1、 PerkinElmer Thermal Specialist 康瑜容 Tiffany KangTiffany.KPage 2 Differential Scanning Calorimetry(DSC)Thermogravimetric Analysis(TGA)Thermomechanical Analysis(TMA)Dynamic Mechanical Analysis(DMA)常用的熱分析方法常用的熱分析方法Page 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-React
2、ion rate,kineticsTGAWeight Loss vs.Temp-Decomposition temperature-%Wt percentage-Oxidative timeTMADimensional Change vs.Temp-CTE(a1,a2)-Tg-Softening point DMAViscoelastic property vs.Temp-Storage/Loss/Complex Modulus(E,E”,E*)-tan d-Viscosity and master curvePage 4 高分子材料結構高分子材料結構Type of Polymer Chain
3、 StructurePage 5 高分子材料結構高分子材料結構Type of Polymer Chain Structure(Continued)Page 6 高分子材料的分類高分子材料的分類PolystryenePolycarbonatePolyurethanesPolysulfoneAmorphousLOW/MEDIUMNylonPETAcetalHIGHPPSPPHDPECrystallineThermoplastics(No chemical change on heating)EpoxiesPolyimidesPolyestersPhenolicsUncuredRubberSilic
4、onesNeopreneEpoxyCuredThermosets(Chemical change on heating)PolymersPage 7 Amorphous vs.Crystalline?Page 8 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 crystall
5、ization during heatingPage 9 Thermosetting Polymer UNCUREDPARTIALLY CUREDTOTALLY CUREDPage 10 Schematic Results in Thermal Analysis Page 12 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 13 What is DSC?示差掃瞄熱卡量計示差掃瞄熱卡量計(Differential Scan
6、ning 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將會出現吸熱或放熱帶，進而可推測樣品之性質。Page 14 Thermal Analysis applications-DSCPage 15 Polymer TransitionsHeatFlowTemperatureTgStre
7、ssReliefOrderingProcessCold CrystallizationCuringTmDHDegradationStart upTransientPage 16 DSC Thermal Curve of PET吸吸 熱熱放放 熱熱Page 17 DSC for curing studies Detection of Tg Onset of cure Maximum rate of cure(peak maximum)End of cure Heat of curePage 18 DSC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
8、融熱熔融熱D DH玻璃轉移溫度玻璃轉移溫度Tg反應熱反應熱D DH熔點熔點Melting 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CpPage 19 DSC的設計方式的設計方式 Page 21 Thermal Analysis applic
9、ations-TGAPage 22 TGA Design ConceptPage 23 TGA Thermal CurvesPage 24 主要元件主要元件p Temperature control device -Furnace,Thermocouplep Weight measurement device -Null BalanceDetectorTare WeightSampleTorque MotorPage 25 TGA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
10、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Page 26 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
11、reproducible compositional data on molding compoundPage 27 Pyris 1 TGA Page 29 Thermal Analysis applications DMA/TMAPage 30 What 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。Page 31 材料的黏彈性
12、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”EPage 32 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變化 e
13、x.Curing process,controlled humidity,Solvent Immersion 什麼時候您需要什麼時候您需要 DMA Page 33 黏性黏性彈性彈性otimeotimeotimed d=0d d=90oootimeod d 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Page 34 Idealized DMA ScanE/PaTemperature/KTm-melting(1)Rubbery Plateau(2)Ta a or TgT Tb b(6)(5)(5)(4)(4)(3)(3)(
14、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 oftenrelated to the toughness.Tg is related to Molecular massup to a limiting
15、 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)Page 35 Frequency effects things too Transitions shift Behavior changesFrequencyE MorefluidMoreelasticPage 36 So frequency can act like tem
16、peratureFrequencyETemperatureEPage 37 DMA 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 BranchingCross linkingEntanglementsPhasesCrystallinityFree VolumeLocalized motionRelaxation MechanismsStressStrainTemperatureHeat HistoryFrequencyPressureHeat setMaterialBehaviorDimens
17、ional StabilityImpact propertiesLong term behaviorEnvironmental resistanceTemperature performanceAdhesionTackPeelPage 38 DMA 是如何運作的是如何運作的?Storage ModulusLoss ModulusStatic ForceDynamic ForceFrequencyfAmplitudeKPositionHold Sampled dPhaseThermocoupleTotal Force LVDTFurnace Options from-190 to 600 CFo
18、rce motorFixturesPage 39 多樣化的夾具選擇多樣化的夾具選擇Options:Single CantileverDual Cantilever3 Point BendingTensionCompressionShearQuartz ShearMaterial PocketPage 40 Exclusive Material Pockets ApplicationsPowders like drugs,excipients,foods,natural products,etc.Gels Uncured adhesivesCoatingsSamples that cant su
19、pport their own weightPocket openSample in PocketPocket closed&sealedPage 41 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
20、found in tan delta around TgPage 42 DMA most sensitive indicator of cure This plot shows DMA results on completely cured and slightly under-cured PCBs Under-cured PCB exhibits a slight increase in E above Tg making the board unacceptableModulus (E)25Temperature(C)250DMA Results onPCBsGood and BadRej
21、ectedAcceptablePage 43 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 effectsPage 44 Page 46 高分子的高分子的
22、 Tg 分析分析-加熱歷史的差異加熱歷史的差異Page 47 結晶測試結晶測試-恆溫結晶恆溫結晶Page 48 Epoxy ResinT(oC)4080120160200240280EndothermicHeat Flow(mW)Run 1D HRun 2113.3 oC62.8 oC30 mw20 oC/min32.76 mgRange:Heating Rate:Weight:Page 49 Page 50 DSC Heat Flow Temperature DSC Tg As Function of Cure Less Cured More Cured Page 51 DSC Heat F
23、low Temperature Decrease in Cure Exotherm As Resin Cure Increases Less Cured More Cured Page 52 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黑碳黑玻璃纖維玻璃纖維Page 53 碳黑碳黑(Carbon)含量分析含量分析PolymerCarbonVolatilesPage 54 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 SystemPage 55 Page 56 TGA Weight loss vs.FTIR Spectrumweight vs TimePage 57 結論結論
