Introduction to thermal analysis techniques DSC TGA DMA

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博精儀器 Introduction to thermal analysis techniques (DSC, TGA & DMA) Perkin. Elmer Thermal Specialist

博精儀器 Introduction to thermal analysis techniques (DSC, TGA & DMA) Perkin. Elmer Thermal Specialist 康瑜容 Tiffany Kang Tiffany. Kang@perkinelmer. com

Thermal analysis methods used Ø Differential Scanning Calorimetry (DSC) Ø Thermogravimetric Analysis (TGA) Ø

Thermal analysis methods used Ø Differential Scanning Calorimetry (DSC) Ø Thermogravimetric Analysis (TGA) Ø Thermomechanical Analysis (TMA) Ø Dynamic Mechanical Analysis (DMA) 博精儀器 Page 2 Thermal-2

Thermal analysis methods used DSC Heat flow vs. Temp - Tm, Tc, Tg -

Thermal analysis methods used DSC Heat flow vs. Temp - Tm, Tc, Tg - DH, curing time, curing degree - Reaction rate, kinetics TGA Weight Loss vs. Temp - Decomposition temperature - %Wt percentage - Oxidative time TMA Dimensional Change vs. Temp - CTE (a 1, a 2) - Tg - Softening point Viscoelastic property vs. Temp - Storage/Loss/Complex Modulus (E’, E”, E*) - tan d - Viscosity and master curve 博精儀器 Page 3 Thermal-3

Polymer material structure Type of Polymer Chain Structure Type Structure Example Linear Poly(vinyl chloride),

Polymer material structure Type of Polymer Chain Structure Type Structure Example Linear Poly(vinyl chloride), Polystyrene Branched short chain Polypropylene Long chain branching Polypropylene Ladder 博精儀器 Page 4 Poly(imidazol pyrrolones) Thermal-4

Polymer material structure Type of Polymer Chain Structure (Continued) Type Star Structure Example Phenol-formaldehyde

Polymer material structure Type of Polymer Chain Structure (Continued) Type Star Structure Example Phenol-formaldehyde resins Network Two crosslinked polymers not bonded to each other Interpenetrating network (IPN) 博精儀器 Page 5 Crosslinked epoxy with vinyl polymer Thermal-5

Classification of polymer materials Polymers Thermoplastics Thermosets (No chemical change on heating) Amorphous Polystryene

Classification of polymer materials Polymers Thermoplastics Thermosets (No chemical change on heating) Amorphous Polystryene Polycarbonate Polyurethanes Polysulfone 博精儀器 Page 6 (Chemical change on heating) Uncured Crystalline LOW/MEDIUM Nylon PET Acetal HIGH PPS PP HDPE Epoxies Polyimides Polyesters Phenolics Cured Rubber Silicones Neoprene Epoxy Thermal-6

Amorphous vs. Crystalline? Amorphous Thermoplastic 博精儀器 Page 7 Crystalline Polymer Thermal-7

Amorphous vs. Crystalline? Amorphous Thermoplastic 博精儀器 Page 7 Crystalline Polymer Thermal-7

Semi-Crystalline Polymer Ø Semi-crystalline polymers contain both amorphous AND crystalline phases Ø Properties dominated

Semi-Crystalline Polymer Ø Semi-crystalline polymers contain both amorphous AND crystalline phases Ø Properties dominated by both Tg and Tm Ø Semi-crystalline polymers can exhibit additional crystallization during heating Semi-Crystalline Polymer 博精儀器 Page 8 Thermal-8

Thermosetting Polymer 博精儀器 Page 9 Thermal-9

Thermosetting Polymer 博精儀器 Page 9 Thermal-9

Schematic Results in Thermal Analysis Quality of sample process -Solid Melting -Crystalline Recrystallization DSC(Ex

Schematic Results in Thermal Analysis Quality of sample process -Solid Melting -Crystalline Recrystallization DSC(Ex ) TGA TMA DMA -Semi-crystalline Sublimation Solid-solid transition -Amorphous Glass transition -Semi-crystalline Softening without Tg Post-crosslinking -General Decomposition Ligand release -Liquid Evaporation -Unspecific Chemical reactions Determination of % 博精儀器 Page 10 Thermal-10

博精儀器 DSC Technique Differential Scanning Calorimetry

博精儀器 DSC Technique Differential Scanning Calorimetry

Question? Ø PE into HDPE, LLDPE and LDPE - What are the different structures?

Question? Ø PE into HDPE, LLDPE and LDPE - What are the different structures? - What's the difference nature? - What is the structure and nature of the association? The process of crystallization why? The impact of processing conditions on crystallization? Crystallinity impact on transparency? Additive effects? DSC solve what problem? 博精儀器 Page 12 Thermal-12

What is DSC ? Ø Differential scanning calorie meter (Differential Scanning Calorimeter): Ø The

What is DSC ? Ø Differential scanning calorie meter (Differential Scanning Calorimeter): Ø The sample is placed under a specific atmosphere of the environment to change or maintain the temperature at a fixed temperature the sample was observed to go into energy changes when the sample is melted, evaporation, crystallization, phase transformation and other physical phenomena or chemical changes, and the pattern will there will be an endothermic or put the tropics, and thus presumably the nature of the sample. 博精儀器 Page 13 Thermal-13

Thermal Analysis applications - DSC Diamond DSC - Principle: Heat flow change vs. temperature

Thermal Analysis applications - DSC Diamond DSC - Principle: Heat flow change vs. temperature - Measures: Phase transition (Tg, Tm, Tc) and heat Curing reaction and other chemical reactions 博精儀器 Page 14 Thermal-14

 Polymer Transitions Stress Relief Heat Flow Tg Tm Cold Crystallization DH Degradation Start

Polymer Transitions Stress Relief Heat Flow Tg Tm Cold Crystallization DH Degradation Start up Transient Curing Ordering Process Temperature 博精儀器 Page 15 Thermal-15

DSC Thermal Curve of PET 吸 熱 放 熱 博精儀器 Page 16 Thermal-16

DSC Thermal Curve of PET 吸 熱 放 熱 博精儀器 Page 16 Thermal-16

DSC for curing studies Ø Ø Ø Detection of Tg Onset of cure Maximum

DSC for curing studies Ø Ø Ø Detection of Tg Onset of cure Maximum rate of cure (peak maximum) End of cure Heat of cure 博精儀器 Page 17 Thermal-17

DSC thermal analysis instrument for the application of differential scanning Phase change point Phase

DSC thermal analysis instrument for the application of differential scanning Phase change point Phase Transition Hot melt H Glass transition temperature Tg Reaction heat H Melting point Activation energy Ea crystallization temperature Crystal Temperature Oxidative Induction O. I. T. Time Cooling crystallization temperature Cold Crystal Temperature Reaction kinetics Dynamic Crystallinity Cross-linked Curing Heat of crystallization Crystal Energy Purity Specific heat Cp Crystallization half- Crystal Period cycle 博精儀器 Page 18 Thermal-18

DSC Design Method Heat Flux DSC Measurement T Direct measurement ∆H Calculate H from

DSC Design Method Heat Flux DSC Measurement T Direct measurement ∆H Calculate H from H = K∆T No complicated mathematical operations Large furnace 博精儀器 Page 19 Thermal Compensation DSC Small furnace Thermal-19

博精儀器 TGA Technique Thermogravimetric Analyzer

博精儀器 TGA Technique Thermogravimetric Analyzer

Thermal Analysis applications - TGA Pyris 1 TGA - Principle: Weight change vs. temperature

Thermal Analysis applications - TGA Pyris 1 TGA - Principle: Weight change vs. temperature - Measures: Compositions and wt% Thermal stability and decomposition temp. 博精儀器 Page 21 Thermal-21

TGA Design Concept Suspended 博精儀器 Page 22 Horizontal Mounted on Thermal-22

TGA Design Concept Suspended 博精儀器 Page 22 Horizontal Mounted on Thermal-22

TGA Thermal Curves 博精儀器 Page 23 Thermal-23

TGA Thermal Curves 博精儀器 Page 23 Thermal-23

TGA The design principle The main components p Temperature control device - Furnace, Thermocouple

TGA The design principle The main components p Temperature control device - Furnace, Thermocouple p Weight measurement device -Null Balance Detector Torque Motor Sample 博精儀器 Page 24 Tare Weight Thermal-24

TGA Thermogravimetric analyzer Ø Moisture content Solvent content Plasticizer content Polymer additive content Pyrolysis

TGA Thermogravimetric analyzer Ø Moisture content Solvent content Plasticizer content Polymer additive content Pyrolysis temperature Ash content Inorganic additive content Oxidation lead time measurement 博精儀器 Page 25 TGA-FTIR/TGA-MS Ø Thermal stability measurement Unstable material test Odor material test Additive type test TGA-GC/MS Ø Unknown species judgment Judging solvent Thermal-25

TGA for compositional analysis Ø Molding compound contains epoxy and filler Ø Epoxy can

TGA for compositional analysis Ø Molding compound contains epoxy and filler Ø Epoxy can be burned off and residue is inert reinforced filler Ø TGA provides accurate and reproducible compositional data on molding compound 博精儀器 Page 26 Thermal-26

博精儀器 TMA/DMA Technique Mechanical Analyzer

博精儀器 TMA/DMA Technique Mechanical Analyzer

Thermal Analysis applications – DMA/TMA DMA 8000 - Principle: Viscoelastic properties vs. temperature (DMA)

Thermal Analysis applications – DMA/TMA DMA 8000 - Principle: Viscoelastic properties vs. temperature (DMA) Dimensional change vs. temperature (TMA) Measures: Glass transition point Storage, Loss modulus and tan delta Coefficient of thermal expansion (CTE) 博精儀器 Page 29 Thermal-29

What is DMA ? Ø DMA (Dynamic Mechanical Analyzer) Dynamic viscoelastic mechanical analyzer The

What is DMA ? Ø DMA (Dynamic Mechanical Analyzer) Dynamic viscoelastic mechanical analyzer The sample is placed under a specific environment, at a temperature of the sample to detect, strength, or frequency change, the situation changes in the mechanical properties, and thus determines the characteristics of the material. 博精儀器 Page 30 Thermal-30

The viscoelastic properties of the material. . . E” E’ 博精儀器 Page 31 E’

The viscoelastic properties of the material. . . E” E’ 博精儀器 Page 31 E’ – Storage Modulus Storage modulus Elastic properties E”– Loss Modulus Loss modulus Viscous nature tan d = E” / E’ Thermal-31

When you need DMA. . . Ø Mechanical properties of viscoelastic Ø ex. (Modulus),

When you need DMA. . . Ø Mechanical properties of viscoelastic Ø ex. (Modulus), (Viscosity), (tan d) … Ø Slight phase change Ø ex. b, g- transition, Tg DSC/TMA Measurements were difficult … Ø Activation Energy Calculation Ø Predict material life Ø ex. Creep Recovery, Time-temp. superposition … Ø Materials and manufacturing process simulation environment chang ex. Curing process, controlled humidity, Solvent Immersion … 博精儀器 Page 32 Thermal-32

Viscoelastic properties of the material. . . DMA is using Sine Wave Concussion ways

Viscoelastic properties of the material. . . DMA is using Sine Wave Concussion ways to measure response analyzer = 0 o time Vis = 90 cou o s o o k time o o 博精儀器 Page 33 time Thermal-33

Idealized DMA Scan (6) Tg (5) Tb (4) Ta or Tg E’/Pa (3) Beta

Idealized DMA Scan (6) Tg (5) Tb (4) Ta or Tg E’/Pa (3) Beta transitions are often related to the toughness. For purely crystalline materials, no Tg occurs. Tg is related to Molecular mass up to a limiting value. In semicrystalline polymers, a crystal-crystal slip, Ta* occurs. Rubbery Plateau (2) Rubbery plateau is related to Me between crosslinks or entanglements. Tll in some amorphous polymers For thermosets, no Tm occurs. Tm - melting (1) Temperature /K (6) (5) local bend motions and stretch 博精儀器 Page 34 (4) side groups (3) gradual main chain (2) large scale chain (1) chain slippage Thermal-34

Frequency effects things too Ø Transitions shift Ø Behavior changes More elastic E’ More

Frequency effects things too Ø Transitions shift Ø Behavior changes More elastic E’ More fluid Frequency 博精儀器 Page 35 Thermal-35

So frequency can act like temperature E’ E’ Temperature 博精儀器 Page 36 Frequency Thermal-36

So frequency can act like temperature E’ E’ Temperature 博精儀器 Page 36 Frequency Thermal-36

DMA Links. . . Structural characteristics of the material Molecular weight MW Distribution Chain

DMA Links. . . Structural characteristics of the material Molecular weight MW Distribution Chain Branching Cross linking Entanglements Phases Crystallinity Free Volume Localized motion Relaxation Mechanisms 博精儀器 Page 37 Finished properties Material Behavior Dimensional Stability Impact properties Long term behavior Environmental resistance Temperature performance Adhesion Tack Peel Processing characteristics Stress Strain Temperature Heat History Frequency Pressure Heat set Thermal-37

DMA How does it work? Force motor Total Force Static Force Dynamic Force Frequency

DMA How does it work? Force motor Total Force Static Force Dynamic Force Frequency f LVDT Amplitude Fixtures Position Storage Modulus K Hold Sample Loss Modulus Phase Thermocouple Furnace Options from -190 to 600 C 博精儀器 Page 38 Thermal-38

Choose a variety of fixtures Options: Single Cantilever Dual Cantilever 3 Point Bending Tension

Choose a variety of fixtures Options: Single Cantilever Dual Cantilever 3 Point Bending Tension Compression Shear Quartz Shear Material Pocket 博精儀器 Page 39 Thermal-39

Exclusive Material Pockets Pocket open Sample in Pocket closed & sealed Ø Applications •

Exclusive Material Pockets Pocket open Sample in Pocket closed & sealed Ø Applications • Powders like drugs, excipients, foods, natural products, etc. • Gels • Uncured adhesives • Coatings • Samples that can’t support their own weight 博精儀器 Page 40 Thermal-40

DMA mode for mechanical properties change Ø This plot shows DMA results (E’ and

DMA mode for mechanical properties change Ø This plot shows DMA results (E’ and tan delta) for cured substrate Ø DMA gives the most sensitive measure of Tg Ø DMA results show that substrate is incompletely cured as 2 split peak was found in tan delta around Tg 博精儀器 Page 41 Thermal-41

DMA most sensitive indicator of cure Ø This plot shows DMA results on completely

DMA most sensitive indicator of cure Ø This plot shows DMA results on completely cured and slightly undercured PCB’s Ø Under-cured PCB exhibits a slight increase in E’ above Tg making the board unacceptable 博精儀器 Page 42 Thermal-42

TMA mode for dimensional change Ø Plot shows results on TMA expansivity of substrate

TMA mode for dimensional change Ø Plot shows results on TMA expansivity of substrate Ø 1 st heat shows that the board contains built in stresses as a result of processing Ø Stresses are released at Tg Ø 2 nd heat shows classic TMA Tg free of stress relief effects 博精儀器 Page 43 Thermal-43

博精儀器 Polymer thermal properties measurement

博精儀器 Polymer thermal properties measurement

Polymers Tg Analysis - Differences heating history 博精儀器 Page 45 Thermal-45

Polymers Tg Analysis - Differences heating history 博精儀器 Page 45 Thermal-45

Crystallization test - thermostatic crystallization 博精儀器 Page 46 Thermal-46

Crystallization test - thermostatic crystallization 博精儀器 Page 46 Thermal-46

Cross-linked test - Warming cross-linked Epoxy Resin Endothermic Range: Heating Rate: Weight: 30 mw

Cross-linked test - Warming cross-linked Epoxy Resin Endothermic Range: Heating Rate: Weight: 30 mw 20 o. C/min 32. 76 mg Run 1 Heat Flow (m. W) 62. 8 o. C 113. 3 o. C Run 2 40 D H 80 120 160 T 博精儀器 Page 47 200 240 280 (o. C) Thermal-47

Cross-linked test - thermostatic cross-linked 博精儀器 Page 48 Thermal-48

Cross-linked test - thermostatic cross-linked 博精儀器 Page 48 Thermal-48

Cross-linked test - affect cross-linking degree DSC Heat Flow 博精儀器 Page 49 DSC Tg

Cross-linked test - affect cross-linking degree DSC Heat Flow 博精儀器 Page 49 DSC Tg As Function of Cure Less Cured More Cured Temperature Thermal-49

Cross-linked test - affect cross-linking degree More Cured DSC Heat Flow Less Cured 博精儀器

Cross-linked test - affect cross-linking degree More Cured DSC Heat Flow Less Cured 博精儀器 Page 50 Temperature Decrease in Cure Exotherm As Resin Cure Increases Thermal-50

Filler Function of the filler Lowering thermal expansion coefficient Increased thermal conductivity coefficient Increased

Filler Function of the filler Lowering thermal expansion coefficient Increased thermal conductivity coefficient Increased dimensional stability Reduce costs Changes in density Changes in viscosity - easy to process Reduce water absorption Commonly used filler Absorbent Epoxy Silica Carbon Black Glass fiber 博精儀器 Page 51 Thermal-51

Black Carbon Content Analysis Carbon black is often used to improve the mixing and

Black Carbon Content Analysis Carbon black is often used to improve the mixing and plastic chemical or physical property. For example, to enhance its anti. UV properties, filling plastic products do enhancers to improve strength or as a volume filler Volatiles Polymer Carbon 博精儀器 Page 52 Thermal-52

TGA/FTIR/Interface System Ø Providing a range of complete systems Ø Has improved the interface

TGA/FTIR/Interface System Ø Providing a range of complete systems Ø Has improved the interface design - heating pipelines and gas sample slot Ø A professional TG-IR software --Time. Base Software 博精儀器 Page 53 Thermal-53

TGA/FTIR Software 博精儀器 Page 54 Thermal-54

TGA/FTIR Software 博精儀器 Page 54 Thermal-54

TGA/FTIR Software TGA Weight loss vs. FTIR Spectrum weight vs Time 博精儀器 Page 55

TGA/FTIR Software TGA Weight loss vs. FTIR Spectrum weight vs Time 博精儀器 Page 55 Thermal-55