热分析技术分析

博精儀器熱分析技術簡介(DSC,TGA&DMA)PerkinElmerThermalSpecialist康瑜容[e-mail]博精儀器Thermal-2Page2DifferentialScanningCalorimetry(DSC)ThermogravimetricAnalysis(TGA)ThermomechanicalAnalysis(TMA)DynamicMechanicalAnalysis(DMA)常用的熱分析方法博精儀器Thermal-3Page3常用的熱分析方法DSCHeatflowvs.Temp-Tm,Tc,Tg-DH,curingtime,curingdegree-Reactionrate,kineticsTGAWeightLossvs.Temp-Decompositiontemperature-%Wtpercentage-OxidativetimeTMADimensionalChangevs.Temp-CTE(a1,a2)-Tg-SofteningpointDMAViscoelasticpropertyvs.Temp-Storage/Loss/ComplexModulus(E’,E”,E*)-tand-Viscosityandmastercurve博精儀器Thermal-4Page4高分子材料結構TypeofPolymerChainStructureTypeStructureExampleLinearBranchedshortchainLongchainbranchingLadderPoly(vinylchloride),PolystyrenePolypropylenePolypropylenePoly(imidazolpyrrolones)博精儀器Thermal-5Page5高分子材料結構TypeofPolymerChainStructure(Continued)TypeStructureExampleStarNetworkInterpenetratingnetwork(IPN)Phenol-formaldehyderesinsTwocrosslinkedpolymersnotbondedtoeachotherCrosslinkedepoxywithvinylpolymer博精儀器Thermal-6Page6高分子材料的分類PolystryenePolycarbonatePolyurethanesPolysulfoneAmorphousLOW/MEDIUMNylonPETAcetalHIGHPPSPPHDPECrystallineThermoplastics(Nochemicalchangeonheating)EpoxiesPolyimidesPolyestersPhenolicsUncuredRubberSiliconesNeopreneEpoxyCuredThermosets(Chemicalchangeonheating)Polymers博精儀器Thermal-7Page7Amorphousvs.Crystalline?AmorphousThermoplasticCrystallinePolymer博精儀器Thermal-8Page8Semi-CrystallinePolymerSemi-CrystallinePolymerSemi-crystallinepolymerscontainbothamorphousANDcrystallinephasesPropertiesdominatedbybothTgandTmSemi-crystallinepolymerscanexhibitadditionalcrystallizationduringheating博精儀器Thermal-9Page9ThermosettingPolymerUNCUREDPARTIALLYCUREDTOTALLYCURED博精儀器Thermal-10Page10SchematicResultsinThermalAnalysisQualityofsampleprocessDSC(Ex)TGATMADMA-Crystalline-Semi-crystalline-Amorphous-Semi-crystalline-General-Liquid-Unspecific-SolidMeltingRecrystallizationSublimationSolid-solidtransitionGlasstransitionSofteningwithoutTgPost-crosslinkingDecompositionLigandreleaseEvaporationChemicalreactionsDeterminationof%博精儀器DSCTechniqueDifferentialScanningCalorimetry博精儀器Thermal-12Page12Question?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?博精儀器Thermal-13Page13WhatisDSC?示差掃瞄熱卡量計(DifferentialScanningCalorimeter):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。博精儀器Thermal-14Page14ThermalAnalysisapplications-DSC-Principle:Heatflowchangevs.temperature-Measures:Phasetransition(Tg,Tm,Tc)andheatCuringreactionandotherchemicalreactionsDiamondDSC博精儀器Thermal-15Page15PolymerTransitionsHeatFlowTemperatureTgStressReliefOrderingProcessColdCrystallizationCuringTmDHDegradationStartupTransient博精儀器Thermal-16Page16DSCThermalCurveofPET吸熱放熱博精儀器Thermal-17Page17DSCforcuringstudiesDetectionofTgOnsetofcureMaximumrateofcure(peakmaximum)EndofcureHeatofcure博精儀器Thermal-18Page18DSC熱示差掃描分析儀之應用相變化點PhaseTransition熔融熱DH玻璃轉移溫度Tg反應熱DH熔點Meltingpoint活化能Ea冷結晶溫度CrystalTemperature氧化導引時間O.I.T.降溫結晶溫度ColdCrystalTemperature反應動力學Dynamic結晶度Crystallinity交連Curing結晶熱CrystalEnergy純度Purity結晶半週期CrystalPeriod比熱Cp博精儀器Thermal-19Page19DSC的設計方式熱流式HeatFluxDSC熱補償式PowerCompensationDSC-量測DT-由DH=kDT計算DH-爐體較大-直接量測DH-不需複雜數學運算-爐體較小博精儀器TGATechniqueThermogravimetricAnalyzer博精儀器Thermal-21Page21ThermalAnalysisapplications-TGAPyris1TGA-Principle:Weightchangevs.temperature-Measures:Compositionsandwt%Thermalstabilityanddecompositiontemp.博精儀器Thermal-22Page22TGADesignConcept懸吊式水平式上置式博精儀器Thermal-23Page23TGAThermalCurves博精儀器Thermal-24Page24主要元件pTemperaturecontroldevice-Furnace,ThermocouplepWeightmeasurementdevice-NullBalanceDetectorTareWeightSampleTorqueMotorTGA的設計原理博精儀器Thermal-25Page25TGA熱重分析儀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TGA-FTIR/TGA-MS熱穩定測量不穩定材質測試異味材質測試添加物種類測試TGA-GC/MS未知物種類判斷混合溶劑判斷博精儀器Thermal-26Page26TGAforcompositionalanalysisMoldingcompoundcontainsepoxyandfillerEpoxycanbeburnedoffandresidueisinertreinforcedfillerTGAprovidesaccurateandreproduciblecompositionaldataonmoldingcompound博精儀器TMA/DMATechniqueMechanicalAnalyzer博精儀器Thermal-29Page29ThermalAnalysisapplications–DMA/TMADMA8000-Principle:Viscoelasticpropertiesvs.temperature(DMA)Dimensionalchangevs.temperature(TMA)Measures:GlasstransitionpointStorage,LossmodulusandtandeltaCoefficientofthermalexpansion(CTE)博精儀器Thermal-30Page30WhatisDMA?DMA(DynamicMechanicalAnalyzer)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。博精儀器Thermal-31Page31材料的黏彈性質…E’–StorageModulus儲存模數彈性性質E”–LossModulus損失模數黏性性質tand=E”/E’E”E’博精儀器Thermal-32Page32黏彈機械性質ex.模數(Modulus),黏度(Viscosity),阻尼相(tand)…微小的相變化ex.b,g-transition,Tg以DSC/TMA測量不易者…活化能(ActivationEnergy)計算預測材料使用壽命ex.CreepRecovery,Time-temp.superposition…模擬製程中材料及環境變化ex.Curingprocess,controlledhumidity,SolventImmersion…什麼時候您需要DMA…博精儀器Thermal-33Page33otimeotimeotimed=0d=90oootimeodkDMA即為利用SineWave震盪方式,測量回應的分析儀材料的黏彈性質…博精儀器Thermal-34Page34IdealizedDMAScanE’/PaTemperature/KTm-melting(1)RubberyPlateau(2)TaorTgTb(6)(5)(4)(3)(2)(1)localbendsidegraduallargechainmotionsandgroupsma