penetration level was
observed to decrease non-linearly until approximately 33 m/min. Further increases in speed
resulted in slightly higher penetration levels. Although the impact of speed on penetration trends
hasn't been published, this relationship mirrors real world experience. An increase in the dye bath
concentration was determined to cause the penetration level to decrease. Also, increased dye bath
pH was linked to increased penetration levels. This observational study confirmed many pH related
experiments conducted by Etters.
Based on the observational study results an empirical dye model was created to link dye
range set-up conditions with the resulting %COWY, %IOWY, Integ, and penetration level. The
empirical model proved to perform well at predicting the response variables. When compared to a
third independent dye range, the empirical model performed well. The correlation coefficients,
slope, and intercept relating the predicted to actual values are listed in table 6-1.


271

Table 6-1: Empirical model performance review
Response Correlation Coef, R
2
Slope Intercept
%COWY 0.91 1.014 -0.000
%IOWY 0.94 1.012 -0.001
Integ 0.97 1.084 -1.344
Penetration Level 0.59 0.680 0.066

The empirical model was compared to actual production yarns from full scale indigo chain
rope dye equipment. Surprising the %IOWY was predicted with exceptional level of accuracy.
Unfortunately, that level of performance was not carried over to the Integ shade prediction. The
empirical model correlated well with measured values but over predicted the actual value. At the
higher Integ levels the differences between actual and empirical model prediction approached 30%.
As a result, the penetration level wasn't predicted well either.
A second indigo dye model was also created based on general dye and diffusion theory. In
the dye theory model, dye coefficients such as fiber diffusion, yarn diffusion, wet pick-up, wash
reduction, and oxidation rate were calculated based on the dye range set-up conditions. Then, using
these dye coefficients the dye theory model calculated the resulting %COWY, %IOWY, Integ, and
indirectly penetration level.
Just like the empirical model, the dye theory model was compared to a third independent
indigo dye range. The resulting comparison demonstrated poorer correlation in predicting %COWY
then the empirical model. However, the dye theory model performed as well as the empirical
model at predicting the %IOWY and Integ. Further, the dye model actually outperformed the
empirical model at predicting penetration level. The correlation coefficients, slopes, and intercepts
from the dye theory model predicted compared to actual values are listed in table 6-2.

Table 6-2: Dye theory model performance review
Response Correlation Coef, R
2
Slope Intercept
%COWY 0.74 0.764 0.007
%IOWY 0.95 0.943 -0.001
Integ 0.97 1.097 -5.764
Penetration Level 0.67 0.806 0.041
272

The dye theory model was compared to actual full scale production dyed cotton yarns. By
adjusting the yarn porosity value used in the calculations to match the actual %IOWY, an excellent
correlation was established for the Integ shade values. The resulting correlation coefficient for
predicted and actual Integ was R
2
of 0.99 with a slope of 0.945 and intercept of 0.643.
The outperformance of the dye theory model compared to the empirical model was due to
the ability to compensate for yarn porosity changes between the observational data collection state,
non-tension, and production state, high tension. Furthermore, potential porosity dependence on
dye range speed was introduced. While six data points were certainly not enough evidence to
present a compelling argument, the strong correlation does warrant further investigation.

Recommendations
1. Expansion of the equilibrium sorption experiments would add more insight in the behavior and
dependence of indigo dye uptake at various dye bath indigo concentrations and pH levels.
Additional data points at lower pH levels are required to confirm the mathematical relationships
presented. Specifically, higher dye bath indigo concentrations at much lower pH levels are required.
While the current study coupled with Etters' previously published results offers a compelling
argument, more data points are required to provide statistically strong support.
2. Additional observational studies need to be conducted from other full scale production chain
rope indigo dye ranges. By adding more data points to the dye theory model, confidence intervals
would be increased and observed general trends clarified. Specifically, a wider range of dye bath pH
levels must be explored which incorporates pH buffering systems. The inability to reproduce
published %IOWY and pH relationship must be further explored. Additionally, the speed and dwell
time effect on response variables needs a greater variety in the range of values. These can only be
achieved by varying the thread-up dwell length.
3. Refinement of the dye theory model nodal mesh would provide more insight in physico-
chemical effects during the indigo dye process. Making changes in the finite difference nodal mesh
which models the fiber and yarn structural characteristics would provide better prediction of dye
273

bath movement within the yarn structure and thereby better prediction of %IOWY, Integ shade, and
indigo distribution or penetration level. Furthermore, it may be possible to decouple the yarn and
fiber diffusion coefficients back into four elements instead of two. This would allow description of
dye affinity or adsorption for the fiber surface and diffusion into the fiber interior. As well as
understanding the difference between dye movement through the dye bath medium and boundary
layer surrounding the individual fibers.
4. Incorporate additional production scale dyed yarn data points to expand dye theory model
prediction and explore the effects of porosity value relating zero and production state tension.
The current dye theory model preformed well at predicting the production yarn %IOWY and Integ
shade. Additional data points are required to confirm the relationship. The relationship between
dye range speed and actual yarn porosity presented is extremely enticing. However more data
points are required from many different indigo chain rope dye ranges to confirm the relationship
presented.
5. Combine current presented information and recommendations to create a commercial quality
indigo dye prediction program. An accurate indigo dye prediction program would greatly assist the
manufacturing quality control engineer. By coupling the prediction software with end item shade
analysis and production history, the production engineer would know how current production
conditions will affect the end item. This would allow for intelligent dye range adjustments to be
made to control %IOWY and indigo distribution. Additionally, the indigo dye prediction software
would assist dye range equipment manufactures. By understanding the dye range mechanical
affects on %IOWY, Integ, and penetration level; certain fixed dye range mechanical properties could
be tailored to a customer's requirements. Finally, the indigo dye prediction software would greatly
assist an indigo dye house when developing new production shades. The ability to predict %IOWY,
Integ, and indigo distribution without the need for trials would reduce development time and costs.

274

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279

APPENDIX
280

Section A-1-2a: Spectrophotometric method to measure indigo dye bath concentration by %T.
Spectronic 21
1. Position sensitivity control to "M" (medium).
2. Adjust wavelength/Nanometer control to read "660".
3. Set dial on face of Spectonic 21 to "Transmittance".

Method
1. Zeroing the machine
2. Fill the test tube with clear water.
3. Place test tube in opening.
4. Line up number on test tube with notch located to the right of the opening. Digital indicator
should zero to 100.0

Test
1. Add approximately 300-400 mls of water to a clean 500 ml volumetric flask.
2. Add a magnetic strring bar and place the flask on a magnestir with rapid agition.
3. Pipet 1 ml of dye box liquor into the swirling water, being careful to wipe any excess from the
outside of the pipet.
4. Agitiate for four minutes or until the Indigo is completely oxidized - bright blue.
5. Remove the magentic bar.
6. Dilute to volume with water and mix until uniform (500 ml).
7. Pour the solution into a test tube.
8. Place in Spectronic 21, making sure numbers are aligned with notch.
9. Read results.

Equation calculation for oz/gal of 20% indigo

= (% 0.0373) + 3.628
Equation A-1-1: oz/gal of 20% indigo related by %T by Spectrophotometric method.



281

Section A-1-2b: Total alkalinity titration method.
1. Pipette 10 ml of liquor into a 250 ml beaker.
2. Add 100 ml of distilled water to the beaker.
3. Place the beaker on the mag stirrer and place a magnet in the liquor.
4. Begin stirring at a brisk level so that the level on the wall never exceeds the 150 ml mark.
5. Place the electrodes of a properly calibrated pH meter into the beaker.
6. Begin adding 0.05N Hcl acid at no more than 1 drop every 2 seconds to allow the pH meter
enough time to equilibrate after each addition. After the pH has dropped below 9.0, add not more
than 1 drop every 4 seconds.
7. Titrate to a pH of 8.28.
8. Calculate the g/l of total alkalinity by equation A-1-2.

/ = 0.2
Equation A-1-2: Calculation of total alkalinity by titration method.




282

Section A-2: Nothing.
Section A-3-1: % Reflectance values of mock dyed 100% cotton yarns used to calculate K/S.
Table A-3-1: % Reflectance values of mock dyed 100% cotton yarns used to calculate K/S.
Wavelength, nm 6.3/1 7.1./1 8.0/1 12.0/1
400 44.2175 46.26 47.10667 47.13
420 47.125 49.46 50.15667 50.27
440 50.29 52.83 53.35333 53.62571
460 52.9825 55.63333 55.94 56.39143
480 55.79 58.49 58.58 59.23714
500 58.2225 60.99333 60.86 61.71857
520 60.575 63.3 62.97 64.02857
540 62.86 65.51 65.02333 66.29143
560 65.1375 67.65333 67.02 68.53429
580 67.11 69.50667 68.81 70.49857
600 68.8975 71.16667 70.41667 72.25
620 70.5625 72.68 71.89 73.85429
640 72.2425 74.21667 73.34667 75.40429
660 73.93 75.83667 74.83 76.87286
680 75.7825 77.7 76.61667 78.47857
700 77.22 79.19 78.06333 79.75429



Section A-3-2: Nothing.


283

Section A-3-3: Balance of data from equilibrium sorption experiment.
Table A-3-3: %IOWY and Integ shade data from equilibrium sorption experiment
Yarn Count Dye Bath g/l Dye Bath pH %IOWY Integ Shade Stock Mix
7.1 0.641 12.25 1.10% 32.7 1
7.1 0.17663 12.8 0.29% 7.4 4
7.1 1.2287 12.8 1.16% 30.9 6
7.1 0.01577 13.17 0.02% 1.2 3
7.1 0.03494 13.3 0.04% 2.2 6
7.1 0.49612 13.19 0.51% 14.0 5
7.1 1.99985 13.21 1.48% 36.9 3
7.1 3.8843 13.24 2.29% 51.0 5
7.1 6.3355 13.1 3.28% 64.0 4
7.1 9.61464 13.31 4.10% 68.7 3
7.1 14.0149 13.2 5.33% 76.3 6
7.1 19.2293 13.43 6.04% 78.5 5
7.1 29.95 13.2 8.51% 91.0 4
8 2.548 11.2 2.98% 61.8 8
8 0.17663 12.8 0.29% 7.1 4
8 1.2287 12.8 1.17% 30.2 6
8 2.564 12.9 2.02% 47.5 7
8 0.01577 13.17 0.03% 1.2 3
8 0.03494 13.3 0.08% 2.3 6
8 0.49612 13.19 0.50% 14.1 5
8 1.99985 13.21 1.41% 35.9 3
8 3.8843 13.24 2.29% 48.3 5
8 6.3355 13.1 3.32% 63.2 4
8 9.61464 13.31 3.93% 67.9 3
8 14.0149 13.2 5.15% 75.4 6
8 19.2293 13.43 5.60% 78.7 5
8 20.191 13.3 6.67% 80.0 8
8 29.95 13.2 8.44% 89.8 4
12 0.641 12.25 1.09% 34.5 1
12 1.602 12.72 1.61% 45.6 1
12 0.17663 12.8 0.30% 7.8 4
12 1.2287 12.8 1.25% 31.4 6
12 2.564 12.9 2.06% 50.5 8
12 0.01577 13.17 0.02% 1.2 3
12 0.03494 13.3 0.06% 2.8 6
12 0.49612 13.19 0.50% 13.8 5
12 1.99985 13.21 1.46% 36.0 3
12 3.8843 13.24 2.31% 49.7 5
12 4.487 13.14 2.85% 59.3 7
12 6.3355 13.1 3.25% 60.7 4
12 9.61464 13.31 4.31% 68.7 3
12 14.0149 13.2 5.04% 75.6 6
12 19.2293 13.43 5.86% 75.8 5
12 29.95 13.2 8.53% 87.5 4

284

Section A-4-1: Observational Study Raw Data -Dye Range Parameters

Table A-4-1: Prime and replica raw data set
Shade
ID
Speed
(m/min)
Dwell
Time
(sec)
Oxidation
Time (sec)
Dye Bath
(gpl
100%
Indigo)
Dye
Bath pH
Dye
Bath
(mV)
Dye Bath
Alkalinity
(gpl)
Dwell
Length
(m)
Oxidation
Length (m)
Nip
Pressures
(psi)
1160 36.6 14.1 59.1 0.891 11.66 745 3.16 8.63 36.03 70
Yarn Skein Response Variables
Yarn
Count
Dye
route Dips
Greige
Weight
Boil Off
Weight
Dyed
Weight
Washed
Weight %COWY
Total
%IOWY
Surface
%IOWY Integ
Penetration
Level
7.1 1 only 1 6.9561 7.0521 6.9425 1.380% 0.128% 0.182% 6.198167 0.70
7.1 1 --> 2 2 7.0316 7.1811 7.0267 2.126% 0.263% 0.471% 13.73814 0.56
7.1 1 --> 3 3 7.0931 7.3064 7.101 3.007% 0.437% 0.802% 21.46723 0.54
7.1 1 --> 4 4 6.9405 7.119 6.9549 2.572% 0.526% 1.141% 28.84153 0.46



% Reflectance Readings


Wave-
length
(nm) Dip 1 Dip 2 Dip 3 Dip 4 Dip 5 Dip 6 Dip 7
400 22.78 15.15 11.40 9.33
420 28.23 19.75 15.23 12.70
440 27.56 18.64 14.14 11.63
460 25.10 16.23 12.06 9.78
480 23.09 14.31 10.38 8.25
500 21.16 12.69 9.07 7.08
520 18.82 10.87 7.49 5.71
540 15.90 8.77 5.95 4.48
560 14.25 7.64 5.07 3.80
580 12.60 6.48 4.26 3.20
600 10.82 5.40 3.56 2.69
620 9.44 4.60 3.07 2.35
640 7.96 3.83 2.62 2.05
660 7.03 3.51 2.49 1.95
680 9.24 4.58 3.15 2.46
700 18.45 10.63 7.54 5.78
285

Table A-4-1: Continued
Shade
ID
Speed
(m/min)
Dwell
Time
(sec)
Oxidation
Time (sec)
Dye Bath
(gpl
100%
Indigo)
Dye
Bath pH
Dye
Bath
(mV)
Dye Bath
Alkalinity
(gpl)
Dwell
Length
(m)
Oxidation
Length (m)
Nip
Pressures
(psi)
1160 36.576 14.1 59.1 0.891 11.66 745 3.16 8.63 36.03 70
Yarn Skein Response Variables
Yarn
Count
Dye
route Dips
Greige
Weight
Boil Off
Weight
Dyed
Weight
Washed
Weight %COWY
Total
%IOWY
Surface
%IOWY Integ
Penetration
Level
12 1 only 1 6.1529 5.9725 6.0856 5.9596 1.894% 0.145% 0.188% 6.4 0.80
12 1--2 2 6.1463 5.9698 6.109 5.9689 2.332% 0.264% 0.405% 12.1 0.56
12 1--3 3 6.5291 6.3408 6.5588 6.3577 3.438% 0.447% 0.731% 19.9 0.56
12 1--4 4 6.3526 6.1746 6.3433 6.1902 2.732% 0.538% 0.949% 24.7 0.47



% Reflectance Readings


Wave-
length
(nm) Dip 1 Dip 2 Dip 3 Dip 4 Dip 5 Dip 6 Dip 7
400 22.62 16.46 11.88 10.47
420 28.00 21.35 15.73 14.13
440 27.21 20.23 14.68 13.00
460 24.70 17.72 12.61 10.98
480 22.66 15.68 10.93 9.35
500 20.73 13.97 9.61 8.13
520 18.42 11.99 8.00 6.61
540 15.56 9.71 6.40 5.21
560 13.96 8.48 5.46 4.43
580 12.35 7.26 4.60 3.72
600 10.63 6.04 3.85 3.11
620 9.30 5.15 3.32 2.70
640 7.88 4.28 2.81 2.30
660 6.98 3.88 2.64 2.19
680 9.11 5.09 3.35 2.76
700 18.00 11.73 8.00 6.56
286

Table A-4-1: Continued

Shade
ID
Speed
(m/min)
Dwell
Time
(sec)
Oxidation
Time (sec)
Dye Bath
(gpl
100%
Indigo)
Dye
Bath pH
Dye
Bath
(mV)
Dye Bath
Alkalinity
(gpl)
Dwell
Length
(m)
Oxidation
Length (m)
Nip
Pressures
(psi)
1160 36.576 14.1 59.1 0.764 11.91 762 2.5 8.63 36.03 70
Yarn Skein Response Variables
Yarn
Count
Dye
route Dips
Greige
Weight
Boil Off
Weight
Dyed
Weight
Washed
Weight %COWY
Total
%IOWY
Surface
%IOWY Integ
Penetration
Level
6.3 I only 1 7.9045 7.5992 7.7051 7.5822 1.394% 0.150% 0.216% 7.2 0.69
6.3 1--2 2 7.616 7.3223 7.4879 7.3162 2.262% 0.281% 0.477% 13.9 0.59
6.3 1--3 3 7.7551 7.4518 7.6594 7.4602 2.786% 0.458% 0.802% 21.5 0.57
6.3 1--4 4 7.781 7.476 7.6616 7.4896 2.483% 0.523% 1.086% 27.7 0.48



% Reflectance Readings


Wave-
length
(nm) Dip 1 Dip 2 Dip 3 Dip 4 Dip 5 Dip 6 Dip 7
400 21.20 14.84 11.38 9.63
420 26.48 19.48 15.24 13.13
440 25.80 18.52 14.16 12.05
460 23.39 16.21 12.09 10.15
480 21.37 14.29 10.39 8.56
500 19.50 12.69 9.10 7.38
520 17.20 10.83 7.49 5.94
540 14.40 8.73 5.98 4.67
560 12.78 7.56 5.06 3.95
580 11.18 6.40 4.25 3.32
600 9.49 5.29 3.54 2.78
620 8.20 4.50 3.04 2.42
640 6.89 3.75 2.61 2.10
660 6.08 3.42 2.44 1.98
680 8.16 4.50 3.14 2.52
700 16.86 10.59 7.47 5.95
287

Table A-4-1: Continued


Shade
ID
Speed
(m/min)
Dwell
Time
(sec)
Oxidation
Time (sec)
Dye Bath
(gpl
100%
Indigo)
Dye
Bath pH
Dye
Bath
(mV)
Dye Bath
Alkalinity
(gpl)
Dwell
Length
(m)
Oxidation
Length (m)
Nip
Pressures
(psi)
1160 36.576 14.1 59.1 0.764 11.91 762 2.5 8.63 36.03 60.00
Yarn Skein Response Variables
Yarn
Count
Dye
route Dips
Greige
Weight
Boil Off
Weight
Dyed
Weight
Washed
Weight %COWY
Total
%IOWY
Surface
%IOWY Integ
Penetration
Level
7.1 1 only 1 6.7962 6.556 6.6875 6.5431 2.006% 0.161% 0.253% 8.2 0.64
7.1 1--2 2 6.8133 6.562 6.7048 6.5562 2.176% 0.302% 0.470% 13.7 0.64
7.1 1--3 3 6.9451 6.69 6.8819 6.6933 2.868% 0.469% 0.821% 21.9 0.57
7.1 1--4 4 6.8598 6.615 6.7976 6.6334 2.760% 0.653% 1.264% 31.4 0.52



% Reflectance Readings


Wave-
length
(nm) Dip 1 Dip 2 Dip 3 Dip 4 Dip 5 Dip 6 Dip 7
400 19.66 15.27 11.17 8.59
420 24.53 19.96 15.01 11.61
440 23.68 18.91 13.99 10.65
460 21.37 16.51 11.95 8.96
480 19.47 14.56 10.27 7.51
500 17.73 12.94 9.00 6.45
520 15.62 11.03 7.40 5.19
540 13.10 8.87 5.90 4.10
560 11.64 7.66 5.00 3.48
580 10.20 6.47 4.20 2.95
600 8.70 5.34 3.48 2.50
620 7.56 4.54 2.99 2.21
640 6.42 3.77 2.54 1.98
660 5.74 3.43 2.35 1.90
680 7.58 4.56 3.06 2.39
700 15.32 10.79 7.31 5.37
288

Table A-4-1: Continued


Shade
ID
Speed
(m/min)
Dwell
Time
(sec)
Oxidation
Time (sec)
Dye Bath
(gpl
100%
Indigo)
Dye
Bath pH
Dye
Bath
(mV)
Dye Bath
Alkalinity
(gpl)
Dwell
Length
(m)
Oxidation
Length (m)
Nip
Pressures
(psi)
1160 36.576 14.1 59.1 0.764 11.91 762 2.5 8.63 36.03 60.00
Yarn Skein Response Variables
Yarn
Count
Dye
route Dips
Greige
Weight
Boil Off
Weight
Dyed
Weight
Washed
Weight %COWY
Total
%IOWY
Surface
%IOWY Integ
Penetration
Level
8 1 only 1 6.0312 5.8294 5.9189 5.7961 1.535% 0.163% 0.210% 7.0 0.78
8 1--2 2 6.0612 5.8525 5.9722 5.8303 2.045% 0.310% 0.418% 12.4 0.74
8 1--3 3 6.0001 5.7917 5.9468 5.7817 2.678% 0.480% 0.743% 20.1 0.65
8 1--4 4 6.1102 5.9038 6.0451 5.8998 2.393% 0.660% 1.208% 30.3 0.55



% Reflectance Readings


Wave-
length
(nm) Dip 1 Dip 2 Dip 3 Dip 4 Dip 5 Dip 6 Dip 7
400 21.30 16.02 11.81 8.99
420 26.56 20.89 15.77 12.26
440 25.92 19.87 14.71 11.25
460 23.58 17.42 12.61 9.44
480 21.62 15.46 10.89 7.95
500 19.78 13.77 9.57 6.82
520 17.51 11.82 7.94 5.49
540 14.74 9.57 6.36 4.31
560 13.11 8.32 5.40 3.64
580 11.51 7.09 4.55 3.06
600 9.80 5.88 3.77 2.56
620 8.50 4.99 3.24 2.23
640 7.18 4.15 2.75 1.96
660 6.36 3.74 2.55 1.84
680 8.46 4.97 3.28 2.34
700 17.06 11.45 7.80 5.47
289

Table A-4-1: Continued


Shade
ID
Speed
(m/min)
Dwell
Time
(sec)
Oxidation
Time (sec)
Dye Bath
(gpl
100%
Indigo)
Dye
Bath pH
Dye
Bath
(mV)
Dye Bath
Alkalinity
(gpl)
Dwell
Length
(m)
Oxidation
Length (m)
Nip
Pressures
(psi)
1160 36.576 14.1 59.1 0.764 11.91 762 2.5 8.63 36.03 60.00
Yarn Skein Response Variables
Yarn
Count
Dye
route Dips
Greige
Weight
Boil Off
Weight
Dyed
Weight
Washed
Weight %COWY
Total
%IOWY
Surface
%IOWY Integ
Penetration
Level
12 1 only 1 3.856 3.7189 3.8039 3.7106 2.286% 0.204% 0.240% 7.8 0.85
12 1--2 2 4.0024 3.8631 3.9669 3.8586 2.687% 0.377% 0.552% 15.7 0.68
12 1--3 3 4.0023 3.8535 3.9861 3.861 3.441% 0.560% 0.887% 23.4 0.63
12 1--4 4 3.9139 3.7728 3.8844 3.791 2.958% 0.725% 1.267% 31.5 0.57



% Reflectance Readings


Wave-
length
(nm) Dip 1 Dip 2 Dip 3 Dip 4 Dip 5 Dip 6 Dip 7
400 20.23 13.84 10.78 8.69
420 25.34 18.15 14.46 11.72
440 24.56 17.15 13.43 10.70
460 22.16 14.91 11.45 9.00
480 20.19 13.09 9.81 7.54
500 18.39 11.61 8.58 6.47
520 16.21 9.88 7.02 5.22
540 13.58 7.95 5.57 4.12
560 12.07 6.85 4.72 3.49
580 10.54 5.76 3.94 2.95
600 8.97 4.76 3.27 2.49
620 7.78 4.06 2.81 2.19
640 6.57 3.39 2.40 1.94
660 5.86 3.12 2.23 1.85
680 7.77 4.09 2.91 2.33
700 15.83 9.63 7.01 5.31
290

Table A-4-1: Continued


Shade
ID
Speed
(m/min)
Dwell
Time
(sec)
Oxidation
Time (sec)
Dye Bath
(gpl
100%
Indigo)
Dye
Bath pH
Dye
Bath
(mV)
Dye Bath
Alkalinity
(gpl)
Dwell
Length
(m)
Oxidation
Length (m)
Nip
Pressures
(psi)
1162 31.0896 16.7 69.5 1.066 11.76 743 3.42 8.63 36.03 70.00
Yarn Skein Response Variables
Yarn
Count
Dye
route Dips
Greige
Weight
Boil Off
Weight
Dyed
Weight
Washed
Weight %COWY
Total
%IOWY
Surface
%IOWY Integ
Penetration
Level
7.1 1 only 1 6.9125 6.6961 6.8589 6.6845 2.431% 0.153% 0.226% 7.4 0.68
7.1 1--2 2 6.9989 6.7661 6.9954 6.7766 3.389% 0.357% 0.716% 19.5 0.50
7.1 1--3 3 6.9641 6.7352 7.0001 6.7439 3.933% 0.527% 1.171% 29.5 0.45
7.1 1--4 4 6.9822 6.7466 7.0094 6.7845 3.895% 0.645% 1.534% 37.0 0.42
7.1 1--5 5 6.9435 6.7046 6.9901 6.7499 4.258% 0.849% 2.028% 46.7 0.42
7.1 1--6 6 6.9078 6.6907 6.9952 6.7343 4.551% 0.998% 2.361% 53.0 0.42
7.1 1--7 7 6.915 6.6881 6.9739 6.7501 4.273% 1.138% 2.680% 57.4 0.42
% Reflectance Readings


Wave-
length
(nm) Dip 1 Dip 2 Dip 3 Dip 4 Dip 5 Dip 6 Dip 7
400 20.08 11.74 8.92 7.52 6.23 5.56 5.03
420 25.40 15.80 12.30 10.38 8.43 7.34 6.60
440 24.71 14.73 11.21 9.30 7.39 6.39 5.72
460 22.34 12.59 9.32 7.67 6.01 5.15 4.61
480 20.36 10.85 7.79 6.28 4.86 4.14 3.71
500 18.59 9.55 6.68 5.34 4.11 3.50 3.15
520 16.44 7.96 5.41 4.28 3.29 2.82 2.55
540 13.85 6.41 4.28 3.39 2.62 2.27 2.06
560 12.41 5.51 3.67 2.92 2.28 1.99 1.83
580 11.05 4.69 3.13 2.50 2.00 1.78 1.66
600 9.52 3.94 2.68 2.18 1.79 1.63 1.55
620 8.28 3.40 2.36 1.96 1.66 1.54 1.49
640 7.03 2.94 2.14 1.84 1.63 1.55 1.51
660 6.24 2.81 2.10 1.85 1.69 1.64 1.62
680 8.00 3.52 2.62 2.26 2.02 1.93 1.87
700 15.81 7.88 5.60 4.64 3.82 3.45 3.18
291

Table A-4-1: Continued


Shade
ID
Speed
(m/min)
Dwell
Time
(sec)
Oxidation
Time (sec)
Dye Bath
(gpl
100%
Indigo)
Dye
Bath pH
Dye
Bath
(mV)
Dye Bath
Alkalinity
(gpl)
Dwell
Length
(m)
Oxidation
Length (m)
Nip
Pressures
(psi)
1162 31.0896 16.7 69.5 1.066 11.76 743 3.42 8.63 36.03 70.00
Yarn Skein Response Variables
Yarn
Count
Dye
route Dips
Greige
Weight
Boil Off
Weight
Dyed
Weight
Washed
Weight %COWY
Total
%IOWY
Surface
%IOWY Integ
Penetration
Level
8 1 only 1 6.0851 5.8856 6.0242 5.8739 2.355% 0.167% 0.235% 7.7 0.71
8 1--2 2 6.0246 5.8307 6.0216 5.8278 3.274% 0.355% 0.651% 18.0 0.54
8 1--3 3 6.0942 5.9039 6.1043 5.9017 3.394% 0.531% 1.048% 26.9 0.51
8 1--4 4 6.0591 5.8724 6.1037 5.8845 3.939% 0.735% 1.598% 38.2 0.46
8 1--5 5 6.1861 5.988 6.2333 6.0167 4.097% 0.926% 2.054% 47.2 0.45
8 1--6 6 6.0467 5.8509 6.11 5.884 4.428% 1.022% 2.237% 50.7 0.46
8 1--7 7 6.0202 5.8246 6.1046 5.8788 4.807% 1.196% 2.665% 57.2 0.45
% Reflectance Readings


Wave-
length
(nm) Dip 1 Dip 2 Dip 3 Dip 4 Dip 5 Dip 6 Dip 7
400 19.57 12.31 9.46 7.18 6.16 5.75 5.13
420 24.81 16.60 12.96 9.88 8.29 7.63 6.74
440 24.19 15.60 11.93 8.89 7.32 6.68 5.87
460 21.93 13.44 10.04 7.35 5.98 5.41 4.73
480 20.02 11.64 8.48 6.03 4.86 4.38 3.81
500 18.29 10.28 7.34 5.14 4.12 3.72 3.23
520 16.19 8.65 5.96 4.13 3.31 3.00 2.61
540 13.60 6.95 4.73 3.28 2.63 2.41 2.10
560 12.17 5.97 4.05 2.83 2.27 2.09 1.86
580 10.80 5.06 3.44 2.44 1.99 1.87 1.66
600 9.27 4.22 2.92 2.13 1.77 1.69 1.53
620 8.06 3.62 2.55 1.91 1.62 1.58 1.45
640 6.81 3.08 2.26 1.79 1.58 1.56 1.45
660 6.06 2.87 2.19 1.82 1.61 1.63 1.51
680 7.81 3.66 2.75 2.22 1.95 1.93 1.76
700 15.62 8.51 6.09 4.51 3.80 3.53 3.17
292

Table A-4-1: Continued


Shade
ID
Speed
(m/min)
Dwell
Time
(sec)
Oxidation
Time (sec)
Dye Bath
(gpl
100%
Indigo)
Dye
Bath
pH
Dye
Bath
(mV)
Dye Bath
Alkalinity
(gpl)
Dwell
Length
(m)
Oxidation
Length (m)
Nip
Pressures
(psi)
1162 31.0896 16.7 69.5 1.129 11.7 747 3.62 8.63 36.03 70.00
Yarn Skein Response Variables
Yarn
Count
Dye
route Dips
Greige
Weight
Boil Off
Weight
Dyed
Weight
Washed
Weight %COWY
Total
%IOWY
Surface
%IOWY Integ
Penetration
Level
6.3 1 only 1 7.9444 7.6489 7.801 7.6285 1.989% 0.171% 0.204% 6.8 0.84
6.3 1--2 2 7.6963 7.3949 7.6295 7.4014 3.172% 0.366% 0.671% 18.5 0.55
6.3 1--3 3 7.696 7.4129 7.6787 7.4273 3.586% 0.588% 1.374% 33.7 0.43
6.3 1--4 4 7.6995 7.3936 7.651 7.4227 3.481% 0.718% 1.629% 38.9 0.44
6.3 1--5 5 7.7576 7.4609 7.758 7.5016 3.982% 0.955% 2.133% 48.7 0.45
6.3 1--5 5 7.5935 7.3037 7.6196 7.3553 4.325% 0.950% 2.088% 47.8 0.45
6.3 1--7 7 7.7599 7.4576 7.7748 7.5221 4.253% 1.311% 2.919% 60.0 0.45
% Reflectance Readings


Wave-
length
(nm) Dip 1 Dip 2 Dip 3 Dip 4 Dip 5 Dip 5 Dip 7
400 20.29 12.05 7.97 7.15 5.94 6.02 4.74
420 25.62 16.25 10.97 9.91 8.01 8.19 6.23
440 25.26 15.27 10.04 8.90 7.07 7.20 5.41
460 23.17 13.13 8.40 7.35 5.78 5.85 4.37
480 21.34 11.35 6.95 6.00 4.67 4.71 3.52
500 19.62 9.99 5.94 5.10 3.94 3.98 2.98
520 17.47 8.38 4.78 4.10 3.17 3.20 2.42
540 14.78 6.75 3.77 3.23 2.53 2.56 1.98
560 13.25 5.79 3.22 2.77 2.19 2.21 1.75
580 11.80 4.91 2.74 2.38 1.92 1.95 1.59
600 10.15 4.11 2.35 2.07 1.71 1.76 1.50
620 8.84 3.54 2.08 1.87 1.60 1.62 1.43
640 7.51 3.05 1.91 1.77 1.58 1.60 1.49
660 6.60 2.86 1.89 1.78 1.61 1.66 1.58
680 8.53 3.63 2.36 2.19 1.93 1.97 1.83
700 16.88 8.28 5.09 4.48 3.68 3.69 3.08
293

Table A-4-1: Continued


Shade
ID
Speed
(m/min)
Dwell
Time
(sec)
Oxidation
Time (sec)
Dye Bath
(gpl
100%
Indigo)
Dye
Bath
pH
Dye
Bath
(mV)
Dye Bath
Alkalinity
(gpl)
Dwell
Length
(m)
Oxidation
Length (m)
Nip
Pressures
(psi)
1162 31.0896 16.7 69.5 1.129 11.7 747 3.62 8.63 36.03 70.00
Yarn Skein Response Variables
Yarn
Count
Dye
route Dips
Greige
Weight
Boil Off
Weight
Dyed
Weight
Washed
Weight %COWY
Total
%IOWY
Surface
%IOWY Integ
Penetration
Level
12 1 only 1 3.7295 3.6009 3.7002 3.5896 2.758% 0.221% 0.290% 9.2 0.76
12 1--2 2 3.997 3.8643 4.0212 3.8692 4.060% 0.456% 0.801% 21.4 0.57
12 1--3 3 3.9658 3.8243 4.0051 3.8387 4.728% 0.723% 1.375% 33.7 0.53
12 1--4 4 3.8058 3.6712 3.8291 3.6938 4.301% 0.939% 1.867% 43.6 0.50
12 1--5 5 3.9635 3.8259 4.021 3.8633 5.099% 1.219% 2.274% 51.4 0.54
12 1--6 6 3.955 3.8093 4.044 3.8612 6.161% 1.547% 3.116% 61.9 0.50
12 1--7 7 3.933 3.7989 3.9968 3.8481 5.209% 1.711% 3.613% 65.7 0.47
% Reflectance Readings


Wave-
length
(nm) Dip 1 Dip 2 Dip 3 Dip 4 Dip 5 Dip 6 Dip 7
400 17.75 11.06 8.21 6.61 5.78 4.69 4.34
420 22.65 14.93 11.24 9.02 7.71 6.05 5.57
440 22.01 13.97 10.23 8.04 6.76 5.25 4.81
460 19.84 11.98 8.51 6.63 5.50 4.25 3.87
480 17.97 10.28 7.02 5.40 4.44 3.43 3.12
500 16.32 9.02 5.99 4.58 3.74 2.90 2.65
520 14.35 7.47 4.82 3.67 3.01 2.37 2.16
540 11.99 5.98 3.80 2.91 2.40 1.93 1.79
560 10.65 5.11 3.24 2.48 2.08 1.71 1.61
580 9.37 4.30 2.75 2.15 1.83 1.56 1.48
600 7.99 3.58 2.34 1.87 1.64 1.45 1.41
620 6.88 3.07 2.07 1.69 1.52 1.39 1.37
640 5.81 2.62 1.89 1.59 1.49 1.43 1.43
660 5.22 2.48 1.84 1.63 1.56 1.54 1.54
680 6.78 3.22 2.35 1.98 1.85 1.78 1.78
700 13.96 7.52 5.09 4.07 3.51 3.02 2.87
294

Table A-4-1: Continued


Shade
ID
Speed
(m/min)
Dwell
Time
(sec)
Oxidation
Time (sec)
Dye Bath
(gpl
100%
Indigo)
Dye
Bath
pH
Dye
Bath
(mV)
Dye Bath
Alkalinity
(gpl)
Dwell
Length
(m)
Oxidation
Length (m)
Nip
Pressures
(psi)
T3675 34.75 14.7 62.2 1.932 11.5 836 4.82 8.63 36.03 70.00
Yarn Skein Response Variables
Yarn
Count
Dye
route Dips
Greige
Weight
Boil Off
Weight
Dyed
Weight
Washed
Weight %COWY
Total
%IOWY
Surface
%IOWY Integ
Penetration
Level
6.3 1 only 1 8.209646 7.9091 8.2466 7.9158 4.267% 0.385% 0.861% 22.8 0.45
6.3 1--2 2 8.15951 7.8608 8.3462 7.8953 6.175% 0.631% 1.739% 41.0 0.36
6.3 1--2 2 8.167399 7.8684 8.2713 7.8062 5.120% 0.653% 1.748% 41.2 0.37
6.3 1--4 4 8.174977 7.8757 8.4725 7.9623 7.578% 1.222% 4.299% 70.1 0.28
6.3 1--5 5 8.167399 7.8684 8.5453 7.9757 8.603% 1.495% 5.891% 78.7 0.25
6.3 1--6 6 8.23736 7.9358 8.5928 8.0797 8.279% 1.741% 7.325% 85.3 0.24

% Reflectance Readings


Wave-
length
(nm) Dip 1 Dip 2 Dip 2 Dip 4 Dip 5 Dip 6 Dip 7
400 11.09 7.17 7.10 4.09 3.44 3.00
420 15.07 9.91 9.83 5.28 4.34 3.72
440 13.96 8.85 8.81 4.58 3.74 3.21
460 11.80 7.27 7.24 3.70 3.05 2.62
480 10.10 5.93 5.91 3.00 2.48 2.15
500 8.82 5.02 5.01 2.55 2.14 1.88
520 7.21 4.00 3.99 2.08 1.78 1.59
540 5.72 3.14 3.13 1.71 1.51 1.40
560 4.81 2.65 2.64 1.53 1.38 1.30
580 4.00 2.26 2.26 1.39 1.29 1.23
600 3.29 1.93 1.91 1.30 1.22 1.19
620 2.82 1.72 1.72 1.26 1.20 1.17
640 2.42 1.57 1.57 1.25 1.22 1.21
660 2.32 1.56 1.56 1.34 1.33 1.31
680 3.07 1.98 1.96 1.58 1.54 1.53
700 7.25 4.20 4.20 2.61 2.32 2.13
295

Table A-4-1: Continued


Shade
ID
Speed
(m/min)
Dwell
Time
(sec)
Oxidation
Time (sec)
Dye Bath
(gpl
100%
Indigo)
Dye
Bath
pH
Dye
Bath
(mV)
Dye Bath
Alkalinity
(gpl)
Dwell
Length
(m)
Oxidation
Length (m)
Nip
Pressures
(psi)
T3675 34.75 14.7 62.2 1.932 11.5 836 4.82 8.63 36.03 70.00
Yarn Skein Response Variables
Yarn
Count
Dye
route Dips
Greige
Weight
Boil Off
Weight
Dyed
Weight
Washed
Weight %COWY
Total
%IOWY
Surface
%IOWY Integ
Penetration
Level
7.1 1 only 1 7.0445 6.8512 7.1585 6.8528 4.485% 0.359% 0.811% 21.7 0.44
7.1 1--2 2 7.07 6.8743 7.3384 6.9061 6.751% 0.691% 1.824% 42.7 0.38
7.1 1--3 3 7.2324 7.0316 7.5021 7.0851 6.691% 1.001% 2.701% 57.7 0.37
7.1 1--4 4 7.1538 6.9599 7.4319 7.0392 6.782% 1.476% 4.598% 71.8 0.32
7.1 1--5 5 7.1736 6.9814 7.5533 7.08 8.192% 1.773% 6.253% 80.4 0.28
7.1 1--6 6 7.1894 6.9918 7.5306 7.1185 7.706% 2.153% 7.877% 87.6 0.27

% Reflectance Readings


Wave-
length
(nm) Dip 1 Dip 2 Dip 3 Dip 4 Dip 5 Dip 6 Dip 7
400 11.62 6.97 5.30 3.99 3.40 2.93
420 15.70 9.58 6.97 5.10 4.33 3.64
440 14.54 8.52 6.11 4.41 3.73 3.13
460 12.32 6.97 4.95 3.57 3.03 2.55
480 10.56 5.69 3.99 2.90 2.46 2.08
500 9.25 4.82 3.37 2.47 2.11 1.83
520 7.61 3.84 2.70 2.02 1.75 1.55
540 6.04 3.01 2.15 1.67 1.48 1.36
560 5.08 2.55 1.85 1.50 1.34 1.27
580 4.22 2.18 1.64 1.37 1.26 1.21
600 3.46 1.86 1.46 1.28 1.19 1.16
620 2.94 1.67 1.37 1.24 1.17 1.15
640 2.51 1.55 1.34 1.25 1.19 1.18
660 2.39 1.56 1.39 1.34 1.29 1.28
680 3.18 1.97 1.66 1.57 1.50 1.49
700 7.55 4.09 3.14 2.55 2.28 2.08
296

Table A-4-1: Continued


Shade
ID
Speed
(m/min)
Dwell
Time
(sec)
Oxidation
Time (sec)
Dye Bath
(gpl
100%
Indigo)
Dye
Bath
pH
Dye
Bath
(mV)
Dye Bath
Alkalinity
(gpl)
Dwell
Length
(m)
Oxidation
Length (m)
Nip
Pressures
(psi)
T3675 34.75 14.7 62.2 1.932 11.5 836 4.82 8.63 36.03 70.00
Yarn Skein Response Variables
Yarn
Count
Dye
route Dips
Greige
Weight
Boil Off
Weight
Dyed
Weight
Washed
Weight %COWY
Total
%IOWY
Surface
%IOWY Integ
Penetration
Level
12 1 only 1 6.1357 5.9461 6.2804 5.9571 5.622% 0.487% 0.841% 22.3 0.58
12 1--2 2 6.146 5.9627 6.4084 5.9993 7.475% 0.897% 1.768% 41.6 0.51
12 1--3 3 5.7399 5.5191 5.9891 5.579 8.516% 1.467% 2.980% 60.6 0.49
12 1--4 4 5.9484 5.9925 6.4706 6.086 7.978% 1.698% 4.228% 69.6 0.40
12 1--5 5 5.82 5.5935 6.2417 5.7228 11.588% 2.189% 7.207% 84.8 0.30
12 1--6 6 6.1973 6.0232 6.5289 6.1572 8.396% 2.463% 8.470% 90.0 0.29

% Reflectance Readings


Wave-
length
(nm) Dip 1 Dip 2 Dip 3 Dip 4 Dip 5 Dip 6 Dip 7
400 11.27 7.11 5.05 4.15 3.17 2.87
420 15.17 9.67 6.54 5.26 3.89 3.49
440 13.98 8.62 5.72 4.56 3.35 3.00
460 11.83 7.08 4.62 3.69 2.74 2.46
480 10.12 5.77 3.73 2.99 2.23 2.01
500 8.87 4.90 3.14 2.54 1.92 1.76
520 7.28 3.91 2.54 2.07 1.61 1.51
540 5.81 3.09 2.03 1.73 1.40 1.33
560 4.92 2.62 1.76 1.54 1.29 1.24
580 4.10 2.24 1.57 1.41 1.22 1.19
600 3.39 1.91 1.41 1.31 1.17 1.14
620 2.92 1.72 1.34 1.28 1.17 1.13
640 2.51 1.60 1.30 1.28 1.20 1.15
660 2.42 1.61 1.37 1.38 1.32 1.29
680 3.18 2.00 1.63 1.61 1.52 1.50
700 7.29 4.18 3.02 2.61 2.22 2.10
297

Table A-4-1: Continued


Shade
ID
Speed
(m/min)
Dwell
Time
(sec)
Oxidation
Time (sec)
Dye Bath
(gpl
100%
Indigo)
Dye
Bath pH
Dye
Bath
(mV)
Dye Bath
Alkalinity
(gpl)
Dwell
Length
(m)
Oxidation
Length (m)
Nip
Pressures
(psi)
4257 31.09 16.7 69.5 2.084 11.62 847 4.71 8.63 36.03 70.00
Yarn Skein Response Variables
Yarn
Count
Dye
route Dips
Greige
Weight
Boil Off
Weight
Dyed
Weight
Washed
Weight %COWY
Total
%IOWY
Surface
%IOWY Integ
Penetration
Level
6.3 1 only 1 8.3432 8.0041 8.3513 7.9669 4.338% 0.416% 0.951% 24.8 0.44
6.3 1--2 2 8.3076 7.9612 8.4339 7.9705 5.938% 0.652% 1.796% 42.2 0.36
6.3 1--3 3 7.7893 7.4662 7.9978 7.4984 7.120% 0.936% 2.622% 56.7 0.36
6.3 1--4 4 7.9303 7.5905 8.1786 7.6566 7.748% 1.383% 4.261% 69.8 0.32
6.3 1--5 5 8.3555 8.0023 8.6951 8.0934 8.658% 1.759% 5.960% 79.0 0.30
6.3 1--6 6 7.6623 7.3511 7.9466 7.4567 8.101% 2.089% 7.179% 84.6 0.29

% Reflectance Readings


Wave-
length
(nm) Dip 1 Dip 2 Dip 3 Dip 4 Dip 5 Dip 6 Dip 7
400 10.36 6.97 5.21 4.03 3.34 2.96
420 14.01 9.50 6.77 5.11 4.11 3.55
440 12.96 8.50 5.95 4.44 3.56 3.07
460 10.95 6.98 4.83 3.61 2.91 2.52
480 9.32 5.71 3.92 2.95 2.40 2.09
500 8.12 4.83 3.32 2.52 2.08 1.84
520 6.62 3.87 2.69 2.06 1.75 1.58
540 5.25 3.05 2.17 1.71 1.51 1.41
560 4.43 2.60 1.88 1.54 1.39 1.33
580 3.68 2.21 1.68 1.41 1.30 1.26
600 3.05 1.90 1.51 1.32 1.25 1.23
620 2.66 1.66 1.43 1.29 1.25 1.25
640 2.34 1.59 1.40 1.30 1.26 1.27
660 2.27 1.59 1.45 1.38 1.36 1.38
680 2.95 1.97 1.70 1.59 1.55 1.56
700 6.82 4.15 3.15 2.61 2.31 2.15
298

Table A-4-1: Continued


Shade
ID
Speed
(m/min)
Dwell
Time
(sec)
Oxidation
Time (sec)
Dye Bath
(gpl
100%
Indigo)
Dye
Bath
pH
Dye
Bath
(mV)
Dye Bath
Alkalinity
(gpl)
Dwell
Length
(m)
Oxidation
Length (m)
Nip
Pressures
(psi)
1169 31.09 16.7 69.5 2.34 11.6 888 6.27 8.63 36.03 70.00
Yarn Skein Response Variables
Yarn
Count
Dye
route Dips
Greige
Weight
Boil Off
Weight
Dyed
Weight
Washed
Weight %COWY
Total
%IOWY
Surface
%IOWY Integ
Penetration
Level
6.3 1 only 1 8.8602 8.6341 9.0951 8.6456 5.339% 0.339% 0.775% 20.8 0.44
6.3 1--2 2 8.1011 7.8951 8.4853 7.9318 7.476% 0.702% 1.773% 41.7 0.40
6.3 1--3 3 8.4191 8.2117 8.8716 8.2815 8.036% 1.108% 2.698% 57.6 0.41
6.3 1--4 4 8.6023 8.3729 9.0466 8.4835 8.046% 1.430% 4.058% 68.6 0.35
6.3 1--5 5 8.3565 8.1541 8.8352 8.2801 8.353% 1.808% 5.701% 77.7 0.32
6.3 1--6 6 8.3364 8.1265 8.9261 8.2935 9.839% 2.126% 6.905% 83.4 0.31
6.3 1--7 7 8.1278 7.9263 8.6595 8.0976 9.250% 2.474% 8.728% 91.0 0.28
% Reflectance Readings


Wave-
length
(nm) Dip 1 Dip 2 Dip 3 Dip 4 Dip 5 Dip 6 Dip 7
400 11.93 7.15 5.24 4.23 3.48 3.08 2.72
420 15.97 9.80 6.91 5.43 4.41 3.79 3.30
440 14.83 8.72 6.03 4.71 3.81 3.26 2.84
460 12.58 7.14 4.86 3.78 3.08 2.65 2.33
480 10.80 5.82 3.92 3.06 2.51 2.18 1.92
500 9.47 4.93 3.31 2.60 2.17 1.90 1.70
520 7.82 3.93 2.67 2.12 1.78 1.61 1.46
540 6.23 3.09 2.14 1.75 1.52 1.41 1.30
560 5.25 2.61 1.85 1.56 1.39 1.32 1.23
580 4.34 2.21 1.64 1.42 1.30 1.26 1.18
600 3.57 1.89 1.47 1.32 1.24 1.22 1.16
620 3.05 1.70 1.40 1.29 1.23 1.22 1.17
640 2.61 1.57 1.37 1.29 1.26 1.28 1.24
660 2.51 1.60 1.42 1.39 1.35 1.41 1.39
680 3.31 2.00 1.70 1.62 1.55 1.60 1.59
700 7.97 4.26 3.16 2.71 2.37 2.25 2.13
299

Table A-4-1: Continued


Shade
ID
Speed
(m/min)
Dwell
Time
(sec)
Oxidation
Time (sec)
Dye Bath
(gpl
100%
Indigo)
Dye
Bath pH
Dye
Bath
(mV)
Dye Bath
Alkalinity
(gpl)
Dwell
Length
(m)
Oxidation
Length (m)
Nip
Pressures
(psi)
1134 31.09 16.7 69.5 2.314 11.89 805 5.17 8.63 36.03 70.00
Yarn Skein Response Variables
Yarn
Count
Dye
route Dips
Greige
Weight
Boil Off
Weight
Dyed
Weight
Washed
Weight %COWY
Total
%IOWY
Surface
%IOWY Integ
Penetration
Level
6.3 1 only 1 7.598 7.2978 7.632 7.274 4.579% 0.358% 0.669% 18.4 0.54
6.3 1--2 2 7.7048 7.4103 7.8917 7.3868 6.496% 0.757% 1.685% 40.0 0.45
6.3 1--3 3 7.7848 7.4763 7.9975 7.4662 6.971% 1.245% 2.699% 57.6 0.46
6.3 1--4 4 7.6821 7.3905 7.9348 7.4245 7.365% 1.500% 3.958% 67.9 0.38
6.3 1--5 5 7.7462 7.4572 8.0651 7.5261 8.152% 1.859% 5.370% 76.0 0.35
6.3 1--6 6 7.727 7.4248 8.1051 7.53 9.163% 2.177% 6.677% 82.4 0.33

% Reflectance Readings




















Wave-
length
(nm) Dip 1 Dip 2 Dip 3 Dip 4 Dip 5 Dip 6 Dip 7
400 12.64 7.21 5.16 4.15 3.55 3.15
420 17.04 9.96 6.78 5.35 4.43 3.87
440 15.90 8.92 5.89 4.64 3.83 3.32
460 13.59 7.33 4.83 3.76 3.12 2.71
480 11.76 5.99 3.92 3.06 2.54 2.23
500 10.34 5.10 3.32 2.62 2.22 1.96
520 8.63 4.07 2.68 2.14 1.83 1.65
540 6.90 3.21 2.14 1.77 1.56 1.44
560 5.88 2.73 1.87 1.58 1.43 1.34
580 4.92 2.34 1.65 1.44 1.34 1.27
600 4.05 1.99 1.49 1.35 1.27 1.23
620 3.43 1.76 1.38 1.29 1.25 1.21
640 2.90 1.63 1.35 1.29 1.29 1.26
660 2.72 1.61 1.38 1.36 1.38 1.36
680 3.54 2.01 1.62 1.57 1.57 1.55
700 8.45 4.23 3.07 2.62 2.38 2.22
300

Table A-4-1: Continued


Shade
ID
Speed
(m/min)
Dwell
Time
(sec)
Oxidation
Time (sec)
Dye Bath
(gpl
100%
Indigo)
Dye
Bath pH
Dye
Bath
(mV)
Dye Bath
Alkalinity
(gpl)
Dwell
Length
(m)
Oxidation
Length (m)
Nip
Pressures
(psi)
1134 31.09 16.7 69.5 2.314 11.89 805 5.17 8.63 36.03 70.00
Yarn Skein Response Variables
Yarn
Count
Dye
route Dips
Greige
Weight
Boil Off
Weight
Dyed
Weight
Washed
Weight %COWY
Total
%IOWY
Surface
%IOWY Integ
Penetration
Level
7.1 1 only 1 6.8377 6.6735 7.0041 6.647 4.954% 0.396% 0.699% 19.1 0.57
7.1 1--2 2 6.9015 6.6689 7.1094 6.6723 6.605% 0.766% 1.742% 41.1 0.44
7.1 1--3 3 6.6829 6.5137 7.0283 6.5492 7.900% 1.260% 2.647% 57.0 0.48
7.1 1--4 4 6.9189 6.6779 7.1999 6.7504 7.817% 1.477% 4.112% 68.9 0.36
7.1 1--5 5 6.8978 6.7207 7.3111 6.8215 8.785% 1.833% 6.694% 82.5 0.27
7.1 1--6 6 7.0832 6.8714 7.5302 7.0116 9.588% 2.150% 7.551% 86.2 0.28
7.1 1--7 7 6.92 6.7401 7.4097 6.9168 9.935% 2.644% 10.504% 97.4 0.25
% Reflectance Readings


Wave-
length
(nm) Dip 1 Dip 2 Dip 3 Dip 4 Dip 5 Dip 6 Dip 7
400 12.45 7.19 5.41 4.22 3.32 3.06 2.57
420 16.76 9.88 7.09 5.40 4.11 3.77 3.00
440 15.61 8.81 6.19 4.67 3.53 3.22 2.57
460 13.30 7.22 5.00 3.78 2.87 2.63 2.13
480 11.45 5.89 4.03 3.06 2.32 2.13 1.75
500 10.08 4.99 3.41 2.61 2.02 1.88 1.57
520 8.40 4.00 2.74 2.14 1.69 1.58 1.37
540 6.71 3.13 2.18 1.74 1.43 1.37 1.23
560 5.69 2.66 1.88 1.55 1.32 1.28 1.17
580 4.77 2.27 1.66 1.42 1.25 1.22 1.13
600 3.92 1.94 1.49 1.32 1.19 1.17 1.11
620 3.33 1.71 1.37 1.26 1.16 1.16 1.11
640 2.81 1.58 1.32 1.27 1.19 1.20 1.17
660 2.65 1.57 1.36 1.34 1.29 1.31 1.29
680 3.47 1.98 1.63 1.57 1.48 1.49 1.48
700 8.17 4.20 3.11 2.64 2.22 2.14 1.96
301

Table A-4-1: Continued


Shade
ID
Speed
(m/min)
Dwell
Time
(sec)
Oxidation
Time (sec)
Dye Bath
(gpl
100%
Indigo)
Dye
Bath pH
Dye
Bath
(mV)
Dye Bath
Alkalinity
(gpl)
Dwell
Length
(m)
Oxidation
Length (m)
Nip
Pressures
(psi)
1134 31.09 16.7 69.5 2.314 11.89 805 5.17 8.63 36.03 70.00
Yarn Skein Response Variables
Yarn
Count
Dye
route Dips
Greige
Weight
Boil Off
Weight
Dyed
Weight
Washed
Weight %COWY
Total
%IOWY
Surface
%IOWY Integ
Penetration
Level
8 1 only 1 6.111 5.8975 6.2071 5.8698 5.250% 0.439% 0.705% 19.3 0.62
8 1--2 2 6.0613 5.8551 6.2451 5.8486 6.661% 0.863% 1.680% 39.9 0.51
8 1--3 3 6.0564 5.8397 6.2566 5.8536 7.139% 1.299% 2.390% 53.5 0.54
8 1--4 4 6.0814 5.8677 6.3564 5.9073 8.329% 1.593% 3.537% 65.2 0.45
8 1--5 5 5.9915 5.7855 6.2681 5.8422 8.342% 2.013% 5.328% 75.8 0.38
8 1--6 6 6.1051 5.8809 6.443 5.9587 9.558% 2.336% 6.044% 79.4 0.39
8 1--7 7 5.4855 5.2819 5.7895 5.3765 9.610% 2.802% 8.573% 90.4 0.33
% Reflectance Readings


Wave-
length
(nm) Dip 1 Dip 2 Dip 3 Dip 4 Dip 5 Dip 6 Dip 7
400 12.11 7.09 5.52 4.43 3.63 3.36 2.81
420 16.32 9.72 7.25 5.69 4.53 4.14 3.39
440 15.16 8.69 6.35 4.94 3.89 3.56 2.90
460 12.89 7.15 5.15 3.98 3.15 2.89 2.37
480 11.09 5.85 4.17 3.22 2.55 2.36 1.93
500 9.75 4.99 3.54 2.75 2.23 2.07 1.71
520 8.16 4.03 2.87 2.26 1.85 1.73 1.48
540 6.55 3.18 2.30 1.84 1.57 1.48 1.31
560 5.61 2.74 2.01 1.65 1.44 1.38 1.24
580 4.75 2.35 1.78 1.50 1.34 1.30 1.19
600 3.96 2.03 1.59 1.38 1.27 1.26 1.16
620 3.39 1.81 1.48 1.33 1.24 1.23 1.17
640 2.89 1.69 1.45 1.33 1.27 1.28 1.21
660 2.75 1.69 1.49 1.41 1.36 1.38 1.34
680 3.49 2.11 1.76 1.64 1.57 1.56 1.54
700 7.93 4.26 3.26 2.79 2.41 2.32 2.09
302

Table A-4-1: Continued


Shade
ID
Speed
(m/min)
Dwell
Time
(sec)
Oxidation
Time (sec)
Dye Bath
(gpl
100%
Indigo)
Dye
Bath pH
Dye
Bath
(mV)
Dye Bath
Alkalinity
(gpl)
Dwell
Length
(m)
Oxidation
Length (m)
Nip
Pressures
(psi)
1134 31.09 16.7 69.5 2.314 11.89 805 5.17 8.63 39.40 70.00
Yarn Skein Response Variables
Yarn
Count
Dye
route Dips
Greige
Weight
Boil Off
Weight
Dyed
Weight
Washed
Weight %COWY
Total
%IOWY
Surface
%IOWY Integ
Penetration
Level
12 1 only 1 3.8875 3.7511 3.9984 3.7398 6.593% 0.511% 0.811% 20.5 0.63
12 1--2 2 3.9071 3.7686 4.0917 3.7811 8.573% 0.929% 1.554% 41.3 0.60
12 1--3 3 4.0031 3.861 4.2138 3.8945 9.138% 1.364% 2.938% 58.4 0.46
12 1--4? 4 3.9513 3.8107 4.162 3.8586 9.219% 1.941% 4.454% 70.7 0.44
12 1--5? 5 4.1207 3.9709 4.398 4.047 10.756% 2.348% 5.787% 78.7 0.41
12 1--6 6 3.8214 3.6823 4.1031 3.7702 11.428% 2.947% 8.498% 90.2 0.35
12 1--7 7 3.9128 3.771 4.186 3.8829 11.005% 3.366% 10.167% 95.3 0.33
% Reflectance Readings


Wave-
length
(nm) Dip 1 Dip 2 Dip 3 Dip 4 Dip 5 Dip 6 Dip 7
400 11.69 7.10 5.10 4.05 3.48 2.90 2.60
420 15.76 9.72 6.66 5.15 4.31 3.54 3.08
440 14.58 8.61 5.81 4.44 3.71 3.02 2.63
460 12.37 7.03 4.71 3.58 3.01 2.46 2.17
480 10.61 5.72 3.80 2.91 2.44 1.99 1.77
500 9.32 4.85 3.23 2.49 2.13 1.76 1.59
520 7.76 3.90 2.62 2.04 1.76 1.49 1.38
540 6.22 3.07 2.10 1.69 1.50 1.30 1.25
560 5.32 2.63 1.84 1.54 1.39 1.24 1.20
580 4.49 2.26 1.63 1.40 1.30 1.17 1.15
600 3.73 1.95 1.48 1.31 1.23 1.14 1.14
620 3.19 1.74 1.39 1.27 1.22 1.13 1.14
640 2.73 1.63 1.37 1.28 1.25 1.18 1.21
660 2.58 1.63 1.43 1.35 1.36 1.30 1.34
680 3.34 2.02 1.68 1.55 1.58 1.50 1.53
700 7.54 4.14 3.08 2.57 2.39 2.10 2.00
303

Table A-4-1: Continued


Shade
ID
Speed
(m/min)
Dwell
Time
(sec)
Oxidation
Time (sec)
Dye Bath
(gpl
100%
Indigo)
Dye
Bath pH
Dye
Bath
(mV)
Dye Bath
Alkalinity
(gpl)
Dwell
Length
(m)
Oxidation
Length (m)
Nip
Pressures
(psi)
t3688 32.92 15.8 65.7 2.417 11.82 867 4.93 8.63 39.40 70.00
Yarn Skein Response Variables
Yarn
Count
Dye
route Dips
Greige
Weight
Boil Off
Weight
Dyed
Weight
Washed
Weight %COWY
Total
%IOWY
Surface
%IOWY Integ
Penetration
Level
7.1 1 only 1 7.1993 6.9937 7.2912 7.0139 4.254% 0.402% 0.857% 22.6 0.47
7.1 1--2 2 7.214 7.0135 7.4253 7.0657 5.872% 0.766% 1.776% 44.9 0.43
7.1 1--3 3 7.2494 7.0394 7.4845 7.1113 6.323% 1.060% 2.900% 58.0 0.37
7.1 1--4 4 7.1546 6.9528 7.5403 7.0535 8.450% 1.501% 5.082% 74.7 0.30
7.1 1--5 5 7.1444 6.9383 7.4825 7.0733 7.843% 1.825% 6.725% 83.3 0.27
7.1 1--6 6 7.1714 6.9694 7.486 7.1378 7.412% 2.167% 8.503% 90.2 0.25
7.1 1--6,6 7 7.1765 6.9675 7.5829 7.1726 8.832% 2.572% 11.771% 99.3 0.22
% Reflectance Readings


Wave-
length
(nm) Dip 1 Dip 2 Dip 3 Dip 4 Dip 5 Dip 6 Dip 7
400 11.30 6.64 5.27 3.80 3.21 2.80 2.40
420 15.28 9.01 6.91 4.80 3.97 3.34 2.83
440 14.10 8.00 6.05 4.15 3.42 2.87 2.44
460 11.93 6.57 4.90 3.36 2.79 2.38 2.05
480 10.17 5.33 3.94 2.71 2.26 1.94 1.69
500 8.89 4.53 3.34 2.34 1.98 1.73 1.53
520 7.27 3.61 2.67 1.89 1.65 1.47 1.34
540 5.76 2.85 2.14 1.59 1.43 1.32 1.22
560 4.86 2.41 1.84 1.43 1.32 1.25 1.16
580 4.04 2.08 1.63 1.33 1.24 1.19 1.12
600 3.32 1.80 1.46 1.26 1.19 1.16 1.11
620 2.85 1.62 1.37 1.23 1.17 1.17 1.11
640 2.45 1.52 1.33 1.25 1.21 1.22 1.15
660 2.32 1.53 1.36 1.33 1.29 1.34 1.26
680 3.05 1.90 1.63 1.53 1.48 1.55 1.44
700 7.29 3.89 3.07 2.45 2.18 2.10 1.88
304

Table A-4-1: Continued


Shade
ID
Speed
(m/min)
Dwell
Time
(sec)
Oxidation
Time (sec)
Dye Bath
(gpl
100%
Indigo)
Dye
Bath pH
Dye
Bath
(mV)
Dye Bath
Alkalinity
(gpl)
Dwell
Length
(m)
Oxidation
Length (m)
Nip
Pressures
(psi)
1156 36.58 14.1 59.1 2.572 11.72 797 5.55 8.63 39.40 70.00
Yarn Skein Response Variables
Yarn
Count
Dye
route Dips
Greige
Weight
Boil Off
Weight
Dyed
Weight
Washed
Weight %COWY
Total
%IOWY
Surface
%IOWY Integ
Penetration
Level
6.3 1 only 1 7.556 7.2736 7.583 7.2751 4.25% 0.333% 0.773% 18.7 0.43
6.3 1--2 2 7.4803 7.2056 7.651 7.2164 6.18% 0.639% 1.381% 38.2 0.46
6.3 1--3 3 7.6443 7.3585 7.8813 7.3934 7.10% 0.961% 2.715% 56.2 0.35
6.3 1--4 4 7.8569 7.5632 8.1077 7.6298 7.20% 1.262% 3.559% 63.9 0.35
6.3 1--5 5 7.5259 7.2366 7.8535 7.3429 8.52% 1.795% 5.705% 78.3 0.31
6.3 1--6 6 7.7609 7.4636 8.1188 7.5897 8.78% 2.090% 6.706% 83.2 0.31
6.3 1--7 7 7.7295 7.4312 8.0923 7.6072 8.90% 2.432% 8.581% 90.5 0.28
% Reflectance Readings


Wave-
length
(nm) Dip 1 Dip 2 Dip 3 Dip 4 Dip 5 Dip 6 Dip 7
400 12.60 7.55 5.36 4.57 3.46 3.11 2.66
420 16.95 10.42 7.09 5.96 4.35 3.84 3.19
440 15.82 9.38 6.21 5.17 3.74 3.28 2.73
460 13.54 7.73 5.03 4.15 3.02 2.66 2.26
480 11.68 6.31 4.05 3.35 2.44 2.14 1.84
500 10.26 5.36 3.41 2.83 2.10 1.87 1.63
520 8.57 4.30 2.76 2.32 1.76 1.60 1.44
540 6.85 3.38 2.21 1.89 1.50 1.41 1.31
560 5.79 2.86 1.90 1.66 1.38 1.32 1.24
580 4.82 2.43 1.67 1.50 1.29 1.25 1.21
600 3.95 2.06 1.50 1.39 1.25 1.23 1.20
620 3.36 1.82 1.41 1.33 1.24 1.24 1.24
640 2.85 1.68 1.39 1.36 1.30 1.32 1.35
660 2.70 1.65 1.42 1.42 1.43 1.47 1.52
680 3.56 2.11 1.72 1.69 1.66 1.71 1.76
700 8.59 4.57 3.24 2.92 2.46 2.37 2.24
305

Table A-4-1: Continued


Shade
ID
Speed
(m/min)
Dwell
Time
(sec)
Oxidation
Time (sec)
Dye Bath
(gpl
100%
Indigo)
Dye
Bath pH
Dye
Bath
(mV)
Dye Bath
Alkalinity
(gpl)
Dwell
Length
(m)
Oxidation
Length (m)
Nip
Pressures
(psi)
1156 36.58 14.1 59.1 2.572 11.72 797 5.55 8.63 39.40 70.00
Yarn Skein Response Variables
Yarn
Count
Dye
route Dips
Greige
Weight
Boil Off
Weight
Dyed
Weight
Washed
Weight %COWY
Total
%IOWY
Surface
%IOWY Integ
Penetration
Level
7.1 1 only 1 6.9734 6.7622 7.0402 6.7304 4.11% 0.318% 0.744% 17.4 0.43
7.1 1--2 2 7.0212 6.7926 7.1906 6.8108 5.86% 0.591% 1.365% 37.8 0.43
7.1 1--3 3 6.8123 6.5915 7.086 6.6331 7.50% 0.987% 2.524% 54.2 0.39
7.1 1--4 4 6.9715 6.7395 7.2619 6.824 7.75% 1.423% 4.099% 68.1 0.35
7.1 1--5 5 6.9565 6.7298 7.3058 6.8297 8.56% 1.724% 5.340% 76.3 0.32
7.1 1--6 6 6.9443 6.7022 7.3574 6.8302 9.78% 2.231% 6.720% 83.3 0.33
7.1 1--7 7 6.8847 6.6635 7.2592 6.8068 8.94% 2.496% 7.807% 87.8 0.32
% Reflectance Readings


Wave-
length
(nm) Dip 1 Dip 2 Dip 3 Dip 4 Dip 5 Dip 6 Dip 7
400 13.21 7.64 5.59 4.24 3.59 3.13 2.82
420 17.66 10.55 7.38 5.42 4.50 3.81 3.39
440 16.52 9.51 6.47 4.69 3.85 3.26 2.88
460 14.16 7.84 5.24 3.79 3.11 2.65 2.37
480 12.27 6.40 4.23 3.06 2.50 2.14 1.93
500 10.81 5.44 3.57 2.58 2.15 1.87 1.69
520 9.11 4.35 2.87 2.11 1.79 1.59 1.48
540 7.31 3.42 2.30 1.75 1.53 1.39 1.34
560 6.22 2.90 1.97 1.56 1.41 1.32 1.28
580 5.20 2.45 1.74 1.44 1.33 1.26 1.24
600 4.28 2.08 1.55 1.34 1.28 1.24 1.23
620 3.61 1.83 1.44 1.30 1.27 1.25 1.25
640 3.06 1.67 1.41 1.33 1.34 1.34 1.37
660 2.88 1.66 1.47 1.42 1.47 1.50 1.56
680 3.79 2.10 1.79 1.66 1.69 1.71 1.82
700 9.00 4.60 3.40 2.77 2.53 2.35 2.35
306

Table A-4-1: Continued


Shade
ID
Speed
(m/min)
Dwell
Time
(sec)
Oxidation
Time (sec)
Dye Bath
(gpl
100%
Indigo)
Dye
Bath pH
Dye
Bath
(mV)
Dye Bath
Alkalinity
(gpl)
Dwell
Length
(m)
Oxidation
Length (m)
Nip
Pressures
(psi)
1156 36.58 14.1 59.1 2.572 11.72 797 5.55 8.63 39.40 70.00
Yarn Skein Response Variables
Yarn
Count
Dye
route Dips
Greige
Weight
Boil Off
Weight
Dyed
Weight
Washed
Weight %COWY
Total
%IOWY
Surface
%IOWY Integ
Penetration
Level
7.1 2 only 1 6.983 6.7611 7.0953 6.7585 4.94% 0.399% 0.812% 20.5 0.49
7.1 2,2 2 6.8036 6.5773 6.9899 6.5918 6.27% 0.728% 1.443% 39.4 0.50
7.1 2,2-3 3 7.0364 6.7992 7.3311 6.8485 7.82% 1.129% 2.753% 56.6 0.41
7.1 2,2-4 4 6.9084 6.6972 7.2414 6.7656 8.13% 1.515% 3.770% 65.6 0.40
7.1 2,2-5 5 7.0571 6.8152 7.4134 6.9268 8.78% 1.980% 5.695% 78.2 0.35


% Reflectance Readings


Wave-
length
(nm) Dip 1 Dip 2 Dip 3 Dip 4 Dip 5 Dip 6 Dip 7
400 11.87 7.40 5.40 4.41 3.51
420 15.95 10.19 7.11 5.69 4.36
440 14.82 9.12 6.18 4.89 3.73
460 12.62 7.49 4.98 3.92 3.01
480 10.86 6.11 4.01 3.15 2.43
500 9.52 5.18 3.38 2.67 2.09
520 7.89 4.15 2.72 2.18 1.75
540 6.30 3.27 2.19 1.81 1.50
560 5.33 2.77 1.89 1.62 1.38
580 4.44 2.35 1.68 1.48 1.30
600 3.65 2.01 1.50 1.40 1.25
620 3.12 1.79 1.40 1.34 1.24
640 2.67 1.67 1.37 1.39 1.31
660 2.55 1.66 1.41 1.50 1.45
680 3.35 2.12 1.71 1.76 1.68
700 7.92 4.47 3.21 2.90 2.48
307

Table A-4-1: Continued


Shade
ID
Speed
(m/min)
Dwell
Time
(sec)
Oxidation
Time (sec)
Dye Bath
(gpl
100%
Indigo)
Dye
Bath pH
Dye
Bath
(mV)
Dye Bath
Alkalinity
(gpl)
Dwell
Length
(m)
Oxidation
Length (m)
Nip
Pressures
(psi)
1156 36.58 14.1 59.1 2.572 11.72 797 5.55 8.63 39.40 70.00
Yarn Skein Response Variables
Yarn
Count
Dye
route Dips
Greige
Weight
Boil Off
Weight
Dyed
Weight
Washed
Weight %COWY
Total
%IOWY
Surface
%IOWY Integ
Penetration
Level
8 1 only 1 6.0265 5.8348 6.1145 5.8318 4.79% 0.369% 0.771% 18.6 0.48
8 1--2 2 6.0783 5.8852 6.2864 5.9 6.82% 0.729% 1.337% 37.3 0.55
8 1--3 3 5.9853 5.7931 6.2608 5.8401 8.07% 1.154% 2.445% 53.3 0.47
8 1--4 4 6.09 5.8885 6.3461 5.96 7.77% 1.532% 3.925% 66.8 0.39
8 1--5 5 6.0606 5.8632 6.3572 5.9571 8.43% 1.927% 5.307% 76.1 0.36
8 1--6 6 6.0638 5.8725 6.4474 5.9869 9.79% 2.310% 6.765% 83.5 0.34
8 1--7 7 6.0695 5.8727 6.4365 6.0203 9.60% 2.687% 8.083% 88.8 0.33
% Reflectance Readings


Wave-
length
(nm) Dip 1 Dip 2 Dip 3 Dip 4 Dip 5 Dip 6 Dip 7
400 12.86 7.76 5.69 4.39 3.66 3.17 2.83
420 17.19 10.61 7.52 5.65 4.60 3.89 3.37
440 15.96 9.55 6.56 4.88 3.93 3.30 2.87
460 13.60 7.88 5.32 3.93 3.17 2.66 2.35
480 11.74 6.46 4.30 3.18 2.57 2.16 1.91
500 10.31 5.49 3.63 2.70 2.21 1.88 1.70
520 8.63 4.40 2.91 2.20 1.82 1.58 1.46
540 6.91 3.46 2.33 1.80 1.55 1.40 1.33
560 5.85 2.93 2.01 1.60 1.42 1.32 1.27
580 4.87 2.48 1.76 1.45 1.32 1.25 1.21
600 4.00 2.11 1.58 1.35 1.27 1.23 1.22
620 3.39 1.87 1.46 1.28 1.24 1.22 1.22
640 2.87 1.73 1.43 1.30 1.29 1.30 1.33
660 2.70 1.70 1.48 1.38 1.42 1.46 1.51
680 3.58 2.18 1.78 1.63 1.65 1.70 1.75
700 8.55 4.72 3.43 2.80 2.53 2.37 2.26
308

Table A-4-1: Continued


Shade
ID
Speed
(m/min)
Dwell
Time
(sec)
Oxidation
Time (sec)
Dye Bath
(gpl
100%
Indigo)
Dye
Bath pH
Dye
Bath
(mV)
Dye Bath
Alkalinity
(gpl)
Dwell
Length
(m)
Oxidation
Length (m)
Nip
Pressures
(psi)
1156 36.58 14.1 59.1 2.572 11.72 797 5.55 8.63 39.40 70.00
Yarn Skein Response Variables
Yarn
Count
Dye
route Dips
Greige
Weight
Boil Off
Weight
Dyed
Weight
Washed
Weight %COWY
Total
%IOWY
Surface
%IOWY Integ
Penetration
Level
8 2 only 1 5.9864 5.791 6.123 5.7978 5.73% 0.438% 0.820% 20.9 0.53
8 2,2 2 6.1299 5.9379 6.3578 5.9582 7.07% 0.804% 1.480% 40.0 0.54
8 2,2-3 3 5.9995 5.8051 6.2847 5.847 8.26% 1.153% 2.411% 53.0 0.48
8 2,2-4 4 6.0744 5.8782 6.3371 5.9483 7.81% 1.555% 3.695% 65.0 0.42
8 2,2-5 5 6.0165 5.8274 6.318782 5.9211 8.43% 2.071% 5.329% 76.2 0.39


% Reflectance Readings


Wave-
length
(nm) Dip 1 Dip 2 Dip 3 Dip 4 Dip 5 Dip 6 Dip 7
400 11.80 7.27 5.67 4.49 3.61
420 15.89 9.96 7.47 5.78 4.50
440 14.70 8.86 6.52 4.99 3.83
460 12.48 7.27 5.28 4.01 3.08
480 10.71 5.94 4.26 3.25 2.49
500 9.40 5.05 3.61 2.75 2.16
520 7.75 4.04 2.91 2.23 1.79
540 6.19 3.19 2.34 1.83 1.54
560 5.24 2.73 2.03 1.64 1.43
580 4.36 2.32 1.78 1.49 1.33
600 3.60 1.99 1.61 1.39 1.29
620 3.05 1.78 1.47 1.33 1.26
640 2.62 1.66 1.45 1.36 1.34
660 2.51 1.67 1.51 1.47 1.48
680 3.31 2.10 1.82 1.73 1.71
700 7.83 4.36 3.43 2.90 2.54
309

Table A-4-1: Continued


Shade
ID
Speed
(m/min)
Dwell
Time
(sec)
Oxidation
Time (sec)
Dye Bath
(gpl
100%
Indigo)
Dye
Bath pH
Dye
Bath
(mV)
Dye Bath
Alkalinity
(gpl)
Dwell
Length
(m)
Oxidation
Length (m)
Nip
Pressures
(psi)
1156 36.58 14.1 59.1 2.572 11.72 797 5.55 8.63 39.40 70.00
Yarn Skein Response Variables
Yarn
Count
Dye
route Dips
Greige
Weight
Boil Off
Weight
Dyed
Weight
Washed
Weight %COWY
Total
%IOWY
Surface
%IOWY Integ
Penetration
Level
12 1 only 1 3.9582 3.8257 4.0678 3.8273 6.33% 0.472% 0.812% 20.6 0.58
12 1--2 2 3.9604 3.8242 4.1419 3.8493 8.31% 0.882% 1.542% 41.1 0.57
12 1--3 3 3.9143 3.7782 4.148 3.8214 9.79% 1.407% 2.839% 57.4 0.50
12 1--4 4 3.8219 3.688 4.0574 3.7553 10.02% 1.860% 4.625% 71.8 0.40
12 1--5 5 3.8788 3.7391 4.1079 3.8222 9.86% 2.278% 6.089% 80.3 0.37
12 1--6 6 3.8516 3.7129 4.1444 3.8153 11.62% 2.747% 8.421% 90.0 0.33
12 1--7 7 3.9529 3.8151 4.2469 3.9385 11.32% 3.149% 9.766% 94.2 0.32
% Reflectance Readings


Wave-
length
(nm) Dip 1 Dip 2 Dip 3 Dip 4 Dip 5 Dip 6 Dip 7
400 11.88 7.26 5.34 4.05 3.43 2.90 2.64
420 15.83 9.93 6.96 5.12 4.23 3.53 3.13
440 14.66 8.84 6.07 4.40 3.62 2.99 2.65
460 12.47 7.23 4.91 3.55 2.93 2.43 2.18
480 10.74 5.90 3.96 2.87 2.37 1.97 1.78
500 9.44 5.02 3.34 2.43 2.05 1.72 1.57
520 7.82 4.00 2.68 1.98 1.70 1.46 1.36
540 6.28 3.15 2.16 1.65 1.46 1.30 1.25
560 5.33 2.66 1.86 1.48 1.35 1.23 1.19
580 4.45 2.26 1.65 1.36 1.27 1.17 1.16
600 3.68 1.94 1.49 1.29 1.23 1.17 1.17
620 3.13 1.70 1.38 1.26 1.21 1.16 1.19
640 2.70 1.57 1.36 1.31 1.29 1.26 1.29
660 2.60 1.57 1.43 1.42 1.40 1.42 1.48
680 3.44 2.00 1.73 1.64 1.63 1.64 1.69
700 7.93 4.30 3.22 2.64 2.41 2.22 2.17
310

Table A-4-1: Continued


Shade
ID
Speed
(m/min)
Dwell
Time
(sec)
Oxidation
Time (sec)
Dye Bath
(gpl
100%
Indigo)
Dye
Bath pH
Dye
Bath
(mV)
Dye Bath
Alkalinity
(gpl)
Dwell
Length
(m)
Oxidation
Length (m)
Nip
Pressures
(psi)
1157 32.92 15.9 65.7 2.497 12.41 847 3.67 8.63 39.40 70.00
Yarn Skein Response Variables
Yarn
Count
Dye
route Dips
Greige
Weight
Boil Off
Weight
Dyed
Weight
Washed
Weight %COWY
Total
%IOWY
Surface
%IOWY Integ
Penetration
Level
6.3 1 only 1 8.142 7.9097 8.2668 7.933 4.51% 0.389% 0.829% 21.4 0.47
6.3 1--2 2 8.1133 7.8832 8.3604 7.9382 6.05% 0.620% 1.543% 41.2 0.40
6.3 1--3 3 8.1656 7.9386 8.458 8.0229 6.54% 0.961% 3.340% 62.1 0.29
6.3 1--4 4 8.0574 7.8317 8.3743 7.9624 6.93% 1.433% 4.997% 74.2 0.29
6.3 1--5 5 8.0475 7.8235 8.4644 7.9766 8.19% 1.799% 7.223% 85.5 0.25
6.3 1--6 6 8.1859 7.9489 8.5703 8.1472 7.82% 2.163% 8.439% 90.0 0.26
6.3 1--6,6 7 7.9508 7.719432 8.3508 7.937 8.18% 2.453% 9.925% 94.6 0.25
% Reflectance Readings


Wave-
length
(nm) Dip 1 Dip 2 Dip 3 Dip 4 Dip 5 Dip 6 Dip 7
400 11.83 7.30 4.93 3.87 3.17 2.83 2.55
420 15.90 10.00 6.42 4.88 3.90 3.39 3.00
440 14.64 8.87 5.57 4.19 3.33 2.89 2.56
460 12.40 7.26 4.51 3.39 2.71 2.37 2.12
480 10.61 5.91 3.64 2.75 2.20 1.93 1.76
500 9.29 5.02 3.09 2.37 1.92 1.72 1.58
520 7.64 3.99 2.48 1.93 1.59 1.47 1.38
540 6.09 3.14 1.99 1.62 1.38 1.32 1.26
560 5.11 2.65 1.72 1.45 1.27 1.24 1.21
580 4.24 2.24 1.52 1.33 1.20 1.18 1.17
600 3.49 1.92 1.38 1.25 1.16 1.17 1.17
620 2.98 1.70 1.30 1.21 1.16 1.18 1.18
640 2.57 1.60 1.30 1.26 1.24 1.28 1.29
660 2.45 1.59 1.34 1.36 1.35 1.43 1.45
680 3.20 2.01 1.58 1.57 1.58 1.62 1.66
700 7.71 4.28 2.95 2.54 2.28 2.16 2.07
311

Table A-4-1: Continued


Shade
ID
Speed
(m/min)
Dwell
Time
(sec)
Oxidation
Time (sec)
Dye Bath
(gpl
100%
Indigo)
Dye
Bath pH
Dye
Bath
(mV)
Dye Bath
Alkalinity
(gpl)
Dwell
Length
(m)
Oxidation
Length (m)
Nip
Pressures
(psi)
1157 32.92 15.9 65.7 2.497 12.41 847 3.67 8.63 39.40 70.00
Yarn Skein Response Variables
Yarn
Count
Dye
route Dips
Greige
Weight
Boil Off
Weight
Dyed
Weight
Washed
Weight %COWY
Total
%IOWY
Surface
%IOWY Integ
Penetration
Level
7.1 1 only 1 7.1734 6.9485 7.2544 6.9731 4.40% 0.434% 0.882% 23.7 0.49
7.1 1--2 2 7.4045 7.1267 7.5365 7.1713 5.75% 0.768% 1.674% 43.3 0.46
7.1 1--3 3 7.4093 7.2019 7.6543 7.2853 6.28% 1.143% 3.005% 59.0 0.38
7.1 1--4 4 7.421 7.2128 7.7295 7.3259 7.16% 1.550% 4.910% 73.7 0.32
7.1 1--5 5 7.4693 7.2597 7.8361 7.4102 7.94% 1.943% 6.729% 83.3 0.29
7.1 1--6 6 7.1638 6.9308 7.4922 7.0949 8.10% 2.331% 7.859% 88.0 0.30
7.1 1--6,6 7 7.3332 7.1254 7.7125 7.3283 8.24% 2.702% 9.470% 93.3 0.29
% Reflectance Readings


Wave-
length
(nm) Dip 1 Dip 2 Dip 3 Dip 4 Dip 5 Dip 6 Dip 7
400 11.16 7.05 5.30 3.93 3.28 2.90 2.57
420 15.05 9.55 6.86 4.91 3.99 3.44 2.95
440 13.78 8.42 5.95 4.22 3.42 2.92 2.52
460 11.56 6.89 4.80 3.41 2.79 2.40 2.10
480 9.85 5.60 3.87 2.77 2.28 1.98 1.75
500 8.60 4.75 3.28 2.39 1.98 1.75 1.59
520 6.99 3.77 2.62 1.93 1.64 1.50 1.38
540 5.54 2.98 2.09 1.62 1.42 1.35 1.28
560 4.66 2.52 1.82 1.46 1.32 1.27 1.23
580 3.84 2.13 1.59 1.34 1.23 1.22 1.20
600 3.17 1.85 1.45 1.27 1.19 1.21 1.21
620 2.69 1.63 1.33 1.22 1.16 1.21 1.22
640 2.34 1.56 1.34 1.27 1.23 1.30 1.34
660 2.24 1.56 1.38 1.36 1.33 1.45 1.54
680 2.96 1.94 1.64 1.55 1.51 1.64 1.77
700 7.06 4.08 3.09 2.50 2.22 2.16 2.18
312

Table A-4-1: Continued


Shade
ID
Speed
(m/min)
Dwell
Time
(sec)
Oxidation
Time (sec)
Dye Bath
(gpl
100%
Indigo)
Dye
Bath pH
Dye
Bath
(mV)
Dye Bath
Alkalinity
(gpl)
Dwell
Length
(m)
Oxidation
Length (m)
Nip
Pressures
(psi)
1157 32.92 15.9 65.7 2.497 12.41 847 3.67 8.63 39.40 70.00
Yarn Skein Response Variables
Yarn
Count
Dye
route Dips
Greige
Weight
Boil Off
Weight
Dyed
Weight
Washed
Weight %COWY
Total
%IOWY
Surface
%IOWY Integ
Penetration
Level
8 1 only 1 9.5909 9.3454 9.7845 9.3589 4.70% 0.405% 0.852% 22.4 0.48
8 1--2 2 9.8043 9.5337 10.0859 9.6053 5.79% 0.731% 1.610% 42.3 0.45
8 1--3 3 9.5334 9.2729 9.8587 9.3787 6.32% 1.176% 3.190% 60.7 0.37
8 1--4 4 9.4579 9.1968 9.8563 9.3389 7.17% 1.553% 5.139% 75.1 0.30
8 1--5 5 9.736 9.4737 10.2325 9.6579 8.01% 1.877% 6.661% 83.0 0.28
8 1--6 6 9.6276 9.3484 10.0819 9.5725 7.85% 2.304% 9.218% 92.5 0.25
8 1--6,6 7 9.6693 9.4075 10.1896 9.6689 8.31% 2.705% 10.476% 96.1 0.26
% Reflectance Readings


Wave-
length
(nm) Dip 1 Dip 2 Dip 3 Dip 4 Dip 5 Dip 6 Dip 7
400 11.41 7.09 5.03 3.84 3.28 2.77 2.48
420 15.32 9.77 6.59 4.89 4.09 3.35 2.93
440 14.10 8.65 5.71 4.19 3.48 2.85 2.49
460 11.91 7.08 4.61 3.38 2.83 2.34 2.08
480 10.20 5.75 3.72 2.74 2.28 1.90 1.71
500 8.93 4.89 3.16 2.36 2.00 1.69 1.54
520 7.34 3.89 2.55 1.92 1.65 1.44 1.35
540 5.84 3.07 2.03 1.60 1.43 1.28 1.24
560 4.91 2.58 1.76 1.44 1.31 1.20 1.19
580 4.06 2.19 1.56 1.31 1.23 1.15 1.16
600 3.35 1.87 1.41 1.24 1.19 1.13 1.16
620 2.86 1.67 1.32 1.19 1.17 1.13 1.17
640 2.49 1.57 1.32 1.22 1.23 1.22 1.29
660 2.40 1.58 1.36 1.30 1.34 1.35 1.46
680 3.16 2.01 1.61 1.51 1.53 1.56 1.67
700 7.42 4.21 2.99 2.46 2.26 2.09 2.07
313

Table A-4-1: Continued


Shade
ID
Speed
(m/min)
Dwell
Time
(sec)
Oxidation
Time (sec)
Dye Bath
(gpl
100%
Indigo)
Dye
Bath pH
Dye
Bath
(mV)
Dye Bath
Alkalinity
(gpl)
Dwell
Length
(m)
Oxidation
Length (m)
Nip
Pressures
(psi)
X3254 27.43 18.9 78.8 2.614 12.29 778 2.85 8.63 39.40 70.00
Yarn Skein Response Variables
Yarn
Count
Dye
route Dips
Greige
Weight
Boil Off
Weight
Dyed
Weight
Washed
Weight %COWY
Total
%IOWY
Surface
%IOWY Integ
Penetration
Level
6.3 1 only 1 7.0863 6.8354 7.0327 6.832 2.89% 0.457% 0.861% 22.8 0.53
6.3 1--2 2 7.0547 6.7858 7.0644 6.8202 4.11% 0.888% 1.643% 42.8 0.54
6.3 1--3 3 7.1753 6.9132 7.2362 6.973 4.67% 1.367% 2.886% 57.9 0.47
6.3 1--5 5 7.2079 6.9466 7.3506 7.0718 5.82% 2.223% 6.482% 82.2 0.34



% Reflectance Readings


Wave-
length
(nm) Dip 1 Dip 2 Dip 3 Dip 4 Dip 5 Dip 6 Dip 7
400 10.98 6.81 5.15 3.19
420 14.90 9.23 6.65 3.82
440 13.81 8.16 5.78 3.26
460 11.67 6.64 4.65 2.64
480 9.97 5.41 3.76 2.17
500 8.73 4.59 3.18 1.87
520 7.14 3.68 2.58 1.60
540 5.68 2.92 2.08 1.40
560 4.79 2.50 1.82 1.32
580 4.00 2.17 1.64 1.28
600 3.30 1.89 1.50 1.26
620 2.84 1.74 1.45 1.30
640 2.45 1.67 1.46 1.41
660 2.35 1.74 1.57 1.60
680 3.06 2.11 1.87 1.81
700 7.14 4.11 3.24 2.46
314

Table A-4-1: Continued


Shade
ID
Speed
(m/min)
Dwell
Time
(sec)
Oxidation
Time (sec)
Dye Bath
(gpl
100%
Indigo)
Dye
Bath pH
Dye
Bath
(mV)
Dye Bath
Alkalinity
(gpl)
Dwell
Length
(m)
Oxidation
Length (m)
Nip
Pressures
(psi)
1156 36.58 14.1 59.1 2.716 11.94 836 6.06 8.63 39.40 70.00
Yarn Skein Response Variables
Yarn
Count
Dye
route Dips
Greige
Weight
Boil Off
Weight
Dyed
Weight
Washed
Weight %COWY
Total
%IOWY
Surface
%IOWY Integ
Penetration
Level
7.1 1 only 1 7.0846 6.8944 7.2006 6.9102 4.44% 0.395% 0.825% 21.1 0.48
7.1 1--2 2 7.2738 7.0726 7.5669 7.1244 6.99% 0.764% 1.694% 43.6 0.45
7.1 1--3 3 7.2817 7.0866 7.684 7.1666 8.43% 1.146% 3.115% 60.1 0.37
7.1 1--4 4 7.2632 7.0713 7.6334 7.1794 7.95% 1.439% 4.487% 70.9 0.32
7.1 1--5 5 7.2981 7.0959 7.7082 7.2403 8.63% 1.977% 7.020% 84.6 0.28
7.1 1--6 6 7.2366 7.0459 7.7565 7.2116 10.09% 2.212% 8.471% 90.1 0.26
7.1 1--7 7 7.3062 7.1145 7.7676 7.3076 9.18% 2.571% 10.845% 97.1 0.24
% Reflectance Readings


Wave-
length
(nm) Dip 1 Dip 2 Dip 3 Dip 4 Dip 5 Dip 6 Dip 7
400 11.54 6.73 5.02 4.06 3.11 2.80 2.50
420 15.49 9.16 6.50 5.14 3.80 3.38 2.95
440 14.41 8.16 5.71 4.45 3.26 2.91 2.52
460 12.27 6.71 4.62 3.58 2.65 2.37 2.08
480 10.57 5.49 3.74 2.90 2.16 1.93 1.71
500 9.27 4.65 3.17 2.47 1.87 1.70 1.53
520 7.65 3.70 2.54 2.00 1.56 1.44 1.32
540 6.13 2.93 2.04 1.67 1.37 1.30 1.22
560 5.18 2.49 1.77 1.50 1.29 1.23 1.17
580 4.31 2.13 1.58 1.38 1.23 1.18 1.13
600 3.57 1.84 1.43 1.31 1.21 1.17 1.14
620 3.07 1.68 1.38 1.29 1.23 1.22 1.18
640 2.62 1.57 1.34 1.30 1.30 1.28 1.26
660 2.54 1.60 1.41 1.44 1.46 1.46 1.46
680 3.31 1.98 1.68 1.66 1.66 1.66 1.70
700 7.75 4.10 3.07 2.67 2.31 2.19 2.12
315

Table A-4-1: Continued


Shade
ID
Speed
(m/min)
Dwell
Time
(sec)
Oxidation
Time (sec)
Dye Bath
(gpl
100%
Indigo)
Dye
Bath pH
Dye
Bath
(mV)
Dye Bath
Alkalinity
(gpl)
Dwell
Length
(m)
Oxidation
Length (m)
Nip
Pressures
(psi)
1156 36.58 14.1 59.1 2.716 11.94 836 6.06 8.63 39.40 70.00
Yarn Skein Response Variables
Yarn
Count
Dye
route Dips
Greige
Weight
Boil Off
Weight
Dyed
Weight
Washed
Weight %COWY
Total
%IOWY
Surface
%IOWY Integ
Penetration
Level
8 1 only 1 9.157 8.8285 9.285 8.8582 5.17% 0.448% 0.828% 21.3 0.54
8 1--2 2 9.2187 8.8819 9.5447 8.9483 7.46% 0.822% 1.590% 42.0 0.52
8 1--3 3 9.2091 8.8697 9.6067 8.9843 8.31% 1.262% 2.837% 57.4 0.44
8 1--4 4 9.1593 8.8267 9.5991 8.9816 8.75% 1.690% 5.299% 76.0 0.32
8 1--5 5 9.1617 8.8393 9.74 9.0191 10.19% 1.936% 6.485% 82.2 0.30
8 1--6 6 12.3627 11.9224 13.1881 12.2615 10.62% 2.426% 9.334% 92.9 0.26

% Reflectance Readings


Wave-
length
(nm) Dip 1 Dip 2 Dip 3 Dip 4 Dip 5 Dip 6 Dip 7
400 11.71 6.98 5.19 3.66 3.18 2.64
420 15.68 9.49 6.71 4.56 3.88 3.16
440 14.53 8.46 5.89 3.95 3.35 2.72
460 12.33 6.97 4.79 3.22 2.73 2.25
480 10.59 5.70 3.89 2.62 2.24 1.85
500 9.25 4.84 3.29 2.25 1.94 1.64
520 7.63 3.86 2.65 1.84 1.63 1.42
540 6.09 3.05 2.14 1.55 1.42 1.28
560 5.14 2.58 1.86 1.41 1.32 1.21
580 4.28 2.22 1.65 1.31 1.26 1.16
600 3.54 1.91 1.49 1.25 1.23 1.15
620 3.04 1.73 1.43 1.25 1.26 1.19
640 2.59 1.61 1.41 1.28 1.33 1.24
660 2.48 1.60 1.47 1.40 1.50 1.39
680 3.27 2.02 1.75 1.62 1.71 1.60
700 7.84 4.25 3.22 2.54 2.40 2.11
316

Table A-4-1: Continued


Shade
ID
Speed
(m/min)
Dwell
Time
(sec)
Oxidation
Time (sec)
Dye Bath
(gpl
100%
Indigo)
Dye
Bath pH
Dye
Bath
(mV)
Dye Bath
Alkalinity
(gpl)
Dwell
Length
(m)
Oxidation
Length (m)
Nip
Pressures
(psi)
1156 36.58 14.1 59.1 2.716 11.94 836 6.06 8.63 39.40 70.00
Yarn Skein Response Variables
Yarn
Count
Dye
route Dips
Greige
Weight
Boil Off
Weight
Dyed
Weight
Washed
Weight %COWY
Total
%IOWY
Surface
%IOWY Integ
Penetration
Level
12 1 only 1 6.2957 6.1185 6.4358 6.1379 5.19% 0.472% 0.790% 19.5 0.60
12 1--2 2 6.231 6.0586 6.515 6.1125 7.53% 0.919% 1.669% 43.2 0.55
12 1--3 3 6.2971 6.1169 6.6442 6.201 8.62% 1.331% 2.966% 58.7 0.45
12 1--4 4 6.2537 6.0728 6.6664 6.1909 9.77% 1.812% 4.964% 74.0 0.37
12 1--5 5 6.1908 6.0126 6.7291 6.1594 11.92% 2.260% 6.244% 81.1 0.36
12 1--6 6 6.2478 6.0675 6.7356 6.2375 11.01% 2.587% 8.617% 90.6 0.30
12 1--7 7 6.3074 6.1333 6.7564 6.3226 10.16% 2.970% 9.696% 94.0 0.31
% Reflectance Readings


Wave-
length
(nm) Dip 1 Dip 2 Dip 3 Dip 4 Dip 5 Dip 6 Dip 7
400 12.42 6.85 5.13 3.83 3.33 2.80 2.59
420 16.73 9.30 6.73 4.84 4.12 3.39 3.09
440 15.50 8.24 5.86 4.17 3.53 2.90 2.64
460 13.18 6.75 4.74 3.36 2.85 2.37 2.16
480 11.32 5.51 3.83 2.72 2.31 1.92 1.77
500 9.93 4.67 3.23 2.32 2.00 1.69 1.46
520 8.24 3.73 2.60 1.89 1.66 1.44 1.37
540 6.58 2.96 2.09 1.59 1.44 1.29 1.25
560 5.57 2.51 1.81 1.44 1.33 1.22 1.21
580 4.65 2.15 1.61 1.33 1.25 1.17 1.16
600 3.83 1.86 1.45 1.27 1.22 1.16 1.18
620 3.28 1.70 1.40 1.27 1.25 1.20 1.22
640 2.79 1.58 1.38 1.32 1.33 1.29 1.33
660 2.63 1.60 1.46 1.45 1.50 1.47 1.53
680 3.47 2.02 1.76 1.69 1.74 1.69 1.77
700 8.32 4.14 3.18 2.60 2.46 2.21 2.18
317

Table A-4-1: Continued


Shade
ID
Speed
(m/min)
Dwell
Time
(sec)
Oxidation
Time (sec)
Dye Bath
(gpl
100%
Indigo)
Dye
Bath pH
Dye
Bath
(mV)
Dye Bath
Alkalinity
(gpl)
Dwell
Length
(m)
Oxidation
Length (m)
Nip
Pressures
(psi)
1134 31.09 16.7 69.5 2.994 11.98 789 6.6 8.63 39.40 70.00
Yarn Skein Response Variables
Yarn
Count
Dye
route Dips
Greige
Weight
Boil Off
Weight
Dyed
Weight
Washed
Weight %COWY
Total
%IOWY
Surface
%IOWY Integ
Penetration
Level
6.3 1 only 1 8.7563 8.5312 9.0642 8.5625 6.25% 0.445% 0.892% 24.2 0.50
6.3 1--2 2 8.3909 8.1668 8.8673 8.242 8.58% 0.863% 2.160% 50.0 0.40
6.3 1--3 3 8.2301 8.0143 8.7259 8.1204 8.88% 1.317% 3.666% 64.8 0.36
6.3 1--4 4 8.3198 8.0998 8.8964 8.2629 9.83% 1.798% 6.038% 80.0 0.30
6.3 1--5 5 8.0571 7.858 8.6747 8.0267 10.39% 2.166% 7.865% 88.0 0.28
6.3 1--6 6 8.182 7.9761 8.9362 8.1966 12.04% 2.681% 10.103% 95.1 0.27
6.3 1--7 7 9.2415 9.0051 9.9958 9.2982 11.00% 3.014% 13.358% 102.6 0.23
% Reflectance Readings


Wave-
length
(nm) Dip 1 Dip 2 Dip 3 Dip 4 Dip 5 Dip 6 Dip 7
400 10.91 6.13 4.65 3.48 3.01 2.60 2.31
420 14.81 8.22 6.02 4.34 3.67 3.06 2.64
440 13.56 7.19 5.20 3.71 3.12 2.60 2.25
460 11.35 5.81 4.18 2.99 2.53 2.14 1.86
480 9.64 4.69 3.37 2.43 2.06 1.75 1.56
500 8.39 3.96 2.85 2.08 1.79 1.55 1.40
520 6.82 3.17 2.31 1.73 1.52 1.37 1.25
540 5.40 2.52 1.88 1.48 1.35 1.24 1.17
560 4.52 2.15 1.64 1.35 1.26 1.19 1.14
580 3.75 1.86 1.47 1.25 1.18 1.14 1.11
600 3.10 1.63 1.35 1.20 1.15 1.15 1.11
620 2.67 1.51 1.30 1.20 1.16 1.19 1.15
640 2.34 1.47 1.31 1.27 1.25 1.29 1.28
660 2.26 1.52 1.39 1.40 1.40 1.48 1.48
680 2.96 1.87 1.64 1.63 1.61 1.72 1.72
700 6.97 3.64 2.88 2.44 2.22 2.18 2.04
318

Table A-4-1: Continued


Shade
ID
Speed
(m/min)
Dwell
Time
(sec)
Oxidation
Time (sec)
Dye Bath
(gpl
100%
Indigo)
Dye
Bath pH
Dye
Bath
(mV)
Dye Bath
Alkalinity
(gpl)
Dwell
Length
(m)
Oxidation
Length (m)
Nip
Pressures
(psi)
1134 31.09 16.7 69.5 2.994 11.98 789 6.6 8.63 39.40 70.00
Yarn Skein Response Variables
Yarn
Count
Dye
route Dips
Greige
Weight
Boil Off
Weight
Dyed
Weight
Washed
Weight %COWY
Total
%IOWY
Surface
%IOWY Integ
Penetration
Level
8 1 only 1 8.741 8.4602 9.0905 8.4991 7.45% 0.577% 0.897% 24.4 0.64
8 1--2 2 8.6098 8.3352 9.1162 8.4211 9.37% 1.143% 1.853% 46.0 0.62
8 1--3 3 8.1409 7.8845 8.6864 7.9923 10.17% 1.534% 3.590% 64.2 0.43
8 1--4 4 8.4871 8.2161 9.1 8.3712 10.76% 1.972% 5.054% 74.6 0.39
8 1--5 5 7.8553 7.6096 8.4208 7.8006 10.66% 2.480% 7.095% 84.9 0.35
8 1--6 6 7.8736 7.622 8.638 7.8505 13.33% 2.947% 8.436% 90.0 0.35
8 1--7 7 8.6011 8.3298 9.3674 8.6612 12.46% 3.533% 10.628% 96.5 0.33
% Reflectance Readings


Wave-
length
(nm) Dip 1 Dip 2 Dip 3 Dip 4 Dip 5 Dip 6 Dip 7
400 10.75 6.43 4.59 3.76 2.99 2.71 2.38
420 14.54 8.55 5.87 4.68 3.57 3.16 2.66
440 13.32 7.52 5.07 4.00 3.05 2.69 2.28
460 11.14 6.13 4.07 3.22 2.50 2.22 1.91
480 9.44 4.97 3.27 2.60 2.05 1.82 1.59
500 8.21 4.22 2.78 2.25 1.81 1.63 1.45
520 6.69 3.39 2.27 1.85 1.55 1.43 1.31
540 5.33 2.72 1.86 1.57 1.38 1.31 1.24
560 4.49 2.34 1.66 1.44 1.30 1.26 1.22
580 3.74 2.04 1.51 1.35 1.27 1.23 1.20
600 3.11 1.79 1.40 1.29 1.25 1.23 1.24
620 2.67 1.64 1.33 1.26 1.24 1.25 1.27
640 2.36 1.63 1.40 1.35 1.37 1.40 1.45
660 2.29 1.67 1.52 1.49 1.53 1.60 1.70
680 2.96 2.01 1.75 1.68 1.71 1.81 1.94
700 6.84 3.89 2.97 2.58 2.33 2.29 2.26
319

Table A-4-1: Continued


Shade
ID
Speed
(m/min)
Dwell
Time
(sec)
Oxidation
Time (sec)
Dye Bath
(gpl
100%
Indigo)
Dye
Bath pH
Dye
Bath
(mV)
Dye Bath
Alkalinity
(gpl)
Dwell
Length
(m)
Oxidation
Length (m)
Nip
Pressures
(psi)
1134 31.09 16.7 69.5 3.133 12.54 801 6.16 8.63 39.40 70.00
Yarn Skein Response Variables
Yarn
Count
Dye
route Dips
Greige
Weight
Boil Off
Weight
Dyed
Weight
Washed
Weight %COWY
Total
%IOWY
Surface
%IOWY Integ
Penetration
Level
6.3 1 only 1 7.3185 7.2391 7.5081 7.033 3.72% 0.470% 0.936% 26.0 0.50
6.3 1--2 2 7.1757 7.0941 7.4719 6.8659 5.33% 0.991% 2.121% 49.5 0.47
6.3 1--3 3 7.3111 7.2613 7.7102 7.0736 6.18% 1.586% 4.255% 69.3 0.37
6.3 1--4 4 7.216 7.1484 7.6962 7.0295 7.66% 2.035% 5.226% 75.6 0.39
6.3 1--5 5 7.097 6.9895 7.6214 6.9277 9.04% 2.699% 7.838% 87.9 0.34
6.3 1--6 6 7.2095 7.1868 7.8637 7.1291 9.42% 3.322% 10.718% 96.7 0.31
6.3 1--7 7 7.1665 7.1341 7.7023 7.0573 7.96% 3.632% 12.695% 101.3 0.29
% Reflectance Readings


Wave-
length
(nm) Dip 1 Dip 2 Dip 3 Dip 4 Dip 5 Dip 6 Dip 7
400 10.10 6.10 4.17 3.58 2.89 2.49 2.31
420 13.66 8.11 5.30 4.45 3.48 2.89 2.62
440 12.55 7.13 4.58 3.83 2.96 2.47 2.25
460 10.54 5.80 3.70 3.11 2.42 2.04 1.88
480 8.93 4.70 2.99 2.52 1.97 1.67 1.56
500 7.77 3.98 2.55 2.19 1.74 1.51 1.43
520 6.32 3.20 2.09 1.82 1.50 1.33 1.28
540 4.99 2.54 1.71 1.55 1.33 1.21 1.17
560 4.21 2.16 1.53 1.42 1.26 1.17 1.15
580 3.51 1.88 1.41 1.34 1.21 1.15 1.13
600 2.92 1.66 1.32 1.29 1.20 1.16 1.14
620 2.54 1.53 1.29 1.29 1.22 1.22 1.18
640 2.25 1.49 1.35 1.38 1.34 1.35 1.32
660 2.22 1.57 1.49 1.53 1.53 1.59 1.56
680 2.92 1.94 1.79 1.80 1.78 1.88 1.84
700 6.56 3.73 2.87 2.63 2.34 2.27 2.17
320

Table A-4-1: Continued


Shade
ID
Speed
(m/min)
Dwell
Time
(sec)
Oxidation
Time (sec)
Dye Bath
(gpl
100%
Indigo)
Dye
Bath pH
Dye
Bath
(mV)
Dye Bath
Alkalinity
(gpl)
Dwell
Length
(m)
Oxidation
Length (m)
Nip
Pressures
(psi)
1134 31.09 16.7 69.5 3.133 12.54 801 6.16 8.63 39.40 70.00
Yarn Skein Response Variables
Yarn
Count
Dye
route Dips
Greige
Weight
Boil Off
Weight
Dyed
Weight
Washed
Weight %COWY
Total
%IOWY
Surface
%IOWY Integ
Penetration
Level
12 1 only 1 3.4995 3.4726 3.667 3.3694 5.60% 0.686% 0.987% 27.9 0.70
12 1--2 2 3.6025 3.5409 3.8154 3.4882 7.75% 1.339% 2.448% 53.4 0.55
12 1--3 3 3.6048 3.5595 3.8785 3.4992 8.96% 2.061% 4.629% 71.9 0.45
12 1--4 4 3.5576 3.5402 3.888 3.495 9.82% 2.679% 6.662% 83.0 0.40
12 1--5 5 3.564 3.5048 3.939 3.5345 12.39% 3.338% 9.695% 94.0 0.34
12 1--6 6 3.6194 3.5478 4.0037 3.5965 12.85% 3.916% 13.240% 102.3 0.30
12 1--7 7 3.6135 3.5623 4.0011 3.637 12.32% 4.354% 15.926% 107.1 0.27
% Reflectance Readings


Wave-
length
(nm) Dip 1 Dip 2 Dip 3 Dip 4 Dip 5 Dip 6 Dip 7
400 9.78 5.82 4.11 3.27 2.72 2.37 2.18
420 13.10 7.57 5.18 3.98 3.22 2.73 2.48
440 11.94 6.63 4.47 3.41 2.75 2.34 2.12
460 10.02 5.41 3.61 2.78 2.26 1.95 1.76
480 8.47 4.38 2.93 2.26 1.85 1.61 1.47
500 7.33 3.72 2.50 1.95 1.62 1.44 1.33
520 5.95 2.99 2.03 1.63 1.40 1.28 1.20
540 4.70 2.37 1.66 1.40 1.24 1.15 1.10
560 3.96 2.02 1.48 1.30 1.18 1.11 1.09
580 3.29 1.76 1.36 1.24 1.15 1.09 1.08
600 2.74 1.55 1.26 1.20 1.14 1.10 1.09
620 2.37 1.42 1.23 1.21 1.15 1.12 1.14
640 2.12 1.40 1.26 1.29 1.26 1.24 1.28
660 2.10 1.47 1.39 1.48 1.45 1.45 1.53
680 2.80 1.83 1.65 1.73 1.68 1.71 1.78
700 6.25 3.52 2.71 2.45 2.20 2.10 2.11
321

Table A-4-1: Continued


Shade
ID
Speed
(m/min)
Dwell
Time
(sec)
Oxidation
Time (sec)
Dye Bath
(gpl
100%
Indigo)
Dye
Bath pH
Dye
Bath
(mV)
Dye Bath
Alkalinity
(gpl)
Dwell
Length
(m)
Oxidation
Length (m)
Nip
Pressures
(psi)
t3735 34.75 19.6 63.9 0.761 11.08 722 2.13 11.37 40.50 40.00
Yarn Skein Response Variables
Yarn
Count
Dye
route Dips
Greige
Weight
Boil Off
Weight
Dyed
Weight
Washed
Weight %COWY
Total
%IOWY
Surface
%IOWY Integ
Penetration
Level
6.3 1 only 1 8.2806 7.9396 8.0993 7.9339 2.01% 0.137% 0.443% 8.2 0.31
6.3 1--2 2 8.1831 7.8587 8.00842 7.8595 1.91% 0.305% 0.765% 18.4 0.40
6.3 1--3 3 8.3069 7.9597 8.2823 7.9829 4.05% 0.577% 1.141% 32.7 0.51
6.3 1--4 4 8.236 7.9002 8.2137 7.934 3.97% 0.666% 1.539% 41.1 0.43
6.3 1--5 5 8.2356 7.8895 8.2191 7.936 4.18% 0.902% 2.312% 51.8 0.39
6.3 1--5,4 6 8.3191 7.9783 8.3805 8.0502 5.04% 1.167% 3.321% 61.9 0.35
6.3
1--5,4-
5 7 8.1713 7.8316 8.2105 7.9057 4.84% 1.358% 3.884% 66.5 0.35
% Reflectance Readings


Wave-
length
(nm) Dip 1 Dip 2 Dip 3 Dip 4 Dip 5 Dip 6 Dip 7
400 19.61 12.55 8.22 7.02 5.70 4.65 4.19
420 24.45 16.56 11.00 9.45 7.36 5.83 5.17
440 23.74 15.60 10.09 8.43 6.49 5.10 4.50
460 21.48 13.50 8.51 6.98 5.33 4.19 3.69
480 19.57 11.75 7.13 5.73 4.36 3.44 3.03
500 17.81 10.36 6.12 4.87 3.68 2.92 2.59
520 15.66 8.68 4.95 3.89 2.98 2.38 2.12
540 13.09 6.96 3.94 3.09 2.39 1.94 1.78
560 11.54 5.91 3.35 2.63 2.07 1.72 1.61
580 10.00 4.94 2.84 2.27 1.82 1.56 1.49
600 8.47 4.08 2.42 1.97 1.64 1.45 1.41
620 7.31 3.48 2.14 1.77 1.52 1.40 1.38
640 6.17 2.94 1.95 1.67 1.50 1.40 1.42
660 5.53 2.72 1.90 1.66 1.53 1.48 1.51
680 7.38 3.52 2.37 2.01 1.81 1.69 1.72
700 15.35 8.50 5.11 4.15 3.42 2.92 2.75
322

Table A-4-1: Continued


Shade
ID
Speed
(m/min)
Dwell
Time
(sec)
Oxidation
Time (sec)
Dye Bath
(gpl
100%
Indigo)
Dye
Bath pH
Dye
Bath
(mV)
Dye Bath
Alkalinity
(gpl)
Dwell
Length
(m)
Oxidation
Length (m)
Nip
Pressures
(psi)
1110 32.92 20.7 67.5 0.733 12.23 813 2.79 11.37 40.50 40.00
Yarn Skein Response Variables
Yarn
Count
Dye
route Dips
Greige
Weight
Boil Off
Weight
Dyed
Weight
Washed
Weight %COWY
Total
%IOWY
Surface
%IOWY Integ
Penetration
Level
7.1 1 only 1 6.9391 6.6999 6.8035 6.6768 1.55% 0.134% 0.370% 6.9 0.36
7.1 1--2 2 6.9948 6.782 6.8888 6.7635 1.57% 0.220% 0.627% 12.9 0.35
7.1 1--2,1 3 6.854 6.62 6.746 6.6079 1.90% 0.365% 0.763% 18.3 0.48
7.1
1--2,1-
2 4 6.9343 6.7022 6.8375 6.6915 2.02% 0.446% 0.875% 23.5 0.51



% Reflectance Readings


Wave-
length
(nm) Dip 1 Dip 2 Dip 3 Dip 4 Dip 5 Dip 6 Dip 7
400 21.96 15.92 13.01 11.02
420 27.54 20.86 17.54 15.13
440 26.78 19.76 16.36 13.96
460 24.19 17.16 13.95 11.73
480 22.11 15.10 12.03 9.95
500 20.18 13.42 10.54 8.65
520 17.70 11.42 8.74 6.98
540 14.85 9.23 6.97 5.50
560 13.22 8.03 5.91 4.65
580 11.58 6.85 4.96 3.91
600 9.85 5.67 4.09 3.23
620 8.50 4.78 3.45 2.76
640 7.15 3.96 2.87 2.34
660 6.37 3.63 2.66 2.20
680 8.53 4.79 3.47 2.84
700 17.48 11.10 8.54 6.88
323

Table A-4-1: Continued


Shade
ID
Speed
(m/min)
Dwell
Time
(sec)
Oxidation
Time (sec)
Dye Bath
(gpl
100%
Indigo)
Dye
Bath pH
Dye
Bath
(mV)
Dye Bath
Alkalinity
(gpl)
Dwell
Length
(m)
Oxidation
Length (m)
Nip
Pressures
(psi)
1110 32.92 20.7 67.5 0.733 12.23 813 2.79 11.37 40.50 40.00
Yarn Skein Response Variables
Yarn
Count
Dye
route Dips
Greige
Weight
Boil Off
Weight
Dyed
Weight
Washed
Weight %COWY
Total
%IOWY
Surface
%IOWY Integ
Penetration
Level
8 1 only 1 6.1777 5.9717 6.0737 5.9531 1.71% 0.131% 0.284% 5.5 0.46
8 1--2 2 6.0447 5.8247 5.939 5.8135 1.96% 0.245% 0.572% 11.3 0.43
8 1--2,1 3 6.1363 5.9296 6.0544 5.9254 2.10% 0.369% 0.726% 16.6 0.51
8
1--2,1-
2 4 6.1302 5.9119 6.0437 5.9109 2.23% 0.455% 0.864% 23.0 0.53



% Reflectance Readings


Wave-
length
(nm) Dip 1 Dip 2 Dip 3 Dip 4 Dip 5 Dip 6 Dip 7
400 24.57 17.14 13.71 11.23
420 30.34 22.27 18.38 15.33
440 29.79 21.15 17.21 14.13
460 27.25 18.48 14.73 11.86
480 25.14 16.37 12.75 10.07
500 23.14 14.60 11.21 8.74
520 20.53 12.55 9.40 7.10
540 17.40 10.23 7.52 5.61
560 15.57 8.96 6.44 4.76
580 13.73 7.74 5.43 3.99
600 11.74 6.45 4.48 3.31
620 10.20 5.46 3.80 2.82
640 8.62 4.53 3.15 2.39
660 7.62 4.10 2.91 2.22
680 10.19 5.39 3.76 2.88
700 20.21 12.11 9.10 6.97
324

Table A-4-1: Continued


Shade
ID
Speed
(m/min)
Dwell
Time
(sec)
Oxidation
Time (sec)
Dye Bath
(gpl
100%
Indigo)
Dye
Bath pH
Dye
Bath
(mV)
Dye Bath
Alkalinity
(gpl)
Dwell
Length
(m)
Oxidation
Length (m)
Nip
Pressures
(psi)
1110 32.92 20.7 67.5 0.733 12.23 813 2.79 11.37 40.50 40.00
Yarn Skein Response Variables
Yarn
Count
Dye
route Dips
Greige
Weight
Boil Off
Weight
Dyed
Weight
Washed
Weight %COWY
Total
%IOWY
Surface
%IOWY Integ
Penetration
Level
12 1 only 1 3.9485 3.8069 3.8929 3.802 2.26% 0.171% 0.375% 7.0 0.46
12 1--2 2 3.9064 3.7635 3.8499 3.7621 2.30% 0.305% 0.630% 13.0 0.48
12 1--2,1 3 3.9594 3.8156 3.9091 3.819 2.45% 0.417% 0.756% 17.9 0.55
12
1--2,1-
2 4 4.0246 3.8837 3.9877 3.8952 2.68% 0.583% 0.930% 25.8 0.63
12
1--2,1-
2,1 5 3.9455 3.805 3.9101 3.8191 2.76% 0.670% 1.041% 29.8 0.64
12
1-2,1-
2,1-2 6 3.8618 3.7262 3.8285 3.747 2.75% 0.821% 1.271% 35.9 0.65
12
1-2,1-
2,1-2,1 7 3.8127 3.6766 3.7908 3.6985 3.11% 0.964% 1.530% 40.9 0.63
% Reflectance Readings


Wave-
length
(nm) Dip 1 Dip 2 Dip 3 Dip 4 Dip 5 Dip 6 Dip 7
400 22.20 15.94 13.27 10.41 9.36 8.07 7.25
420 27.85 20.82 17.82 14.23 12.93 11.16 10.02
440 26.95 19.65 16.59 12.98 11.74 10.04 8.89
460 24.22 17.04 14.11 10.82 9.71 8.26 7.26
480 22.01 14.98 12.14 9.10 8.09 6.73 5.87
500 20.02 13.30 10.63 7.86 6.90 5.71 4.97
520 17.58 11.34 8.85 6.33 5.52 4.54 3.94
540 14.72 9.18 7.06 5.00 4.34 3.57 3.11
560 13.10 7.99 6.01 4.24 3.67 3.04 2.65
580 11.46 6.80 5.06 3.57 3.10 2.59 2.28
600 9.75 5.64 4.17 2.97 2.61 2.21 1.96
620 8.42 4.78 3.52 2.57 2.25 1.93 1.74
640 7.08 3.96 2.94 2.20 1.97 1.73 1.59
660 6.33 3.63 2.72 2.10 1.89 1.68 1.57
680 8.44 4.78 3.53 2.70 2.41 2.10 1.93
700 17.23 11.05 8.60 6.28 5.48 4.58 4.01
325

Table A-4-1: Continued


Shade
ID
Speed
(m/min)
Dwell
Time
(sec)
Oxidation
Time (sec)
Dye Bath
(gpl
100%
Indigo)
Dye
Bath pH
Dye
Bath
(mV)
Dye Bath
Alkalinity
(gpl)
Dwell
Length
(m)
Oxidation
Length (m)
Nip
Pressures
(psi)
t3706 34.75 19.6 63.9 0.94 11.48 861 2.22 11.37 40.50 40.00
Yarn Skein Response Variables
Yarn
Count
Dye
route Dips
Greige
Weight
Boil Off
Weight
Dyed
Weight
Washed
Weight %COWY
Total
%IOWY
Surface
%IOWY Integ
Penetration
Level
6.3 1 only 1 8.2635 7.95 8.1871 7.9431 2.98% 0.163% 0.497% 9.4 0.33
6.3 1--2 2 8.3017 7.9697 8.2575 7.9723 3.61% 0.305% 0.776% 18.9 0.39
6.3 1--3 3 8.2384 7.918 8.2369 7.9335 4.03% 0.501% 1.046% 29.9 0.48
6.3 1--4 4 8.2754 7.9427 8.3124 7.969 4.65% 0.598% 1.507% 40.5 0.40
6.3 1--5 5 8.3279 7.9936 8.4145 8.028 5.27% 0.716% 1.936% 47.1 0.37
6.3 1--6 6 8.302 7.9718 8.3508 8.0209 4.75% 0.913% 2.765% 56.7 0.33
6.3 1--6,6 7 8.3061 7.9788 8.3878 8.0325 5.13% 1.102% 3.588% 64.2 0.31
% Reflectance Readings


Wave-
length
(nm) Dip 1 Dip 2 Dip 3 Dip 4 Dip 5 Dip 6 Dip 7
400 18.24 12.35 8.81 7.18 6.28 5.20 4.51
420 22.94 16.34 11.88 9.81 8.46 6.78 5.82
440 22.23 15.39 10.97 8.81 7.53 5.97 5.10
460 19.94 13.27 9.27 7.29 6.17 4.89 4.15
480 18.07 11.51 7.82 5.98 5.04 3.98 3.40
500 16.35 10.16 6.75 5.08 4.27 3.38 2.89
520 14.30 8.48 5.46 4.05 3.41 2.73 2.35
540 11.86 6.81 4.33 3.18 2.70 2.19 1.91
560 10.43 5.78 3.68 2.70 2.30 1.90 1.68
580 9.01 4.82 3.11 2.30 1.99 1.69 1.52
600 7.60 3.98 2.62 1.97 1.74 1.52 1.39
620 6.50 3.38 2.29 1.75 1.58 1.41 1.31
640 5.44 2.83 2.01 1.58 1.45 1.32 1.24
660 4.92 2.61 1.93 1.52 1.41 1.32 1.25
680 6.56 3.40 2.46 1.88 1.70 1.54 1.42
700 13.96 8.24 5.49 4.09 3.53 2.96 2.60
326

Table A-4-1: Continued


Shade
ID
Speed
(m/min)
Dwell
Time
(sec)
Oxidation
Time (sec)
Dye Bath
(gpl
100%
Indigo)
Dye
Bath pH
Dye
Bath
(mV)
Dye Bath
Alkalinity
(gpl)
Dwell
Length
(m)
Oxidation
Length (m)
Nip
Pressures
(psi)
t3706 34.75 19.6 63.9 0.94 11.48 861 2.22 11.37 40.50 40.00
Yarn Skein Response Variables
Yarn
Count
Dye
route Dips
Greige
Weight
Boil Off
Weight
Dyed
Weight
Washed
Weight %COWY
Total
%IOWY
Surface
%IOWY Integ
Penetration
Level
8 1 only 1 9.1853 8.8494 9.1124 8.8452 2.97% 0.177% 0.517% 9.9 0.34
8 1--2 2 9.2492 8.9176 9.241 8.9307 3.63% 0.325% 0.788% 19.4 0.41
8 1--3 3 9.3365 9.0043 9.3891 9.0301 4.27% 0.501% 1.064% 30.5 0.47
8 1--4 4 9.2811 8.9443 9.389 8.9828 4.97% 0.664% 1.509% 40.6 0.44
8 1--5 5 9.2993 8.9629 9.3567 9.0165 4.39% 0.828% 2.083% 49.1 0.40
8 1--6 6 9.2632 8.9339 9.406 9.0083 5.28% 1.124% 3.184% 60.7 0.35
8 1--6,6 7 9.3886 9.0562 9.5544 9.1498 5.50% 1.262% 3.760% 65.6 0.34
% Reflectance Readings


Wave-
length
(nm) Dip 1 Dip 2 Dip 3 Dip 4 Dip 5 Dip 6 Dip 7
400 17.65 12.10 8.97 7.14 6.11 4.89 4.47
420 22.11 15.93 12.12 9.71 8.19 6.33 5.76
440 21.39 14.99 11.16 8.73 7.27 5.57 5.04
460 19.18 12.93 9.37 7.24 5.97 4.55 4.12
480 17.36 11.23 7.89 5.95 4.87 3.71 3.36
500 15.73 9.89 6.78 5.07 4.12 3.15 2.87
520 13.77 8.27 5.45 4.04 3.29 2.55 2.33
540 11.44 6.63 4.30 3.19 2.61 2.04 1.88
560 10.10 5.63 3.63 2.71 2.22 1.79 1.65
580 8.75 4.72 3.04 2.31 1.93 1.58 1.49
600 7.40 3.90 2.56 1.98 1.68 1.43 1.36
620 6.35 3.33 2.22 1.75 1.51 1.34 1.27
640 5.35 2.79 1.91 1.56 1.38 1.25 1.19
660 4.86 2.59 1.82 1.51 1.36 1.25 1.19
680 6.40 3.37 2.33 1.88 1.63 1.45 1.38
700 13.32 8.02 5.42 4.09 3.41 2.78 2.56
327

Table A-4-1: Continued


Shade
ID
Speed
(m/min)
Dwell
Time
(sec)
Oxidation
Time (sec)
Dye Bath
(gpl
100%
Indigo)
Dye
Bath pH
Dye
Bath
(mV)
Dye Bath
Alkalinity
(gpl)
Dwell
Length
(m)
Oxidation
Length (m)
Nip
Pressures
(psi)
1142 34.75 19.6 63.9 0.946 11.49 742 3.4 11.37 40.50 40.00
Yarn Skein Response Variables
Yarn
Count
Dye
route Dips
Greige
Weight
Boil Off
Weight
Dyed
Weight
Washed
Weight %COWY
Total
%IOWY
Surface
%IOWY Integ
Penetration
Level
7.1 1 only 1 7.2284 7.0323 7.2354 7.0342 2.89% 0.207% 0.507% 9.6 0.41
7.1 1--2 2 7.3446 7.1456 7.4288 7.1571 3.96% 0.359% 0.839% 21.8 0.43
7.1 1--3 3 7.3514 7.1554 7.4505 7.1775 4.12% 0.455% 1.076% 30.8 0.42
7.1 1--4 4 7.2888 7.0958 7.4793 7.1321 5.40% 0.619% 1.523% 40.8 0.41
7.1 1--5 5 7.1916 6.9923 7.3246 7.0431 4.75% 0.756% 1.928% 47.0 0.39
7.1 1--6 6 7.251 7.055 7.4416 7.1208 5.48% 0.956% 2.795% 57.0 0.34
7.1 1--6,6 7 7.2646 7.0636 7.4684 7.1509 5.73% 1.125% 3.410% 62.7 0.33
% Reflectance Readings


Wave-
length
(nm) Dip 1 Dip 2 Dip 3 Dip 4 Dip 5 Dip 6 Dip 7
400 18.11 11.10 8.77 7.16 6.19 5.25 4.57
420 22.76 14.61 11.78 9.67 8.15 6.74 5.76
440 21.83 13.61 10.78 8.61 7.22 5.89 5.03
460 19.51 11.69 9.09 7.12 5.94 4.80 4.10
480 17.61 10.09 7.63 5.83 4.85 3.89 3.33
500 15.89 8.86 6.55 4.95 4.11 3.30 2.84
520 13.93 7.35 5.30 3.95 3.30 2.65 2.30
540 11.59 5.90 4.20 3.12 2.65 2.13 1.90
560 10.24 5.03 3.57 2.67 2.28 1.87 1.70
580 8.92 4.23 3.01 2.29 2.01 1.67 1.55
600 7.55 3.52 2.54 1.97 1.78 1.52 1.44
620 6.50 3.04 2.23 1.77 1.64 1.44 1.41
640 5.50 2.61 1.99 1.64 1.58 1.43 1.44
660 4.98 2.47 1.94 1.64 1.63 1.50 1.54
680 6.53 3.19 2.46 2.04 1.94 1.78 1.78
700 13.46 7.31 5.45 4.24 3.75 3.23 2.97
328

Table A-4-1: Continued


Shade
ID
Speed
(m/min)
Dwell
Time
(sec)
Oxidation
Time (sec)
Dye Bath
(gpl
100%
Indigo)
Dye
Bath pH
Dye
Bath
(mV)
Dye Bath
Alkalinity
(gpl)
Dwell
Length
(m)
Oxidation
Length (m)
Nip
Pressures
(psi)
1142 34.75 19.6 63.9 0.946 11.49 742 3.4 11.37 40.50 40.00
Yarn Skein Response Variables
Yarn
Count
Dye
route Dips
Greige
Weight
Boil Off
Weight
Dyed
Weight
Washed
Weight %COWY
Total
%IOWY
Surface
%IOWY Integ
Penetration
Level
12 1 only 1 6.3876 6.2068 6.4218 6.218 3.46% 0.207% 0.560% 10.9 0.37
12 1--2 2 6.3814 6.2032 6.4725 6.2262 4.34% 0.381% 0.818% 20.9 0.47
12 1--3 3 6.3095 6.1344 6.4446 6.168 5.06% 0.602% 1.128% 32.3 0.53
12 1--4 4 6.2744 6.0969 6.4446 6.141 5.70% 0.744% 1.533% 41.0 0.49
12 1--5 5 6.352 6.1726 6.5428 6.2305 6.00% 0.922% 1.989% 47.8 0.46
12 1--6 6 6.4709 6.286 6.6476 6.3654 5.75% 1.177% 2.875% 57.8 0.41
12 1--6,6 7 6.347 6.1699 6.5511 6.2549 6.18% 1.395% 3.524% 63.6 0.40
% Reflectance Readings


Wave-
length
(nm) Dip 1 Dip 2 Dip 3 Dip 4 Dip 5 Dip 6 Dip 7
400 16.18 11.29 8.42 6.95 6.01 4.98 4.40
420 20.37 14.85 11.29 9.25 7.82 6.33 5.52
440 19.61 13.89 10.30 8.27 6.91 5.54 4.81
460 17.56 11.96 8.64 6.87 5.70 4.52 3.94
480 15.85 10.38 7.22 5.67 4.66 3.70 3.22
500 14.36 9.17 6.21 4.84 3.99 3.15 2.77
520 12.56 7.63 5.01 3.89 3.21 2.56 2.26
540 10.46 6.14 3.97 3.09 2.58 2.08 1.86
560 9.26 5.25 3.40 2.66 2.24 1.85 1.69
580 8.08 4.43 2.88 2.29 1.98 1.68 1.55
600 6.85 3.69 2.45 1.99 1.77 1.54 1.45
620 5.93 3.19 2.16 1.80 1.65 1.46 1.40
640 5.07 2.74 1.96 1.69 1.61 1.47 1.44
660 4.66 2.59 1.91 1.69 1.68 1.57 1.55
680 5.99 3.33 2.41 2.08 2.00 1.82 1.79
700 12.16 7.59 5.19 4.21 3.72 3.14 2.91
329

Table A-4-1: Continued


Shade
ID
Speed
(m/min)
Dwell
Time
(sec)
Oxidation
Time (sec)
Dye Bath
(gpl
100%
Indigo)
Dye
Bath pH
Dye
Bath
(mV)
Dye Bath
Alkalinity
(gpl)
Dwell
Length
(m)
Oxidation
Length (m)
Nip
Pressures
(psi)
1126 34.75 19.6 63.9 1.051 11.38 792 3.32 11.37 40.50 40.00
Yarn Skein Response Variables
Yarn
Count
Dye
route Dips
Greige
Weight
Boil Off
Weight
Dyed
Weight
Washed
Weight %COWY
Total
%IOWY
Surface
%IOWY Integ
Penetration
Level
6.3 1 only 1 8.7651 8.4139 8.6682 8.4 3.02% 0.188% 0.539% 10.4 0.35
6.3 1--2 2 8.2092 7.8849 8.1745 7.8886 3.67% 0.342% 0.837% 21.7 0.41
6.3 1--3 3 8.2085 7.8872 8.2382 7.8986 4.45% 0.544% 1.270% 35.8 0.43
6.3 1--4 4 8.3558 8.0246 8.4065 8.0616 4.76% 0.727% 1.847% 45.9 0.39
6.3 1--5 5 8.5064 8.1656 8.5507 8.2185 4.72% 0.915% 2.615% 55.2 0.35
6.3 1--6 6 8.2067 7.8703 8.2531 7.9356 4.86% 1.010% 2.894% 58.0 0.35

% Reflectance Readings


Wave-
length
(nm) Dip 1 Dip 2 Dip 3 Dip 4 Dip 5 Dip 6 Dip 7
400 17.20 11.28 7.93 6.42 5.51 5.09
420 21.84 14.99 10.74 8.62 7.16 6.59
440 21.06 14.00 9.78 7.70 6.31 5.79
460 18.84 12.01 8.16 6.37 5.17 4.74
480 16.95 10.34 6.76 5.22 4.22 3.86
500 15.31 9.08 5.77 4.43 3.56 3.27
520 13.32 7.50 4.62 3.54 2.86 2.65
540 11.01 5.99 3.64 2.80 2.28 2.13
560 9.64 5.05 3.07 2.37 1.95 1.85
580 8.30 4.21 2.59 2.04 1.72 1.66
600 6.93 3.49 2.19 1.77 1.53 1.49
620 5.91 2.98 1.91 1.59 1.40 1.39
640 4.99 2.55 1.73 1.48 1.34 1.35
660 4.53 2.37 1.66 1.44 1.31 1.34
680 6.03 3.10 2.11 1.76 1.56 1.56
700 12.91 7.35 4.75 3.75 3.15 2.99
330

Table A-4-1: Continued


Shade
ID
Speed
(m/min)
Dwell
Time
(sec)
Oxidation
Time (sec)
Dye Bath
(gpl
100%
Indigo)
Dye
Bath pH
Dye
Bath
(mV)
Dye Bath
Alkalinity
(gpl)
Dwell
Length
(m)
Oxidation
Length (m)
Nip
Pressures
(psi)
1126 34.75 19.6 63.9 1.051 11.38 792 3.32 11.37 40.50 40.00
Yarn Skein Response Variables
Yarn
Count
Dye
route Dips
Greige
Weight
Boil Off
Weight
Dyed
Weight
Washed
Weight %COWY
Total
%IOWY
Surface
%IOWY Integ
Penetration
Level
8 1 only 1 9.4125 9.2 9.4641 9.1953 2.87% 0.192% 0.525% 10.1 0.37
8 1--2 2 9.2127 9.0388 9.3955 9.0539 3.95% 0.350% 0.806% 20.3 0.43
8 1--3 3 9.4864 9.2298 9.6258 9.2625 4.29% 0.521% 1.087% 31.2 0.48
8 1--4 4 9.3524 9.1666 9.618 9.2176 4.92% 0.657% 1.461% 39.7 0.45
8 1--5 5 9.6241 9.1361 9.6072 9.2005 5.16% 0.933% 2.377% 52.6 0.39
8 1--6 6 9.4108 9.0548 9.5177 9.1357 5.11% 1.060% 2.924% 58.3 0.36

% Reflectance Readings


Wave-
length
(nm) Dip 1 Dip 2 Dip 3 Dip 4 Dip 5 Dip 6 Dip 7
400 17.77 11.87 8.95 7.35 5.75 5.19
420 22.37 15.71 12.11 9.99 7.52 6.74
440 21.44 14.64 11.02 8.92 6.61 5.88
460 19.11 12.56 9.22 7.38 5.40 4.79
480 17.22 10.85 7.73 6.05 4.40 3.89
500 15.55 9.55 6.61 5.14 3.71 3.28
520 13.58 7.94 5.33 4.11 2.98 2.65
540 11.27 6.37 4.19 3.25 2.38 2.12
560 9.90 5.39 3.53 2.75 2.04 1.84
580 8.55 4.51 2.97 2.35 1.80 1.64
600 7.21 3.73 2.49 2.01 1.60 1.48
620 6.19 3.20 2.16 1.78 1.47 1.37
640 5.27 2.73 1.93 1.64 1.43 1.35
660 4.83 2.56 1.84 1.60 1.43 1.36
680 6.32 3.31 2.37 2.00 1.69 1.59
700 13.10 7.76 5.38 4.27 3.33 3.04
331

Table A-4-1: Continued


Shade
ID
Speed
(m/min)
Dwell
Time
(sec)
Oxidation
Time (sec)
Dye Bath
(gpl
100%
Indigo)
Dye
Bath pH
Dye
Bath
(mV)
Dye Bath
Alkalinity
(gpl)
Dwell
Length
(m)
Oxidation
Length (m)
Nip
Pressures
(psi)
1126B 34.75 19.6 63.9 1.157 11.05 817 1.56 11.37 40.50 40.00
Yarn Skein Response Variables
Yarn
Count
Dye
route Dips
Greige
Weight
Boil Off
Weight
Dyed
Weight
Washed
Weight %COWY
Total
%IOWY
Surface
%IOWY Integ
Penetration
Level
6.3 1 only 1 8.1808 7.8405 8.0988 7.8212 3.29% 0.177% 0.520% 9.9 0.34
6.3 1--2 2 8.2137 7.871 8.1732 7.8627 3.84% 0.328% 0.807% 20.3 0.41
6.3 1--3 3 8.2085 7.8738 8.2324 7.8896 4.55% 0.514% 1.103% 31.6 0.47
6.3 1--4 4 8.1237 7.792 8.225 7.814 5.56% 0.625% 1.347% 37.5 0.46
6.3 1--5 5 7.7693 7.4351 7.8435 7.475 5.49% 0.757% 1.916% 46.8 0.40
6.3 1--6 6 8.323 7.9781 8.4272 8.0408 5.63% 0.999% 2.889% 57.9 0.35

% Reflectance Readings


Wave-
length
(nm) Dip 1 Dip 2 Dip 3 Dip 4 Dip 5 Dip 6 Dip 7
400 17.47 11.66 8.46 7.43 6.14 4.94
420 22.07 15.33 11.29 9.93 7.96 6.21
440 21.33 14.39 10.42 9.04 7.14 5.52
460 19.10 12.43 8.85 7.61 5.99 4.62
480 17.27 10.79 7.46 6.35 4.97 3.83
500 15.64 9.51 6.43 5.44 4.23 3.26
520 13.66 7.92 5.20 4.38 3.41 2.66
540 11.35 6.35 4.12 3.46 2.72 2.16
560 9.98 5.39 3.48 2.95 2.33 1.87
580 8.63 4.50 2.94 2.50 2.02 1.67
600 7.26 3.72 2.48 2.13 1.77 1.51
620 6.23 3.20 2.18 1.88 1.62 1.41
640 5.26 2.72 1.93 1.70 1.51 1.36
660 4.77 2.54 1.85 1.63 1.48 1.33
680 6.26 3.24 2.30 2.02 1.75 1.52
700 13.11 7.66 5.16 4.38 3.59 2.88
332

Table A-4-1: Continued


Shade
ID
Speed
(m/min)
Dwell
Time
(sec)
Oxidation
Time (sec)
Dye Bath
(gpl
100%
Indigo)
Dye
Bath pH
Dye
Bath
(mV)
Dye Bath
Alkalinity
(gpl)
Dwell
Length
(m)
Oxidation
Length (m)
Nip
Pressures
(psi)
1126B 34.75 19.6 63.9 1.157 11.05 817 1.56 11.37 40.50 40.00
Yarn Skein Response Variables
Yarn
Count
Dye
route Dips
Greige
Weight
Boil Off
Weight
Dyed
Weight
Washed
Weight %COWY
Total
%IOWY
Surface
%IOWY Integ
Penetration
Level
8 1 only 1 12.302 11.8549 12.2783 11.8331 3.57% 0.202% 0.550% 10.7 0.37
8 1--2 2 9.2127 8.8729 9.2975 8.8858 4.79% 0.312% 0.779% 19.0 0.40
8 1--3 3 9.2118 8.8698 9.3328 8.899 5.22% 0.499% 1.102% 31.6 0.45
8 1--4 4 9.2176 8.8863 9.4257 8.933 6.07% 0.688% 1.517% 40.7 0.45
8 1--5 5 9.1641 8.8245 9.3425 8.8805 5.87% 0.865% 2.077% 49.0 0.42
8 1--6 6 9.1681 8.8336 9.3633 8.9096 6.00% 1.055% 2.732% 56.4 0.39

% Reflectance Readings


Wave-
length
(nm) Dip 1 Dip 2 Dip 3 Dip 4 Dip 5 Dip 6 Dip 7
400 16.99 12.28 8.46 6.91 5.89 5.12
420 21.56 16.12 11.27 9.10 7.57 6.45
440 20.74 15.10 10.43 8.22 6.77 5.73
460 18.47 13.03 8.85 6.92 5.67 4.79
480 16.61 11.32 7.48 5.76 4.70 3.97
500 15.00 9.99 6.44 4.93 4.01 3.38
520 13.07 8.37 5.22 3.97 3.24 2.75
540 10.81 6.75 4.14 3.16 2.59 2.22
560 9.47 5.73 3.50 2.71 2.22 1.93
580 8.15 4.81 2.94 2.32 1.95 1.71
600 6.83 3.99 2.49 2.00 1.71 1.54
620 5.84 3.41 2.19 1.79 1.57 1.44
640 4.93 2.90 1.94 1.65 1.48 1.36
660 4.50 2.69 1.85 1.60 1.45 1.35
680 5.87 3.44 2.31 1.94 1.70 1.56
700 12.46 8.03 5.17 4.04 3.40 2.99
333

Table A-4-1: Continued


Shade
ID
Speed
(m/min)
Dwell
Time
(sec)
Oxidation
Time (sec)
Dye Bath
(gpl
100%
Indigo)
Dye
Bath pH
Dye
Bath
(mV)
Dye Bath
Alkalinity
(gpl)
Dwell
Length
(m)
Oxidation
Length (m)
Nip
Pressures
(psi)
1126 34.75 19.6 63.9 1.117 11.55 771 2.79 11.37 40.50 40.00
Yarn Skein Response Variables
Yarn
Count
Dye
route Dips
Greige
Weight
Boil Off
Weight
Dyed
Weight
Washed
Weight %COWY
Total
%IOWY
Surface
%IOWY Integ
Penetration
Level
6.3 1 only 1 8.1062 7.7651 8.0002 7.7641 3.03% 0.186% 0.540% 10.4 0.34
6.3 1--2 2 8.2555 7.9106 8.2317 7.9256 4.06% 0.382% 0.833% 21.5 0.46
6.3 1--3 3 8.3467 8.01 8.3753 8.0304 4.56% 0.546% 1.218% 34.6 0.45
6.3 1--4 4 8.3702 8.0196 8.3981 8.0532 4.72% 0.662% 1.562% 41.5 0.42
6.3 1--5 5 8.2585 7.9182 8.3323 7.9726 5.23% 0.833% 2.222% 50.8 0.37
6.3 1--6 6 8.2929 7.9479 8.363 8.0079 5.22% 1.083% 3.241% 61.2 0.33
6.3 1--6,6 7 8.3391 7.9963 8.4083 8.0759 5.15% 1.235% 3.864% 66.4 0.32
% Reflectance Readings


Wave-
length
(nm) Dip 1 Dip 2 Dip 3 Dip 4 Dip 5 Dip 6 Dip 7
400 16.85 11.19 7.94 6.81 5.78 4.73 4.25
420 21.42 14.78 10.65 9.19 7.54 6.08 5.41
440 20.68 13.76 9.71 8.24 6.69 5.33 4.72
460 18.55 11.80 8.17 6.86 5.52 4.36 3.87
480 16.70 10.15 6.79 5.63 4.49 3.55 3.16
500 15.12 8.94 5.83 4.82 3.84 3.04 2.71
520 13.17 7.40 4.69 3.85 3.07 2.45 2.20
540 10.92 5.95 3.73 3.07 2.48 2.00 1.83
560 9.58 5.06 3.16 2.62 2.13 1.75 1.62
580 8.29 4.26 2.69 2.26 1.87 1.58 1.48
600 6.97 3.56 2.30 1.97 1.66 1.45 1.38
620 5.98 3.08 2.02 1.76 1.52 1.36 1.31
640 5.04 2.64 1.83 1.63 1.45 1.34 1.30
660 4.56 2.50 1.76 1.60 1.44 1.36 1.32
680 6.06 3.24 2.25 1.98 1.74 1.61 1.53
700 12.84 7.37 4.86 4.06 3.42 2.88 2.65
334

Table A-4-1: Continued


Shade
ID
Speed
(m/min)
Dwell
Time
(sec)
Oxidation
Time (sec)
Dye Bath
(gpl
100%
Indigo)
Dye
Bath pH
Dye
Bath
(mV)
Dye Bath
Alkalinity
(gpl)
Dwell
Length
(m)
Oxidation
Length (m)
Nip
Pressures
(psi)
1126 34.75 19.6 63.9 1.117 11.55 771 2.79 11.37 40.50 40.00
Yarn Skein Response Variables
Yarn
Count
Dye
route Dips
Greige
Weight
Boil Off
Weight
Dyed
Weight
Washed
Weight %COWY
Total
%IOWY
Surface
%IOWY Integ
Penetration
Level
8 1 only 1 6.2123 6.0011 6.1837 5.9981 3.04% 0.204% 0.562% 11.0 0.36
8 1--4 4 6.0963 5.8867 6.2185 5.9163 5.64% 0.879% 1.553% 41.3 0.57
8 1--5 5 6.0526 5.8445 6.147 5.8863 5.18% 0.926% 2.153% 49.9 0.43
8 1--6 6 6.2229 6.005099 6.3646 6.061 5.99% 1.279% 3.107% 60.0 0.41
8 1--6,6 7 6.0154 5.8229 6.1585 5.8883 5.76% 1.403% 3.387% 62.5 0.41


% Reflectance Readings


Wave-
length
(nm) Dip 1 Dip 2 Dip 3 Dip 4 Dip 5 Dip 6 Dip 7
400 16.92 7.06 5.97 5.02 4.66
420 21.53 9.58 7.87 6.50 5.96
440 20.66 8.54 6.95 5.68 5.21
460 18.40 7.06 5.72 4.63 4.25
480 16.48 5.78 4.66 3.74 3.45
500 14.86 4.92 3.97 3.19 2.95
520 12.86 3.93 3.17 2.56 2.38
540 10.59 3.11 2.54 2.06 1.95
560 9.25 2.64 2.16 1.79 1.71
580 7.94 2.27 1.89 1.60 1.55
600 6.62 1.95 1.67 1.45 1.43
620 5.64 1.73 1.52 1.34 1.35
640 4.73 1.59 1.44 1.30 1.34
660 4.30 1.57 1.43 1.31 1.36
680 5.75 1.95 1.76 1.55 1.61
700 12.53 4.12 3.51 2.95 2.84
335

Table A-4-1: Continued


Shade
ID
Speed
(m/min)
Dwell
Time
(sec)
Oxidation
Time (sec)
Dye Bath
(gpl
100%
Indigo)
Dye
Bath pH
Dye
Bath
(mV)
Dye Bath
Alkalinity
(gpl)
Dwell
Length
(m)
Oxidation
Length (m)
Nip
Pressures
(psi)
1126A 34.75 19.6 63.9 1.174 10.98 826 1.57 11.37 40.50 40.00
Yarn Skein Response Variables
Yarn
Count
Dye
route Dips
Greige
Weight
Boil Off
Weight
Dyed
Weight
Washed
Weight %COWY
Total
%IOWY
Surface
%IOWY Integ
Penetration
Level
6.3 1 only 1 8.2781 7.934 8.196 7.9298 3.30% 0.195% 0.584% 11.6 0.33
6.3 1--2 2 8.3137 7.9781 8.2875 7.9807 3.88% 0.337% 0.832% 21.5 0.41
6.3 1--3 3 8.3089 7.9721 8.329 7.9888 4.48% 0.489% 1.106% 31.7 0.44
6.3 1--5 5 8.2309 7.9008 8.3304 7.9474 5.44% 0.812% 2.084% 49.1 0.39
6.3 1--6 6 8.2494 7.9121 8.3354 7.9723 5.35% 1.033% 2.924% 58.3 0.35


% Reflectance Readings


Wave-
length
(nm) Dip 1 Dip 2 Dip 3 Dip 4 Dip 5 Dip 6 Dip 7
400 16.20 11.15 8.47 5.86 4.89
420 20.62 14.64 11.27 7.55 6.12
440 19.82 13.74 10.40 6.75 5.46
460 17.61 11.86 8.85 5.65 4.57
480 15.78 10.28 7.48 4.68 3.80
500 14.20 9.05 6.44 3.98 3.24
520 12.31 7.51 5.21 3.22 2.64
540 10.11 6.03 4.12 2.58 2.13
560 8.83 5.11 3.49 2.22 1.86
580 7.54 4.27 2.93 1.93 1.66
600 6.27 3.55 2.47 1.71 1.50
620 5.36 3.05 2.16 1.57 1.41
640 4.52 2.61 1.92 1.48 1.36
660 4.16 2.46 1.82 1.47 1.34
680 5.45 3.15 2.31 1.74 1.53
700 11.83 7.30 5.18 3.44 2.90
336

Table A-4-1: Continued


Shade
ID
Speed
(m/min)
Dwell
Time
(sec)
Oxidation
Time (sec)
Dye Bath
(gpl
100%
Indigo)
Dye
Bath pH
Dye
Bath
(mV)
Dye Bath
Alkalinity
(gpl)
Dwell
Length
(m)
Oxidation
Length (m)
Nip
Pressures
(psi)
t3738 34.75 19.6 63.9 1.409 11.36 874 2.35 11.37 40.50 40.00
Yarn Skein Response Variables
Yarn
Count
Dye
route Dips
Greige
Weight
Boil Off
Weight
Dyed
Weight
Washed
Weight %COWY
Total
%IOWY
Surface
%IOWY Integ
Penetration
Level
6.3 1 only 1 8.2544 7.9397 8.1588 7.9409 2.76% 0.210% 0.611% 12.4 0.34
6.3 1--2 2 8.2514 7.945 8.2044 7.9675 3.26% 0.428% 0.959% 26.9 0.45
6.3 1--3 3 8.3209 8.012 8.3459 8.0561 4.17% 0.645% 1.444% 39.4 0.45
6.3 1--4 4 8.2785 7.9614 8.3492 8.0302 4.87% 1.028% 2.584% 54.8 0.40
6.3 1--5 5 8.2834 7.9686 8.3555 8.0528 4.86% 1.268% 3.389% 62.5 0.37
6.3 1--6 6 8.2551 7.9297 8.344 8.0413 5.22% 1.661% 4.650% 72.0 0.36
6.3 1--6,6 7 8.3067 7.9951 8.4212 8.119 5.33% 1.869% 5.491% 77.1 0.34
% Reflectance Readings


Wave-
length
(nm) Dip 1 Dip 2 Dip 3 Dip 4 Dip 5 Dip 6 Dip 7
400 15.83 9.91 7.38 5.51 4.71 3.86 3.50
420 20.69 13.58 10.21 7.26 6.11 4.87 4.39
440 19.71 12.52 9.18 6.37 5.33 4.21 3.78
460 17.30 10.53 7.57 5.19 4.32 3.43 3.09
480 15.33 8.92 6.18 4.21 3.51 2.79 2.53
500 13.71 7.71 5.24 3.56 2.99 2.42 2.21
520 11.74 6.18 4.16 2.84 2.41 1.97 1.81
540 9.53 4.84 3.26 2.26 1.94 1.65 1.55
560 8.30 4.08 2.77 1.96 1.72 1.50 1.43
580 7.07 3.41 2.36 1.73 1.55 1.40 1.34
600 5.87 2.83 2.01 1.54 1.41 1.31 1.25
620 4.97 2.43 1.78 1.42 1.33 1.26 1.22
640 4.14 2.10 1.61 1.35 1.29 1.27 1.20
660 3.76 1.97 1.57 1.35 1.30 1.31 1.22
680 4.97 2.54 1.92 1.56 1.46 1.43 1.30
700 11.45 6.23 4.29 3.10 2.72 2.36 2.10
337

Table A-4-1: Continued


Shade
ID
Speed
(m/min)
Dwell
Time
(sec)
Oxidation
Time (sec)
Dye Bath
(gpl
100%
Indigo)
Dye
Bath pH
Dye
Bath
(mV)
Dye Bath
Alkalinity
(gpl)
Dwell
Length
(m)
Oxidation
Length (m)
Nip
Pressures
(psi)
1099 32.92 20.7 67.5 1.827 11.71 867 3.11 11.37 40.50 40.00
Yarn Skein Response Variables
Yarn
Count
Dye
route Dips
Greige
Weight
Boil Off
Weight
Dyed
Weight
Washed
Weight %COWY
Total
%IOWY
Surface
%IOWY Integ
Penetration
Level
6.3 1 only 1 7.8393 7.7815 7.976 7.7521 2.50% 0.250% 0.665% 14.2 0.38
6.3 1--2 2 7.86 7.8393 8.1362 7.8361 3.79% 0.482% 1.024% 29.2 0.47
6.3 1--3 3 7.9407 7.9407 8.3054 7.9527 4.59% 0.789% 1.758% 44.6 0.45
6.3 1--4 4 7.9155 7.9155 8.3465 7.943 5.45% 0.916% 2.343% 52.2 0.39
6.3 1--5 5 7.9914 7.9914 8.4123 8.0618 5.27% 1.249% 3.742% 65.4 0.33
6.3 1--6 6 7.9182 7.9182 8.3955 7.9999 6.03% 1.488% 4.678% 72.2 0.32

% Reflectance Readings


Wave-
length
(nm) Dip 1 Dip 2 Dip 3 Dip 4 Dip 5 Dip 6 Dip 7
400 14.89 9.33 6.61 5.63 4.37 3.75
420 19.50 12.71 8.92 7.37 5.56 4.67
440 18.45 11.65 7.94 6.50 4.86 4.06
460 16.04 9.73 6.53 5.31 3.95 3.33
480 14.10 8.20 5.34 4.33 3.23 2.75
500 12.53 7.04 4.53 3.67 2.75 2.37
520 10.70 5.68 3.63 2.95 2.25 1.96
540 8.62 4.48 2.87 2.38 1.86 1.66
560 7.43 3.76 2.44 2.07 1.64 1.51
580 6.22 3.14 2.10 1.82 1.49 1.40
600 5.12 2.62 1.81 1.62 1.38 1.32
620 4.35 2.28 1.63 1.50 1.33 1.28
640 3.66 2.03 1.53 1.47 1.32 1.29
660 3.39 1.93 1.49 1.47 1.34 1.32
680 4.49 2.47 1.82 1.71 1.50 1.45
700 10.57 5.81 3.85 3.33 2.66 2.36
338

Table A-4-1: Continued


Shade
ID
Speed
(m/min)
Dwell
Time
(sec)
Oxidation
Time (sec)
Dye Bath
(gpl
100%
Indigo)
Dye
Bath pH
Dye
Bath
(mV)
Dye Bath
Alkalinity
(gpl)
Dwell
Length
(m)
Oxidation
Length (m)
Nip
Pressures
(psi)
1099 32.92 20.7 67.5 1.738 11.71 873 3.07 11.37 40.50 40.00
Yarn Skein Response Variables
Yarn
Count
Dye
route Dips
Greige
Weight
Boil Off
Weight
Dyed
Weight
Washed
Weight %COWY
Total
%IOWY
Surface
%IOWY Integ
Penetration
Level
7.1 1 only 1 7.13 6.9251 7.1227 6.9058 2.85% 0.274% 0.687% 15.0 0.40
7.1 1--2 2 7.1819 6.9748 7.2357 6.978 3.74% 0.445% 0.996% 28.2 0.45
7.1 1--3 3 6.9886 6.7835 7.1097 6.8007 4.81% 0.699% 1.506% 40.5 0.46
7.1 1--4 4 6.9426 6.7426 7.12 6.7755 5.60% 0.868% 2.107% 49.4 0.41
7.1 1--5 5 7.201 6.9919 7.3966 7.0434 5.79% 1.199% 3.289% 61.6 0.36
7.1 1--6 6 7.1282 6.9184 7.3011 6.9913 5.53% 1.388% 4.546% 71.3 0.31
7.1 1--6,3 7 7.068 6.8735 7.3049 6.9644 6.28% 1.701% 5.162% 75.2 0.33
% Reflectance Readings


Wave-
length
(nm) Dip 1 Dip 2 Dip 3 Dip 4 Dip 5 Dip 6 Dip 7
400 14.21 9.55 7.18 6.03 4.78 3.92 3.62
420 18.66 12.96 9.75 7.96 6.13 4.95 4.52
440 17.58 11.89 8.72 7.04 5.34 4.30 3.91
460 15.22 9.95 7.17 5.76 4.34 3.50 3.20
480 13.35 8.40 5.87 4.70 3.53 2.87 2.63
500 11.84 7.24 4.99 3.98 2.99 2.46 1.94
520 10.11 5.86 4.00 3.19 2.43 2.02 1.88
540 8.18 4.62 3.16 2.55 1.98 1.68 1.60
560 7.08 3.90 2.69 2.18 1.73 1.52 1.47
580 5.96 3.25 2.29 1.90 1.57 1.39 1.35
600 4.95 2.72 1.98 1.68 1.43 1.31 1.29
620 4.23 2.37 1.77 1.55 1.37 1.27 1.26
640 3.58 2.10 1.67 1.49 1.35 1.28 1.26
660 3.33 2.00 1.64 1.49 1.38 1.30 1.29
680 4.33 2.55 2.01 1.75 1.56 1.41 1.39
700 9.91 5.97 4.24 3.51 2.84 2.37 2.26
339

Table A-4-1: Continued


Shade
ID
Speed
(m/min)
Dwell
Time
(sec)
Oxidation
Time (sec)
Dye Bath
(gpl
100%
Indigo)
Dye
Bath pH
Dye
Bath
(mV)
Dye Bath
Alkalinity
(gpl)
Dwell
Length
(m)
Oxidation
Length (m)
Nip
Pressures
(psi)
1099 32.92 20.7 67.5 1.827 11.71 867 3.11 11.37 40.50 40.00
Yarn Skein Response Variables
Yarn
Count
Dye
route Dips
Greige
Weight
Boil Off
Weight
Dyed
Weight
Washed
Weight %COWY
Total
%IOWY
Surface
%IOWY Integ
Penetration
Level
8 1 only 1 9.2313 8.896 9.177 8.8828 3.16% 0.314% 0.704% 15.7 0.45
8 1--2 2 9.192 8.8576 9.2629 8.8629 4.58% 0.610% 1.051% 30.1 0.58
8 1--3 3 9.2144 8.8863 9.3232 8.9124 4.92% 0.946% 1.615% 42.4 0.59
8 1--6 6 9.3212 8.8924 9.4782 9.0115 6.59% 1.815% 4.990% 74.2 0.36



% Reflectance Readings


Wave-
length
(nm) Dip 1 Dip 2 Dip 3 Dip 4 Dip 5 Dip 6 Dip 7
400 14.02 9.11 6.90 3.71
420 18.46 12.39 9.38 4.61
440 17.39 11.34 8.35 4.01
460 15.05 9.46 6.86 3.28
480 13.17 7.96 5.61 2.69
500 11.66 6.83 4.76 2.32
520 9.92 5.51 3.82 1.92
540 7.98 4.35 3.03 1.63
560 6.84 3.67 2.58 1.48
580 5.70 3.05 2.20 1.36
600 4.70 2.57 1.90 1.28
620 4.00 2.24 1.71 1.24
640 3.38 2.00 1.60 1.24
660 3.15 1.93 1.57 1.27
680 4.18 2.48 1.91 1.41
700 9.84 5.70 4.06 2.33
340

Table A-4-1: Continued


Shade
ID
Speed
(m/min)
Dwell
Time
(sec)
Oxidation
Time (sec)
Dye Bath
(gpl
100%
Indigo)
Dye
Bath pH
Dye
Bath
(mV)
Dye Bath
Alkalinity
(gpl)
Dwell
Length
(m)
Oxidation
Length (m)
Nip
Pressures
(psi)
1099 32.92 20.7 67.5 1.615 11.61 863 3.12 11.37 40.50 40.00
Yarn Skein Response Variables
Yarn
Count
Dye
route Dips
Greige
Weight
Boil Off
Weight
Dyed
Weight
Washed
Weight %COWY
Total
%IOWY
Surface
%IOWY Integ
Penetration
Level
12 1 only 1 6.2704 6.0839 6.3259 6.0759 3.98% 0.293% 0.649% 13.7 0.45
12 1--2 2 6.3197 6.137 6.4326 6.1427 4.82% 0.543% 0.982% 27.7 0.55
12 1--3 3 6.2591 6.0727 6.4005 6.0945 5.40% 0.883% 1.669% 43.2 0.53
12 1--4 4 6.3126 6.1273 6.5078 6.172 6.21% 1.084% 2.499% 53.9 0.43
12 1--5 5 6.1723 5.9917 6.3383 6.0469 5.78% 1.322% 3.318% 61.9 0.40
12 1--6 6 6.2837 6.0954 6.4653 6.1761 6.07% 1.534% 4.365% 70.1 0.35
12 1--6,3 7 6.2179 6.032 6.4599 6.1393 7.09% 1.915% 5.421% 76.7 0.35
% Reflectance Readings


Wave-
length
(nm) Dip 1 Dip 2 Dip 3 Dip 4 Dip 5 Dip 6 Dip 7
400 15.29 9.62 6.82 5.55 4.70 4.05 3.46
420 19.99 12.97 9.17 7.20 6.02 5.11 4.28
440 18.80 11.88 8.13 6.33 5.25 4.46 3.69
460 16.28 9.96 6.67 5.15 4.28 3.62 3.01
480 14.30 8.42 5.45 4.19 3.48 2.96 2.47
500 12.70 7.26 4.63 3.54 2.96 2.53 2.15
520 10.89 5.89 3.71 2.87 2.42 2.07 1.80
540 8.84 4.67 2.95 2.30 1.97 1.73 1.55
560 7.67 3.95 2.51 1.99 1.74 1.55 1.43
580 6.49 3.31 2.15 1.76 1.56 1.40 1.34
600 5.40 2.78 1.88 1.58 1.44 1.31 1.28
620 4.62 2.44 1.70 1.48 1.37 1.27 1.28
640 3.91 2.17 1.60 1.44 1.36 1.28 1.31
660 3.64 2.10 1.61 1.47 1.38 1.27 1.36
680 4.72 2.67 1.94 1.69 1.54 1.42 1.49
700 10.63 6.04 3.99 3.26 2.80 2.44 2.28
341

Table A-4-1: Continued


Shade
ID
Speed
(m/min)
Dwell
Time
(sec)
Oxidation
Time (sec)
Dye Bath
(gpl
100%
Indigo)
Dye
Bath pH
Dye
Bath
(mV)
Dye Bath
Alkalinity
(gpl)
Dwell
Length
(m)
Oxidation
Length (m)
Nip
Pressures
(psi)
x3319 27.43 25 81 1.848 12.19 801 2.55 11.37 40.50 40.00
Yarn Skein Response Variables
Yarn
Count
Dye
route Dips
Greige
Weight
Boil Off
Weight
Dyed
Weight
Washed
Weight %COWY
Total
%IOWY
Surface
%IOWY Integ
Penetration
Level
6.3 1 only 1 7.2411 6.9752 7.1837 6.9426 2.99% 0.361% 0.788% 19.4 0.46
6.3 1--2 2 7.2213 6.9499 7.2304 6.9491 4.04% 0.657% 1.229% 34.9 0.53
6.3 1--6 6 7.0463 6.7812 7.2084 6.879 6.30% 2.210% 6.007% 79.9 0.37




% Reflectance Readings


Wave-
length
(nm) Dip 1 Dip 2 Dip 3 Dip 4 Dip 5 Dip 6 Dip 7
400 12.41 7.98 3.14
420 16.61 10.98 3.77
440 15.48 9.97 3.23
460 13.23 8.28 2.67
480 11.42 6.84 2.20
500 10.02 5.83 1.94
520 8.33 4.67 1.66
540 6.65 3.69 1.48
560 5.61 3.13 1.39
580 4.65 2.65 1.33
600 3.83 2.25 1.32
620 3.25 1.99 1.32
640 2.79 1.82 1.40
660 2.60 1.76 1.48
680 3.38 2.17 1.61
700 8.24 4.79 2.27
342

Table A-4-1: Continued


Shade
ID
Speed
(m/min)
Dwell
Time
(sec)
Oxidation
Time (sec)
Dye Bath
(gpl
100%
Indigo)
Dye
Bath pH
Dye
Bath
(mV)
Dye Bath
Alkalinity
(gpl)
Dwell
Length
(m)
Oxidation
Length (m)
Nip
Pressures
(psi)
x3319 27.43 25 81 1.848 12.19 801 2.55 11.37 40.50 40.00
Yarn Skein Response Variables
Yarn
Count
Dye
route Dips
Greige
Weight
Boil Off
Weight
Dyed
Weight
Washed
Weight %COWY
Total
%IOWY
Surface
%IOWY Integ
Penetration
Level
12 1 only 1 3.7058 3.5809 3.7472 3.5754 4.64% 0.484% 0.823% 21.1 0.59
12 1--2 2 3.6324 3.5067 3.6773 3.5192 4.86% 0.947% 1.511% 40.6 0.63
12 1--3 3 3.759 3.6322 3.8482 3.6585 5.95% 1.426% 2.462% 53.5 0.58
12 1--6 6 3.7118 3.5766 3.857 3.6567 7.84% 2.595% 6.728% 83.3 0.39



% Reflectance Readings


Wave-
length
(nm) Dip 1 Dip 2 Dip 3 Dip 4 Dip 5 Dip 6 Dip 7
400 11.65 7.15 5.53 3.15
420 15.58 9.74 7.20 3.82
440 14.43 8.68 6.31 3.27
460 12.29 7.16 5.14 2.68
480 10.57 5.87 4.18 2.20
500 9.27 5.00 3.56 1.93
520 7.68 4.00 2.87 1.62
540 6.15 3.16 2.31 1.43
560 5.19 2.69 2.01 1.32
580 4.33 2.30 1.78 1.26
600 3.59 1.97 1.60 1.22
620 3.07 1.76 1.49 1.22
640 2.66 1.66 1.46 1.27
660 2.51 1.61 1.47 1.34
680 3.25 1.96 1.70 1.47
700 7.58 4.15 3.22 2.14
343

Table A-4-1: Continued


Shade
ID
Speed
(m/min)
Dwell
Time
(sec)
Oxidation
Time (sec)
Dye Bath
(gpl
100%
Indigo)
Dye
Bath pH
Dye
Bath
(mV)
Dye Bath
Alkalinity
(gpl)
Dwell
Length
(m)
Oxidation
Length (m)
Nip
Pressures
(psi)
q1910 34.75 19.4 63.9 1.831 11.54 875 4.56 11.37 40.50 40.00
Yarn Skein Response Variables
Yarn
Count
Dye
route Dips
Greige
Weight
Boil Off
Weight
Dyed
Weight
Washed
Weight %COWY
Total
%IOWY
Surface
%IOWY Integ
Penetration
Level
6.3 1 only 1 8.2323 7.9272 8.3113 7.9373 4.85% 0.304% 0.767% 18.5 0.40
6.3 1--2 2 8.2581 7.9618 8.4448 8 6.07% 0.519% 1.273% 35.9 0.41
6.3 1--3 3 8.485 8.1695 8.6831 8.2328 6.29% 0.770% 2.292% 51.6 0.34
6.3 1--4 4 8.3714 8.0747 8.7107 8.1577 7.88% 1.223% 4.101% 68.2 0.30
6.3 1--5 5 8.3184 8.0223 8.6216 8.1279 7.47% 1.433% 5.208% 75.5 0.28
6.3 1--6 6 8.2286 7.9186 8.5442 8.0586 7.90% 1.806% 6.792% 83.6 0.27
6.3 1--6,6 7 8.3819 8.0795 8.7471 8.2544 8.26% 2.010% 8.190% 89.2 0.25
% Reflectance Readings


Wave-
length
(nm) Dip 1 Dip 2 Dip 3 Dip 4 Dip 5 Dip 6 Dip 7
400 12.54 7.89 5.79 4.22 3.72 3.13 2.85
420 16.85 10.93 7.79 5.49 4.79 3.90 3.51
440 15.81 9.93 6.87 4.78 4.14 3.37 3.03
460 13.58 8.23 5.61 3.87 3.35 2.75 2.48
480 11.76 6.78 4.53 3.12 2.70 2.23 2.02
500 10.37 5.79 3.85 2.67 2.34 1.98 1.80
520 8.63 4.60 3.06 2.15 1.89 1.63 1.51
540 6.92 3.61 2.44 1.76 1.59 1.43 1.34
560 5.87 3.05 2.09 1.57 1.43 1.31 1.25
580 4.91 2.58 1.82 1.43 1.32 1.25 1.19
600 4.04 2.18 1.62 1.33 1.24 1.20 1.16
620 3.42 1.91 1.47 1.27 1.19 1.17 1.14
640 2.89 1.71 1.39 1.26 1.18 1.17 1.15
660 2.71 1.68 1.40 1.30 1.21 1.22 1.21
680 3.59 2.17 1.69 1.51 1.39 1.36 1.36
700 8.67 4.84 3.37 2.62 2.32 2.04 1.94
344

Table A-4-1: Continued


Shade
ID
Speed
(m/min)
Dwell
Time
(sec)
Oxidation
Time (sec)
Dye Bath
(gpl
100%
Indigo)
Dye
Bath pH
Dye
Bath
(mV)
Dye Bath
Alkalinity
(gpl)
Dwell
Length
(m)
Oxidation
Length (m)
Nip
Pressures
(psi)
q1910 34.75 19.4 63.9 1.831 11.54 875 4.56 11.37 40.50 40.00
Yarn Skein Response Variables
Yarn
Count
Dye
route Dips
Greige
Weight
Boil Off
Weight
Dyed
Weight
Washed
Weight %COWY
Total
%IOWY
Surface
%IOWY Integ
Penetration
Level
7.1 1 only 1 7.2029 7.0332 7.3818 7.0399 4.96% 0.310% 0.760% 18.2 0.41
7.1 1--2 2 7.333 7.1592 7.552 7.1788 5.49% 0.640% 1.296% 36.4 0.49
7.1 1--3 3 7.2629 7.0885 7.5579 7.1394 6.62% 0.994% 2.462% 53.5 0.40
7.1 1--4 4 7.3773 7.2105 7.7982 7.2833 8.15% 1.484% 4.344% 69.9 0.34
7.1 1--5 5 7.2513 7.0835 7.671 7.1767 8.29% 1.705% 5.098% 74.8 0.33
7.1 1--6 6 7.1983 7.0364 7.6291 7.1597 8.42% 1.984% 6.156% 80.6 0.32
7.1 1--6,6 7 7.2217 7.0393 7.6763 7.1922 9.05% 2.450% 8.627% 90.7 0.28
% Reflectance Readings


Wave-
length
(nm) Dip 1 Dip 2 Dip 3 Dip 4 Dip 5 Dip 6 Dip 7
400 12.44 7.84 5.71 4.19 3.74 3.32 2.80
420 16.73 10.85 7.68 5.45 4.81 4.21 3.46
440 15.77 9.86 6.77 4.73 4.16 3.62 2.97
460 13.60 8.17 5.50 3.81 3.36 2.93 2.44
480 11.79 6.71 4.44 3.06 2.71 2.36 1.97
500 10.45 5.74 3.76 2.62 2.34 2.07 1.76
520 8.75 4.56 2.98 2.10 1.89 1.70 1.49
540 7.04 3.57 2.37 1.72 1.60 1.47 1.32
560 5.99 3.02 2.01 1.53 1.44 1.35 1.22
580 5.03 2.55 1.76 1.39 1.33 1.27 1.18
600 4.15 2.16 1.55 1.29 1.26 1.23 1.15
620 3.52 1.88 1.41 1.23 1.21 1.19 1.12
640 2.96 1.69 1.33 1.23 1.22 1.20 1.16
660 2.75 1.65 1.35 1.29 1.26 1.27 1.21
680 3.63 2.12 1.64 1.50 1.44 1.43 1.37
700 8.60 4.70 3.29 2.57 2.35 2.14 1.92
345

Table A-4-1: Continued


Shade
ID
Speed
(m/min)
Dwell
Time
(sec)
Oxidation
Time (sec)
Dye Bath
(gpl
100%
Indigo)
Dye
Bath pH
Dye
Bath
(mV)
Dye Bath
Alkalinity
(gpl)
Dwell
Length
(m)
Oxidation
Length (m)
Nip
Pressures
(psi)
q1910 34.75 19.4 63.9 1.831 11.54 875 4.56 11.37 40.50 40.00
Yarn Skein Response Variables
Yarn
Count
Dye
route Dips
Greige
Weight
Boil Off
Weight
Dyed
Weight
Washed
Weight %COWY
Total
%IOWY
Surface
%IOWY Integ
Penetration
Level
8 1 only 1 9.3656 9.0787 9.5368 9.0704 5.05% 0.334% 0.736% 17.1 0.45
8 1--2 2 9.2041 8.899 9.4735 8.9336 6.46% 0.649% 1.253% 35.5 0.52
8 1--3 3 9.2402 8.9373 9.6106 9.0075 7.53% 1.042% 2.284% 51.5 0.46
8 1--4 4 9.3055 9.0069 9.7547 9.1089 8.30% 1.467% 4.250% 69.2 0.35
8 1--5 5 9.3216 9.035 9.7564 9.1587 7.98% 1.667% 4.942% 73.9 0.34
8 1--6 6 9.5513 9.2395 10.0173 9.4061 8.42% 1.982% 6.549% 82.5 0.30
8 1--6,6 7 9.4464 9.1405 10.0175 9.3583 9.59% 2.447% 8.610% 90.6 0.28
% Reflectance Readings


Wave-
length
(nm) Dip 1 Dip 2 Dip 3 Dip 4 Dip 5 Dip 6 Dip 7
400 12.96 7.94 5.73 4.20 3.76 3.25 2.77
420 17.29 10.94 7.67 5.41 4.80 4.07 3.36
440 16.26 9.91 6.77 4.69 4.16 3.49 2.88
460 14.05 8.23 5.51 3.80 3.38 2.84 2.38
480 12.19 6.75 4.43 3.06 2.72 2.28 1.94
500 10.79 5.78 3.77 2.61 2.35 2.00 1.73
520 9.11 4.61 3.01 2.11 1.92 1.66 1.48
540 7.34 3.63 2.41 1.74 1.62 1.44 1.32
560 6.29 3.08 2.08 1.54 1.46 1.33 1.24
580 5.32 2.62 1.84 1.41 1.36 1.25 1.19
600 4.41 2.22 1.64 1.31 1.28 1.20 1.16
620 3.77 1.97 1.51 1.26 1.24 1.18 1.15
640 3.19 1.77 1.45 1.24 1.23 1.19 1.18
660 2.98 1.72 1.46 1.27 1.28 1.26 1.22
680 3.84 2.20 1.75 1.48 1.47 1.43 1.38
700 8.82 4.78 3.37 2.54 2.36 2.13 1.92
346

Table A-4-1: Continued


Shade
ID
Speed
(m/min)
Dwell
Time
(sec)
Oxidation
Time (sec)
Dye Bath
(gpl
100%
Indigo)
Dye
Bath pH
Dye
Bath
(mV)
Dye Bath
Alkalinity
(gpl)
Dwell
Length
(m)
Oxidation
Length (m)
Nip
Pressures
(psi)
q1910 34.75 19.4 63.9 1.831 11.54 875 4.56 11.37 40.50 40.00
Yarn Skein Response Variables
Yarn
Count
Dye
route Dips
Greige
Weight
Boil Off
Weight
Dyed
Weight
Washed
Weight %COWY
Total
%IOWY
Surface
%IOWY Integ
Penetration
Level
12 1 only 1 6.3961 6.2118 6.5552 6.2301 5.53% 0.365% 0.760% 18.1 0.48
12 1--2 2 6.4423 6.2676 6.6617 6.3022 6.29% 0.743% 1.405% 38.6 0.53
12 1--3 3 6.4742 6.2971 6.7834 6.3538 7.72% 1.062% 2.284% 51.5 0.47
12 1--4 4 6.4341 6.2628 6.8095 6.3536 8.73% 1.618% 3.944% 67.0 0.41
12 1--5 5 6.6569 6.4754 7.0561 6.5851 8.97% 1.891% 5.059% 74.6 0.37
12 1--6 6 6.3026 6.1314 6.6941 6.2694 9.18% 2.194% 6.088% 80.3 0.36
12 1--6,6 7 6.2438 6.0627 6.6495 6.2253 9.68% 2.695% 8.236% 89.3 0.33
% Reflectance Readings


Wave-
length
(nm) Dip 1 Dip 2 Dip 3 Dip 4 Dip 5 Dip 6 Dip 7
400 12.78 7.56 5.88 4.32 3.82 3.41 2.89
420 17.00 10.36 7.85 5.57 4.86 4.27 3.55
440 15.90 9.34 6.91 4.83 4.20 3.68 3.04
460 13.67 7.72 5.63 3.92 3.40 2.99 2.48
480 11.82 6.31 4.53 3.15 2.73 2.41 2.01
500 10.42 5.38 3.84 2.69 2.35 2.11 1.78
520 8.73 4.29 3.06 2.18 1.91 1.73 1.51
540 7.03 3.37 2.44 1.79 1.60 1.48 1.33
560 5.98 2.84 2.09 1.59 1.44 1.34 1.25
580 5.02 2.41 1.83 1.46 1.34 1.28 1.19
600 4.15 2.04 1.62 1.35 1.25 1.21 1.16
620 3.54 1.79 1.48 1.30 1.21 1.18 1.14
640 2.99 1.63 1.41 1.30 1.22 1.21 1.17
660 2.79 1.61 1.42 1.35 1.27 1.26 1.24
680 3.67 2.05 1.71 1.56 1.46 1.45 1.39
700 8.66 4.50 3.39 2.65 2.37 2.19 1.95
347

Table A-4-1: Continued


Shade
ID
Speed
(m/min)
Dwell
Time
(sec)
Oxidation
Time (sec)
Dye Bath
(gpl
100%
Indigo)
Dye
Bath pH
Dye
Bath
(mV)
Dye Bath
Alkalinity
(gpl)
Dwell
Length
(m)
Oxidation
Length (m)
Nip
Pressures
(psi)
x3313 32.92 20.7 67.5 1.762 12.31 795 3.12 11.37 40.50 40.00
Yarn Skein Response Variables
Yarn
Count
Dye
route Dips
Greige
Weight
Boil Off
Weight
Dyed
Weight
Washed
Weight %COWY
Total
%IOWY
Surface
%IOWY Integ
Penetration
Level
6.3 1 only 1 7.0088 6.7264 7.0731 6.8342 5.15% 0.384% 0.777% 18.9 0.49
6.3 1--2 2 7.2426 6.9697 7.2378 6.957 3.85% 0.625% 1.221% 34.7 0.51
6.3 1--3 3 7.1191 6.8402 7.1819 6.8554 5.00% 0.985% 2.327% 52.0 0.42
6.3 1--4 4 7.3453 7.058 7.4495 7.0843 5.55% 1.284% 3.179% 60.6 0.40
6.3 1--5 5 7.1441 6.874 7.2638 6.9278 5.67% 1.590% 4.411% 70.4 0.36
6.3 1--6 6 7.2771 7.0013 7.3976 7.0653 5.66% 1.847% 5.147% 75.1 0.36

% Reflectance Readings


Wave-
length
(nm) Dip 1 Dip 2 Dip 3 Dip 4 Dip 5 Dip 6 Dip 7
400 12.20 7.93 5.70 4.73 3.99 3.57
420 16.25 10.89 7.50 6.03 5.02 4.42
440 15.18 9.88 6.58 5.25 4.32 3.77
460 13.01 8.18 5.34 4.25 3.48 3.05
480 11.30 6.77 4.34 3.46 2.84 2.48
500 9.99 5.80 3.69 2.95 2.44 2.16
520 8.36 4.65 2.95 2.40 1.98 1.79
540 6.72 3.68 2.38 1.97 1.67 1.55
560 5.73 3.14 2.06 1.75 1.52 1.44
580 4.81 2.66 1.81 1.59 1.41 1.36
600 3.99 2.27 1.62 1.48 1.34 1.32
620 3.44 2.04 1.53 1.44 1.33 1.34
640 2.91 1.84 1.47 1.43 1.34 1.36
660 2.76 1.85 1.53 1.54 1.48 1.53
680 3.55 2.30 1.83 1.78 1.69 1.73
700 8.21 4.90 3.45 3.04 2.66 2.53
348

Table A-4-1: Continued


Shade
ID
Speed
(m/min)
Dwell
Time
(sec)
Oxidation
Time (sec)
Dye Bath
(gpl
100%
Indigo)
Dye
Bath pH
Dye
Bath
(mV)
Dye Bath
Alkalinity
(gpl)
Dwell
Length
(m)
Oxidation
Length (m)
Nip
Pressures
(psi)
x3313 32.92 20.7 67.5 1.762 12.31 795 3.12 11.37 40.50 40.00
Yarn Skein Response Variables
Yarn
Count
Dye
route Dips
Greige
Weight
Boil Off
Weight
Dyed
Weight
Washed
Weight %COWY
Total
%IOWY
Surface
%IOWY Integ
Penetration
Level
7.1 1 only 1 5.8487 5.7 5.8979 5.6788 3.47% 0.359% 0.742% 17.3 0.48
7.1 1--2 2 6.5628 6.3415 6.6026 6.3355 4.12% 0.615% 1.146% 32.8 0.54
7.1 1--3 3 6.499 6.2929 6.5905 6.3009 4.73% 1.011% 2.175% 50.2 0.46
7.1 1--4 4 6.5925 6.3731 6.7401 6.4029 5.76% 1.360% 3.362% 62.3 0.40



% Reflectance Readings


Wave-
length
(nm) Dip 1 Dip 2 Dip 3 Dip 4 Dip 5 Dip 6 Dip 7
400 12.95 8.44 5.89 4.70
420 17.18 11.61 7.83 6.06
440 16.15 10.54 6.89 5.25
460 13.91 8.72 5.60 4.23
480 12.14 7.25 4.55 3.44
500 10.77 6.20 3.87 2.91
520 9.07 4.97 3.10 2.37
540 7.32 3.92 2.48 1.94
560 6.24 3.33 2.14 1.71
580 5.23 2.80 1.87 1.55
600 4.32 2.38 1.66 1.43
620 3.70 2.12 1.56 1.39
640 3.11 1.91 1.49 1.36
660 2.96 1.89 1.55 1.46
680 3.84 2.38 1.85 1.71
700 8.95 5.18 3.55 2.94
349

Table A-4-1: Continued


Shade
ID
Speed
(m/min)
Dwell
Time
(sec)
Oxidation
Time (sec)
Dye Bath
(gpl
100%
Indigo)
Dye
Bath pH
Dye
Bath
(mV)
Dye Bath
Alkalinity
(gpl)
Dwell
Length
(m)
Oxidation
Length (m)
Nip
Pressures
(psi)
x3313 32.92 20.7 67.5 1.762 12.31 795 3.12 11.37 40.50 40.00
Yarn Skein Response Variables
Yarn
Count
Dye
route Dips
Greige
Weight
Boil Off
Weight
Dyed
Weight
Washed
Weight %COWY
Total
%IOWY
Surface
%IOWY Integ
Penetration
Level
8 1 only 1 5.8101 5.6212 5.8169 5.6029 3.48% 0.396% 0.766% 18.4 0.52
8 1--2 2 5.7765 5.64 5.8693 5.6401 4.07% 0.698% 1.187% 33.9 0.59
8 1--3 3 5.726 5.5375 5.8057 5.5472 4.84% 1.055% 2.052% 48.7 0.51
8 1--4 4 5.8234 5.6296 5.946 5.6582 5.62% 1.445% 3.132% 60.2 0.46



% Reflectance Readings


Wave-
length
(nm) Dip 1 Dip 2 Dip 3 Dip 4 Dip 5 Dip 6 Dip 7
400 12.33 7.92 6.04 4.84
420 16.40 10.81 8.08 6.22
440 15.36 9.87 7.07 5.37
460 13.21 8.23 5.74 4.33
480 11.52 6.85 4.67 3.52
500 10.20 5.89 3.96 2.99
520 8.56 4.74 3.17 2.43
540 6.92 3.77 2.55 1.99
560 5.90 3.23 2.20 1.77
580 4.95 2.74 1.93 1.60
600 4.11 2.35 1.72 1.48
620 3.53 2.11 1.61 1.44
640 2.99 1.90 1.53 1.43
660 2.83 1.91 1.60 1.53
680 3.64 2.39 1.90 1.77
700 8.47 5.08 3.64 3.03
350

Table A-4-1: Continued


Shade
ID
Speed
(m/min)
Dwell
Time
(sec)
Oxidation
Time (sec)
Dye Bath
(gpl
100%
Indigo)
Dye
Bath pH
Dye
Bath
(mV)
Dye Bath
Alkalinity
(gpl)
Dwell
Length
(m)
Oxidation
Length (m)
Nip
Pressures
(psi)
x3313 32.92 20.7 67.5 1.762 12.31 795 3.12 11.37 40.50 40.00
Yarn Skein Response Variables
Yarn
Count
Dye
route Dips
Greige
Weight
Boil Off
Weight
Dyed
Weight
Washed
Weight %COWY
Total
%IOWY
Surface
%IOWY Integ
Penetration
Level
12 1 only 1 3.7928 3.6563 3.8136 3.6513 4.30% 0.500% 0.810% 20.4 0.62
12 1--2 2 3.6681 3.5419 3.6959 3.5516 4.35% 0.848% 1.339% 37.3 0.63
12 1--3 3 3.6897 3.5664 3.7866 3.5817 6.17% 1.298% 2.361% 52.4 0.55
12 1--4 4 3.7325 3.5998 3.8364 3.6348 6.57% 1.727% 3.586% 64.1 0.48
12 1--5 5 3.7053 3.581 3.8509 3.6372 7.54% 2.167% 4.842% 73.2 0.45
12 1--6 6 3.7607 3.6263 3.912 3.6989 7.88% 2.614% 5.975% 79.7 0.44

% Reflectance Readings


Wave-
length
(nm) Dip 1 Dip 2 Dip 3 Dip 4 Dip 5 Dip 6 Dip 7
400 11.65 7.71 5.70 4.55 3.83 3.27
420 15.46 10.50 7.47 5.80 4.74 3.98
440 14.38 9.43 6.55 5.02 4.07 3.41
460 12.30 7.79 5.33 4.05 3.28 2.79
480 10.65 6.40 4.34 3.30 2.67 2.28
500 9.38 5.47 3.68 2.80 2.29 1.99
520 7.82 4.37 2.95 2.27 1.88 1.67
540 6.29 3.46 2.37 1.87 1.59 1.47
560 5.35 2.94 2.05 1.66 1.47 1.37
580 4.49 2.49 1.80 1.51 1.36 1.30
600 3.72 2.12 1.61 1.40 1.31 1.28
620 3.22 1.90 1.52 1.37 1.33 1.31
640 2.74 1.71 1.46 1.37 1.35 1.35
660 2.63 1.72 1.53 1.47 1.50 1.54
680 3.39 2.17 1.82 1.71 1.72 1.73
700 7.80 4.62 3.45 2.87 2.60 2.41
351

Table A-4-1: Continued


Shade
ID
Speed
(m/min)
Dwell
Time
(sec)
Oxidation
Time (sec)
Dye Bath
(gpl
100%
Indigo)
Dye
Bath pH
Dye
Bath
(mV)
Dye Bath
Alkalinity
(gpl)
Dwell
Length
(m)
Oxidation
Length (m)
Nip
Pressures
(psi)
4223 32.92 20.7 67.5 2.07 12.49 907 3.75 11.37 40.50 40.00
Yarn Skein Response Variables
Yarn
Count Dye route Dips
Greige
Weight
Boil Off
Weight
Dyed
Weight
Washed
Weight %COWY
Total
%IOWY
Surface
%IOWY Integ
Penetration
Level
6.3 1 only 1 7.0745 6.9739 7.1606 6.8906 2.68% 0.333% 0.694% 15.3 0.48
6.3 1--2 2 7.0767 6.9669 7.2175 6.8938 3.60% 0.630% 0.992% 28.1 0.63
6.3 1-2,2 3 7.0788 6.9842 7.2548 6.9179 3.87% 0.961% 1.379% 38.1 0.70
6.3 1-2,2,2 4 7.0893 6.985 7.2603 6.9307 3.94% 1.094% 1.784% 45.0 0.61
6.3 1-2,2,2,2 5 7.0793 6.9933 7.2746 6.9562 4.02% 1.461% 2.491% 53.8 0.59
6.3 1-2,2,2,2,2 6 7.025 6.916 7.252 6.9043 4.86% 1.551% 2.859% 57.6 0.54
6.3
1-
2,2,2,2,2,2 7 7.0844 6.9686 7.3252 6.9766 5.12% 1.828% 3.468% 63.2 0.53
% Reflectance Readings


Wave-
length
(nm) Dip 1 Dip 2 Dip 3 Dip 4 Dip 5 Dip 6 Dip 7
400 14.19 9.39 7.44 6.35 5.36 4.82 4.33
420 18.75 12.78 10.13 8.53 6.96 6.13 5.46
440 17.70 11.80 9.17 7.60 6.17 5.43 4.81
460 15.32 9.95 7.61 6.26 5.06 4.48 3.95
480 13.40 8.41 6.26 5.11 4.13 3.67 3.25
500 11.89 7.26 5.33 4.33 3.51 3.14 2.78
520 10.04 5.85 4.26 3.48 2.83 2.57 2.29
540 8.09 4.64 3.37 2.79 2.30 2.13 1.92
560 6.96 3.91 2.87 2.40 2.00 1.87 1.72
580 5.82 3.27 2.44 2.09 1.77 1.69 1.57
600 4.79 2.74 2.09 1.85 1.61 1.56 1.46
620 4.05 2.37 1.85 1.68 1.49 1.47 1.39
640 3.42 2.08 1.68 1.59 1.44 1.45 1.39
660 3.20 2.00 1.66 1.56 1.42 1.45 1.40
680 4.27 2.59 2.04 1.85 1.61 1.59 1.51
700 10.09 6.04 4.43 3.67 3.08 2.84 2.56
352

Table A-4-1: Continued


Shade
ID
Speed
(m/min)
Dwell
Time
(sec)
Oxidation
Time (sec)
Dye Bath
(gpl
100%
Indigo)
Dye
Bath pH
Dye
Bath
(mV)
Dye Bath
Alkalinity
(gpl)
Dwell
Length
(m)
Oxidation
Length (m)
Nip
Pressures
(psi)
4223 32.92 20.7 67.5 2.07 12.49 907 3.75 11.37 40.50 40.00
Yarn Skein Response Variables
Yarn
Count
Dye
route Dips
Greige
Weight
Boil Off
Weight
Dyed
Weight
Washed
Weight %COWY
Total
%IOWY
Surface
%IOWY Integ
Penetration
Level
7.1 1 only 1 6.475 6.3967 6.5935 6.3195 3.08% 0.343% 0.701% 15.6 0.49
7.1 1--2 2 6.5846 6.5142 6.7445 6.4489 3.54% 0.640% 0.977% 27.6 0.66





% Reflectance Readings


Wave-
length
(nm) Dip 1 Dip 2 Dip 3 Dip 4 Dip 5 Dip 6 Dip 7
400 14.36 9.79
420 18.81 13.24
440 17.73 12.20
460 15.32 10.24
480 13.35 8.63
500 11.81 7.46
520 10.00 6.02
540 8.04 4.77
560 6.88 4.01
580 5.73 3.33
600 4.71 2.78
620 3.98 2.39
640 3.36 2.10
660 3.17 2.01
680 4.25 2.62
700 10.14 6.19
353

Table A-4-1: Continued


Shade
ID
Speed
(m/min)
Dwell
Time
(sec)
Oxidation
Time (sec)
Dye Bath
(gpl
100%
Indigo)
Dye
Bath pH
Dye
Bath
(mV)
Dye Bath
Alkalinity
(gpl)
Dwell
Length
(m)
Oxidation
Length (m)
Nip
Pressures
(psi)
4223 32.92 20.7 67.5 2.07 12.49 907 3.75 11.37 40.50 40.00
Yarn Skein Response Variables
Yarn
Count
Dye
route Dips
Greige
Weight
Boil Off
Weight
Dyed
Weight
Washed
Weight %COWY
Total
%IOWY
Surface
%IOWY Integ
Penetration
Level
8 1 only 1 5.7344 5.661 5.8671 5.6131 3.64% 0.321% 0.693% 15.3 0.46
8 1--2 2 5.6597 5.5909 5.8276 5.5547 4.23% 0.634% 0.995% 28.2 0.64





% Reflectance Readings


Wave-
length
(nm) Dip 1 Dip 2 Dip 3 Dip 4 Dip 5 Dip 6 Dip 7
400 14.29 9.50
420 18.79 12.85
440 17.78 11.85
460 15.42 9.95
480 13.46 8.39
500 11.93 7.24
520 10.12 5.84
540 8.15 4.63
560 7.01 3.91
580 5.86 3.26
600 4.82 2.73
620 4.07 2.36
640 3.44 2.09
660 3.21 2.00
680 4.29 2.59
700 10.14 6.00
354

Table A-4-1: Continued


Shade
ID
Speed
(m/min)
Dwell
Time
(sec)
Oxidation
Time (sec)
Dye Bath
(gpl
100%
Indigo)
Dye
Bath pH
Dye
Bath
(mV)
Dye Bath
Alkalinity
(gpl)
Dwell
Length
(m)
Oxidation
Length (m)
Nip
Pressures
(psi)
4223 32.92 20.7 67.5 2.07 12.49 907 3.75 11.37 40.50 40.00
Yarn Skein Response Variables
Yarn
Count
Dye
route Dips
Greige
Weight
Boil Off
Weight
Dyed
Weight
Washed
Weight %COWY
Total
%IOWY
Surface
%IOWY Integ
Penetration
Level
12 1 only 1 3.5474 3.4913 3.6178 3.4652 3.62% 0.398% 0.746% 17.5 0.53
12 2 only 1 3.6069 3.5505 3.6872 3.522 3.85% 0.480% 0.813% 20.6 0.59
12 1--2 2 3.7068 3.6437 3.7792 3.6242 3.72% 0.757% 1.065% 30.5 0.71
12 1--2,1 3 3.5935 3.543 3.6935 3.5284 4.25% 0.902% 1.317% 36.9 0.68
12 1--2,2 3 3.6744 3.6178 3.805 3.6117 5.17% 1.026% 1.538% 41.1 0.67


% Reflectance Readings


Wave-
length
(nm) Dip 1 Dip 1 Dip 2 Dip 3 Dip 3 Dip 6 Dip 7
400 12.96 11.86 8.98 7.76 7.05
420 17.20 15.87 12.21 10.58 9.62
440 16.21 14.78 11.22 9.60 8.62
460 13.93 12.54 9.37 7.94 7.09
480 12.14 10.81 7.86 6.55 5.81
500 10.75 9.52 6.78 5.59 4.95
520 9.05 7.88 5.44 4.47 3.96
540 7.29 6.31 4.29 3.52 3.13
560 6.21 5.35 3.62 2.98 2.66
580 5.21 4.45 3.04 2.53 2.28
600 4.28 3.66 2.54 2.15 1.95
620 3.61 3.10 2.20 1.87 1.74
640 3.05 2.66 1.96 1.71 1.62
660 2.89 2.55 1.90 1.68 1.61
680 3.84 3.36 2.45 2.11 1.98
700 9.12 8.05 5.66 4.64 4.17
355

Table A-4-1: Continued


Shade
ID
Speed
(m/min)
Dwell
Time
(sec)
Oxidation
Time (sec)
Dye Bath
(gpl
100%
Indigo)
Dye
Bath pH
Dye
Bath
(mV)
Dye Bath
Alkalinity
(gpl)
Dwell
Length
(m)
Oxidation
Length (m)
Nip
Pressures
(psi)
x3313 32.92 20.7 67.5 1.93 12.33 800 3.26 11.37 40.50 40.00
Yarn Skein Response Variables
Yarn
Count
Dye
route Dips
Greige
Weight
Boil Off
Weight
Dyed
Weight
Washed
Weight %COWY
Total
%IOWY
Surface
%IOWY Integ
Penetration
Level
12 1 only 1 3.6373 3.5076 3.6763 3.5062 4.81% 0.530% 0.819% 20.9 0.65
12 1--2 2 3.7084 3.5745 3.7704 3.5885 5.48% 0.957% 1.407% 38.7 0.68
12 1--3 3 3.6452 3.5159 3.7292 3.5398 6.07% 1.489% 2.513% 54.1 0.59
12 1--4 4 3.7243 3.5849 3.8534 3.6266 7.49% 1.857% 3.874% 66.4 0.48
12 1--5 5 3.6299 3.5014 3.7814 3.5641 8.00% 2.271% 4.897% 73.6 0.46
12 1--6 6 3.605 3.466 3.7744 3.5592 8.90% 2.730% 6.648% 83.0 0.41

% Reflectance Readings


Wave-
length
(nm) Dip 1 Dip 2 Dip 3 Dip 4 Dip 5 Dip 6 Dip 7
400 11.68 7.46 5.57 4.40 3.74 3.16
420 15.55 10.15 7.21 5.57 4.60 3.83
440 14.36 9.04 6.29 4.79 3.94 3.25
460 12.22 7.44 5.09 3.87 3.20 2.65
480 10.53 6.11 4.13 3.15 2.61 2.17
500 9.27 5.20 3.49 2.67 2.26 1.90
520 7.67 4.16 2.81 2.18 1.85 1.60
540 6.16 3.30 2.27 1.79 1.59 1.41
560 5.24 2.81 1.97 1.60 1.46 1.32
580 4.37 2.39 1.74 1.46 1.37 1.26
600 3.63 2.06 1.58 1.37 1.32 1.24
620 3.20 1.87 1.51 1.35 1.33 1.28
640 2.67 1.71 1.46 1.35 1.37 1.32
660 2.56 1.76 1.55 1.48 1.52 1.49
680 3.32 2.17 1.84 1.70 1.71 1.66
700 7.61 4.48 3.36 2.81 2.56 2.31
356

Table A-4-1: Continued


Shade
ID
Speed
(m/min)
Dwell
Time
(sec)
Oxidation
Time (sec)
Dye Bath
(gpl
100%
Indigo)
Dye
Bath
pH
Dye
Bath
(mV)
Dye Bath
Alkalinity
(gpl)
Dwell
Length
(m)
Oxidation
Length (m)
Nip
Pressures
(psi)
4223 32.92 20.67 67.5 2.011 12.7 924 4.12 11.37 40.50 40.00
Yarn Skein Response Variables
Yarn
Count
Dye
route Dips
Greige
Weight
Boil Off
Weight
Dyed
Weight
Washed
Weight %COWY
Total
%IOWY
Surface
%IOWY Integ
Penetration
Level
6.3 1 only 1 7.03 6.771999 7.0441 6.7844 4.02% 0.262% 0.701% 15.6 0.37
6.3 1--2 2 7.021 6.725472 7.043 6.7478 4.72% 0.519% 0.944% 26.3 0.55





% Reflectance Readings


Wave-
length
(nm) Dip 1 Dip 2 Dip 3 Dip 4 Dip 5 Dip 6 Dip 7
400 14.13 10.18
420 18.70 13.85
440 17.66 12.77
460 15.22 10.68
480 13.28 9.02
500 11.76 7.82
520 9.94 6.29
540 7.98 4.95
560 6.87 4.18
580 5.74 3.49
600 4.71 2.88
620 3.97 2.48
640 3.31 2.15
660 3.07 2.04
680 4.10 2.64
700 9.88 6.42
357

Table A-4-1: Continued


Shade
ID
Speed
(m/min)
Dwell
Time
(sec)
Oxidation
Time (sec)
Dye Bath
(gpl
100%
Indigo)
Dye
Bath
pH
Dye
Bath
(mV)
Dye Bath
Alkalinity
(gpl)
Dwell
Length
(m)
Oxidation
Length (m)
Nip
Pressures
(psi)
4223 32.92 20.67 67.5 2.011 12.7 924 4.12 11.37 40.50 40.00
Yarn Skein Response Variables
Yarn
Count
Dye
route Dips
Greige
Weight
Boil Off
Weight
Dyed
Weight
Washed
Weight %COWY
Total
%IOWY
Surface
%IOWY Integ
Penetration
Level
7.1 1 only 1 6.301 6.07168 6.3521 6.1162 4.62% 0.298% 0.689% 15.1 0.43
7.1 1--2 2 6.0678 5.845112 6.191 5.9095 5.92% 0.545% 0.942% 26.3 0.58





% Reflectance Readings


Wave-
length
(nm) Dip 1 Dip 2 Dip 3 Dip 4 Dip 5 Dip 6 Dip 7
400 14.39 9.99
420 18.94 13.57
440 17.91 12.60
460 15.48 10.60
480 13.57 8.98
500 12.02 7.80
520 10.22 6.31
540 8.22 4.98
560 7.10 4.21
580 5.95 3.52
600 4.88 2.92
620 4.11 2.50
640 3.42 2.15
660 3.18 2.06
680 4.27 2.65
700 10.15 6.40
358

Table A-4-1: Continued


Shade
ID
Speed
(m/min)
Dwell
Time
(sec)
Oxidation
Time (sec)
Dye Bath
(gpl
100%
Indigo)
Dye
Bath
pH
Dye
Bath
(mV)
Dye Bath
Alkalinity
(gpl)
Dwell
Length
(m)
Oxidation
Length (m)
Nip
Pressures
(psi)
4223 32.92 20.67 67.5 2.011 12.7 924 4.12 11.37 40.50 40.00
Yarn Skein Response Variables
Yarn
Count
Dye
route Dips
Greige
Weight
Boil Off
Weight
Dyed
Weight
Washed
Weight %COWY
Total
%IOWY
Surface
%IOWY Integ
Penetration
Level
8 1 only 1 5.582 5.377141 5.6381 5.4209 4.85% 0.278% 0.636% 13.2 0.44
8 1--2 2 5.621 5.414709 5.7319 5.484 5.86% 0.520% 0.913% 25.1 0.57





% Reflectance Readings


Wave-
length
(nm) Dip 1 Dip 2 Dip 3 Dip 4 Dip 5 Dip 6 Dip 7
400 15.70 10.35
420 20.49 14.00
440 19.55 13.00
460 17.06 10.97
480 15.05 9.33
500 13.42 8.12
520 11.44 6.58
540 9.22 5.20
560 7.99 4.41
580 6.70 3.68
600 5.49 3.04
620 4.61 2.61
640 3.83 2.24
660 3.50 2.11
680 4.81 2.75
700 11.48 6.67
359

Table A-4-1: Continued


Shade
ID
Speed
(m/min)
Dwell
Time
(sec)
Oxidation
Time (sec)
Dye Bath
(gpl
100%
Indigo)
Dye
Bath
pH
Dye
Bath
(mV)
Dye Bath
Alkalinity
(gpl)
Dwell
Length
(m)
Oxidation
Length (m)
Nip
Pressures
(psi)
4223 32.92 20.67 67.5 2.011 12.7 924 4.12 11.37 40.50 40.00
Yarn Skein Response Variables
Yarn
Count
Dye
route Dips
Greige
Weight
Boil Off
Weight
Dyed
Weight
Washed
Weight %COWY
Total
%IOWY
Surface
%IOWY Integ
Penetration
Level
12 1 only 1 3.525 3.395633 3.5906 3.4191 5.74% 0.360% 0.690% 15.2 0.52
12 1--2 2 3.5068 3.3781 3.5844 3.4127 6.11% 0.734% 1.047% 30.0 0.70





% Reflectance Readings


Wave-
length
(nm) Dip 1 Dip 2 Dip 3 Dip 4 Dip 5 Dip 6 Dip 7
400 14.50 9.13
420 19.11 12.33
440 18.06 11.38
460 15.59 9.55
480 13.63 8.05
500 12.07 6.93
520 10.23 5.59
540 8.23 4.41
560 7.09 3.73
580 5.93 3.11
600 4.85 2.58
620 4.09 2.22
640 3.42 1.93
660 3.18 1.82
680 4.30 2.38
700 10.24 5.70
360

Table A-4-1: Continued


Shade
ID
Speed
(m/min)
Dwell
Time
(sec)
Oxidation
Time (sec)
Dye Bath
(gpl
100%
Indigo)
Dye
Bath pH
Dye
Bath
(mV)
Dye Bath
Alkalinity
(gpl)
Dwell
Length
(m)
Oxidation
Length (m)
Nip
Pressures
(psi)
t3663 34.75 19.6 63.9 2.053 11.84 865 4.29 11.37 40.50 40.00
Yarn Skein Response Variables
Yarn
Count
Dye
route Dips
Greige
Weight
Boil Off
Weight
Dyed
Weight
Washed
Weight %COWY
Total
%IOWY
Surface
%IOWY Integ
Penetration
Level
6.3 1 only 1 8.1651 7.8331 8.1628 7.8071 4.21% 0.299% 0.776% 18.9 0.39
6.3 1--2 2 8.3718 8.0264 8.4349 8.0296 5.09% 0.602% 1.338% 37.3 0.45
6.3 1--3 3 8.2892 7.9509 8.4839 7.9736 6.70% 0.959% 2.362% 52.4 0.41
6.3 1--4 4 8.2337 7.9014 8.4259 7.951 6.64% 1.268% 3.931% 66.9 0.32
6.3 1--5 5 8.0853 7.756 8.3329 7.8362 7.44% 1.602% 5.611% 77.8 0.29
6.3 1--6 6 8.301 7.9584 8.5545 8.0585 7.49% 1.750% 6.144% 80.6 0.28
6.3 1--7 7 8.3284 7.9843 8.6764 8.1288 8.67% 2.127% 7.807% 87.8 0.27
% Reflectance Readings


Wave-
length
(nm) Dip 1 Dip 2 Dip 3 Dip 4 Dip 5 Dip 6 Dip 7
400 12.87 7.86 5.86 4.40 3.62 3.33 2.88
420 17.39 10.92 7.87 5.68 4.57 4.14 3.50
440 16.14 9.83 6.87 4.92 3.93 3.56 2.99
460 13.70 8.06 5.54 3.97 3.17 2.89 2.47
480 11.76 6.57 4.46 3.21 2.58 2.37 2.04
500 10.28 5.57 3.75 2.73 2.22 2.06 1.81
520 8.52 4.42 2.99 2.21 1.82 1.71 1.55
540 6.79 3.46 2.39 1.82 1.55 1.50 1.38
560 5.74 2.93 2.04 1.62 1.40 1.37 1.29
580 4.78 2.47 1.80 1.46 1.30 1.29 1.22
600 3.92 2.10 1.59 1.34 1.22 1.23 1.19
620 3.32 1.84 1.46 1.27 1.17 1.18 1.16
640 2.81 1.67 1.38 1.23 1.15 1.17 1.15
660 2.64 1.62 1.38 1.24 1.17 1.20 1.19
680 3.45 2.04 1.66 1.44 1.34 1.34 1.34
700 8.51 4.57 3.30 2.55 2.18 2.07 1.92
361

Table A-4-1: Continued


Shade
ID
Speed
(m/min)
Dwell
Time
(sec)
Oxidation
Time (sec)
Dye Bath
(gpl
100%
Indigo)
Dye
Bath pH
Dye
Bath
(mV)
Dye Bath
Alkalinity
(gpl)
Dwell
Length
(m)
Oxidation
Length (m)
Nip
Pressures
(psi)
1472 34.75 19.6 63.9 2.259 11.85 858 4.17 11.37 40.50 40.00
Yarn Skein Response Variables
Yarn
Count
Dye
route Dips
Greige
Weight
Boil Off
Weight
Dyed
Weight
Washed
Weight %COWY
Total
%IOWY
Surface
%IOWY Integ
Penetration
Level
6.3 1 only 1 8.032 7.8333 8.2375 7.8335 5.16% 0.369% 0.814% 20.6 0.45
6.3 1--2 2 8.2171 8.0055 8.534 8.0456 6.60% 0.680% 1.487% 40.2 0.46
6.3 1--3 3 7.9604 7.7594 8.3303 7.8241 7.36% 1.140% 3.216% 61.0 0.35
6.3 1--4 4 8.2216 8.0146 8.6908 8.1186 8.44% 1.579% 5.254% 75.8 0.30
6.3 1--5 5 8.1625 7.9496 8.6538 8.078 8.86% 1.893% 6.629% 82.9 0.29
6.3 1--6 6 8.1076 7.896 8.5833 8.0701 8.70% 2.320% 9.206% 92.5 0.25
6.3 1--6,6 7 8.1482 7.9452 8.6776 8.1481 9.22% 2.776% 12.658% 101.2 0.22
% Reflectance Readings


Wave-
length
(nm) Dip 1 Dip 2 Dip 3 Dip 4 Dip 5 Dip 6 Dip 7
400 12.13 7.48 5.11 3.85 3.32 2.79 2.40
420 16.28 10.29 6.72 4.93 4.16 3.42 2.90
440 15.12 9.19 5.85 4.24 3.57 2.93 2.47
460 12.87 7.56 4.72 3.42 2.91 2.41 2.06
480 11.06 6.17 3.80 2.77 2.35 1.97 1.70
500 9.69 5.22 3.20 2.36 2.04 1.74 1.53
520 8.00 4.15 2.56 1.92 1.70 1.48 1.33
540 6.35 3.25 2.04 1.59 1.45 1.31 1.21
560 5.33 2.73 1.76 1.43 1.32 1.22 1.14
580 4.39 2.30 1.55 1.30 1.23 1.15 1.10
600 3.58 1.94 1.39 1.21 1.17 1.10 1.06
620 3.04 1.71 1.29 1.16 1.13 1.08 1.05
640 2.58 1.58 1.26 1.15 1.14 1.09 1.08
660 2.44 1.55 1.26 1.17 1.18 1.13 1.13
680 3.22 1.93 1.50 1.34 1.32 1.28 1.28
700 8.04 4.37 2.94 2.33 2.13 1.90 1.79
362

Table A-4-1: Continued


Shade
ID
Speed
(m/min)
Dwell
Time
(sec)
Oxidation
Time (sec)
Dye Bath
(gpl
100%
Indigo)
Dye
Bath pH
Dye
Bath
(mV)
Dye Bath
Alkalinity
(gpl)
Dwell
Length
(m)
Oxidation
Length (m)
Nip
Pressures
(psi)
1472 34.75 19.6 63.9 2.158 11.88 846 4.4 11.37 40.50 40.00
Yarn Skein Response Variables
Yarn
Count
Dye
route Dips
Greige
Weight
Boil Off
Weight
Dyed
Weight
Washed
Weight %COWY
Total
%IOWY
Surface
%IOWY Integ
Penetration
Level
12 1 only 1 6.447 6.2519 6.6002 6.2628 5.57% 0.414% 0.801% 20.0 0.52
12 1--2 2 6.3497 6.1528 6.5768 6.1785 6.89% 0.754% 1.457% 39.6 0.52
12 1--3 3 6.3301 6.1345 6.6115 6.1922 7.78% 1.154% 2.757% 56.6 0.42
12 1--4 4 6.4312 6.2393 6.8487 6.3386 9.77% 1.672% 4.750% 72.6 0.35
12 1--5 5 6.4161 6.2238 6.8584 6.3486 10.20% 2.008% 6.186% 80.8 0.32
12 1--6 6 6.5723 6.379 6.9502 6.527 8.95% 2.355% 7.485% 86.5 0.31
12 1--6,6 7 6.3727 6.1859 6.7831 6.3583 9.65% 2.824% 9.110% 92.2 0.31
% Reflectance Readings


Wave-
length
(nm) Dip 1 Dip 2 Dip 3 Dip 4 Dip 5 Dip 6 Dip 7
400 12.33 7.56 5.54 4.06 3.46 3.09 2.71
420 16.46 10.34 7.28 5.15 4.31 3.79 3.26
440 15.19 9.20 6.34 4.42 3.70 3.24 2.79
460 12.90 7.55 5.13 3.57 3.00 2.66 2.32
480 11.08 6.17 4.14 2.89 2.43 2.17 1.91
500 9.72 5.23 3.49 2.46 2.11 1.90 1.71
520 8.08 4.17 2.79 1.99 1.74 1.60 1.46
540 6.48 3.28 2.22 1.66 1.48 1.40 1.32
560 5.47 2.77 1.91 1.48 1.35 1.29 1.23
580 4.54 2.34 1.67 1.36 1.26 1.20 1.18
600 3.74 1.99 1.47 1.26 1.19 1.15 1.14
620 3.19 1.75 1.36 1.20 1.16 1.13 1.12
640 2.74 1.62 1.31 1.22 1.18 1.14 1.14
660 2.59 1.58 1.31 1.25 1.23 1.17 1.19
680 3.39 1.98 1.56 1.44 1.37 1.33 1.32
700 8.02 4.36 3.14 2.46 2.21 2.02 1.89
363

Table A-4-1: Continued


Shade
ID
Speed
(m/min)
Dwell
Time
(sec)
Oxidation
Time (sec)
Dye Bath
(gpl
100%
Indigo)
Dye
Bath
pH
Dye
Bath
(mV)
Dye Bath
Alkalinity
(gpl)
Dwell
Length
(m)
Oxidation
Length (m)
Nip
Pressures
(psi)
x3626 31.09 21.7 71.5 2.283 11.8 783 4.48 11.37 40.50 40.00
Yarn Skein Response Variables
Yarn
Count
Dye
route Dips
Greige
Weight
Boil Off
Weight
Dyed
Weight
Washed
Weight %COWY
Total
%IOWY
Surface
%IOWY Integ
Penetration
Level
6.3 1 only 1 7.6676 7.3705 7.5957 7.3264 3.06% 0.269% 0.695% 15.4 0.39
6.3 1--2 2 7.5517 7.2591 7.5283 7.2227 3.71% 0.512% 1.085% 31.1 0.47
6.3 1--3 3 7.775 7.4737 7.8205 7.4725 4.64% 0.905% 2.283% 51.5 0.40
6.3 1--4 4 7.6524 7.3559 7.8012 7.3751 6.05% 1.257% 3.558% 63.9 0.35
6.3 1--5 5 7.6481 7.3518 7.8006 7.4118 6.10% 1.588% 4.585% 71.6 0.35
6.3 1--6 6 7.7748 7.4736 7.9554 7.5411 6.45% 1.915% 6.496% 82.3 0.29
6.3 1--7 7 7.7656 7.4647 7.977 7.5723 6.86% 2.168% 7.223% 85.5 0.30
% Reflectance Readings


Wave-
length
(nm) Dip 1 Dip 2 Dip 3 Dip 4 Dip 5 Dip 6 Dip 7
400 14.31 8.98 5.88 4.60 3.98 3.26 3.04
420 19.21 12.51 7.94 6.01 5.07 4.04 3.69
440 17.94 11.31 6.94 5.19 4.34 3.44 3.13
460 15.36 9.31 5.58 4.15 3.46 2.77 2.54
480 13.37 7.73 4.50 3.35 2.81 2.27 2.08
500 11.77 6.59 3.80 2.84 2.40 1.97 1.82
520 9.94 5.27 3.04 2.30 1.96 1.66 1.56
540 7.94 4.13 2.42 1.88 1.65 1.44 1.38
560 6.86 3.50 2.08 1.68 1.50 1.34 1.31
580 5.81 2.96 1.83 1.52 1.39 1.26 1.25
600 4.80 2.48 1.62 1.40 1.32 1.21 1.21
620 4.09 2.18 1.50 1.33 1.29 1.21 1.22
640 3.40 1.92 1.39 1.29 1.29 1.22 1.24
660 3.15 1.84 1.41 1.33 1.35 1.29 1.34
680 4.04 2.34 1.68 1.53 1.54 1.43 1.49
700 9.66 5.35 3.34 2.71 2.49 2.15 2.11
364

Table A-4-1: Continued


Shade
ID
Speed
(m/min)
Dwell
Time
(sec)
Oxidation
Time (sec)
Dye Bath
(gpl
100%
Indigo)
Dye
Bath pH
Dye
Bath
(mV)
Dye Bath
Alkalinity
(gpl)
Dwell
Length
(m)
Oxidation
Length (m)
Nip
Pressures
(psi)
x3626 31.09 21.7 71.5 2.134 11.76 789 4.58 11.37 40.50 40.00
Yarn Skein Response Variables
Yarn
Count
Dye
route Dips
Greige
Weight
Boil Off
Weight
Dyed
Weight
Washed
Weight %COWY
Total
%IOWY
Surface
%IOWY Integ
Penetration
Level
8 1 only 1 6.1223 5.9148 6.1102 5.8681 3.30% 0.323% 0.731% 16.8 0.44
8 1--2 2 6.0951 5.8885 6.1361 5.8684 4.20% 0.547% 1.152% 33.0 0.47
8 1--3 3 6.0795 5.8735 6.1711 5.8636 5.07% 0.772% 1.951% 47.3 0.40
8 1--4 4 6.0613 5.8559 6.2155 5.8792 6.14% 1.261% 3.184% 60.7 0.40
8 1--5 5 6.1556 5.947 6.2897 5.9884 5.76% 1.548% 4.060% 67.9 0.38
8 1--6 6 6.1024 5.8956 6.2778 5.955 6.48% 1.738% 4.785% 72.9 0.36

% Reflectance Readings


Wave-
length
(nm) Dip 1 Dip 2 Dip 3 Dip 4 Dip 5 Dip 6 Dip 7
400 13.69 8.60 6.29 4.86 4.25 3.84
420 18.39 11.95 8.63 6.36 5.50 4.86
440 17.06 10.78 7.59 5.51 4.72 4.15
460 14.51 8.85 6.14 4.41 3.77 3.32
480 12.57 7.31 4.96 3.57 3.05 2.70
500 11.04 6.22 4.19 3.03 2.60 2.32
520 9.27 4.97 3.34 2.46 2.12 1.91
540 7.41 3.89 2.65 2.00 1.76 1.62
560 6.35 3.31 2.28 1.77 1.59 1.49
580 5.36 2.80 1.99 1.59 1.45 1.38
600 4.43 2.37 1.73 1.46 1.36 1.31
620 3.78 2.09 1.59 1.38 1.31 1.28
640 3.15 1.84 1.49 1.33 1.28 1.28
660 2.93 1.79 1.48 1.36 1.32 1.34
680 3.77 2.24 1.78 1.55 1.51 1.50
700 9.00 5.03 3.59 2.82 2.54 2.39
365

Table A-4-1: Continued


Shade
ID
Speed
(m/min)
Dwell
Time
(sec)
Oxidation
Time (sec)
Dye Bath
(gpl
100%
Indigo)
Dye
Bath pH
Dye
Bath
(mV)
Dye Bath
Alkalinity
(gpl)
Dwell
Length
(m)
Oxidation
Length (m)
Nip
Pressures
(psi)
1139 28.35 24.1 78.4 2.261 11.69 810 5.09 11.37 40.50 40.00
Yarn Skein Response Variables
Yarn
Count
Dye
route Dips
Greige
Weight
Boil Off
Weight
Dyed
Weight
Washed
Weight %COWY
Total
%IOWY
Surface
%IOWY Integ
Penetration
Level
6.3 1 only 1 8.2729 7.9479 8.207 7.9275 3.26% 0.290% 0.709% 15.9 0.41
6.3 1--2 2 8.3119 7.9733 8.3618 7.9816 4.87% 0.609% 1.181% 33.7 0.52
6.3 1--3 3 8.3462 8.0196 8.4306 8.05 5.12% 1.042% 2.285% 51.5 0.46
6.3 1--3,2 4 8.3676 8.0251 8.4956 8.0903 5.86% 1.258% 2.984% 58.8 0.42
6.3 1-3,2-3 5 8.2123 7.8902 8.3684 7.9789 6.06% 1.624% 4.320% 69.7 0.38
6.3
1-3,2-
3,2 6 8.2672 7.9373 8.4549 8.057 6.52% 1.986% 5.539% 77.4 0.36
6.3
1-3,2-
3,2-3 7 8.2995 7.9644 8.5276 8.1316 7.07% 2.410% 7.229% 85.5 0.33
% Reflectance Readings


Wave-
length
(nm) Dip 1 Dip 2 Dip 3 Dip 4 Dip 5 Dip 6 Dip 7
400 13.76 8.27 5.80 4.90 4.01 3.42 2.90
420 18.33 11.39 7.65 6.32 5.06 4.18 3.43
440 17.25 10.31 6.73 5.50 4.36 3.59 2.94
460 14.89 8.52 5.47 4.45 3.53 2.92 2.42
480 12.99 7.03 4.45 3.62 2.88 2.40 2.00
500 11.50 6.00 3.77 3.09 2.47 2.09 1.78
520 9.70 4.79 3.01 2.50 2.01 1.74 1.53
540 7.79 3.79 2.42 2.04 1.69 1.52 1.38
560 6.70 3.22 2.09 1.82 1.55 1.43 1.32
580 5.62 2.73 1.83 1.63 1.43 1.35 1.27
600 4.64 2.34 1.63 1.52 1.36 1.30 1.27
620 3.93 2.05 1.50 1.44 1.30 1.27 1.26
640 3.32 1.88 1.45 1.44 1.33 1.32 1.32
660 3.10 1.85 1.46 1.50 1.40 1.40 1.44
680 4.09 2.31 1.73 1.71 1.57 1.55 1.57
700 9.65 5.07 3.40 3.02 2.55 2.30 2.13
366

Table A-4-1: Continued


Shade
ID
Speed
(m/min)
Dwell
Time
(sec)
Oxidation
Time (sec)
Dye Bath
(gpl
100%
Indigo)
Dye
Bath pH
Dye
Bath
(mV)
Dye Bath
Alkalinity
(gpl)
Dwell
Length
(m)
Oxidation
Length (m)
Nip
Pressures
(psi)
x3669 31.09 21.7 71.5 2.277 11.92 880 5.14 11.37 40.50 40.00
Yarn Skein Response Variables
Yarn
Count
Dye
route Dips
Greige
Weight
Boil Off
Weight
Dyed
Weight
Washed
Weight %COWY
Total
%IOWY
Surface
%IOWY Integ
Penetration
Level
6.3 1 only 1 7.8172 7.4743 7.7695 7.4467 3.95% 0.362% 0.755% 17.9 0.48
6.3 1--2 2 8.216 7.867 8.3122 7.8683 5.66% 0.680% 1.346% 37.5 0.51
6.3 1--3 3 8.3614 7.97 8.5573 8.0045 7.37% 1.075% 2.515% 54.1 0.43
6.3 1--4 4 7.8534 7.56 8.2356 7.6236 8.94% 1.442% 4.041% 67.7 0.36
6.3 1--5 5 8.384 8.0202 8.6356 8.1199 7.67% 1.798% 5.721% 78.4 0.31
6.3 1--6 6 8.3886 8.0244 8.6667 8.154 8.00% 2.114% 7.003% 84.5 0.30

% Reflectance Readings


Wave-
length
(nm) Dip 1 Dip 2 Dip 3 Dip 4 Dip 5 Dip 6 Dip 7
400 13.21 7.71 5.57 4.23 3.49 3.05
420 17.80 10.67 7.35 5.37 4.35 3.71
440 16.54 9.52 6.39 4.62 3.73 3.16
460 14.03 7.75 5.13 3.72 3.00 2.56
480 12.10 6.31 4.14 3.03 2.46 2.09
500 10.61 5.37 3.50 2.59 2.15 1.87
520 8.86 4.30 2.82 2.13 1.78 1.58
540 7.06 3.38 2.26 1.76 1.52 1.40
560 6.01 2.89 1.97 1.59 1.40 1.32
580 5.03 2.47 1.76 1.46 1.31 1.26
600 4.14 2.12 1.58 1.37 1.24 1.23
620 3.51 1.88 1.47 1.31 1.21 1.22
640 2.95 1.73 1.44 1.31 1.22 1.26
660 2.75 1.71 1.43 1.35 1.25 1.32
680 3.56 2.09 1.67 1.52 1.39 1.46
700 8.70 4.48 3.19 2.58 2.20 2.11
367

Table A-4-1: Continued


Shade
ID
Speed
(m/min)
Dwell
Time
(sec)
Oxidation
Time (sec)
Dye Bath
(gpl
100%
Indigo)
Dye
Bath pH
Dye
Bath
(mV)
Dye Bath
Alkalinity
(gpl)
Dwell
Length
(m)
Oxidation
Length (m)
Nip
Pressures
(psi)
1139 28.35 24.1 78.4 2.307 11.77 822 5.62 11.37 40.50 40.00
Yarn Skein Response Variables
Yarn
Count
Dye
route Dips
Greige
Weight
Boil Off
Weight
Dyed
Weight
Washed
Weight %COWY
Total
%IOWY
Surface
%IOWY Integ
Penetration
Level
7.1 1 only 1 7.2476 7.0441 7.3261 7.0477 4.00% 0.351% 0.767% 18.5 0.46
7.1 1--2 2 7.2488 7.0476 7.4163 7.0762 5.23% 0.708% 1.338% 37.3 0.53
7.1 1--3 3 7.218 7.0199 7.4125 7.0754 5.59% 1.042% 2.061% 48.8 0.51
7.1 1-3,1 4 7.0859 6.8954 7.2841 6.9645 5.64% 1.249% 3.124% 60.1 0.40
7.1 1-3,1-2 5 7.263 7.0584 7.5089 7.1656 6.38% 1.588% 4.651% 72.0 0.34
7.1 1-3,1-3 6 6.9719 6.7815 7.243 6.9018 6.81% 1.839% 5.282% 75.9 0.35
7.1
1-3,1-
3,3 7 7.2627 7.0641 7.5541 7.204 6.94% 2.036% 6.052% 80.1 0.34
% Reflectance Readings


Wave-
length
(nm) Dip 1 Dip 2 Dip 3 Dip 4 Dip 5 Dip 6 Dip 7
400 12.76 7.67 6.12 4.87 3.87 3.48 3.19
420 17.03 10.49 8.22 6.26 4.88 4.32 3.93
440 15.87 9.46 7.23 5.46 4.21 3.73 3.38
460 13.55 7.79 5.87 4.41 3.41 3.04 2.76
480 11.70 6.39 4.76 3.59 2.78 2.48 2.26
500 10.27 5.44 4.02 3.04 2.38 2.16 1.99
520 8.57 4.34 3.21 2.47 1.96 1.79 1.67
540 6.89 3.44 2.57 2.01 1.65 1.56 1.48
560 5.85 2.92 2.19 1.76 1.49 1.43 1.38
580 4.91 2.48 1.92 1.60 1.39 1.36 1.31
600 4.05 2.13 1.69 1.47 1.31 1.30 1.28
620 3.47 1.89 1.57 1.42 1.29 1.30 1.27
640 2.96 1.75 1.52 1.42 1.31 1.34 1.32
660 2.80 1.75 1.55 1.47 1.38 1.40 1.40
680 3.63 2.18 1.85 1.66 1.50 1.54 1.53
700 8.56 4.67 3.62 2.95 2.43 2.30 2.20
368

Table A-4-1: Continued


Shade
ID
Speed
(m/min)
Dwell
Time
(sec)
Oxidation
Time (sec)
Dye Bath
(gpl
100%
Indigo)
Dye
Bath
pH
Dye
Bath
(mV)
Dye Bath
Alkalinity
(gpl)
Dwell
Length
(m)
Oxidation
Length (m)
Nip
Pressures
(psi)
1134 26.52 25.7 83.8 3.228 11.4 873 6.15 11.37 40.50 40.00
Yarn Skein Response Variables
Yarn
Count
Dye
route Dips
Greige
Weight
Boil Off
Weight
Dyed
Weight
Washed
Weight %COWY
Total
%IOWY
Surface
%IOWY Integ
Penetration
Level
6.3 1 only 1 8.3125 8.1211 8.5311 8.1202 5.05% 0.536% 1.134% 32.5 0.47
6.3 1--2 2 8.4711 8.2729 8.7909 8.3016 6.26% 0.985% 2.517% 54.1 0.39
6.3 1--3 3 8.1344 7.949 8.4708 8.0168 6.56% 1.390% 3.911% 66.7 0.36
6.3 1--4 4 8.0632 7.8635 8.4996 7.9789 8.09% 1.873% 6.196% 80.8 0.30
6.3 1--5 5 8.4616 8.2617 8.9728 8.4229 8.61% 2.404% 9.286% 92.8 0.26
6.3 1--6 6 8.2664 8.0742 8.7887 8.2648 8.85% 2.716% 11.748% 99.2 0.23

% Reflectance Readings


Wave-
length
(nm) Dip 1 Dip 2 Dip 3 Dip 4 Dip 5 Dip 6 Dip 7
400 8.80 5.75 4.49 3.36 2.72 2.42
420 11.99 7.57 5.77 4.17 3.27 2.87
440 10.84 6.59 4.97 3.56 2.79 2.46
460 8.98 5.33 4.00 2.89 2.30 2.04
480 7.45 4.30 3.23 2.35 1.89 1.69
500 6.37 3.63 2.74 2.04 1.67 1.51
520 5.10 2.90 2.21 1.69 1.45 1.33
540 4.01 2.31 1.81 1.47 1.29 1.22
560 3.38 1.99 1.60 1.36 1.23 1.18
580 2.81 1.73 1.45 1.27 1.16 1.12
600 2.37 1.55 1.34 1.23 1.14 1.11
620 2.07 1.42 1.28 1.19 1.13 1.10
640 1.87 1.36 1.26 1.21 1.16 1.13
660 1.86 1.38 1.30 1.29 1.22 1.21
680 2.42 1.68 1.52 1.46 1.38 1.37
700 5.46 3.32 2.70 2.22 1.90 1.81
369

Table A-4-1: Continued


Shade
ID
Speed
(m/min)
Dwell
Time
(sec)
Oxidation
Time (sec)
Dye Bath
(gpl
100%
Indigo)
Dye
Bath pH
Dye
Bath
(mV)
Dye Bath
Alkalinity
(gpl)
Dwell
Length
(m)
Oxidation
Length (m)
Nip
Pressures
(psi)
1134 29.26 23.5 75.9 3.497 11.62 897 5.13 11.37 40.50 40.00
Yarn Skein Response Variables
Yarn
Count
Dye
route Dips
Greige
Weight
Boil Off
Weight
Dyed
Weight
Washed
Weight %COWY
Total
%IOWY
Surface
%IOWY Integ
Penetration
Level
6.3 1 only 1 8.1467 7.9327 8.4423 7.9751 6.42% 0.572% 1.173% 33.5 0.49
6.3 1--2 2 8.0416 7.8292 8.4436 7.9149 7.85% 1.018% 2.575% 54.7 0.40
6.3 1--3 3 8.1968 7.9807 8.7331 8.1307 9.43% 1.740% 5.540% 77.4 0.31
6.3 1--4 4 8.8101 8.5772 9.5213 8.7939 11.01% 2.221% 7.437% 86.3 0.30
6.3 1--5 5 8.1834 7.9693 8.8128 8.2008 10.58% 2.837% 10.632% 96.5 0.27
6.3 1--6 6 8.2567 8.0436 8.9386 8.344 11.13% 3.520% 15.773% 106.8 0.22

% Reflectance Readings


Wave-
length
(nm) Dip 1 Dip 2 Dip 3 Dip 4 Dip 5 Dip 6 Dip 7
400 8.39 5.54 3.61 3.07 2.53 2.15
420 11.38 7.28 4.57 3.79 3.04 2.51
440 10.33 6.39 3.95 3.26 2.61 2.16
460 8.62 5.20 3.21 2.67 2.18 1.81
480 7.18 4.22 2.62 2.18 1.80 1.55
500 6.14 3.57 2.25 1.89 1.60 1.39
520 4.92 2.86 1.84 1.60 1.39 1.25
540 3.89 2.29 1.56 1.39 1.25 1.15
560 3.28 1.96 1.40 1.29 1.19 1.11
580 2.75 1.72 1.29 1.20 1.13 1.07
600 2.32 1.53 1.22 1.15 1.11 1.05
620 2.02 1.41 1.17 1.13 1.09 1.05
640 1.86 1.38 1.19 1.15 1.13 1.09
660 1.84 1.41 1.27 1.22 1.22 1.21
680 2.38 1.72 1.47 1.41 1.40 1.39
700 5.27 3.31 2.37 2.09 1.90 1.76
370

Section A- 4-2a: Convergence test - standard errors from empirical model %COWY parameter.
Table A-4-2a: Convergence test - standard errors from empirical model %COWY parameter.
Replica Yarn Count Speed Dye Bath pH speed^2 pHxspeed
0 0.003113 0.003133 0.01738 0.02172 0.000914 0.01364
1 0.00315 0.003396 0.018228 0.021433 0.000958 0.014312
2 0.00313 0.003355 0.017996 0.021339 0.000951 0.01421
3 0.00314 0.00342 0.018731 0.021787 0.000964 0.014765
4 0.003112 0.003084 0.017408 0.021387 0.000915 0.013797
5 0.003115 0.003153 0.017462 0.021557 0.00094 0.013836
6 0.003113 0.00314 0.017343 0.021474 0.000932 0.013792
7 0.0031 0.003098 0.017026 0.020976 0.000919 0.013469
8 0.00307 0.003052 0.016932 0.020782 0.000914 0.013297
9 0.003068 0.003037 0.0168 0.020657 0.000908 0.013199
10 0.003062 0.00301 0.016887 0.020668 0.000891 0.012464
11 0.00306 0.002926 0.016651 0.020338 0.000825 0.010533
12 0.003 0.002943 0.016492 0.020163 0.000823 0.010474
13 0.00298 0.002965 0.01632 0.020056 0.000824 0.01046
14 0.00297 0.002928 0.016272 0.02 0.00082 0.010441
15 0.00298 0.002958 0.016713 0.020503 0.000838 0.01073
16 0.002985 0.002952 0.016678 0.020059 0.000835 0.010561
17 0.002975 0.002985 0.01681 0.020034 0.000841 0.010593
18 0.002978 0.002926 0.016542 0.019788 0.000837 0.010441
19 0.002978 0.002915 0.016484 0.01984 0.000837 0.010467
20 0.002979 0.00291 0.016437 0.019681 0.000833 0.010433

Section A-4-2b: Convergence test - standard errors from empirical model %IOWY parameter.
Table A-4-2b: Convergence test - standard errors from empirical model %IOWY parameter.
Replica Yarn Count speed dye pH
0 0.002927 0.002615 0.016024 0.019996
1 0.002895 0.002653 0.016316 0.018978
2 0.002864 0.002628 0.016038 0.018823
3 0.002844 0.002658 0.016224 0.018855
4 0.00281 0.002469 0.015318 0.01855
5 0.002798 0.002544 0.015398 0.018731
6 0.002756 0.002528 0.015238 0.018597
7 0.002694 0.002502 0.01498 0.018202
8 0.00268 0.002483 0.014918 0.018067
9 0.002645 0.00246 0.014809 0.017961
10 0.002598 0.002419 0.014756 0.017865
11 0.002545 0.00232 0.014578 0.017354
12 0.002531 0.002287 0.014245 0.016994
13 0.002528 0.002269 0.013943 0.016748
14 0.002522 0.00225 0.013844 0.016644
15 0.002509 0.002271 0.014003 0.016852
16 0.002507 0.002267 0.013973 0.016531
17 0.002505 0.002263 0.013961 0.016384
18 0.002501 0.002239 0.013747 0.016199
19 0.0025 0.002232 0.013637 0.016157
20 0.002502 0.002252 0.013757 0.016186

371

Section A-4-2c: Convergence test - standard errors from empirical model Integ parameter.
Table A-4-2c: Convergence test - standard errors from empirical model Integ parameter.
Replica Yarn Count speed dye pH
0 0.00324 0.002894 0.017737 0.022134
1 0.00315 0.002874 0.01767 0.020554
2 0.003058 0.002856 0.017427 0.020453
3 0.003011 0.002794 0.017054 0.019819
4 0.002984 0.002596 0.016104 0.019501
5 0.003008 0.002677 0.016204 0.019712
6 0.002993 0.002664 0.016064 0.019604
7 0.002981 0.002654 0.015895 0.019314
8 0.002943 0.002643 0.015879 0.01923
9 0.002924 0.002623 0.015789 0.01915
10 0.002901 0.002579 0.015733 0.019048
11 0.002858 0.002505 0.015736 0.018733
12 0.002843 0.002488 0.015494 0.018484
13 0.002821 0.00249 0.015302 0.018381
14 0.0028 0.00247 0.015197 0.01827
15 0.00274 0.002443 0.015062 0.018127
16 0.00272 0.002435 0.015011 0.017759
17 0.00271 0.002421 0.014939 0.017532
18 0.00269 0.002413 0.014815 0.017459
19 0.00267 0.002409 0.014718 0.017438
20 0.00268 0.002412 0.014737 0.017339


Section A-4-2d: Convergence test - standard errors from empirical model Penetration Level
parameter.
Table A-4-2d: Convergence test - standard errors from empirical model penetration level parameter.
Replica Yarn Count speed dye pH speedxpH speed^2
0 0.00158 0.001596 0.005862 0.011468 0.007098 0.000474
1 0.001542 0.001644 0.005836 0.010732 0.007072 0.000471
2 0.001548 0.001627 0.005711 0.01069 0.007045 0.000468
3 0.001535 0.001561 0.005602 0.010299 0.006884 0.000447
4 0.001521 0.001432 0.00523 0.010235 0.006492 0.000431
5 0.001448 0.001417 0.005111 0.009974 0.006299 0.000428
6 0.001432 0.001411 0.005069 0.00928 0.006276 0.000424
7 0.001426 0.001395 0.004984 0.009734 0.006139 0.00042
8 0.001401 0.001375 0.00496 0.009651 0.006065 0.000417
9 0.001381 0.00137 0.004932 0.009603 0.006027 0.000415
10 0.001368 0.001347 0.004919 0.009538 0.005648 0.000404
11 0.001352 0.001315 0.004819 0.009392 0.004787 0.000378
12 0.001348 0.001319 0.00475 0.009294 0.004746 0.000377
13 0.001334 0.001319 0.004678 0.009185 0.004767 0.000374
14 0.001321 0.001297 0.004646 0.009123 0.00468 0.000371
15 0.00131 0.001247 0.004562 0.00894 0.004608 0.000362
16 0.001288 0.001246 0.004558 0.008766 0.00454 0.000362
17 0.001281 0.001245 0.004541 0.008665 0.004502 0.00036
18 0.001279 0.001225 0.004409 0.008546 0.004456 0.000359
19 0.001278 0.001226 0.004387 0.008601 0.004485 0.00036
20 0.001279 0.001227 0.004383 0.008546 0.00448 0.000359
372

Section A-4-3a: Computer program to calculate dye coefficients given the input dye range set-up
conditions and target %COWY, %IOWY, and Integ shade values.


#include <stdio.h>
#include <fcntl.h>
#include <stdlib.h>
#include <math.h>


int main ()
{
FILE * pFile;
FILE * oFile;
double AA[61][61], BB[61][61], RBLgm[61], RBL1gm[61], Cj[61], Cj1[61], d[61],
TBL[61], TBL1[61], RBL[61], RBL1[61], OBL[61], OBL1[61];
double AAinvt[61][62], X[61], Xrbl[61], Xiowy[61], temp[61], IOWY[61],
COWY[61], IOWYoxd[61], temp1, Multi, fraction_dye_affinity
, fraction_oxy_affinity;
double OBLgm[61], OBL1gm[61], dumb[61], IOWYstep[61], gms_ctn_node[61],
liter_per_node[61], Df_constantAO[10], Dy_constantAO[10],
WP_constantAO[10], wash_constantAO[10];
double IOWYpre[61], COWYpre[61], dip_error[10], pickup_error[10],
Df_dip[5][10], Dy_dip[5][10], WP_dip[5][10], wash_dip[5][10];
double dye_bath_dist[5][10][61], air_dist[5][10][61], IOWY_dist[5][10][61],
COWY_dist[5][10][61], Integ_save[5][10], IOWY_save[5][10],
COWY_save[5][10];
float input[1][20], num_time_steps, oxd_time_steps;
double Mt, Dy, DOy, Df, dt, DT, dr, radius, Monophenate_Ion, CompA, CompB, A,
AO[10], AO_old, AO_conv[10], AO_change, wash, old_wash, wetpickup,
gmIplit, gmNaOHplit, pH, Air, normal_ave[10], WP_normal_ave;
double lamda, alpha, beta, Ur, UOr, K, porosity, Kph, L, percent_to_grams,
grams_to_percent, Integ, num_cycles;
double IOWYtarget, IOWYsurface_target, COWYtarget, IOWYsurface,
IOWYoutside_old, IOWYtotal, COWYtotal, IOWYsurface_ratio,
IOWYtotal_ratio, COWYtotal_ratio;
double dwelltime, oxd_time, totalgramsperindigo, new_stdev[10], old_stdev[10],
Df_temp, Dy_temp, WP_temp, Df_total[10], Dy_total[10], WP_total[10];
double mean_dip, mean_pickup, slope, demon, Df_run_ave[10], Dy_run_ave[10],
WP_run_ave[10], Df_AO[10], Dy_AO[10], WP_AO[10], wash_AO[10];
long rows, cols;
int x, num_nodes, ts, yarn_count, num_yarns;
int z, ctx, cty, ctz, current_dip, num_dips;
int i, j, pivot, k;
double PI25DT = 3.141592653589793238462643;

// Iniatialization
num_dips=7; // this is now number of dips in data
num_cycles=1;
cols=1;
num_yarns = 4; // number of yarn counts processed
DT=0.01; // Define a actual time step to be used in dyeing and oxidation
num_nodes=21;
rows=num_nodes-1;
porosity=0.65;
Ur = 0.0;
K = 1.0;
percent_to_grams = (0.0154 * porosity)/(1.0 - porosity);
grams_to_percent = 1.0/percent_to_grams;
totalgramsperindigo = 2.3884;
AO_old = 0.0;
wash = 0.1;
373

mean_dip = 0.0;
mean_pickup = 0.0;
slope = 1.0;
Df = 4.6e-10;
Dy = 1.18e-6;
wetpickup = 0.05;
yarn_count = 1;

for (cty = 1; cty <= num_yarns; cty++)
{
for (ctx = 1; ctx<=num_dips; ctx++)
{
new_stdev[ctx] = 0.5;
old_stdev[ctx] = 0.5;
Df_total[ctx] = 0.0;
Dy_total[ctx] = 0.0;
WP_total[ctx] = 0.0;
AO[ctx] = 0.02;
Df_AO[ctx] = 4.6e-10;
Dy_AO[ctx] = 1.18e-6;
WP_AO[ctx] = 0.05;
}
}
for (cty=0; cty<=num_yarns; cty++)
{
for (ctx = 0; ctx <= num_dips; ctx++) wash_dip[cty][ctx] = 0.01;
}
while (AO_change < 0.99 || AO_change > 1.01)
{ //while loop to cycle thru until stdev reaches limit
yarn_count = 1;
// Open each yarn count
while (yarn_count <= num_yarns)
{
printf ("Processing yarn # %i\n", yarn_count);
wash = wash_dip[yarn_count][1];
slope = 1.0;
while (slope < -0.005 || slope > 0.005
{
IOWYsurface_ratio = IOWYtotal_ratio = COWYtotal_ratio = 0.99;
for (ctx=0; ctx <= (num_dips+1); ctx++)
{
Df_constantAO[ctx]=0.0;
Dy_constantAO[ctx]=0.0;
WP_constantAO[ctx]=0.0;
dip_error[ctx]=0.0;
pickup_error[ctx]=0.0;
}
for (ctx=0; ctx<=rows; ctx++)
{
IOWYpre[ctx] = 0.0;
COWYpre[ctx] = 0.0;
IOWY[ctx] = 0.0;
IOWYoxd[ctx] = 0.0;
COWY[ctx] = 0.0;
}
for (x=0; x<=19; x++) input[0][x]=0.0;

for (current_dip = 1; current_dip <= num_dips; current_dip++)
{
printf ("Processing dip # %i\n", current_dip);
if (yarn_count == 1) oFile = fopen ("yarninput1.txt", "rb" );
if (yarn_count == 2) oFile = fopen ("yarninput2.txt", "rb" );
374

if (yarn_count == 3) oFile = fopen ("yarninput3.txt", "rb" );
if (yarn_count == 4) oFile = fopen ("yarninput4.txt", "rb" );
if (oFile==NULL) {fputs ("File error",stderr); exit (1);}
while (input[0][0] != current_dip)
{
for (z=0; z<1; z++)
{
for (x = 0; x <=19; x++) fscanf (oFile, "%f", &input[0][x]);
}
}
fclose (oFile);
printf ("%i\t%e\t%e\n", yarn_count, input[0][2], input[0][3]);
Df = Df_AO[current_dip];
Dy = Dy_AO[current_dip];
wetpickup = WP_AO[current_dip];
dwelltime = input[0][5];
oxd_time = input[0][6];
num_time_steps = dwelltime/DT;
dt = DT;
radius = (-0.1655+(1.951/sqrt(input[0][2])))/20.0; //cm
dr = radius/(rows); //cm
DOy = 0.219; //oxygen diffusion coefficient cm2/sec
Ur = 0.0;
UOr = -1.0 * input[0][19] * input[0][14]*100/60; //air velocity cm/sec
A = input[0][15];
IOWYsurface_ratio=0.0;
IOWYtotal_ratio=0.0;
COWYtotal_ratio=0.0;
gmIplit = input[0][7]; //g/l
gmNaOHplit = input[0][8]; // g/l
pH = input[0][9]; //dye bath pH
Integ = input[0][11]; //shade
IOWYtarget = input[0][10];
IOWYsurface_target = 0.0; // %IOWY at the surface from Integ conversion
COWYtarget = input[0][12];
// Conversion of Integ to target %IOWY at the surface of the yarn
IOWYsurface_target = 0.0;
IOWYsurface_target = -0.02646465 + (9.53859e-4*Integ) + (1.35931e-5*pow
((Integ-55.2088),2)) + (3.909e-8*pow((Integ-55.2088),3));
IOWYsurface_target = IOWYsurface_target + (2.42444e-9*pow((Integ-55.2088),4))
+ (6.4303e-11*pow((Integ-55.2088),5));
for (ctx = 0; ctx<=rows; ctx++)
{
gms_ctn_node[ctx] = 1.54*porosity*2.0*PI25DT*ctx*dr*dr;
liter_per_node[ctx] = (1-porosity)*2.0*PI25DT*ctx*dr*dr;
}
gms_ctn_node[0] = 1.54*porosity*PI25DT*0.25*dr*dr;
liter_per_node[0] = (1-porosity)*PI25DT*0.25*dr*dr;
gms_ctn_node[rows] = 1.54*porosity*PI25DT*(radius*dr-(0.25*dr*dr));
liter_per_node[rows] = (1-porosity)*PI25DT*(radius*dr-(0.25*dr*dr));
while (COWYtotal_ratio < 0.995 || COWYtotal_ratio > 1.005 ||
IOWYsurface_ratio<0.995 || IOWYsurface_ratio>1.005||IOWYtotal_ratio<0.995
||IOWYtotal_ratio>1.005)
{
x=i=j=k=ctx=cty=0;
pivot=0;
IOWYtotal=0.0;
COWYtotal=0.0;
IOWYsurface=0.0;
// Set-up initial conditions
for (ctx = 0; ctx<=rows; ctx++)
{
375

X[ctx]=0.0;
Cj[ctx]=0.0;
Cj1[ctx]=0.0;
d[ctx]=0.0;
temp[ctx]=0.0;
RBL[ctx]=0.0;
RBL1[ctx]=0.0;
RBLgm[ctx]=0.0;
RBL1gm[ctx]=0.0;
IOWY[ctx]=0.0; //these will change for multiple dips
IOWYoxd[ctx]=0.0;
COWY[ctx]=0.0;
IOWYstep[ctx]=0.0;
dumb[ctx]=0.0;
OBL[ctx]=0.0;
OBL1[ctx]=0.0;
OBLgm[ctx]=0.0;
OBL1gm[ctx]=0.0;
TBL[ctx] = RBL[ctx] + OBL[ctx];
TBL1[ctx] = RBL1[ctx] + OBL1[ctx];
for(cty = 0; cty<=rows; cty++)
{
AA[ctx][cty]=0.0;
BB[ctx][cty]=0.0;
}
}
Cj[rows]=gmIplit;
Cj1[rows]=gmIplit;
lamda = (Dy*dt)/(2.0*dr*dr);
alpha = (Ur*dt)/(4.0*dr);
beta = (Dy*dt)/(4.0*dr);
for (ctx = 0; ctx <rows; ctx++)
{
AA[ctx][ctx]=1.0 + (2.0*lamda);
BB[ctx][ctx]=1.0 + (-2.0*lamda);
}
for (ctx = 1; ctx <(rows-1); ctx++)
{
AA[ctx][ctx+1]=(-beta/(ctx*dr))-lamda+(alpha);
AA[ctx+1][ctx]=(beta/((ctx+1)*dr))-lamda-(alpha);
BB[ctx][ctx+1]=(beta/(ctx*dr))+lamda-(alpha);
BB[ctx+1][ctx]=(-beta/((ctx+1)*dr))+lamda+(alpha);
}
AA[0][1]=-2.0*lamda;
AA[1][0]=(beta/dr)-lamda-(alpha);
BB[0][1]=2.0*lamda;
BB[1][0]=(-beta/dr)+lamda+(alpha);
Monophenate_Ion = 1.0/(1.0 + (pow(10,(9.5-pH))) + (pow(10,(pH-12.7))));
CompA = (0.016492 * Monophenate_Ion) + 0.003465;
CompB = (-0.244296 * Monophenate_Ion) + 0.816158;
for (ts = 1; ts <= num_time_steps; ts++)
{
for (ctx = 0; ctx <= rows; ctx++)
{
Cj[ctx]=Cj1[ctx];
RBL[ctx]=RBL1[ctx];
OBL[ctx]=OBL1[ctx];
TBL[ctx]=TBL1[ctx];
RBLgm[ctx]=RBL1gm[ctx];
OBLgm[ctx]=OBL1gm[ctx];
temp[ctx]=0.0;
}
376



Mt = (((4.0/pow(PI25DT,0.5))*(pow((Df*dwelltime/(0.0009*0.0009)),0.5)))
-(Df*dwelltime/(0.0009*0.0009))-((1.0/(3.0*pow(PI25DT,0.5)))*(pow((Df*
dwelltime/(0.0009*0.0009)),(3.0/2.0)))))/num_time_steps;
for (ctx = 0; ctx < rows; ctx++)
{
if (Cj[ctx] <= 0.0) IOWYstep[ctx] = 0.0;
else IOWYstep[ctx] = Mt*CompA*pow(Cj[ctx],CompB);
d[ctx] = -1.0 * gms_ctn_node[ctx] * IOWYstep[ctx] / liter_per_node[ctx];
}
d[rows-1] = d[rows-1] + (Cj[rows]*2.0*((beta/(radius))+lamda-alpha));
if (Cj[rows] <= 0.0) IOWYstep[rows] = 0.0;
else IOWYstep[rows] = Mt*CompA*pow(Cj[rows],CompB);
// Find new dye concentration by Guass-Jordan elimination
for (ctx = 0; ctx <rows; ctx++)
{
for (cty = 0; cty <rows; cty++) temp[ctx]=temp [ctx]+BB[ctx][cty]*Cj[cty];
}
for (ctx = 0; ctx <rows; ctx++)
{
temp[ctx] = temp[ctx]+d[ctx];
}
for (ctx = 0; ctx < rows; ctx++)
{
for (cty = 0; cty < rows; cty++) AAinvt[ctx][cty] = AA[ctx][cty];
}
for (ctx = 0; ctx <rows; ctx++)
{
AAinvt[ctx][rows]=temp[ctx];
}
for (i = 0; i < rows; i++)
{
if (AAinvt[i][i] == 0)
{
pivot = 0;
j = i + 1;
while ((pivot == 0) && (j <= rows))
{
if (AAinvt[j][i] != 0.0)
{
pivot = j;
}
j = j + 1;
}
if (pivot == 0 ) printf("Stop, matrix is singular");
}
if(pivot == (j-1))
{
for (j = 0; j < (rows+1); j++)
{
temp1 = AAinvt[i][j];
AAinvt[i][j]=AAinvt[pivot][j];
AAinvt[pivot][j] = temp1;
}
}
for (j = (i+1); j < rows; j++)
{
Multi = -AAinvt[j][i] / AAinvt[i][i];
for (k = i; k < (rows+1); k++)
{
AAinvt[j][k] = AAinvt[j][k] + (Multi * AAinvt[i][k]);
377

}
}
}
Cj1[rows-1] = AAinvt[rows-1][rows] / AAinvt[rows-1][rows-1];
for (j = (rows-2); j >= 0; j--)
{
Cj1[j] = AAinvt[j][rows];
for ( k = (j+1); k < rows; k++)
{
Cj1[j] = Cj1[j] - (AAinvt[j][k] * Cj1[k]);
}
Cj1[j] = Cj1[j] / AAinvt[j][j];
}
// End Gauss-Jordan
{
IOWY[0] = IOWY[0] + IOWYstep[0];
}
for (ctx = 1; ctx < rows; ctx++)
{
{
IOWY[ctx] = IOWY[ctx] + IOWYstep[ctx];
}
}
IOWY[rows] = IOWY[rows] + IOWYstep[rows];
for (ctx = 0; ctx <= rows; ctx++)
dye_bath_dist[yarn_count][current_dip][ctx] = Cj1[ctx];
} // Close time step loop for process in dye box
// Nip process
for (ctx = 0; ctx <= rows; ctx++)
{
RBL1[ctx] = Cj1[ctx];
RBL1gm[ctx] = Cj1[ctx] * liter_per_node[ctx] * wetpickup;
OBL1gm[ctx] = (COWYpre[ctx] - IOWYpre[ctx]) * gms_ctn_node[ctx] * wash;
if (OBL1gm[ctx] < 0.0) OBL1gm[ctx] = 0.0;
}
IOWYtotal=0.0;
IOWYsurface=0.0;
COWYtotal=0.0;
oxd_time_steps = oxd_time/DT;
dt=DT;
Air = 0.2541; // gm per liter of oxygen
for (ctx = 0; ctx<=rows; ctx++)
{
Cj[ctx]=0.0; // g/l of oxygen
Cj1[ctx]=0.0;
d[ctx]=0.0;
X[ctx]=0.0;
Xrbl[ctx]=0.0;
Xiowy[ctx]=0.0;
for(cty = 0; cty<=rows; cty++)
{
AA[ctx][cty]=0.0;
BB[ctx][cty]=0.0;
}
}
Cj1[rows]=Air;
lamda = (DOy*dt)/(2.0*dr*dr);
alpha = (UOr*dt)/(4.0*dr);
beta = (DOy*dt)/(4.0*dr);
for (ctx = 0; ctx <rows; ctx++)
{
AA[ctx][ctx]=1.0 + (2.0*lamda);
378

BB[ctx][ctx]=1.0 + (-2.0*lamda);
}
for (ctx = 1; ctx <(rows-1); ctx++)
{
AA[ctx][ctx+1]=(-beta/(ctx*dr))-lamda+(alpha);
AA[ctx+1][ctx]=(beta/((ctx+1)*dr))-lamda-(alpha);
BB[ctx][ctx+1]=(beta/(ctx*dr))+lamda-(alpha);
BB[ctx+1][ctx]=(-beta/((ctx+1)*dr))+lamda+(alpha);
}
AA[0][1]=-2.0*lamda;
AA[1][0]=(beta/dr)-lamda-(alpha);
BB[0][1]=2.0*lamda;
BB[1][0]=(-beta/dr)+lamda+(alpha);
// Start time step for oxidation
for (ts = 1; ts <= oxd_time_steps; ts++)
{
for (ctx = 0; ctx <= rows; ctx++)
{
Cj[ctx]=Cj1[ctx];
RBL[ctx]=RBL1[ctx];
RBLgm[ctx]=RBL1gm[ctx];
OBLgm[ctx]=OBL1gm[ctx];
temp[ctx]=0.0;
}
for (ctx = 0; ctx <= rows; ctx++)
{
if (Cj[ctx] <= 0.0)
{
Xrbl[ctx] = 0.0;
Xiowy[ctx] = 0.0;
X[ctx] = Xrbl[ctx] + Xiowy[ctx];
}
else
{
if (RBLgm[ctx] > 0.0) X[ctx]=1/(AO[current_dip]*Cj[ctx]*
liter_per_node[ctx]*dt/(RBLgm[ctx]+(IOWY[ctx]*gms_ctn_node[ctx])));
else if (IOWY[ctx] > 0.0) X[ctx]=1/(AO[current_dip]*Cj[ctx]*
liter_per_node[ctx]*dt/((IOWY[ctx]*gms_ctn_node[ctx])));
else X[ctx]=0.0;
}
if (X[ctx] > 1.0) X[ctx]=1.0;
d[ctx] = -1.0 * X[ctx] * Cj[ctx] * dt;
if (d[ctx] > 0.0) d[ctx] = 0.0;
}
d[rows-1] = d[rows-1] + (Cj[rows]*2*((beta/radius)+lamda-alpha));
// Find new oxygen concentration by Guass-Jordan elimination
for (ctx = 0; ctx <rows; ctx++)
{
for (cty = 0; cty <rows; cty++) temp[ctx]=temp[ctx]+BB[ctx][cty]*Cj[cty];
}
for (ctx = 0; ctx <rows; ctx++)
{
temp[ctx] = temp[ctx]+d[ctx];
}
for (ctx = 0; ctx < rows; ctx++)
{
for (cty = 0; cty < rows; cty++) AAinvt[ctx][cty] = AA[ctx][cty];
}
for (ctx = 0; ctx <rows; ctx++)
{
AAinvt[ctx][rows]=temp[ctx];
}
379

for (i = 0; i < rows; i++)
{
if (AAinvt[i][i] == 0)
{
pivot = 0;
j = i + 1;
while ((pivot == 0) && (j <= rows))
{
if (AAinvt[j][i] != 0.0)
{
pivot = j;
}
j = j + 1;
}
if (pivot == 0 ) printf("Stop, matrix is singular");
}
if(pivot == (j-1))
{
for (j = 0; j < (rows+1); j++)
{
temp1 = AAinvt[i][j];
AAinvt[i][j]=AAinvt[pivot][j];
AAinvt[pivot][j] = temp1;
}
}
for (j = (i+1); j < rows; j++)
{
Multi = -AAinvt[j][i] / AAinvt[i][i];
for (k = i; k < (rows+1); k++)
{
AAinvt[j][k] = AAinvt[j][k] + (Multi * AAinvt[i][k]);
}
}
}
Cj1[rows-1] = AAinvt[rows-1][rows] / AAinvt[rows-1][rows-1];

for (j = (rows-2); j >= 0; j--)
{
Cj1[j] = AAinvt[j][rows];
for ( k = (j+1); k < rows; k++)
{
Cj1[j] = Cj1[j] - (AAinvt[j][k] * Cj1[k]);
}
Cj1[j] = Cj1[j] / AAinvt[j][j];
}
// End Gauss-Jordan
Mt = (((4.0/pow(PI25DT,0.5))*(pow((Df*oxd_time/(0.0009*0.0009)),0.5)))
-(Df*oxd_time/(0.0009*0.0009))-((1.0/(3.0*pow(PI25DT,0.5)))*(pow(
(Df*oxd_time/(0.0009*0.0009)),(3.0/2.0)))))/oxd_time_steps;
for (ctx = 0; ctx <=rows; ctx++)
{
if (RBLgm[ctx] > 0.0)
{
dumb[ctx] = (AO[current_dip]*Cj1[ctx]*liter_per_node[ctx]*
dt)/RBLgm[ctx];
if (dumb[ctx] > 1.0)
{
RBL1gm[ctx] = 0.0;
RBL1[ctx] = 0.0;
OBL1gm[ctx] = OBLgm[ctx] + RBLgm[ctx];
}
else
380

{
RBL1gm[ctx] = RBLgm[ctx] - (dumb[ctx]*RBLgm[ctx]);
RBL1[ctx] = RBL[ctx] - (dumb[ctx]*RBLgm[ctx]/(liter_per_node[ctx]
*wetpickup));
OBL1gm[ctx] = OBLgm[ctx] + (dumb[ctx]*RBLgm[ctx]);
if (RBL1gm[ctx] <= 0.0) RBL1gm[ctx] = 0.0;
if (RBL1[ctx] <= 0.0) RBL1[ctx] = 0.0;
IOWY[ctx] = IOWY[ctx] + ((CompA*pow(RBL1[ctx],CompB))*Mt);
RBL1gm[ctx] = RBL1gm[ctx] - ((CompA*pow(RBL1[ctx],CompB)) * Mt
* gms_ctn_node[ctx]);
RBL1[ctx] = RBL1[ctx] - (((CompA*pow(RBL1[ctx],CompB)) * Mt
* gms_ctn_node[ctx])/(liter_per_node[ctx] * wetpickup));
if (RBL1gm[ctx] <= 0.0) RBL1gm[ctx] = 0.0;
if (RBL1[ctx] <= 0.0) RBL1[ctx] = 0.0;
}
}
else if (IOWY[ctx] > 0.0)
{
dumb[ctx]=((AO[current_dip]*Cj1[ctx]*liter_per_node[ctx]*dt)
/(IOWY[ctx]*gms_ctn_node[ctx]));
if (dumb[ctx] > 1.0)
{
IOWYoxd[ctx] = IOWYoxd[ctx] + IOWY[ctx];
IOWY[ctx] = 0.0;
}
else
{
IOWYoxd[ctx] = IOWYoxd[ctx] + (dumb[ctx]*IOWY[ctx]);
IOWY[ctx] = IOWY[ctx] - (dumb[ctx]*IOWY[ctx]);
if (IOWY[ctx] <= 0.0) IOWY[ctx]=0.0;
}
}
}
for (ctx = 0; ctx <= rows; ctx++) air_dist[yarn_count][current_dip][ctx]
=Cj1[ctx];
} // end oxidation time step loop
for (ctx = 0; ctx <= rows; ctx++)
{
IOWYoxd[ctx] = IOWYoxd[ctx] + IOWYpre[ctx];
COWY[ctx]=IOWYoxd[ctx]*totalgramsperindigo+IOWY[ctx]*totalgramsperindigo;
COWY[ctx] =COWY[ctx]+(OBL1gm[ctx]*totalgramsperindigo/gms_ctn_node[ctx]);
COWY[ctx] =COWY[ctx]+(RBL1gm[ctx]*totalgramsperindigo/gms_ctn_node[ctx]);
IOWYtotal = IOWYtotal+(IOWYoxd[ctx]*gms_ctn_node[ctx])+(IOWY[ctx]
*gms_ctn_node[ctx]);
COWYtotal = COWYtotal + (COWY[ctx]*gms_ctn_node[ctx]);
}
IOWYtotal = IOWYtotal / (1.54*porosity*PI25DT * radius * radius);
COWYtotal = COWYtotal / (1.54*porosity*PI25DT * radius * radius);
IOWYsurface = IOWYoxd[rows] + IOWY[rows];
IOWYsurface_ratio = IOWYsurface_target/IOWYsurface;
IOWYtotal_ratio = IOWYtarget/IOWYtotal;
COWYtotal_ratio = COWYtarget/COWYtotal;
IOWY_save[yarn_count][current_dip] = IOWYtotal;
COWY_save[yarn_count][current_dip] = COWYtotal;
Integ_save[yarn_count][current_dip] = 0.0;
Integ_save[yarn_count][current_dip] = 45.60937 + (592.19421*IOWYsurface) -
(9928.5539*pow((IOWYsurface-0.045773),2))
+ (1.83538e+5*pow((IOWYsurface-0.045773),3));
Integ_save[yarn_count][current_dip] = Integ_save[yarn_count][current_dip]
- (1.522451e+6*pow((IOWYsurface-0.045773),4))
+ (4.27080e+6*pow((IOWYsurface-0.045773),5));

381

printf("%e\t%e\t%e\n", IOWYsurface_ratio, IOWYtotal_ratio, COWYtotal_ratio);
if (current_dip > 1)
{
Df = Df * IOWYsurface_ratio;
Dy = Dy * IOWYtotal_ratio;
wetpickup = wetpickup * COWYtotal_ratio;
}
else
{
Dy = Dy * IOWYtotal_ratio;
Df = Df * IOWYsurface_ratio;
wetpickup = wetpickup * COWYtotal_ratio;
}
} // Close Dy & Df convergence loop
// Save IOWY & COWY amount and distribution
for (ctx = 0; ctx<=rows; ctx++)
{
IOWYpre[ctx] = IOWYoxd[ctx];
COWYpre[ctx] = COWY[ctx];
}
for (ctx=0; ctx<=rows; ctx++) IOWY_dist[yarn_count][current_dip][ctx]
=IOWYoxd[ctx];
for (ctx = 0; ctx <= rows; ctx++) COWY_dist[yarn_count][current_dip][ctx]
= COWY[ctx];
IOWYsurface_ratio = IOWYtotal_ratio = COWYtotal_ratio = 0.99;
Df_constantAO[current_dip] = Df;
Dy_constantAO[current_dip] = Dy;
WP_constantAO[current_dip] = wetpickup;
wash_constantAO[current_dip] = wash;
Df_AO[current_dip] = Df;
Dy_AO[current_dip] = Dy;
WP_AO[current_dip] = wetpickup;
} // This ends the yarn count calculations at specific oxidation rate value
// Convergence loop for wash efficiency number, which yields constant wet pick-up
mean_dip = 0.0;
mean_pickup = 0.0;
slope = 0.0;
demon = 0.0;
old_wash = wash;
for (ctx = 2; ctx <=(num_dips-1); ctx++)
{
mean_dip = mean_dip + ctx;
mean_pickup = mean_pickup + WP_constantAO[ctx];
}
mean_dip = mean_dip/(num_dips-2);
mean_pickup = mean_pickup/(num_dips-2);
for (ctx = 2; ctx <= (num_dips-1); ctx++)
{
dip_error[ctx] = ctx - mean_dip;
pickup_error[ctx] = WP_constantAO[ctx] - mean_pickup;
slope = slope + (dip_error[ctx]*pickup_error[ctx]);
}
for (ctx = 2; ctx<=(num_dips-1); ctx++) demon = demon +
(dip_error[ctx]*dip_error[ctx]);
slope = slope/demon;
wash = wash * (1.0 + ((slope/0.0001)/100));
if ((old_wash + wash) <= 0.005)
{
wash = 0.0;
slope = 0.0;
wash_constantAO[current_dip] = wash;
}
382

if (wash <= 0.0)
{
wash = 0.0;
wash_constantAO[current_dip] = wash;
}
printf("slope, wash %e\t%e\n", slope, wash);
} // Close wash convergence loop
// Open and save other yarn counts
for (ctx = 1; ctx <=num_dips; ctx++)
{
Df_dip[yarn_count][ctx] = Df_constantAO[ctx];
Dy_dip[yarn_count][ctx] = Dy_constantAO[ctx];
WP_dip[yarn_count][ctx] = WP_constantAO[ctx];
wash_dip[yarn_count][ctx] = wash_constantAO[ctx];
}
yarn_count = yarn_count + 1;
}
// this is the oxidation optimumize section
for (ctx = 1; ctx <=num_dips; ctx++)
{
new_stdev[ctx] = 0.0;
normal_ave[ctx] = 0.0;
}
for (cty = 1; cty <=num_yarns; cty++)
{
for (ctx = 1; ctx <=num_dips; ctx++)
{
Df_AO[ctx] = 0.0;
Dy_AO[ctx] = 0.0;
WP_AO[ctx] = 0.0;
}
}
for (ctx = 1; ctx <=num_dips; ctx++)
{
for (cty = 1; cty <=num_yarns; cty++)
{
Df_total[ctx] = Df_total[ctx] + Df_dip[cty][ctx];
Dy_total[ctx] = Dy_total[ctx] + Dy_dip[cty][ctx];
WP_total[ctx] = WP_total[ctx] + WP_dip[cty][ctx];
Df_AO[ctx] = Df_AO[ctx] + Df_dip[cty][ctx];
Dy_AO[ctx] = Dy_AO[ctx] + Dy_dip[cty][ctx];
WP_AO[ctx] = WP_AO[ctx] + WP_dip[cty][ctx];
}
}
for (ctx = 1; ctx<=num_dips; ctx++)
{
Df_run_ave[ctx] = Df_total[ctx] / (num_cycles * num_yarns);
Dy_run_ave[ctx] = Dy_total[ctx] / (num_cycles * num_yarns);
WP_run_ave[ctx] = WP_total[ctx] / (num_cycles * num_yarns);
Df_AO[ctx] = Df_AO[ctx] / num_yarns;
Dy_AO[ctx] = Dy_AO[ctx] / num_yarns;
WP_AO[ctx] = WP_AO[ctx] / num_yarns;
}
for (cty = 1; cty <=num_yarns; cty++)
{
for (ctx = 1; ctx <=num_dips; ctx++)
{
Df_dip[cty][ctx] = Df_dip[cty][ctx]/Df_run_ave[ctx];
Dy_dip[cty][ctx] = Dy_dip[cty][ctx]/Dy_run_ave[ctx];
WP_dip[cty][ctx] = WP_dip[cty][ctx]/WP_run_ave[ctx];
}
}
383

for (ctx = 1; ctx <= num_dips; ctx++)
{
for (cty = 1; cty <=num_yarns; cty++)
{
normal_ave[ctx] = normal_ave[ctx] + Df_dip[cty][ctx] + Dy_dip[cty][ctx]
+ WP_dip[cty][ctx];
}
}
for (ctx = 1; ctx<=num_dips; ctx++) normal_ave[ctx] = normal_ave[ctx]
/ (3.0 * num_yarns);
for (ctx = 1; ctx <= num_dips; ctx++)
{
for (cty = 1; cty <=num_yarns;cty++)
{
new_stdev[ctx] = new_stdev[ctx] + pow((Df_dip[cty][ctx]
- normal_ave[ctx]), 2.0);
new_stdev[ctx] = new_stdev[ctx] + pow((Dy_dip[cty][ctx]
- normal_ave[ctx]), 2.0);
new_stdev[ctx] = new_stdev[ctx] + pow((WP_dip[cty][ctx]
- normal_ave[ctx]), 2.0);
}
}
for (ctx = 1; ctx <= num_dips; ctx++)
{
new_stdev[ctx] = new_stdev[ctx] / ((3.0 * num_yarns) - 1.0);
new_stdev[ctx] = pow(new_stdev[ctx], 0.5);
AO_conv[ctx] = old_stdev[ctx] / new_stdev[ctx];
old_stdev[ctx] = new_stdev[ctx];
AO[ctx] = AO[ctx] * AO_conv[ctx];
}
AO_change = 0.0;
for (ctx = 1; ctx <=num_dips; ctx++)
{
if (AO_conv[ctx] > AO_change) AO_change = AO_conv[ctx];
}
num_cycles = num_cycles + 1.0;
printf("This completes an oxidation loop!!!!!!!!\n");
for (ctx=1; ctx <= num_dips; ctx++) printf("%e\t%e\t%e\t%e\n", num_cycles,
AO[ctx], AO_conv[ctx], new_stdev[ctx]);
} // Close stdev convergence loop to optimize oxidation
for (ctx = 1; ctx <= num_dips; ctx++)
{
for (cty = 1; cty <= num_yarns; cty++) wash_AO[ctx] = wash_AO[ctx]
+ wash_dip[cty][ctx];
}
pFile = fopen ("output_model.out","a");
fprintf(pFile, "number of cycles to converge: %e\n", num_cycles);
fprintf(pFile, "Dips\t Df\t Dy\t pickup\t Oxidation\n");
for (x = 1; x <= num_dips; x++)
{
fprintf(pFile, "%i\t%e\t%e\t%e\t%e\n", x, Df_AO[x], Dy_AO[x],
WP_AO[x], AO[x]);
}
fprintf(pFile, "yarns\t wash\n");
for (x = 1; x <= num_yarns; x++) fprintf(pFile, "%i\t%e\n", x,
wash_dip[x][1]);
for (cty = 1; cty <= num_yarns; cty++)
{
fprintf(pFile, "yarn: %i IOWY\t COWY\t Integ\n", cty);
for (ctx = 1; ctx <=num_dips; ctx++)
{
fprintf(pFile, "dip:\t %i\t%e\t%e\t%e\n", ctx, IOWY_save[cty][ctx],
384

COWY_save[cty][ctx], Integ_save[cty][ctx]);
}
}
cty = 1;
for (ctz = 1; ctz <=num_dips ; ctz++) fprintf(pFile, "%i\t", ctz);
fprintf(pFile, "\n");
for (ctx = 0; ctx <=rows; ctx++)
{
for (ctz = 1; ctz <=num_dips ; ctz++) fprintf(pFile, "%e\t",
dye_bath_dist[cty][ctz][ctx]);
fprintf(pFile, "\n");
}
cty = num_yarns;
for (ctz = 1; ctz <=num_dips ; ctz++) fprintf(pFile, "%i\t", ctz);
fprintf(pFile, "\n");
for (ctx = 0; ctx <=rows; ctx++)
{
for (ctz = 1; ctz <=num_dips ; ctz++) fprintf(pFile, "%e\t",
dye_bath_dist[cty][ctz][ctx]);
fprintf(pFile, "\n");
}
cty = 1;
for (ctz = 1; ctz <=num_dips ; ctz++) fprintf(pFile, "%i\t", ctz);
fprintf(pFile, "\n");
for (ctx = 0; ctx <=rows; ctx++)
{
for (ctz = 1; ctz <=num_dips ; ctz++) fprintf(pFile, "%e\t",
air_dist[cty][ctz][ctx]);
fprintf(pFile, "\n");
}
cty = num_yarns;
for (ctz = 1; ctz <=num_dips ; ctz++) fprintf(pFile, "%i\t", ctz);
fprintf(pFile, "\n");
for (ctx = 0; ctx <=rows; ctx++)
{
for (ctz = 1; ctz <=num_dips ; ctz++) fprintf(pFile, "%e\t",
air_dist[cty][ctz][ctx]);
fprintf(pFile, "\n");
}
cty = 1;
for (ctz = 1; ctz <=num_dips ; ctz++) fprintf(pFile, "%i\t", ctz);
fprintf(pFile, "\n");
for (ctx = 0; ctx <=rows; ctx++)
{
for (ctz = 1; ctz <=num_dips ; ctz++) fprintf(pFile, "%e\t",
IOWY_dist[cty][ctz][ctx]);
fprintf(pFile, "\n");
}
cty = num_yarns;
for (ctz = 1; ctz <=num_dips ; ctz++) fprintf(pFile, "%i\t", ctz);
fprintf(pFile, "\n");
for (ctx = 0; ctx <=rows; ctx++)
{
for (ctz = 1; ctz <=num_dips ; ctz++) fprintf(pFile, "%e\t",
IOWY_dist[cty][ctz][ctx]);
fprintf(pFile, "\n");
}
cty = 1;
for (ctz = 1; ctz <=num_dips ; ctz++) fprintf(pFile, "%i\t", ctz);
fprintf(pFile, "\n");
for (ctx = 0; ctx <=rows; ctx++)
{
385

for (ctz = 1; ctz <=num_dips ; ctz++) fprintf(pFile, "%e\t",
COWY_dist[cty][ctz][ctx]);
fprintf(pFile, "\n");
}
cty = num_yarns;
for (ctz = 1; ctz <=num_dips ; ctz++) fprintf(pFile, "%i\t", ctz);
fprintf(pFile, "\n");
for (ctx = 0; ctx <=rows; ctx++)
{
for (ctz = 1; ctz <=num_dips ; ctz++) fprintf(pFile, "%e\t",
COWY_dist[cty][ctz][ctx]);
fprintf(pFile, "\n");
}
fclose (pFile);
return 0;
}


386

Section A-4-3b: Computer program to calculate %COWY, %IOWY, and Integ shade values given the
input dye range set-up conditions.

#include <stdio.h>
#include <fcntl.h>
#include <stdlib.h>
#include <math.h>


int main ()
{
FILE * pFile;
FILE * oFile;
FILE * o2File;
FILE * o3File;
FILE * o4File;
double AA[61][61], BB[61][61], RBLgm[61], RBL1gm[61], Cj[61], Cj1[61], d[61], TBL[61], TBL1[61], RBL[61], RBL1[61], OBL[61], OBL1[61];
double AAinvt[61][62], X[61], Xrbl[61], Xiowy[61], temp[61], IOWY[61], COWY[61], IOWYoxd[61], temp1, Multi, fraction_dye_affinity,
fraction_oxy_affinity;
double OBLgm[61], OBL1gm[61], dumb[61], IOWYstep[61], gms_ctn_node[61], liter_per_node[61], Df_constantAO[10],
Dy_constantAO[10], WP_constantAO[10], wash_constantAO[10];
double IOWYpre[61], COWYpre[61], dip_error[10], pickup_error[10], Df_dip[5][10], Dy_dip[5][10], WP_dip[5][10], wash_dip[5][10];
double dye_bath_dist[5][10][61], air_dist[5][10][61], IOWY_dist[5][10][61], COWY_dist[5][10][61], Integ_save[5][10], IOWY_save[5][10],
COWY_save[5][10];
float input[1][22], num_time_steps, oxd_time_steps;
double Mt, Dy, DOy, Df, dt, DT, dr, radius, Monophenate_Ion, CompA, CompB, A, AO[10], AO_old, AO_conv[10], AO_change, wash,
old_wash, wetpickup, gmIplit, gmNaOHplit, pH, Air, normal_ave[10], WP_normal_ave;
double lamda, alpha, beta, Ur, UOr, K, porosity, Kph, L, percent_to_grams, grams_to_percent, Integ, num_cycles;
double IOWYtarget, IOWYsurface_target, COWYtarget, IOWYsurface, IOWYoutside_old, IOWYtotal, COWYtotal, IOWYsurface_ratio,
IOWYtotal_ratio, COWYtotal_ratio;
double dwelltime, oxd_time, totalgramsperindigo, new_stdev[10], old_stdev[10], Df_temp, Dy_temp, WP_temp, Df_total[10],
Dy_total[10], WP_total[10];
double mean_dip, mean_pickup, slope, demon, Df_run_ave[10], Dy_run_ave[10], WP_run_ave[10], Df_AO[10], Dy_AO[10], WP_AO[10],
wash_AO[10];
double speed, mV, nip_pressure, Total_IOWY_pre, Total_COWY_pre;
long rows, cols;
int x, num_nodes, ts, yarn_count, num_yarns;
int z, ctx, cty, ctz, current_dip, num_dips;
int i, j, pivot, k;
double PI25DT = 3.141592653589793238462643;

// Iniatialization
num_dips=5; // this is now number of dips in data
num_cycles=1;
cols=1;
num_yarns = 1; // number of yarn counts processed
DT=0.01; // Define a actual time step to be used in dyeing and oxidization
num_nodes=21;
rows=num_nodes-1;
porosity=0.65;
Ur = 0.0;
K = 1.0;
percent_to_grams = (0.0154 * porosity)/(1.0 - porosity);
grams_to_percent = 1.0/percent_to_grams;
totalgramsperindigo = 2.3884;
AO_old = 0.0;
wash = 0.1;
mean_dip = 0.0;
mean_pickup = 0.0;
slope = 1.0;
387

yarn_count = 1;
for (cty = 1; cty <= num_yarns; cty++)
{
for (ctx = 1; ctx<=num_dips; ctx++)
{
new_stdev[ctx] = 0.5;
old_stdev[ctx] = 0.5;
Df_total[ctx] = 0.0;
Dy_total[ctx] = 0.0;
WP_total[ctx] = 0.0;
AO[ctx] = 0.02;
}
}
for (cty=0; cty<=num_yarns; cty++)
{
for (ctx = 0; ctx <= num_dips; ctx++) wash_dip[cty][ctx] = 0.01;
}
yarn_count = 1;
printf ("Processing yarn # %i\n", yarn_count);
slope = 1.0;
Total_IOWY_pre = 0.0;
Total_COWY_pre = 0.0;
for (ctx=0; ctx <= (num_dips+1); ctx++)
{
Df_constantAO[ctx]=0.0;
Dy_constantAO[ctx]=0.0;
WP_constantAO[ctx]=0.0;
dip_error[ctx]=0.0;
pickup_error[ctx]=0.0;
}
for (ctx=0; ctx<=rows; ctx++)
{
IOWYpre[ctx] = 0.0;
COWYpre[ctx] = 0.0;
IOWY[ctx] = 0.0;
IOWYoxd[ctx] = 0.0;
COWY[ctx] = 0.0;
}
for (x=0; x<=19; x++) input[0][x]=0.0;
for (current_dip = 1; current_dip <= num_dips; current_dip++)
{
printf ("Processing dip # %i\n", current_dip);
if (yarn_count == 1) oFile = fopen ("yarninput1.txt", "rb" );
if (yarn_count == 2) oFile = fopen ("yarninput2.txt", "rb" );
if (yarn_count == 3) oFile = fopen ("yarninput3.txt", "rb" );
if (yarn_count == 4) oFile = fopen ("yarninput4.txt", "rb" );
if (oFile==NULL) {fputs ("File error",stderr); exit (1);}
while (input[0][0] != current_dip)
{
for (z=0; z<1; z++)
{
for (x = 0; x <=21; x++) fscanf (oFile, "%f", &input[0][x]);
}
}
fclose (oFile);
printf ("%i\t%e\t%e\n", yarn_count, input[0][2], input[0][3]);
dwelltime = input[0][5];
oxd_time = input[0][6];
num_time_steps = dwelltime/DT;
dt = DT;
radius = (-0.1655+(1.951/sqrt(input[0][2])))/20.0; //cm
dr = radius/(rows); //cm
388

DOy = 0.219; //oxygen diffusion coefficient cm2/sec
Ur = 0.0;
UOr = -1.0 * input[0][19] * input[0][14]*100/60; //air velocity propagation cm/sec
A = input[0][15]; // dye affinity 1/sec
IOWYsurface_ratio=0.0;
IOWYtotal_ratio=0.0;
COWYtotal_ratio=0.0;
gmIplit = input[0][7]; //gm/lit
gmNaOHplit = input[0][8]; // gm/lit
pH = input[0][9]; //dye bath pH
Integ = input[0][11]; //shade
IOWYtarget = input[0][10];
IOWYsurface_target = 0.0; // %IOWY at the surface from Integ conversion
COWYtarget = input[0][12];
mV = input[0][20];
nip_pressure = input[0][21];
speed = input[0][4];
if (current_dip == 1)
{
Df = exp(-27.3480169 + (0.7766363*gmIplit) + (0.4031649*pH));
Dy = exp(-17.3699775 - (0.503326*gmIplit) + (0.588888*pH) - (0.0736707*dwelltime));
AO[current_dip] = exp(-10.4653532 + (0.1263413*speed) + (0.0685300*oxd_time) - (0.0010179*mV));
}
else if (current_dip == 2)
{
Df = exp(-27.3480169 - 0.3903350 + (0.7766363*gmIplit) + (0.4031649*pH));
Dy = exp(-17.3699775 - 0.0516144 - (0.503326*gmIplit) + (0.588888*pH) - (0.0736707*dwelltime));
AO[current_dip] = exp(-10.4653532 -0.4685870 + (0.1263413*speed) + (0.0685300*oxd_time) - (0.0010179*mV));
}
else if (current_dip == 3)
{
Df = exp(-27.3480169 + 0.2868312 + (0.7766363*gmIplit) + (0.4031649*pH));
Dy = exp(-17.3699775 - 0.454878 - (0.503326*gmIplit) + (0.588888*pH) - (0.0736707*dwelltime));
AO[current_dip] = exp(-10.4653532 -0.6931914 + (0.1263413*speed) + (0.0685300*oxd_time) - (0.0010179*mV));
}
else if (current_dip == 4)
{
Df = exp(-27.3480169 + 0.5783337 + (0.7766363*gmIplit) + (0.4031649*pH));
Dy = exp(-17.3699775 - 1.032697 - (0.503326*gmIplit) + (0.588888*pH) - (0.0736707*dwelltime));
AO[current_dip] = exp(-10.4653532 -0.9826215 + (0.1263413*speed) + (0.0685300*oxd_time) - (0.0010179*mV));
}
else if (current_dip == 5)
{
Df = exp(-27.3480169 + 0.9180302 + (0.7766363*gmIplit) + (0.4031649*pH));
Dy = exp(-17.3699775 - 1.392668 - (0.503326*gmIplit) + (0.588888*pH) - (0.0736707*dwelltime));
AO[current_dip] = exp(-10.4653532 -0.6885056 + (0.1263413*speed) + (0.0685300*oxd_time) - (0.0010179*mV));
}
else if (current_dip == 6)
{
Df = exp(-27.3480169 + 1.0879995 + (0.7766363*gmIplit) + (0.4031649*pH));
Dy = exp(-17.3699775 - 1.4830235 - (0.503326*gmIplit) + (0.588888*pH) - (0.0736707*dwelltime));
AO[current_dip] = exp(-10.4653532 -1.3461714 + (0.1263413*speed) + (0.0685300*oxd_time) - (0.0010179*mV));
}
else if (current_dip == 7)
{
Df = exp(-27.3480169 + 0.9494075 + (0.7766363*gmIplit) + (0.4031649*pH));
Dy = exp(-17.3699775 - 1.4538142 - (0.503326*gmIplit) + (0.588888*pH) - (0.0736707*dwelltime));
AO[current_dip] = exp(-10.4653532 -1.3170116 + (0.1263413*speed) + (0.0685300*oxd_time) - (0.0010179*mV));
}
wash = -0.1043059 + (0.0043698*speed) - (0.0174137*dwelltime) + (0.00064822*mV) - (0.06827879*gmIplit);
wetpickup = 0.07959512 - (0.000159807*nip_pressure) - (0.01133595*gmIplit) - (3960.68825*Dy);
IOWYsurface_target = 0.0;
389

IOWYsurface_target = -0.02646465 + (9.53859e-4*Integ) + (1.35931e-5*pow((Integ-55.2088),2)) + (3.909e-8*pow((Integ-55.2088),3));
IOWYsurface_target = IOWYsurface_target + (2.42444e-9*pow((Integ-55.2088),4)) + (6.4303e-11*pow((Integ-55.2088),5));
for (ctx = 0; ctx<=rows; ctx++)
{
gms_ctn_node[ctx] = 1.54*porosity*2.0*PI25DT*ctx*dr*dr;
liter_per_node[ctx] = (1-porosity)*2.0*PI25DT*ctx*dr*dr;
}
gms_ctn_node[0] = 1.54*porosity*PI25DT*0.25*dr*dr;
liter_per_node[0] = (1-porosity)*PI25DT*0.25*dr*dr;
gms_ctn_node[rows] = 1.54*porosity*PI25DT*(radius*dr-(0.25*dr*dr));
liter_per_node[rows] = (1-porosity)*PI25DT*(radius*dr-(0.25*dr*dr));
x=i=j=k=ctx=cty=0;
pivot=0;
IOWYtotal=0.0;
COWYtotal=0.0;
IOWYsurface=0.0;
// Set-up initial conditions
for (ctx = 0; ctx<=rows; ctx++)
{
X[ctx]=0.0;
Cj[ctx]=0.0;
Cj1[ctx]=0.0;
d[ctx]=0.0;
temp[ctx]=0.0;
RBL[ctx]=0.0;
RBL1[ctx]=0.0;
RBLgm[ctx]=0.0;
RBL1gm[ctx]=0.0;
IOWY[ctx]=0.0; //these will change for multiple dips
IOWYoxd[ctx]=0.0; //here
COWY[ctx]=0.0; // here
IOWYstep[ctx]=0.0;
dumb[ctx]=0.0;
OBL[ctx]=0.0;
OBL1[ctx]=0.0;
OBLgm[ctx]=0.0;
OBL1gm[ctx]=0.0;
TBL[ctx] = RBL[ctx] + OBL[ctx];
TBL1[ctx] = RBL1[ctx] + OBL1[ctx];
for(cty = 0; cty<=rows; cty++)
{
AA[ctx][cty]=0.0;
BB[ctx][cty]=0.0;
}
}
Cj[rows]=gmIplit;
Cj1[rows]=gmIplit;
lamda = (Dy*dt)/(2.0*dr*dr);
alpha = (Ur*dt)/(4.0*dr);
beta = (Dy*dt)/(4.0*dr);
for (ctx = 0; ctx <rows; ctx++)
{
AA[ctx][ctx]=1.0 + (2.0*lamda);
BB[ctx][ctx]=1.0 + (-2.0*lamda);
}
for (ctx = 1; ctx <(rows-1); ctx++)
{
AA[ctx][ctx+1]=(-beta/(ctx*dr))-lamda+(alpha);
AA[ctx+1][ctx]=(beta/((ctx+1)*dr))-lamda-(alpha);
BB[ctx][ctx+1]=(beta/(ctx*dr))+lamda-(alpha);
BB[ctx+1][ctx]=(-beta/((ctx+1)*dr))+lamda+(alpha);
}
390

AA[0][1]=-2.0*lamda;
AA[1][0]=(beta/dr)-lamda-(alpha);
BB[0][1]=2.0*lamda;
BB[1][0]=(-beta/dr)+lamda+(alpha);
Monophenate_Ion = 1.0/(1.0 + (pow(10,(9.5-pH))) + (pow(10,(pH-12.7))));
CompA = (0.016492 * Monophenate_Ion) + 0.003465;
CompB = (-0.244296 * Monophenate_Ion) + 0.816158;
for (ts = 1; ts <= num_time_steps; ts++)
{
for (ctx = 0; ctx <= rows; ctx++)
{
Cj[ctx]=Cj1[ctx];
RBL[ctx]=RBL1[ctx];
OBL[ctx]=OBL1[ctx];
TBL[ctx]=TBL1[ctx];
RBLgm[ctx]=RBL1gm[ctx];
OBLgm[ctx]=OBL1gm[ctx];
temp[ctx]=0.0;
}
Mt = (((4.0/pow(PI25DT,0.5))*(pow((Df*dwelltime/(0.0009*0.0009)),0.5)))-(Df*dwelltime/(0.0009*0.0009))-
((1.0/(3.0*pow(PI25DT,0.5)))*(pow((Df*dwelltime/(0.0009*0.0009)),(3.0/2.0)))))/num_time_steps;
for (ctx = 0; ctx < rows; ctx++)
{
if (Cj[ctx] <= 0.0) IOWYstep[ctx] = 0.0;
else IOWYstep[ctx] = Mt*CompA*pow(Cj[ctx],CompB);
d[ctx] = -1.0 * gms_ctn_node[ctx] * IOWYstep[ctx] / liter_per_node[ctx];
}
d[rows-1] = d[rows-1] + (Cj[rows]*2.0*((beta/(radius))+lamda-alpha));
if (Cj[rows] <= 0.0) IOWYstep[rows] = 0.0;
else IOWYstep[rows] = Mt*CompA*pow(Cj[rows],CompB);
// Find new dye concentration by Guass-Jordan elimination
for (ctx = 0; ctx <rows; ctx++)
{
for (cty = 0; cty <rows; cty++) temp[ctx] = temp [ctx] + BB[ctx][cty]*Cj[cty];
}
for (ctx = 0; ctx <rows; ctx++)
{
temp[ctx] = temp[ctx]+d[ctx];
}
for (ctx = 0; ctx < rows; ctx++)
{
for (cty = 0; cty < rows; cty++) AAinvt[ctx][cty] = AA[ctx][cty];
}
for (ctx = 0; ctx <rows; ctx++)
{
AAinvt[ctx][rows]=temp[ctx];
}
for (i = 0; i < rows; i++)
{
if (AAinvt[i][i] == 0)
{
pivot = 0;
j = i + 1;
while ((pivot == 0) && (j <= rows))
{
if (AAinvt[j][i] != 0.0)
{
pivot = j;
}
j = j + 1;
}
if (pivot == 0 ) printf("Stop, matrix is singular");
391

}
if(pivot == (j-1))
{
for (j = 0; j < (rows+1); j++)
{
temp1 = AAinvt[i][j];
AAinvt[i][j]=AAinvt[pivot][j];
AAinvt[pivot][j] = temp1;
}
}
for (j = (i+1); j < rows; j++)
{
Multi = -AAinvt[j][i] / AAinvt[i][i];
for (k = i; k < (rows+1); k++)
{
AAinvt[j][k] = AAinvt[j][k] + (Multi * AAinvt[i][k]);
}
}
}
Cj1[rows-1] = AAinvt[rows-1][rows] / AAinvt[rows-1][rows-1];
for (j = (rows-2); j >= 0; j--)
{
Cj1[j] = AAinvt[j][rows];
for ( k = (j+1); k < rows; k++)
{
Cj1[j] = Cj1[j] - (AAinvt[j][k] * Cj1[k]);
}
Cj1[j] = Cj1[j] / AAinvt[j][j];
}
// End Gauss-Jordan
{
IOWY[0] = IOWY[0] + IOWYstep[0];
}

for (ctx = 1; ctx < rows; ctx++)
{
{
IOWY[ctx] = IOWY[ctx] + IOWYstep[ctx];
}
}
IOWY[rows] = IOWY[rows] + IOWYstep[rows];
for (ctx = 0; ctx <= rows; ctx++) dye_bath_dist[yarn_count][current_dip][ctx] = Cj1[ctx];
} // Close time step loop for process in dye box
// Nip process
for (ctx = 0; ctx <= rows; ctx++)
{
RBL1[ctx] = Cj1[ctx];
RBL1gm[ctx] = Cj1[ctx] * liter_per_node[ctx] * wetpickup;
OBL1gm[ctx] = (COWYpre[ctx] - IOWYpre[ctx]) * gms_ctn_node[ctx] * wash;
if (OBL1gm[ctx] < 0.0) OBL1gm[ctx] = 0.0;
}
IOWYtotal=0.0;
IOWYsurface=0.0;
COWYtotal=0.0;
oxd_time_steps = oxd_time/DT;
dt=DT;
Air = 0.2541; // gm per liter of oxygen
for (ctx = 0; ctx<=rows; ctx++)
{
Cj[ctx]=0.0; // gm/lit of oxygen
Cj1[ctx]=0.0;
d[ctx]=0.0;
392

X[ctx]=0.0;
Xrbl[ctx]=0.0;
Xiowy[ctx]=0.0;
for(cty = 0; cty<=rows; cty++)
{
AA[ctx][cty]=0.0;
BB[ctx][cty]=0.0;
}
}
Cj1[rows]=Air;
lamda = (DOy*dt)/(2.0*dr*dr);
alpha = (UOr*dt)/(4.0*dr);
beta = (DOy*dt)/(4.0*dr);
for (ctx = 0; ctx <rows; ctx++)
{
AA[ctx][ctx]=1.0 + (2.0*lamda);
BB[ctx][ctx]=1.0 + (-2.0*lamda);
}
for (ctx = 1; ctx <(rows-1); ctx++)
{
AA[ctx][ctx+1]=(-beta/(ctx*dr))-lamda+(alpha);
AA[ctx+1][ctx]=(beta/((ctx+1)*dr))-lamda-(alpha);
BB[ctx][ctx+1]=(beta/(ctx*dr))+lamda-(alpha);
BB[ctx+1][ctx]=(-beta/((ctx+1)*dr))+lamda+(alpha);
}
AA[0][1]=-2.0*lamda;
AA[1][0]=(beta/dr)-lamda-(alpha);
BB[0][1]=2.0*lamda;
BB[1][0]=(-beta/dr)+lamda+(alpha);
// Start time step for oxidization
for (ts = 1; ts <= oxd_time_steps; ts++)
{
for (ctx = 0; ctx <= rows; ctx++)
{
Cj[ctx]=Cj1[ctx];
RBL[ctx]=RBL1[ctx];
RBLgm[ctx]=RBL1gm[ctx];
OBLgm[ctx]=OBL1gm[ctx];
temp[ctx]=0.0;
}
for (ctx = 0; ctx <= rows; ctx++)
{
if (Cj[ctx] <= 0.0)
{
Xrbl[ctx] = 0.0;
Xiowy[ctx] = 0.0;
X[ctx] = Xrbl[ctx] + Xiowy[ctx];
}
else
{
if (RBLgm[ctx] > 0.0) X[ctx]=1/(AO[current_dip]*Cj[ctx]*liter_per_node[ctx]*dt/(RBLgm[ctx]+(IOWY[ctx]*gms_ctn_node[ctx])));
else if (IOWY[ctx] > 0.0) X[ctx]=1/(AO[current_dip]*Cj[ctx]*liter_per_node[ctx]*dt/((IOWY[ctx]*gms_ctn_node[ctx])));
else X[ctx]=0.0;
}
if (X[ctx] > 1.0) X[ctx]=1.0;
d[ctx] = -1.0 * X[ctx] * Cj[ctx] * dt;
if (d[ctx] > 0.0) d[ctx] = 0.0;
}
d[rows-1] = d[rows-1] + (Cj[rows]*2*((beta/radius)+lamda-alpha));
// Find new oxygen concentration by Guass-Jordan elimination
for (ctx = 0; ctx <rows; ctx++)
{
393

for (cty = 0; cty <rows; cty++) temp[ctx] = temp [ctx] + BB[ctx][cty]*Cj[cty];
}
for (ctx = 0; ctx <rows; ctx++)
{
temp[ctx] = temp[ctx]+d[ctx];
}
for (ctx = 0; ctx < rows; ctx++)
{
for (cty = 0; cty < rows; cty++) AAinvt[ctx][cty] = AA[ctx][cty];
}
for (ctx = 0; ctx <rows; ctx++)
{
AAinvt[ctx][rows]=temp[ctx];
}
for (i = 0; i < rows; i++)
{
if (AAinvt[i][i] == 0)
{
pivot = 0;
j = i + 1;
while ((pivot == 0) && (j <= rows))
{
if (AAinvt[j][i] != 0.0)
{
pivot = j;
}
j = j + 1;
}
if (pivot == 0 ) printf("Stop, matrix is singular");
}
if(pivot == (j-1))
{
for (j = 0; j < (rows+1); j++)
{
temp1 = AAinvt[i][j];
AAinvt[i][j]=AAinvt[pivot][j];
AAinvt[pivot][j] = temp1;
}
}
for (j = (i+1); j < rows; j++)
{
Multi = -AAinvt[j][i] / AAinvt[i][i];
for (k = i; k < (rows+1); k++)
{
AAinvt[j][k] = AAinvt[j][k] + (Multi * AAinvt[i][k]);
}
}
}
Cj1[rows-1] = AAinvt[rows-1][rows] / AAinvt[rows-1][rows-1];
for (j = (rows-2); j >= 0; j--)
{
Cj1[j] = AAinvt[j][rows];
for ( k = (j+1); k < rows; k++)
{
Cj1[j] = Cj1[j] - (AAinvt[j][k] * Cj1[k]);
}
Cj1[j] = Cj1[j] / AAinvt[j][j];
}
// End Gauss-Jordan
Mt = (((4.0/pow(PI25DT,0.5))*(pow((Df*oxd_time/(0.0009*0.0009)),0.5)))-(Df*oxd_time/(0.0009*0.0009))-
((1.0/(3.0*pow(PI25DT,0.5)))*(pow((Df*oxd_time/(0.0009*0.0009)),(3.0/2.0)))))/oxd_time_steps;
for (ctx = 0; ctx <=rows; ctx++)
394

{
if (RBLgm[ctx] > 0.0)
{
dumb[ctx] = (AO[current_dip]*Cj1[ctx]*liter_per_node[ctx]*dt)/RBLgm[ctx];
if (dumb[ctx] > 1.0)
{
RBL1gm[ctx] = 0.0;
RBL1[ctx] = 0.0;
OBL1gm[ctx] = OBLgm[ctx] + RBLgm[ctx];
}
else
{
RBL1gm[ctx] = RBLgm[ctx] - (dumb[ctx]*RBLgm[ctx]);
RBL1[ctx] = RBL[ctx] - (dumb[ctx]*RBLgm[ctx]/(liter_per_node[ctx]*wetpickup));
OBL1gm[ctx] = OBLgm[ctx] + (dumb[ctx]*RBLgm[ctx]);
if (RBL1gm[ctx] <= 0.0) RBL1gm[ctx] = 0.0;
if (RBL1[ctx] <= 0.0) RBL1[ctx] = 0.0;
IOWY[ctx] = IOWY[ctx] + ((CompA*pow(RBL1[ctx],CompB))*Mt);
RBL1gm[ctx] = RBL1gm[ctx] - ((CompA*pow(RBL1[ctx],CompB)) * Mt * gms_ctn_node[ctx]);
RBL1[ctx] = RBL1[ctx] - (((CompA*pow(RBL1[ctx],CompB)) * Mt * gms_ctn_node[ctx])/(liter_per_node[ctx] * wetpickup));
if (RBL1gm[ctx] <= 0.0) RBL1gm[ctx] = 0.0;
if (RBL1[ctx] <= 0.0) RBL1[ctx] = 0.0;
}
}
else if (IOWY[ctx] > 0.0)
{
dumb[ctx]=((AO[current_dip]*Cj1[ctx]*liter_per_node[ctx]*dt)/(IOWY[ctx]*gms_ctn_node[ctx]));
if (dumb[ctx] > 1.0)
{
IOWYoxd[ctx] = IOWYoxd[ctx] + IOWY[ctx];
IOWY[ctx] = 0.0;
}
else
{
IOWYoxd[ctx] = IOWYoxd[ctx] + (dumb[ctx]*IOWY[ctx]);
IOWY[ctx] = IOWY[ctx] - (dumb[ctx]*IOWY[ctx]);
if (IOWY[ctx] <= 0.0) IOWY[ctx]=0.0;
}
}
}
for (ctx = 0; ctx <= rows; ctx++) air_dist[yarn_count][current_dip][ctx] = Cj1[ctx];
} // end oxidization time step loop
for (ctx = 0; ctx<=rows; ctx++) if (RBL1[ctx] >0.0) printf("Node: %i\t RBL Not all oxidized\n", ctx);
for (ctx = 0; ctx<=rows; ctx++) if (IOWY[ctx] >0.0) printf("Node: %i\t IOWY Not all oxidized\n", ctx);
for (ctx = 0; ctx <= rows; ctx++)
{
IOWYoxd[ctx] = IOWYoxd[ctx] + IOWYpre[ctx];
COWY[ctx] = IOWYoxd[ctx]*totalgramsperindigo + IOWY[ctx]*totalgramsperindigo;
COWY[ctx] = COWY[ctx] + (OBL1gm[ctx]*totalgramsperindigo/gms_ctn_node[ctx]);
COWY[ctx] = COWY[ctx] + (RBL1gm[ctx]*totalgramsperindigo/gms_ctn_node[ctx]);
IOWYtotal = IOWYtotal + (IOWYoxd[ctx]*gms_ctn_node[ctx])+ (IOWY[ctx]*gms_ctn_node[ctx]);
COWYtotal = COWYtotal + (COWY[ctx]*gms_ctn_node[ctx]);
}
IOWYtotal = IOWYtotal / (1.54*porosity*PI25DT * radius * radius);
COWYtotal = COWYtotal / (1.54*porosity*PI25DT * radius * radius);
IOWYsurface = IOWYoxd[rows] + IOWY[rows];
IOWYsurface_ratio = IOWYsurface_target/IOWYsurface; // greater then 1 means to increase diffusion coeff Df
IOWYtotal_ratio = IOWYtarget/IOWYtotal; // greater then 1 means to increase diffusion coeff Dy
COWYtotal_ratio = COWYtarget/COWYtotal;
IOWY_save[yarn_count][current_dip] = IOWYtotal;
COWY_save[yarn_count][current_dip] = COWYtotal;
Integ_save[yarn_count][current_dip] = 0.0;
395

Integ_save[yarn_count][current_dip] = 45.60937 + (592.19421*IOWYsurface) - (9928.5539*pow((IOWYsurface-0.045773),2)) +
(1.83538e+5*pow((IOWYsurface-0.045773),3));
Integ_save[yarn_count][current_dip] = Integ_save[yarn_count][current_dip] - (1.522451e+6*pow((IOWYsurface-0.045773),4))+
(4.27080e+6*pow((IOWYsurface-0.045773),5));
Total_IOWY_pre = IOWYtotal;
Total_COWY_pre = COWYtotal;
// Save IOWY & COWY amount and distribution
for (ctx = 0; ctx<=rows; ctx++)
{
IOWYpre[ctx] = IOWYoxd[ctx];
COWYpre[ctx] = COWY[ctx];
}
for (ctx = 0; ctx <= rows; ctx++) IOWY_dist[yarn_count][current_dip][ctx] = IOWYoxd[ctx];
for (ctx = 0; ctx <= rows; ctx++) COWY_dist[yarn_count][current_dip][ctx] = COWY[ctx];
IOWYsurface_ratio = IOWYtotal_ratio = COWYtotal_ratio = 0.99;
Df_constantAO[current_dip] = Df;
Dy_constantAO[current_dip] = Dy;
WP_constantAO[current_dip] = wetpickup;
wash_constantAO[current_dip] = wash;
Df_AO[current_dip] = Df;
Dy_AO[current_dip] = Dy;
WP_AO[current_dip] = wetpickup;
} // This ends the yarn count calculations at specific oxidization rate value
for (ctx = 1; ctx <=num_dips; ctx++)
{
Df_dip[yarn_count][ctx] = Df_constantAO[ctx]; // reset Df_dip after each AO step
Dy_dip[yarn_count][ctx] = Dy_constantAO[ctx];
WP_dip[yarn_count][ctx] = WP_constantAO[ctx];
wash_dip[yarn_count][ctx] = wash_constantAO[ctx];
}
for (ctx = 1; ctx <= num_dips; ctx++)
{
for (cty = 1; cty <= num_yarns; cty++) wash_AO[ctx] = wash_AO[ctx] + wash_dip[cty][ctx];
}
pFile = fopen ("output_model.out","a");
fprintf(pFile, "number of cycles to converge: %e\n", num_cycles);
fprintf(pFile, "Dips\t Df\t Dy\t pickup\t Oxidization\n");
for (x = 1; x <= num_dips; x++)
{
fprintf(pFile, "%i\t%e\t%e\t%e\t%e\n", x, Df_AO[x], Dy_AO[x], WP_AO[x], AO[x]);
}
fprintf(pFile, "yarns\t wash\n");
for (x = 1; x <= num_yarns; x++) fprintf(pFile, "%i\t%e\n", x, wash_dip[x][1]);

for (cty = 1; cty <= num_yarns; cty++)
{
fprintf(pFile, "yarn: %i IOWY\t COWY\t Integ\n", cty);
for (ctx = 1; ctx <=num_dips; ctx++)
{
fprintf(pFile, "%e\t%e\t%e\n", IOWY_save[cty][ctx], COWY_save[cty][ctx], Integ_save[cty][ctx]);
}
}
fclose (pFile);
return 0;
}
396

Section A-5-1: Observational Study Raw Data -Dye Range Parameters

Table A-5-1: Independent indigo dye range raw data set

Shade
ID
Speed
(m/min)
Dwell
Time
(sec)
Oxidation
Time (sec)
Dye Bath
(gpl
100%
Indigo)
Dye
Bath pH
Dye
Bath
(mV)
Dye Bath
Alkalinity
(gpl)
Dwell
Length
(m)
Oxidation
Length (m)
Nip
Pressures
(psi)
443 29.00 20.1 73.6 1.262 12.18 813 2.58 9.70 38.90 95.00
Yarn Skein Response Variables
Yarn
Count
Dye
route Dips
Greige
Weight
Boil Off
Weight
Dyed
Weight
Washed
Weight %COWY
Total
%IOWY
Surface
%IOWY Integ
Penetration
Level
6.3 1 only 1 8.2301 7.885 8.1841 7.8671 1.72% 0.166% 0.437% 8.1 0.38
6.3 1--2 2 7.7329 7.3991 7.7581 7.3974 2.75% 0.286% 0.740% 17.2 0.39
6.3 1--3 3 8.3473 8.0082 8.4238 8.0085 3.09% 0.455% 1.034% 29.5 0.44
6.3 1--4 4 7.7045 7.3799 7.7854 7.4011 3.38% 0.510% 1.269% 35.8 0.40
6.3 1--5 5 8.2838 7.9276 8.3811 7.9722 3.61% 0.744% 2.164% 50.1 0.34
6.3 1--6 6 8.3773 8.0322 8.44 8.0778 4.30% 0.885% 2.836% 57.4 0.31

% Reflectance Readings

Wave-
length
(nm) Dip 1 Dip 2 Dip 3 Dip 4 Dip 5 Dip 6 Dip 7
400 19.43 13.08 9.08 7.95 5.99 5.19
420 24.21 16.95 12.03 10.62 7.70 6.55
440 23.52 16.01 11.13 9.70 6.89 5.83
460 21.30 13.98 9.51 8.20 5.80 4.90
480 19.39 12.24 8.09 6.83 4.78 4.04
500 17.66 10.86 7.00 5.84 4.07 3.44
520 15.57 9.17 5.66 4.68 3.25 2.75
540 13.12 7.40 4.48 3.68 2.58 2.20
560 11.61 6.28 3.76 3.09 2.18 1.89
580 10.10 5.21 3.11 2.58 1.87 1.65
600 8.65 4.31 2.61 2.18 1.64 1.48
620 7.52 3.70 2.26 1.91 1.48 1.37
640 6.50 3.16 2.01 1.72 1.41 1.32
660 5.93 2.98 1.94 1.67 1.40 1.34
680 7.72 3.93 2.59 2.21 1.78 1.66
700 15.16 9.11 5.91 4.95 3.68 3.26
397

Table A-5-1: Continued

Shade
ID
Speed
(m/min)
Dwell
Time
(sec)
Oxidation
Time (sec)
Dye Bath
(gpl
100%
Indigo)
Dye
Bath pH
Dye
Bath
(mV)
Dye Bath
Alkalinity
(gpl)
Dwell
Length
(m)
Oxidation
Length (m)
Nip
Pressures
(psi)
443 29.00 20.1 73.6 1.262 12.18 813 2.58 9.70 38.90 95.00
Yarn Skein Response Variables
Yarn
Count
Dye
route Dips
Greige
Weight
Boil Off
Weight
Dyed
Weight
Washed
Weight %COWY
Total
%IOWY
Surface
%IOWY Integ
Penetration
Level
7.1 1 only 1 6.9605 6.7511 7.0156 6.7396 1.84% 0.180% 0.533% 10.3 0.34
7.1 1--2 2 6.9388 6.7247 7.0592 6.7256 2.87% 0.312% 0.765% 18.3 0.41
7.1 1--3 3 7.1311 6.9206 7.3021 6.9363 3.40% 0.490% 1.013% 28.8 0.48
7.1 1--4 4 7.0685 6.8668 7.2129 6.8864 2.94% 0.612% 1.498% 40.4 0.41
7.1 1--5 5 7.2281 7.0148 7.4632 7.0448 4.26% 0.732% 1.911% 46.8 0.38
7.1 1--6 6 7.0234 6.8175 7.1867 6.852 4.60% 0.911% 2.825% 57.3 0.32

% Reflectance Readings



Wave-
length
(nm) Dip 1 Dip 2 Dip 3 Dip 4 Dip 5 Dip 6 Dip 7
400 17.74 12.72 9.40 7.36 6.47 5.42
420 22.38 16.60 12.49 9.81 8.43 6.90
440 21.50 15.58 11.53 8.84 7.54 6.10
460 19.20 13.50 9.81 7.42 6.32 5.05
480 17.26 11.77 8.34 6.13 5.21 4.15
500 15.58 10.39 7.22 5.23 4.44 3.50
520 13.55 8.76 5.84 4.17 3.54 2.79
540 11.22 7.05 4.62 3.27 2.79 2.22
560 9.80 5.96 3.86 2.74 2.35 1.89
580 8.35 4.93 3.19 2.30 1.99 1.64
600 6.99 4.07 2.66 1.94 1.72 1.46
620 6.00 3.49 2.30 1.72 1.54 1.34
640 5.10 2.97 2.03 1.57 1.45 1.30
660 4.69 2.79 1.96 1.55 1.44 1.31
680 6.33 3.72 2.61 2.01 1.85 1.63
700 13.33 8.61 6.04 4.47 3.92 3.27
398

Table A-5-1: Continued

Shade
ID
Speed
(m/min)
Dwell
Time
(sec)
Oxidation
Time (sec)
Dye Bath
(gpl
100%
Indigo)
Dye
Bath pH
Dye
Bath
(mV)
Dye Bath
Alkalinity
(gpl)
Dwell
Length
(m)
Oxidation
Length (m)
Nip
Pressures
(psi)
443 29.00 20.10 73.60 1.196 12.06 807 2.51 9.70 38.90 95
Yarn Skein Response Variables
Yarn
Count
Dye
route Dips
Greige
Weight
Boil Off
Weight
Dyed
Weight
Washed
Weight %COWY
Total
%IOWY
Surface
%IOWY Integ
Penetration
Level
7.1 1 only 1 7.0115 6.8131 7.0888 6.7928 1.97% 0.157% 0.438% 8.1 0.36
7.1 1--2 2 7.0284 6.831 7.1646 6.8207 2.79% 0.285% 0.737% 17.1 0.39
7.1 1--3 3 7.0272 6.8247 7.1861 6.8223 3.19% 0.431% 0.960% 26.9 0.45
7.1 1--4 4 7.2151 7.0028 7.369 7.0351 3.12% 0.546% 1.315% 36.8 0.42
7.1 1--5 5 7.207 6.9949 7.4293 7.0223 4.09% 0.687% 1.866% 46.2 0.37
7.1 1--6 6 7.1864 6.9674 7.3599 7.0164 4.70% 0.865% 2.665% 55.7 0.32

% Reflectance Readings


Wave-
length
(nm) Dip 1 Dip 2 Dip 3 Dip 4 Dip 5 Dip 6 Dip 7
400 19.83 13.28 9.85 7.79 6.53 5.49
420 24.69 17.19 12.97 10.31 8.58 6.97
440 23.93 16.18 12.02 9.42 7.69 6.20
460 21.62 14.08 10.27 7.98 6.43 5.18
480 19.68 12.32 8.79 6.65 5.30 4.25
500 17.92 10.92 7.65 5.69 4.51 3.61
520 15.75 9.25 6.21 4.56 3.59 2.88
540 13.25 7.47 4.93 3.60 2.83 2.30
560 11.70 6.35 4.13 3.02 2.39 1.96
580 10.12 5.26 3.41 2.52 2.02 1.69
600 8.63 4.34 2.84 2.13 1.74 1.49
620 7.48 3.72 2.46 1.86 1.55 1.38
640 6.42 3.18 2.15 1.70 1.45 1.32
660 5.86 3.00 2.05 1.65 1.44 1.36
680 7.72 4.00 2.73 2.18 1.85 1.68
700 15.37 9.19 6.40 4.88 3.95 3.36
399

Table A-5-1: Continued

Shade
ID
Speed
(m/min)
Dwell
Time
(sec)
Oxidation
Time (sec)
Dye Bath
(gpl
100%
Indigo)
Dye
Bath pH
Dye
Bath
(mV)
Dye Bath
Alkalinity
(gpl)
Dwell
Length
(m)
Oxidation
Length (m)
Nip
Pressures
(psi)
418 32.00 18.20 66.70 1.658 11.83 814 3.29 9.70 38.90 95
Yarn Skein Response Variables
Yarn
Count
Dye
route Dips
Greige
Weight
Boil Off
Weight
Dyed
Weight
Washed
Weight %COWY
Total
%IOWY
Surface
%IOWY Integ
Penetration
Level
6.3 1 only 1 7.8005 7.4685 7.7353 7.4733 3.57% 0.322% 0.725% 16.6 0.44
6.3 1--2 2 8.2502 7.9087 8.294 7.9319 4.87% 0.556% 1.263% 35.7 0.44
6.3 1--3 3 8.2 7.8407 8.3168 7.9097 6.07% 0.811% 2.327% 52.0 0.35
6.3 1--4 4 7.9116 7.5711 8.0109 7.6461 5.81% 1.049% 3.291% 61.6 0.32
6.3 1--5 5 7.7039 7.3753 7.8447 7.4811 6.36% 1.372% 4.751% 72.7 0.29
6.3 1--6 6 8.2011 7.8532 8.3437 7.9801 6.50% 1.670% 6.416% 81.9 0.26

% Reflectance Readings


Wave-
length
(nm) Dip 1 Dip 2 Dip 3 Dip 4 Dip 5 Dip 6 Dip 7
400 13.64 7.99 5.82 4.81 3.84 3.28
420 18.04 10.83 7.57 6.15 4.77 3.98
440 16.94 9.81 6.67 5.37 4.14 3.44
460 14.65 8.17 5.50 4.39 3.42 2.85
480 12.75 6.75 4.49 3.58 2.82 2.35
500 11.26 5.75 3.80 3.04 2.42 2.05
520 9.49 4.60 3.04 2.45 1.97 1.69
540 7.60 3.62 2.41 1.97 1.64 1.45
560 6.48 3.06 2.06 1.74 1.48 1.33
580 5.37 2.57 1.80 1.55 1.37 1.25
600 4.43 2.19 1.60 1.42 1.29 1.20
620 3.77 1.95 1.48 1.35 1.25 1.20
640 3.22 1.79 1.44 1.35 1.29 1.23
660 3.07 1.80 1.49 1.42 1.38 1.33
680 4.03 2.27 1.81 1.69 1.58 1.54
700 9.48 4.95 3.55 3.06 2.61 2.35
400

Table A-5-1: Continued

Shade
ID
Speed
(m/min)
Dwell
Time
(sec)
Oxidation
Time (sec)
Dye Bath
(gpl
100%
Indigo)
Dye
Bath pH
Dye
Bath
(mV)
Dye Bath
Alkalinity
(gpl)
Dwell
Length
(m)
Oxidation
Length (m)
Nip
Pressures
(psi)
402 28.00 20.80 76.30 1.986 12.24 841 3.53 9.70 38.90 95
Yarn Skein Response Variables
Yarn
Count
Dye
route Dips
Greige
Weight
Boil Off
Weight
Dyed
Weight
Washed
Weight %COWY
Total
%IOWY
Surface
%IOWY Integ
Penetration
Level
6.3 1 only 1 7.7818 7.4511 7.7775 7.4437 3.13% 0.320% 0.725% 16.6 0.44
6.3 1--2 2 8.1611 7.8115 8.2261 7.8274 4.04% 0.550% 1.176% 33.6 0.47
6.3 1--3 3 7.8049 7.4705 7.9675 7.5075 5.37% 0.856% 2.150% 49.9 0.40
6.3 1--4 4 7.7129 7.3701 7.8701 7.4395 5.50% 1.164% 3.670% 64.8 0.32
6.3 1--5 5 7.8049 7.482 8.0171 7.559 5.87% 1.561% 5.577% 77.6 0.28
6.3 1--6 6 8.2905 7.945 8.4682 8.0669 5.31% 1.830% 6.629% 82.9 0.28

% Reflectance Readings


Wave-
length
(nm) Dip 1 Dip 2 Dip 3 Dip 4 Dip 5 Dip 6 Dip 7
400 13.25 8.47 6.07 4.59 3.58 3.16
420 17.46 11.43 7.96 5.83 4.43 3.78
440 16.47 10.41 7.05 5.10 3.84 3.27
460 14.25 8.70 5.80 4.18 3.16 2.72
480 12.45 7.25 4.74 3.42 2.60 2.26
500 11.02 6.20 4.01 2.90 2.24 1.98
520 9.37 4.98 3.22 2.35 1.84 1.66
540 7.57 3.91 2.56 1.89 1.53 1.44
560 6.49 3.29 2.17 1.65 1.40 1.34
580 5.42 2.73 1.87 1.47 1.28 1.25
600 4.49 2.30 1.64 1.35 1.22 1.21
620 3.86 2.02 1.51 1.30 1.21 1.21
640 3.26 1.79 1.41 1.25 1.22 1.23
660 3.12 1.80 1.49 1.34 1.35 1.38
680 4.03 2.35 1.84 1.60 1.58 1.60
700 9.14 5.27 3.69 2.91 2.49 2.34
401

Table A-5-1: Continued

Shade
ID
Speed
(m/min)
Dwell
Time
(sec)
Oxidation
Time (sec)
Dye Bath
(gpl
100%
Indigo)
Dye
Bath pH
Dye
Bath
(mV)
Dye Bath
Alkalinity
(gpl)
Dwell
Length
(m)
Oxidation
Length (m)
Nip
Pressures
(psi)
402 28.00 20.80 76.30 1.986 12.24 841 3.53 9.70 38.90 95
Yarn Skein Response Variables
Yarn
Count
Dye
route Dips
Greige
Weight
Boil Off
Weight
Dyed
Weight
Washed
Weight %COWY
Total
%IOWY
Surface
%IOWY Integ
Penetration
Level
7.1 1 only 1 7.0215 6.8197 7.1193 6.8162 3.14% 0.354% 0.806% 20.3 0.44
7.1 1--2 2 7.0354 6.8369 7.2252 6.8568 4.41% 0.621% 1.488% 40.2 0.42
7.1 1--3 3 7.2442 7.0315 7.5124 7.0802 5.56% 0.885% 2.607% 55.1 0.34
7.1 1--4 4 7.0342 6.8316 7.272 6.8981 5.17% 1.210% 3.406% 62.6 0.36
7.1 1--5 5 7.0837 6.882 7.3738 6.963 5.86% 1.605% 4.657% 72.0 0.34
7.1 1--6 6 7.0648 6.8578 7.2998 6.9678 5.17% 1.974% 7.055% 84.8 0.28

% Reflectance Readings


Wave-
length
(nm) Dip 1 Dip 2 Dip 3 Dip 4 Dip 5 Dip 6 Dip 7
400 12.19 7.42 5.62 4.84 4.01 3.12
420 16.21 10.07 7.23 6.18 4.99 3.82
440 15.08 9.04 6.35 5.40 4.34 3.30
460 12.84 7.49 5.20 4.43 3.56 2.75
480 11.07 6.15 4.25 3.62 2.93 2.27
500 9.70 5.22 3.59 3.06 2.51 1.98
520 8.06 4.16 2.88 2.47 2.04 1.64
540 6.41 3.25 2.29 1.97 1.67 1.40
560 5.41 2.74 1.96 1.72 1.50 1.30
580 4.46 2.29 1.70 1.52 1.36 1.21
600 3.68 1.95 1.51 1.37 1.27 1.17
620 3.15 1.74 1.42 1.31 1.24 1.16
640 2.66 1.57 1.34 1.25 1.22 1.16
660 2.57 1.59 1.42 1.35 1.33 1.30
680 3.36 2.01 1.73 1.61 1.57 1.51
700 8.01 4.42 3.37 2.95 2.61 2.25
402

Table A-5-1: Continued

Shade
ID
Speed
(m/min)
Dwell
Time
(sec)
Oxidation
Time (sec)
Dye Bath
(gpl
100%
Indigo)
Dye
Bath pH
Dye
Bath
(mV)
Dye Bath
Alkalinity
(gpl)
Dwell
Length
(m)
Oxidation
Length (m)
Nip
Pressures
(psi)
402 28.00 20.80 76.30 1.986 12.24 841 3.53 9.70 38.90 95
Yarn Skein Response Variables
Yarn
Count
Dye
route Dips
Greige
Weight
Boil Off
Weight
Dyed
Weight
Washed
Weight %COWY
Total
%IOWY
Surface
%IOWY Integ
Penetration
Level
8 1 only 1 9.3167 8.9763 9.3606 8.8991 3.03% 0.405% 0.821% 21.0 0.49
8 1--2 2 9.228 8.9051 9.4013 8.8917 4.31% 0.706% 1.382% 38.2 0.51
8 1--3 3 9.8658 9.4983 10.167 9.5727 5.76% 1.166% 2.780% 56.8 0.42
8 1--4 4 8.9274 8.5972 9.2155 8.7022 5.91% 1.481% 4.331% 69.8 0.34
8 1--5 5 9.2807 8.9442 9.6769 9.1161 6.89% 1.893% 6.248% 81.1 0.30
8 1--6 6 9.1866 8.8523 9.5417 9.0438 6.49% 2.194% 7.096% 84.9 0.31

% Reflectance Readings


Wave-
length
(nm) Dip 1 Dip 2 Dip 3 Dip 4 Dip 5 Dip 6 Dip 7
400 11.87 7.60 5.33 4.17 3.32 2.99
420 15.78 10.32 6.84 5.19 4.04 3.56
440 14.68 9.27 6.00 4.51 3.50 3.07
460 12.51 7.66 4.90 3.69 2.90 2.55
480 10.78 6.30 4.00 3.03 2.39 2.13
500 9.45 5.36 3.39 2.58 2.07 1.87
520 7.83 4.29 2.73 2.10 1.72 1.59
540 6.23 3.39 2.19 1.73 1.47 1.40
560 5.25 2.87 1.90 1.54 1.35 1.31
580 4.32 2.42 1.66 1.39 1.25 1.24
600 3.55 2.07 1.49 1.30 1.21 1.22
620 3.05 1.85 1.41 1.27 1.20 1.24
640 2.60 1.67 1.36 1.26 1.21 1.27
660 2.52 1.72 1.46 1.38 1.36 1.45
680 3.34 2.17 1.74 1.62 1.57 1.66
700 7.97 4.62 3.30 2.73 2.38 2.32
403

Table A-5-1: Continued

Shade
ID
Speed
(m/min)
Dwell
Time
(sec)
Oxidation
Time (sec)
Dye Bath
(gpl
100%
Indigo)
Dye
Bath pH
Dye
Bath
(mV)
Dye Bath
Alkalinity
(gpl)
Dwell
Length
(m)
Oxidation
Length (m)
Nip
Pressures
(psi)
471 32.00 18.20 66.70 2.094 12.12 838 3.42 9.70 38.90 95
Yarn Skein Response Variables
Yarn
Count
Dye
route Dips
Greige
Weight
Boil Off
Weight
Dyed
Weight
Washed
Weight %COWY
Total
%IOWY
Surface
%IOWY Integ
Penetration
Level
6.3 1 only 1 7.9307 7.5955 7.9387 7.585 4.52% 0.333% 0.746% 17.5 0.45
6.3 1--2 2 8.2671 7.9191 8.3645 7.9288 5.62% 0.631% 1.248% 35.3 0.51
6.3 1--3 3 7.9353 7.5908 8.0965 7.6303 6.66% 0.996% 2.267% 51.3 0.44
6.3 1--4 4 7.6814 7.3619 7.8528 7.4163 6.67% 1.286% 3.834% 66.1 0.34
6.3 1--5 5 8.2861 7.9359 8.4814 8.0135 6.87% 1.602% 5.328% 76.2 0.30
6.3 1--6 6 7.9222 7.5824 8.0857 7.6956 6.64% 1.973% 7.164% 85.2 0.28

% Reflectance Readings


Wave-
length
(nm) Dip 1 Dip 2 Dip 3 Dip 4 Dip 5 Dip 6 Dip 7
400 12.93 8.01 5.89 4.38 3.62 3.02
420 17.05 10.81 7.71 5.58 4.52 3.64
440 16.03 9.84 6.81 4.88 3.93 3.16
460 13.84 8.22 5.61 4.02 3.24 2.63
480 12.07 6.81 4.58 3.28 2.65 2.16
500 10.67 5.84 3.87 2.79 2.29 1.89
520 9.05 4.71 3.12 2.27 1.89 1.61
540 7.30 3.71 2.48 1.85 1.58 1.40
560 6.21 3.13 2.12 1.63 1.43 1.31
580 5.15 2.60 1.82 1.46 1.31 1.22
600 4.25 2.20 1.60 1.34 1.23 1.18
620 3.62 1.94 1.47 1.28 1.20 1.18
640 3.09 1.77 1.43 1.29 1.23 1.25
660 2.93 1.76 1.48 1.36 1.34 1.38
680 3.88 2.31 1.85 1.65 1.59 1.62
700 8.91 5.01 3.64 2.88 2.54 2.30
404

Table A-5-1: Continued

Shade
ID
Speed
(m/min)
Dwell
Time
(sec)
Oxidation
Time (sec)
Dye Bath
(gpl
100%
Indigo)
Dye
Bath pH
Dye
Bath
(mV)
Dye Bath
Alkalinity
(gpl)
Dwell
Length
(m)
Oxidation
Length (m)
Nip
Pressures
(psi)
471 32.00 18.20 66.70 2.094 12.12 838 3.42 9.70 38.90 95
Yarn Skein Response Variables
Yarn
Count
Dye
route Dips
Greige
Weight
Boil Off
Weight
Dyed
Weight
Washed
Weight %COWY
Total
%IOWY
Surface
%IOWY Integ
Penetration
Level
7.1 1 only 1 7.0215 7.0117 7.3237 6.9992 4.45% 0.375% 0.782% 19.1 0.48
7.1 1--2 2 7.0354 7.0328 7.4309 7.0457 5.66% 0.655% 1.379% 38.1 0.48
7.1 1--3 3 7.2442 7.2045 7.6625 7.2414 6.36% 0.951% 2.484% 53.8 0.38
7.1 1--4 4 7.0342 7.0233 7.4485 7.0942 6.05% 1.493% 4.629% 71.9 0.32
7.1 1--5 5 7.0837 7.0282 7.5511 7.1115 7.44% 1.714% 5.414% 76.7 0.32
7.1 1--6 6 7.0648 6.9459 7.4152 7.0605 6.76% 2.162% 7.680% 87.3 0.28

% Reflectance Readings


Wave-
length
(nm) Dip 1 Dip 2 Dip 3 Dip 4 Dip 5 Dip 6 Dip 7
400 12.52 7.66 5.72 4.01 3.60 2.96
420 16.58 10.35 7.42 5.04 4.43 3.57
440 15.52 9.33 6.55 4.38 3.84 3.08
460 13.32 7.76 5.40 3.59 3.17 2.57
480 11.56 6.39 4.40 2.93 2.59 2.11
500 10.18 5.45 3.73 2.49 2.23 1.85
520 8.54 4.38 3.00 2.04 1.85 1.57
540 6.84 3.44 2.37 1.67 1.56 1.36
560 5.75 2.90 2.02 1.50 1.42 1.27
580 4.73 2.41 1.74 1.36 1.31 1.20
600 3.88 2.05 1.53 1.27 1.24 1.16
620 3.30 1.82 1.42 1.23 1.22 1.16
640 2.82 1.68 1.37 1.27 1.26 1.23
660 2.68 1.68 1.42 1.37 1.37 1.36
680 3.55 2.18 1.78 1.64 1.63 1.60
700 8.41 4.63 3.47 2.71 2.51 2.25
405

Table A-5-1: Continued

Shade
ID
Speed
(m/min)
Dwell
Time
(sec)
Oxidation
Time (sec)
Dye Bath
(gpl
100%
Indigo)
Dye
Bath pH
Dye
Bath
(mV)
Dye Bath
Alkalinity
(gpl)
Dwell
Length
(m)
Oxidation
Length (m)
Nip
Pressures
(psi)
471 32.00 18.20 66.70 2.094 12.12 838 3.42 9.70 38.90 95
Yarn Skein Response Variables
Yarn
Count
Dye
route Dips
Greige
Weight
Boil Off
Weight
Dyed
Weight
Washed
Weight %COWY
Total
%IOWY
Surface
%IOWY Integ
Penetration
Level
12 1 only 1 6.1779 5.7167 5.9994 5.7123 4.95% 0.398% 0.772% 18.7 0.52
12 1--2 2 5.9573 5.7311 6.1273 5.7502 6.91% 0.755% 1.384% 38.2 0.55
12 1--3 3 6.0513 5.8758 6.2831 5.9182 6.93% 1.136% 2.339% 52.1 0.49
12 1--4 4 5.9588 5.7315 6.1815 5.8074 7.85% 1.607% 4.211% 69.0 0.38
12 1--6 6 5.8451 5.6216 6.1025 5.7299 8.55% 2.210% 6.725% 83.3 0.33
12 1--6 6 6.0562 5.8765 6.3204 5.9896 7.55% 2.330% 6.360% 81.6 0.37

% Reflectance Readings


Wave-
length
(nm) Dip 1 Dip 2 Dip 3 Dip 4 Dip 6 Dip 6 Dip 7
400 12.59 7.72 5.83 4.21 3.21 3.17
420 16.56 10.38 7.58 5.30 3.94 3.86
440 15.47 9.36 6.68 4.62 3.40 3.34
460 13.28 7.78 5.49 3.79 2.83 2.78
480 11.53 6.41 4.48 3.10 2.32 2.29
500 10.20 5.47 3.80 2.64 2.03 2.00
520 8.60 4.41 3.07 2.16 1.68 1.69
540 6.94 3.47 2.44 1.76 1.43 1.45
560 5.88 2.92 2.09 1.57 1.32 1.35
580 4.85 2.41 1.80 1.41 1.22 1.27
600 4.01 2.03 1.58 1.30 1.17 1.23
620 3.41 1.80 1.46 1.25 1.16 1.22
640 2.93 1.65 1.43 1.26 1.22 1.29
660 2.81 1.65 1.48 1.36 1.35 1.43
680 3.72 2.17 1.86 1.63 1.57 1.67
700 8.49 4.69 3.59 2.77 2.36 2.39
406

Table A-5-1: Continued

Shade
ID
Speed
(m/min)
Dwell
Time
(sec)
Oxidation
Time (sec)
Dye Bath
(gpl
100%
Indigo)
Dye
Bath pH
Dye
Bath
(mV)
Dye Bath
Alkalinity
(gpl)
Dwell
Length
(m)
Oxidation
Length (m)
Nip
Pressures
(psi)
401 28.00 20.80 76.30 2.211 12.11 820 3.72 9.70 38.90 95
Yarn Skein Response Variables
Yarn
Count
Dye
route Dips
Greige
Weight
Boil Off
Weight
Dyed
Weight
Washed
Weight %COWY
Total
%IOWY
Surface
%IOWY Integ
Penetration
Level
8 1 only 1 9.3795 9.0347 9.4691 9.0311 3.76% 0.422% 0.827% 21.2 0.51
8 1--2 2 9.3241 8.9773 9.5306 9.013 5.10% 0.751% 1.481% 40.1 0.51
8 1--3 3 9.2045 8.8731 9.4807 8.9362 5.78% 1.178% 2.841% 57.5 0.41
8 1--4 4 9.2051 8.8685 9.492 8.967 5.96% 1.573% 4.330% 69.8 0.36
8 1--6 6 9.1474 8.8177 9.5895 8.9952 7.67% 2.379% 7.711% 87.4 0.31


% Reflectance Readings

Wave-
length
(nm) Dip 1 Dip 2 Dip 3 Dip 4 Dip 5 Dip 6 Dip 7
400 11.81 7.38 5.31 4.17 2.97
420 15.74 9.97 6.80 5.25 3.55
440 14.62 8.94 5.97 4.56 3.08
460 12.45 7.41 4.89 3.74 2.58
480 10.69 6.06 3.96 3.04 2.13
500 9.34 5.15 3.36 2.60 1.87
520 7.73 4.11 2.71 2.12 1.58
540 6.14 3.24 2.16 1.73 1.36
560 5.19 2.75 1.88 1.55 1.28
580 4.29 2.32 1.66 1.41 1.21
600 3.53 1.97 1.48 1.30 1.16
620 2.99 1.75 1.36 1.23 1.13
640 2.57 1.62 1.34 1.24 1.16
660 2.48 1.66 1.44 1.36 1.30
680 3.24 2.06 1.71 1.58 1.48
700 7.82 4.44 3.24 2.70 2.15