Fast Scanning Calorimetry PDF
Preview Fast Scanning Calorimetry
Christoph Schick · Vincent Mathot Editors Fast Scanning Calorimetry Fast Scanning Calorimetry Christoph Schick • Vincent Mathot Editors Fast Scanning Calorimetry Editors ChristophSchick VincentMathot InstituteofPhysics SciTeB.V. UniversityofRostock KatholiekeUniversiteitLeuven Rostock,Germany Geleen,TheNetherlands ISBN978-3-319-31327-6 ISBN978-3-319-31329-0 (eBook) DOI10.1007/978-3-319-31329-0 LibraryofCongressControlNumber:2016934413 ©SpringerInternationalPublishingSwitzerland2016 Thisworkissubjecttocopyright.AllrightsarereservedbythePublisher,whetherthewholeorpartof the material is concerned, specifically the rights of translation, reprinting, reuse of illustrations, recitation, broadcasting, reproduction on microfilms or in any other physical way, and transmission or information storage and retrieval, electronic adaptation, computer software, or by similar or dissimilarmethodologynowknownorhereafterdeveloped. The use of general descriptive names, registered names, trademarks, service marks, etc. in this publicationdoesnotimply,evenintheabsenceofaspecificstatement,thatsuchnamesareexempt fromtherelevantprotectivelawsandregulationsandthereforefreeforgeneraluse. Thepublisher,theauthorsandtheeditorsaresafetoassumethattheadviceandinformationinthis book are believed to be true and accurate at the date of publication. Neither the publisher nor the authors or the editors give a warranty, express or implied, with respect to the material contained hereinorforanyerrorsoromissionsthatmayhavebeenmade. Printedonacid-freepaper ThisSpringerimprintispublishedbySpringerNature TheregisteredcompanyisSpringerInternationalPublishingAGSwitzerland Preface ThermalAnalysisandCalorimetryencloseanalyticaltechniquesthatarecrucialfor the study of thermal properties of substances and materials. While it has been a recognized area of research for centuries, the activities in the past 50 years have increased tremendously. This is primarily due to the growing demand at the beginningofthesecondhalfofthetwentiethcenturyformaterialscharacterization and the subsequent availability of quantitative, commercial equipment starting in thesixtiesofthepreviouscentury. Thus, in addition to further improvement of existing calorimeters, often with sample masses to gram scale, new capabilities arose by the introduction of isoperibolic, scanning, twin calorimeters. In such calorimeters, two measuring cells—onewithasampleandonewithout—allowmeasurementofthedifferences between the two thermal responses as caused by a temperature-time program in combination with isothermal stays. The newly developed twin calorimeters with smallerfurnacesandcellsmadeitpossibletorunonmuchlowersamplemasses,at 1–100mgscale.TheresultingDifferentialScanningCalorimeters(DSCs)wereand still are capable of measuring at constant scan rates, about 10 ˚C/min, for both coolingandheatingramps. In the past 20 years, for various reasons given below, efforts were made to increasethescanrateof‘conventional’DSCs,andsomeofthemweresuccessful.It was expected that with increased scan rate less sample mass would be needed, because in such a case the sample’s response increases. In order to achieve high scanrates,thecellsoftheDSCshouldbeassmallaspossibletopreventsignificant thermallag. Adjusting the sample handling and taking advantage of the relatively (com- paredtootherandearliertypesofDSC)smallcellsincaseofpowercompensation typeofDSC,itindeedturnedouttobepossibletooperateathigherrates,typical at200˚C/min,anduptoabout750˚C/min,workingwithmilligramtomicrogram sample masses. This was, and still is, quite an interesting and valuable feature. Sincethemeasurementscanstillbequantitative,evenathigherscanrates,usinga DSC in this way in combination with a proper handling of the sample, the v vi Preface capabilities attained were assigned to the (generic) naming High Performance DSC (HPerDSC).Theadvantage istheabilitytostudythesometimesconsider- able dependence of thermal response on the scan rate applied. Moreover, the globaldisseminationandapplicationofHPerDSCwasfacilitatedbythefactthat existing commercial equipment can be used at no extra cost, resulting in easy accesstothebenefitsofHPerDSC. Another effort, following a different technical route, resulted in the Rapid Heating andCooling(RHC, upto2000˚C/min)DSC.However,even thoughthis instrument probably marks the highest attainable level of scan rate capabilities usingsamplepans,theinstrumenthasnotbeencommercialized. One motivation for increasing cooling and heating rates at arose in the second half of the twentieth century from fundamental studies of the crystallization and meltingbehaviorofsmallsystems,includingthebehaviorofpolymersystemsthat couldcontainmetastablecrystalliteshaving1,2or3nano-sizeddimensions.These can cause extensive reorganization phenomena as reflected by recrystallization, coldcrystallization,annealingetc.,phenomenawhichoccurfrequentlyduringday- by-day measurements. The understanding of such phenomena would certainly benefitfromexperimentsapplyingheatingratescomparabletotheratesofreorga- nization,includinghigherscanratesthanexistingatthattime. A second motivation was to study the influence of conditions in practice, including processing and subsequent amorphization and partial to full crystalliza- tionofpolymers,metalsetc.athighcoolingrates.Frompractice,itisknownthat high cooling rates, on the order of typically 100–10,000 ˚C/s, occur during processing by, for example, blow molding and injection molding. Obviously, many processes take place at rates ranging from slow to extremely fast, and the desiretohaveaccesstomuchhigherratesthanpossiblebyconventionalDSC,both in cooling and heating, is a logical one. However, such high scan rates are not achievablebythetechniques/methodsusedforHPerDSC. Fulfillment ofthese motivations onlybecame possibleduringthepast20years by the availability of Micro-Electro-Mechanical Systems (MEMS)-based sensor technology,leadingtochip-basedcalorimetersthatenableFastScanningCalorim- etry(FSC).Anothersteptowardsoptimalthermalcharacterizationwasrealizedby adding fast scan rates to the available range of scan rates, both in cooling and in heating. Asanexample,thecommerciallyavailableFlashDSC1hasatemperaturerange of approximately -95 to 420 ˚C with a two-stage intracooler. Scan rates typically runfromapproximately1–1000˚C/s(incaseofcooling)and1–10,000˚C/s(incase of heating), by which overlap with conventional DSC and HPer DSC is obtained. Evenlower/higherratesof-0.1/4000˚C/sincoolingand0.5/40,000˚C/sinheating respectively have been successfully applied. The sample mass is again decreased andtakentobeinbetweenapproximately10ngand10μg. Presently, at various universities, even higher constant scan rates can be achieved,upto1,000,000 ˚C/s,bywhichatremendouswideheating-raterangeis realized of at least ten orders of magnitude, all the way from microcalorimetry to FSC,whichopensmanyotherapplications. Preface vii TherecentcommercializationofFSCthuscontributessignificantlytotheuseof chipcalorimetry,especiallywhenunderstandingtherelationshipsbetweenkinetics of processes and expectations based on thermodynamics of small, nano- to micrometre-sizedsystemsasoccurringinpolymermaterialsandmetals. Ofimportanceforstudyofthekineticsisthedropintimescalefromsecondsto millisecondsfromconventionalDSCtoFSC,respectively. Asanexample,bymatchingtheheatingrateoftheFSCinsuchawaythatitcan compete with the specific rates of reorganization, melting, chemical reactions, evaporation, denaturation, decomposition etc., these processes can be hindered or suppressed. Asanotherexample,thecapabilityoffastcoolingisamajoradvantageofFSC regarding crystallization and vitrification phenomena. By applying appropriate cooling rates for many substances, the critical cooling rate for crystallization can be surpassed, resulting in an amorphous sample. This is an extremely useful capability,becauseitenablesthestudyofsubsequentphenomenalike(de)vitrifica- tion, crystallization, and melting. Subsequent measurement of overall crystalliza- tion rates as function of temperature across a temperature range of choice has becomeamajortopic.Inprinciple,nucleationandsubsequentgrowthphenomena canbeseparated. Inaddition,theshortesttimesreachablebyFSCaresimilartothelongesttimes accessible by highly-efficient dynamic Monte Carlo simulations of polymer crys- tallization.ThishasleadtoapowerfultoolforinterpretationandpredictionofFSC experiments regarding kinetics, one that is more successful than analytical approachesappliedhitherto. Inadditiontotheaforementionedcapabilities,FSCisparamountwhenmaximal sensitivityisneededtoenablestudyofverysmall-masssubstances,likethinfilms, sections cut from samples, fractions obtained by separation techniques, and rem- nantsforforensicinvestigations. The impact of FSC is sure to increase along various routes. Pharmaceuticals, food, and other fields are expected to be studied as well. The first offline/ex situ combinations with other analyticaltechniques, such as simultaneous X-ray insitu measurements,havebeensuccessful.Becauseofthis,athoroughevaluationofboth thermalbehaviorand(non-)structuralmorphologyofsystemsathighscanrateswill becomeoneofthehotresearchtopicsinthenextdecade. Thisbookisintendedforbothnewcomersintheareasofresearchdiscussedand moreexperiencedresearchers.Amongstotherthings,animportantaimistoguide the reader through phenomena like metastability and reorganization of small systems, which, without proper knowledge, could easily be a frustrating, time- consuming labyrinth. Such confusion can be avoided by using the information alreadydocumentedbyexperts. We appreciate the cooperationwith the authors, reviewers, and representatives ofSpringerAGverymuch. Enjoy! Geleen,TheNetherlands VincentMathot Rostock,Germany ChristophSchick Contents PartI AdvancedInstrumentation,TechniquesandMethods 1 MaterialCharacterizationbyFastScanningCalorimetry: PracticeandApplications. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3 J€urgenE.K.SchaweandStefanPogatscher 2 Non-AdiabaticScanningCalorimeterforControlled FastCoolingandHeating. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 81 EvgenyZhuravlevandChristophSchick 3 Quasi-adiabatic,Membrane-Based,HighlySensitive FastScanningNanocalorimetry. . . . . . . . . . . . . . . . . . . . . . . . . . 105 J.Rodr´ıguez-ViejoandA.F.Lopeand´ıa 4 FastScanningCalorimetry–FastThermal DesorptionTechnique:TheThinWireApproach. . . . . . . . . . . . . 151 DeepanjanBhattacharya,UlyanaCubeta,andVladislavSadtchenko 5 FastScanningCalorimetryofSilkFibroinProtein: SampleMassandSpecificHeatCapacityDetermination. . . . . . . 187 PeggyCebe,BenjaminP.Partlow,DavidL.Kaplan, AndreasWurm,EvgenyZhuravlev,andChristophSchick 6 ScanningACNanocalorimetryandItsApplications. . . . . . . . . . . 205 KechaoXiaoandJoostJ.Vlassak 7 IsoconversionalKineticsbyFastScanningCalorimetry. . . . . . . . 237 NicolasSbirrazzuoli,NathanaelGuigo,andSergeyVyazovkin 8 ReliableAbsoluteVaporPressuresofExtremelyLow VolatileCompoundsfromFastScanningCalorimetry. . . . . . . . . 259 MathiasAhrenberg,AlexandrOstonen,J€urnW.P.Schmelzer, MartinBeck,ChristinSchmidt,OlafKeßler,UdoKragl, SergeyP.Verevkin,andChristophSchick ix
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