DifferentialScanningCalorimetry

DerrickDean
UniversityofAlabamaatBirmingham
 Agenda

Briefoverviewofpolymers
DSCBasics
Applications
Meltingtransitions,Tm
Theglasstransition,Tg
ThermalStability

ModulatedDSC,MDSC
VariationsinDSC
2
 ThermalAnalysisUsefulFor

QualityControl
Characterization
Processing
EndUseApplication
 MostCommonlyUsed
ThermalAnalysisTechniques
Technique ParameterMeasured
DifferentialScanning dH/dT
Calorimetry(DSC)
Thermogravimetry (TGA) Mass
Derivative Thermogravimetry dM/dT
(DTGA)
Thermomechanical Analysis Deformation,Volumeor Length
(TMA)
(Dilatometry;Penetration)
DynamicMechanical Modulus/Damping
Analysis(DMA)
DielectricAnalysis (DEA) Permitivity/LossFactor
Major Polymer Transitions
 TwoMainTransitionsin
ThermoplasticPolymers
GlassTransition,Tg
Indicatesminimum/maximumservice
temperature
Veryimportantinamorphouspolymers
Meltingtemperature,Tm
Definesminimumprocessingandmaximum
servicetemperature
 TransitionsandRelaxations
WhyImportant?
Rangeatwhichpropertieschange
Modulus
Brittleness
Impactstrength
Wear
Permeability
Thermalconductivity
Strength
Dielectricconstant
Stressstrainproperties
Electricalconductivity
 TransitionsandRelaxations
Ifweexaminepolymerpropertieswithrespect
totemperatureand/orfrequency
wefindthatthereisarangeoverwhichthe
LogE

propertieschange(eg.,SillyPutty)

Log

LogE
Athighfrequenciesnomotion>unrelaxed
Atlowfrequenciesitflows>relaxed

IfTischangedinsteadof,
T
samefeaturesresult.

Relaxation significantsharporsteepchangeinpropertiesinarelatively
narrowtemperatureorfrequencyrange.
 TransitionsandRelaxations
Relaxation significantsharporsteepchangeinpropertiesinarelatively
narrowtemperatureorfrequencyrange.

Canberelatedtovarioustypesofpolymer
motion: - CH2 - CH -
CH3

-
1. Sidechainrotation(PP,PMMAorPS) CH3
- CH2 - CH -

- CH2 - C -

2. SmallsegmentsasinPE: C=O

CH3

3. Longersegments(2030carbonatoms,asat
Tg)
 TransitionsandRelaxations
Transition adiscontinuouschangeinthermodynamicproperties
ofamaterial.

Includeschangesofstate:
Crystallinetoamorphous Tm
Crystalline1tocrystalline2 polymorphism
Amorphoustoglass Tg

Atatransitiontherewillbeadiscontinuouschangeinthermodynamic
properties,whichcanbeobservedtodefinethetransitiontemperature.
Specificvolume
Heatcapacity
Specificheat(Enthalpy)
 TransitionsandRelaxations
1st OrderTransition Transitionforwhich
thefirstorderderivativeoffreeenergyisa
thermodynamicfunctionthatis
discontinuouswhenplottedvs.
temperature.
2nd OrderTransition Transitionforwhichthe
secondorderderivativeoffreeenergyisa
thermodynamicfunctionthatisdiscontinuous
whenplottedvs.temperature.

Cp
Tm isafirstorder
v transition
T
Tg isasecondorder
transition
T

Tg isasecondorder
V transition

T
T
 TransitionsandRelaxations

ChangeisgreatestatTm andTg,andlesssoat
lowertemperaturerelaxations.
ManypolymersbecomebrittlebelowTg nomeansto
absorbenergyofimpact(PS,PMMA)
Someremainductile(PC,PET),becauseofalarge
secondaryrelaxationatT<Tgwhichcanabsorbenergy
andbecomebrittleatmuchlowerT,belowthe
secondaryrelaxation.
 RelativeSensitivityofThermal
AnalysisInstruments

Technique PropertyMeasured RelativeSignalChangeatTg

DifferentialScanning Heatflow(heat capacity) 0.2

Calorimetry
Thermomechanical Analysis Expansion Coefficient; 3
DimensionChangeor
Softening
DielectricAnalysis Permittivity anddielectric 100
loss
DynamicMechanical Mechanicalstrengthand 200
Analysis energyloss
 WhatDoesaDSCMeasure?
ADSCmeasuresthedifferenceinheatflow
rate(mW=mJ/sec)betweenasampleand
inertreferenceasafunctionoftimeand
temperature

14
 PopularityofDSC
Technique
Speedofoperation
Easeofoperation
Smallsamplesize
 InformationObtainedfrom
DSC
GlassTransitiontemperatures
Meltingpointsandboilingpoints
Crystallizationtimeandtemperature
Percentcrystallinity
Heatsoffusionandreaction
Specificheat
Oxidativestability
Rateofcure
Degreeofcure
Reactionkinetics
Purity
Thermalstability
 TypesofDSC
HeatFlux PowerCompensation

Sameheatflowsintobothsamples;T=0.
Whenachangeoccurs(endoorexo)aT
signalisgeneratedwhichisproportionalto
theheatflowdifference.
WhenaTisdetected,anadditionalcircuit
willincreaseordecreaseheatingpowerOf
samplefurnace.Thiscompensatingheating
power,P,isproportionaltoheatabsorbed
orreleased.
 DSCHeatFlow

Cp Sample Heat Capacity

dH
DSC heat flow signal Sample Specific Heat x Sample Weight
dt

dH dT
Cp f (T, t)
dt dt
f (T, t) Heat flow that is function of time
dT
Heating Rate at an absolute temperature (kinetic)
dt

18
 TypicalDSCOutput:
TransitionsofInterestinaDSC

Oxidation
or
HeatFlow>exothermic

Decomposition

Melting
Glass
Transition CrossLinking
Crystallization (Cure)

Temperature
 DSCSignals
DSCmeasuresthedifferenceinheatflowrate
(mW =mJ/sec)betweenasampleandinert
referenceasafunctionoftimeandtemperature
HeatFlow
Endothermic:heatflowsinto thesampleasaresult
ofeitherheatcapacity(heating)orsome
endothermicprocess(Tg,melting,evaporation,etc.)
Exothermic:heatflowsoutof thesampleasaresult
ofeitherheatcapacity(cooling)orsomeexothermic
process(crystallization,cure,oxidation,etc.)
 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.

21
 PhysicalOriginsofPeaksinDSC
Endothermic Exothermic
CrystallineTransition X X

Fusion X
Crystallization X
Vaporization X
Sublimation X
Adsorption X
Desorption X
GlassTransition BaselineChange, Nopeaks

LiquidCrystaltransition X

Physical Aging X
ChemicalOriginofPeaksinDSC
Endothermic Exothermic
Chemisorption X
Dehydration X
Decomposition X X
Oxidative X
Degradation
Oxidation in X
Gaseous
Atmosphere
Adsorption X
SolidStatereaction X X
Combustion X

Polymerization X
Curing X
 SampleSize

5to15mgforthermoplasticsorelastomers
MightnobeabletodetermineTGofhighly
crosslinkedsample
Melting/Crystallizing
Lessthan10mg
Heatofreaction
Assmallascanbeaccuratelymeasured
Composites:Dependsonfillerloading
 GeneralExperimental
Setup
Calbration:ASTME967,E968,D3417,D3418
Sameheatingrateasexperiment
Sameatmosphereandpurgeflowrates(50cc/min)
Sametemperaturerangeasexperiment
Pan:
Flatbottom
Goodsampletopancontact
Inerttoreactivesamples
Reference:
Samepanassample,butitshouldbeempty
PanCellContact:
Symmetricplacementofreferenceandsample
 ReportingDSCData
ASTME472,D3418
Identificationofallsubstancesandtheirsources
Detailsofmaterialhistories,pretreatments,purities,
etc.
Calibrationprocedures,temperatures,cellconstants
used.
Detailsofanypreconditioning
Temperatureprogram
MethodfordetrminingTg,Tm
Instrumentused
 Tm and Crystallinity Measurement by
Differential Scanning Calorimetry, DSC
% Xtallinity =Hexp/Ho
Where Hexp is Heat of fusion for the polymer

H0 is Heat of fusion for 100% crystalline polymer

0.2

0.0

-0.2
236.86C
Heat Flow (W/g)

48.50J/g

-0.4

-0.6

-0.8
250.61C

-1.0
160 180 200 220 240 260 280 300
Exo Up Temperature (C) Universal V3.8B TA Instruments
 MeltingandCrystallization

Meltingistheendothermictransitionfroma
crystallinesolidtoaliquidamorphousstate
Crystallizationistheexothermictransition
fromamorphoustocrystalline(normallyfrom
liquidtosolidduringcooling)
ColdCrystallizationistheexothermic
transitionduringheatingfromasolid
amorphousstatetoasolidcrystallinestate.
 TypicalDSCOutput:
TransitionsofInterestinaDSC

Oxidation
or
HeatFlow>exothermic

Decomposition

Melting
Glass
Transition CrossLinking
Crystallization (Cure)

Temperature
 MeasurementofMelting
0.0

ExtrapolatedOnset
-0.2
&IntegratedArea
242.65C
-77.27J/g

-0.4

221.83C
271.52C
End
Heat Flow (W/g)

-0.6
Start

-0.8
12.28C
Width@
Halfheight
-1.0

-1.2 Peak&
256.26C
Height
-0.8930W/g
-1.4
160 180 200 220 240 260 280 300 320 340
Exo Up Temperature (C)
 MeasurementofMelting
0.0

-0.2
242.65C
-77.27J/g

-0.4
Heat Flow (W/g)

-0.6

-0.8

-1.0

-1.2

256.26C

-1.4
160 180 200 220 240 260 280 300 320 340
Exo Up Temperature (C)
 DSCMelting

Polymers
Thepeaktemperatureisthemeltpoint
Betweentheextrapolatedonsetandthepeak,crystalperfection
maybeoccurring
Betweenthepeakandtheendthesampleisfinishedmelting
andreturningtotheDSCtemperature
Pure,lowmolecularweightmaterials
(mw<500g/mol)(smallmolecules)
Theextrapolatedonsetisthemeltingtemperature
Allofthecrystalsaremeltedatthepeak
Betweenthepeakandtheendthesampleisfinishedmelting
andreturningtotheDSCtemperature
 Tm isaffectedby:
Mwt
ChemicalStructure
Additives
Candisruptpackingofserveasnucleating
sites
Effectofheating/coolingrate

Crystallizationkinetics

Effectsofpolymerstructure/composition

Effectsofthermal/mechanicalprocessing
 Effect of Aromaticity on Melting

Polymer % Aromatic Melting Range

-CH2 - CH2 - 0 105 - 135C

PET 39 250 - 275C
-(Ph)-O- 62 300 - 315C
-(Ph)-S- 70 300 - 360C

34
 Effect of Branching on Melting

Polyolefin Branching Tm

LDPE irregular ~ 105C

random lengths

LLDPE irregular ~ 127C

fixed lengths

HDPE none ~ 135C

PP regular ~ 150C
fixed lengths
35
 Effect of Polymer Type on Melting

Class Structure Melting Range

Polyolefins -CH 2 -CH2 - 85 - 174C
Polyamides -CH2
-NH-C(O)-CH2
- 190 - 265C
Polyesters -CH 2-O-C(O)-CH 2 - 220 - 270C
Polyphenylene
Sulfides -Ph-S- 300 - 360C

36
Effect of Molecular Weight on Melting

Olefin Formula Mole. Wt. Tm

(g/mol) (C)
C12H26 170 -10
C24H50 339 54
C30H62 423 66
C35H72 493 75

37
 EffectofHydrogen
BondingonMelting

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

Nylon x,y where:

x = carbons in diamine section
y = carbons in diacid section

38
 EffectofProcessingon
Crystallinity
Firstheatvs.secondheat
forPP
0.5
PP Pellet
PP Cup
PP Quenched from Melt
PP Slow Cooled
0.0 152.08C
77.88J/g

153.18C
95.98J/g
Heat Flow (W/g)

-0.5
167.94C
152.84C
91.62J/g

-1.0 150.18C
88.10J/g

166.25C
-1.5

168.21C
167.52C
-2.0
60 80 100 120 140 160 180 200
Exo Up Temperature (C) Universal V4.4A TA Instruments
 ObservationofCrystallization

Crystallizationisatwostepprocess:
Nucleation
Growth

Theextrapolatedonsetisthenucleationtemperature

Thepeakmaximumisthecrystallizationtemperature
 ObservationofCrystallization
1.0

Peak

0.9
160.65C

0.8
Heat Flow (W/g)

0.7
183.75C
14.68J/g

0.6

ExtrapolatedOnset
&IntegratedArea
0.5

0.4
0 50 100 150 200 250
Exo Up Temperature (C)
 EffectofNucleatingAgents

2.0

crystallization POLYPROPYLENE POLYPROPYLENE

WITHOUT WITHNUCLEATING
NUCLEATINGAGENTS AGENTS
1.5
Heat Flow (W/g)

0.0

1.0
-0.5
Heat Flow (W/g)

-1.0

melting
0.5
-1.5
60 80 100 120 140 160 180 200
Exo Up
Temperature (C)

0.0
40 50 60 70 80 90 100 110 120 130 140 150 160
Exo Up
Temperature (C)
DSC:Applications

Effectofheating/coolingrate

Crystallizationkinetics

Effectsofpolymerstructure/composition

Effectsofthermal/mechanicalprocessing

43
 DSC: Effect of Heating Rate on
Nylon 66 Melting Behavior

Heat transfer rates; thermal gradients

exo

0.2 mW
0.5C/min Increased heating rate causes:
1 mW Can change appearance of
HEAT FLOW

2C/min curve
5 mW Can cause Tm increase and be
5 mW 10C/min less accurate
20C/min If heating rate is low, sample
10 mW
may anneal as it is tested.
50C/min
endo

1 2
240 260 280 3
300 4
Temperature (C)

44
EffectofSampleMass
 DSC: Crystallization Kinetics

Twostepprocess
Nucleation
Crystalgrowth
Nucleationmaybe
Natural
Induced(usingnucleationagents)
Thermallyinfluencedprocess
Naturalnucleation
Crystalgrowth
ModeledbyIsothermalKineticsusingthe
AutocatalyticModel

46
 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 (t )

47
 DSC: Isothermal Crystallization of
Polyethylene Terephthalate
T1 T1<T2<T3<T4
T

T2

T3
T4

Blank run

0 1 2 3 4 5 6
Time (min)
48
 Effect of Annealing
Poly(ethyletherketone) (PEEK) on Melting

0.0
PEEK
HeatFlow(W/g)

0.1
303.61C

PEEK annealed
0.2 @ 300C

0.3
260 280 300 320 340 360 380
49 Temperature(C)
 EffectofDrawRatioonCrystallinityfor
HDPEFibers

6
HDPE 115%.001 HDPE 115%
HDPE 240.001 HDPE 240%
HDPE 700 HDPE 700%

104 J/g

4
Heat Flow (W/g)

120 J/g

160 J/g

-2
80 100 120 140 160
Exo Up Temperature (C) Universal V4.4A TA Instruments

50
 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.

51
 TheGlassTransition
Temperature,Tg

Observedinamorphousthermoplasticsbut
notallsemicrystallinethermoplastics
Observedinthermosets
Exceptions:
Extremelyhighcrosslinkdensities
Veryrigidbackbones
 TheGlassTransition

TheGlassTransitionis1.)thereversiblechange
oftheamorphousregionofapolymerfrom,or
to,aviscousorrubberyconditionto,orfrom,a
hardandrelativelybrittleone.2.)onsetoflarge
scale,cooperativemotionofthepolymerchains.
TheGlassTransitionTemperatureisa
temperaturetakentorepresentthetemperature
range overwhichtheglasstransitiontakesplace
DetectedbyDSCasanincreaseinCp
 Tg MeasurementbyDSC
Tg ofPMMA
Sample: PMMA sample File: J:...\MSE 430-Fall 2010\Team 2\PMMA.001
Size: 10.6500 mg DSC Operator: AH
Method: Ramp Run Date: 01-Oct-2010 12:51
Instrument: DSC Q100 V9.8 Build 296
-0.15

-0.20
Heat Flow (W/g)

-0.25

103.43C
-0.30

109.58C(H)

-0.35 115.78C

-0.40
40 60 80 100 120 140 160
Exo Up Temperature (C) Universal V4.4A TA Instruments
 -0.15
MeasurementofTg
Extrapolated
Start
Onset

-0.20 53.49C
Midpoint&
88.27C Change
Heat Flow (W/g)

-0.25 93.01C(H)
0.04705W/g

98.33C
-0.30
125.49C

Extrapolated End
End
-0.35
20 40 60 80 100 120 140 160
Exo Up Temperature (C)
 MeasurementofTg
-0.15

-0.20
Heat Flow (W/g)

-0.25
93.01C(H)

-0.30

-0.35
20 40 60 80 100 120 140 160
Exo Up Temperature (C)
 SomePropertiesAffectedatTg

Physical property Response on heating through Tg

Specific Volume Increases V,

Modulus Decreases 1/E, Tg
Coefficient of Increases
thermal expansion CTE
Specific Heat Increases
Cp
Enthalpy Increases
H&
Entropy Increases Temperature
S
 TgisAffectedby:
Heatingrate
Molecularweight
Chemicalstructure
Crystallinity
Crosslinking
Plasticizer
PhysicalAging
Blends/copolymers
Composites

Anythingthateffectsthemobilityofthe
molecules,affectstheHeatCapacity,whichin
turnaffectstheTg
 DSC:HeatingRate

Heating Rate Sensitivity Reproducibility

(C/min)
5 poor very good
20* good good
40 very good poor

* Recommended heating rate for measuring Tg.

59
EffectofHeating
RateontheTg
 OptimizingMeasurementofTg

If Tg is hard to see:
Use larger sample weight
Use higher heating rate
Use MDSC
Factors that Affect the Tg
Molecular Weight

RedrawnfromthedataofT.G.FoxandP.J.Flory,
J.Appl.Phys.,1950,21,581
 Effect of Molecular Weight
on the Tg (for Styrene Oligomers/Polymers)

Molecular Weight Tg
104 -138C
524 - 40C
2,210 40C
3,100 62C
15,100 86C
36,000 94C
170,000 100C
Turi, pg 249 Kumler, 1977

63
Bulky Substituents

- CH2 - CH2 -
Tg ~ 800C
Polyethylene

- CH2 - CH -

-
CH3 Tg ~ 100C
AtacticPolypropylene
- CH2 - CH -

Tg ~1000C

AtacticPolystyrene
Poly(methyl methacrylate)
CH3

- CH2 - C -

C=O
Flexible Substituents

O T ~1050C
g

CH3
Poly(ethyl methacrylate)
CH3

- CH2 - C -

C=O

O T ~650C
g

CH2 - CH3
Poly(butyl methacrylate) Poly(dodecyl methacrylate)
Poly(propyl methacrylate) Poly(octyl methacrylate)
CH3 CH3 CH3 CH3

- CH2 - C - - CH2 - C - - CH2 - C - - CH2 - C -

C=O C=O C=O C=O

O Tg ~350C O Tg ~200C O Tg ~200C O Tg ~650C

(CH2)2 - CH3 (CH2)3 - CH3 (CH2)7 - CH3 (CH2)11 - CH3
The Effect of Intermolecular
Interactions

- CH2 - CH -
Tg ~ 100C

-
CH3
AtacticPolypropylene

- CH2 - CH - Tg ~870C
-
Cl
PVC
 EffectofHydrogenBonding
ontheTg

Polyamide Tg(C) HBonding

Nylon12,2 59 Least
Nylon10,2 56
Nylon8,2 93
Nylon6,2 159 Most

67
The Effect of Cross - Linking
The Effect of Crystallization
 The Effect of Plasticizer on
Tg
0.4
Pure Polystyrene
10%
20%
30%
64.39C
0.2 67.19C(H)
Polymer + Solvent 70.04C

or Plasticizer 48.80C
Heat Flow (W/g)

52.85C(H) 56.83C
0.0 38.89C

45.26C(H)
51.72C

-0.2
103.45C

109.86C(H)
116.47C

-0.4
0 20 40 60 80 100 120 140 160
Exo Up Temperature (C) Universal V4.4A TA Instruments
 The Effect of Plasticizer on
Tg

Sample: 10%DGD File: J:...\jasmine\P&J.DGD\10%

Size: 10.1000 mg DSC Operator: Precious Sample: 30%DGD File: J:...\jasmine\P&J.DGD\30%
Method: Ramp Run Date: 06-Mar-2012 13:08 Size: 11.1000 mg DSC Operator: Precious
Instrument: DSC Q100 V9.8 Build 296 Method: Ramp Run Date: 06-Mar-2012 14:36
Instrument: DSC Q100 V9.8 Build 296
0.1 0.002
0.2

0.005

0.0 0.000
0.1

Deriv. Heat Flow (W/(gC))

Deriv. Heat Flow (W/(gC))

0.000
Heat Flow (W/g)

Heat Flow (W/g)

-0.1 -0.002

0.0 -0.005

-0.010 -0.2 -0.004

-0.1

-0.015
-0.3 -0.006
0 20 40 60 80 100 120
0 20 40 60 80 100 120
Exo Up Temperature (C) Universal V4.4A TA Instruments
Exo Up Temperature (C) Universal V4.4A TA Instruments
 Effect of Plasticizer on the Tg

forPolyamides

WaterContent(%) Tg(C)
0.35 94
0.70 84
1.17 71
1.99 56
2.70 45
4.48 40
6.61 23
10.33 6
72
 Physical Aging--Relaxation and
Recovery

Thermallyreversible
SpecificVolume

InvolveschangesbelowTg
Melt
Associatedwithnonequilibrium
frommeltstate
Affectstheamorphousphaseonly
A Volumeandenthalpychangewith
time
Thechangeinenthalpywithtimeis
Glass
B Temperature calledrelaxationorphysicalaging
Tg
 EffectofAgingontheGlass
Transition[M.Todoki,PolymerDataHandbook]

Cold Crystallization
Glass Transition
As-Spun
2 days
28 days

196 days
3 years and
2 months
4 years and
11 months

0 50 100 150
74 Temperature (C)
 DSC:EffectofAgingTimeat95C
onShapeofPolystyreneTg
0. 00
Anneal Times = 0, 10, 100 & 1000 minutes

- 0. 05
Heat Fl ow ( W/ g)

- 0. 10

- 0. 15

- 0. 20

- 0. 25
80 90 100 110 120 130
75 Temper at ur e ( C)
 PhysicalAging

Heating the material above the Tg then cooling it through the Tg at a rate
equal to or greater than the final heating rate reduces the relaxation effect.
 PhysicalAging
EffectonMechanical
Properties
Generallossofductility
Modulusincreases
Yieldstrengthincreases
Impactstrength,elongation,
fractureenergydecrease
Effect of Miscible and Immiscible
Blends on Tg
Tg2
Tg1
Endotherm
Tgmixture
TwoPhase

SinglePhase

Temperature
CuringofThermosets
Crosslinking
 ThermosettingPolymers
Curingreactioncanbefollowedby
monitoringawidevarietyofphysical
propertiesincluding:
Heatofreaction
Heatcapacity
Viscosity
Modulus
Others
 DSCThermosetCure:FirstandSecondHeat

-0.04

-0.08 First 155.93C

Heat Flow (W/g)

Tg
-0.12 Residual Cure

102.64C
-0.16 Second Tg 20.38J/g

-0.20

-0.24
0 50 100 150 200 250 300
Temperature (C)
 IsothermalCureofEpoxy
Resin
2.5 100

2.0

80

1.5

Temperature (C)
Heat Flow (W/g)

1.0 60

0.5

40

0.0

-0.5 20
0 5 10 15 20 25
Exo Up Time (min) Universal V4.4A TA Instruments
 OxidativeInductionTime

Heat
flow Oxidative Induction Time

Time
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)
85
= kinetic response of sample
Heat Flow Due to Heat Capacity

86
 Kinetic Heat Flow

Isothermal Temperature

The magnitude of measured kinetic

heat flow is a function of time at a
Heat Flow

constant temperature.

0 87 t1 t2
time
 Standard DSC Measures the Sum of Heat Flow

Heat Flow due to

Kinetic Events
Heat Flow

Heat Flow due to

Heat Capacity

88 Temperature
 Heat Flow Can Be Separated

f(T,t)
Heat Flow

Heat Flow due to

Kinetic Events

dT Heat Flow due to

Cp
dt Heat Capacity

Temperature
89
 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)

Total = Heat Capacity + Kinetic

Heat Flow Component Component
(DSC)
= Heating Rate + Time
Dependent Dependent

= MDSC Reversing + MDSC Nonreversing

90
 Distribution of Transitions in
MDSC Experiments

Total = Heat Capacity + Kinetic

Component Component

= Reversing Heat Flow + Nonreversing Heat Flow

glass transition enthalpic relaxation

melting (some) evaporation
crystallization
decomposition
cure
melting (some)
91
 Physical Measurement Technique

Apply Stimulus Measure Response

Stimulus Response
FTIR IR Radiation Absorbance
Wavelength
NMR Magnetic Field Resonance
Frequency
X-Ray Diffraction X-Ray Radiation Angle of
Diffraction
MDSC Sinusoidal Amplitude of
Heating Rate Heat Flow

92
 Raw Signals in MDSC

All Modulated DSC Signals are derived from

three measured parameters.

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

93
 MDSC Raw Signal

0.2
COLD CRYSTALLIZATION
8 MODULATED HEAT FLOW
(Response) CRYSTALLIZATION DURING MELTING
Deriv. Modulated Temp (C/min)

Modulated Heat Flow (W/g)

0.0
6
GLASS TRANSITION NOTE: ALL TRANSITIONS OF
INTEREST ARE CONTAINED IN
MELTING
MDSC RAW DATA SIGNALS
4 -0.2

2
-0.4

0 MODULATED HEATING RATE

(Stimulus)
-0.6
50 100 150 200 250 300
94
Temperature (C)
 Temperature Change (MDSC)
240 240

230 230

Modulated Temp (C)

A
Temperature (C)

ACTUAL MEASURED TEMPERATURE

220 220

CALCULATED AVERAGE
TEMPERATURE
210 210

200 200
38 39 40 41 42 43 44 45
Exo Up Time (min) Universal V2.5D TA Instruments

95
 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

96
 Total Heat Flow: Average of Modulated Heat
Flow Signal
0.2 0.2

0.1
Modulated Heat Flow (W/g)

Heat Flow (W/g)

0.0 0.0

-0.1

-0.2 -0.2

-0.3

-0.4 -0.4
50 100 150 200 250 300
Temperature (C)
97
 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 98DSC experiments at different heating rates.
 Conventional DSC Cp Measurement

HFS HFMT
Cp K x 0
HFMT
Heat Rate x wt
HF
Where:

K = Calibration constant
endo HFS
HFS = Differential heat flow
with sample
Temp.
HFMT = Differential heat flow
with empty pans
wt = weight of sample
99
 Alternative DSC Cp Measurement

HFHR2 HFHR1
Cp K x
(HR2 HR1) wt 0
HFHR1
Where:
HF
K = Calibration constant

HFHR1 = Differential heat flow of HFHR2
sample at HR1 endo
HFHR2 = Differential heat flow of
sample at HR2 Temp.
HR2 = Heating rate 2
HR1 = Heating rate 1
wt = weight
100 of sample
Deriv. Modulated Temp (C/min)
Heat Capacity from MDSC Raw Signals

0.6

Modulated Heat Flow (W/g)

6

Complex Cp (J/g/C)
HEAT CAPACITY
4
10
0.2
2

MODULATED HEAT FLOW 0

5
-0.2
2

4
0 MODULATED HEATING RATE
-0.6
50 100 150 200 250 300
Temperature
101 (C)
 MDSC Signals - Reversing Heat Flow
(Heat Capacity Component)

ReversingHeatFlowistheheatcapacitycomponentofthetotalheatflow.Itiscalculated
byconvertingthemeasuredheatcapacityintoaheatflowsignalusingtheclassicalheat
flowequationasatheoreticalbasis.
Reversing Heat Flow = Cp x Avg. Heat Rate

BasisforCalculation
dH dT
Where : Cp f (T, t)
dH dt dt
total heat flow
dt
Cp measured heat capacity
dT
average heating rate
dt
dT
Cp heat capacity component (Reversing )
dt
102
f (T, t) heat flow from kinetic process (Nonrevers ing)
 Reversing Heat Flow from MDSC Raw Signals

8 0.15

4 0.05

Rev Heat Flow (W/g)

Complex Cp (J/g/C)

HEAT CAPACITY

0 -0.05

REVERSING HEAT FLOW

-4 -0.15

-8 -0.25
50 100 150 200 250 300
103
Temperature (C)
 Quench Cooled PET:
Total vs. Reversing Heat Flow

0.1 0.15

]Rev Heat Flow (W/g)

0.0 0.05
Heat Flow (W/g)

TOTAL

-0.1 -0.05

REVERSING
-0.2 -0.15

[
-0.3 -0.25
50 100 150 200 250 300
Temperature (C)
104
 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
Cp heat capacity component (reversing)
dt
f (T, t) kinetic component (nonreversing)
105
 Quench-Cooled PET: Deconvoluted Signals

0.25 0.25

0.15 0.1 0.15

Nonrev Heat Flow (W/g)

Rev Heat Flow (W/g)

Heat Flow (W/g)

NONREVERSING
0.05 0.0 0.05

TOTAL
-0.05 -0.1 -0.05
REVERSING

-0.15 -0.2 -0.15

-0.25 -0.25
50 100 150 200 250 300
Temperature (C)
106
Glass Transition of Polymer Resin

107
MDSC: Glass Transition of Epoxy Coating

108
MDSC: Glass Transition of Epoxy Coating

109
 PET/ABS Blend
Conventional DSC

-0.2 120.92C
67.38C first heat on molded part
70.262C (H)
235.36C
-0.3 22.63J/g

-0.4
Heat Flow (W/g)

111.82C
-0.5 9.016J/g

249.75C
-0.6
second heat after 10C/min cooling
(Curve shifted on Y axis to avoid overlap)
-0.7
9.22 mg sample, nitrogen purge
10C/minute heating rate
-0.8
50 100 150 200 250
110 Temperature (C)
 PET/ABS - MDSC

-0.10 first heat on molded part -0.04

-0.02

) Nonrev. Heat Flow (W/g)

-0.11 -0.05

) Rev. Heat Flow (W/g)

-0.03
Heat Flow (mW)

-0.12 -0.04 -0.06

67.00C
-0.13 +72.89C (H)
-0.05 -0.07
PET Tg
104.45C
107.25C (H)
-0.14 -0.06 -0.08
8.46mg sample ABS Tg
nitrogen purge

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

(
-0.15 -0.09
20 40 60 80 100 120 140 160 180 200
111 Temperature (C)
 DSC of Polymer Blend

112
 MDSC of Polymer Blend

113
 MDSC: Detection of Two Glass
Transitions in PC/PEE Blend
3 CONSECUTIVE HEATING RUNS AFTER 2deg/min COOLING
+

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

141. 45 C -0.001
-0.02
+
62. 58 C
3
Rev Heat Flow (W/g)

2
-0.04
1 -0.002

DERIVATIVE
-0.06

MDSC 0.424C, 40 sec. period -0.003

-0.08
4C/min underlying ramp rate

-0.10 -0.004

-0.12 NOTE 81C WIDTH OF GLASS TRANSITION

-0.005
40 60 80 100 120 140 160
Temperature (C)
114
 FAST MDSC ON THE Q1000

2.0 -0.15
1
2
1 First Heat 1
2
1
2 Second Heat 2

1.8 2
1
2
First Heat Shows Small MDSC Conditions: -0.20
[ ] Rev Cp (J/g/C)

[ ] Heat Flow (W/g)

Tg Near 70c 1 30 sec. period
2 2
+/- 0.3c amplitude
2 10 cpm
1.6 1
2
2
1 1
2 2
-0.25
2 2
1 1 1
1
2
1.4 2
1 1 1
21 1
1 2
2 1 1
1
1 1 -0.30
1.2 2
2
2
Residual Cure Occurs at 2 2

Low Temperature Tg of
First Heat
1.0 -0.35
0 50 100 150 200 250
Exo Up Universal V3.1B TA Instruments
Temperature (C)

115
 MDSC: Heat Capacity for PET During
Isothermal Steps
1.6 140
PLOT vs TIME
Heat Capacity
Heat Capacity (J/g/C)

120

Temperature (C)
1.4

100
Temperature
1.2
80
MDSC 0.30C, 40 sec. period
1C isothermal steps

1.0 60
0.4 0.6 0.8 1.0 1.2 1.4 1.6 1.8 2.0
116 Time (day)
 MDSC: PET Heat Capacity
During GlassTransition &
Cold Crystallization

COLD CRYSTALLIZATION
1.6 (First-Order Transition)
Heat Capacity (J/g/C)

1.5

1.4
GLASS TRANSITION
(Second-Order Transition)
1.3

1.2
MDSC 0.30C, 40 sec. period
1C isothermal steps
1.1

60 70 80 90 100 110 120 130

Temperature (C)
117
 Isothermal Epoxy Cure

6 14.5
H of Cure
DMA 1Hz 14.0
Nonrev. Heat Flow (mW)

) Heat Capacity (mJ/C)

30

4 13.5

) E' (GPa)
Heat 20
Capacity 13.0

2 10 12.5

(
Isothermal 80C 12.0
helium purge
0
0.5C amplltude

(
60 second period
0 11.5
0 5 10 15 20 25 30 35 40
118 Time (min)
MDSC: Heat Capacity vs. Cure Time
Result at 70C Cure=
TM
Epoxy-Amine System MDSC
) Nonreversing Heat Flow (mW/g)

120 2.5
t 1/2 Cp = 97 mi

) Heat Capacity (J/g/K)

t1/2 Cp
Heat Capacity X vit = 0.53
90
2.0
exo
60

1.5
30 Nonreversing Heat Flow

(
0 1.0
(

0 100 200 300

Time (min)

=
Thermochimica Acta, 268, 121-142 (1995), Dr. B. Van Mele, et al
119
at Vrije Universiteit Brussels (Belgium)
 MDSC: Experimental Considerations

Modulation Period? Sample

Dimensions?

Calibration?

Phase Purge
Correction? Gas?

Sample
Preparation?
120
Modulation Amplitude?
 ModulatedDSC
Isothermalapproach
Theapproachassumesthatthereactionfollows
autocatalyzed exothermicsystemsandobeysthegeneral
rateequation: d
k (T ) 1
m n

dt
whered/dt =reactionrate(1/sec)
=fractionalconversionk(T)=specificrateconstantat
temperatureT
Thisapproachrequiresthreeormoreisothermal
experimentstogeneratethekineticparameters:
Activationenergy(Ea),PreexponentialfactorZHeat
ofreaction(H),Reactionorder(n,m)Rateconstant
(k)

121
 IsothermalDSCThermogramsat120Cfor
NeatresinandNanocomposites
0.08

1% F-MWCNT EPON 828

1% COOH-MWCNT EPON 828

Neat Epoxy

0.06

0.04



Heat Flow (W/g)

0.02

0.00








-0.02






-0.04
0 50 100 150 200 250
Exo Up Time (min) Universal V4.5A TA I

122
 ActivationEnergiesandRateConstantfor
theNeatResinandNanocomposites
Rate constant
Average Ea
Sample min-1
(H) J/g kJ/mol
TIso120 C

Neat Epoxy 319.6 47.5 0.0428

1.0 % COOH-MWCNT/EPON
239.8 61.7 0.0390
828

1.0 % F-MWCNT/EPON 828 263.4 47.7 0.0428

123
 IsothermalCureBehaviorofNeat
EpoxyResinandNanocompositesat
1.000E7
120C
Ne at Epoxy
1.000E6 1% F-MWCNT EPON828
1% COOH-M WCNT EPON828

1.000E5

10000
G' (Pa)

1000

100.0

10.00

1.000

0.1000
0 1000.0 2000.0 3000.0 4000.0 5000.0 6000.0 7000.0 8000.0
time (s)
124
 Gelation,Vitrification andDegreeof
ConversionandoftheNeatResinand
Nanocomposites
Gel point
Degree of
time
Sample tvitr(min) Tg (C) Conversion
(min)
(%)
C

Neat Epoxy 81.4 149 119 95

1.0 % COOH-
58 185 120 96
MWCNT/EPON 828

1.0 % F-MWCNT/EPON
78.5 160 119 96
828

125
 HeatCapacity

185.11min

148.61min

1.8

158.94min
Rev Cp (J/(gC))

Neat Epoxy



1% COOH-MWCNT EPON828

1% F-MWCNT EPON828
1.4

0 50 100 150 200 250
Time (min) Universal V4.5A TA Instruments
 CarbonNanotubeReactionSchemes
A)
F + H2N R NH2
HN

O O
R NH2
NH2 + H2C CH R CH CH2
NH
R

H OH O
N
R N CH CH2 R CH CH2

B) O O O
C OH + HC CH R CH CH2
2

O OH O
C O CH2 CH R CH CH2
127
MDSC: Sample Preparation

Thin,LowMassSamples
MinimizeThermalGradients
AllowforFasterPeriods,Larger
ModulationAmplitudes

Thicker,HeavierSamples
MinimizeBaselineCurvature
ImproveSensitivity
128
MDSC:SamplePansStandardCrimped

Low, Consistent Mass

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

129
MDSC:SamplePansStandardHermetic

Useforliquid/volatilesamples
HigherMass,LessSensitivity
UseHeatSinkCompound

130
 MDSC:PurgeGas
Nitrogen
Economical
Wide Operating Range
Provides Good Sensitivity

Helium
Higher Thermal Conductivity
Facilitates Wider Range of Modulation
Conditions
Reduces Baseline Curvature

131
 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

132
 MDSC:HeatCapacityCalibration

ProvidesforAccurateHeatCapacity
Measurements
UseEitherSapphireDisc(widetemperature
range)orHDPE(polymermelt)
Chooseonepointoraveragevalues
EffectsofExperimentalConditions

133
 VariationsinDSC

PressureDSC
PhotoDSC