PROCESS TRAINING

CRYSTALLIZATION

Milan K. Ghorai
Feb 2017
Confidential
AGENDA

1. Objectives & drivers

2. Steps of crystallization
3. R&D evaluation of optimization levers
4. Take-aways and applications
5. Conclusion
OBJECTIVES &
DRIVERS
 WHY CRYSTALLIZATION IS IMPORTANT?
Crystallized gypsum fraction

Good crystallization = elongated crystals

Confidential

Compromise must be found with other process constrains

 Fluidity
 Bond
 Cutting, knife rehydration
 …
How can we make these smalls crystals?
How much strength does it bring?
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 WHY CRYSTALLIZATION IS IMPORTANT?
Process & product optimizations

Board weight reduction

 Stabilize the process and reduce cost of additives
 Direct impact on compressive strength (NP), bond (flex), …
 Indirect impact on fluidity
Line speed increase

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Good rehydration at the knife while keeping good fluidity

Water gauge reduction
 Longer initial set with good knife hydration
Board defects
 Blisters, blows, core split, shatter end, soft boards, …
Other board properties
 Acoutics, stiffness, ….
Both process & product are linked to
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Dec 2016 of crystallization
 SCOPE OF THE STUDY
Process improvments

State-of-the art and previous works

 Separate works on accelerator, stucco grinding, ageing, process efficiency
 No real insight on micro-structure properties and strength

GPI/CREE approach
 Revisiting the fundamentals: dissolution, precipitation, growth, germination…
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 Work windowing combining setting times, WG, bond, stiffening, and final
microstructure
 Predicting optimal performances which be achieved through crystallization

Setting rate
Fundamental Board
Strength
phenomena strength
development

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2 – STEPS OF GYPSUM
CRYSTALLIZATION
 STEPS OF GYPSUM CRYSTALLIZATION
What happens during the set?
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 STEPS OF GYPSUM CRYSTALLIZATION
Fundamental phenomena

Dissolution Precipitation Growth

 Creates a reservoir of Calcium and  Induced by sursaturation  Leads to acicular crystals
Sulfate ions  Need germination sites
 Speed driven by precipitation
 Depends on surface area available
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 STEPS OF GYPSUM CRYSTALLIZATION
Along the board line

Disintegration Stiffening
In mixer
Extruder

Fast crystal
growth
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Cutter

Dry board End of

Final microstructure
rehydration
Dryer Z1 entry

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 EXPERIMENTAL TOOLS
Setting and microstructure characterization

Setting monitoring
 Stucco and slurry particle size
 TRS + residual hemihydrate content Thermocouple « Adiabatic » cell

 Rheology

Microstructure observation

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Freeze casting of gypsum during the set

 Residual hemihydrate particles
 Voids resulting from stucco dissolution
 Statistics on crystal length, width , aspect ratio Blade and cell

 B.E.T. surface area

Strength evaluation
 Ball indentation on dense gypsum bar
Freeze drying equipment

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 DISINTEGRATION
Stucco particle dispersion

Stucco particles break upon mixer

shear
 Fragilities generated by calcination cracks
 Create much finer granulometry than the
initial stucco
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 surface area x2 7 Platre VS

2s
6
5s
10s
5
20s
30s
Supersaturation of solution with Ca2+, 4

%
SO42- ions is instantaneous 3

 Quick dissolution of a very small fraction of 2

1
the smallest particles
0
 Does not depends on stucco 0,1 1 10
Grain Size [µm]
100 1000

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 SLURRY STIFFENING
Viscosity measurement
Liquid to paste transition
 Monitored via rheology : fast increase of slurry resistance to blade oscillation
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l
k
j
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 SLURRY STIFFENING
Visualization of percolation of gypsum crystals

Microstructure at percolation
 New technique: freeze casting of gypsum slurry and water evaporation
 High resolution SEM imaging

STUCCO GRAINS GYPSUM CRYSTALS

Confidential

Percolation at ~15% rehydration

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 MICROSTRUCTURE EVOLUTION
SEM and TRS monitoring
INITIAL FINAL
Setting kinetics
1,0 4

0,9
3,5
0,8
3

Temperature rate (°C/min)

0,7

Elastic modulus [MPa]

2,5
0,6

0,5 2

0,4
1,5
0,3
1
0,2
0,5
0,1

0,0 0
0 2 4 6 8 10 12 14
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Time [min]

Hemihydrate particles At max reaction speed Dissolution voids

Percolated crystals
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 END OF REHYDRATION
SEM and TRS monitoring Large grains
 Impurities
100µm  Undissolved plaster grains

Air bubbles
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Air bubbles

Dissolution voids
Lightweight board same size as initial large
Standard board (DSG)
plaster grains
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3 – LEVERS TO OPTIMIZE
KINETICS AND MATRIX
STRENGTH
 OPTIMIZATION OF KINETICS AND MATRIX STRENGTH
Tested in CREE 2013-2016

Additives
Accelerator
Retarders
Sulfate (Potash)
Other chemicals
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Stucco
Disintegration
Granulometry

Process
Slurry temperature

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 IMPACT OF GYPSUM ACCELERATOR
Impact on kinetics
Typical accelerator (gypsum seeds) provides high number of
germination sites
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KINETICS

• Non linear acceleration with increasing additive content

• Similar behavior for stiffening time
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 IMPACT OF GYPSUM ACCELERATOR
Typical formulation
Presence of HRA
Increasing amount of gypsum accelerator favors single needles
(rather than
MICROSTRUCTURE

Aspect ratio 4 8 9
agglomerates)
Number of gypsum
grains 
( of crystal size )
Doesn’t modify
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0% HRA 0,1% HRA 0,6% HRA significantly the crystal

aspect ratio
Indentation modulus vs HRA content
log( Indentation modulus in N/mm)
STRENGTH

500
0,1 1
log(HRA content in %)

More crystals + single needles  increased entanglement

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 IMPACT OF PLAST RETARD
Setting kinetics
0% 0,02% 0,05% 0,1% Range : 0-9 g/m²
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Inhibition of inital growth of crystals Retarding effect is LINEAR with PR content

Second part of setting curve remains Similar behavior for stiffening time
very fast

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 IMPACT OF PLAST RETARD
Impact at low concentration

-8%
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+50% +100%

Still linear and significant effect Constant strength up to 0,01% PR (~1g/m²)

on kinetics at low PR content Limited loss up to 0,02% PR (~2g/m²)

 Neutral impact at low dosage (<0,01%, 1g/m2)

 Reduce crystal aspect ratio and strength at high dosage
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 HRA/PLAST RETARD COMBINATION
For improved fluidity
Constant setting time with HRA in [0,1-2%] range (9-180g/m²)
and Plast Retard in [0,0045 – 0,05%] range (0,4 - 4 g/m²)
Setting time Strength
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Possible gain in strength with better fluidity at same set time

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 IMPACT OF ADDITIVES
Summary

HRA accelerator: more gypsum needles = higher entanglement

Non linear impacts (acceleration, strength increase)
Saturation effect at high content
 interest of combination with limited amount of K2SO4
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Retarder (Plast retard)

At high concentration, strength reduction via poor cristal aspect ratio
Up to 0,01% (0,9 g/m²), no significant impact on microstructure/strength despite 50%
retardation

Combination HRA/PR :
Modified initial setting without impacting end of rehydration
Possible increase of strength at high HRA/PR contents, to be confirmed

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 IMPACT OF STUCCO PARTICLE SIZE
Impact of disintegration on PSD

Disintegration increases with mixing

time and shear
 Destroy in coarse fraction (40-200µm)
 Enrichment in fine fraction (<10µm)
 Weak disintegration below ~30µm
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Effects
 Change fluidity, not so much stiffenning
 Limited or no effect on strength and
microstructure
Factors
 Mixer speed
 Residence time
side effect of mixing on filling rate,
residence time, …
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 IMPACT OF STUCCO PARTICLE SIZE
Plaster PSD

Three plaster fractions

Coarse: main peak ~50µm
Reference: d50=30µm
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Intermediate : 3µm-15µm
Fine (alpha): d50=2µm

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 IMPACT OF STUCCO PARTICLE SIZE
Setting kinetics

1/ Fluidity range 130-300mm

 Ref @ 180mm, with the same formulation

2/ Slowdown at the end of rehydration

 Better rehydration efficiency with less
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coarse

3/ Initial set: still under study

 Steeper slope at early advancement with
coarse fraction to be confirmed
 Plast Retard potency may depend on the
stucco surface area?

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 IMPACT OF PLASTER GRAIN SIZE
Strength

Improved strength with finer stucco

 Shape and number of crystals?
 Attributed mainly to absence of defects
linked to non-rehydrated stucco and
dissolution voids
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 IMPACT OF STUCCO PARTICLE SIZE
Microstructure

Standard Voids of similar size

Plaster PSD range to biggest initial
HH grains

Particle Size
Distribution
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INITIAL MICROSTRUCTURE FINAL MICROSTRUCTURE x1000

Less voids with small

No big plaster plaster grains
grains
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 W/P 80%
IMPACT OF SLURRY TEMPERATURE Vaujours CP1 plaster
Fluidifier Flube CA40F: 0,3%
At same formulation Plastretard: 0,01%
HRA: 0,2%

Slurry temperature decreased from 30°C to 9°C

Setting time
+65% Strength +20%
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Slower setting rate Better strength

Up to +20% in strength for 10 vs 30°C

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 PROCESS PARAMETERS
Summary
PARTICLE SIZE
● Removing big particles (>40-50µm)
  Lower fluidity
  Faster end of reaction : easier to reach 100% conversion before drier
  Higher strength
● Stucco PSD plays on all steps of gypsum crystallization
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 Effect is different from HRA contraction or Plast retard

TEMPERATURE
● Improved strength for colder slurries
 Need to have -5/10°C temperature reduction
 +15-20% for 15-30°C colder
● Retardation can be compensated by HRA
 Still slower end of setting  compensation by less coarse particles?

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 CONCLUSION
Matrix strength optimisation
HIGHER
STRENGTH
Less coarse
More HRA
LEVERS

particles
• More crystals • Lower average size, faster dissolution
• Smaller crystals • More homogeneous microstructure
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(no dissolution voids, no undissolved stucco)

Combination with By finer grinding

Retarder
IMPLEMENTATION

 Delayed stiffening  Faster hydration  Lower fluidity

without modification of before dryer
end of setting No slow down at end of setting

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IMPLICATIONS FOR
PLASTER BOARD
MANUFACTURING
 TARGETS FOR CRYSTALLIZATION
Sample analysis (R&D center)

Crystal shape (SEM)

 Number and density of crystals are the
important factors but difficult to extract
 Crystal length (6-10µm) & width (0,5-
~
1,2µm) are good indicators but not absolute
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Crystal surface area (B.E.T.)

 Relatively sensitive to the shape of
crystals , but error bar is important
 5 m2/g possible
~
 <2,5m2/g is bad, >3,5m2/g is good

Strength (indentation)
 Compressive strength of dense barrel 
can be measured

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 INDICATORS OF GOOD CRYSTALLIZATION
At plant side

Rehydration time (TRS)

 Calculate 50% and 100% setting times MRR2
MRR1
 Temperature rise slope (MRR) correlates more
or less with crystallization
 Range of 5 to 6°C/min is a sign or good crystallization
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Stiffening time (needle test)

 Reveals too much early crystallization
 Can be controlled via HRA/retarder ratio

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 LEVERS TO IMPROVE CRYSTALLIZATION Retarder
Accelerator

Too fluid
Accelerator addition Bad knife set
 Min 50% hydration at the cutter but can be Bad crystallization
(much) more
 70% for lightweight
 Sometimes 80 or 90% reported in some plants
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Accelerator/retarder addition Too viscous

 To allow more HRA addition at constant fluidity
 or To improve initial stiffening time and reduce
HRA
the water gauge
 Requires typically 20 to 30% more HRA than
standard dosage

Do you have the HRA milling capacity for that ?

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 LEVERS TO IMPROVE CRYSTALLIZATION
Stucco

Stucco granulometry: coarse reduction

 By grinding: main bottleneck is the fluidity,
lumps ..  balance between fines (<10µm)
and coarse (>60-80µm)
 Need to achieve a narrower granulometry
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How to reduce coarse fraction without increasing Surface area and WD?
Stucco granulometry fine tuning
 Depends on milling technology
 CP mill has limited flexibility, Pfeiffer and
hammer mills more accurate
 to be confirmed
 Balance between ageing and stucco PSD

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 INDICATOR OF GOOD CRYSTALLIZATION
Quality control – step 0

Standard stucco & additives parameters

 Good baseline to get medium or good crystallization

Parameter Typical range cf presentations

• Control plan SPA
Stucco Blaine 4,000-6,000 cm2/g • Bantam
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• Habito
Disintegration 9,000-11,000 cm2/g
Phases >80% HH
Storage/Ageing <3-4 hours
Slurry temperature <32°C
HRA Blaine >8,000cm2/g
MRR >5°C/min

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CONCLUSIONS
 CONCLUSIONS
Many impacts, many levers, many constraints

Crystallization has a practical importance in the process

 For compressive strength, pore morphology remains the 1st order parameter
The challenge is too optimize strength in acceptable process
conditions
 Smaller crystals can be made at fast hydration speed, then balance between
Confidential

strength and initial set

Fundamental phenomena are now understood, still some gaps
 Fine tuning of narrower particle size on-going
 Influence of some additives is not yet fully understood
At plant level
 Balance between fluidity and strength, for instance with retarder+HRA
 Respect of standard Control Plan targets should provide acceptable strength

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 CONCLUSIONS
Our process is challenging
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41 / Gypsum Process seminar Dec 2016 10m → 106 x 10µm ! 10µm

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Thank you!