熱分析技術 簡介 (DSC, TGA & DMA) PerkinElmer Thermal Specialist 康瑜容 Tiffany Kang Tiffany.Kang@perkinelmer.com

Differential Scanning Calorimetry (DSC) 常用的熱分析方法 Differential Scanning Calorimetry (DSC) Thermogravimetric Analysis (TGA) Thermomechanical Analysis (TMA) Dynamic Mechanical Analysis (DMA) Page 2 3

常用的熱分析方法 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 (a1, a2) Tg Softening point DMA Viscoelastic property vs. Temp Storage/Loss/Complex Modulus (E’, E”, E*) tan d Viscosity and master curve                                                                                            Page 3

高分子材料結構 Type Structure Example Poly(vinyl chloride), Polystyrene Type of Polymer Chain Structure Type Structure Example Poly(vinyl chloride), Polystyrene Polypropylene Poly(imidazol pyrrolones) Linear Branched short chain Long chain branching Ladder Page 4

高分子材料結構 Type Structure Example Phenol-formaldehyde resins Star Network Type of Polymer Chain Structure (Continued) Type Structure Example Phenol-formaldehyde resins Two crosslinked polymers not bonded to each other Crosslinked epoxy with vinyl polymer Star Network Interpenetrating network (IPN) Page 5

高分子材料的分類 Amorphous Crystalline Thermoplastics Uncured Cured Thermosets Polystryene Polycarbonate Polyurethanes Polysulfone Amorphous LOW/MEDIUM Nylon PET Acetal HIGH PPS PP HDPE Crystalline Thermoplastics (No chemical change on heating) Epoxies Polyimides Polyesters Phenolics Uncured Rubber Silicones Neoprene Epoxy Cured Thermosets (Chemical change on heating) Polymers Page 6 5

Amorphous vs. Crystalline? Amorphous Thermoplastic Crystalline Polymer Page 7

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

Thermosetting Polymer Page 9

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

DSC Technique Differential Scanning Calorimetry

Question? PE分成HDPE, LLDPE及LDPE - 結構有何不同? - 性質有何差異? - 結構和性質有何關聯性? 結晶的過程為何? 加工條件對結晶有何影響? 結晶度對透明度的影響? 添加劑的影響? DSC可解決哪些問題? Page 12

( Differential Scanning Calorimeter ) : What is DSC ? 示差掃瞄熱卡量計 ( Differential Scanning Calorimeter ) : 將樣品置於特定氣氛之下改變其溫度環境或維持在一固定溫度之中去觀察樣品其能量變化，當樣品發生熔融、蒸發、結晶、相轉變等物理現象，或化學變化時，圖譜中將會出現吸熱或放熱帶，進而可推測樣品之性質。 Page 13

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 Page 14

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

DSC Thermal Curve of PET 吸 熱 放 熱 Page 16

DSC for curing studies Detection of Tg Onset of cure Maximum rate of cure (peak maximum) End of cure Heat of cure Page 17

DSC熱示差掃描分析儀之應用 相變化點 熔融熱 玻璃轉移溫度 反應熱 熔點 活化能 冷結晶溫度 氧化導引時間 降溫結晶溫度 反應動力學 Phase Transition 熔融熱 H 玻璃轉移溫度 Tg 反應熱 熔點 Melting point 活化能 Ea 冷結晶溫度 Crystal Temperature 氧化導引時間 O.I.T. 降溫結晶溫度 Cold Crystal Temperature 反應動力學 Dynamic 結晶度 Crystallinity 交連 Curing 結晶熱 Crystal Energy 純度 Purity 結晶半週期 Crystal Period 比熱 Cp Page 18

DSC的設計方式 熱流式 Heat Flux DSC 直接量測DH 量測DT 不需複雜數學運算 由DH = kDT計算DH 爐體較小 熱補償式 Power Compensation DSC 直接量測DH 不需複雜數學運算 爐體較小 量測DT 由DH = kDT計算DH 爐體較大 Page 19

TGA Technique Thermogravimetric Analyzer

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

TGA Design Concept 懸吊式 水平式 上置式 Page 22

TGA Thermal Curves Page 23

TGA 的設計原理 主要元件 Temperature control device - Furnace, Thermocouple Weight measurement device -Null Balance Torque Motor Detector There are two major parts of TGA. One is temperature control device, which includes furnace and sensitivity thermalcouple. The other device is microelectrobalance , we all understand that balance is the most important part in TGA. Balance quality effects the sensitivity and stability of TGA. All of our TGA uses null balance design. What is null balance? Let`s look at this plot, changing sample weight will change position of the balance.When detector sensed this change, it will trigger the torque motor to recovery the initial position of the balance. The advantage of this design is that the sample pan maintain in the middle of the furnace. Sample Tare Weight Page 24

TGA熱重分析儀 TGA-FTIR/TGA-MS 水份含量 熱穩定測量 溶劑含量 不穩定材質測試 塑化劑含量 異味材質測試 高分子添加物含量 添加物種類測試 TGA-GC/MS 未知物種類判斷 混合溶劑判斷 水份含量 溶劑含量 塑化劑含量 高分子添加物含量 裂解溫度 灰份含量 無機添加物含量 氧化導引時間測量 Page 25

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

TMA/DMA Technique Mechanical Analyzer

Thermal Analysis applications – DMA/TMA 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) Page 29

DMA (Dynamic Mechanical Analyzer) 動態黏彈機械分析儀 What is DMA ? DMA (Dynamic Mechanical Analyzer) 動態黏彈機械分析儀 將樣品置於特定環境下，偵測樣品在溫度、力量、或頻率改變下，其機械性質變化的情形，進而判定材料的特性。 Page 30

材料的黏彈性質… E’ – Storage Modulus 儲存模數 彈性性質 E”– Loss Modulus E” 損失模數 黏性性質 tan d = E” / E’ E” E’ Page 31

ex. 模數(Modulus), 黏度(Viscosity), 阻尼相(tan d) … 微小的相變化 什麼時候您需要 DMA … 黏彈機械性質 ex. 模數(Modulus), 黏度(Viscosity), 阻尼相(tan d) … 微小的相變化 ex. b,g- transition, Tg以DSC/TMA測量不易者 … 活化能(Activation Energy)計算 預測材料使用壽命 ex. Creep Recovery, Time-temp. superposition … 模擬製程中材料及環境變化 ex. Curing process, controlled humidity, Solvent Immersion … Page 32

DMA即為利用Sine Wave震盪方式, 測量回應的分析儀 材料的黏彈性質… DMA即為利用Sine Wave震盪方式, 測量回應的分析儀 黏性 彈性 o time  = 0  = 90 o  k Page 33

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

Frequency effects things too Transitions shift Behavior changes More elastic E’  More fluid Frequency Page 35

So frequency can act like temperature Page 36

DMA 連結... 材料結構特性 成品特性 Material 製程加工特性 Molecular weight MW Distribution Chain Branching Cross linking Entanglements Phases Crystallinity Free Volume Localized motion Relaxation Mechanisms Stress Strain Temperature Heat History Frequency Pressure Heat set Material Behavior Dimensional Stability Impact properties Long term behavior Environmental resistance Temperature performance Adhesion Tack Peel Page 37

DMA 是如何運作的? f Total Force Static Force Dynamic Force Frequency Force motor Total Force Static Force Dynamic Force LVDT f Frequency Storage Modulus Amplitude K Fixtures Hold Sample Position Loss Modulus d Phase Thermocouple Furnace Options from -190 to 600 C Page 38

多樣化的夾具選擇 Options: Single Cantilever Dual Cantilever 3 Point Bending Tension Compression Shear Quartz Shear Material Pocket Page 39

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

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

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

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

更多熱分析的應用… Page 44

高分子熱性質量測

高分子的 Tg 分析 -- 加熱歷史的差異 Page 46

結晶測試 -- 恆溫結晶 Page 47

交連測試 -- 升溫交連 Epoxy Resin Endothermic Range: 30 mw Heating Rate: 20 oC/min Weight: 32.76 mg Run 1 62.8 oC D H Heat Flow (mW) 113.3 oC Run 2 40 80 120 160 200 240 280 T (oC) Page 48

交連測試 -- 恆溫交連 Page 49

交連測試 -- 交連度的影響 DSC Tg As Function of Cure DSC Heat Flow Less Cured Temperature DSC Tg As Function of Cure Less Cured More Page 50

交連測試 -- 交連度的影響 DSC Heat Flow Decrease in Cure Exotherm As Resin Cure Temperature Decrease in Cure Exotherm As Resin Cure Increases Less Cured More DSC Heat Flow Page 51

填充物的功能 填充物 Filler 常用的填充物 降低熱膨脹係數 增高熱導係數 增加尺寸安定性 降低成本 改變密度 改變黏度-方便加工 降低吸水性 常用的填充物 吸水性 環氧樹脂 二氧化矽 碳黑 玻璃纖維 Page 52

碳黑(Carbon)含量分析 碳黑經常用來與塑膠混合以改進其化學或物理性質。例如增強其抗紫外線特性，充做增強劑以提高塑膠製品強度或做為體積填充物 Polymer Carbon Volatiles 以左圖為例，除易揮發性有機物及增量劑、外其餘皆是Polymer及Carbon其含量分別約為52﹪及29﹪可直接由Y軸中讀出 Page 53

TGA/FTIR/Interface System 提供整套完整系統 具有完善的介面設計--加熱管線與氣體樣品槽 具有專業的TG-IR軟體--TimeBase Software Page 54

TGA/FTIR Software This is a fire retardant sample test with TGA-FTIR. Customer want to know that does any toxic compound might be produced after decomposition. After real time testing, we get the maximal absorption peak at 531 second, and it has a CN absorption peak at about 2200 wavelength . Page 55

TGA/FTIR Software TGA Weight loss vs.FTIR Spectrum weight vs Time This is the same sample,shows the TGA weight loss v.s. FTIR spectrum . Page 56

Thank you for your attention ! 結論 Thank you for your attention ! Page 57