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1、 博博博博 精精精精 儀儀儀儀 器器器器熱分析技術熱分析技術熱分析技術熱分析技術 簡介簡介簡介簡介(DSC, TGA & DMA)(DSC, TGA & DMA)PerkinElmer Thermal Specialist 康瑜容 Tiffany Kang博博博博 精精精精 儀儀儀儀 器器器器Thermal-Thermal-2 2Differential Scanning Calorimetry (DSC) Thermogravimetric Analysis (TGA) Thermomechanical Analysis (TMA)Dynamic Mechanical Analysis (D
2、MA)常用的熱分析方法常用的熱分析方法博博博博 精精精精 儀儀儀儀 器器器器Thermal-Thermal-3 3常用的熱分析方法常用的熱分析方法DSC Heat flow vs. Temp- Tm, Tc, Tg- DH, curing time, curing degree- Reaction rate, kineticsTGAWeight Loss vs. Temp - Decomposition temperature- %Wt percentage- Oxidative timeTMADimensional Change vs. Temp - CTE (a1, a2)- Tg- So
3、ftening point DMAViscoelastic property vs. Temp - Storage/Loss/Complex Modulus (E, E”, E*)- tan d- Viscosity and master curve博博博博 精精精精 儀儀儀儀 器器器器Thermal-Thermal-4 4高分子材料結構高分子材料結構Type of Polymer Chain StructureTypeStructureExampleTypeStructureExampleLinearLinearBranchedBranchedshortchainshortchainLong
4、chainLongchainbranchingbranchingLadderLadderPoly(vinylchloride),PolystyrenePoly(vinylchloride),PolystyrenePolypropylenePolypropylenePolypropylenePolypropylenePoly(imidazolpyrrolones)Poly(imidazolpyrrolones)博博博博 精精精精 儀儀儀儀 器器器器Thermal-Thermal-5 5高分子材料結構高分子材料結構Type of Polymer Chain Structure (Continued
5、)TypeStructureExampleTypeStructureExampleStarStarNetworkNetworkInterpenetratingInterpenetratingnetwork(IPN)network(IPN)Phenol-formaldehyderesinsPhenol-formaldehyderesinsTwocrosslinkedpolymersnotTwocrosslinkedpolymersnotbondedtoeachotherbondedtoeachotherCrosslinkedepoxywithvinylCrosslinkedepoxywithvi
6、nylpolymerpolymer博博博博 精精精精 儀儀儀儀 器器器器Thermal-Thermal-6 6高分子材料的分類高分子材料的分類PolystryenePolycarbonatePolyurethanesPolysulfoneAmorphousLOW/MEDIUMNylonPETAcetalHIGHPPSPPHDPECrystallineThermoplastics(Nochemicalchangeonheating)EpoxiesPolyimidesPolyestersPhenolicsUncuredRubberSiliconesNeopreneEpoxyCuredThermos
7、ets(Chemicalchangeonheating)Polymers博博博博 精精精精 儀儀儀儀 器器器器Thermal-Thermal-7 7Amorphous vs. Crystalline?AmorphousAmorphousThermoplasticThermoplasticCrystallineCrystallinePolymerPolymer博博博博 精精精精 儀儀儀儀 器器器器Thermal-Thermal-8 8Semi-Crystalline PolymerSemi-CrystallineSemi-CrystallinePolymerPolymerSemi-crystal
8、line polymers contain both amorphous AND crystalline phasesProperties dominated by both Tg and TmSemi-crystalline polymers can exhibit additional crystallization during heating博博博博 精精精精 儀儀儀儀 器器器器Thermal-Thermal-9 9Thermosetting Polymer博博博博 精精精精 儀儀儀儀 器器器器Thermal-Thermal-1010Schematic Results in Therm
9、al AnalysisQualityofsampleprocessDSC(ExQualityofsampleprocessDSC(Ex) )TGATMADMATGATMADMA- -CrystallineCrystalline- -Semi-crystallineSemi-crystalline-Amorphous-Amorphous-Semi-crystalline-Semi-crystalline-General-General-Liquid-Liquid-Unspecific-Unspecific-SolidMelting-SolidMeltingRecrystallizationRec
10、rystallizationSublimationSublimationSolid-solidtransitionSolid-solidtransitionGlasstransitionGlasstransitionSofteningwithoutTgSofteningwithoutTgPost-crosslinkingPost-crosslinkingDecompositionDecompositionLigandreleaseLigandreleaseEvaporationEvaporationChemicalreactionsChemicalreactionsDeterminationo
11、f%Determinationof% 博博博博 精精精精 儀儀儀儀 器器器器DSC TechniqueDSC TechniqueDifferential Scanning CalorimetryDifferential Scanning CalorimetryDifferential Scanning Calorimetry博博博博 精精精精 儀儀儀儀 器器器器Thermal-Thermal-1212Question?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
12、影響?DSC可解決哪些問題?博博博博 精精精精 儀儀儀儀 器器器器Thermal-Thermal-1313What is DSC ?示差掃瞄熱卡量計示差掃瞄熱卡量計( 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、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現吸熱或放熱帶，
13、進而可推測樣品之性質。博博博博 精精精精 儀儀儀儀 器器器器Thermal-Thermal-1414Thermal Analysis applications - DSC- -Principle:Principle: Heat flow change vs. temperatureHeat flow change vs. temperature- -Measures:Measures: Phase transition ( Phase transition (TgTg, Tm, , Tm, TcTc) and heat ) and heat Curing reaction and other
14、chemical reactions Curing reaction and other chemical reactionsDiamond DSCDiamond DSC博博博博 精精精精 儀儀儀儀 器器器器Thermal-Thermal-1515 Polymer TransitionsHeatFlowTemperatureTgStressReliefOrderingProcessCold CrystallizationCuringTmDHDegradationStart upTransient博博博博 精精精精 儀儀儀儀 器器器器Thermal-Thermal-1616DSC Thermal
15、 Curve of PET吸吸 熱熱放放 熱熱博博博博 精精精精 儀儀儀儀 器器器器Thermal-Thermal-1717DSC for curing studiesDetection of TgOnset of cureMaximum rate of cure (peak maximum)End of cureHeat of cure博博博博 精精精精 儀儀儀儀 器器器器Thermal-Thermal-1818DSC熱示差掃描分析儀之應用熱示差掃描分析儀之應用相變化點相變化點Phase Transition熔融熱熔融熱 H玻璃轉移溫度玻璃轉移溫度Tg反應熱反應熱 H熔點熔點Melting
16、point活化能活化能Ea冷結晶溫度冷結晶溫度Crystal Temperature氧化導引時間氧化導引時間O.I.T.降溫結晶溫度降溫結晶溫度Cold Crystal Temperature反應動力學反應動力學Dynamic結晶度結晶度Crystallinity交連交連Curing結晶熱結晶熱Crystal Energy純度純度Purity結晶半週期結晶半週期Crystal Period比熱比熱Cp博博博博 精精精精 儀儀儀儀 器器器器Thermal-Thermal-1919DSC的設計方式的設計方式熱流式熱流式熱流式熱流式 Heat Flux DSCHeat Flux DSC熱補償式熱補償
17、式熱補償式熱補償式 Power Compensation DSCPower Compensation DSC- -量測量測量測量測 T T- - 由由由由 H = H = k k T T計算計算計算計算 H H- - 爐體較大爐體較大爐體較大爐體較大- -直接量測直接量測直接量測直接量測 H H- - 不需複雜數學運算不需複雜數學運算不需複雜數學運算不需複雜數學運算- - 爐體較小爐體較小爐體較小爐體較小 博博博博 精精精精 儀儀儀儀 器器器器TGA TechniqueTGA TechniqueThermogravimetric AnalyzerThermogravimetric Analyz
18、erThermogravimetric Analyzer博博博博 精精精精 儀儀儀儀 器器器器Thermal-Thermal-2121Thermal Analysis applications - TGAPyris 1 TGAPyris 1 TGA- -Principle:Principle: Weight change vs. temperatureWeight change vs. temperature- -Measures:Measures: Compositions and wt% Compositions and wt% Thermal stability and decompos
19、ition temp. Thermal stability and decomposition temp.博博博博 精精精精 儀儀儀儀 器器器器Thermal-Thermal-2222TGA Design Concept懸吊式懸吊式懸吊式懸吊式水平式水平式水平式水平式上置式上置式上置式上置式博博博博 精精精精 儀儀儀儀 器器器器Thermal-Thermal-2323TGA Thermal Curves博博博博 精精精精 儀儀儀儀 器器器器Thermal-Thermal-2424主要元件主要元件p Temperature control device - Furnace, Thermocoup
20、lep Weight measurement device -Null BalanceDetectorTare WeightSampleTorque MotorTGATGA 的設計原理的設計原理的設計原理的設計原理博博博博 精精精精 儀儀儀儀 器器器器Thermal-Thermal-2525TGA熱重分析儀熱重分析儀水份含量水份含量溶劑含量溶劑含量塑化劑含量塑化劑含量高分子添加物含量高分子添加物含量裂解溫度裂解溫度灰份含量灰份含量無機添加物含量無機添加物含量氧化導引時間測量氧化導引時間測量TGA-FTIR/TGA-MS熱穩定測量熱穩定測量不穩定材質測試不穩定材質測試異味材質測試異味材質測試添加
21、物種類測試添加物種類測試TGA-GC/MS未知物種類判斷未知物種類判斷混合溶劑判斷混合溶劑判斷博博博博 精精精精 儀儀儀儀 器器器器Thermal-Thermal-2626TGA for compositional analysisMolding compound contains epoxy and fillerEpoxy can be burned off and residue is inert reinforced fillerTGA provides accurate and reproducible compositional data on molding compound 博博
22、博博 精精精精 儀儀儀儀 器器器器TMA/DMA TechniqueTMA/DMA TechniqueMechanical AnalyzerMechanical AnalyzerMechanical Analyzer博博博博 精精精精 儀儀儀儀 器器器器Thermal-Thermal-2929Thermal Analysis applications DMA/TMADMA 8000DMA 8000- -Principle:Principle: ViscoelasticViscoelastic properties vs. temperature (DMA) properties vs. tem
23、perature (DMA) Dimensional change vs. temperature (TMA) Dimensional change vs. temperature (TMA)Measures:Measures: Glass transition point Glass transition point Storage, Loss modulus and tan delta Storage, Loss modulus and tan delta Coefficient of thermal expansion (CTE) Coefficient of thermal expan
24、sion (CTE)博博博博 精精精精 儀儀儀儀 器器器器Thermal-Thermal-3030What is DMA ? DMA (Dynamic Mechanical Analyzer) 動態黏彈機械分析儀動態黏彈機械分析儀 將樣品置於特定環境下，偵測樣品在將樣品置於特定環境下，偵測樣品在溫度溫度、力量力量、或或頻率頻率改變下，其機械性質變化的情形，進而判改變下，其機械性質變化的情形，進而判定材料的特性。定材料的特性。博博博博 精精精精 儀儀儀儀 器器器器Thermal-Thermal-3131材料的黏彈性質材料的黏彈性質E Storage Modulus 儲存模數儲存模數 彈性性質彈性
25、性質E” Loss Modulus 損失模數損失模數 黏性性質黏性性質tan d d = E” / EE”E博博博博 精精精精 儀儀儀儀 器器器器Thermal-Thermal-3232黏彈機械性質黏彈機械性質 ex. 模數(Modulus), 黏度(Viscosity), 阻尼相(tan d) 微小的相變化微小的相變化 ex. b,g- transition, Tg以DSC/TMA測量不易者 活化能活化能(Activation Energy)計算計算預測材料使用壽命預測材料使用壽命 ex. Creep Recovery, Time-temp. superposition 模擬製程中材料及環境
26、變化 ex. Curing process, controlled humidity, Solvent Immersion 什麼時候您需要什麼時候您需要 DMA 博博博博 精精精精 儀儀儀儀 器器器器Thermal-Thermal-3333黏性黏性彈性彈性otimeotimeotime = 0 = 90oootimeo kDMA即為利用即為利用Sine Wave震盪方式震盪方式, 測量回應的分析儀測量回應的分析儀材料的黏彈性質材料的黏彈性質博博博博 精精精精 儀儀儀儀 器器器器Thermal-Thermal-3434Idealized DMA ScanE/PaTemperature /KTm
27、- melting (1)Rubbery Plateau (2)Ta a or TgT Tb b (6)(5)(5)(4)(4)(3)(3)(2)(2)(1) (1) localbendsidegradual largechainmotions andgroupsmainscaleslippagestretchchainchainT Tg g (6)(6)Rubbery plateau is related to Me between crosslinks or entanglements.For thermosets, no Tm occurs.Beta transitions are of
28、tenrelated to the toughness.Tg is related to Molecular massup to a limiting value.For purely crystalline materials, no Tg occurs.In semicrystalline polymers,a crystal-crystal slip, Ta* occurs.Tll in some amorphouspolymers(5)(5)(4)(4)(3)(3)博博博博 精精精精 儀儀儀儀 器器器器Thermal-Thermal-3535Frequency effects thin
29、gs tooTransitions shiftBehavior changesFrequencyE MorefluidMoreelastic博博博博 精精精精 儀儀儀儀 器器器器Thermal-Thermal-3636So frequency can act like temperatureFrequencyETemperatureE博博博博 精精精精 儀儀儀儀 器器器器Thermal-Thermal-3737DMA 連結連結. .材料結構特性材料結構特性製程加工特性製程加工特性成品特性成品特性Molecular weightMW DistributionChain BranchingCros
30、s linkingEntanglementsPhasesCrystallinityFree VolumeLocalized motionRelaxation MechanismsStressStrainTemperatureHeat HistoryFrequencyPressureHeat setMaterialBehaviorDimensional StabilityImpact propertiesLong term behaviorEnvironmental resistanceTemperature performanceAdhesionTackPeel博博博博 精精精精 儀儀儀儀 器
31、器器器Thermal-Thermal-3838DMA 是如何運作的是如何運作的?Storage ModulusLoss ModulusStatic ForceDynamic ForceFrequencyfAmplitudeKPositionHold Sample PhaseThermocoupleTotal ForceLVDTFurnaceOptionsfrom-190to600CForcemotorFixtures博博博博 精精精精 儀儀儀儀 器器器器Thermal-Thermal-3939多樣化的夾具選擇多樣化的夾具選擇Options:Single CantileverDual Canti
32、lever3 Point BendingTensionCompressionShearQuartz ShearMaterial Pocket博博博博 精精精精 儀儀儀儀 器器器器Thermal-Thermal-4040Exclusive Material Pockets ApplicationsPowders like drugs, excipients, foods, natural products, etc.Gels Uncured adhesivesCoatingsSamples that cant support their own weightPocketopenSampleinP
33、ocketPocketclosed&sealed博博博博 精精精精 儀儀儀儀 器器器器Thermal-Thermal-4141DMA mode for mechanical properties changeThis plot shows DMA results (E and tan delta) for cured substrateDMA gives the most sensitive measure of TgDMA results show that substrate is incompletely cured as 2 split peak was found in tan de
34、lta around Tg博博博博 精精精精 儀儀儀儀 器器器器Thermal-Thermal-4242DMA most sensitive indicator of cureThis plot shows DMA results on completely cured and slightly under-cured PCBsUnder-cured PCB exhibits a slight increase in E above Tg making the board unacceptable博博博博 精精精精 儀儀儀儀 器器器器Thermal-Thermal-4343TMA mode f
35、or dimensional changePlot shows results on TMA expansivity of substrate1st heat shows that the board contains built in stresses as a result of processing Stresses are released at Tg2nd heat shows classic TMA Tg free of stress relief effects博博博博 精精精精 儀儀儀儀 器器器器Thermal-Thermal-4444更多熱分析的應用更多熱分析的應用更多熱分析
36、的應用更多熱分析的應用 博博博博 精精精精 儀儀儀儀 器器器器高分子熱性質量測高分子熱性質量測高分子熱性質量測高分子熱性質量測博博博博 精精精精 儀儀儀儀 器器器器Thermal-Thermal-4646高分子的高分子的 Tg 分析分析 - 加熱歷史的差異加熱歷史的差異博博博博 精精精精 儀儀儀儀 器器器器Thermal-Thermal-4747結晶測試結晶測試 - 恆溫結晶恆溫結晶博博博博 精精精精 儀儀儀儀 器器器器Thermal-Thermal-4848交連測試交連測試交連測試交連測試 - - 升溫交連升溫交連升溫交連升溫交連Epoxy ResinT(oC)408012016020024
37、0280EndothermicHeatFlow(mW)Run1D HRun2113.3oC62.8oC30mw20oC/min32.76mgRange:HeatingRate:Weight:博博博博 精精精精 儀儀儀儀 器器器器Thermal-Thermal-4949交連測試交連測試交連測試交連測試 - - 恆溫交連恆溫交連恆溫交連恆溫交連博博博博 精精精精 儀儀儀儀 器器器器Thermal-Thermal-5050交連測試交連測試交連測試交連測試 - - 交連度的影響交連度的影響交連度的影響交連度的影響 DSC Heat Flow Temperature DSC Tg As Function
38、 of Cure Less Cured More Cured 博博博博 精精精精 儀儀儀儀 器器器器Thermal-Thermal-5151交連測試交連測試交連測試交連測試 - - 交連度的影響交連度的影響交連度的影響交連度的影響DSC Heat Flow Temperature Decrease in Cure Exotherm As Resin Cure Increases Less Cured More Cured 博博博博 精精精精 儀儀儀儀 器器器器Thermal-Thermal-5252填充物填充物 Filler常用的填充物常用的填充物吸水性吸水性環氧樹脂環氧樹脂二氧化矽二氧化矽碳
39、黑碳黑玻璃纖維玻璃纖維填充物的功能填充物的功能填充物的功能填充物的功能降低熱膨脹係數降低熱膨脹係數降低熱膨脹係數降低熱膨脹係數增高熱導係數增高熱導係數增高熱導係數增高熱導係數增加尺寸安定性增加尺寸安定性增加尺寸安定性增加尺寸安定性降低成本降低成本降低成本降低成本改變密度改變密度改變密度改變密度改變黏度改變黏度改變黏度改變黏度- - - -方便加工方便加工方便加工方便加工降低吸水性降低吸水性降低吸水性降低吸水性博博博博 精精精精 儀儀儀儀 器器器器Thermal-Thermal-5353碳黑碳黑(Carbon)含量分析含量分析碳黑經常用來與塑膠混合以改進其化學或物理碳黑經常用來與塑膠混合以改進其
40、化學或物理碳黑經常用來與塑膠混合以改進其化學或物理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，充做增強劑性質。例如增強其抗紫外線特性，充做增強劑性質。例如增強其抗紫外線特性，充做增強劑性質。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以提高塑膠製品強度或做為體積填充物以提高塑膠製品強度或做為體積填充物以提高塑膠製品強度或做為體積填充物以左圖為例，除易揮發性有機以左圖為例，除易揮發性有機以左圖為例，除易揮發性有機以左圖為例，除易揮發性有機物及增量劑、外其餘皆是物及增量劑、外其餘皆是物及增量劑、外其餘皆是物及增量劑、外其餘皆是PolymerPoly
41、mer及及及及CarbonCarbon其含量分別其含量分別其含量分別其含量分別約為約為約為約為5252 及及及及2929 可直接由可直接由可直接由可直接由Y Y軸中軸中軸中軸中讀出讀出讀出讀出PolymerCarbonVolatiles博博博博 精精精精 儀儀儀儀 器器器器Thermal-Thermal-5454提供整套完整系統提供整套完整系統具有完善的介面設計具有完善的介面設計-加熱管線與氣體樣品槽加熱管線與氣體樣品槽具有專業的具有專業的TG-IR軟體軟體-TimeBase SoftwareTGA/FTIR/Interface System博博博博 精精精精 儀儀儀儀 器器器器Thermal-Thermal-5555TGA/FTIR SoftwareTGA/FTIR Software博博博博 精精精精 儀儀儀儀 器器器器Thermal-Thermal-5656TGA Weight loss vs.FTIR Spectrumweight vs TimeTGA/FTIR SoftwareTGA/FTIR Software博博博博 精精精精 儀儀儀儀 器器器器Thermal-Thermal-5757結論結論Thank you for your attention !Thank you for your attention !
