Glass : Selected Properties and Crystallization

611 Pages·2014·32.237 MB·English

by  Abyzov, Alexander S., Androsch, René, Baidakov, Vladimir G., Fokin, Vladimir M., Gutzov, Stoyan, Gutzow, Ivan S., Johari, Gyan P., Jordanov, Nikolai, Karamanov, Alexander, Leko, Viktor K., Ludwig, Frank-Peter, Markovska, Irena, Pascova, Radost, Penkov, Ivan, Pevzner, Boris Z., Polyakova, Irina G., Schick, Christoph, Schmelzer, Jürn W. P., Tarakanov, Sergey V., Vedishcheva, Natalia M., Wilde, Gerhard, Wright, Adrian C., Wurm, Andreas, Zanotto, Edgar D., Zhuravlev, Evgeny

Schmelzer(Ed.)
Glass
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Glass
|
Selected Properties and Crystallization
Edited by
Jürn W.P. Schmelzer
Editor
Dr.rer.nat.habil.JürnW.P.Schmelzer
UniversityofRostock
InstituteofPhysics
WismarscheStr.43–45
18057Rostock
Germany
ISBN978-3-11-029838-3
e-ISBN978-3-11-029858-1
Set-ISBN978-3-11-029859-8
LibraryofCongressCataloging-in-PublicationData
ACIPcatalogrecordforthisbookhasbeenappliedforattheLibraryofCongress.
BibliographicinformationpublishedbytheDeutscheNationalbibliothek
TheDeutscheNationalbibliothekliststhispublicationintheDeutscheNationalbibliografie;
detailedbibliographicdataareavailableintheInternetathttp://dnb.dnb.de.
©2014WalterdeGruyterGmbH,Berlin/Boston
Coverimage:Thecovershowscrystalsoflithiummeta-silicateonthesurfaceofsamplesof
80Li OSiO ⋅20CaOSiO -glassformingmeltsformedduringitscoolingtoaglass.Thepicturewas
2 2 2
suppliedbyProf.VladimirM.Fokin(St.Petersburg,Russia&SãoCarlos,Brazil)
Typesetting:PTP-Berlin,Protago-TEX-ProductionGmbH,Berlin
Printingandbinding:CPIbuchbücher.deGmbH,Birkach
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Foreword
Thepresentmonographoffersanoverviewbyateamofrenownedexpertsonglasssci-
enceaboutestablishedfactsandopenproblemsintheexperimentalandtheoretical
analysisofselectedpropertiesandcrystallizationofglasses.
Thebookisacontinuationoftwowell-knownmonographsonglassscienceau-
thored by the current editor, Jürn W.P. Schmelzer, in cooperation with Ivan S. Gut-
zow(I.S.Gutzow&J.W.P.Schmelzer,TheVitreousState:Thermodynamics,Structure,
Rheology,andCrystallization,Springer,1995;2013andJ.W.P.Schmelzer&I.S.Gutzow,
GlassesandtheGlassTransition,Wiley-VCH,2011).Thesetwopreviousbooksdescribe
generalfeaturesofglasses,theglasstransitionandphaseformationinglass-forming
melts,theirexperimentalandtheoreticalanalysis.Additionally,inthesecondbook,
OlegMazurinandAlexanderPrivenpresentdifferenttheoreticalapproachesforthe
predictionofglasspropertiesanddatacollectionmethods.
Thissuccessfulcooperationamongexperiencedglassexperts,whichstartedin
thesecondofthementionedbooks,isextendedinthismonographtoincludeava-
rietyofproblemsintheanalysisofglasspropertiesandcrystallization.Inthisnew
book,thegeneralfeaturesofglassesdescribedinthetwopreviousmonographsare
exemplifiedfordifferenttypesofglass-formingsilicate,metallicandpolymersystems.
Inaddition,thewidefieldofphaseformationprocessesandtheireffectonglassprop-
ertiesareillustratedbymeansofseveraltheoreticallyandexperimentallyrelevantex-
amples.Thebookcontainsoverviewsontechnologicallyimportantclassesofglasses,
theirtreatmenttoachievedesiredproperties,theoreticalapproachesforthedescrip-
tionofstructure-propertyrelationships,andnewconceptsinthetheoreticaltreatment
of crystallization in glass-forming systems. The book contains overviews about the
stateoftheartandaboutspecificfeaturesfortheanalysisandapplicationofimpor-
tantclassesofglass-formingsystems,anddescribesnewdevelopmentsintheoretical
interpretation by well-known glass scientists. Thus, the book offers comprehensive
andabundantinformationthatisdifficulttocomebyorhasnotyetbeenmadepublic.
Six chapters are authored by excellent representatives of the Soviet/Russian
schoolofglassscience:Leko(crystallizationkineticsofsilicaglass-formingsystems);
Pevzner&Tarakanov(originofbubbleformationinsilicameltsandmethodsoftheir
removal); Vedishcheva& A.C.Wright, UK (structure property relationshipsand the
chemicalstructureofoxideglasses);Polyakova(mainphasesofsilicaandtherelation
ofsomeoftheirpropertieswiththeelectronicstructureofSi-SiandSi-Obonding);
Fokin,Karamanov,Abyzovetal.(stressinducedphaseselectionandbubbleforma-
tion,theirtechnologicalsignificanceforthedevelopmentofdifferenttypesofglass-
ceramics, and the understanding and control of the sinter crystallization process);
andBaidakov(testingtheclassicalnucleationtheorybymoleculardynamicssimula-
tionsofcrystallizationofaLennard-Jonesmodelsystem).Mostofthesechaptersare
devotedtoacomprehensive descriptionof theauthors’own experimentalresearch
vi | Foreword
andtheirtheoreticalinterpretationofthemainresults,whichhavehardlyanyana-
loguesintheliteratureofglassscience.Inanumberofcases,theseresultshavebeen
publishedonlyinRussian,whichconsiderablyrestrictsaccesstothem.Thisworkis
supplementedbyachapterwrittenbyrepresentativesofanotheroutstandingschool
of glass science that dates back to one of the founding groups (Stranski, Kaischew
andcoworkers)ofthetheoryoffirst-orderphasestransitions,whichhasbeenheaded
fordecadesbyIvanGutzow(I.Gutzowetal.(analysisofmainphysicalpropertiesof
thecrystallineandamorphousmodificationsofsilicawithmainemphasisontheir
thermodynamic characterization, in particular the solubility of the different silica
modifications in water and aqueous solutions)). This chapter offers an overview of
thestateoftheartintheanalysisofoneofthemostimportantandabundantglass
systems,aswellasnewinsightsforabetterunderstandingofsinteringprocesses.
This spectrum of topics is further expanded by contributions on the theory of
crystallizationofglass-formingliquids.Thesecontributionsnotonlytestthebasicas-
sumptionsoftheclassicalnucleationtheoryforamodelsystem(Baidakov)butalso
coveraspectsthatgobeyondthestandardclassicalapproaches(Johari&Schmelzer).
Theyprovideanoverviewofnewperspectivesopenedupbyultrafastthermalpro-
cessingandnano-calorimetrydevelopedbyC.Schickandcoworkers(ultra-fastther-
malprocessingandnano-calorimetryatheatingandcoolingratesupto1MK/s),and
an overviewof the initialstagesof crystallizationby G.Wilde (early stagesof crys-
talformationinglass-formingmetallicalloys).Inadditiontowell-establishedresults,
anumberofopenproblemsaresetforththatrequirefurtherin-depthanalysis(e.g.,
influenceofthermalhistoryoncrystalnucleationandgrowthinpolymers(Schicket
al.),kineticstabilityversusfragilityasameasureoftheglass-formingabilityofmetal-
licalloys,highernucleationdensitiesthanthoseproposedbyclassicaltheoryinsome
metallicsystems,effectofrapidquenchingandplasticdeformationoncrystalnucle-
ation(Wilde),originofthehighsensitivityofsilicaglasscrystallizationonavarietyof
factorsandtherelationbetweentherateofcrystallizationandviscosity(Leko),confir-
mationofbasicassumptionsofclassicalnucleationtheoryformodelLennard-Jones
systems(Baidakov),andtheoriginofdeviationsfromclassicaltheoryinhighlyvis-
cousglass-formingliquids(Johari&Schmelzer).Adetailedoverviewofthecontentof
thevariouschaptersisgivenbytheeditorinthepreface.
I congratulate Jürn W.P. Schmelzer for putting together this third monograph,
whichdealswithseveralundeniablyrelevantaspectsofthepropertiesandcrystal-
lizationofglass.Istronglyrecommenditasamust-readforteachers,glassscientists,
graduatestudentsandanyoneinterestedand/orinvolvedintheresearchanddevel-
opmentofvitreousmaterials.
April2014 EdgarDutraZanotto
DirectoroftheCenterforResearch,TechnologyandEducationin
VitreousMaterials(www.certev.ufscar.br)
FederalUniversityofSãoCarlos,SãoCarlos,Brazil
Contents
Foreword|v
Preface|xv
Listofcontributingauthors|xxi
ChristophSchick,EvgenyZhuravlev,RenéAndrosch,AndreasWurm,
andJürnW.P.Schmelzer
1 InfluenceofThermalPrehistoryonCrystalNucleationandGrowthin
Polymers|1
1.1 Introduction|1
1.2 StateoftheArt|2
1.2.1 DependenceofthePropertiesofGlass-formingMeltsonMelt
History|2
1.2.2 PolymerCrystallization|6
1.2.3 DifferentialFastScanningCalorimetry|9
1.3 Experimental|14
1.3.1 Samples|14
1.3.2 SuppressionofHomogeneousNucleationatFastCooling|16
1.3.3 Non-isothermalOrderingKinetics|28
1.3.4 IsothermalOrderingKinetics|36
1.3.5 IdentificationofDifferentNucleiPopulations|48
1.3.6 EnthalpyRelaxationandCrystalNucleationintheGlassyState|52
1.3.7 SummaryofExperimentalResultsandConclusions|72
1.4 IlluminationoftheNucleationandGrowthMechanism|74
1.4.1 Low-temperatureEndothermsandHomogeneousNucleation|74
1.4.2 SomeBriefTheoreticalConsiderations|78
1.5 ConclusionsandOutlook|80
GerhardWilde
2 EarlyStagesofCrystalFormationinGlass-formingMetallicAlloys|95
2.1 Introduction|95
2.2 MarginalGlass-formers|98
2.2.1 NucleationversusGrowthControl|98
2.2.2 ProcessingPathwayModifications|101
2.2.3 NucleationandGrowthKinetics|105
2.2.4 CharacterizationoftheAmorphousPhase|109
2.2.5 NanocrystalFormationatTemperaturesWellBelowT |115
g
2.3 Deformation-inducedNanocrystalFormation|124
2.4 BulkMetallicGlasses|127
2.5 ConclusionsandHypotheses|131
viii | Contents
IvanGutzow,RadostPascova,NikolaiJordanov,StoyanGutzov,IvanPenkov,
IrenaMarkovska,JürnW.P.Schmelzer,andFrank-PeterLudwig
3 CrystallineandAmorphousModificationsofSilica:Structure,
ThermodynamicProperties,Solubility,andSynthesis|137
3.1 Introduction|137
3.2 PropertiesofSilicaModifications:LiteratureSearch|140
3.2.1 ClassicalSiO -literature|141
2
3.2.2 OriginalLiteratureSourcesontheDifferentSilicaModifications|141
3.2.3 InternetSearch|142
3.3 PhaseDiagramofSiO |142
2
3.3.1 Fenner’sClassicalDiagram|142
3.3.2 Flörke’sDiagram|143
3.3.3 Contemporary(p−T)-phaseDiagramsofSiO |144
2
3.4 ModificationsofSiO andTheirSynthesis|148
2
3.4.1 MineralogicalCharacteristicsoftheSiO -modifications|148
2
3.4.2 SynthesisofQuartz|148
3.4.3 SynthesisandStabilizationofβ-cristobalite|151
3.4.4 SynthesisofKeatite:ClassicalAspects|159
3.4.5 SynthesisofCoesite|160
3.4.6 Stishovite:SynthesisandThermalStability|160
3.4.7 SynthesisofAmorphousModificationsofSilica|163
3.5 StructureandThermodynamicPropertiesofthe
SiO -modifications|164
2
3.6 SolubilityoftheDifferentSiO -modifications|170
2
3.6.1 GeneralThermodynamicDependencies|170
3.6.2 SolubilityDiagramofSiO .Ostwald’sRuleofStages|175
2
3.6.3 SolubilityofSiO :SizeEffects|181
2
3.6.4 DifferentSiO -modificationsatHydrothermalConditions:
2
TechnologicalAspects|183
3.7 ResourcesoftheSilicaModifications|186
3.7.1 MineralResourcesofQuartz|186
3.7.2 PlantResourcesofSilica|187
3.7.3 IndustrialWasteasSourcesofSilica|188
3.7.4 CoesiteandStishoviteasImpactiteRemnants|188
3.8 SomeParticularlyInterestingPropertiesofSilica|189
3.9 GeneralDiscussion:TechnicalPerspectives|190
IrinaG.Polyakova
4 TheMainSilicaPhasesandSomeofTheirProperties|197
4.1 Introduction|197
4.2 SpecificPropertiesofSilicaResultingfromtheElectronicStructureof
Silicon|198
Contents | ix
4.2.1 SpecificPropertiesofSilicaCompoundsandDifferencesasCompared
toChemicalAnalogs:SiliconandCarbon|198
4.2.2 ElectronStructureoftheSiliconAtomanditsInteractionwith
Oxygen|201
4.2.3 Consequencesofπ-BondinginSilica|202
4.2.4 IncreaseinSiliconCoordinationNumberasaResultof
s-p-d-hybridization|203
4.2.5 Implicationofs-p-d-hybridizationforChemicalReactionsandPhysical
TransformationsofSilica|205
4.3 PhasesofSilicaandTheirProperties|207
4.3.1 DenseOctahedralSilicas:HighPressurePhases|209
4.3.2 Clathrasils:FriableSilicaPhases|210
4.3.3 Exception:FibrousSilica|211
4.3.4 ProperSilicas|211
4.3.5 MainCrystallineTetrahedralSilicas|213
4.3.6 AmorphousSilica|223
4.3.7 Polyamorphism|225
4.4 QuartzandSomeofItsProperties|228
4.4.1 EnantiomorphismofQuartz|228
4.4.2 Twins(Zwillinge)inQuartz|229
4.4.3 AnisotropyofQuartz|232
4.4.4 ThermalExpansionofQuartz|233
4.4.5 High-Lowor(α −β)-TransformationinQuartz|241
4.4.6 Pressure-inducedAmorphizationofCrystallineSilica|245
4.5 HydrothermalSynthesisofQuartz|245
4.5.1 BriefHistory|246
4.5.2 TemperatureDropMethod|247
4.5.3 MainProblemsofHydrothermalSynthesisofQuartz|250
4.6 ConcludingRemarks|261
4.7 Appendix:TheCrystalSkulls|261
NataliaM.VedishchevaandAdrianC.Wright
5 ChemicalStructureofOxideGlasses:AConceptforEstablishing
Structure–PropertyRelationships|269
5.1 Introduction|269
5.2 StructuralModels|270
5.3 ThermodynamicApproach|274
5.4 ConceptofChemicalStructure|277
5.5 Short-rangeOrder|281
5.5.1 Na O–B O Glasses|281
2 2 3
5.5.2 Li O–B O GlassesandMelts|283
2 2 3
5.5.3 Na O–SiO Glasses|287
2 2
5.5.4 Na O–B O –SiO Glasses|289
2 2 3 2