Thermal Analysis Thermal Analysis Information for Users User Com Application Handbook Selected Applications

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1 Thermal Analysis Thermal Analysis Information for Users User Com Application Handbook Selected Applications

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3 Selected Applications Thermal Analysis ポリマーの熱分析 TM METTLER TOLEDO Selected Applications 3

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5 Henry Le Chatelier 1899 William Roberts-Austen DTA UserCom Dr. Angela Hammer Materials Characterization Nicolas Fedelich Samuele Giani Dr. Elke Hempel Ni Jing Dr. Melanie Nijman Dr. Rudolf Riesen Dr. Jürgen Schawe Dr. Markus Schubnell METTLER TOLEDO Selected Applications 5

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7 DTA SDTA DSC TGA EGA TMA DMA TOA TCL DSC TGA TMA DMA TGA TMA DMA DSC DSC TGA TMA DMA TGA TMA DMA DSC TGA TMA DMA METTLER TOLEDO Selected Applications 7

8 1. Introduction 1: 6 DSC: TGA: TMA: PET KU600 W DSC TGA TMA DMA DSC TGA TMA 1.3 DTA DTA DTA C K : mv 1.4 SDTA DTA DTA DTA SDTA 1.5 DSC DSC : mw DSC 1.6 TGA TGA TG T g TGA TGA 1.7 EGA EGA EGA EGA TGA TGA 1.8 TMA TMA TMA 8 METTLER TOLEDO Selected Applications

9 TMA 1.9 DMA DMA 1.12 DMA 1.10 TOA Thermo-optical Analysis TOA DSC 1.11 TCL Thermochemiluminescence TCL DSC DTA TGA TMA DMA TOA TCL EGA liquid fraction : METTLER TOLEDO Selected Applications 9

10 2. DSC Thermoplastics 2 PET 3 PET DSC K/min 50 ml/min 2.1 DSC PET [1] OIT PET PET Polyethylene Terephtalate 2 PET PET PET µm 2.2 FRS5 DSC 1 STAR e 3 10 mg 2.3 DSC DSC DSC [2] DSC 3 PET DSC DSC 3 PET 1st heating DSC DSC c p STAR e 10 METTLER TOLEDO Selected Applications

11 T g [2, 3, 4, 5] DSC T g c p CTE TMA DMA 2/3 2/3 K PET PET T melt = 256 = K T g = /3 = K 79.6 DSC c p 80% 100 X 100% PET DSC 420 K/min DSC 1 1st run 4 1 st run 3 DSC 2 nd run 4 PET DSC 1st 1st 2nd METTLER TOLEDO Selected Applications 11

12 Thermoplastics 5 DSC 6 PET 1 st run 2 nd run 2 nd run 1 st run 5 2 nd run 50 K/min PET 6 PET DSC K/min K/min METTLER TOLEDO Selected Applications

13 7 PET 8 PET DSC [6, 7] 300 K/min TOPEM TOPEM IsoStep ADSC 9 PET TOPEM 80 TOPEM 40uL 0.2 K/min 9 TOPEM c p Hz TOPEM [8, 9] DSC c p 8 PET DSC J/g 9 PET TOPEM METTLER TOLEDO Selected Applications 13

14 Thermoplastics 10: PET TOPEM TOPEM PET OIT/OOT [10,11] OIT,OOT DSC PE PET PEPE OITPE min 20 /min min OIT 40ul PE OOT OIT 11: PE OIT 11 PE OIT 2.4 [1] Total Analysis with DSC, TMA and TGA-EGA, UserCom9, [2] Interpreting DSC curves, Part 1: Dynamic measurements, User- Com11, 1 7. [3] The glass transition from the point of view of DSC-measurements; Part 1: Basic principles, User- Com10, [4] The glass transition temperature measured by different TA techniques, Part 1: Overview, User- Com17, 1 4. [5] R. Riesen, The glass transition temperature measured by different TA technique, Part 2: Determination of glass transition temperatures, UserCom18, 1 5. [6] M. Wagner, DSC Measurements at high heating rates - advantages and limitations, UserCom19, 1 5. [7] R. Riesen, Influence of the heating rate: Melting and chemical reactions, UserCom23, [8] TOPEM The new multifrequency temperature-modulated technique, UserCom22, 6 8. [9] J. Schawe, Analysis of melting processes using TOPEM, User- Com25, [10] Oxidative stability of petroleum oil fractions, UserCom10, 7 8. [11] A. Hammer, The characterization of olive oils by DSC, UserCom28, METTLER TOLEDO Selected Applications

15 3. TGA TMA DMA 3.1 TGA TMA DMA TGA TMA DMA DSC 3.2 TGA TGA TGA TGA TGA TGA DTG TGA/DSC DSC TGA/DSC DSC DSC DSC [2, 3] TGA- FTIR TGA-MS 3.3 TMA TMA DLTMA TMA: Dynamic Load TMA 12: PET TGA/DTG DSC TGA DSC : 20 K/min : 30~ : PET TMA 12 PET TGA DTG 9 2 DSC DSC 300 METTLER TOLEDO Selected Applications 15

16 Thermoplastics 14 PET TMA CTE mm K/min, , N, : 13 TMA mm PET : 20 K/min, : 30 ~ 310, 0.1 N 0.5 N, 14 15: ~160 PET DLTMA DLTMA DLTMA DSC DLTMA Dynamic Load TMA [4] DLTMA 15 PET DLTMA DLTMA METTLER TOLEDO Selected Applications

17 3.4 DMA DMA 16: -150 ~ 270 PET DMA DMA DMA E, G E,G tan DMA DSC 16 PET DMA 5 mm 0.49 mm PET :1 Hz, :2 K/min, : -150 ~ : PET DMA TMA TGA/DSC DMA PET 1 2 TGA/DSC DSC TMA DMA tan DSC TGA/DSC TMA DMA x x x (DSC signal x x x x (DSC signal x x (x) x x x x x (x) x (x) OIT x 2: METTLER TOLEDO Selected Applications 17

18 Thermosets 2 DSC TGA TMA DMA PET OIT PET TGA DSC,TMA DMA 3.6 [1] A. Hammer, Thermal analysis of polymers. Part 1: DSC of thermoplastics, UserCom 31, 1 6. [2] R. Riesen, Heat capacity determination at high temperatures by TGA/DSC. Part 1: DSC standard procedures, UserCom 27, 1 4. [3] R. Riesen, Heat capacity determination at high temperatures by TGA/DSC. Part 2: Applications, UserCom 28, 1 4. [4] PET, Physical curing by dynamic load TMA, UserCom 5, 15. 3: PET DSC 20 K/min TGA/DSC 20 K/min, DSC, N 2 TMA 20 K/min DMA 1 Hz, 2 K/min, tan delta METTLER TOLEDO Selected Applications

19 4. DSC 4.1 DSC DSC ADSC DSC TGA TMA DMA KU600 KU FRS5 DSC 1 DSC TGA/DSC 1 TMA/SD- TA840 e DMA/SDTA861 e STAR e 4.3 (DSC DSC DSC [3] 18 DSC : KU600: 10 K/min DSC 3 19: KU600: K/min METTLER TOLEDO Selected Applications 19

20 Thermosets 20: KU600: KU K/min KU DSC % MFK [5, 6] KU600 21: KU600: DSC DSC METTLER TOLEDO Selected Applications

21 MFK % c p KU600 [4] DIN % c p +/-0.4 mg K/min 5 DSC c p 20 DSC 0.3 J/gK c p 1 K/min 0.5 K 48s ADSC DSC 22: KU mg 5 K/min 23: KU600 c p ADSC: ADSC [7] IsoStep TOPEM c p KU600 KU600 METTLER TOLEDO Selected Applications 21

22 Thermosets DSC DSC 4.4 [1] A. Hammer, Thermal analysis of polymers. Part 1: DSC of thermo plastics, UserCom 31, 1 6. [2] A. Hammer, Thermal analysis of polymers. Part 2: TGA, TMA and DMA of thermoplastics, UserCom 31, 1 5. [3] Interpreting DSC curves. Part 1: Dynamic measurements, UserCom 11, 1 6. [4] METTLER TOLEDO Collected Applications Handbook: Thermosets, Volume 1. [5] Model free kinetics, UserCom 2, 7. [6] Ni Jing, Model free kinetics, UserCom 21, 6 8. [7] ADSC in the glass transition region, UserCom 6, : KU600 ADSC 22 METTLER TOLEDO Selected Applications

23 5. TGA TMA DMA 5.1 TGA TMA DMA 5.2 TGA [2] 25 KU µl 20 K/min TMA TMA TMA KU mm 2 3 mm 25: KU600 TGA/ DSC 1 20 K/min TGA DSC / 50 ml/min DTG DSC DTG TGA 26: KU600 DSC TGA DSC METTLER TOLEDO Selected Applications 23

24 Thermosets 27: KU600 DLTMA TMA 0.02N DLTMA TMA Tg DLTMA TMA [3] 5 K/min N 1 N 6 3 mm 27 DLTMA DLTMA 40 µm 200 µm tan KU µm 3 mm 1N 5 K/min : TMA KU600 TMA DMA [4] DMA [5,6] 29 KU600 KU METTLER TOLEDO Selected Applications

25 5 mm 0.56 mm 2 2 K/min K/min K/min 1 Hz 5 N 20 µm 30 2 G' G" tan 29 [7] KU KU600 DSC TGA TMA DMA 29: KU DMA 2% DIN ASTM E KU N 30 µm Hz METTLER TOLEDO Selected Applications 25

26 Elastomers 5.7 [1] A. Hammer, Thermal analysis of polymers, Part 3: DSC of thermosets, UserCom 33, 1 5. [2] Elastomer Analysis in the TGA 850, UserCom 3, 7 8. [3] PET, Physical curing by dynamic load TMA, UserCom 5, 15. [4] Georg Widmann, Interpreting DMA curves, Part 1, UserCom 15, 1 5. [5] Jürgen Schawe, Interpreting DMA curves, Part 2, UserCom 16, 1 5. [6] Klaus Wrana, Determination of the glass temperature by DMA, UserCom 16, [7] METTLER TOLEDO Collected Applications Handbook: Thermosets, Volume 1 31: T g 26 METTLER TOLEDO Selected Applications

27 6. DSC TGA 6.1 [5,6] DSC TGA EPDM SBR NBR EVA 6.2 FRS5 DSC 1 TGA /DSC 1 TMA/ SDTA840 e 841 e DMA/ SDTA861 e 32 2EPDM EPG EPG SBR SBR /BR SBR /NR NR SBR NR SBR 32: EPDM DSC DSC METTLER TOLEDO Selected Applications 27

28 Elastomers 33: 2 SBR DSC 4:1 34 EPDM EPG K DSC DSC ADSC TOPEM IsoStep DSC ADSC DSC 34: EPDM METTLER TOLEDO Selected Applications

29 35 SBR ADSC DSC A B DSC 36 NBR NBR DSC : SBR ADSC C1 C2 DSC 1 0 K/min 2 K/min 36: NBR DSC METTLER TOLEDO Selected Applications 29

30 Elastomers n MFK AMFK 37 NBR MFK MKF K/min 2 K/min 5 K/min 37 3 NBR kj/mol 60% 110 kj/mol 37: NBR TGA TGA 38 SBR TGA TGA 3 38: SBR TGA DTG % % METTLER TOLEDO Selected Applications

31 31.5% 2.3% TGA 39 SBR/NR 10 mbar 1000 mbar 10 K/min 2 39: SBR/NR TGA 40: EVA TGA TGA DTG 10 mbar 1000 mbar DTG 9.9% 35.7% 40 3 EVA TGA Al OH 3 ATH Mg OH 2 MDH 3 TGA DTG EVA EVA TGA DSC 6.4 [1] A. Hammer, Thermal analysis of polymers. Part 1: DSC of thermoplastics, UserCom 31, 1 6. [2] A. Hammer, Thermal analysis of polymers. Part 2: TGA, TMA and DMA of thermoplastics, UserCom 32, 1 5. [3] A. Hammer, Thermal analysis of polymers. Part 3: DSC of thermosets, UserCom 33, 1 5. [4] A. Hammer, Thermal analysis of polymers. Part 4: UserCom 34, 1 5. [5] METTLER TOLEDO Collected Applications Handbook: ELASTO- MERS, Volume 1. [6] METTLER TOLEDO Collected Applications Handbook: ELASTO- MERS, Volume 2. METTLER TOLEDO Selected Applications 31

32 7. TMA DMA Elastomers EPDM 7.1 DSC TGA DSC TGA [2,3] 7.2 TMA / TMA EPDM 2 mm 2 mm 1.5 mm 44.3% 34.7% 21.0% EPDM 0.01 N 1 N N 30 DLTMA DLTMA Dynamic Load TMA 32 METTLER TOLEDO Selected Applications

33 N 1 N a. b. c. d. e. DSC TMA DMA DMA 44 SBR 2 DMA 1st run 2nd run G G tan TMA TMA 43 EPDM FPM FPM 2% FPM 43 EPDM FPM 2 mm 2.5 mm SBR DMA EPDM 25 % EDPM DMA DMA METTLER TOLEDO Selected Applications 33

34 Elastomers 45 1 Hz 10 Hz, 100 Hz 1000 Hz SBR DMA G G tan G Gtan 1st run G 10 9 Pa 10 6 Pa 3 G 1 Mpa G 40 2nd run G tan 1st run Multi Freqency 1 Hz Hz 2 10 Frequency Series 45 2K/min 1Hz 10 Hz 100 Hz 1000 Hz SBR DMA 5 DMA 46 2 phr SBR WLF Williams, Landel and Ferry 46 2 phr parts per hundred SBR 1 mhz 1000 Hz SBR 34 METTLER TOLEDO Selected Applications

35 54 Hz SBR 30 kpa 10-6 Hz 10-5 Hz10-2 Hz 1 Mpa 10-5 Hz 10-2 Hz 3 G 800 MPa DSC,TGA,TMA, DMA EPDM Time-Temperature Superposition principle : TTS 47 SBR -10 DMA DSC TGA TMA DMA x x x x x x / x x x x DLTMA x x x x x x x x 4 METTLER TOLEDO Selected Applications 35

36 Elastomers SBR 7.5 [1] Ni Jing, A. Hammer, Thermal analysis of polymers, Part 5: DSC and TGA of elastomers, UserCom 35, 1 5. [2] METTLER TOLEDO Collected Applications Handbook: Elastomers, Volume 1. [3] METTLER TOLEDO Collected Applications Handbook: Elastomers, Volume 2. [4] Ni Jing, Elastomer seals: Creep behavior and glass transition by TMA, UserCom 28, METTLER TOLEDO Selected Applications

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38 8. Fore more Information Thermal Analysis in Practice Elastomers Vol Validation in Thermal Analysis Elastomers Vol Food Elastomers Vol. 1 and Vol Pharmaceuticals Thermosets Volume Thermoplastics Thermosets Volume EGA Evolved Gas Analysis Thermosets Volume タイトル 品番 タイトル 品番 Tutorial Kit Tutorial Kit UserCom (e) METTLER TOLEDO Selected Applications

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40 Application Handbook Thermal Analysis in Practice 327 Thermosets 315 Thermoplastics 150 Elastomers 275 Pharmaceuticals 100 Food 50 Evolved Gas Analysis 65 Validation in Thermal Analysis Vol. 1 2 Vol. 1 Vol. 2 Vol. 1 2 Vol. 1 Vol. 2 Tutorial Kit For more infomation TEL: FAX: sales.admin.jp@mt.com F F Subject to technical changes 11/2013 Mettler-Toledo AG, A Marketing MatChar / MarCom Analytical

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