열분석법(thermal analysis)cfs2.tistory.com/upload_control/download.blog?fhandle=... · 2015. 1....

열분석법(Thermal Analysis)-생산기술연구원/2005.03.09~03.23-

심인철

케미랩(Chemilab)

목 차

• 열분석 소개• DSC(DTA)의 원리 및 응용• 기타 열분석 기술 소개• 열분석 응용• 시험규격• 분석 팁• 질의 응답

A Short Reviews of Thermal Techniques

• DSC온도나 시간의 함수로 시료의 열 흐름(출입)을 측정.

[종류]Heat FluxPower Compensation

[측정 변수]유리전이(Tg)열이력에 의한 영향

용융(Tm)Oxidative Induction Time비열

Polymorphism결정화

경화

반응속도정수

etc.

• TGA온도나 시간의 함수로 시료의 무게변화를 측정.

[종류]Torque converter를 이용한 Null Type Balance 사용.

[측정변수]열분해/열안정성수분함량/고형분 측정성분(비율)/첨가제 함량 분석Oxidative Induction Time산화/환원 반응분해반응 속도정수/분해 메커니즘 추정Curie Point 측정Fingerprintetc.

• TMA일정한 정적인 힘이 가해진 상태에서 온도나

시간의 함수로 시료의 치수 변화를 측정.(Non-Oscillating mode)

[종류]Magnetic force motorDrive force motor

[측정변수]Static Modulus/Young’s Modulus선형열팽창계수(CTE)등변위에 대한 응력측정

DilatometryTg, Tm 측정Extension Testetc.

• DM(T)A일정한 주파수를 가진 힘이 가해진 상태 하

에서 온도나 시간의 함수로 시료의 변위를

측정.[종류]

Fixed frequencyResonant frequency

[측정변수]Dymamic moded modulus(Storage, loss M)Tangent deltaTg, TmLow energy transition응력/변형Long term Mechanical property의 예측Miscibility study방음/방진 시험etc.

•기타 열분석 기술DPASDTASTMADEATG-MSTG-IR

•응용 기술ADSC(MDSC)Maxres TGATTS

DSC and DTA

Differential Scanning Calorimetry& Differential Thermal Analysis

DSCDifferential Scanning Calorimetry

• A Differential Scanning Calorimeter (DSC) measures the amount of energy (heat) absorbed or released by a sample as it is heated, cooled or held at a constant (isothermal) temperature. The precise measure of sample temperature is also made with a DSC.

Historical aspects

• 1887 Le Chatelier; father of thermal analysisclay and mineral consisted of thermal analysis

determination

other investigators; Ashley, Wholin, Rieke, Wallach

• 1899 Roberts-Aausten; two-thermocouple system• 1908 Burgess; single- and double-thermocouple

systems

Houldsworth and Cobb; differential thermocouple

• 1950s Ston, Borchardt and Daniels; DTA for chemistry• 1960s Polymer chemistry• 1963 Differential scanning calorimetry(DSC)

DSCDifferent Types of DSC Instruments

Power Compensation DSC Quantitative DTA

Derives dHUses thermocouples

Measures dH directlyUses platinum resistance thermometers

DSC

Temperature or Time

DSCApplications

Oxidation Induction Time (OIT) testing

Isothermal Crystallization Studies

Polymorphic Drug Studies

Specific Heat Measurement

Purity Measurement

Dynamic Kinetics studies

Isothermal Kinetics studies

Melting Point

Degree of Crystallinity

Thermal History Studies

Analysis of Wax & Oils

Quality Control of Raw Materials

Curing Studies

Glass Transition Measurements

Instrumental factors

• Furnace atmosphere• Furnace size and shape• Sample-holder material• Sample-holder geometry• Wire and bead size of thermocouple junction• Heating rate• Speed and response of recording instrument• Thermocouple location in sample

Sample Characteristics

• Particle size• Thermal conductivity• Heat capacity• Packing density• Swelling or shrinkage of sample• Amount of sample • Effect of diluent• Degree of crystallinity

Applications

• Physical origin

Phenomena Endothermal Exothermal

Crystalline transition x x

Fusion x

Vaporization x

Sublimation x

Adsorption x

Curie point transition x

Glass transition Change of base line

Liquid crystal transition x

Heat capacity transition Change of base line

Applications

• Chemical origin

Phenomena Endotherm Exotherm

Chemisorption x

Desilvation x

Dehydration x

Decomposition x x

Oxidative degradation x

Oxidation in gaseous atmosphere x

Reduction in gaseous atmosphere x

Redox reactions x x

Solid-state reaction x x

Combustion x

Polymerization x

Pre-curing(resins) x

Catalytic reactions x

Inorganic compound

• DTA

Qualitative Qquantitative

data data

Identification dH of phase

and transitions

characterization

dH of dissociation

Solid-solid reactions

reactions

Kinetics

High temperature

reactions

• DSC

dH of phase and dissociation

reactions

Kinetics

Organic compound

• DSC and DTA

Exploatory Melting and Quantitative Chemical

surveys boiling points studies reactions

Identification Polymer dH of transition Cataysis

phase transition

Thermal Reaction

stability Purity Kinetics

determination

Phase

equilibria

Polymers

• DSC and DTA

Qualitative Quantitative

measurements measurements

Detection of Qualitative Thermochemical Kinetics

Tg, Tm, etc identification measurements

Decomposition

Thermal stability Flammability dHm, dHc

measurements detection Crystallization

Specific heat

Oxidation reaction Polymerization

dH of

Others polymerization

Others

Effect of Sample Size on Sensitivity and Resolution

IndiumIndiumIndium

Hea

t Flo

w (m

W)

Peak from:to:

Onset =J/g =

155.50160.50156.5128.51

Peak from:to:

Onset =J/g =

155.50161.40156.5628.49

Peak from:to:

Onset =J/g =

155.50162.70156.5428.71

Peak = 158.93

Peak = 158.30

Peak = 157.74

25

50

4.998 mg10.001 mg20.072 mg

100

75

0145.00

Temperature150.00 155.00 165.00 170.00

( C)o

160.00

Melting Point & Degree of Crystallinity

25.0 50.0 75.0 100.0 125.0 150.0 175.0 200.0

10.0

15.0

20.0

25.0

30.0

35.0

40.0

Mon Aug 22 13:16:13 1994

Hea

t Flo

w (m

W)

Application LaboratoryTemperature ( C)

X1 22.666 C

X2 135.000 C Peak 127.373 C

Area 1611.915 mJ H 198.781 J/g

Height 23.315 mW

Onset 118.769 C

Curve 1: DSC File info: hdpe2 Thu Jul 12 14:18:44 1990Sample Weight: 8.109 mgHigh Density Polyethylene @ 10C/min

PERKIN-ELMER7 Series Thermal Analysis System

TEMP1: 15.0 C TIME1: 0.0 min RATE1: 10.0 C/minTEMP2: 200.0 C

Thermal History Studies

100.0 150.0 200.0 250.0 300.0-10.0

-5.0

0.0

5.0

10.0

15.0

20.0

25.0

30.0

35.0

40.0

45.0

50.0

55.0

60.0

Mon Aug 22 13:40:34 1994

Hea

t Flo

w (m

W)

Temperature ( C)

# 1 POLYESTER INITIAL HEATING:polyeHeat Flow (mW)

Curve 1: DSC File info: polye Mon Jul 22 12:23:59 1985Sample Weight: 14.273 mgPOLYESTER INITIAL HEATING



# 2 POLYESTER AFTER QUENCHING FROM THE MELTHeat Flow (mW)

Analysis of Low Melting Wax

58.0 62.0 66.0 70.030.0

35.0

40.0

45.0

50.0

55.0

60.0

Mon Aug 22 13:47:18 1994

Hea

t Flo

w (m

W)

B.CasselTemperature ( C)

Peak 65.49 CH 60.02 J/g

Onset 64.67 C

Peak 70.54 CH 161.74 J/g

Onset 69.23 C

Curve 1: DSC File info: dtc02 Mon Feb 20 16:12:35 1989Sample Weight: 3.502 mgDotriacontane 2 C/min



CALORIMETRY CONSIDERATIONS

• SAMPLING VARIABLESSAMPLE SIZESAMPLE GEOMETRYSAMPLE PANSSAMPLE CONDITIONING

CALORIMETRY CONSIDERATIONS

• INSTRUMENTAL/TEST VARIABLESSCAN RATEPURGE GAS CALIBRATIONCOOLANT

CONSTANT CALORIMETRY REGARDLESS OF SAMPLE SIZE.

150.0 152.0 154.0 156.0 158.0 160.0 162.0 164.0-20.0

-10.0

0.0

10.0

20.0

30.0

40.0

50.0

60.0

70.0

80.0

90.0

100.0

Wed Feb 15 12:18:25 1995

Hea

t Flo

w (m

W)

CALORIMETRIC TEST Tech.Support LabTemperature ( C)

Peak 157.57 CH 28.46 J/g

Onset 156.55 C

Curve 1: DSC File info: indium004 Tue Feb 14 16:30:54 1995Sample Weight: 4.998 mgIndium (4.998mg.)



Peak 157.92 CH 28.52 J/g

Onset 156.48 C

Peak 158.66 CH 28.52 J/g

Onset 156.5 C

Indium 20.072 mg.

Indium 10.002 mg.

Indium 4.998 mg.

Indium 4.998 mg.Indium 10.002 mg.Indium 20.072 mg.

Indium 4.998 mg.

SAMPLING VARIABLESSAMPLE GEOMETRY

• GEOMETRY AFFECTS PEAK HEIGHT• GEOMETRY AFFECTS PEAK WIDTH• GEOMETRY AFFECTS PEAK POSITION• GEOMETRY DOES NOT AFFECT ONSET• GEOMETRY DOES NOT AFFECT CALORIMETRY

150.0

Foil samplePellet Sample

112.5

341310

145.00

Hea

t Flo

w

75.0

(mW

)

37.5

0.0150.00 155.00 165.00 170.00 175.00

Temperature ( C)o

160.00

SAMPLING VARIABLESSCANNING RATE

• SCAN RATE AFFECTS PEAK POSITION• SCAN RATE DOES NOT AFFECT CALORIMETRY

Hea

t Flo

w (m

W)

1 C/min5 C/min

10 C/min20 C/min

o

o

o

o

25

50

40 C/mino

100

75

0154.00 156.00 158.00 160.00 162.00 164.00 166.00

341311

Temperature ( C)o

SAMPLE CONDITIONING

100.0 150.0 200.0 250.0-1.5

-1.0

-0.5

0.0

0.5

1.0

1.5

2.0

2.5

3.0

3.5

4.0

4.5

5.0

Tue Jan 31 08:15:53 1995

SAME SAMPLE, DIFFERENT THERMAL HISTORY

Spec

ific

Hea

t (J/

gC

)

AFTER 40 C/MIN COOL & ANNEAL @65 BCTemperature ( C)

# 1 PET SCAN ISO:PET009Total C P (J/g C)

Curve 1: DDSC File info: PET009 Thu Jan 12 11:08:23 1995Sample Weight: 16.170 mgPET SCAN ISO


# 2 PET SCAN ISO:PET007Total C P (J/g C)

1. Shock Cooled from the Melt2. Cooled at 40 oC/min, thenannealed at 70 oC.

TGAThermogravimetric Analysis

A Thermogravimetric Analyzer (TGA) measures the change in mass of a sample as the sample is heated, cooled or held at a constant (isothermal) temperature.

TGA Design

+ Balance

QuartzPurge in

Sample in pan

MicrofurnaceThermocouple

Purge out

Sensor

TGATypical Experiment

100.0 200.0 300.0 400.0 500.0 600.0

0.0

10.0

20.0

30.0

40.0

50.0

60.0

70.0

80.0

90.0

100.0

110.0

Thu Aug 25 07:45:35 1994

Wei

gh

t (W

t. %

)

n2-air royTemperature ( C)

Onset 438.85 C

Curve 1: TGA File info: wh-po Thu Sep 16 09:35:25 1993Sample Weight: 33.043 mg

white poly(ethylene)


TEMP1: 30.0 C TIME1: 0.0 min RATE1: 20.0 C/minTEMP2: 1000.0 C TIME2: 5.0 min

TGAApplications

• Component Separation & Quantitation

• Kinetics Studies• Oxidation/Reduction

Effects

• Proximate Analysis of Coal & Energy Materials

• Study of Flame Retardants

• Curie Point Temperature• Thermal Stability• Decomposition Studies• Effects of Fillers &

Additives

• Fingerprinting• Moisture Determination

Determining the Effect of Fillers & Additives

200.0 400.0 600.0 800.0 1000.00.0

10.0

20.0

30.0

40.0

50.0

60.0

70.0

80.0

90.0

100.0

Thu Aug 25 07:47:28 1994

Wei

gh

t (W

t. %

)

n2-air royTemperature ( C)

# 1 white poly(ethylene):wh-po% Weight (Wt. %)

Curve 1: TGA File info: wh-po Thu Sep 16 09:35:25 1993Sample Weight: 33.043 mgwhite poly(ethylene)


TEMP1: 30.0 C TIME1: 0.0 min RATE1: 20.0 C/minTEMP2: 1000.0 C TIME2: 5.0 min

# 2 black poly(ethylene):po0914b

% Weight (Wt. %)

Component Separation

100.0 200.0 300.0 400.0 500.0 600.0 700.0 800.00.0

10.0

20.0

30.0

40.0

50.0

60.0

70.0

80.0

90.0

100.0

Wed Aug 24 15:41:32 1994

Wei

gh

t (W

t. %

)

BCasselTemperature ( C)

Y -17.65 Wt. %

Y -44.95 Wt. %

Y -34.44 Wt. %

Curve 1: TGA File info: rub5 Wed Jul 8 12:16:42 1987Sample Weight: 3.044 mgRubber step-wise


TEMP1: 100.0 C TIME1: 0.0 min RATE1: 100.0 C/minTEMP2: 325.0 C TIME2: 3.0 min RATE2: 100.0 C/minTEMP3: 500.0 C TIME3: 3.0 min RATE3: 100.0 C/minTEMP4: 900.0 C

TMA/DMA/Dilatometry

• A technique in which the deformation of a substance is measured under

non-oscillatory load as a function of temperature as the substance is subjected to a controlled temperature program.~TMA

• Thermodilatometry; dimentions of a subatanceare measured~Dilatometry

• A technique in which the dynamic modulus and /or damping of a substance is measured under oscillatory load as a function of temperature as the substance is subjected to a controlled temperature program.~DMA

TMA Penetration Experiment

50.0 75.0 100.0 125.0 150.0 175.0 200.01.00

1.05

1.10

1.15

1.20

1.25

1.30

1.35

1.40

1.45

1.50

Tue Sep 6 14:59:56 1994

Pene

tratio

n (m

m)

B.TWOMBLYTemperature ( C)

Onset 175.87 C

Curve 1: TMA in PenetrationFile info: T5exx1 Wed Oct 4 16:18:08 1989Sample Height: 1.354 mmPOLYPROPYLENE BLEND


TEMP1: -125.0 C TIME1: 0.0 min RATE1: 10.0 C/minTEMP2: 250.0 C

TMA Expansion Analysis

-200.0 -100.0 0.0 100.0 200.05.30

5.32

5.34

5.36

5.38

5.40

5.42

5.44

5.46

5.48

Tue Sep 6 15:09:24 1994

Expa

nsio

n (m

m)

ASTM D696 B.TWOMBLYTemperature ( C)

Cx 2.75 x 10 -5 / C

Onset 137.08 C

Cx 2.737 x 10 -4 / C

Curve 1: TMA in ExpansionFile info: T5refE Tue Aug 29 16:43:28 1989Sample Height: 5.315 mmREFERENCE MATERIAL E



TMA Extension Experiment

-50.0 0.0 50.0 100.0 150.0 200.0 6.0

7.0

8.0

9.0

10.0

11.0

12.0

13.0

Tue Sep 6 15:12:19 1994

Exte

nsio

n (m

m)

INITIAL RUN B.CasselTemperature ( C)

Curve 1: TMA in ExtensionFile info: nylnextg Sun Aug 7 14:34:43 1988Sample Height: 8.640 mmNYLON MONOFILEMENT



DMA 7e Operation

The DMA 7e Can Perform Many Tests

Temperature Scan ModeIsothermal (Time) Scan ModeFrequency Scan ModeDynamic Stress Scan ModeStatic Stress Scan Mode (Creep Ramp)Creep AnalysisStress Relaxation (Recovery Analysis)Creep-Recovery AnalysisConstant Length Analysis (Shrinkage Force)Constant Force Analysis (TMA)

Perform many different types of tests

– melt, Tg, alpha, beta and gamma transitons, – recrystallization, – cure, – modulus, – damping, – shrinkage, – heat deflection, – brittle point tests and many more ...

Run many types of samples

– plastic, – automotive, – construction, – aerospace, – business products,– metal, – ceramic, – food, – cosmetic, – environmental, – biological materials.

케미랩(Chemilab)

• www.chemilab.com• 분석 기술 자문/분석 의뢰, 수행• Toptac2000 제조, 판매• 실리콘 코팅제 제조, 판매• 고분자 관련 제품 개발 컨설팅• 기업 기술 자문• 열분석 관련 한국표준과학연구원 주관 산자부

프로젝트 수행 기업

감사합니다

열분석법(Thermal Analysis)-생산기술연구원/2005.03.09~03.23-목 차A Short Reviews of Thermal TechniquesDSC and DTADifferential Scanning Calorimetry& Differential Thermal AnalysisDSCDifferential Scanning CalorimetryHistorical aspectsDSCDifferent Types of DSC InstrumentsDSCDSCApplicationsInstrumental factorsSample CharacteristicsApplicationsApplicationsInorganic compoundOrganic compoundPolymersMelting Point & Degree of CrystallinityThermal History StudiesTGAThermogravimetric AnalysisTGA DesignTGATypical ExperimentTGAApplicationsDetermining the Effect of Fillers & AdditivesComponent SeparationTMA/DMA/Dilatometry케미랩(Chemilab)감사합니다

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