Escolar Documentos
Profissional Documentos
Cultura Documentos
(DSC)
Basic Theory &
Applications Training
2009 TA Instruments
Agenda
Understanding DSC
Experimental Design
Calibration
Optimization of DSC Conditions
Interpretation of Undesirable Events in DSC Data
Applications
DSC 2010
DSC 2910
DSC 2920
Q1000
Q100
Q10
DSC Training Course
Q2000
Q200
AutoQ20
Agenda
0 .0
-0 .1
-0 .2
-0 .3
-0 .4
Endothermic
25
50
75
E xo U p
100
125
150
T e m p e r a tu re ( C )
0 .1
0 .0
-0 .1
0
20
Exo U p
40
60
80
100
120
140
160
T e m pe ra tu re ( C )
Temperature
Sample Platform
Chromel Area Detector
Reference Platform
Constantan Body
Base Surface
Constantan Wire
Chromel Wire
Chromel Wire
Temperature
Temperature
dH
dT
= Cp
+ f (T, t)
dt
dt
dT
= Heating Rate
dt
Agenda
Sample Pan
Thermoelectric Disc
(Constantan)
Chromel
Disc
Chromel
Disc
Heating
Block
Chromel Wire
Alumel Wire
Thermocouple
Junction
Perfectly Symmetrical?
Heat Flow
Measurement Model
qs
qs =
qr
T fs Ts
Rs
qr =
T fr Tr
Rr
Ts
Tr
Rs
Rr
q = q s qr
q=
Tfs
Tfr
Tr Ts T
=
R
R
This model assumes that the sample and reference calorimeter thermal resistances
are identical, the temperature of the furnace at the sample and reference
calorimeters are equal and does not include other known heat flows.
DSC Training Course
10
11
Violations of Assumptions
Pan and calorimeter heat capacities are ignored
Rs
Rr
Ts
Cs
Q = Ts - Tr
R
Tfr
Tr
Thermal
Resistance
Imbalance
Cr
B
Thermal
Capacitance
Imbalance
Not Being
Measured w/
Conventional
DSC
C
Heating
Rate
Imbalance
12
Agenda
Tzero
Thermocouple
13
Tf
Rs
Rr
Ts
Tr
To
Cs
Cr
Sample Platform
Chromel Area Detector
Reference Platform
Constantan Body
Base Surface
Constantan Wire
Chromel Wire
Chromel Wire
qs
Cs
Differential Temperatures
T = Ts Tr
qr
T0 = T0 Ts
Cr
Tr
Ts
dT
0
R r qs = R Cs dt
s
Rs
qr =
T0
T0 + T
dT
Cr
Rr
dt
The sample and reference calorimeter thermal resistances and heat capacities
obtained from Tzero calibration are used in the heat flow rate measurements.
14
qT 4 =
Thermal Resistance
Imbalance
Heating Rate
Difference
1
dT
dT
T
1
+ T0 + (Cr C s ) s Cr
Rr
d
d
Rs Rr
Principal DSC
Heat Flow
Heat Capacity
Imbalance
The four term Tzero heat flow rate measurement includes effects of the thermal
resistance and heat capacity imbalances as well as the difference in the heating
rates of the sample and reference calorimeters. When the assumptions of
conventional DSC are applied, only the first term remains and the conventional
heat flow rate measurement is obtained.
DSC Training Course
qs
C
Tr
Ts
R
Rr
T0
q=
1
T
1
dT
dT
+ T0 + (Cr Cs ) s Cr
Rr
d
d
Rs Rr
15
qs
C
Tr
Ts
R
Rr
q=
1
T
1
dT
dT
+ T0 + (Cr Cs ) s Cr
Rr
d
d
Rs Rr
16
17
50
50
40
40
-100
100
200
0.05
0.04
0.04
0.03
0.03
0.02
0.02
60
60
Characteristics
of the thermal resistances and heat capacities:
70
Both curves should be smooth, with no steps, spikes or inflection points.
Thermal resistances should always have negative slope that gradually decreases.
Heat capacities should always have positive slope that gradually decreases.
0.01
300
Temperature (C)
18
Agenda
19
Conventional Baseline
T zero Baseline
0.4
0.2
0.0
-0.2
-0.4
-100
100
200
300
400
Temperature (C)
50
4.94C
5.40W
-29.38C
31.23W
-50
-100
-50
Exo Up
50
100
150
200
250
300
350
Temperature (C)
20
Agenda
21
Advanced Tzero
model includes
the pans
Q2000
m pr c pan
m ps c pan
T ps
Rp
qs
Q200
Rp
qr
Ts
Tr
Cr
Cs
Cpan
Rp
Rs
T pr
Rs
Rr
T0
Heat Flow
Heat Flow Sensor
22
Q1000
Q100
Q10
23
Q1000
Q100
Q10
-5
Peak
Height Increases
Peak Width Decreases
Height/Width Increases
Height
-10
-15
-20
Width at Half-Height
-25
-30
140
145
150
155
160
165
170
175
180
Temperature (C)
24
Improved Sensitivity/Resolution-Q2000
2
-2
-4
Q2000
Tzero Pan
(Tzero pan)
-6
Standard Pan
Q1000
-8
-10
-12
154
155
Exo Up
156
157
158
159
160
Temperature (C)
Q100/200
Q1000/2000
1st Generation
Q-Series
7.50.4
20.82.1
36.34.4
2nd Generation
Q-Series
8.40.4
303.4
608
Improvement
12%
44%
65%
25
Definitions
Definitions (cont.)
26
Definitions (cont.)
Definitions (cont.)
27
Crystallization
Melting
Glass
Transition
Cross-Linking
(Cure)
Composite graph
Temperature
Experimental Design
28
29
Start Temperature
End Temperature
-0.5
-1.0
-1.5
Wax 10C/min
-2.0
-2.5
20
Exo Up
40
60
80
100
Temperature (C)
120
140
160
Universal V3.9A TA Instruments
30
Heating/Cooling Methods
Typical Heating Method
1) Equilibrate at 0C
2) Ramp 10C/min. to 300C
Heat-Cool-Reheat Method
Typical Heat-Cool-Heat Method
1)
2)
3)
4)
5)
6)
7)
Equilibrate @ 25C
Ramp 10C/min. to 300C
Mark cycle end 0
Ramp 10C/min. to 25C
Mark cycle end 0
Ramp 10C/min. to 300C
Mark cycle end 0
31
Equilibrate at 60C
Isothermal for 5.00 min.
Ramp 20C/min. to 200C
Isothermal for 5.00 min.
Select gas: 2
Abort next seg. if W/g > 1.0
Isothermal for 200.00 min.
32
Instrument Calibration
Miscellaneous
Purge Gas
Cooling Accessories
Environment
Sample Preparation
Selecting Experimental Conditions
33
Calibration
Verification
Miscellaneous
34
Premelt
Calorimetric Calibration
5
157.44C
-5
-10
Cell Const.: 1.0766
Onset Slope: -20.82 mW/C
-15
150
155
160
Temperature (C)
165
170
35
Temperature Calibration
Temperature Calibration
0
Heat Flow (W/g)
50
Extrapolated Onset
156.61C
28.36J/g
40
-1
30
-2
20
-3
HEATING RATE
10
-4
157.09C
PEAK
-5
150
152
154
156
158
160
Temperature (C)
0
162
164
36
Temperature Calibration
Enthalpy
(cell constant)
Temperature
Cyclopentane* -150.77C
Cyclopentane* -135.09C
Cyclopentane* -93.43C
Cyclohexane# -83C
Water# 0C
Gallium# 29.76C
Phenyl Ether# 30C
p-NitrotolueneE 51.45C
NaphthaleneE 80.25C
Indium# 156.60C
Tin# 231.95C
Lead* 327.46C
Zinc# 419.53C
* GEFTA recommended
Thermochim. Acta, 219 (1993) 333.
# ITS 90 Fixed Point
E Zone refined organic compound
(sublimes)
37
= T4
Q20/10
= T1
38
T4P & T4
Calibration
Select which
calibration to perform
Tzero Calibration
T4P & T4
Calibration
39
T4P & T4
Calibration
Start experiment
DSC Training Course
T4P & T4
Calibration
40
T4P & T4
Calibration
T4P & T4
Calibration
41
T4P & T4
Calibration
T4P & T4
Calibration
Start experiment
DSC Training Course
42
T4P & T4
Calibration
Data is analyzed
automatically
T4P & T4
Calibration
43
Baseline Calibration
Slope
Curvature
44
Baseline Curvature
0.6
Conventional Baseline
T zero Baseline
0.4
0.2
0.0
-0.2
-0.4
-100
100
200
300
400
Temperature (C)
45
T1 Calibration
T1 Calibration
Select type of
calibration to run
46
T1 Baseline Cal
Enter parameters
Step 1 of 11
T1 Baseline Cal
Review summary
Step 2 of 11
47
T1 Baseline Cal
Enter sample
information
Step 3 of 11
T1 Baseline Cal
Finish entering
sample information
Step 4 of 11
48
T1 Baseline Cal
Review checklist
Step 5 of 11
T1 Baseline Cal
49
T1 Baseline Cal
Step 7 of 11
T1 Baseline Cal
File is opened
automatically
Step 8 of 11
50
T1 Baseline Cal
T1 Baseline Cal
Click on Accept
to save calibration
Step 10 of 11
51
T1 Baseline Cal
Step 11 of 11
T1 Calibration
Select type of
calibration to run
52
T1 Temperature Cal
Enter parameters
Step 1 of 7
T1 Temperature Cal
Review summary
Step 2 of 7
53
T1 Temperature Cal
Enter sample
information
Step 3 of 7
T1 Temperature Cal
Finish entering
sample information
Step 4 of 7
54
T1 Temperature Cal
Review checklist
Step 5 of 7
T1 Temperature Cal
Step 6 of 7
55
T1 Temperature Cal
Step 7 of 7
SRM 2232
SRM 2220
SRM 2222
SRM 2225
Indium
Tin
Biphenyl
Mercury
Tm = 156.5985C
Tm = 231.95C
Tm = 69.41C
Tm = -38.70C
Phone: 301-975-6776
Fax: 301-948-3730
Email: SRMINFO@nist.gov
Website: http://ts.nist.gov/srm
56
57
Verifying Baseline
Standard mode
Empty cell, -90C-400C (w/ RCS)
Plot mW vs. temperature on a 1mW scale
Verifying Baseline
0 .4
0 .2
0 .0
-0 .2
-0 .4
-1 0 0
100
200
300
400
Tem perature (C )
58
Verifying Baseline
0 .5
0 .4
0 .3
1 7 6 .6 6 C
0 .0 2 1 3 8 m W
0 .2
2 1 m ic ro W b o w
4 2 m ic ro W d r ift
0 .1
0 .0
-0 .0 0 3 2 5 2 m W
-0 .1
-0 .0 4 5 6 2 m W
-0 .2
-0 .3
-0 .4
-0 .5
-1 0 0
100
200
300
400
T e m p e ra tu re (C )
Verifying Baseline
0.4
0.2
-0.4
-100
100
200
300
400
Tem perature (C )
59
Verifying Baseline
0.4
0.2
-0.4
-100
100
200
300
400
Tem perature (C )
Melting of In 156.6C
Heat of Fusion 28.71J/g
60
1 5 6 .6 4 C
-2 8 .6 0 J /g
0
-5
Temp is within
0.04C
-1 0
Heat of fusion is
within 0.11J/g
-1 5
-2 0
1 5 7 .0 6 C
-2 5
140
145
150
155
160
165
170
175
180
Te m pe ra ture (C )
61
Platinum Software
DSC
62
Perform a
diagnostic check of
the instrument
List based on
options (e.g.,
Autosampler, MFC,
Cooler Type)
63
Event Scheduler
Temperature Calibration
Up to 5 temperature standards
64
Instrument Preparation
Purge Gas
Type of purge gas and flow rate affect calibration and therefore
should be controlled
Nitrogen is preferred because it is inert and calibration is least
affected by changes in flow rate
Cooling Accessories
Warm-up Time/Environment
65
Purge Port
All TA DSCs
50(N2) or 25(He)
(Purge in ml/min)
If you have a 2900s DSC, purge the vacuum port with 50ml/min
if using a RCS or LNCA.
If purge gas is too slow - possible moisture accumulation &
early aging of the cell
If purge gas is too fast excessive noise
DSC Training Course
66
67
Volatile content
Decomposition temperature
DSC results are of little value once the sample has lost 5% weight due
to decomposition (not desolvation)
Decomposition is a kinetic process (time + temperature dependent).
The measured decomposition temperature will shift to lower
temperatures at lower heat rates
68
Maximum Temperature
Sample Preparation
69
0.5
0.0
-0.5
69.41C
73.37C(H)
+ 0.4881mW
-1.0
143.70C
34.95J/g
-1.5
-2.0
40
60
80
100
120
140
Temperature
160
180
200
220
(oC)
70
Use sealed glass ampoules or stainless steel pans, which can take
high pressure (>1000psi), in order to study decomposition by DSC
Sample Pans
Sample form
Volatilization
Temperature range
71
Aluminum:
Copper:
Gold:
up to 600C
up to 725C (in N2)
up to 725C
Graphite:
Platinum:
72
73
Thermocouple Output
Magnitude of T
Signal/Noise
Baseline Quality
Resolution
74
Standard Lid
Small samples
High Sensitivity
Tzero
Hermetic Lid
Tzero Lid
Larger Samples
High Performance
Tzero
Low-Mass Pan
Hermetic seals
Tzero Pan
75
Monohydrate
Pharmaceutical
sample
76
Sample Shape
Sample Shape
77
Sample Shape
78
79
Heat cell to 200C for 10 min to drive off any remaining solvent
Solvents are Last Resort for 2900 Series
Clean w/ brush
80
81
Air purge
Open lid
Heat @ 20C/min to appropriate temp (max of 550C) No
Isothermal @ the upper temperature
Cool back to room temp & brush cell again
82
http://www.tainstruments.com/
83
Interpretation of Undesirable
Events in DSC Data
2009 TA Instruments
Topics
84
Figure 5
85
Event 3 (cont.)
When water condenses in the cell, it can condense on the sample
Event 3 (cont.)
86
Event 3 (cont.)
Water in the Sample
Many samples contain water and, therefore, can
undergo a transition near 0C due to this water.
However, just because the sample contains water does
not mean it will have a melting transition near 0C.
Water that is physically or chemically associated with
sample material generally will not freeze and, therefore,
cannot melt.
Unassociated water or free water in the sample has
the same properties as bulk water. However, the actual
melting point is often lower than 0C due to impurities
dissolved in the water.
DSC Training Course
Figure 5
87
Event 4 (cont.)
An exothermic shift (less endothermic) in the baseline while
heating results in the baseline moving back closer to zero (0
mW) heat flow. This type of shift is much less common and in
order for this to occur while heating, there must either be a
reduction in molecular mobility or a reduction in sample mass.
Most of the time, this type of positive shift is due to evaporation
of some component within the sample.
88
Event 4 (cont.)
Depending on the thermal history of amorphous (glassy)
Event 4 (cont.)
By heating a sample above the glass transition temperature and
89
Figure 6
90
Some Definitions
Enthalpic Relaxation
Enthalpic Recovery
91
Increases
Coefficient of
Expansion
Decreases
Heat Capacity
Decreases
Enthalpy
Decreases
Entropy
Decreases
Max Tg
V
Storage
time
H
M
S
Equilibrium
Liquid
Equilibrium
Glass
KauzmannTemp; Lowest Tg
(Entropy of Crystal)
Temperature
Where H = High relative cooling rate
M = Medium relative cooling rate
S = Slow relative cooling rate
Cooled @ 40C/min
PMMA
6.36mg
Heating @ 20C/min
Cooled @ 1C/min
92
Figure 7
Enthalpy/Volume Diagrams
ui
liq
Enthalpy or Volume
Tg
s
du
Equilibrium Conditions
Temperature
DSC Training Course
93
Enthalpy or Volume
Enthalpy/Volume Diagrams
Below Tg, there
is very little
molecular
mobility, so the
cooling rate will
determine
whether the
sample stays in
equilibrium
Tg
ui
liq
s
du
Equilibrium
Conditions
Temperature
DSC Training Course
For Example
Enthalpy or Volume
Tg
ui
liq
s
du
Non-equilibrium
states
1C/year
s
solidu
Equilibrium Conditions
Temperature
DSC Training Course
94
Enthalpy/Volume Diagrams
Enthalpy or Volume
Tg
Non-equilibrium states
Temperature
DSC Training Course
95
Figure 5
Events 5 and 6
Exothermic Peaks in the Data between the Tg and Melting Temperatures
3.
96
97
Figure 8
98
Figure 9
Figure 5
99
Event 7 (cont.)
100
Figure 10
Event 7 (cont.)
The question is: How can DSC provide such a wrong answer?
The answer is that it does not.
The error is due to the integration limits selected by the
operator.
Total signal of DSC is often misleading because it measures
only the sum of all exothermic and endothermic processes.
Figure 11 shows that slower heating rates provide more
exothermic (crystal perfection) activity in the temperature
region between 150 and 220C.
The increased crystal perfection that occurs at slower heating
rates causes the melting point to increase to higher
temperatures.
101
Figure 11
Event 7 (cont.)
The shape of the melting peak is also affected by
102
Figure 12
Figure 5
103
Event 8: Decomposition
Beginning at about 310C in Figure 1, the sample of PET begins
to decompose.
Depending on the chemistry of the sample and type of sample
pan used, decomposition can either be endothermic or
exothermic.
Decomposition usually involves a release of some volatiles. The
process of off-gasing is usually erratic, and the data can become
noisy and nonreproducible.
Decomposing samples in a DSC will adversely affect the baseline
and may corrode the DSC cell.
Applications
Thermoplastics
Thermosets
Pharmaceuticals
Heat Capacity
Glass Transition
Melting and Crystallization
Additional Applications Examples
104
Thermoplastic Polymers
Semi-Crystalline or Amorphous
Crystalline Phase
melting temperature Tm
(endothermic peak)
Amorphous Phase
glass transition
temperature (Tg)
(causing Cp)
Tg < Tm
Crystallizable polymer can crystallize
on cooling from the melt at Tc
(Tg < Tc < Tm)
DSC Training Course
Tg
Melting
Crystallization
Oxidative Induction Time (OIT)
General Recommendations
105
Thermoplastic Polymers
Heat/Cool/Heat
1.5
1.0
Cool
0.5
Second Heat
0.0
First Heat
-0.5
-1.0
-1.5
20
60
100
140
180
220
260
Temperature (C)
106
107
Thermosetting Polymers
A+B
GLUE
Tg
Curing
Residual Cure
General Recommendations
108
The greater the temperature difference between the Tg of the First and
Second Heats the lower the degree of cure of the sample as received
-0.08
First
155.93C
Tg
Residual Cure
-0.12
-0.16
Second
Tg
102.64C
20.38J/g
-0.20
-0.24
0
50
100
150
200
Temperature (C)
250
300
109
Determination of % Cure
2.0
DSC Conditions:
Heating Rate = 10C/min.
Temperature Range = -50C to 250C
N2 Purge = 50mL/min.
1.5
145.4J/g
54.55 % cured
1.0
Under-cured Sample
-12.61C(H)
0.5
79.33J/g
75.21 % cured
-5.27C(H)
0.0
Optimally-cured Sample
50
100
Temperature (C)
150
200
250
Universal V2.4F TA Instruments
110
Pharmaceuticals
Tg
Melting
Purity
Polymorphs
General Recommendations
111
10 min @ 55C
100 min
1000 min
Phenacetin
Hermetic Pan
Approx 1.5mg
112
1.0
Decomposition
0.5
60
Weight (%)
80
40
0.0
20
0
50
100
150
200
250
300
350
400
Temperature (C)
113
Sulfanilimide
Comparison of 1 & 10C/min Heating Rates on
Melting of three Polymorphs for Sulfanilimide
What is it?
114
115
Cp = [(dH/dt)/(dT/dt)] x K
K = calibration constant
116
HFS HFMT
Heat Rate x wt
HFMT
HF
Where:
K
= Calibration constant
HFS
endo
Temp.
HFS
= weight of sample
HFHR2 HFHR1
(HR2 HR1) wt
Where:
K
= Calibration constant
HFHR1 = Differential heat flow of
sample at HR1
HFHR2 = Differential heat flow of
sample at HR2
HR2 = Heating rate 2
HR1 = Heating rate 1
wt
= weight of sample
0
HFHR1
HF
HFHR2
endo
Temp.
117
Baseline is flat
Absolute zero heat flow value established as part of method
97.00C
0.9111J/g/C
1.0
97.00C
0.8758J/g/C
0.5
0.0
-0.5
50
100
Temperature (C)
150
200
Universal V3.1B TA Instruments
118
Amorphous Content
Aging
Side Chains
Polymer Backbone
Copolymer Composition
Anything that effects the mobility of the molecules,
affects the Heat Capacity
119
120
Glass Transitions
Polystyrene
2.0
-0.4
1.5
Heat Capacity
Heat Flow
-0.7
Temperature Below Tg
- lower Cp
- lower Volume
- lower CTE
- higher stiffness
- higher viscosity
- more brittle
- lower enthalpy
1.0
-0.6
-0.5
-0.8
-0.9
0.5
-1.0
70
Exo Up
90
110
Temperature (C)
121
Polystyrene
9.67mg
10C/min
122
Polystyrene
9.67mg
10C/min
123
Heating Rate
Heating & Cooling
Aging
Molecular Weight
Plasticizer
Filler
Crystalline Content
Copolymers
Side Chains
Polymer Backbone
Hydrogen Bonding
124
Use MDSC
Or use Quasi-Isothermal MDSC
125
Heat Flow @
80C
Tg
Onset (C)
Tg
Midpoint (C)
Width of
Tg (C)
2.5
-0.84
95.9
100.9
5.0
5.0
-1.66
96.0
102.0
6.0
10.0
-3.31
96.3
102.8
6.5
20.0
-6.62
98.3
105.1
6.8
126
Melting
Melting of Indium
0
-5
Extrapolated
Onset
Temperature
156.60C
28.50J/g
Indium
5.7mg
10C/min
Heat of
Fusion
-10
-15
-20
Peak Temperature
157.01C
-25
150
Exo Up
155
160
Temperature (C)
165
Universal V4.0B TA Instruments
127
Melting of PET
-1
Extrapolated
Onset
Temperature
-3
236.15C
52.19J/g
-4
Heat of
Fusion
-5
PET
6.79mg
10C/min
-6
Peak Temperature
-7
200
210
220
230
Exo Up
240
249.70C
250
260
270
Universal V4.0B TA Instruments
Temperature (C)
Comparison of Melting
0
-5
156.60C
28.50J/g
PET
6.79mg
10C/min
236.15C
52.19J/g
249.70C
-10
-15
Indium
5.7mg
10C/min
-20
157.01C
-25
140
160
Exo Up
180
200
220
Temperature (C)
240
260
280
Universal V4.0B TA Instruments
128
Analyzing/Interpreting Results
Baseline Due to Cp
129
Baseline Type
Where is the
Cp baseline?
130
Where is the
Cp baseline?
Where is the
Cp baseline?
131
Xenoy 13.44 mg
MDSC Heat-Only
Is this Melting?
Phenacetin
Hermetic Pan
Approx 1.5mg
132
Is this Melting?
Onset differs by
almost 30C
Melt
10C/min
50C/min
100C/min
2
150C/min
0
-40
40
80
120
160
Temperature (C)
200
240
280
133
DSC at 1C/min
DSC at 10C/min
DSC at 50C/min
99.3% Pure
Melting of
Eutectic Mixture
100% Pure
96.0% Pure
95.0% Pure
NBS 1514
Thermal Analysis
Purity Set
Approx. 1mg
Crimped Al Pans
2C/min
134
135.0
125.20C
137.75C
-1.2
-1.4
-1.8
-2.0
Purity: 99.53mol %
Melting Point: 134.92C (determ ined)
Depression: 0.25C
Delta H: 26.55kJ/mol (corrected)
Correction: 9.381%
Molecular Weight: 179.2g/mol
Cell Constant: 0.9770
Onset Slope: -10.14mW/C
RMS Deviation: 0.01C
134.0
-1.6
134.5
Temperature (C)
-1.0
133.5
-2
10
124
126
128
130
132
134
136
Exo Up
133.0
138
Temperature (C)
Calculation of % Crystallinity
135
ATHAS Databank
136
26.9kJ / mol
1000 = 140 J / g
192 g / mol
137
134.62C
0.5
75.43C
242.91C
74.71J/g
78.99C(I)
-0.5
80.62C
127.72C
53.39J/g
-1.0
50
100
256.24C
150
200
250
300
Temperature (C)
PET
1.0
134.62C
100
0.5
0.0
75.43C
242.91C
74.71J/g
78.99C(I)
-0.5
-1.0
80.62C
127.72C
53.39J/g
% crystallinity = 100* (
Hm - Hc)/ Hlit
256.24C
-1.5
50
100
150
200
250
300
Temperature (C)
138
PET % Crystallinity
PET % Crystallinity
139
0.5
60
0.0
40
-0.5
20
Integral (J/g)
Quenched PET
9.56mg
10C/min
1.0
134.63C
105.00C
275.00C
127.68C
0.6877J/g
-1.0
230.06C
71.96J/g
230.06C
-1.5
-50
Exo Up
50
100
150
Temperature (C)
200
250
300
350
Crystallization
140
Crystallization
Nucleation
Growth
Crystallization
141
Sample: PET
Weight: 10.66mg
crystallization
POLYPROPYLENE
WITHOUT
NUCLEATING AGENTS
POLYPROPYLENE
WITH NUCLEATING
AGENTS
1.5
0.0
1.0
-0.5
-1.0
melting
0.5
-1.5
60
80
Exo Up
0.0
40
50
Exo Up
100
120
140
160
180
200
Temperature (C)
60
70
80
90
100
110
120
130
140
150
160
Temperature (C)
142
Temperature
Melt Temperature
Isothermal Crystallization
Temperature
Zero Time
Time
Isothermal Crystallization
5
117.4 oC
Polypropylene
117.8 oC
118.3 oC
118.8 oC
119.3 oC
119.8 oC
120.3 oC
-1
Time (min)
143
Supercooling of Water
250
-4.36C
+
200
150
100
50
+
-15.55C
-50
-30
-25
-20
-15
-10
-5
10
Temperature (C)
144