热重分析TGA-完整版资料.pdf

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