熱分析技術分析

1、熱分析技術分析熱分析技術分析第1頁Page 2 Differential Scanning Calorimetry (DSC) Thermogravimetric Analysis (TGA) Thermomechanical Analysis (TMA)Dynamic Mechanical Analysis (DMA)常見熱分析方法熱分析技術分析第2頁Page 3 常見熱分析方法 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熱分析技術分析第3頁Page 4 高分子材料結(jié)構(gòu)Type of Polymer Chain StructureType Structur

3、e ExampleLinearBranched short chainLong chain branchingLadderPoly(vinyl chloride), PolystyrenePolypropylenePolypropylenePoly(imidazol pyrrolones)熱分析技術分析第4頁Page 5 高分子材料結(jié)構(gòu)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熱分析技術分析第5頁Page 6 高分子材料分類PolystryenePolycarbonatePolyurethanesPolysulfoneAmorphousLOW/MEDIUMNylonPETAcetalHIGHPPSPPHDPECrystallineThermoplastics(No chemical change on heating)EpoxiesPolyimidesPolyestersPhenolicsUncu

5、redRubberSiliconesNeopreneEpoxyCuredThermosets(Chemical change on heating)Polymers熱分析技術分析第6頁Page 7 Amorphous vs. Crystalline?Amorphous ThermoplasticCrystalline Polymer熱分析技術分析第7頁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熱分析技術分析第8頁Page 9 Thermosetting Polymer熱分析技術分析第9頁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 %熱分析技術分析第10頁DSC TechniqueDifferential Scanning Calorimetry熱分析技術分析第11頁Pa

8、ge 12 Question?PE分成HDPE, LLDPE及LDPE - 結(jié)構(gòu)有何不一樣? - 性質(zhì)有何差異? - 結(jié)構(gòu)和性質(zhì)有何關聯(lián)性?結(jié)晶過程為何?加工條件對結(jié)晶有何影響?結(jié)晶度對透明度影響?添加劑影響?DSC可解決哪些問題?熱分析技術分析第12頁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(huán)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(fā)生熔融、蒸發(fā)、結(jié)晶、相轉(zhuǎn)變等物理現(xiàn)象，或化學變化時，圖譜中將會出現(xiàn)吸熱或放熱帶，進而可推測樣品之性質(zhì)。熱分析技術分析第1

9、3頁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熱分析技術分析第14頁Page 15 Polymer TransitionsHeatFlowTemperatureTgStressReliefOrderingProcessCold CrystallizationCu

10、ringTmDHDegradationStart upTransient熱分析技術分析第15頁Page 16 DSC Thermal Curve of PET吸 熱放 熱熱分析技術分析第16頁Page 17 DSC for curing studiesDetection of TgOnset of cureMaximum rate of cure (peak maximum)End of cureHeat of cure熱分析技術分析第17頁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(zhuǎn)移溫度Tg反應熱H熔點Melting point活化能E

11、a冷結(jié)晶溫度Crystal Temperature氧化導引時間O.I.T.降溫結(jié)晶溫度Cold Crystal Temperature反應動力學Dynamic結(jié)晶度Crystallinity交連Curing結(jié)晶熱Crystal Energy純度Purity結(jié)晶半週期Crystal Period比熱Cp熱分析技術分析第18頁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(shù)學運算 爐體較小熱分析技術分析第19頁TGA TechniqueThermogravim

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

13、mperature control device - Furnace, Thermocouple Weight measurement device -Null BalanceDetectorTare WeightSampleTorque MotorTGA 設計原理熱分析技術分析第24頁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(wěn)定測量不穩(wěn)定材質(zhì)測試異味材質(zhì)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熱分析技術分析第25頁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熱分析技術分析第26頁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熱分析技術分析第27頁TMA/DMA TechniqueMech

16、anical Analyzer熱分析技術分析第28頁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)熱分析技術分析第29頁Page 3

17、0 What is DMA ? DMA (Dynamic Mechanical Analyzer) 動態(tài)黏彈機械分析儀 將樣品置於特定環(huán)境下，偵測樣品在溫度、力量、或頻率改變下，其機械性質(zhì)變化情形，進而判定材料特征。熱分析技術分析第30頁Page 31 材料黏彈性質(zhì)E Storage Modulus 儲存模數(shù) 彈性性質(zhì)E” Loss Modulus 損失模數(shù) 黏性性質(zhì)tan d = E” / EE”E熱分析技術分析第31頁Page 32 黏彈機械性質(zhì) ex. 模數(shù)(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(huán)境變化 ex. Curing process, controlled humidity, Solvent Immersion 什麼時候您需要 DMA 熱分析技術分析第32頁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(zhì)熱分析技術分析第33頁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)熱分析技術分析第34頁Page 35 Frequency effects things tooTransitions shiftBehavior ch

21、angesFrequencyEMorefluidMoreelastic熱分析技術分析第35頁Page 36 So frequency can act like temperatureFrequencyETemperatureE熱分析技術分析第36頁Page 37 DMA 連結(jié).材料結(jié)構(gòu)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熱分析技術分析第37頁Page 38 DMA 是怎樣運作?Storage ModulusLoss ModulusStatic ForceDynamic ForceFrequencyfAmplitudeKPositionHo

23、ld SampledPhaseThermocoupleTotal Force LVDTFurnace Options from -190 to 600 CForce motorFixtures熱分析技術分析第38頁Page 39 多樣化夾具選擇Options:Single CantileverDual Cantilever3 Point BendingTensionCompressionShearQuartz ShearMaterial Pocket熱分析技術分析第39頁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熱分析技術分析第40頁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熱分析技術分析第41頁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熱分析技術分析第42頁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熱分析技術分析第43頁Page 44 更多熱分析應用熱分析技術分析第44頁高分子熱性質(zhì)量測熱分析技術分析第45頁Page 46 高分子 Tg 分析 - 加熱歷史差異熱分析技術分析第46頁Page 47 結(jié)晶測試 - 恆溫結(jié)晶熱分析技術分析第47頁Page 48 交連測試 - 升溫交連Epoxy ResinT (