热分析技术分析

1、热分析技术分析热分析技术分析第1页Page 2 Differential Scanning Calorimetry (DSC) Thermogravimetric Analysis (TGA) Thermomechanical Analysis (TMA)Dynamic Mechanical Analysis (DMA)常见熱分析方法热分析技术分析第2页Page 3 常见熱分析方法 DSC Heat flow vs. Temp Tm, Tc, Tg DH, curing time, curing degree Reaction rate, kineticsTGAWeight Loss vs.

2、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 curve热分析技术分析第3页Page 4 高分子材料結構Type of Polymer Chain StructureType Structur

3、e ExampleLinearBranched short chainLong chain branchingLadderPoly(vinyl chloride), PolystyrenePolypropylenePolypropylenePoly(imidazol pyrrolones)热分析技术分析第4页Page 5 高分子材料結構Type of Polymer Chain Structure (Continued)Type Structure ExampleStarNetworkInterpenetrating network (IPN)Phenol-formaldehyde resin

4、sTwo crosslinked polymers not bonded to each otherCrosslinked epoxy with vinyl polymer热分析技术分析第5页Page 6 高分子材料分類PolystryenePolycarbonatePolyurethanesPolysulfoneAmorphousLOW/MEDIUMNylonPETAcetalHIGHPPSPPHDPECrystallineThermoplastics(No chemical change on heating)EpoxiesPolyimidesPolyestersPhenolicsUncu

5、redRubberSiliconesNeopreneEpoxyCuredThermosets(Chemical change on heating)Polymers热分析技术分析第6页Page 7 Amorphous vs. Crystalline?Amorphous ThermoplasticCrystalline Polymer热分析技术分析第7页Page 8 Semi-Crystalline PolymerSemi-Crystalline PolymerSemi-crystalline polymers contain both amorphous AND crystalline pha

6、sesProperties dominated by both Tg and TmSemi-crystalline polymers can exhibit additional crystallization during heating热分析技术分析第8页Page 9 Thermosetting Polymer热分析技术分析第9页Page 10 Schematic Results in Thermal AnalysisQuality of sample process DSC(Ex) TGA TMA DMA CrystallineSemi-crystalline-Amorphous-Sem

7、i-crystalline-General-Liquid-Unspecific-Solid MeltingRecrystallizationSublimationSolid-solid transitionGlass transitionSoftening without TgPost-crosslinkingDecompositionLigand releaseEvaporationChemical reactionsDetermination of %热分析技术分析第10页DSC TechniqueDifferential Scanning Calorimetry热分析技术分析第11页Pa

8、ge 12 Question?PE分成HDPE, LLDPE及LDPE - 結構有何不一样? - 性質有何差異? - 結構和性質有何關聯性?結晶過程為何?加工條件對結晶有何影響?結晶度對透明度影響?添加劑影響?DSC可解決哪些問題?热分析技术分析第12页Page 13 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。热分析技术分析第1

9、3页Page 14 Thermal Analysis applications - DSCPrinciple: Heat flow change vs. temperatureMeasures: Phase transition (Tg, Tm, Tc) and heat Curing reaction and other chemical reactionsDiamond DSC热分析技术分析第14页Page 15 Polymer TransitionsHeatFlowTemperatureTgStressReliefOrderingProcessCold CrystallizationCu

10、ringTmDHDegradationStart upTransient热分析技术分析第15页Page 16 DSC Thermal Curve of PET吸 熱放 熱热分析技术分析第16页Page 17 DSC for curing studiesDetection of TgOnset of cureMaximum rate of cure (peak maximum)End of cureHeat of cure热分析技术分析第17页Page 18 DSC熱示差掃描分析儀之應用相變化點Phase Transition熔融熱H玻璃轉移溫度Tg反應熱H熔點Melting point活化能E

11、a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热分析技术分析第18页Page 19 DSC設計方式熱流式 Heat Flux DSC熱補償式 Power Compensation DSC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 爐體較小热分析技术分析第19页TGA TechniqueThermogravim

12、etric Analyzer热分析技术分析第20页Page 21 Thermal Analysis applications - TGAPyris 1 TGAPrinciple: Weight change vs. temperatureMeasures: Compositions and wt% Thermal stability and decomposition temp.热分析技术分析第21页Page 22 TGA Design Concept懸吊式水平式上置式热分析技术分析第22页Page 23 TGA Thermal Curves热分析技术分析第23页Page 24 主要元件 Te

13、mperature control device - Furnace, Thermocouple Weight measurement device -Null BalanceDetectorTare WeightSampleTorque MotorTGA 設計原理热分析技术分析第24页Page 25 TGA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热分析技术分析第25页Page 26 TGA for composi

14、tional 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热分析技术分析第26页Page 27 Pyris 1 TGA Features:Most sensitive balance in the world with 10-7 g sensitivityIsoth

15、ermal and isolated balance chamber for better stabilityIsolation convection of balance and sample purge gas to have best sensitivity and stabilityIon discharge component for keeping from electrostatic disturbanceVariety of sample pans for sample decomposition analysis热分析技术分析第27页TMA/DMA TechniqueMech

16、anical Analyzer热分析技术分析第28页Page 29 Thermal Analysis applications DMA/TMADMA 8000Principle: 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)热分析技术分析第29页Page 3

17、0 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，其機械性質變化情形，進而判定材料特征。热分析技术分析第30页Page 31 材料黏彈性質E Storage Modulus 儲存模數 彈性性質E” Loss Modulus 損失模數 黏性性質tan d = E” / EE”E热分析技术分析第31页Page 32 黏彈機械性質 ex. 模數(Modulus), 黏度(Viscosity), 阻尼相(tan d) 微小相變化 ex. b,g- transition, Tg

18、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 什麼時候您需要 DMA 热分析技术分析第32页Page 33 黏性彈性otimeotimeotime = 0 = 90oootimeo kDMA即為利用Sine Wave震盪方式, 測量回應分析儀材料黏彈性質热分析技术分析第33页Page 34 Idealized DMA

19、 ScanE/PaTemperature /KTm - melting (1)Rubbery Plateau (2)Ta or TgTb (6)(5)(4)(3)(2)(1) localbendsidegraduallargechainmotionsandgroupsmainscaleslippagestretchchainchainTg (6)Rubbery plateau is related to Me between crosslinks or entanglements.For thermosets, no Tm occurs.Beta transitions are oftenre

20、lated 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)(4)(3)热分析技术分析第34页Page 35 Frequency effects things tooTransitions shiftBehavior ch

21、angesFrequencyEMorefluidMoreelastic热分析技术分析第35页Page 36 So frequency can act like temperatureFrequencyETemperatureE热分析技术分析第36页Page 37 DMA 連結.材料結構特征製程加工特征成品特征Molecular weightMW DistributionChain BranchingCross linkingEntanglementsPhasesCrystallinityFree VolumeLocalized motionRelaxation MechanismsStress

22、StrainTemperatureHeat HistoryFrequencyPressureHeat setMaterialBehaviorDimensional StabilityImpact propertiesLong term behaviorEnvironmental resistanceTemperature performanceAdhesionTackPeel热分析技术分析第37页Page 38 DMA 是怎样運作?Storage ModulusLoss ModulusStatic ForceDynamic ForceFrequencyfAmplitudeKPositionHo

23、ld SampledPhaseThermocoupleTotal Force LVDTFurnace Options from -190 to 600 CForce motorFixtures热分析技术分析第38页Page 39 多樣化夾具選擇Options:Single CantileverDual Cantilever3 Point BendingTensionCompressionShearQuartz ShearMaterial Pocket热分析技术分析第39页Page 40 Exclusive Material Pockets ApplicationsPowders like dr

24、ugs, excipients, foods, natural products, etc.Gels Uncured adhesivesCoatingsSamples that cant support their own weightPocket openSample in PocketPocket closed & sealed热分析技术分析第40页Page 41 DMA mode for mechanical properties changeThis plot shows DMA results (E and tan delta) for cured substrateDMA give

25、s the most sensitive measure of TgDMA results show that substrate is incompletely cured as 2 split peak was found in tan delta around Tg热分析技术分析第41页Page 42 DMA most sensitive indicator of cureThis plot shows DMA results on completely cured and slightly under-cured PCBsUnder-cured PCB exhibits a sligh

26、t increase in E above Tg making the board unacceptable热分析技术分析第42页Page 43 TMA mode for 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热分析技术分析第43页Page 44 更多熱分析應用热分析技术分析第44页高分子熱性質量測热分析技术分析第45页Page 46 高分子 Tg 分析 - 加熱歷史差異热分析技术分析第46页Page 47 結晶測試 - 恆溫結晶热分析技术分析第47页Page 48 交連測試 - 升溫交連Epoxy ResinT (