热重分析TGA-完整版资料.pdf
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热热重重分分析析(TGA)Theory&Applications12.57%Water(0.8753mg)19.47%CarbonMonoxide(1.355mg)30.07%CarbonDioxide(2.093mg)-20246Deriv.Weight(%/min)20406080100120Weight(%)02004006008001000Temperature(C)UniversalV3.4ATAInstruments2TGA:
TheTechniqueThermogravimetricAnalysis(TGA)measurestheamountandrateofchangeintheweightofamaterialasafunctionoftemperatureortimeinacontrolledatmosphere.热重分析的结果用热重曲线或微分热重曲线表示。
样品在热环境中发生化学变化、分解、成分改变时可能伴随着重量的变化。
热重分析就是在不同的热条件(以恒定速度升温或等温条件下延长时间)下对样品的质量变化加以测量的动态技术。
3WhatTGACanTellYouThermalStabilityofMaterialsOxidativeStabilityofMaterialsCompositionofMulti-componentSystemsEstimatedLifetimeofaProductDecompositionKineticsofMaterialsTheEffectofReactiveorCorrosiveAtmospheresonMaterialsMoistureandVolatilesContentofMaterials热稳定性氧化稳定性组成产品寿命分解动力学反应或腐蚀气氛对材料的影响材料水分和挥发份含量4MechanismsofWeightChangeinTGA?
WeightLoss:
?
Decomposition:
Thebreakingapartofchemicalbonds.?
Evaporation:
Thelossofvolatileswithelevatedtemperature.?
Reduction:
Interactionofsampletoareducingatmosphere(hydrogen,ammonia,etc).?
Desorption.?
WeightGain:
?
Oxidation:
Interactionofthesamplewithanoxidizingatmosphere.?
Absorption.Allofthesearekineticprocesses(i.e.thereisarateatwhichtheyoccur).5DTG曲线微分型曲线TG曲线积分型曲线6初始热分解温度(B、G)反应终了温度(C、H)最大失重速率温度7影影响响热热重重测测定定的的因因素素:
PurgeGasTGA:
AlwayspurgethroughbalancehousingwithdryinertgasTGA:
Onlyintroducereactive/corrosivegasesthroughsamplearea/furnacehousingNitrogenmostcommon.Heliumoftenprovidesbestbaselinebutwillmakefurnaceworkhardathightemperature.Aircansometimesimproveresolutionbecauseofdifferencesintheoxidativestability(versusthermalstability)ofcomponents.气氛不同反应机理的不同。
8TGA:
PurgeGasFlow60ml/min90ml/min10ml/min40ml/minStandardFurnaceEGAFurnace9TestforOxygenContaminationofN2PurgeGas0100200300400500600406080100120-10123Temperature(C)Weight(%)-Deriv.Weight(%/C)320.79C10minuteN2pre-purge+CopperOxalate10EffectofOxygenonCopperOxalateDecomposition300350400450500550600Temperature(C)414243444546Weight(%)HighOxygenMediumOxygenLowOxygen11TGA:
BaselineConsiderationsGoodwaytoquantifyhowtheTGA/SDTisworking.Especiallyimportantformeasuringsmallweightlossesassociatedwithvolatilizationorsmallamountsofresidue.Runclean,empty,taredpan,overtemperaturerangeofinterest,atdesiredheatingrate.Plotweightingvs.temperature.12TGA:
AccurateResiduals-20020406080100120Weight(%)02004006008001000Temperature(C)UniversalV3.9ATAInstruments-2024-2024PolyolefinBaselineExpandedScale0.28%13TGA:
SamplePreparation(cont.)UsebrasstweezerstoeliminatestaticeffectsTareacleansamplepanbeforeeveryrunDistributesampleevenlyoverbottomofpanLiquidsamples-usehermeticpanwithapin-holelid14Platinum(usefulformostmaterials)?
EasytoClean?
Nonporous?
AlloyswithmostmetalsAlumina(Ceramic)?
Corrosives/Inorganics?
LargesamplesAluminum(TGA)(designedforone-timeuse)?
Lowercost?
Lowertemperaturelimit(=600C)TGA:
SamplePanSelection15TGA:
SamplePans-Types/SizesCeramicPlatinumAluminum50L100L100L250L500LPlatinumandAluminumpanshaveattachedwirebail.Ceramicpanshaveremovablewirebail.16EffectofSampleSize020406080100Weight(%)0100200300400500600Temperature(C)Polystyrene17.6mgPolystyrene10.2mgPolystyrene5.4mgPolystyrene2.7mgUniversalV4.2DTAInstruments17EffectofHeatingRate020406080100Weight(%)0100200300400500600Temperature(C)Polystyrene20C/minPolystyrene10C/minPolystyrene5C/minPolystyrene1C/min18MassEffectSemi-crystallinePE436.28癈457.57癈-20020406080100120Weight(%)0100200300400500600Temperature(癈)0.492mg48.422mgUniversalV3.8ATAInstruments19PanShapeEffectAmorphousPMMA365.01癈369.13癈-20020406080100120Weight(%)0100200300400500Temperature(癈)4.6mg;spreadevenly4.6mg;intallS.S.pan(150mg)UniversalV3.8ATAInstruments20SampleMorphologyEffectsPET419.58癈424.58癈020406080100120Weight(%)0100200300400500600Temperature(癈)2.9mg;amorphousPET2.8mg;crystallinePETUniversalV3.8ATAInstruments2.9mg;amorphousPET2.8mg;semi-crystallinePET21ShiftinOnsetwithRampRate524.26C563.82C-20020406080100120Weight(%)400450500550600650700Temperature(C)2.5C/min5C/min10C/min20C/minUniversalV3.7ATAInstruments22TimetoCompleteDegradation-20020406080100120Weight(%)20406080100120140160180Time(min)2.5C/min5C/min10C/min20C/minjUniversalV3.7ATAInstruments23Q5000IRHigh-HeatingRateTGAAnalysis24TypicalApplicationsThermalStabilityCompositionalAnalysisOxidativeStability25ThermalStabilityofPolymersMethodLog:
1:
Selectgas:
1-N22:
Ramp20.00C/minto650.00C3:
Selectgas:
2-Air4:
Ramp20.00C/minto1000.00CPVCPMMAPET650.00C55.59%650.00C5.928%LDPEPEEK650.00C14.32%020406080100Weight(%)502504506508501050Temperature(C)26BlockversusRandomCopolymers0100200300400500050100Temperature(C)Weight(%)S-MSRANDOMS-MSBLOCKP-MSPSsize:
8mgprog:
6C/minatm:
300Pavacuum27EffectofEpoxyCureTemperature260280300320340360380400420440020406080100Temperature(C)Weight(%)100C125C150C175C200CProg:
10C/min28CuriePoint(居里温度)Determination05010015020025030035040098100102104Temperature(C)Weight(%)Initialweightgainafterplacementofmagnet240.67CCuriePoint29ThermalStabilityofanExplosiveMaterial99.88%(51.76mg)ExplosiveMaterialSize:
51.8240mgBalanceGas:
Air40.0ml/minSampleGas:
Air60.0ml/minMethodLog:
1:
Ramp3.00癈/minto400.00癈020406080100Weight(%)020406080100Time(min)30ThermalStabilityofanExplosiveMaterial99.88%(51.76mg)ExplosiveMaterialSize:
51.8240mgBalanceGas:
Air40.0ml/minSampleGas:
Air60.0ml/minMethodLog:
1:
Ramp3.00癈/minto400.00癈020406080100Weight(%)050100150200250300350400Temperature(癈)31TGAofanAdhesive25.18mgofanadhesive10C/min0123Deriv.Weight(%/C)020406080100Weight(%)0100200300400500600Temperature(C)32InsetViewShowsStrangeResult0123Deriv.Weight(%/癈)020406080100Weight(%)0100200300400500600Temperature(癈)Isthisreal?
33Usetimebasedderivativeoftemperaturetoplottheheatingrate34AberrationinHeatingRate51015Deriv.Temperature(癈/min)-10123Deriv.Weight(%/癈)020406080100120Weight(%)430440450460470480Temperature(癈)Usuallymeansthatthesampletouchedthethermocouple35TGAofDrugASample:
DrugASize:
22.5850mgHeatingRate:
10C/min36TGAofDrugAMonohydrate4.946%(0.7505mg)-20246Deriv.Weight(%/min)80859095100105Weight(%)050100150200250300Temperature(C)UniversalV3.4CTAInstrumentsSample:
DrugAMonohydrateSize:
15.1740mgHeatingRate:
10C/minWaterweightlossDecomposition37TGAofDrugAMicrospheresSample:
DrugAMicrospheresSize:
14.2940mgHeatingRate:
10C/min38TGAAnalysisofCold/AllergyTablet1.154%(0.2134mg)2.346%(0.4338mg)02468101214Deriv.Weight(%/min)5060708090100Weight(%)050100150200250300Temperature(C)UniversalV3.4CTAInstrumentsSample:
Cold/AllergyTabletSize:
18.4890mgHeatingRate:
10C/minVolatilesDecomposition39-2147HeatFlow(W/g)-0.6-0.30.00.30.60.9Deriv.Weight(%/C)60667278849096102Weight(%)0200400600800Temperature(C)DSC-TGASodiumTungstateSmallSampleSize(3mg)and10C/minHeatingRateDehydrationSolidstateandmeltingtransitions40DehydrationSensitivity0.2078%(0.01795mg)114.96癈1.094J/g0.00550.01150.01750.02350.02950.03550.0415Deriv.Weight(%/癈)99.454399.7543100.0543100.3543Weight(%)-0.35-0.30-0.25-0.20HeatFlow(W/g)406080100120140160180Temperature(癈)41TGA-DSCSodaAsh857.18癈851.38癈186.8J/g0.10.2Deriv.Weight(%/癈)-8-6-4-20HeatFlow(W/g)708090100Weight(%)0200400600800100012001400Temperature(癈)300350400450500550600473.63癈314.87癈16.62(24.57)J/g350.90癈316.33癈7.949J/gDehydrationHeatflowIntegrationsautomaticallynormalizedusingweightatstartoftransitionPolymorphicphasetransitionsMeltingtransition42CompositionalAnalysisCalciumOxalate12.57%Water(0.8753mg)19.47%CarbonMonoxide(1.355mg)30.07%CarbonDioxide(2.093mg)-20246Deriv.Weight(%/min)20406080100120Weight(%)02004006008001000Temperature(C)Instrument:
TGAQ50V2.34Build127UniversalV3.4ATAInstrumentsSample:
CaOxSize:
6.9610mgHeatingRate:
10C/min4316.87%AceticAcid(3.240mg)-20020406080100120Weight(%)0100200300400500600700Temperature(C)UniversalV3.3BTAInstrumentsEVACopolymer%VinylAcetate=%AceticAcid*MolecularWeight(VA)/MolecularWeight(AA)VA%=16.85(86.1/60.1)=24.2%Sample:
EVA(25%)Size:
19.2030mgHeatingRate:
10C/min44PETw/CarbonBlackFiller78.64%(11.26mg)20.64%(2.957mg)CarbonBlackFilledPETInN220.00癈/minto650.00癈SwitchtoAirRamp20.00癈/minto1000.00癈-0.50.00.51.01.52.0Deriv.Weight(%/癈)020406080100Weight(%)02004006008001000Temperature(癈)HowmuchCarbonBlackwasinthissample?
45PET85.65%(16.01mg)13.99%(2.614mg)InN220.00癈/minto650.00癈SwitchtoAirRamp20.00癈/minto1000.00癈PET-0.50.00.51.01.52.0Deriv.Weight(%/癈)020406080100Weight(%)02004006008001000Temperature(癈)46ComparisonofFilled&Un-FilledPET85.65%(16.01mg)13.99%(2.614mg)78.64%(11.26mg)20.64%(2.957mg)MethodLog:
1:
Ramp20.00癈/minto650.00癈2:
Selectgas:
23:
Ramp20.00癈/minto1000.00癈6.65%CarbonBlack020406080100Weight(%)02004006008001000Temperature(癈)PETFilledPET47Styrene-ButadieneRubberAnalysis02004006008001,0000255075100Temperature(C)Wt(%)8.4%Oil50.4%PolymerAir36.2%CarbonBlack5%InertFillerSampleweight:
30mgProgramrate:
20CAtmosphere:
N,Air248FilledPolymerAnalysisPolymerCarbonBlackAir(A)PolymerCarbonBlackAir(B)LightOilPolymer+HeavyOilCarbonBlackAir(C)100010010000WEIGHT(%)TEMPERATURE(C)InertfillerInertfillerInertfiller49OxidativeStabilityEpoxy020040060080060708090100TEMPERATURE(C)WEIGHT(%)WithoutFlameRetardantWithFlameRetardantSize:
20mgProg.:
10C/minAtm.:
Air50ResolutionEnhancementbyChangingPurge020406080100120Weight(%)05101520253035Time(min)UniversalV3.3BTAInstrumentsPETN2AirN2w/switchtoairgasswitch51传传统统TGA与与高高分分辨辨TGA之之比比较较聚聚氨氨酯酯52传传统统TGA与与高高分分辨辨TGA之之比比较较CharacterizationofaPTFE/PEEK/CarbonFiberBlend53DecompositionKineticsBackground?
Includesisothermalandconstantheatingratemethods.?
Constantheatingratemethodisthefastestandwillbediscussedhere.?
BasedonmethodofFlynnandWallPolymerLetters,19,323,(1966).Requirescollect