Differential Scanning Calorimetry (DSC)

Theory and Experimental Conditions Glass Transition Melting and Crystallization Heat Capacity MDSC

DSC: The Technique

Differential Scanning Calorimetry (DSC) measures the temperatures and heat flows associated with transitions in materials as a function of time and temperature in a controlled atmosphere. These measurements provide quantitative and qualitative information about physical and chemical changes that involve endothermic or exothermic processes, or changes in heat capacity.

TA Instruments DSCs

DSC 2010

DSC 2910

DSC 2920

DSC: What DSC Can Tell You

Glass Transitions Melting and Boiling Points Crystallization time and temperature Percent Crystallinity Heats of Fusion and Reactions Specific Heat Oxidative/Thermal Stability Rate and Degree of Cure Reaction Kinetics Purity

DSC: Definitions
A calorimeter measures the heat into or out of a sample. A differential calorimeter measures the heat of a sample relative to a reference. A differential scanning calorimeter does all of the above and heats the sample with a linear temperature ramp. Endothermic heat flows into the sample. Exothermic heat flows out of the sample.

DSC: Heat Flow/Specific Heat Capacity

H = Cp T or in differential form dH/dt = Cp dT/dt + thermal events where: Cp = specific heat (J/gC) T = temperature (C) H = heat (J) dH/dt = heat flow (J/min.) mW = mJ/sec dT/dt = heating rate (C/min.)
assuming work & mass loss are zero

DSC: Measurement of HF and T Sample Ref

constantan Cu-Ni chromel alumel Ni-Cr Ni-Al Ag furnace

Platinel Control Thermocouple

DSC: Temperature Measurement Sample Ref

Sample Temperature Ts

Furnace Temperature

DSC: Heat Flow Measurement

Sample Ref

Potential Difference U Temperature Difference T Heat Flow dQ/dt

Alumel wire (sample temp)

Chromel wires (T)

DSC: Cell Schematic Diagram

Dynamic Sample Chamber Reference Pan Sample Pan

Lid

Gas Purge Inlet

Chromel Disc Heating Block

Chromel Disc

Alumel Wire Chromel Wire

Thermocouple Junction Thermoelectric Disc (Constantan)

DSC: Cell Components

Silver Furnace: Sample Purge: for good temperature uniformity for excellent oxidative stability measurements

Purge Preheated: for very low noise from turbulence Air Cool: for fast return to room temperature

DSC: Heat Flux Principle

The differential temperature ( T ) between the sample and reference is converted to differential heat flow in a way that is analogous to current flow in Ohms Law.
I = E/R where: I = current E = voltage (potential) R = electrical resistance

Heat Flow =

T R

k 1 k 2 where: T = temperature difference (potential) R = thermal resistance of constantan disk k 1 = factory-set calibration value k 2 = user-set calibration value

DSC: How Heat Flux is Measured temperature difference T. The temperature difference is measured as the voltage difference U between the sample and reference constantan/chromel junctions. The voltage is adjusted for thermocouple response S and is proportional to heat flow. T = U / S T in C U in V S in V/C
Heat flow through the chromel wafer causes a

DSC: Related Instrumentation

Modulated DSC (MDSC) : sinusoidal oscillation superimposed on linear temperature ramp Differential Thermal Analysis (DTA) Pressure DSC (PDSC) Differential Photocalorimetry (DPC) Dual Sample DSC SDT 2960 Simultaneous DSC-TGA

DTA

Differential Thermal Analysis (DTA) : measures the temperatures and temperature differences (between sample and reference) associated with transitions in materials as a function of time and temperature in a controlled atmosphere

PDSC

Pressure DSC (PDSC) : capability of operating at elevated pressure or at a vacuum (TAI PDSC: 1 Pa - 7 Mpa)

DPC & Dual Sample DSC

Differential Photocalorimetry (DPC) : sample is exposed to UV/Vis radiation

Dual Sample DSC: Allows two samples to be ran simultaneously

SDT 2960

SDT 2960 Simultaneous DSC-TGA: measures heat flow and weight changes simultaneously

DSC: Heat Flow Measurements

Calorimeter Signals Time Temperature Heat Flow Signal Change Heat Flow, absolute Heat Flow, shift Exothermic Peak Endothermic Peak Isothermal Onset Properties Measured Specific Heat Glass Transition Crystallization or Cure Melting Oxidative Stability

DSC: Typical DSC Transitions

Heat Flow -> exothermic

Oxidation or Decomposition

Melting Glass Transition Crystallization Cross-Linking (Cure)

Temperature

DSC: Experimental Design

Available Method Segments Method Design Rules Typical Methods (Examples)

DSC: Available Method Segments

JUMP EQUILIBRATE INITIAL TEMPERATURE RAMP ISOTHERMAL ISO-TRACK STEP INCREMENT REPEAT SEGMENT x FOR y TIMES REPEAT SEGMENT x TILL y C * Available on DSC 29XX only # Available on MDSC 29XX only ABORT NEXT SEG* SAMPLING INTERVAL SELECT GAS EXTERNAL EVENT DATA STORAGE AIR COOL* LNCA CONTROL* MARK END OF CYCLE* MODULATE#

DSC: Method Design Rules

Start Temperature Generally, the baseline should have three (3) minutes to completely stabilize prior to the transition of interest. Therefore, at 10C/min., start at least 30C below the transition onset temperature End Temperature Allow a three (3) minute baseline after the transition of interest in order to correctly select integration or analysis limits

DSC: Heating/Cooling Method

Heating Method (NOTE: No equilibrate segment necessary if starting at or near ambient temperature.) 1) Ramp 10C/min. to 300C Cooling Method 1) Equilibrate at 300C 2) Ramp 10C/min. to 25C

DSC: Heat-Cool-Reheat Method

Heat-Cool-Reheat Method 1) 2) 3) 4) 5) 6) 7) LNCA control: High 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

The first segment in this method allows for rapid cooling

DSC: Oxidative Stability (OIT) Method

OIT Method 1) 2) 3) 4) 5) 6) 7) Equilibrate at 60C Isothermal for 5.00 min. Ramp 20C/min. to 200C Isothermal for 5.00 min. Abort next seg. if W/g > 1.0 Select gas: 2 Iso-track for 200.00 min.

DSC: Modulated DSC Method

MDSC Method 1) 2) 3) 4) 5) 6) Data storage: off Equilibrate at -20C Modulate 1C every 60 seconds Isothermal for 5.00 min. Data storage: on Ramp 3C/min. to 300C

DSC: Calibration & Sample Preparation

Instrument Calibration Differential Heat Flow (Cell Constant) Temperature Baseline Miscellaneous Purge Gas Cooling Accessories Environment Sample Preparation Selecting Experimental Conditions Routine Maintenance/Sample Press

DSC: Heat Flow Calibration

Differential Heat Flow (ASTM E968) Heat of fusion (melting) standards Heat capacity (no transition) Miscellaneous Use specific purge gas at specified rate Calibrate w/cooling accessory functioning if it will be used to run samples Single point used for heat of fusion which is typically accurate to +/- 1-2% from -50C to 350C Calibration should not change w/heating rate

DSC: Heat Flow Calibration

Prepare a 10 to 15 mg. sample of indium and premelt prior to first use Use this sample a maximum of 10 times Calibrate at least once a month Typical values for cell constant: 1.0 to 1.2

DSC: Calorimetric Calibration

5
157.44C

0 Heat Flow (mW)

-5

Sample: Indium, 5.95 mg. CALIBRATION MODE; 10C/MIN CALIBRATION BASED ON 28.42J/g

-10
Cell Const.: 1.0766 Onset Slope: -20.82 mW/C

-15 150 155 160 165 170

DSC: Temperature Calibration

ASTM Method E967 Pure metals (indium, lead, etc.) typically used Extrapolated onset is used as melting temperature Sample is fully melted at the peak Miscellaneous With metal standards, calibration should change very little with heating rate With metal standards, it is not practical to calibrate for changes in heating rate on polymer samples

DSC: Temperature Calibration

1 0 Heat Flow (W/g) -1 30 -2 20 -3
HEATING RATE Extrapolated Onset 156.61C 28.36J/g

50 40 Deriv. Temperature (C/min)

-4 -5 150 152 154 156

10
157.09C PEAK

0 162 164

158

160

DSC: Temperature Calibration

Calibrate at least once a month Use at least two calibration points up to a maximum of five points Use tin, lead, and zinc one time only

DSC: Recommended Temperature & Enthalpy Standards

Enthalpy (cell constant)
Benzoic acid (147.3 J/g) Tm = 123C Urea (241.8 J/g) Tm = 133C Indium (28.45 J/g) Tm = 156.6C Anthracene (161.9 J/g) Tm = 216C

Temperature

Cyclopentane* -150.77C Cyclopentane* -135.09C Cyclopentane* -93.43C Cyclohexane# -83C Water# 0C Gallium# 29.76C Phenyl Ether# 30C p-Nitrotoluene 51.45C Naphthalene 80.25C Indium# 156.60C Tin# 231.95C

* GEFTA recommended Thermochim. Acta, 219 (1993) 333. # ITS 90 Fixed Point Zone refined organic compound (sublimes)

DSC: Traceable Calibration Materials

NIST DSC calibration materials: SRM 2232 Indium Tm = 156.5985C SRM 2220 Tin Tm = 231.95C SRM 2222 Biphenyl Tm = 69.41C SRM 2225 Mercury Tm = -38.70C SRM 2221b Zinc Tm = In Preparation NIST: Gaithersburg, MD 20899-0001 Phone: 301-975-6776 Fax: 301-948-3730 Email: [email protected] www: HTTP://ts.nist.gov/srm

DSC: Traceable Calibration Materials

LGC DSC Calibration Materials: LGC2601: Indium (TA p/n: 915060-901) LGC2608: Lead LGC2609: Tin LGC2611: Zinc Laboratory of the Government Chemist, UK Phone: 44 (0) 181 943 7565 Fax: 44 (0) 181 943 7554 Email: [email protected]

DSC: Traceable Calibration Materials

Certified materials used to establish traceability of instrument calibration ISO/GLP certification often requires third party calibration of instruments: Service provided by TA Instruments service representative using certified materials Certificate of Calibration issued showing traceability of calibration to a national laboratory

DSC: Effect of Heating Rate on Indium Melting Temperature

1 0 Heat Flow (W/g) -1 -2
Heating Rates = 2, 5, 10, & 20C/min

-3 -4 -5 154

156

158

160 162 164 Temperature (C)

166

168

170

DSC: Effect of Heating Rate on Indium Melting Temperature

Heat Rate 2C/min 5 10 20

Onset 156.49C 156.54 156.61 156.76

Peak 156.61C 156.75 156.87 157.08

H 28.46 J/g 28.45 28.46 28.44

Onset Variation to 10C/min -0.12C -0.07 0 +0.15

DSC: Polymer Sample w/Internal Temperature Calibration Material

2 Layers of Polymer Film

Melting Point Standard, e.g. Indium

Typical weight of polymer sample is 10mg (2 films at 5mg each) with 1-3mg of Indium

DSC: Indium Sample Placed Between Two HDPE Film Samples

Sample: Linear Polyethylene-Indium Size: 10.0000 mg Method: VarHeat Comment: DSC @ 2,5,10%20C/min; crimped pans, HS Cmpd

DSC

Operator: Lab Run Date: 11-Jun-97 12:43

0 Heat Flow (W/g)

-2

Polyethylene Melt

Indium Melt

-4

-6 20 40 60 80 100 120 Temperature (C) 140 160 180

DSC: Effect of Heating Rate on HDPE and Indium Melting

0 Heat Flow (W/g)

-2

Indium Melt Polyethylene Melt

-4

-6

-8 20 40 60 80 100 120 Temperature (C) 140 160 180

When Placed Between Polymer Films

0.5

0.0 Heat Flow (W/g)

-0.5

-1.0
Heating Rates = 2, 5, 10 & 20C/min

-1.5

-2.0 154 156 158 160 162 164 166 168 170 Temperature (C)

DSC: Effect of Heating Rate on Indium Melting When Placed Between Polymer Film Onset Variation When Calibrated at 10C/min.
Heating Rate 2C/min 5 10 20 Standard Sample -0.12C -0.07 0 +0.15 Polymer Sandwich Sample +.03C +.16 +0.44 +0.82

DSC: Baseline Calibration

Slope Calibration should provide flat baseline with empty pans Polymers should always have an endothermic slope due to increasing heat capacity with increasing temperature Curvature Not normally part of calibration procedure Can be eliminated if necessary with baseline subtraction Curvature can cause errors in analyses

DSC: Baseline Slope

0.5 0.0 Heat Flow (W/g) -0.5 -1.0 -1.5 -2.0 20 40 60 80 100 120 140 160 180 200
10 mg Polystyrene Empty Pans

DSC: Baseline Curvature

0.1 0.4 Heat Flow (W/g) 0.0
Heating @ 1C/min

0.2

-0.1

0.0
Heating @ 3.5C/min

-0.2 -0.2 100 150 200 250 300 Temperature (C) 350

SDT 2960 Calibration

DTA Baseline and TGA Weight Calibration Temperature Calibration empty beams calibration weights up to 5 temperature standards DSC Heat Flow Calibration sapphire

Heat Flow (W/g)

SDT 2960 DSC Heat Flow Calibration

Two scans from ambient to 1500C at 20 C/min empty alumina pans sapphire in alumina sample pan Use Thermal Solutions/Thermal Advantage NT Software to analyze E-curve will be calculated and transferred to the module when the user accepts the results

DSC: 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
If used, they should be operating and equilibriated prior to calibration or sample runs

Warm-up Time/Environment
Electronics should be given at least one hour to stabilize for important samples if the instrument has been turned OFF Electronics are effected by ambient temperature. Avoid areas such as hoods or near an air conditioner

DSC: Recommended Purge Gas Flow Rates & Effect of Flow Rate
Purge Port (mL/min.) Module DSC 2920/2910/2010 Purge 50 (N2 ) 25 (He) Cool Vacuum 50* 50

* Only needed for subambient or MDSC use. Use dry nitrogen or He gas

Purge Gas Flow Rate Too Slow: Moisture Accumulation and Early Aging of the Cell Purge Gas Flow Rate Too Fast: Excessive Noise

DSC: Effect of Flow Rate on Cell Constant

1.80 1.70 1.60 Helium Cell Constant

Cell Constant

1.50 1.40 1.30 1.20 1.10 1.00 0 10 20 30 40 50 60 70 80 90 100 110 Nitrogen Cell Constant

DSC: Sample Preparation

Sample Weight
Selection of the optimum weight is dependent on a number of factors. The sample to be analyzed must be representative of the total sample The change in heat flow due to the transition of interest should be in the range of 0.1 - 10mW - metal or chemical melting: <5mg - polymer Tg or melting: 10mg - composites or blends: >10mg The accuracy of the analytical balance - sample weight should be accurate to +1%

DSC: Heat Flow Change During a Transition

1.0 0.5 Heat Flow (mW) 0.0
69.41C 73.37C(H) + 0.4881mW 161.17C 1.593mW

-0.5 -1.0 -1.5 -2.0 40

143.70C 34.95J/g

60

80

100 120 140 160 Temperature (C)

180

200

220

DSC: Sample Preparation (cont.)

Sample Shape
Keep sample as thin as possible and cover as much of the pan bottom as possible Samples should be cut rather than crushed to obtain a thin sample Lids should be used with sample pans in order to keep the sample in contact with the bottom of the pan

Sample Pans
Use lightest, flattest pan possible Use hermetic pans to prevent evaporation if it occurs in the same temperature range as the transition of interest

DSC: Experimental Conditions

Reference Pan
Always use a reference pan of the same type used to prepare the sample Never use a material in the reference pan that has a transition in the temperature range of interest Because DSC measures the difference in heat flow between a sample and reference, the baseline stabilizes faster if the difference in heat capacity between the sample and reference is kept small by adding weight (same material as pan) to the reference pan so that it is similar in total weight to the sample pan.

DSC: Effect of Reference Pan Weight on DSC Baseline

4 2 Heat Flow (mW) 0 -2 -4 -6 -8

REFERENCE PAN WITH 2 LIDS 1.688mW REFERENCE PAN WITH 1.5 LIDS -0.6018mW -1.953mW REFERENCE PAN WITH LID Sample: Epoxy Weight: Approx. 10mg Heat Rate: 20C -10.04mW NO REFERENCE PAN

-10 -12 90 110 130 150 Temperature C

170

DSC: Comparison of DSC Tg Using No Reference Pan and One of Equal Cp to Sample

0.2 0 Heat Flow (mW) -0.2 -0.4

NO REFERENCE Cp REF = Cp SAMPLE

-0.6 -0.8 90

110

130

150

170

DSC: Experimental Conditions

Heating/Cooling Rates
High rates increase sensitivity

dQ dt
heat flow measured by DSC

=
=

Cp
heat capacity or weight of sample

x
x

dT dt
heating rate

+
+

f (T, t)
time dependent or kinetic component

Low rates increase resolution by providing more time at any temperature

Purge Gas
nitrogen increases sensitivity because it is a relatively poor thermal conductor helium increases resolution because it is a good conductor of heat to or from the sample

DSC: Experimental Conditions General Summary

Condition Sample Size Heat Rate Ref Pan Weight Purge Gas To Increase Sensitivity Increase Increase Increase Nitrogen* To Increase Resolution Decrease Decrease No Effect Helium*

*instrument should be calibrated with the same

purge gas as used to run a sample

DSC: Sample Pan Types

Pan Type Aluminum Copper Gold Graphite Al Hermetic Al Alodined Hermetic Gold Hermetic High Volume (100L) Al Solid Fat Index (SFI) Platinum Upper Temp Limit 600C 725C (in N2) 725C 725C (in N2) 600C (3 atm.) 600C (3 atm.) 725C (6 atm.) 250C (safety lid) 600C (no cover) 725C (no cover)

DSC: Sample Pan Selection Standard Aluminum Pans

Use a thin layer Distribute material evenly

DSC: Sample Preparation Hermetic Pans

Spread Material Evenly Do not overfill!!

DSC: Sample Pan Selection

Sample Type solid (nonvolatile) solid (volatile) liquid aqueous solution foods/biologicals Measurement Tg,Tm OIT Cp Cp Tn,Tc,Tg,Tm Cp OIT Cp,Tm,Tg denaturation Pan Type std., hermetic, open SFI, open std. hermetic hermetic, SFI, open hermetic SFI, open alodined or gold hermetic high volume

DSC: Recommended Cell Maintenance

Cleaning the DSC cell (bakeout) (use this procedure for cleaning a contaminated cell) Air purge = 50mL/min. Ramp 20C/min. to 600C Isothermal for 10 min. Cool cell to room temperature Brush out cell with fiberglass brush Check for improved baseline performance NEVER use solvents to clean DSC cell

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

DSC: Selecting Experimental Conditions

Thermoplastic Polymers
Perform a Heat-Cool-Heat Experiment at 10C/min. First heat data is a function of the material and an unknown thermal history Cooling segment data provides information on the crystallization properties of the polymer and gives the sample a known thermal history Second heat data is a function of the material with a known thermal history

DSC: Thermoplastic: Heat/Cool/Heat

0.4 0.2 Heat Flow (W/g) 0.0
First Heat Cooling Second Heat

300 ] Temperature (C) [ 250 200 150 100 50 0 0 20 40 60 80

-0.2 -0.4 -0.6 -0.8

DSC: Thermoplastic: Heat Flow vs. Temperature for Heat/Cool/Heat

0.4 0.2 Heat Flow (W/g) 0.0
Second Heat
191.41C

Cool
223.01C 48.03J/g

First Heat

-0.2 -0.4 -0.6 -0.8 20 40 60 80 100 120 140 160 180 200 220 240 260 280 Temperature (C)

DSC: Selecting Experimental Conditions

Thermoplastic Polymers (con't)
Interpreting Heat-Cool-Heat Results: One of the primary benefits of doing Heat-Cool-Heat is for the comparison of two or more samples which can differ in material, thermal history or both If the materials are different then there will be differences in the Cool and Second Heat results If the materials are the same and they have had the same thermal history then all three (H-C-H) segments will be similar If the materials are the same but they have had different thermal histories then the Cool and Second Heat segments are similar but the First Heats are different

Selecting Experimental Conditions During first heat the maximum temperature must be higher than the melting peak end; eventually an isothermal period must be introduced too high temperature/time: decomposition could occur too low temperature/time: possibly subsequent memory effect because of the fact that crystalline order is not completely destroyed For non-crystallizable (amorphous) thermoplastics the maximum temperature should be slightly above Tg (removal of relaxation effects, avoid decomposition)

Thermosetting Polymers
A+B C Thermosetting polymers react (cross-link) irreversibly. A+B will give out heat (exothermic) when they crosslink (cure). After cooling and reheating C will have only a glass transition Tg.

GLUE

DSC: Selecting Experimental Conditions

Thermosetting Polymers
Anneal the sample, then Heat-Cool-Heat at 10C/min. Anneal approximately 25C above Tg onset for 1 minute to eliminate enthalpic relaxation from Tg First Heat is used to measure Tg and residual cure (unreacted resin). Stop at a temperature below the onset of decomposition Cooling segment gives the sample a known thermal history Second Heat is used to measure the Tg of the fully cured sample. 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

DSC: Effect of Annealing on the Shape of the Glass Transition

0.0
annealed

0.4 Heat Flow (W/g)

Heat Flow (W/g)

-0.1
aged

0.2

-0.2 0.0 -0.3 -0.2 -0.4 0 10 20 30 40 50 60 70 80 90 100

DSC: Thermoset: Comparison of First and Second Heating Runs

-0.04 -0.08 Heat Flow (W/g) -0.12 -0.16 -0.20 -0.24 0 50 100 150 200 Temperature (C) 250 300
Second First
155.93C

Tg

Residual Cure
102.64C 20.38J/g

Tg

DSC: Determination of % Cure

2.0

1.5

DSC Conditions: Heating Rate = 10C/min. Temperature Range = -50C to 250C N2 Purge = 50mL/min. 145.4J/g 54.55 % cured Under-cured Sample

Heat Flow (W/g)

1.0

-12.61C(H)

0.5

-5.27C(H)
0.0

79.33J/g 75.21 % cured

Optimally-cured Sample

NOTE: Curves rescaled and shifted for readability

DSC: Characterization of Epoxy Prepreg

DSC: The Glass Transition (Tg)

What is it? How is it observed and measured? What affects the Glass Transition?

DSC: What is the Glass Transition?

The Glass Transition is the reversible change of the amorphous region of a polymer from, or to, a viscous or rubbery condition to, or from, a hard and relatively brittle one. The Glass Transition Temperature is a temperature taken to represent the temperature range over which the glass transition takes place.

DSC: Some Properties Affected at Tg

Physical property Specific Volume Modulus Coefficient of thermal expansion Specific Heat Enthalpy Entropy Response on heating through Tg Increases V, 1/E, Decreases Increases Increases Increases Increases

Tg

CTE Cp H& Temperature S

DSC: Measurements of the Tg

exo
To = Temperature of First Deviation ( o C) Tf = Extrapolated Onset Temperature ( o C) Tm = Midpoint Temperature ( o C) Ti = Inflection Temperature ( o C) Te = Extrapolated Endset Temperature ( o C)

To

Tf Tm

1/2h

HEAT FLOW

1/2h

Ti

Tr = Temperature of Return-to-Baseline (oC)

Te

Tr

endo

TEMPERATURE (C)

DSC: Polyethylene Terephthalate Glass Transition

-0.6
71. 54 C

Heat Flow (mW)

-0.7

-0.8

0. 3005m W

-0.9

79. 88 C

-1.0 40 60 80 100 120

DSC: What Affects the Glass Transition?

Heating Rate Heating & Cooling Aging Molecular Weight Plasticizer Filler

Crystalline Content Copolymers Side Chains Polymer Backbone Hydrogen Bonding

DSC: Heating Rate

Heating Rate (C/min) 5 20* 40

Sensitivity
poor good very good

Reproducibility
very good good poor

* Recommended heating rate for measuring Tg.

DSC: Heating/Cooling of Polystyrene

0.15 0.10 0.05
10 C/min HEATING

DSC Heat Flow (W/g)

10 C/min COOLING

0.00 -0.05 -0.10 75 80 85 90 95 100 105 110 115 Temperature (C)

MDSC: Heating/Cooling of Polystyrene

1.00 0.90 0.80
5 C/min COOLING

Heat Capacity (J/g/C)

0.70 0.60 0.50 75 80 85 90 95 100 105 110 115

5 C/min HEATING

Effect of Cooling Rate on Tg

2.0 Heat Capacity (J/gC) 1.8 1.6 1.4 1.2 1.0 20 40 60 80 100 120 Temperature (C) 140 160
Heat Capacity Measured After Cooling at Quench, 20, 10, 5, 2, 1 and 0.2C/min Quench

increased amorphous fraction

20 10 0.2

DSC: Effect of Aging on the Glass Transition [M. Todoki, Polymer Data Handbook]

Cold Crystallization Glass Transition As-Spun 2 days 28 days 196 days 3 years and 2 months 4 years and 11 months

50

100

150

DSC: Effect of Annealing on Polystyrene

Sample: Size: Method: Comment: Polystyrene; effect anneal @ 95 11.6600 mg Operator: Anneal Times Run Date: DSC @ 10C/min; N2 @ 50cc/min; 12.8mg A1 in ref.; crimped pans

DSC

Lab 3-Jun-97

16:41

0.2

0.1 Heat Flow (W/g)

0.0

Anneal Times = 0, 10, 100 & 1000 minutes

-0.1

-0.2

-0.3 40 60 80 100 120 Temperature (C) 140 160

DSC: Effect of Annealing Time at 95C on Shape of Polystyrene Tg

0. 00
Anneal Times = 0, 10, 100 & 1000 minutes

Heat Fl ow ( W g) /

- 0. 05 - 0. 10 - 0. 15 - 0. 20 - 0. 25 80 90 100 110 120 130

DSC: Effect of Molecular Weight on the Tg (for Styrene Oligomers/Polymers)

Molecular Weight 104 524 2,210 3,100 15,100 36,000 170,000
Turi, pg 249 Kumler, 1977

Tg -138C - 40C 40C 62C 86C 94C 100C

DSC: Effect of Plasticizer on the Tg

for Polyamides Water Content (%) 0.35 0.70 1.17 1.99 2.70 4.48 6.61 10.33 Tg (C) 94 84 71 56 45 40 23 6

DSC: Effect of Filler and Crystalline Content on the Tg

Decreases magnitude of Cp shift Broadens temperature range of Glass Transition Increases the Tg

DSC: Copolymers
490

450 Tg (K) 410 370 0 20 40 60 80 100

PPO (wt. %)

DSC: Effect of Side Chains on the Tg

for - CH2 - CH(R) -

Side Chain -H

Tg (C) -36 -12 64 100 120 161

-CH 3 -CH 2(CH 3 )

C6H5
cyclohexyl

-C6H4 - (4 - C6H5 )

DSC: Effect of Polymer Backbone on the Tg

for - O - (CH2 )n N 2 3 4 Tg (C) -41 -78 -84

DSC: Effect of Hydrogen Bonding on the Tg

Polyamide Nylon 12,2 Nylon 10,2 Nylon 8,2 Nylon 6,2

Tg (C) 59 56 93 159

HBonding Least Most

DSC: Melting and Crystallization

Terminology Observations of Melting and Crystallization Crystallinity Calculations Applications

DSC: Terminology
Amorphous Phase - The portion of material whose molecules are randomly oriented in space. Liquids and glassy or rubbery solids. Thermosets and some thermoplastics. Crystalline Phase - The portion of material whose molecules are regularly arranged into well defined structures consisting of repeat units. Very few polymers are 100% crystalline. Semi-crystalline Polymers - Polymers whose solid phases are partially amorphous and partially crystalline. Most common thermoplastics are semi-crystalline. Endothermic - A transition which absorbs energy. Exothermic - A transition which releases energy. Melting - The endothermic transition upon heating from a crystalline solid to the liquid state. This process is also called fusion. The melt is another term for the polymer liquid phase. Crystallization - The exothermic transition upon cooling from liquid to crystalline solid. Crystallization is a function of time and temperature. Cold Crystallization - The exothermic transition upon heating from the amorphous rubbery state to the crystalline state. This only occurs in semi-crystalline polymers that have been quenched (very rapidly cooled from the melt) into a highly amorphous state. Enthalpy of Melting/Crystallization - The heat energy required for melting or released upon crystallization. This is calculated by integrating the area of the DSC peak on a time basis.

Observation of Melting
0.0

Extrapolated Onset Temperature 236.94C 45.30J/g Area under the curve (Heat of Fusion)

-0.2

-0.4

Heat Flow (W/g)

12.73C
-0.6

Width @ half height

-0.8

250.61C
-1.0

Peak Temperature

DSC: Melting Points and Ranges

To is the onset to melting Tp is the melting peak temperature Te is the end of melting

Pure, low molecular weight materials (mw<500 g/mol) To is used as the melting temperature (T m) Between To and Tp the sample is melting Between Tp and Te the molten sample is returning to the DSC temperature Polymers Tp is used as the melting temperature (T m) Between To and Tp crystal perfection is occurring (both melting and crystallization occurs simultaneously) Between Tp and Te the sample is finishing melting and returning to the DSC temperature

DSC: Polyethylene and Indium Melting

5 0 Heat Flow (mW) -5 -10 -15 -20 100 110 120 130 140 150 160 170 Temperature (C)
126.96C 191.7J/g 157.59C 28.46J/g

131.12C 157.85C

Baseline Types: Linear

0.3

12.20C

0.2

Heat Flow (W/g)

0.1

16.10C

22.27(24.02)J/g
0.0 -20
Exo Up

1.754J/g

-10

10

20

30

40
Universal V2.5D TA Instruments

Temperature (C)

Baseline Types: Sigmoidal

0.3
12.20C

0.2

Heat Flow (W/g)

0.1

23.04J/g

DSC: Observation of Crystallization

1.0 0.5 Heat Flow (mW) 0.0 -0.5
163.24C 152.62C

Tc

Tn

-1.0 -1.5 100 120

139.47C 36.60J/g

Te

140

160

180

200

Temperature (C)

DSC: Crystallization Point

Crystallization is a two step process: Nucleation Growth The onset temperature is the nucleation (TN ) The peak maximum is the crystallization temperature (TC )

DSC: PET/ABS Blend "As Received"

-0.2
120. 92 C 67. 38 C

Heat Flow (W/g)

-0.4

70. 26 C( H) 111. 82 C 9. 016J / g 235. 36 C 22. 63J/ g

-0.6

STANDARD DSC FIRST HEAT ON MOLDED PART

-0.8 50 100 150 Temperature (C) 200

249. 75 C

250

DSC: Calculation of % Crystallinity

Sample must be pure material, not copolymer or filled Must know enthalpy of melting for 100% crystalline material (H lit ) You can use a standard H lit for relative crystallinity
For standard samples: % crystallinity = 100* Hm / Hlit For samples with cold crystallization: % crystallinity = 100* (Hm - Hc)/ Hlit

DSC: Polymer Crystallinity - Polyolefin

190 EXO 170 150 HEAT FLOW % Crystallinity = 141 X 100% 290 = 49% TEMPERATURE (C)
H = 141 J/g

130 110 90

Size: 10.5mg Prog: 5 C/min

ENDO 0

8 6 TIME (min)

10

12

14

DSC: Applications

Effect of heating/cooling rate Crystallization kinetics Effects of polymer structure/composition Effects of thermal/mechanical processing

DSC: Effect of Heating Rate on Nylon 66 Melting Behavior

exo

0.2 mW

0.5C/min

HEAT FLOW

1 mW 2C/min 5 mW 5 mW 10 mW 10C/min 20C/min 50C/min

endo 1

240 2

260 280 300 3 Temperature (C)

DSC: Effect of Cooling Rate on Crystallization of HDPE

70

32C/min
Heat Flow (mW) 50

16
30

8 4 2 1 0.5
120 130

10

-10 100 110

Temperature (C)

DSC: Crystallization Kinetics

Two step process Nucleation Crystal growth Nucleation may be Natural Induced (using nucleation agents) Thermally influenced process Natural nucleation Crystal growth Modeled by Isothermal Kinetics using the Autocatalytic Model

DSC: Isothermal Crystallization Procedure

Heat to 10C above TM Hold for 5 minutes to remove local order Cool rapidly to below melt onset (DO NOT OVERSHOOT TEMP) Hold isothermally Record time to crystallization peak (tc)

DSC: Isothermal Crystallization of Polyethylene Terephthalate

T1

T1 < T2 < T3 < T4

T2

T3 T4

Blank run

3 Time (min)

DSC: Effect of Nucleating Agents on Crystallization

NUCLEATED POLYPROPYLENE

Exothermic

NON-NUCLEATED POLYPROPYLENE

DSC: Supercooling of Water

250
-4.36C +

200 Heat Flow (mW) 150 100 50 0 -50 -30 -25 -20 -15 -10 -5 0 5 10 Temperature (C)
+ -15.55C

DSC: Purity of Pharmaceutical Compounds

135.0 -0.8 -1.0 Heat Flow (mW/mg) -1.2 -1.4 -1.6 -1.8 -2.0 -2.2
Purity: 99.55 mole % Melting Pt: 134.9C Depression: 0.24C Delta H: 26.4 kJ/mole Correction: 8.11% Mol. Weight: 179.2 g/mole Cell Const: 0.977 Onset Slope: 10.14 mW/C

134.5

133.5

133.0 8 10

Total Area/Partial Area 4 6 2

132.5

Temperature (C)

134.0

DSC: Effect of Polymer Type on Melting

Class Polyolefins Polyamides Polyesters Polyphenylene Sulfides

Structure -CH2-CH 2 -CH2-NH-C(O)-CH 2-CH -O-C(O)-CH 2 2

Melting Range 85 - 174C 190 - 265C 220 - 270C 300 - 360C

-Ph-S-

DSC: Effect of Molecular Weight on Melting

Olefin Formula C12H26 C24H50 C30H62 C35H72

Mole. Wt. (g/mol) 170 339 423 493

Tm (C) -10 54 66 75

DSC: Effect of Hydrogen Bonding on Melting

Polyamide Nylon 12,2 Nylon 10,2 Nylon 8,2 Nylon 6,2 Tm 236 242 279 326 H Bonding Least Most

Nylon x,y where: x = carbons in diamine section y = carbons in diacid section

DSC: Effect of Annealing Poly(ethyletherketone) (PEEK) on Melting

0.0

PEEK
Heat Flow (W/g) -0.1
303.61C

-0.2

PEEK annealed @ 300C

-0.3 260

280

300

320

340

360

380

DSC: Effect of Draw Ratio on Melting Temperature

137

Tm (C)

133

129

1.0

3.0

5.0

7.0

DSC: Effect of Aromaticity on Melting

Polymer -CH2 - CH2 PET -(Ph)-O-(Ph)-S-

% Aromatic 0 39 62 70

Melting Range 105 - 135C 250 - 275C 300 - 315C 300 - 360C

DSC: Effect of Branching on Melting

Polyolefin LDPE LLDPE HDPE PP Branching irregular random lengths irregular fixed lengths none regular fixed lengths Tm ~ 105C ~ 127C ~ 135C ~ 150C

DSC: Melting and Crystallization Summary

Melting and crystallization are phase changes from organized solid to amorphous phases and vice-versa. Melting is a one-step process while crystallization involves nucleation and crystal growth. The enthalpy of melting can be used to measure crystallinity or filler. Any process that makes it easier for molecules to be organized will raise the melting temperature.

DSC: Specific Heat Capacity

What is it? How is it observed and measured? Methods for calculating specific heat capacity What affects the specific heat capacity of a polymer?

DSC: What is Specific Heat Capacity?

Specific Heat Capacity (Cp) is the amount of heat required to raise the temperature of one gram of a particular material one kelvin of temperature. Specific Heat Capacity is due to the molecular motion in a material (units of J/g K). Heat Capacity is the amount of heat required to raise the temperature of a material one kelvin of temperature. This is unnormalized specific heat (units of J/K). Specific heat is the specific heat capacity of an analyte compared to the specific heat capacity of a reference material (dimensionless).

DSC: How are Heat Capacity and Specific Heat Measured?

In a DSC experiment, heat capacity is measured as the absolute value of the heat flow, divided by the heating rate, and multiplied by a calibration constant.

dH/dt = Cp (dT/dt) or

Cp = [(dH/dt)/(dT/dt)] x E
E = calibration constant

DSC: How Heating Rate Shifts Heat Flow

0 -2 Heat Flow (mW) -4 -6
106. 85 C - 8. 104m W 106. 85 C - 2. 137m W 106. 85 C - 40175m W

5C/min 10C/min

-8 -10 40 60 80 100 120 140

20C/min

160

180

200

DSC: Specific Heat Capacity Equation

Cp =

E x H x 60 Hr x M

Cp = Specific Heat Capacity (J/g/C) E = Calibration Constant (dimensionless) H = Heat Flow (mW) 60 = conversion constant (min sec) Hr = Heating Rate (C/min) M = Sample Mass (mg)
DSC: Specific Heat Capacity Step 1. Run Empty Pans
Create Thermal Method, e.g., 1) Equilibrate @ 50C 2) Isothermal for 10 min. 3) Ramp 20C/min to 300C 4) Isothermal for 10 min. Run Empty Pans to determine background heat flow Subtract background heat flow from subsequent

DSC: Specific Heat Capacity Step 2. Determine Value of E

E is temperature-dependant Heat sapphire disc (Cp standard) through thermal profile At temperature of interest, calculate E

DSC: Specific Heat Capacity Step 2. Determine Value of E (cont.)

For example, at 380 K (106.85C), sapphire Cp = 0.9161 J/g/C M = 25.20mg Hr = 20C/min Measured Heat Flow = 7.25 mW
Cp Hr M

E=

(0.9161 mJ/mg/C) x (20C/min) x (25.20 mg) (7.25 mW (mJ/sec)) x (60 sec/min)

H

DSC: Specific Heat Capacity Step 3. Measure Unknown Sample

Use exact same thermal profile as empty pans and sapphire Measure sample mass, e.g., 14.20 mg Measure Heat Flow at 380K, e.g., 4.60 mW Substitute E into equation on page 103.
E H

Cp =

(1.06) x (4.60 mW (mJ/sec)) x (60 sec/min) (20C/min) x (14.20 mg)

Hr M

Cp = 1.030 mJ/mg/C (J/g/C)

DSC: What Affects the Specific Heat Capacity?

Amorphous Content Aging Side Chains Polymer Backbone Copolymer Composition

DSC: Effect of Amorphous Content on Cp

Amorphous Cp is greater than Crystalline Cp Amorphous Content increases Specific Heat Capacity

Crystalline polymers contain more order and thus fewer degrees of molecular motion. Less molecular motion results in lower specific heat capacity.

DSC: Effect of Annealing (Crystallization) on Cp of PEEK

2.2 2.0 1.8 1.6 1.4 1.2 100
Amorphous PEEK PEEK annealed at 300C PEEK annealed at 330C

Complex Cp (J/g/C)

110

120

130

140

150

160

DSC: Effect of Aging on the Specific Heat Capacity of Polystyrene

406 272 240 120

Endotherm

66 24 3 0

tg (h)

360

380 Temperature (K)

400

420

DSC: Effect of Side Chains on Specific Heat Capacity

Polymer PE PP PS

Side Chain -H -CH -Ph

Cp (J/g/C) 2.763 2.752 2.139

As the steric bulk of the side chain increases, molecular mobility decreases resulting in lower specific heat.

DSC: Effect of Polymer Backbone on Specific Heat Capacity of Polyoxyalkenes @ -153C

[
1 2 3 4 8

O ( CH2n)

]
Cp (J/g/C) 0.6226 0.6918 0.7088 0.7597 0.7736

# of Methylenes

As the number of methylenes increase, mobility is increased in the polymer, resulting in higher heat capacity.
B. Wunderlich, ATHAS Cp Data Bank, 1985.

DSC: Effect of Copolymer Composition on Specific Heat Capacity of PE/PP Copolymer @ -93C

Composition (%PP) 6.0 7.5 15.5

Copolymer (Type) block random random

Cp (J/C/mol) 15.12 16.39 18.54

As PP concentration is increase, the number of methylenes increases, resulting in a rise in specific heat capacity. Also, with randomness comes entropy, increase in mobility, and increase in specific heat capacity.

DSC: Modulated DSCTM

Theory Signals Applications Experimental Conditions Calibration

MDSC Theory

Heat Flow Equation

dH dT = Cp + f (T , t ) dt dt

dH = Total Heat Flow measured dt by the calorimeter

Cp = Specific Heat Capacity

dT = Underlying Heating Rate dt

f(T,t) = kinetic response of sample

Heat Flow Due to Heat Capacity

0 (2) (4) (6) (8) (10) 40 60 80 100 120 140 160 180 200
106.85C -8.104mW 106.85C -2.137mW 106.85C -4.018mW

5C/min 10C/min

Heat Flow (mW)

20C/min

Kinetic Heat Flow

Isothermal Temperature

Heat Flow

The magnitude of measured kinetic heat flow is a function of time at a constant temperature.

t1

time

t2

Standard DSC Measures the Sum of Heat Flow

Heat Flow due to Kinetic Events

Heat Flow

Heat Flow due to Heat Capacity

Heat Flow Can Be Separated

f(T,t)

Heat Flow

Heat Flow due to Kinetic Events

Cp

dT dt

Heat Flow due to Heat Capacity

Temperature

General Theory of MDSC

Heat flow from DSC experiments is composed of two parts but DSC can only measure the sum of the two. dH/dt = Cp (dT/dt) + + f (T,t) Kinetic Component Time Dependent

Total = Heat Capacity Heat Flow Component (DSC) = Heating Rate Dependent

= MDSC Reversing + MDSC Nonreversing

Distribution of Transitions in MDSC Experiments

Total = Heat Capacity Component + Kinetic Component

= Reversing Heat Flow + Nonreversing Heat Flow

glass transition melting (some) enthalpic relaxation evaporation crystallization decomposition cure melting (some)

Physical Measurement Technique

Apply Stimulus
FTIR NMR

Measure Response
Stimulus
IR Radiation

Response
Absorbance Wavelength Resonance Frequency Angle of Diffraction Amplitude of Heat Flow

Magnetic Field

X-Ray Diffraction X-Ray Radiation MDSC Sinusoidal Heating Rate

Raw Signals in MDSC

All Modulated DSC Signals are derived from three measured parameters.

Time Modulated Temperature (Stimulus) Modulated Heat Flow (Response)

MDSC Raw Signal

0.2
COLD CRYSTALLIZATION

Deriv. Modulated Temp (C/min)

6
GLASS TRANSITION NOTE: ALL TRANSITIONS OF INTEREST ARE CONTAINED IN MDSC RAW DATA SIGNALS MELTING

0.0

-0.2

-0.4

MODULATED HEATING RATE (Stimulus)

-0.6 50 100 150 200 250 300

Modulated Heat Flow (W/g)

MODULATED HEAT FLOW (Response)

CRYSTALLIZATION DURING MELTING

Temperature Change (MDSC)

240 240

230

P
ACTUAL MEASURED TEMPERATURE

230

220

220

CALCULATED AVERAGE TEMPERATURE

210

210

200
Exo Up

38

39

40

41

42

43

44

45

200

Time (min)

Universal V2.5D TA Instruments

MDSC Signals: Total Heat Flow

The average value of the modulated heat flow signal. This signal is qualitatively and quantitatively equivalent to the heat flow signal from conventional DSC at the same average heating rate. Definition: The sum of all thermal events in the sample Calculation: Fourier Transformation analysis of the modulated heat flow signal is used to continuously calculate its average value

Modulated Temp (C)

Temperature (C)

Total Heat Flow: Average of Modulated Heat Flow Signal

0.2 0.1 0.0 -0.1 -0.2 -0.3 -0.4 50 100 150 200 Temperature (C) 250 300 -0.4 -0.2 0.0 Heat Flow (W/g) 0.2

Modulated Heat Flow (W/g)

MDSC Signals: Heat Capacity

AMHF Cp = xK AMHR
Where: AMHF = Amplitude of Modulated Heat Flow AMHR = Amplitude of Modulated Heating Rate K = Heat Capacity Calibration Factor Definition: The amount of heat required to raise the temperature of a material 1C. Calculation: The basis for making the heat capacity measurement in MDSC can be explained from a series of

Conventional DSC Cp Measurement

Cp = K x

HFS HFMT Heat Rate x wt

0 HF

HFMT

Where: K = Calibration constant HFS = Differential heat flow with sample HFMT = Differential heat flow with empty pans wt = weight of sample

endo

HFS Temp.

Alternative DSC Cp Measurement

Cp = K x
Where:

HFHR2 HFHR1 (HR2 HR1) wt

0 HFHR1 HF HFHR2 Temp.

K = Calibration constant HFHR1 = Differential heat flow of sample at HR1 HFHR2 = Differential heat flow of sample at HR2 HR2 HR1 = Heating rate 2 = Heating rate 1

endo

Heat Capacity from MDSC Raw Signals

Deriv. Modulated Temp (C/min) 0.6
HEAT CAPACITY

10

4 0.2 2 0 -0.2 2 4

MODULATED HEAT FLOW

0 50

MODULATED HEATING RATE

100 150 200 Temperature (C)

250

-0.6 300

MDSC Signals - Reversing Heat Flow (Heat Capacity Component)

Reversing Heat Flow is the heat capacity component of the total heat flow. It is calculated by converting the measured heat capacity into a heat flow signal using the classical heat flow equation as a theoretical basis.

Reversing Heat Flow = Cp x Avg. Heat Rate

Basis for Calculation Where :

dH = total heat flow dt Cp = measured heat capacity dT = average heating rate dt dT Cp = heat capacity component (Reversing)

dH dT = Cp + f (T, t) dt dt

Modulated Heat Flow (W/g)

6 Complex Cp (J/g/C)

Reversing Heat Flow from MDSC Raw Signals

8 0.15

0.05

Complex Cp (J/g/C)

HEAT CAPACITY

0
REVERSING HEAT FLOW

-0.05

-4

-0.15

-8 50 100 150 200 250 300

-0.25

Temperature (C)

Quench Cooled PET: Total vs. Reversing Heat Flow

0.1 0.15 ]Rev Heat Flow (W/g) [ -0.3 50 100 150 200 250 300 -0.25

0.0 Heat Flow (W/g)

TOTAL

0.05

-0.1
REVERSING

-0.05

-0.2

-0.15

Rev Heat Flow (W/g)

MDSC Signals - Nonreversing Heat Flow (Kinetic Component)

Nonreversing Heat Flow is the kinetic component of the total heat flow. It is calculated by subtracting the heat capacity component from the total heat flow using the classical heat flow equation as a theoretical basis.

Nonreversing = Total Reversing Basis for Calculation

dH dT = Cp + f (T, t) dt dt dH = total heat flow dt dT = heat capacity component (reversing) Cp dt f (T, t) = kinetic component (nonreversing)

Quench-Cooled PET: Deconvoluted Signals

0.25 0.25

Nonrev Heat Flow (W/g)

0.15 Heat Flow (W/g)

NONREVERSING

0.1

0.15 Rev Heat Flow (W/g)

0.05
TOTAL REVERSING

0.0

0.05

-0.05

-0.1

-0.05

-0.15

-0.2

-0.15

-0.25 50 100 150 200 250 300

-0.25

Glass Transition of Polymer Resin

MDSC: Glass Transition of Epoxy Coating

-0.20 -0.22 Heat Flow (mW) -0.24 -0.26 -0.28 -0.30 0 20 40 60 80 100 120
REVERSING

0.00
NOTE: Sensitivity is 100W Full Scale

TOTAL

-0.04 -0.06 -0.08 -0.10 140

Rev Heat Flow (mW)

-0.02

PET/ABS Blend - Conventional DSC

-0.2 -0.3 -0.4 -0.5 -0.6 -0.7 -0.8
111.82C 9.016J/g 249.75C 67.38C 70.262C (H) 120.92C

first heat on molded part

235.36C 22.63J/g

Heat Flow (W/g)

second heat after 10C/min cooling

(Curve shifted on Y axis to avoid overlap) 9.22 mg sample, nitrogen purge 10C/minute heating rate

50

100

150 200 Temperature (C)

250

PET/ABS - MDSC
first heat on molded part

-0.10 -0.11 Heat Flow (mW) -0.12 -0.13 -0.14 -0.15 20

-0.02 ) Nonrev. Heat Flow (W/g) -0.03 -0.04 -0.05 -0.06

-0.04 -0.05 -0.06 -0.07 -0.08 -0.09

PET Tg
8.46mg sample nitrogen purge

67.00C +72.89C (H) 104.45C 107.25C (H)

ABS Tg

2C/minute heating rate, 1C amplitude, 60 second period

40

60

80

100

120

140

160

180

200

) Rev. Heat Flow (W/g)

MDSC: Detection of Two Glass Transitions in PC/PEE Blend

3 CONSECUTIVE HEATING RUNS AFTER 2deg/min COOLING 141. 45 C 62. 58 C

-0.02

Rev Heat Flow (W/g)

-0.001

3 2

-0.04 -0.06 -0.08 -0.10 -0.12 40

NOTE 81C WIDTH OF GLASS TRANSITION

1 DERIVATIVE

-0.002

MDSC 0.424C, 40 sec. period 4C/min underlying ramp rate

-0.003

-0.004

-0.005 60 80 100 120 140 160

Temperature (C)

MDSC: Heat Capacity for PET During Isothermal Steps

1.6
PLOT vs TIME

140

Heat Capacity

Heat Capacity (J/g/C)

1.4 100

Temperature
1.2 80
MDSC 0.30C, 40 sec. period 1C isothermal steps

1.0 0.4 0.6 0.8 1.0 1.2 1.4 1.6 1.8 2.0

60

Temperature (C)

120

Deriv. Rev Heat Flow (W/g/min)

MDSC: PET Heat Capacity During Glass Transition & Cold Crystallization
1.6
COLD CRYSTALLIZATION (First-Order Transition)

Heat Capacity (J/g/C)

1.5 1.4 1.3 1.2 1.1 60 70 80 90

MDSC 0.30C, 40 sec. period 1C isothermal steps
GLASS TRANSITION (Second-Order Transition)

100

110

120

130

Temperature (C)

Isothermal Epoxy Cure

6

H of Cure
DMA 1Hz
30

14.5 14.0 ) E' (GPa) 13.5 13.0 12.5 12.0

0

Nonrev. Heat Flow (mW)

4 Heat Capacity

20

Isothermal 80C helium purge 0.5C amplltude 60 second period

10

11.5

) Heat Capacity (mJ/C)

MDSC: Heat Capacity vs. Cure Time

Epoxy-Amine System MDSC
) Nonreversing Heat Flow (mW/g) 120
TM

Result at 70C Cure=

t1/2Cp = 97 mi

2.5 ) Heat Capacity (J/g/K) (

Heat Capacity
90

t1/2Cp

X vit = 0.53

2.0 60

exo
1.5

30

Nonreversing Heat Flow

1.0 300

0 0 100 Time (min)

=

200

Thermochimica Acta, 268, 121-142 (1995), Dr. B. Van Mele, et al at Vrije Universiteit Brussels (Belgium)

MDSC: Experimental Considerations

Modulation Period? Sample Dimensions?

Calibration? Phase Correction? Purge Gas?

MDSC: Sample Preparation

Thin, Low Mass Samples Minimize Thermal Gradients Allow for Faster Periods, Larger Modulation Amplitudes Thicker, Heavier Samples Minimize Baseline Curvature Improve Sensitivity

MDSC: Sample Pans Standard Crimped

Low, Consistent Mass Best Choice for MDSC Measurements Solids, Powders, Films Volatility may be an issue

MDSC: Sample Pans Standard Hermetic

Use for liquid/volatile samples Higher Mass, Less Sensitivity Use Heat Sink Compound

MDSC: Purge Gas

Nitrogen Economical Wide Operating Range Provides Good Sensitivity Helium Higher Thermal Conductivity Facilitates Wider Range of Modulation Conditions

MDSC: Purge Gas Flow Rates

Use Purge Gas Flow Rate of 50 mL/min. (N2) & 25 ml/min (He) Faster rates increase noise Slower rates decrease sensitivity, increase baseline curvature Flow Purge Gas through Vacuum Port at 50 mL/min. Improves response of furnace Facilitates wider range of modulation parameters

MDSC: Baseline Calibration

Identical to Standard DSC experiment Eliminates Baseline Drift Does not affect curvature -Slower heating rates contribute to curvature -Heavier sample masses minimize
Baseline Calibration - 2920 MDSC (4) Sample: Empty Pans

<

-4

DSC File: D:\TA\DSC\...BASE1102.001

Delta V) (

-6

Baseline Calibration Slope: -0.0005 Offset: -8.564 Cell Number: 319

-8
-90.29C

287.04C

-10 -200

-100

0 100 200 Temperature (C)

300

400

MDSC: Heat Flow (Cell Constant) Calibration

Identical to Standard DSC Calibration
v Baseline Calibration - 2920 MDSC (4)

Sample: Indium Metal

DSC File: D:\TA\DSC\DATA\CAL0512.001

-5 Heat Flow (mW) -10 -15 -20 -25 150

157.74C

Cell Constant Calibration Indium Standard Heat: 28.71 J/g Cell Constant: 1.5555 Onset Slope: -40.63 mW/C Cell Number: 319

152

154

156 158 Temperature (C)

160

162

164

MDSC: Cell Constant Effect on Modulated Heat Flow

4 Modulated Heat Flow (mW)

-2

E = 0.5 E = 1.0 E = 1.6

25 75 125 175 Temperature (C) 225 275

-4

MDSC: Heat Capacity Calibration

Provides for Accurate Heat Capacity Measurements Use Either Sapphire Disc (wide temperature range) or HDPE (polymer melt) Choose one-point or average values Effects of Experimental Conditions

MDSC: Heat Capacity CalibrationFrequency Dependence

1.3

1.2

1.1

10 Sec 20 Sec 30 Sec 40 Sec 50 Sec 60 Sec 70 Sec 80 Sec 90 Sec 100 Sec

K(Cp)
0.9 0.8

MDSC: Heat Capacity Calibration Frequency Dependence (cont.)

0.95

0.93

0.91

K(Cp)
0.89 40 Sec 50 Sec 60 Sec 70 Sec 80 Sec 90 Sec 100 Sec 0 10 20 30 40 50 60 70 80 90 100 0.87 0.85

Temperature (C)

MDSC: Heat Capacity Calibration Amplitude Dependence

0.94 0.93 0.92 0.91 0.9

K(Cp)

0.89 0.88 0.87 0.86 0.85 0.10C 0.25C 0.50C 0.75C 1.00C 1.25C 1.50C 1.75C 2.00C

MDSC: Heat Capacity Calibration Heating Rate Dependence

0.94

0.92

0.9

K(Cp)
0.88 1C/min 3C/min 5C/min Isothermal 0.86 0.84 0 10 20 30 40 50 60 70 80 90 100

Temperature (C)

Effect of Modulation Conditions on K

He purge @ 25 ml/min.
1.60 1.50 1.40 K 1.30 1.20 1.2 1.10 1.00 10 20 30 40 50 Period (sec) 60 70 80 90 0.1 100 0.4 0.2 1

2 1.8 1.6 1.4

A m pl itu de ( C )

0.8