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Solid State Chemi S try and it S

a ppli C ation

S

Second e dition Student e dition

Anthony R. West

Periodic Table of the Elements

NotesIUPAC 2009

Standard atomic weights abridged to four significant digits (Table 4 published in Pure Appl. Chem. 83, 359-396 (2011); doi:10.1351/PAC-REP-10-09-14). The uncertainty in the last digit of the standard atomic weight value is listed in parentheses following the value. In the absence of parentheses, the uncertainty is one in that last digit. An interval in square brackets provides the lower and upper bounds of the standard atomic weight for that element. No values are listed for elements which lack isotopes with a characteristic isotopic a bundance in natural terrestrial samples. See PAC for more details.“Aluminum” and “cesium”are commonly used alternative spellings for “aluminium”and “caesium.”

Claims for the discovery of all the remaining elements in the last row of the Table, namely elements with atomic numbers 113,115,117 and 118, and for which no assignments have yet been made, are being considered by a IUPAC and IUPAP Joint Working Party.

For updates to this table, see iupac.org/reports/periodic_table/. This version is dated 1 June 2012.

Copyright © 2012 IUPAC, the International Union of Pure and Applied Chemistry.

SolidStateChemistry anditsApplications

SecondEdition

SolidStateChemistry anditsApplications

SecondEdition

StudentEdition

ANTHONYR.WEST

DepartmentofMaterialsScienceandEngineering, UniversityofSheffield,UK

Thiseditionfirstpublished2014

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LibraryofCongressCataloging-in-PublicationData

West,AnthonyR. Solidstatechemistryanditsapplications/AnthonyR.West.–Secondedition,studentedition. pagescm Includesindex.

ISBN978-1-119-94294-8(pbk.) 1.Solidstatechemistry.I.Title. QD478.W472014 541 .0421–dc23

AcataloguerecordforthisbookisavailablefromtheBritishLibrary.

ISBN:9781119942948

2013029528

CoverimagescreatedusingCrystalMaker R software.CrystalMakerSoftwareLtd,www.crystalmaker.com

Setin10/12ptTimesbyAptaraInc.,NewDelhi,India 12014

ForSheena,Isla,Graeme,JennyandSusie

1CrystalStructuresandCrystalChemistry1

1.1UnitCellsandCrystalSystems1 1.2Symmetry 3

1.2.1RotationalSymmetry;SymmetryElementsandOperations3

1.2.2Quasicrystals6

1.2.3MirrorSymmetry6

1.2.4CentreofSymmetryandInversionAxes6

1.2.5PointSymmetryandSpaceSymmetry9

1.3SymmetryandChoiceofUnitCell10

1.4Lattice,BravaisLattice11

1.5LatticePlanesandMillerIndices14

1.6IndicesofDirections16

1.7 d-SpacingFormulae17

1.8CrystalDensitiesandUnitCellContents17

1.9DescriptionofCrystalStructures18

1.10ClosePackedStructures–CubicandHexagonalClosePacking19

1.11RelationshipbetweenCubicClosePackedandFaceCentredCubic21

1.12HexagonalUnitCellandClosePacking21

1.13DensityofClosePackedStructures22

1.14UnitCellProjectionsandAtomicCoordinates24

1.15MaterialsThatCanBeDescribedasClosePacked25 1.15.1Metals25 1.15.2Alloys25 1.15.3IonicStructures26

1.15.3.1TetrahedralandOctahedralSites26 1.15.3.2RelativeSizesofTetrahedralandOctahedralSites28

1.15.3.3LocationofTetrahedralandOctahedralSitesinan fcc UnitCell; BondLengthCalculations29

1.15.3.4DescriptionofCrystalStructures;FractionalAtomicCoordinates30

1.15.4CovalentNetworkStructures31

1.15.5MolecularStructures31

1.15.6FullerenesandFullerides31

1.16StructuresBuiltofSpace-FillingPolyhedra33

1.17SomeImportantStructureTypes35

1.17.1RockSalt(NaCl),ZincBlendeorSphalerite(ZnS),Fluorite(CaF2 ), Antifluorite(Na2 O)35

1.17.1.1RockSaltStructure37 1.17.1.2ZincBlende(Sphalerite)Structure38 1.17.1.3Antifluorite/FluoriteStructure39

1.17.1.4BondLengthCalculations41 1.17.2Diamond42 1.17.3Wurtzite(ZnS)andNickelArsenide(NiAs)43 1.17.4CaesiumChloride(CsCl)47 1.17.5OtherAXStructures48

1.17.6Rutile(TiO2 ),CadmiumIodide(CdI2 ),CadmiumChloride(CdCl2 )and CaesiumOxide(Cs2 O)49

1.17.7Perovskite(SrTiO3 )54

1.17.7.1ToleranceFactor57

1.17.7.2BaTiO3 57

1.17.7.3TiltedPerovskites:GlazerNotation58

1.17.7.4CaCu3 Ti4 O12 ,CCTO62

1.17.7.5Anion-DeficientPerovskites62

1.17.7.6Stoichiometry–PropertyRelations62

1.17.8RheniumTrioxide(ReO3 ),PerovskiteTungstenBronzes,TetragonalTungsten BronzesandTunnelStructures63

1.17.9Spinel66

1.17.10Olivine70

1.17.11Corundum,IlmeniteandLiNbO3 72

1.17.12Fluorite-RelatedStructuresandPyrochlore72

1.17.13Garnet75

1.17.14Perovskite-RockSaltIntergrowthStructures:K2 NiF4 ,Ruddlesden–Popper PhasesandLayeredCuprateSuperconductors76

1.17.15TheAluminiumDiborideStructure(AlB2 )80

1.17.16SilicateStructures–SomeTipstoUnderstandingThem81

2CrystalDefects,Non-StoichiometryandSolidSolutions83

2.1PerfectandImperfectCrystals83

2.2TypesofDefect:PointDefects84

2.2.1SchottkyDefect85

2.2.2FrenkelDefect85

2.2.2.1TheKroger–VinkNotationforCrystalDefects86

2.2.2.2ThermodynamicsofSchottkyandFrenkelDefectFormation87

2.2.3ColourCentres90

2.2.4VacanciesandInterstitialsinNon-StoichiometricCrystals:Extrinsicand IntrinsicDefects91

2.2.5DefectClustersorAggregates92

2.2.6InterchangedAtoms:Order–DisorderPhenomena95

2.3SolidSolutions95

2.3.1SubstitutionalSolidSolutions96

2.3.2InterstitialSolidSolutions98

2.3.3MoreComplexSolidSolutionMechanisms:AliovalentSubstitution99

2.3.3.1IonicCompensationMechanisms99

2.3.3.2ElectronicCompensation:Metals,Semi-andSuperconductors102

2.3.4ThermodynamicallyStableandMetastableSolidSolutions104

2.3.5ExperimentalMethodsforStudyingSolidSolutions104

2.3.5.1X-rayPowderDiffraction,XRD104

2.3.5.2DensityMeasurements105

2.3.5.3ChangesinOtherProperties–ThermalActivityandDTA/DSC107 2.4ExtendedDefects108

2.4.1CrystallographicShearStructures108

2.4.2StackingFaults110

2.4.3SubgrainBoundariesandAntiphaseDomains(Boundaries)110

2.5DislocationsandMechanicalPropertiesofSolids111

2.5.1EdgeDislocations112

2.5.2ScrewDislocations114

2.5.3DislocationLoops115

2.5.4DislocationsandCrystalStructure117

2.5.5MechanicalPropertiesofMetals118

2.5.6Dislocations,VacanciesandStackingFaults120

2.5.7DislocationsandGrainBoundaries122

3BondinginSolids 125

3.1Overview:Ionic,Covalent,Metallic,vanderWaalsandHydrogenBonding inSolids 125

3.2IonicBonding126

3.2.1IonsandIonicRadii126

3.2.2IonicStructures–GeneralPrinciples130

3.2.3TheRadiusRatioRules133

3.2.4BorderlineRadiusRatiosandDistortedStructures135

3.2.5LatticeEnergyofIonicCrystals136

3.2.6Kapustinskii’sEquation140

3.2.7TheBorn–HaberCycleandThermochemicalCalculations141

3.2.8StabilitiesofRealandHypotheticalIonicCompounds143

3.2.8.1InertGasCompounds143

3.2.8.2LowerandHigherValenceCompounds144

3.2.9EffectofPartialCovalentBondingonCrystalStructures145

3.2.10EffectiveNuclearCharge147

3.2.11ElectronegativityandPartiallyChargedAtoms147

3.2.12CoordinatedPolymericStructures–Sanderson’sModel149

3.2.13Mooser–PearsonPlotsandIonicities150

3.2.14BondValenceandBondLength151

3.2.15Non-BondingElectronEffects153

3.2.15.1d-ElectronEffects153

3.2.15.2InertPairEffect161

3.3CovalentBonding161

3.3.1Particle-WaveDuality,AtomicOrbitals,WavefunctionsandNodes162

3.3.2OrbitalOverlap,SymmetryandMolecularOrbitals163

3.3.3ValenceBondTheory,ElectronPairRepulsion,Hybridisationand OxidationStates169

3.4MetallicBondingandBandTheory173

3.4.1BandStructureofMetals179

3.4.2BandStructureofInsulators179

3.4.3BandStructureofSemiconductors:Silicon179

3.4.4BandStructureofInorganicSolids181

3.4.4.1III–V,II–VIandI–VIICompounds181

3.4.4.2TransitionMetalCompounds182

3.4.4.3FullerenesandGraphite184

3.5BandsorBonds:aFinalComment185

4Synthesis,ProcessingandFabricationMethods187

4.1GeneralObservations187

4.2SolidStateReactionorShake’nBakeMethods187

4.2.1NucleationandGrowth,EpitaxyandTopotaxy188

4.2.2PracticalConsiderationsandSomeExamplesofSolidStateReactions191

4.2.2.1Li4

4.2.2.3Na β /β alumina193

4.2.3CombustionSynthesis194

4.2.4Mechanosynthesis195

4.3LowTemperatureorChimieDouceMethods196

4.3.1AlkoxideSol–GelMethod196

4.3.1.1SynthesisofMgAl2 O4 197

4.3.1.2SynthesisofSilicaGlass197

4.3.1.3SpinningofAluminaFibres197

4.3.1.4PreparationofIndiumTinOxide(ITO)andOtherCoatings198

4.3.1.5FabricationofYSZCeramics198

4.3.2Sol–GelMethodUsingOxyhydroxidesandColloidChemistry198

4.3.2.1SynthesisofZeolites199

4.3.2.2PreparationofAlumina-BasedAbrasivesandFilms200

4.3.3CitrateGelandPechiniProcesses200

4.3.4UseofHomogeneous,Single-SourcePrecursors201

4.3.5HydrothermalandSolvothermalSynthesis202

4.3.6MicrowaveSynthesis204

4.3.7IntercalationandDeintercalation205

4.3.7.1GraphiteIntercalationCompounds207

4.3.7.2PillaredClaysandLayeredDoubleHydroxides208

4.3.7.3SynthesisofGraphene209

4.3.8ExampleofaDifficultSynthesisMadePossiblebyChimieDouce Methods:BiFeO3 211

4.3.9MoltenSaltSynthesis,MSS212

4.4Gas-PhaseMethods213

4.4.1Vapour-PhaseTransport213

4.4.2ChemicalVapourDeposition,CVD216

4.4.2.1AmorphousSilicon217

4.4.2.2DiamondFilms219

4.4.3SputteringandEvaporation221

4.4.4AtomicLayerDeposition,ALD222

4.4.5AerosolSynthesisandSprayPyrolysis223

4.5High-PressureMethods225

4.6CrystalGrowth226

4.6.1CzochralskiMethod226

4.6.2BridgmanandStockbargerMethods226

4.6.3ZoneMelting227

4.6.4PrecipitationfromSolutionorMelt:FluxMethod227

4.6.5VerneuilFlameFusionMethod228

5CrystallographyandDiffractionTechniques229

5.1GeneralComments:MolecularandNon-MolecularSolids229

5.1.1IdentificationofCrystallineSolids229

5.1.2StructureofNon-MolecularCrystallineSolids229

5.1.3Defects,ImpuritiesandStoichiometryofCrystallineSolids230

5.2CharacterisationofSolids231

5.3X-RayDiffraction232

5.3.1GenerationofX-Rays232

5.3.1.1LaboratorySourcesUtilisingInnerShellElectronicTransitions232

5.3.1.2SynchrotronX-raySources235

5.3.2InteractionofX-RayswithMatter235

5.3.3OpticalGratingandDiffractionofLight236

5.3.4CrystalsandDiffractionofX-Rays238

5.3.4.1TheLaueEquations238

5.3.4.2Bragg’sLaw239

5.3.5X-RayDiffractionMethods240

5.3.6ThePowderMethod–PrinciplesandUses240

5.3.6.1FocusingofX-rays:TheoremofaCircle243

5.3.6.2CrystalMonochromators244

5.3.6.3PowderDiffractometers244

5.3.6.4GuinierFocusingCameras245

5.3.6.5APowderPatternofaCrystallinePhaseisits‘Fingerprint’246

5.3.6.6PowderPatternsandCrystalStructures247

5.3.7Intensities248

5.3.7.1ScatteringofX-raysbyanAtom:AtomicScatteringFactorsorForm Factors249

5.3.7.2ScatteringofX-raysbyaCrystal–SystematicAbsences250

5.3.7.3GeneralEquationforPhaseDifference, δ 253

5.3.7.4IntensitiesandStructureFactors255

5.3.7.5TemperatureFactors258

5.3.7.6R-FactorsandStructureDetermination259

5.3.7.7StructureRefinementfromPowderData:RietveldRefinement259

5.3.8X-RayCrystallographyandStructureDetermination–WhatisInvolved?260

5.3.8.1ThePattersonMethod263

5.3.8.2FourierMethods264

5.3.8.3DirectMethods264

5.3.8.4ElectronDensityMaps265

5.4ElectronDiffraction265

5.5NeutronDiffraction266

5.5.1CrystalStructureDetermination267

5.5.2MagneticStructureAnalysis268

5.5.3InelasticScattering,SoftModesandPhaseTransitions269

6OtherTechniques:Microscopy,Spectroscopy,ThermalAnalysis271

6.1DiffractionandMicroscopicTechniques:WhatDoTheyHaveinCommon?271

6.2OpticalandElectronMicroscopyTechniques272

6.2.1OpticalMicroscopy272

6.2.1.1PolarisingMicroscope273

6.2.1.2ReflectedLightMicroscope276

6.2.2ElectronMicroscopy276

6.2.2.1ScanningElectronMicroscopy280

6.2.2.2ElectronProbeMicroanalysis,EPMA,andEnergy-DispersiveX-ray Spectroscopy,EDSorEDX281

6.2.2.3AugerElectron(Emission)MicroscopyandSpectroscopy,AES282

6.2.2.4Cathodoluminescence,CL284

6.2.2.5TransmissionElectronMicroscopy,TEM,andScanning TransmissionElectronMicroscopy,STEM287

6.2.2.6ElectronEnergyLossSpectroscopy,EELS288

6.2.2.7High-AngleAnnularDarkField,HAADF/Z-ContrastSTEM289

6.3SpectroscopicTechniques291

6.3.1VibrationalSpectroscopy:IRandRaman293

6.3.2VisibleandUltraviolet(UV)Spectroscopy296

6.3.3NuclearMagneticResonance(NMR)Spectroscopy298

6.3.4ElectronSpinResonance(ESR)Spectroscopy301

6.3.5X-RaySpectroscopies:XRF,AEFS,EXAFS303

6.3.5.1EmissionTechniques303

6.3.5.2AbsorptionTechniques305

6.3.6ElectronSpectroscopies:ESCA,XPS,UPS,AES,EELS308

6.3.7MossbauerSpectroscopy312

6.4ThermalAnalysis(TA)314

6.4.1Thermogravimetry(TG)315

6.4.2DifferentialThermalAnalysis(DTA)andDifferentialScanning Calorimetry(DSC)315

6.4.3Applications317

6.5StrategytoIdentify,AnalyseandCharacterise‘Unknown’Solids321

7PhaseDiagramsandtheirInterpretation325

7.1ThePhaseRule,theCondensedPhaseRuleandSomeDefinitions325

7.2One-ComponentSystems330

7.2.1TheSystemH2 O331

7.2.2TheSystemSiO2 332

7.2.3CondensedOne-ComponentSystems333

7.3Two-ComponentCondensedSystems333

7.3.1ASimpleEutecticSystem333

7.3.1.1LiquidusandSolidus335

7.3.1.2Eutectic335

7.3.1.3LeverRule335

7.3.1.4EutecticReaction336

7.3.1.5TheLiquidus,SaturationSolubilitiesandFreezingPointDepression337

7.3.2BinarySystemswithCompounds337

7.3.2.1CongruentMelting337

7.3.2.2IncongruentMelting,PeritecticPoint,PeritecticReaction337

7.3.2.3Non-EquilibriumEffects339

7.3.2.4UpperandLowerLimitsofStability340

7.3.3BinarySystemswithSolidSolutions340

7.3.3.1CompleteSolidSolution340

7.3.3.2FractionalCrystallisation341

7.3.3.3ThermalMaximaandMinima342

7.3.3.4PartialSolidSolutionSystems342

7.3.4BinarySystemswithSolid–SolidPhaseTransitions344

7.3.5BinarySystemswithPhaseTransitionsandSolidSolutions:Eutectoids andPeritectoids345

7.3.6BinarySystemswithLiquidImmiscibility:MgO–SiO2 347

7.3.7SomeTechnologicallyImportantPhaseDiagrams348

7.3.7.1TheSystemFe–C:IronandSteelMaking348

7.3.7.2TheSystemCaO–SiO2 :CementManufacture349

7.3.7.3TheSystemNa–S:Na/SBatteries350

7.3.7.4TheSystemNa2 O–SiO2 :GlassMaking351

7.3.7.5TheSystemLi2 O–SiO2 :MetastablePhaseSeparationandSynthetic Opals352

7.3.7.6PurificationofSemiconductingSibyZoneRefining353

7.3.7.7TheSystemZrO2 –Y2 O3 :Yttria-StabilisedZirconia,YSZ,Solid Electrolyte354

7.3.7.8TheSystemBi2 O3 –Fe2 O3 :MultiferroicBiFeO3 354

7.4SomeTipsandGuidelinesforConstructingBinaryPhaseDiagrams355

8ElectricalProperties359

8.1SurveyofElectricalPropertiesandElectricalMaterials359

8.2MetallicConductivity361

8.2.1OrganicMetals:ConjugatedSystems362

8.2.1.1Polyacetylene362

8.2.1.2Poly-p-PhenyleneandPolypyrrole364

8.2.2OrganicMetals:Charge-TransferComplexes365

8.3Superconductivity366

8.3.1ThePropertyofZeroResistance366

8.3.2PerfectDiamagnetism;theMeissnerEffect368

8.3.3CriticalTemperature Tc ,CriticalField Hc andCriticalCurrent Jc 368

8.3.4TypeIandTypeIISuperconductors:TheVortex(Mixed)State370

8.3.5SurveyofSuperconductingMaterials371

8.3.6CrystalChemistryofCupratePerovskites374

8.3.7YBa2 Cu3 O7– δ ,YBCO376

8.3.7.1CrystalStructure376

8.3.7.2AtomValencesandtheSuperconductingMechanism378

8.3.7.3OxygenContentofYBa2 Cu3 O7–δ 378

8.3.7.4DeterminationofOxygenContent,7–δ 380

8.3.8Fullerides381

8.3.9ApplicationsofSuperconductors381

8.4Semiconductivity382

8.4.1ElementalandCompoundSemiconductorswithDiamondand ZincBlendeStructures384

8.4.2ElectricalPropertiesofSemiconductors386

8.4.3OxideSemiconductors388

8.4.4ApplicationsofSemiconductors389

8.5IonicConductivity392

8.5.1AlkaliHalides:VacancyConduction393

8.5.1.1ActivationEnergyforIonHopping:GeometricConsiderations394

8.5.1.2IonicConductivityofNaClCrystals396

8.5.1.3ExtrinsicConductivityinNaCl:ControlbyAliovalentDoping397

8.5.2SilverChloride:InterstitialConduction399

8.5.3AlkalineEarthFluorides401

8.5.4SolidElectrolytes(orFastIonConductors,SuperionicConductors)401

8.5.4.1GeneralConsiderations401

8.5.4.2 β -Alumina403

8.5.4.3Nasicon409

8.5.4.4HollanditesandPriderites409

8.5.4.5SilverandCopperIonConductors411

8.5.4.6FluorideIonConductors413

8.5.4.7OxideIonConductors414

8.5.4.8Li+ IonConductors418

8.5.4.9ProtonConductors421

8.5.4.10MixedIonic/ElectronicConductors421

8.5.4.11ApplicationsofSolidElectrolytesandMixedConductors422

8.6DielectricMaterials430

8.6.1FromDielectricstoConductors433

8.7Ferroelectrics436

8.8Pyroelectrics441

8.9Piezoelectrics441

8.10ApplicationsofFerro-,Pyro-andPiezoelectrics441

9MagneticProperties445

9.1PhysicalProperties445

9.1.1BehaviourofSubstancesinaMagneticField446

9.1.2EffectsofTemperature:CurieandCurie–WeissLaws448

9.1.3MagneticMoments449

9.1.4MechanismsofFerro-andAntiferromagneticOrdering:Superexchange452

9.1.5SomeMoreDefinitions453

9.2MagneticMaterials,theirStructuresandProperties455

9.2.1MetalsandAlloys455

9.2.2TransitionMetalMonoxides458

9.2.3TransitionMetalDioxides459

9.2.4Spinels459

9.2.5Garnets462

9.2.6IlmenitesandPerovskites464

9.2.7Magnetoplumbites464

9.3Applications:Structure–PropertyRelations464

9.3.1TransformerCores464

9.3.2PermanentMagnets466

9.3.3MagneticInformationStorage466

9.4RecentDevelopments467

9.4.1Magnetoresistance:GiantandColossal467

9.4.2Multiferroics469

10OpticalProperties:LuminescenceandLasers473

10.1VisibleLightandtheElectromagneticSpectrum473

10.2SourcesofLight,ThermalSources,BlackBodyRadiationandElectronicTransitions473

10.3ScatteringProcesses:Reflection,DiffractionandInterference476

10.4LuminescenceandPhosphors476

10.5ConfigurationalCoordinateModel478

10.6SomePhosphorMaterials480

10.7Anti-StokesPhosphors481

10.8StimulatedEmission,AmplificationofLightandLasers482

10.8.1TheRubyLaser484

10.8.2NeodymiumLasers485

10.8.3SemiconductorLasersandtheLight-EmittingDiode,LED486 10.9Photodetectors488

10.10Fibre-Optics490 10.11SolarCells 492

AppendixD:HowtoRecogniseClosePacked(Eutactic)Structures515

AppendixE:PositiveandNegativeAtomicCoordinates517

AppendixF:TheElementsandSomeofTheirProperties519

Preface

Thisbookisaslimmeddown,studenteditionof‘SolidStateChemistryanditsApplications’whosesecond editionisscheduledforpublicationin2015/6.Itismodelledontheauthors’‘BasicSolidStateChemistry’,but hasbeencompletelyrewrittenwithabout40%newmaterialaddedandallthediagramsdrawnprofessionally, infullcolour.Theninechaptersin‘Basic’havebecometeninthisneweditionsince‘MagneticandOptical Properties’issplitintoseparatechapters.

Intheperiodsincethesecondeditionof‘Basic’waspublishedin1999,wehavewitnessedmanymajornew discoveriesanddevelopmentsinthesolidstatechemistryofinorganicmaterialswithtopicssuchascolossal magnetoresistance,multiferroics,lightemittingdiodesandgraphene.Newmaterialssynthesistechniques haveevolvedsuchasmechanosynthesis,microwave-hydrothermalsynthesisandatomiclayerdepositionand ofcourse,therehavebeenmanyimprovementsinthetechniquesusedtocharacterisesolidsincludinguse ofsynchrotronsfordiffractionandspectroscopyaswellashighresolutionscanningtransmissionelectron microscopypermittingatomic-levelidentificationandstructuralimaging.Itwasfeltthatanupdatedversion ofboth‘Basic’and‘SolidStateChemistryanditsApplications’waslongoverdue,therefore.

Amajorfeatureofthisneweditionistheextensivecoverageofthecrystalstructuresofimportant familiesofinorganicsolids.Purchasersofthebookwillbeabletodownload,free,abespokeandeasyto-useCrystalMaker R viewerprogram.TheCrystalViewersoftwareisaccompaniedbymorethan100 crystalstructuremodelswhichuserswillbeabletoviewontheircomputerswiththefacilitytorotatethe structures,viewthemfromdifferentorientationsandeitherhighlightorhidedifferentstructuralfeatures. CrystalViewerandtheaccompanyingstructurefilescanbedownloadedfromthecompanionwebsiteat http://www.wiley.com/go/west/solidstatechemistrystudent.

Manypeoplehavehelpedandencouragedmeinpreparingthisnewedition.Specialthanksaredueto: JohnMcCallumwhoproducedmanyofthecrystalstructuredrawingsandfiles,FrancesKirkwhoprepared thewholemanuscript,inelectronicformat,andWileystaffSarahHallandSarahTilleyfortheirenthusiastic encouragementandinvolvement:inparticular,SarahHallwasinstrumentalinmakingtheCrystalMaker R arrangementsandSarahTilleyoversawalltheartworkpreparations.

Chemistry–SolidStateChemistry–MaterialsChemistry–Materials

ScienceandEngineering

Chemistryisanevolvingsubject!Traditionally,therehavebeenthreebranchesofchemistry:organic,physical andinorganic,withsomeargumentsinfavourofincludinganalyticalasafourthbranch.Analternative,fairly newclassification(favouredbytheauthor!)divideschemistryintotwobroadareas:molecular(whichincludes liquidsandgases)andnon-molecular(orsolidstate).Thewaysinwhichwethinkabout,make,analyseand usemolecularandnon-molecularsubstancesarecompletelydifferent,asshownbyacomparisonofone ‘simple’substanceineachcategory,tolueneandaluminiumoxide:

Comparisonofthechemistriesofmolecularandnon-molecularmaterials

CharacteristicTolueneAluminiumoxide

FormulaFixed,C6 H5 CH3

Aredefects present?

Notallowed:missingormis-placed atomsgiverisetodifferentmolecules

Usuallyfixed,Al2 O3 ,butforotheroxidesmaybe variable,e.g.Fe1-x O

Unavoidable:smallconcentrationofvacancies, interstitialsanddislocationsarealwayspresent Doping possibilities Notpossiblewithoutproducinga differentmolecule

Structure andits determination

Properties and applications

Molecularstructurecanbedetermined spectroscopically:NMR/MassSpec/IR. Determinepackingarrangement,bond lengthsandangles,bysinglecrystal X-raydiffraction.Usually,structural informationisthencomplete.

Controlledbymolecularformulaand configuration;cannotbemodifiedby doping.Someproperties(e.g. pharmaceuticalactivity)maydepend onmolecularpackingarrangementsin crystals.

Dopingorsolidsolutionformationallows controlandoptimisationofproperties,e.g. rubyisCr-dopedAl2 O3

Fullcharacterisationofasolidrequiresstructural andcompositionalinformationacrossthe lengthscalesfromlocal,tounitcell,nanoand microscales.Manydiffraction,spectroscopic andmicroscopictechniquesareneededfor fullcharacterisation.

Properties/applicationsdependoncrystal structure,defects,dopants,surfacestructure, particlesizeandwhetherthematerialisa powder,singlecrystal,film,etc.Considerthe diverseapplicationsofAl2 O3 :filmsand ceramicsusedasinsulators;powdersusedas abrasive;withCr3+ dopants,rubyisusedfor lasers;poroussolidsusedascatalystsupports.

Thus,fortoluene,onceitsformulaandmolecularstructurehadbeendeterminedtherewerefewremaining issuestoberesolvedotherthan,perhaps,thedetailedpackingarrangementofmoleculesincrystallinetoluene atlowtemperaturesorthepossiblediscoveryandevaluation,eventoday,ofas-yetunknownchemical, biologicalorpharmaceuticalpropertiesofpuretoluene.

Alumina,bycontrast,isahighlycomplexmaterial;itsproperties,andthereforepotentialapplications, dependondifferentaspectsofitsstructure(bulk,defect,surface,nano),themethodsneededtofabricateit indifferentformsandshapes,thepossibilityofdopingtomodifyitspropertiesandthecharacterisationor determinationofitsstructure(anditscomposition,whetherhomogeneousorheterogeneous,ifdoped)across alllengthscales.Thisissolidstatechemistry!

Thebiggestcontrastbetweenmolecularandnon-molecularmaterialsisthatthelattercanbedoped, allowingmodificationandcontrolofpropertiessuchasmagnetism,superconductivityandcolour/optical bandgap.Bycontrast,attemptstodopemoleculesareinevitablyfrustratedsincereplacingoneatominthe moleculebyanother,orcreatingdefectssuchasmissingatoms,leadtoentirelydifferentmolecules.

Inrecentdecades, materialschemistry hasemergedasadistinctbranchofchemistrywhichcoversbothnonmolecular,solidstatematerials(oxides,halides,etc.)andmanymolecularmaterials(especially,functional polymersandorganicsolidswithpotentiallyusefulphysicalproperties).Materialschemistrycutsacrossthe traditionaldisciplinesofchemistrybutalsoincludessomethingextrawhichisaninterestinthephysical propertiesofcompoundsandmaterials.Inthepast,solidstatephysicsandmaterialssciencehavebeenthe usual‘home’forphysicalproperties;butnow,theyareanintrinsicpartofsolidstateandmaterialschemistry.

Thedistinctionbetween materialschemistry and materialsscience isoftenunclearbutcanbesummarised broadlyasfollows:

Materialschemistry

Synthesis–structuredetermination–physicalproperties–newmaterials

Materialsscience

Processingandfabrication–characterisation–optimisationofpropertiesandtesting–improved/new materialsforengineeringapplicationsinproductsordevices.

Materialssciencefocusesonmaterialsthatarealreadyknowntobeusefulorhavethepotentialto bedevelopedforapplications,eitherbycompositionalcontroltooptimisepropertiesorbyfabricationinto desiredforms,shapesorproducts.Materialssciencethereforeincludeswhateveraspectsofchemistry,physics andengineeringthatarenecessarytoachievethedesiredaims.

Materialschemistryismuchmorethanjustasubsetofmaterialsscience,however,sinceitisfreedfrom theconstraintofafocusonspecificapplications;materialschemistslovetosynthesisenewmaterialsand measuretheirproperties,someofwhichmayturnouttobeusefulandcontributetothedevelopmentofnew industries,buttheydothiswithinanoverarchinginterestinnewchemistry,newstructuresandimproved understandingofstructure–composition–propertyrelationships.

Acuriousfactisthat,intheearlydaysofchemistry,inorganicchemistryhadasitsmainfocus,theelements oftheperiodictableandtheirnaturallyoccurringoreasy-to-makecompoundssuchasoxidesandhalides. Inorganicchemistrysubsequentlydiversifiedtoincludeorganometallicchemistryandcoordinationchemistry butinterestingly,manytraditionalinorganicmaterialshavereturnedtocentre-stageandarenowattheheart ofsolidstatematerialsscience.Examplesinclude:Cr-dopedAl2 O3 forlasers;dopedSisemiconductors

xxi Chemistry–SolidStateChemistry–MaterialsChemistry–MaterialsScienceandEngineering

formicroelectronics;dopedZrO2 asthesolidelectrolyteinsolidoxidefuelcells;BaTiO3 asthebasisof thecapacitorindustrywithatotalannualproductionworldwideexceeding1012 units;copperoxide-based materialsforsuperconductorapplications;andmany,manymore.Thescopefordevelopingnewsolidstate materials/applicationsisinfinite,judgingbythe‘simple’exampleofAl2 O3 describedabove.Mostsuch materialstendnottosufferfromproblemssuchasvolatilisation,degradationandatmosphericattack,which areoftenadrawbackofmolecularmaterials,andcanbeusedsafelyintheenvironment.

Itisimportanttorecognisealsothatphysicalpropertiesofinorganicsolidsoftendependonstructureat differentlengthscales,asshownbythefollowingexamples:

Optical properties of ruby:- Al2O3:Cr

CdS colloids, colour and band gap depend on particle size β-/ γ-Ca2SiO4 and their different hydration capabilities

Strength of metals and ceramics

Thusinthecaseofruby,whichisanaturalgemstoneandwasthefirstmaterialinwhichLASERaction–light amplificationbystimulatedemissionofradiation–wasdemonstrated,twostructuralaspectsareimportant. Oneisthehostcrystalstructureofcorundum, α -Al2 O3 andtheotheristheCr3+ dopantwhichsubstitutes atrandomforabout1%oftheAl3+ ionsinthecorundumlattice:theCr-Obondlengthsandtheoctahedral sitesymmetryarecontrolledbythehoststructure;thetwotogethercombinetogivetheredrubycolourby meansofd–dtransitionswithintheCrchromophoreandthepossibilityofaccessingthelong-livedexcited statesthatarenecessaryforLASERaction.

Aremarkableexampleoftheeffectofcrystalstructuredetailsattheunitcellscaleonpropertiesisshown bydicalciumsilicate,Ca2 SiO4 whichisreadilypreparedintwopolymorphicformsatroomtemperature.One, the β -polymorph,reactswithwatertogiveasemicrystallinecalciumsilicatehydratewhichsetsrock-solid andisamainconstituentofconcrete;theotherpolymorph, γ -Ca2 SiO4 ,doesnotreactwithwater.Justthink, theentireconstructionindustryrestsonthedetailedpolymorphismofdicalciumsilicate!Itisnotsufficient thatoneofthekeycomponentsofcementhastherightcomposition,Ca2 SiO4 ;inaddition,theprecisemanner inwhichionsarepackedtogetherinthesolidstateiscriticaltoitshydrationpropertiesandwhetherornotit turnsintoconcrete.

Atthenanoscale,crystallineparticlesmaycontainmanyhundredsofunitcellsbutoftentheirproperties aredifferentfrompowders,ceramicsorsinglecrystalsofthesamematerialwithlarger-sizedgrainssimply becauseoftheinfluenceofsurfaceenergies.Insmallnanoparticles,surfacefreeenergiesandstructures

increasinglydominatethetotalfreeenergyofamaterial,asshownbythecolour,andassociatedbandgap,of CdSnanoparticles(orcolloidsinolderterminology)whichcanbefine-tunedbycontrollingtheparticlesize.

Somepropertiesaredeterminedbystructureatthemicron(1 μm = 103 nm = 104 ˚ A = 10 3 mm)scale andthisisthereasonwhy‘microstructure’featuresstronglyinthecharacterisationofmetalsandceramics, primarilyusingopticalandelectronmicroscopytechniques.Frequently,impurities/dopantsmayprecipitate atgrainboundariesandsurfacesandthesecanhaveadramaticinfluenceonforinstance,themechanical properties.

Theseexamplesillustratetheawesomechallengesthatmustbemetbeforeaninorganicsolidcanbe regardedasfullycharacterisedacrossthelengthscales.This,coupledwiththeenormousnumberofinorganic crystalstructuresthatareknown,andthepossibilitytointroducedopantswhichmodifyproperties,underlines whysolidstatechemistryisacentralsubjecttomanyareasofphysicalscience,engineeringandtechnology.

Thisbookconcernssolidstatechemistryandfocusesoninorganicsolids:theircrystalstructures,defect structuresandbonding;themethodsusedtosynthesisethemanddeterminetheirstructures;theirphysical propertiesandapplications.Organicandothermolecularmaterialsareincludedinthecoverageiftheir propertiesinthesolidstatecomplement,orrelateto,thoseofinorganicsolids.Physicalpropertiesarean intrinsicpartofsolidstatechemistrysincethewholeareaofstructure–propertyrelationsrequirestheinsights andinputofchemistrytosynthesiseandcharacterisematerials,aswellasagoodunderstandingofphysical propertiesandthefactorsthatcontrolthem.

CompanionWebsite

Thistextbookissupportedbyawebsitewhichcontainsavarietyofsupplementaryresources: http://www.wiley.com/go/west/solidstatechemistrystudent

OnlineyouwillfindPowerPointslidesofallfiguresfromthebook,aswellassolutionstothesetofquestions. ThewebsitealsogivesyouaccesstoaCrystalMaker R viewerprogram.TheCrystalViewersoftwareis availableforWindowsandMac,andisaccompaniedbyabroadarrayofcrystalstructuresforyoutoview andmanipulate.

CrystalViewer

CrystalViewerisavisualisationprogramfordisplayingandmanipulatingcrystalstructures.The CrystalViewersoftwarefacilitatestheexplorationofcrystalstructuresfromthebookinthreedimensions,allowinguserstoviewthestructuresindifferentorientations,andhighlight/hidedifferentstructuralfeaturessoastoaidtheinterpretationofcomplexcrystalstructures.TheCrystalViewerprogramis accompaniedbyover100crystalstructurefiles;manyofthesestructuresrelatedirectlytoillustrations fromthebook,identifiedbytheirfigurenumbers,andavarietyofadditionalstructuresareprovidedto complementtheconceptsandapplicationsdiscussedinthetext.

TheCrystalViewersoftwareandaccompanyingstructurefilescanbedownloadedfromthecompanion websiteathttp://www.wiley.com/go/west/solidstatechemistrystudent

Anexampleofhowacrystalstructurecanappearverydifferent,dependingonwhichaspectsare emphasised,isshownhereforCaCu3 Ti4 O12 ,inwhichthetwodiagramshighlighteithertheTiO6 octahedraortheCuO4 squareplanarunits.

CrystalMaker®CrystalMaker Software Ltd, www.crystalmaker.com
CaCu3Ti4O12

CrystalStructureLibrary

ACrystalStructureLibraryisavailableonthecompanionwebsitecontaining>100structureswhichcanbe examinedindetailusingtheCrystalViewerSoftware.Thestructureswhichcorresponddirectlytofiguresin thebookarelistedbelow,withtherelevantfigurenumbernotedinparentheses.Manymorecrystalstructures areavailableonline,includingmineralsandotherinorganicstructures.Furtherstructuresmaybeaddedfrom timetotime.

MajorInorganicStructureTypes(andrelevantbookdiagrams)

β -alumina,NaAl11 O17 (8.23and8.24)

BaTiO3 (8.40)

bcc metal(2.12)

Brass,ZnCu(2.11)

Brownmillerite,Ca2 (Fe,Al)2 O5 (1.42)

CaC2 (1.10)

CaCu3 Ti4 O12 (1.42)

CdCl2 (1.40)

Cdl2 (1.39)

ChevrelPhase,BaMo6 S8 (8.6)

Corundum, α -Al2 O3 (1.46)

CsCl(1.36)

Diamond(1.33)

fcc metal(1.20)

Fluorite/antifluorite,CaF2 (1.29,1.30and1.34)

Garnet,Y3 Fe5 O12 (1.49)

GdFeO3 (1.41)

hcp metal(1.21)

Hollandite(8.27)

Ilmenite,FeTiO3 (1.46)

K2 NiF4 (1.50)

Layereddoublehydroxides(4.11)

Li3 N(8.32)

LiCoO2 /α -NaFeO2 (8.35)

LiNbO3 (1.46)

Magnetoplumbite(9.14)

MgB2 (1.51)

Nasicon,NaZr2 (PO4 )3 (8.27)

Nickelarsenide,NiAs(1.35)

Olivine,LiFePO4 (1.45)

PbFCl,matlockite(8.6)

PbO(3.14)

Perovskite,SrTiO3 (1.41)

Pyrochlore(1.48)

Rocksalt,NaCl(1.2,1.29and1.31)

Rutile,TiO2 (1.37)

Spinel(1.44)

Tetragonaltungstenbronze(1.43)

Wurtzite,ZnS(1.35)

YBa2 Cu3 O6 (8.8)

YBa2 Cu3 O7 (8.8)

Zincblende/sphalerite,ZnS(1.29and1.33)

ZrCuSiAs(8.6)

Biography

TonyWest obtainedhisBScdegreeinChemistryatUniversityCollegeSwanseaandhisPhDattheUniversity ofAberdeen,whereheworkedwithProfessorF.P.Glasseronsilicatechemistry.Hewasappointedasa LecturerinAberdeenin1971anddevelopedalifetimeinterestinthethen-emergingfieldofsolidstate chemistrywithspecialinterestinthesynthesisofnewoxidematerials,theircrystalstructuresandelectrical properties.HewasawardedaDScfromAberdeenin1984androsethroughtherankstobecomeProfessor ofChemistryin1989beforemovingtotheUniversityofSheffield,DepartmentofMaterialsScienceand Engineering,asHeadofDepartmentin1999,aposthehelduntil2007.

Tonywasfoundingeditorofthe JournalofMaterialsChemistry andsubsequentlyestablishedtheMaterials ChemistryForum,whichhasnowbecometheMaterialsChemistryDivisionoftheRoyalSocietyofChemistry. HeorganisedtheFirstInternationalConferenceonMaterialsChemistry,MCI,inAberdeen,1993,andcoorganisedthefirstMaterialsDiscussion,MDI,inBordeaux,1998.HealsoservedasPresidentoftheInorganic ChemistryDivisionofIUPAC,2004–2007.

TonyisaFellowoftheRoyalSocietyofChemistry,theInstituteofPhysics,theInstituteofMaterials, MineralsandMining(IOM3 ),andtheRoyalSocietyofEdinburgh.Overtheyearshehasreceivedseveral awards,includinganIndustrialAwardinSolidStateChemistryfromtheRSC(1996),theGriffithsMedal andPrizefromtheIOM3 (2008),theEpsilondeOroAwardfromtheSpanishSocietyofGlassandCeramics (2007)andtheChemicalRecordLectureshipfromtheChemicalSocietiesofJapan(2007).Hehasbeen awardedthe2013JohnB.GoodenoughAwardinMaterialsChemistrybytheRSC,alifetimeawardwhich recognisesexceptionalandsustainedcontributionstothefieldofmaterialschemistry.

1

CrystalStructuresandCrystalChemistry

Solidstatechemistryisconcernedmainlywithcrystallineinorganicmaterials,theirsynthesis,structures, propertiesandapplications.Agoodplacetobeginiswith crystalstructures and crystalchemistry.All necessarycrystalstructureinformationiscontainedindataonunitcells,theirdimensionsandthepositionsor atomiccoordinatesofatomsinsidetheunitcell.Crystalchemistrycombinesthisbasicstructuralinformation withinformationabouttheelements,theirprincipaloxidationstates,ionicradii,coordinationrequirements andpreferencesforionic/covalent/metallicbonding.AworkingknowledgeofthePeriodicTableandthe propertiesofelementsis,ofcourse,invaluabletobeableappreciatecrystalchemistry,butconversely, knowledgeofcrystalstructuresandespeciallycrystalchemistryprovidesaveryusefulwaytogainincreased understandingoftheelementsandtheircompounds.

Manyofthepropertiesandapplicationsofcrystallineinorganicmaterialsrevolvearoundasurprisingly smallnumberofstructuretypes.Inthischapter,themainfamiliesofinorganicstructuresarereviewed, especiallythosewhichhaveinterestingproperties;moredetailsofthevastarrayofstructuresmaybefound intheencyclopaedictextbyWellsandalsointheWyckoff CrystalStructures bookseries.First,however,we mustconsidersomebasicconceptsofcrystallography.

1.1UnitCellsandCrystalSystems

Crystalsarebuiltupofregulararrangementsofatomsinthreedimensions;thesearrangementscanbe representedbyarepeatunitormotifcalledthe unitcell.Theunitcellisdefinedas thesmallestrepeating unitwhichshowsthefullsymmetryofthecrystalstructure.Letusseeexactlywhatthismeans,firstintwo dimensions.AsectionthroughtheNaClstructureisshowninFig.1.1(a);possiblerepeatunitsaregivenin (b)to(e).Ineach,therepeatunitisasquareandadjacentsquaresshareedgesandcorners.Adjacentsquares areidentical,astheymustbebydefinition;thus,allthesquaresin(b)haveCl ionsattheircornersand centres.Therepeatunitsin(b),(c)and(d)areallofthesamesizeand,infact,differonlyintheirrelative position.Thechoiceoforiginoftherepeatunitistosomeextentamatterofpersonaltaste,eventhough itssize,shapeandorientationarefixed.TherepeatunitofNaClisusuallychosenas(b)or(c)ratherthan (d)becauseitiseasiertodrawandvisualisethestructureasawholeiftherepeatunitcontainsatomsorions atspecialpositionssuchascornersandedgecentres.Anotherguidelineisthatusuallytheoriginischosenso thatthesymmetryofthestructureisevident(nextsection).

SolidStateChemistryanditsApplications,SecondEdition, StudentEdition.AnthonyR.West. ©2014JohnWiley&Sons,Ltd.Published2014byJohnWiley&Sons,Ltd. CompanionWebsite:http://www.wiley.com/go/west/solidstatechemistrystudent

Another random document with no related content on Scribd:

The Project Gutenberg eBook of Dark Dawn

This ebook is for the use of anyone anywhere in the United States and most other parts of the world at no cost and with almost no restrictions whatsoever. You may copy it, give it away or re-use it under the terms of the Project Gutenberg License included with this ebook or online at www.gutenberg.org. If you are not located in the United States, you will have to check the laws of the country where you are located before using this eBook.

Title: Dark Dawn

Author: Henry Kuttner

Release date: May 27, 2022 [eBook #68184]

Language: English

Original publication: United States: Standard Magazines, Inc, 1947

Credits: Greg Weeks, Mary Meehan, Alex White & the online Distributed Proofreaders Canada team at https://www.pgdpcanada.net

DARK DAWN

Writing under the pseudonym Keith Hammond.

[Transcriber's Note: This etext was produced from Thrilling Wonder Stories, August 1947.

Extensive research did not uncover any evidence that the U.S. copyright on this publication was renewed.]

Blinded by an atomic blast, Dan Gresham joins forces with the radiant Swimmers to preserve an undersea civilization!

The Albacore was eight hundred miles out of Suva, feeling her way through the Pacific toward a destination unmarked except on the charts. She was a Navy cruiser jury-rigged into a floating laboratory, Navy manned, but carrying a dozen specialized technicians as passengers.

For days she had waited outside the danger area, till circling planes radioed word that the test atomic blast had apparently subsided. Then the Albacore went into a flurry of preparations. It was a miracle that the watch had sighted Gresham in his rubber boat, and a triple miracle that he was alive.

His eyes bandaged, he sat out on deck, while Black, the neurologist, leaned on the rail beside him and stared aft. Presently Black took out a pack of cigarettes, automatically held it out to Gresham, and then remembered that the man was blind.

“Cigarette?” he said.

“Yes, thanks. Is that you, Dr. Black?” Gresham’s voice was very low.

“Uh-huh. Here. I was watching that shark. He’s followed us from Suva.”

“Big one?”

“One of the biggest I ever saw,” Black said. “That’s the baby who tried to take a chunk out of you when we picked you up. He kept biting at our oars!”

“A pity he didn’t get me,” Gresham said. He tossed the cigarette away. “No use. If I can’t see the smoke, I can’t enjoy it.”

The neurologist studied his patient.

“We don’t know that you’re permanently blinded, after all. This is so new.”

“I was looking straight at it,” Gresham said bitterly. “It must have been miles and miles away, but I could feel it burning my eyes out in

one flash. Don’t tell me!”

“All right. I won’t. But this is a completely new type of atomic blast. It isn’t uranium. It’s a controlled chain reaction based on an artificial element—there must be new types of radiation involved.”

“Fine. The next time there’s a war, we can blind everybody.” Gresham laughed grimly. “I’ll be sorry for myself for a few months, probably. Then I’ll get a Seeing-Eye dog and become a useful member of society again. Huh!” He paused. When he spoke again his voice was different, doubtful, as if he didn’t quite realize he spoke aloud. “Or maybe not,” he said. “Maybe I’ll never be—useful—any more. Maybe I’m not just imagining....”

“Imagining?” Black said, interested. “What?”

Gresham jerked his bandaged face away.

“Nothing!” he declared sharply. “Forget it.”

Black shrugged. “Tell me about yourself, Gresham,” he suggested. “We haven’t had much time yet to get acquainted. How did you happen to be out here just now?”

Gresham shook his head irritably. “Just at the wrong spot and the wrong time? Maybe it was meant that way from the start. Predestination—how do I know? Oh, I had enough after the war. I bummed around the islands. I—like the sea.” His voice softened. “Like isn’t strong enough. I love the sea. I can’t stay away from it. There’s a fascination—I signed on here and there as a deck-hand, a stevedore—I didn’t care what. I just wanted to soak myself in the big things. Sun and sea and sky Well, I can still feel the sun and the wind, and I can hear the water. But I can’t see it.”

There was no real conviction in the way he finished that last sentence. He turned his bandaged eyes a little to Black’s left and his face grew strained, as if he were looking at something far out at sea.

“You know about the radar sonics, don’t you?” the neurologist said.

“Oh, sure. I’ll learn to bounce a radar beam around me and keep from walking into walls. But—” Gresham’s voice died. He seemed to be staring as if through the bandages and his own blindness at something far away. In spite of himself Black turned to follow that blinded stare. And at a great distance off he saw, or thought he saw something in the glare of the sun-track splash water and dive....

“Dr. Black,” Gresham was saying in that strained, doubtful voice. “Dr. Black, how are you on psychiatry?”

“Why, fair.” Black kept the surprise out of his tone with an effort. “Why?”

“Have you noticed any symptoms of—aberration in me?”

“Nothing unusual. Nervous shock, of course. That atomic blast catching you certainly would have caused a strain.”

Gresham said, “After the blast went off I floated for I don’t know how long before you picked me up. I—started to imagine things. Delirium, you could say But I don’t know I—forget it, will you? Maybe later I’ll feel like talking. Just forget I said anything, Dr. Black.”

After all, there was nothing to talk about, to put into coherent words. For what had happened was inexplicable. It was part of the terra incognita that the key of nuclear energy had unlocked.

Even Daniel Gresham, drowsing the years away in his tropical lotuslands, could not help hearing about the new atomic experiments. He had stopped keeping track of time back in 1946, because around the archipelagoes time was a variable, and hours could last for seconds or months, depending on whether you were at a kava-kava festival with the golden-skinned Melanesians or simply stretched flat on the warm deck, while white canvas billowed overhead and waves splashed quietly along the keel.

But the radio wouldn’t stop talking. It talked about the uranium piles constructed for experiments, and the new lithium hydride methods, and the technicians who were endlessly charting, testing, studying— and finding fresh mysteries always beyond. And this latest test—a completely new type of atomic blast, one that had never existed

before on earth, except, perhaps, so long ago that the planet was a white-hot, molten mass.

Briefly, the holocaust had blazed out and vanished. But it had left traces in the instruments planted in the path of the fury, and it had left its trace, too, in an intricate, sensitive instrument cage inside Daniel Gresham’s skull.

Thoughts can be measured; they are electric energy. The machine that transmits them can be functionally altered. And, adrift on his raft, Gresham had found a very strange substitute for his lost vision....

The Albacore’s boat came back with recording instruments from a floating buoy, and Black paced slowly up and down the deck, studying a coil of paper and trying to ignore the piping of sea-birds that flapped overhead, and the look of strained attention on Gresham’s face. It didn’t belong there, on a blind man’s face. Gresham sat as he had sat yesterday, bandaged eyes turned toward the sea beyond the boat as if he could see something out there invisible to ordinary eyes.

“Doctor, what does that look like out there?” he asked suddenly.

Startled, Black followed the direction of his pointing finger.

“Why, a porpoise, I think. It—no, now it’s gone.” He stared at his patient in amazement. “Gresham, are you still blind?”

Gresham laughed softly. “There’s a bandage over my eyes, isn’t there? Of course I’m blind.”

“Then how did you know about the porpoise?”

“It isn’t a porpoise.”

Black took a long breath. “What the devil’s the matter with you, Gresham?” he said.

“I wish I knew. I—” Gresham’s voice hesitated. Then he said with a sudden rush, “You could call it hallucination. I can see things. But not

with my own eyes.”

“Yes?” Black’s tone was hushed. He was terribly afraid of interrupting this mood of explanation. “Go on.”

“Right now, for example,” Gresham said in his soft voice, “I’m seeing this ship, from about half a mile away. I can see the smoke, and the little figures on deck. I can see myself, and you. From a distance. Once in a while a wave blocks my sight. You’re holding something white.”

Black stared off into the blue distance, where what had seemed a porpoise had broken water once and vanished. He could see nothing but ocean now.

“I told you I started imagining things on the raft,” Gresham went on. “I kept seeing things from different angles. I knew I was blind, but there were flashes ... green vistas ... blue sky and white clouds....”

“Memory. Imagination.”

“It isn’t a porpoise,” Gresham said.

Black made an effort and pulled his mind into better coordination.

“Now listen,” he said. “All right. You were in the direct path of some new radiations. These figures—” He rustled the paper in his hand. “They don’t check exactly. There was an untyped form of radiation in this area after the atomic blast. But—” He went off at a tangent. “It isn’t a porpoise? What is it, then?”

“I don’t know. It’s intelligent. It’s trying to communicate with me.”

“Good Heavens!” Black said, genuinely startled now. The look he bent upon Gresham was dubious.

“I know, I know.” Gresham must have sensed in the silence that doubtful glance. “Maybe I’m making it all up. I did spot the—porpoise —but maybe my hearing’s improved. The rest—well, I haven’t got any proof except what I know I’ve seen—and felt. I tell you, it’s something intelligent out there. It’s trying to communicate and it can’t.” He rubbed his forehead above the bandages, his face taking on the old look of strain. “I can’t make sense out of it. Too—alien, I

guess. But it’s trying hard....” Suddenly he laughed. “I can imagine how you’re looking at me. Would you like to try some tests, Dr. Black? Knee-jerks, maybe?”

“Come on below with me,” Black said briefly. Gresham laughed again and got up....

An hour later they were back on deck. Black looked worried.

“Listen, Gresham,” he said earnestly “I don’t know what’s happened to you. I admit that. The encephalogram was—puzzling. Your brain emits radiations that don’t check with anything we’ve seen before. Some peculiar things are possible, theoretically. For instance, a radio isn’t really likely to pick up transmitted waves, but it does. And telepathy’s theoretically possible. Suppose your brain has been altered a little by your exposure to the atomic blast. There are powers latent in the human mind, new senses that we know little about.”

“I suppose you have to find new words for it,” Gresham said as Black stumbled and paused. “But I don’t care what the scientific diagnosis is. I can see again. Not with my own eyes. But I can see.”

He was silent for a moment, and to Black it seemed that the blind man’s whole face looked rapt, as if he gazed upon things more beautiful than a man with eyes ever saw. When Gresham spoke, his voice was rapt, too.

“I can see!” he repeated, almost to himself. “I don’t care what else happens. Something alive and intelligent and—and desperate is near me. I see through its eyes. Its thoughts are too different to understand. It’s trying to tell me something, and it can’t. I don’t care. All I care about is seeing, and the things I see.”

He hesitated.

“Beautiful,” he murmured. “All my life I’ve loved beautiful things. That’s why you found me out here, in the tropics, away from cities and ugliness. And now!” He laughed a little and his voice changed.

“If I could see your face, I wouldn’t be talking this way,” he said. “But I can’t, so I can say what I feel. Beauty is all that matters, and in a

way I’m glad even this has happened, if it means I can go on seeing things like—like this.”

“Like what?” Black leaned forward tensely. “Tell me.”

Gresham shook his head. “I can’t. There aren’t any words.”

The two men sat silent for awhile, Black frowning and studying the rapt, blind face before him, Gresham staring through his bandages and through the eyes of another being, at things he could not speak of.

Something glistened among the waves, very far away, turned over in the water and sank again.

The next morning, Gresham did not awaken. To Black it resembled catalepsy. The man lay quietly, his heart faintly beating, his respiration almost stopped. Once or twice a ripple of motion crossed his features and he grimaced. But that was all. He lay for a long while, half-alive.

But he was double alive, triply—a hundredfold—elsewhere.

Around dawn it began to happen to him, he thought afterward. He felt first a something reaching out for him. His internal vision kept catching glimpses and then snapping shut again like a camera lens. There was a thought, beating against a barrier, trying to get through to him. But it was too alien. It could not reach through.

Gresham’s half-sleeping mind could not understand. He reached out into other minds around him, seeking contact. Bird minds—sparks of life rising and falling on the winds, dim, formless bits of cloud. And other small minds, in the waters, vague, weaving through green voids. But in the end he always came back to the Swimmer.

And in the end, the Swimmer must have realized it could not communicate, knew at last there was only one way left. It had to show him what it wanted to tell. And there was only one way to show him.

So it swam down, down in the pearly light of dawn, with the sea and sky an enormous emptiness and the Albacore a small dark shape miles away, and Gresham’s body hidden within it, asleep, while his mind sank with the Swimmer through the fathomless seas.

Down and down, into the great deeps under the atolls, where abysses lie deeper than Everest is high. The Swimmer could plumb them, for the Swimmer was not human. Intelligent, yes, but— different. Life under the waters would follow a different course from life in the air. And cities under the sea would be very different, too.

Gresham had never known this feeling of bodily freedom before. He shared with the Swimmer the physical sensation of motion in a supporting medium through which he could move freely in any direction. It was a strange, strong body that housed his mind temporarily, but no visual image of it formed.

There were sensations of indescribable difference—a smooth, flowing, muscular thrust that exploded into bursts of action as he drove downward. And an aching, straining discomfort gradually ceased as he sank. The race of the Swimmer was meant to live in the pressure of the deeps, and now the pressure began to fold in comfortingly. Once more the Swimmer’s body felt completely its own, and that deep, sensuous pleasure made it take an intricate path downward, as a bird plays in its own element or a dolphin gambols in the waves.

The dark began to close in. But Gresham began to be aware of a new, strange light from below, an unearthly dawn, in a light-band no human eyes could ever see except in this incredible manner. He could never describe the color of the abysmal dawn, a tremendous slow brightening of sunless day permeating the vastness of underseas.

Shadows of the deep water swam past, shapes of terror and mystery and fantastic beauty. Once the leviathan bulk of the great whale went by, and once a goblin picnic of tiny colored lanterns—fish with luminous spots driving in an insanely gay flight before the shadow of a barracuda that swept like death after them.

But the sea-bottom was dark. Perhaps only in some spots was this land of veiled shadows to be found. The immense glow of the submarine dawn drew itself in and focused on small areas as Gresham’s mind went downward with the Swimmer. And then a gargantuan black wall, without top or end or bottom, loomed before him.

Perspective swung round dizzily, and Gresham saw that it was no topless wall, but the bottom of the sea. Crags lifted from it. Atolls and hills jutted into the faint fringes of light, crawling with weeds, blanketed with undersea growth. But the great plain and the valleys were in shadow.

Anchored by glowing ropes that vanished in darkness below, swung latticed spheres of light. There were dozens of them, like shining toy balloons expanding in size as the Swimmer swept nearer and nearer. Across the lattices a troubled whirling ran, shaking vortices of darkness that made the spheres fade and brighten like lanterns, and then pulse into dimness again.

The Swimmer’s headlong sweep, like flight through green air, carried Gresham straight toward the nearest globe. Between the lattices an opening like a shutter widened, gaped, closed.

And this was a city of the underseas.

For five days Gresham’s body lay all but motionless in his bunk on the Albacore, while the ship drove forward over fathomless abysses where Gresham’s mind moved among mysteries. Dr. Black spent as much time as he could spare beside the cataleptic sleeper, watching the vague shadows of expression that moved now and again across his face—wonder, sometimes revulsion, sometimes strain and dread. But only the shadows of the real emotions which Gresham’s mind knew, far away.

On the fifth day he woke.

Black saw his hands rise quickly to the bandaged eyes, and Gresham sat up abruptly, making an inarticulate sound in his throat. His face for a moment was wild with dismay and horror.

“It’s all right,” Black said quietly. “It’s all right, Gresham. You’ve been asleep and dreaming, but you’re safe now. Wake up!”

“Safe!” Gresham said bitterly. “Blind again, you mean. And—” His face convulsed once in a grimace of revolt; then he had himself under control and his hands which had been clawing futilely at the bandage as if they could pull away blindness from his eyes, fell quietly to the blanket.

“What was it?” Black asked. “You were dreaming? Would you like to tell me?”

It did not come all at once. The story covered many days in fragmentary sessions, but in the end Gresham told.

“You’ll find a diagnosis to cover it,” he said to Black. “You’ll have to decide I’m a schizophrenic—is that the word—and I’m having hallucinations. It doesn’t matter to me. I know what happened. There were cities down there....”

He had never known true beauty until he moved with the Swimmer through those incredible floating towns under the water. Our own race, chained by fetters of gravitation to the ground, never knew such wonders. Our bodies have been deformed, unsuccessful adaptations ever since we learned to walk upright. But a species without enslavement to gravity, developing in sheer beauty and sheer freedom, perfectly adapted to their green aquaeous world, had come into existence underseas.

“They can build as they like,” Gresham said softly. “Gravity doesn’t affect them, you see. There were houses—if you could call them houses—made in spirals and coils and spheres. They can float free within the globes if they like. Some of the houses move in orbits. Some of them—oh, I can’t tell you. I lived there with them for a long

while, but I can’t describe them and I can’t tell you what the people were like. There aren’t words.

“He had to take me down to make me understand what he wanted. The Swimmer, I mean. But his city, like his mind, is too alien to tell about. I can only say it was beautiful, the kind of beauty I’ve loved all my life and tried to find for years. I’m going back down there, Black.”

“Why?” Black had a note-pad on his knee and his pen was moving smoothly across it as Gresham’s quiet voice went on. “Tell me about it, Gresham.”

“It was the atomic explosion,” the blind man said. “The radiations released some sort of balance, away down there, and their machines aren’t working as they should any more. That’s what caused those whirlpools of darkness in the light and made the lattices around the cities shake. And they need the lattices. They have an enemy down there—another race, or maybe a branch of their own race.

“It’s strange to think of wars going on down there just as they have here, and one race enslaving another, as the Swimmer’s people did. I thought at first they were—well, call it evil. I saw how they ruled. Evil is a foolish word. The Swimmer people are so beautiful and strong and wild, you can’t apply our rules to their lives. I lived among them. I saw that other race, in the dark of the sea-bottom, banished from that wonderful, strange light a human couldn’t even see.

“At first I thought it was cruelty that kept the—the others—enslaved. And then I happened to see one of the Others.” His voice faltered and a shadow of revulsion crossed the bandaged face. “I saw what was left after a minor uprising, and I saw how the Others kill, and what they look like. After that I knew. If the decision were mine, I’d exterminate them all. I can’t help that feeling. It’s instinct. There are things too degenerate to live.

“It’s all been going on down there for I don’t know how many centuries, how many milleniums. Think of it, Black! Empires rising and falling, races ruling and races enslaved, sciences developing along lines we’ll never understand and nobody guessing it until the Swimmer came to the surface.

“His race is intelligent. They must have realized the new radiations and the explosion had come from another intelligent race. They’ve seen sunken ships and drowned men, they knew we lived here in the air. But they’re so alien ... No communication is really possible between us. If it weren’t for the accident that did—whatever it did—to my brain, no human might ever have known.

“Well, I’m going back. There’s trouble down there. They need help.” Gresham paused and laughed harshly. “Why do I keep thinking I can help them? I can’t even share their thoughts. All I can do is find some creature to take me down into the depths, so I can see with its eyes. I can watch, if I can’t help. I can move through those wonderful cities again, and see the Swimmer’s people.” His voice faltered and he gave his mind up for an instant to the memory of that race and its beauty and wildness and strange, alien enchantment.

“The Swimmer himself had to stay,” Gresham said. “The machines— you’d never guess they were machines to see them—weren’t working well. All who could had to help the machines, help to keep the dark race—the Others—away from the cities. So the Swimmer’s mind let go of mine and I had to come back.”

“What can you do?” Black asked. “Is there any way to get in touch again?”

Gresham turned his blinded face toward the ocean. He was silent for a moment.

“That shark,” he said. “The big one. He’s still following us.”

Black had to rise and lean over the rail to make sure.

“Yes, I can see him now. He’s with us.”

“That’ll do,” Gresham said confidently. “An intelligent mind can control a non-intelligent one for awhile. I’ll take the shark’s body and go back.”

“You’re tired, Gresham,” Black said. “We can talk about this later I’m going to give you a sedative and I want you to rest.”

Gresham laughed. “See that gull up there? What would you say if it circled three times and landed on the rail beside you?”

Black looked up. The gull sailed in one wide circle, two circles, three —and swooped down toward the rail. Its yellow feet gripped and closed and it perched there turning its head from side to side and looking at Black with eyes that fantastically seemed to him for a moment Gresham’s eyes, as if the blind man in the bird’s dim brain looked out and saw him.

Gresham laughed again.

“You’ve got a notebook on your knee,” he said. “You have no idea how queer you look through a bird’s eyes, Black. All out of focus and strange.”

“Let it go,” Black said in a choked voice. The gull tipped forward and spread its wings, its eyes going blank again with mindless birdthoughts.

“Yes,” Gresham said. “The shark will do....”

Black sat beside the bunk and watched the sleeping face of the blind man, his own mind in a turmoil. He could not believe or accept Gresham’s story, but in spite of himself he found images slipping through his brain as he saw emotions flicker across the cataleptic face. He saw the green abysses gliding by, he saw the nameless undersea dawn brightening in the depths, felt the great shark’s body bend its banded muscles and drive on and on toward a city of floating spheres that illuminated the dark like lanterns lighted by no human hands.

Suddenly Gresham sat straight up among the blankets. The blood rushed into his face and he said, “Huh!” in a choked, inarticulate voice.

“Gresham?” Black said, laying a hand on his arm. “Are you awake? What is it?”

He was not awake. He did not turn his head or feel the hand or hear the voice. All his faculties were focused on something very far away, deep down in the abysses beneath the boat. He was like a man in a nightmare. His breath came fast now, through bared teeth, and his face convulsed into the lines of a man fighting for his life.

“The dark!” he said thickly. “The dark! Where did the lattices go? What’s wrong? Oh, what’s happening here?” But that was the last articulate speech he made, and the last words Black had time to hear, for suddenly Gresham began to struggle violently with the blankets, striving to throw them off, lashing out with clenched fists whenever Black tried to hold him.

In the end they had to strap him to the bunk to keep him from injuring himself and those around him. He lay there struggling furiously, resting in panting silence and then fighting against the restraining bands again. His face was wild with a ferocity that sent cold shivers through Black’s mind, a less than human ferocity.

And in the writhing of his body against the straps, in the way it bowed and lashed straight again, and the strangely fluid motions of his struggle, Black tried not to think he saw the movement of a shark’s body fighting in deep water against an alien foe.

“Blood!” Gresham muttered, deep in his throat. “Blood—so much blood—can’t see, but—there’s another—kill, kill! Kill them all!”

And it seemed to Black that the little cabin was dark with the dark of the undersea and blinded with blood that spread through the dim water, and boiling with the terrible combat of an unknown struggle.

He knew to an instant when the shark died. He could tell by the last spasmodic convulsion of Gresham’s body on the bed, the double lashing motion and the sudden silence. He even thought he saw for an instant the blankness of death itself flicker across Gresham’s face, the brush of it touching the edges of the mind that had controlled the shark’s mind.

After that there was only silence, and the slumber of deep exhaustion....

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