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Ramiro Pérez Campos

Antonio Contreras Cuevas

Characterization of Metals and Alloys

CharacterizationofMetalsandAlloys

RamiroPérezCampos•AntonioContrerasCuevas

Editors

CharacterizationofMetals andAlloys

Editors RamiroPérezCampos

CentrodeFísicaAplicaday TecnologíaAvanzada(CFATA)

Querétaro,México

RodrigoA.EsparzaMuñoz CentrodeFísicaAplicaday TecnologíaAvanzada(CFATA)

Querétaro,México

AntonioContrerasCuevas

ISBN978-3-319-31693-2ISBN978-3-319-31694-9(eBook) DOI10.1007/978-3-319-31694-9

LibraryofCongressControlNumber:2016952548

©SpringerInternationalPublishingSwitzerland2017

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Theuseofgeneraldescriptivenames,registerednames,trademarks,servicemarks,etc.inthispublication doesnotimply,evenintheabsenceofaspecificstatement,thatsuchnamesareexemptfromtherelevant protectivelawsandregulationsandthereforefreeforgeneraluse. Thepublisher,theauthorsandtheeditorsaresafetoassumethattheadviceandinformationinthisbook arebelievedtobetrueandaccurateatthedateofpublication.Neitherthepublishernortheauthorsor theeditorsgiveawarranty,expressorimplied,withrespecttothematerialcontainedhereinorforany errorsoromissionsthatmayhavebeenmade.

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Preface

“CharacterizationofMetalsandAlloys”includesacompilationofthebestresearch workspresentedinSymposium5B“Structuralandchemicalcharacterizationof metals,alloysandcompounds,”fromtheXXIVInternationalMaterialsResearch Congress(IMRC-2015).TheXXIVInternationalMaterialsResearchCongress washeldonAugust16–20,2015,inCancún,Mexico.IMRCwasorganizedby theSociedadMexicanadeMateriales(SMM).About1850registeredparticipants frommorethan50countriesparticipatedinthe36differentsymposia,workshops, plenarylectures,andtutorialcourses. The36symposiathatcomprisethetechnical programofIMRC-2015aregroupedinseveralclusters,namely,Nanoscienceand Nanotechnology,Bio-inspiredMaterials,MaterialsforEnergy,Fundamentalsof MaterialsScience,MaterialsCharacterization,MaterialsforSpecificApplications, MagneticandElectronicMaterials,andGeneral.

Thearticlescontainedinthisbookincludecharacterizationofmaterialsprepared bydifferentfabricationandproductionmethods;thebookcoversstate-of-the-artand experimentaltechniquescommonlyusedinmodernmaterialscharacterizationof metalsandalloys.Inaddition,thebookintroducesadvancedtechniques,including: scanningprobemicroscopy,aberration-correctedscanningtransmissionelectron microscopy,Ramanspectroscopy,Fouriertransforminfraredspectroscopy,andfield emissionscanningelectronmicroscopy(FESEM).Thisbookcoversseveralaspects ofthestructuralandchemicalcharacterizationofthematerialssuchasmetals, alloys,steels,welding,nanomaterials,andcoatings.Thematerialsareamorphous, crystalline,powders,coatings,fibers,andthinfilms,andwerepreparedwithdifferenttechniques.Structuralcharacterizationtechniquesinclude:scanningelectron microscopy(SEM),X-raydiffraction(XRD),transmissionelectronmicroscopy (TEM),aberration-correctedscanningtransmissionelectronmicroscopy(STEM), Ramanspectroscopy,opticalmicroscopy(OM),Fouriertransforminfraredspectroscopy(FTIR),differentialthermalanalysis(DTA),electrochemicalimpedance spectroscopy(EIS),differentialscanningcalorimetry(DSC),finiteelementmethod (FEM),thermoluminescence(TL),andlaseremission.

Thestructureofthebookisclassifiedinnineparts:(1)CharacterizationofSteels UsedintheOilIndustry,(2)CharacterizationofCopperAlloys,(3)Characterization

ofSteelsbyApplyingHeatTreatment,(4) CharacterizationofThinLayersand Coatings,(5)CharacterizationofMaterialsObtainedbyMechanicalMilling,(6) CharacterizationofMaterialsforMedicalApplications,(7)Characterizationof MaterialsforIndustrialApplications,(8)CharacterizationofWeldingandJoining ofMaterials,and(9)CharacterizationofIntermetallicMaterials.

SantiagodeQuerétaro,MéxicoDr.RamiroPérezCampos DistritoFederal,MéxicoDr.AntonioContrerasCuevas SantiagodeQuerétaro,MéxicoDr.RodrigoA.EsparzaMuñoz

Acknowledgments

WewouldliketothankSpringereditorialforpublishingthisbook,aswellasthe committeeassignedfortheeditionofthebookandthereviewersofthearticlesfor theirvaluablecomments,whichhavecertainlyhelpedtoimprovethequalityofthe manuscripts.WealsowishtothanktheSociedadMexicanadeMateriales(SMM), CentrodeFísicaAplicadayTecnologíaAvanzada(CFATA)fromUniversidad NacionalAutónomadeMéxico(UNAM),andInstitutoMexicanodelPetróleo (IMP)fortheirsupportinorganizingtheSymposium5B“Structuralandchemical characterizationofmetals,alloysandcompounds,”belongingtoXXIVInternational MaterialsResearchCongress(IMRC-2015)fromwhichthearticlesareincludedin thisbook.Additionally,wewouldliketothankalltheauthorsofthearticleswho haveworkedtoimprovethequalityofthearticlesconsideringreviewers’comments, whicharetheresultoftheirvaluableresearchworkandmakepossibletheedition ofthisbook.

Finally,wewouldliketothankthosewhohaveworkedtomakethiscongressan excitingandfruitfulmeeting.

ListofAbbreviations

AAustenite

AEAuxiliaryelectrode

AFAcicularferrite

AISIAmericanIronandSteelInstitute

APIAmericanPetroleumInstitute

ASMEAmericanSocietyofMechanicalEngineers

ASTMAmericanStandardTestingMachine

ATAgingtime

BBainite

BMBasemetal

CBDChemicalbathdeposition

CCTContinuouscoolingtransformation

CSACanadianStandardsAssociation

DNVDetNorskeVeritas

DPIDigitalprocessingimage

DSAWDoublesubmergedarcwelding

DSCDifferentialscanningcalorimetry

EaActivationenergy

EDMElectricaldischargemachining

EDSEnergy-dispersivespectroscopy

EDXEnergy-dispersiveX-ray

EISElectrochemicalimpedancespectroscopy

ERWElectricresistancewelding

FFerrite

FEAFiniteelementanalysis

FTIRFouriertransforminfraredspectroscopy

GMAWGasmetalarcwelding

HAHydroxyapatite

HAZHeat-affectedzone

HEHydrogenembrittlement

HEMHigh-energymilling

HICHydrogen-inducedcracking

HRTEMHigh-resolutiontransmissionelectronmicroscopy

HSLAHigh-strengthlowalloys

HTHeattreatment

HVHardnessVickers

IEAWIndirectelectricarcwelding

IMRCInternationalMaterialsResearchCongress

IRSInfraredspectroscopy

ISOInternationalStandardsOrganization

LPCVDLow-pressurechemicalvapordeposition

MMartensite

MPFMappingofpolycrystallineflow

MPYMils-inchperyear

NACENationalAssociationofCorrosionEngineers

NDTNondestructivetesting

OESOpticalemissionspectroscopy

OMOpticalmicroscopy

PPerlite

PCPolarizationcurves

PWHTPost-weldheattreatment

REReferenceelectrode

RSRamanspectroscopy

SAESocietyofAutomotiveEngineers

SAWSubmergedarcwelding

SCCStresscorrosioncracking

SCESaturatedcalomelelectrode

SEMScanningelectronmicroscopy

SMMSociedadMexicanadeMateriales

SSStainlesssteel

SSRTSlowstrainratetest

STEMScanningtransmissionelectronmicroscopy

TEMTransmissionelectronmicroscopy

TGAThermalgravimetricanalysis

TLThermoluminescence

TMCPThermomechanicalcontrolledprocessing

UTSUltimatetensilestrength

UV-VisUltraviolet–visiblespectroscopy

YSYieldstrength

BiographyofEditors

Dr.RamiroPérezCampos receivedhisbachelor’sandmaster’sdegreesinphysics attheNationalPolytechnicInstituteinMéxico.HeobtainedhisPh.D.inphysics attheUniversityofAlberta,Canada,in1983.Healsocarriedoutpostdoctoral workattheKFAinJülich,Germany.HewasawardedanAlexanderVonHumboldt postdoctoralscholarship.Heistheauthorofmorethan170scientificpapers,allof themrelatedtotheapplicationsofthetransmissionelectronmicroscopeinmaterials science.Dr.RamiroPérezCamposhascultivatedlinesofresearchrelatedwith theoreticalsimulationsofimagesobtainedbytransmissionelectronmicroscopy (TEM).Theoreticalsimulationshavebeenbasedonelectrondiffractionusingthe theoryofBetheandthemultilayermodel.Currently,heisthedirectorofCentro deFísicaAplicadayTecnologíaAvanzada(CFATA)fromUniversidadNacional AutónomadeMéxico(UNAM).

Dr.AntonioContrerasCuevas receivedhisbachelor’sdegreeinmechanicalengineeringin1994.Hereceivedamaster’sdegreeinmetallurgyandmaterialsscience atUniversidadMichoacanain1997.HeobtainedhisPh.D.in2002inmetallurgy andmaterialssciencefromUniversidadNacionalAutónomadeMéxico(UNAM). Since2003,hehasbeenapipelinematerialsresearcherfortheMexicanPetroleum Institute.HeisamemberofNACEandtheMexicanMaterialsSociety,andhe belongstotheNationalResearchSystem.Hismainresearchareasincludestress corrosioncracking(SCC),rootcauseanalysis(RCA),materialscharacterization, synthesisandcharacterizationofcompositematerials,andpipelineintegrity.Heis theauthorofmorethan60scientificpapersrelatedtomaterialscharacterizationby differenttechniques.

Dr.RodrigoA.EsparzaMuñoz obtainedhisPh.D.inmetallurgyandmaterials scienceattheUniversidadMichoacanadeSanNicolásdeHidalgo(UMSNH), México,in2007.Hecarriedouttwopostdoctoralstays,oneoftheminthe UniversidadNacionalAutónomadeMéxico(UNAM)andtheotheroneinthe UniversityofTexasatSanAntonio(UTSA).Heistheauthorofmorethan50

scientificpapers,mostofthemrelatedtothecharacterizationofnanomaterials usinghigh-resolutiontransmissionelectronmicroscopyandaberration-corrected scanningtransmissionelectronmicroscopy.HeisaresearcheratCentrodeFísica AplicadayTecnologíaAvanzada(CFATA)fromUniversidadNacionalAutónoma deMéxico(UNAM).

Contents

PartICharacterizationofSteelsUsedintheOilIndustry

1MechanicalandMetallurgicalPropertiesofGradeX70 SteelLinepipeProducedbyNon-conventionalHeatTreatment .......3 C.Natividad,R.García,V.H.López,L.A.Falcón, andM.Salazar

2CorrosionInhibitionofX52PipelineSteelinChloride SolutionsUsingNonionicSurfactant .....................................13 L.M.Quej,A.Contreras,andJ.Aburto

3EffectontheMicrostructureandMechanicalProperties oftheStructuralSteelWeldedinMarineEnvironment ................29 M.Flores,J.J.Ruiz,F.Macías,andJ.Acevedo

PartIICharacterizationofCopperAlloys

4MappingofPolycrystallineFlowDuringHotDeformation byInSituTensionTestofSheetCopperAlloy ..........................41 J.D.Muñoz-Andrade,E.Garfias-García, andO.Vega-Hernández

5DeterminationoftheActivationEnergyofCopperDuring InSituTensionTestingbySEM ...........................................49 D.MoránGarcía,E.Garfias-García,andJ.D.Muñoz-Andrade

6EffectofCopperAdditionsonSecondaryCarbide PrecipitationinHighChromiumwithCastIron .......................61 F.V.Guerra,A.Bedolla-Jacuinde,I.Mejía,J.Zuno-Silva, andE.Cardoso-Legorreta

PartIIICharacterizationofSteelsApplyingHeatTreatment

7ThermalBehaviorofanHSLASteelandtheImpactin PhaseTransformation:SubmergedArcWelding(SAW) ProcessApproachtoPipelines ............................................85

P.S.Costa,F.A.Reyes-Valdés,R.Saldaña-Garcés, E.R.Delgado,andA.Salinas-Rodríguez

8EffectofHydrogenonaMicroalloyedSteelPermeate .................99

D.C.RojasOlmos,S.C.CarranzaFlorida,J.A.OrtegaHerrera, M.A.DoñuRuiz,N.LópezPerrusquia, andM.ArredondoRamírez

PartIVCharacterizationofThinLayersandCoatings

9MechanicalPropertiesofSiO2 CoatingsforCorrosion Protectionof304StainlessSteel ..........................................109

J.ReyesMiranda,M.AguilarSánchez,E.GarfiasGarcía, D.Y.MedinaVelazquez,andÁ.deJ.MoralesRamírez

10SynthesisandPhysicalPropertiesCharacterizationof CdSe1 y Sy NanolayersDepositedbyChemicalBath DepositionatLow-TemperatureTreatment .............................117

J.E.Flores-Mena,J.I.Contreras-Rascón,J.Diaz-Reyes, andR.S.Castillo-Ojeda

PartVCharacterizationofMaterialsObtained byMechanicalMilling

11MagneticPropertiesandKineticofCrystallization inAmorphousGdx Sm1 x Co5 AlloysObtainedby MechanicalMilling .........................................................135

J.L.Hidalgo,J.T.Elizalde,andJ.A.Matutes

12MetallurgicalStudyofMechanicalMillingMechanismin EutecticNanopowders:TheRoleofHeterogeneities ...................145 H.Rojas-Chávez,M.L.Mondragón-Sánchez, J.A.Andraca-Adame,andD.Jaramillo-Vigueras

PartVICharacterizationofMaterialsforMedical Applications

13BiosynthesisofSilverNanoparticlesUsingExtractsof MexicanMedicinalPlants .................................................157

J.L.López,C.Baltazar,M.Torres,A.Ruíz,R.Esparza, andG.Rosas

14SynthesisandThermalCharacterization ofHydroxyapatitePowdersObtainedby Sol-GelTechnique ..........................................................167 Y.Jiménez-Flores,N.Camacho,J.B.Rojas-Trigos, andM.Suárez

PartVIICharacterizationofMaterialsforIndustrial Applications

15MicrowaveAssistedSol-GelSynthesis andCharacterizationofM–TiO2 (MDPt,Au)Photocatalysts .........183 R.Hernández,S.M.Durón-Torres,K.Esquivel, andC.Guzmán

16MicromachinedandCharacterizationofCooleda-Si:B:H MicrobolometerArrayintheTerahertzRegion ........................191 A.Orduña,C.G.Treviño,A.Torres,R.Delgado, andM.A.Dominguez

17InfluenceofDrillingParametersbyEDMontheHSLA SteelMicrostructure ........................................................201 L.M.Zúñiga,H.M.Hernández,E.E.Granda,W.N.P.Hung, andR.Muñoz

PartVIIICharacterizationofWeldingandJoining ofMaterials

18EvaluationofDistortioninWeldingUnionsof304 StainlessSteelwithEllipticTrajectoryUsingaWeldingRobot .......217 L.A.Carrasco-González,E.Hurtado-Delgado, andF.A.Reyes-Valdés

19WeldBeadGeometryofNi-BasedAlloyDepositedbyPTA ProcessforPipeConductionofShaleGas ...............................229 C.Echavarria-Figueroa,F.García-Vázquez, J.Ruiz-Mondragón,H.M.Hernández-García, D.González-González,andA.Vargas

PartIXCharacterizationofIntermetallicMaterials

20ChemicalReductionSynthesisofIronAluminumPowders ...........241 N.N.Zurita-Méndez,G.Carbajal-DelaTorre, L.Ballesteros-Almanza,M.Villagómez-Galindo, A.Sánchez-Castillo,andM.A.Espinosa-Medina

AuthorIndex ......................................................................251

SubjectIndex .....................................................................253

CharacterizationofSteelsUsedintheOil Industry

Thispartincludesthreechaptersrelatedtocharacterizationofsteelsofcommon useintheoilandpetrochemicalindustry.Thefirstchapterincludesamechanical andmicrostructuralcharacterizationofAPIX70steelafteranon-conventionalheat treatmentisapplied.AfterapplyingtheheattreatmenttoX70steel,ityieldedtensile propertiessimilartothoseexhibitedbyanX100steel.Thesebenefitsareobtained bytakingadvantageofthetemperatureatwhichtheNbCbegintosolubilize promotingpartialausteniticgraingrowthfollowedbyrapidcoolingsothata predominantacicularferritemicrostructureisobtained.Thesecondchapterisabout corrosioninhibitionofAPI X52pipelinesteelinchloridesolutionsaddingnonionicsurfactantevaluated byelectrochemicalimpedancespectroscopy(EIS)and potentiodynamicpolarizationcurves.Standardfreeenergycalculationsuggested thatsurfactantisadsorbedphysicallyintotheX52steelsurfaceandconsequentlya decreaseincorrosionrateisobserved.

Thethirdchaptershowsastudyonthemicrostructureandmechanicalproperties injoiningASTMA36structuralsteelweldedinmarineenvironmentatseveral depths(10,20,30,and40m).Theresultsshowthatthereisaninverserelationship betweentheincreaseindepthatwhichthe weldingisperformed andthemechanical properties.

APIsteels(X52andX70)evaluatedaresteelsofhighstrengthandhaveagood corrosionresistancewiththesuitablecathodicprotectionsystemandcoating.Both ofthemareusedinthetransportationofhydrocarbides.Ontheotherhand,ASTM A36steelisusedverycommonlyinstructuralmarineapplications.

Themaintechniquesusedinthecharacterizationofthesematerialsare:

•Scanningelectronmicroscopy(SEM).

•X-raydiffraction(XRD).

•Electrochemicalimpedancespectroscopy(EIS).

•Polarizationcurves.

•Opticalmicroscopy(OM).

•Mechanicaltests.

Chapter1

MechanicalandMetallurgicalProperties ofGradeX70SteelLinepipeProduced byNon-conventionalHeatTreatment

C.Natividad,R.García,V.H.López,L.A.Falcón,andM.Salazar

Abstract AnonconventionalheattreatmentinAPIX70steelsampleswascarried outbyheatingthesteelupto1050 ı Candholdingfor30minatthistemperature. Subsequently,thesampleswerecooledin waterandair.Therehasbeenrecentlya growingdemandforhigher-gradelinepipesthatcanhelptoreducethetotalcost oflonglinepipes.Theapplicationofhigh-strengthlinepipessuchasAPIX70 andX80gradeshasbeenincreasinginrecentyears.Theuseofhigh-strength linepipesteelsimprovestheefficiencyoftransportationbyenablinglargevolumes underhighinternalpressure.Increasingyieldstrengthandthereforethinnerwall thicknessenabletheindustrytoreducethecostsofallcomponentsthroughthe limitationofstringweight.Inthiswork,anAPIX70hasbeendevelopedthrough nonconventionalheattreatmenttocreatethesuitablemicrostructure(acicular ferrite)whichprovidesgoodtoughnessandsourservicepropertiesduetothebainite obtainedinthemicrostructure.Toassess theeffectoftheheattreatment,mechanical propertieswereevaluated.Theseresultswererelatedwiththemicrostructuresand precipitatedistributioninthesteel.

Keywords APIX70•Nonconventionalheattreatment•Acicularferrite• Bainite•Sourservice

C.Natividad( )•R.García•V.H.López. InstitutodeInvestigaciónenMetalurgiayMateriales (IIMM)delaUniversidad MichoacanadeSanNicolásdeHidalgo,Morelia,Michoacán,México e-mail: consnatividad@yahoo.com.mx

L.A.Falcón

FacultaddeMetalurgiadelaUniversidadAutónomadeCoahuila,Monclova,Coahuila,Mexico M.Salazar

InstitutoMexicanodelPetróleo,EjeCentralLázaroCárdenasNorte152,SanBartolo Atepehuacan,C.P.07730México,México

©SpringerInternationalPublishingSwitzerland2017 R.PérezCamposetal.(eds.), CharacterizationofMetals andAlloys,DOI10.1007/978-3-319-31694-9_1

1.1Introduction

Offshoreandgasexplorationandproductionismovingintowaterdepthsgreater than3000m,whicharechallengingthewell-establisheddesignsandpipesused. Pipesfortheseapplicationsareexposedtohighcollapsepressure,tohighaxial loads,andpartlytofatigueinthegirthwelds.Intheearly1960s,mediumcarbon steelwasthematerialusedinlinepipeindustry.Thetechnologicaldevelopmentin weldingprocesses,useofmicroalloying elementinsteel,and thermomechanical controlprocess(TMCP)haveenabledtheindustryinproducinghigh-strengthsteels, thereforemovingtolow-carbonsteelswithhighstrengthaswellasweldability. Thishasfurtherhelpedinreducingthespecificsteelconsumptioninoilandgas transportation.Thecurrentfocusonlesswallthicknessatstrengthlevelleadstothe useofX80andX100gradesofsteel[1–4].

MechanicalandcorrosionpropertiesofAPIX70areimprovedbytheadditionof alloyingandcontrolofparametersonTMCP,suchassoakingtemperature,rolling temperature,finishingtemperature,coolingrate,andcoolinginterrupttemperature [5–15].Sulfidestresscracking(SSC)isakindofhydrogen-relatedproblemof linepipesteelsfortransportationofcrudeoilandnaturalgascontaininghydrogen sulfide.Thedemandforhigh-strengthsteelforlinepipewithsourgasresistance hasincreased.Manufacturingthiskindofsteelpiperequiresastrictsteel-making practiceandacontrolledthermomechanicalschedulewithanadditionalaccelerated coolingprocedure.ItiswellknownthattheAPIX70steelissusceptibletocorrosion insolutionscontainingNaClandH2 S[16–19].Hydrogenuptakedecreasesthe tensilepropertiessuchasyieldstrength,ultimatestrength,andelongation[20] andcausescrackingknownashydrogen-inducedcracking(HIC).Withtheaimof improvingSSCresistanceofAPIX70steel,varioustechniquesduringsteel-making processesarerequiredsuchasadditionofproperalloyingelements,microstructure control,highcleanness,andCatreatment[1, 9–11, 21–24].

Amongvarioustypesofmicrostructure,acicularferritehasbeenknownasthe optimummicrostructurewhichhasexcellentcombinationofhighstrengthand goodtoughness,mainlyduetoitsrelativelyhighdensityofdislocationsandfinegrainednature[25–28].However,judiciousselectionofmicroalloyingelementsand optimizationofprocessparametersisessentialtoobtaintherequiredmicrostructure [29].Thecoarseferritegrainsandtherelativelylowdislocationdensityenhanced hydrogenbuildupinthestress-concentratedzoneaheadofthecracktip,facilitating decohesionandcrackingofparticlesinthiszone[30, 31].Therefore,mostof theAPIX70toX100gradeslinepipesteelsutilizetheacicularferritestructure toobtainthebalancedpropertiesrequiredforlinepipeapplications.However, acicularferriteinlinepipesteelsnucleatedmainlyatnucleationsitesofdislocation substructureswithindeformedaustenitegrain,unlikethebainite,whichnucleatedat grainboundaryofaustenite.Increasedacicularferritecontentinthemicrostructure improvedHICresistanceandSSCresistance,whilebainiteandmartensite/austenite constituentsareharmfulfortheresistanceinsourenvironments[14, 32].Thesteels withafine-grained,bainite-ferritestructurepossessamuchbettercombination

ofstrengthandSCCresistancethanthosewithaferrite C pearlitestructure.An increaseinthepearlitecontentinthemicrostructurehasadetrimentaleffectonthe SCCresistanceoflinepipesteelswithaferrite C pearlitestructure[33].

Becauseishasgreaterrequirementsforweldinghigh-strengthsteels,suchasX80 andX100,itproposedtoobtainasteelofequalorhigherstrengththanX80froman APIX70steelbyapplyinganonconventionalheattreatmentinordertoachievethe acicularferrite-dominatedmicrostructure.

1.2Experimental

ThematerialusedinthepresentstudywasAPI5LX70pipewithanoutside diameterof740mmandawallthicknessof11.35mm.Thechemicalcomposition ofthissteelisshowninTable 1.1.Specimensof 70 mm 150 mmwereheat-treated at1050 ı Cfor30minandcooledinwaterorair.Heat-treatedandas-receivedplates weremachinedindogboneshapeaccordingtoASTMA370[34]fortensiletesting. ImpacttestwithCharpyV-notchspecimens(CVN 10 mm 10 mm 55 mm)was carriedoutat0 ı CaccordingtoASTME23[35].

Microhardnessmeasurementswereconductedintheas-receivedsteelandin theheat-treatedsamples.Theas-receivedsteelwasetchedfor15sin2.5%nital. Microstructuralanalysiswascarried outbyoptical(OM)andscanningelectron microscopy(SEM).

1.3ResultsandDiscussion

Figure 1.1 showsthemicrostructureoftheAPIX70steelinthedifferentconditions: as-received,nonconventionalheat-treatedwater-cooled,andheat-treatedair-cooled. Intheas-receivedmaterial,Fig. 1.1ashowsamicrostructurecharacterizedby polygonalferritegrains(F)andperlitebands(P),typicalofthistypeofsteel.

Figure 1.1bshowsamicrostructurecomposed offineacicularferrite(AF)and bainite(B)whichwastheresultofthenonconventionalheattreatmentwhenthe samplewascooledrapidlywithwater.

ThistypeofmicrostructureispreferredtoreducethesusceptibilitytoSCC,as reportedbyreferences[32, 33].Figure 1.1crevealsthatwhenthesteelwascooled

Table1.1 ChemicalcompositionofX70steel(wt.%)

Fig.1.1 OpticalimagesofthemicrostructureofAPIX70steel:(a)as-received,(b)heat-treated water-cooled,and(c)heat-treatedair-cooled.F,ferrite(grayphase);P,perlite(darkphase);AF, acicularferrite;andB,Bainite

moreslowly,themicrostructureissimilartotheoneobtainedbyanormalizing heattreatment:polygonalferriteandperliteareaswithlongergrainsizethanthe as-receivedmaterial.

Figure 1.2 showsthestress-straincurvesobtainedfromAPIX70withand withoutheattreatment.Tensilepropertiesandimpactresultsaresummarizedin Table 1.2 alongwithimpactresults.

Theresultsobtainedbytensiletestsshowthatheattreatmentwithwatercoolingleadstohighertensilestrengthasisreportedby[1–4].Althoughductility decreased,ithasbeenreportedthatthemicrostructureofacicularferriteandbainite obtainedwiththenonconventionalheattreatmentisresistanttoSCC[33]butnot forsourenvironments[14, 32].Accordingtotheliterature,fortheimpacttest, theminimumimpactenergyrequirementsforadesignfactorof0.625is48J [36];inthepresentwork,itwas60Jofenergyabsorbed.Inthefracturesurfaces analyzedbySEM,itisevidentthatbothspecimensexhibitedakindofductile fracture,sincetheyshowedmicro-plasticdeformation,nucleation,andcoalescence ofmicrovoidsaroundnonmetallicinclusions(Fig. 1.3a).Theseinclusionswere

Elongation(%)

Fig.1.2 Stress-elongationcurvesforAPIX70steel

Table1.2 SummaryofmechanicalpropertiesobtainedforAPIX70steelwithandwithout heattreatment

UTS ultimatetensilestrength, YS yieldstrength, RUPTURE fracturestressorrupturestrength, EL elongation, EA energyabsorbed

identifiedbyenergy-dispersiveX-rayspectroscopy(EDX),attachedtotheSEM,as wellasiron-manganesesulfides.Figure 1.3dshowstheEDXspectracorresponding totheseinclusions.TheinclusionsaremainlycomposedbyFe,Mn,S,Mg,andCa. Theseelementscanform(Fe,Mn)S,MnS,andglobularinclusionsorFe-Mn-Sas reportedinliterature[37].

ThelimitsofhardnessrecommendedforavoidingSSCareintherangeof20–30 HRC(240–250Hv),butthe22HRCanditsequivalentintheotherhardnessscale isthemorecommonreportedbythestandard[36].Althoughthelimitsofhardness arenotalwaysaneffectiveguidefortheselectionofmaterial,theselimitsarethe morecommonrequirementsfortheline-pipesinsourservice.Theresultsofthe hardnessmeasurementsobtainedarepresentedinFig. 1.4.Hardnessobtainedfrom heat-treatedwater-cooledsamplesincreasedinarangeof280–310Hv.Fortheroom temperature-cooledspecimen,thehardnessdecreasedfrom180to200Hv,andfor theas-receivedspecimen,itshardnesswas200–220Hv.

Fig.1.3 SEMmicrographsobtainedfromfracturedsampleswater-cooledbytensiletest,(a) showsthetypicalfractureductile,(b and c)showsaglobularinclusion,and(d)X-raycompositionalspectrumofinclusionsisshowedin(c)

Fig.1.4 Hardness measurementsinas-received andheat-treatedAPIX70 steel

1.4Conclusions

HeattreatmentappliedtoanAPI5LX70pipesteelto1050 ı Cfor30minfollowing water-coolingyieldsacicularferriteandbainitemicrostructurewithmechanical strength250MPahigherthanas-receivedsteel.Althoughhardnessincreasedwith heat-treating,theaveragevalueisbelowthepermissiblelimitforservice.Theresults obtainedwiththenonconventionalheattreatmentyieldsimilarpropertiesasAPI 5LX120steel.However,thehighhardnessofthissteelpreventsitsusewithsour hydrocarbons.Thefindingsofthisstudyimplythatispossibletoreducethewall thicknessoflinepipestotransportsweetcrudeoil.

Acknowledgements TheauthorswouldliketothankCONACYTforsponsoringthepostdoctorate stayofC.Natividadandfinancialsupportofthisinvestigation.

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CorrosionInhibitionofX52PipelineSteel inChlorideSolutionsUsingNonionicSurfactant

Abstract TwoconcentrationsofNPE-4nonionicsurfactantandcorrosioninhibitor (CI)commerciallyavailablewereaddedtoNaCl(2.45%and3%)andoceanwater solutions(OWS)inordertostudythecorrosionprocessofAPIX52pipeline steel.CorrosioninhibitionofX52pipelinesteelinchloridesolutionswasevaluated byusingelectrochemicalimpedancespectroscopy(EIS)andpotentiodynamic polarizationcurves.EISanalysesshowedthat3%NaClwasthemorecorrosive solutionforX52steel.AddingCIto3%NaClsolutionimprovesthecorrosion resistanceofX52steel;however,addingCItoOWS,thecorrosioncontrolofX52 steelwasmoreevidentpreventingthepitting,saltsembedding,andcorrosionunder deposits.X52steelexposuretosolutionsaddingsurfactantascorrosioninhibitor afterhavingbeenevaluatedthroughpolarizationcurvesdisplayedlowcorrosion rates(0.88mm/year).Standardfreeenergycalculationsuggestedthatsurfactantis adsorbedphysicallyintotheX52steelsurface.Meanwhile,itwasobservedthatCI wasmoredifficulttoadsorbonX52steelsurface,andconsequentlycorrosionwas higherthanaddingsurfactanttochloridesolutions.

Keywords X52steel•Surfactant•Corrosion inhibitor•Polarizationcurves• Electrochemicalimpedancespectroscopy(EIS)

2.1Introduction

Inoilindustry,theinternalcleaningofpipelinesiscarriedoutusingacidenvironmentlikeinhibitedHCl[1–4].Thistypeofsolutioniswidelyrecommendedas thecheapestwaytodissolvedepositofcarbonatecompoundsinsidethepipelines andincludesasurfactantthatactsasanadditivecapableofinhibitingthecorrosive effectofHCl.Migahedetal.studiedtheinhibitionprocessofinternalcorrosion ofpipelinesusingnonionicsurfactantsinthepresenceof1MHClsolution[1].

L.M.Quej( )•A.Contreras•J.Aburto

InstitutoMexicanodelPetróleo,EjeCentralLázaroCárdenasNorte152, Col.SanBartoloAtepehuacan,C.P.07730México,Mexico

e-mail: lquej@imp.mx

©SpringerInternationalPublishingSwitzerland2017 R.PérezCamposetal.(eds.), CharacterizationofMetals andAlloys,DOI10.1007/978-3-319-31694-9_2

Migahed’sworkssuggestedthatsurfactantsactasgoodcorrosioninhibitorsusing lowconcentrationsandtheadsorptionofsurfactantmoleculesonsteelincreases withincreasingthetensioactivemolecularsizethanforhighconcentrationsand lowmolecularsize.Anotherworkevaluatedthecorrosioninhibitionofmildsteel usingnonionicsurfactantsinthepresenceof0.05MNaClsolutionwithrotating cylinderelectrodeat1000rpm[5].Thisworkreportedthatthesurfactantisadsorbed onmetalsurfacesactingasacorrosioninhibitor.However,theinhibitoryaction dependssignificantlyfromthecriticalmicellarconcentration(CMC)[6, 7].Another studycharacterizedtheprotectiveeffectofcationicsurfactantsoncarbonsteel surfacesinthepresenceof1MHCl[8].

Theresultsofthisstudyrevealedthattherealandimaginaryimpedanceresponse washigherwithincreasingthedosageofsurfactant.However,theelectricaldouble layercapacitancevalueshavenegativeeffectswhenthesurfactantconcentration isincreased,duetotheadsorptionofsurfactantmoleculesonmetalsurface.Itis importanttomentionthatothers’worksconsideredtheuseofanionic,cationic,and nonioniccompoundsthatinhibitthesteelcorrosionprocessinacidsolutions[9–12]. Moreover,theoilrecoveryinMéxicoiseverytimemoredifficultduetoheavyand extra-heavypetroleumproduction.Inaddition,thedepositedsediment,solids,and saltsdissolvedcanprovoketheincreaseoftheviscosityinthepetroleum.

Theproductionofheavyandextra-heavyoilpresentsimportantchallengesthat requiresignificanttechnologicaldevelopmentsintheoilindustry.Also,thehigh viscosityofthepetroleumcanprovokecorrosionbyerosion.Itiswellknown thatsurfactantsareusedforreducingtheviscosityintheheavyandextra-heavy petroleum[13, 14].Thus,thesurfactantdosageintoheavypetroleumisableto improveitsfluidityandeasytransportation.Inthisway,thechemicalpropertiesof nonionicNPE-4surfactanthavebeenappliedinheavyandextra-heavypetroleum production[13].Accordingtopreviouslydescribed,theelectrochemicalstudyof surfactantsanditsinhibitorypropertiesincontactwithsalts,likechloridesolutions orcarbonatecompoundsthatarefoundinsidethepipelineduringtheheavyand extra-heavypetroleumproductionandcanberelatedtotheembeddingorcorrosion underdepositsgeneratedontheinternalpipelinesurface,isofgreatinterest.

Inthepresentwork,inhibitionofX52pipelinesteelcorrosioninthepresence ofoceanwaterandtwoconcentrationsofNaClsolutionsaswellastwodosagesof nonionicNPE-4surfactantandcorrosioninhibitor(CI)commerciallyavailablewas studied.Tocarryoutthisstudy,theelectrochemicalimpedancespectroscopy(EIS) andpotentiodynamicpolarizationcurveswereproposedbecauseofitsusefulness andtherewasconsiderationtostudythecorrosionprocessinshorttime.First,the EIScharacterizationofthepipelinesteelwasperformedinanaqueoussolution mainlycomposedofoceanwatersolution(OWS)andtwoconcentrationsofNaCl asablank.EISanalysiswascarriedoutusingequivalentcircuits,whereitispossible todiscussthemodificationsoftheEISdiagramswiththepresenceofdifferent stepsoccurringsimultaneously.Basedonpolarizationcurves,theadsorptionand inhibitionpropertieswereevaluated.Theelectrochemicalbehaviorwasrelatedto themodificationofthestepsinvolvedinthecorrosionprocessofthepipelinesteel inthechloridesolutions,obtaininggoodinhibitorypropertiesforthesurfactant.

2.2Experimental

2.2.1SteelUsed(Electrode)

ArodfromX52pipelinesteelwith0.5cm2 ofexposurearealikeworkingelectrode (WE)wasused.Rodgraphiteasanauxiliaryelectrode(AE)andasaturatedcalomel electrode(SCE)asareferenceelectrodewereused.Inallmetalliccoupons(WE), theexposedsurfaceswerepreparedbymechanicalgrindingwithupto600-grit water-cooledSiCpaperssoastoobtainareproduciblesurfaceandsubsequently cleanedinanultrasonicbathfor1mininacetone.Nominalchemicalcomposition ofX52pipelinesteelisshowninTable 2.1

2.2.2TestSolutions

TheNaClcorrosivesolutionstestswerepreparedasfollow:2.45gand3.0gofNaCl wereweighedanddissolvedin1000mLofdeionizedwater.OWSwasprepared accordingtoASTMD1141standard[15].Fortheelectrochemicalevaluation, aconstantvolumeof100mLofeachblankwasused.Theformerdissolution ofnonionicsurfactantandCIcommerciallyavailablewaspreparedinisopropyl alcoholtoreach30,000mg/L(solutionA).Inthisway,solutionAwasusedto prepare30and60mg/Lofeachmolecule.Theelectronicstructure,mesoscopic simulations,andanalyticalcharacterizationofNPE-4moleculewerereportedin previouswork[13].

2.2.3ElectrochemicalEvaluations

Allelectrochemicalcharacterizationswerecarriedout inanelectrochemicalcell withthree-electrodearrangement.Electrochemicaltestingwasperformedina potentiostat-galvanostatAUTOLABmodelPGSTAT30atopen-circuitpotential (OCP).TheEIStestswereobtainedusing10mVofperturbationand10kHzto 10mHzoffrequencyafter1hofexposureofworkingelectrodeat30ı Cand600rpm inthecorrosivesolutions.Potentiodynamicpolarizationcurvesweremeasuredby potentialscanningfrom ˙300 mVvs.OCPatasweeprateof1mV/s.

Table2.1 ChemicalcompositionoftheAPIX52pipelinesteel(wt%)

2.3ResultsandDiscussion

2.3.1Electrode

TheelectrodesusedintheelectrochemicalevaluationsweremachinedfromAPI X52pipelinesteel.Thissteelhasthemicrostructuretypicaloflow-carbonsteels, whichconsistedofperlite(darkgrains)andferrite.Theaveragegrainsizeinthis steelwasaround10–20 masisshowninFig. 2.1.Low-carbonsteelstendtohave aferrite-perlitestructurecontaining littleperliteinthegrainboundaries mainly.

2.3.2ElectrochemicalImpedanceSpectroscopy(EIS)

NyquistplotsforX52steelexposedtothethreesolutionsareshowninFig. 2.2. Significantchangestowardlowrealandimaginaryimpedancevaluesareobserved intheprofileobtainedin3%NaCl.Meanwhile,OWSshowedanincreasein impedancevalues.Inaddition,thepresenceofinductiveloopatlowfrequencies isobtainedinallelectrolytes.

Recently,itwasreportedthattheinductivebehaviorcanberelatedtothe adsorptionoftheneutralizingamineson1018steelsurface[16].Inthepresentstudy, thisbehaviorisassociatedwiththepittingcorrosionandmetallicdissolutionofX52 pipelinesteelbychlorideenvironments.Asafirstapproachforfittingtheimpedance diagramsshowninFig. 2.2,aRandlesequivalentcircuitwasusedomittingthe

Fig.2.1 TypicalmicrostructureofAPIX52steel

Fig.2.2 NyquistdiagramsofX52steelexposedtothreechloridesolutionsobtainedafter1h,at 30 ı Cand600rpm

inductiveresponseandusingBoukampprogram[17].Thisequivalentcircuitis relatedtothecorrosionmechanismoccurringatthedifferentinterfacesinvolving solutionresistance(Rs ),corrosionproductproperties(Rcp and Ccp ),chargetransfer resistanceassociatedwithX52steeloxidation(Rct ),andcapacitancecontributionof theelectricaldoublelayer(Cedl )onX52steel/chloridesolutioninterfaceasisshown inTable 2.2.Thecapacitancevalueswereevaluatedfromconstantphaseelement (CPE: Qi ,specifically Y0i ),usingtheequationreportedinpreviouswork[18].

Theionicconductivityofthechloridesolutionsintheabsenceofsurfactant andCIissimilar(Rs 10 cm2 ).Ithadbeenestablishedthatanincreaseinthe pseudocapacitancevaluescanberelatedwiththedecreaseofresistanceproperties andtheformationofironoxideswithaporousandnon-protectivenatureonthe metalsurface[19].Inthismanner,thepseudocapacitancevalues(C )obtainedfor 3%NaClcanberelatedtotheformationofmoreactiveironoxidesonX52steel surfacethanX52exposedto2.45%NaClandOWS.Thisbehaviorisinagreement withthequalitativeanalysisofNyquistdiagramsshowedinFig. 2.2.Besides,itcan becorroboratedthattheporousnatureofthecorrosionproductsformedontheX52 steelinchloridesolutionsgiven n values(n < 1).The Ecorr valuesforeachsystem wereasfollows: 0:610 Vvs.SCEfor3%NaCl, 569 Vvs.SCEfor2.45%NaCl, and 0:567 Vvs.SCEforOWScorroboratingthat3%NaClsolutionwasmore activetothecorrosionprocess.

Thepresenceofsurfactanteliminated theinductiveloopassociatedtopitting corrosionandmetallicdissolutionofX52steelexposedtochlorideenvironments. Thus,abeneficialeffectof60mg/LnonionicNPE-4surfactantin2.45%NaCl (Fig. 2.3a)and30mg/LnonionicNPE-4surfactantin3%NaCl(Fig. 2.3b)was

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H-B—Histoire Diplomatique de Frédéric II. 4to. Paris, 1859.

H-B La Vie de Pierre de la Vigne. 8vo. Paris, 1865

I--A Le Livre de l’Agriculture. 2 vols. 8vo. Paris, 1866.

I--B Traité des Simples 3 vols 4to Paris, 1877

I-H Description de Palerme au X Siècle. 8vo. Paris, 1845.

I-K Histoire des Berbères 4 vols 8vo Alger, 1856

J Curiosités de l’Histoire du Moyen Age. 12mo. Paris, 1859.

J Histoire de la Corse 2 vols 8vo Paris, 1833

J Histoire de la Chimie. 2 vols. 8vo. Paris, 1891.

J P Voyage en Espagne. 2 vols. 8vo. Paris, 1891.

J—Études sur l’Arabie 8vo Paris, 1839

L B Le Coran Analysé. 8vo. Paris, 1878.

L—Le Droit du Seigneur 8vo Paris, 1878

L Mœurs et Usages au Moyen Age. 8vo. Paris, 1878.

L—Sciences et Lettres au Moyen Age. Folio. Paris, 1877.

L Historial du Jongleur. 8vo. Paris, 1829.

L P—Les Arabes en Sicile et en Italie. 8vo. Paris, 1867.

L R Voyage dans l’Arabie Heureuse. 12mo. Paris, 1725.

L—Histoire du Bas Empire. 13 vols. 8vo. Paris, 1820.

L B La Civilisation des Arabes. 8vo. Paris, 1884.

L Histoire Secrète des Couvents. 12mo. Bruxelles.

L Abul Casis 8vo Paris, 1874

L Histoire de la Médecine Arabe. 2 vols. 8vo. Paris, 1876.

L La Satire en France au Moyen Age 8vo Paris, 1877

L La Grande Grèce. 12mo. Paris, 1881.

L La Divination 8vo Paris, 1875

L Les Premières Civilisations. 8vo. Paris, 1874.

L La Grèce et l’Orient en Provence 12mo Paris, 1878

L La Kabylie et les Coutumes Kabyles. 3 vols. 8vo. Paris, 1872.

L Essai Philosophique sur le Monachisme 12mo Paris, 1777

L Histoire de l’Inquisition d’Espagne. 4 vols. 8vo. Paris, 1817.

L-L—Basques et Navarrais 8vo Paris, 1878

L Documents sur le Cid. 8vo. Paris, 1860.

M—Les Prêtres et les Moines à travers les Ages 8vo Paris, 1857

M Histoire des Sultans Mamlouks. 2 vols. 4to. Paris, 1837.

M—Traité des Monnaies Musulmanes. 8vo. Paris.

M Histoire de la Langue Romane. 8vo. Paris, 1840.

M—Moines et Nonnes 12mo Paris, 1881

M L’Afrique. 3 vols. 4to. Paris, 1667.

M—Les Signes Numéraux chez les Peuples de l’Antiquité et du Moyen Age. 4to. Rome, 1864.

M La Piété du Moyen Age. 8vo. Paris, 1855.

M L Histoire de l’Isle de Chypre. 3 vols. 8vo. Paris, 1855.

M L Traités de Paix des Arabes du Moyen Age Folio Paris, 1866

M Croyances et Légendes de l’Antiquité. 8vo. Paris, 1863.

M Essai sur les Légendes Pieuses du Moyen Age 8vo Paris, 1843

M Histoire des Religions de la Grèce Antique. 3 vols. 8vo. Paris, 1857.

M La Magie et l’Astrologie 12mo Paris, 1860

M Zoroastre. 8vo. Paris, 1857.

M La Vie au Temps des Cours d’Amour 8vo Paris, 1876

M La Vie au Temps des Trouvères. 8vo. Paris.

M Histoire de Don Pedro I 12mo Paris, 1865

M Histoire des Croisades. 4 vols. 8vo. Paris, 1867.

M—Histoire de France 19 vols 8vo Paris, 1870

M Histoire des Races Maudites de la France et de l’Espagne. 2 vols. 8vo. Paris, 1847.

M—Le Pays Basque 8vo Paris, 1859

M Histoire de Malte. 2 vols. 8vo. Bruxelles, 1841.

M—-Histoire Littéraire des Troubadours. 3 vols. 12mo. Paris, 1774.

M Histoire de Sardaigne. 2 vols. 8vo. Paris, 1825.

M-I-D Voyage en Sicile. 8vo. Paris, 1846.

M S-Y Histoire des Comtes de Toulouse. 4 vols. 8vo. Paris

M Histoire des Mathématiques. 2 vols. 4to. Paris, 1758.

M Légendes Historiques Siciliennes. 8vo. Palermo, 1890.

N—Description de l’Arabie 4to Paris, 1779

O Des Effets de la Religion de Mohammed. 8vo. Paris, 1810.

P—Histoire de la Soie 2 vols 8vo Paris, 1862

P Femmes Arabes. 8vo. Paris, 1858.

P—Histoire des Antiquités de la Ville de Nismes. 8vo. Nismes, 1842.

P Histoire des Albigeois 3 vols 8vo Paris, 1870

P La Religion des pré-Israélites. 8vo. Utrecht, 1862.

P Voyage en Barbarie 2 vols 8vo Paris, 1789

P ’A La Décoration Arabe. Folio. Paris, 1885.

Q Le Droit Musulman 2 vols 8vo Paris, 1871

R Histoire Générale de l’Architecture. 2 vols. 8vo. Paris, 1859.

R Extraits des Historiens Arabes relatifs aux Croisades 8vo Paris, 1829

R L’Art Militaire chez les Arabes au Moyen Age. 8vo. Paris, 1848.

R Les Invasions des Sarrasins en France 8vo Paris

R Monumens Arabes, Persans, et Turcs. 2 vols. 8vo. Paris, 1828.

R—Notice sur Mahomet 8vo Paris, 1860

R Relation des Voyages dans l’Inde. 2 vols. 18mo. Paris, 1845.

R—Averroes et l’Averroïsme 8vo Paris, 1852

R Dictionnaire des Fiefs et des Droits Seigneureaux. 4to. Paris, 1765.

R Histoire de la Médecine. 2 vols. 8vo. Paris, 1846.

R Histoire d’Espagne. 9 vols. 8vo. Paris, 1839.

R Les Irrigations. 3 vols. 8vo. Paris, 1888.

R La Papauté au Moyen Age. 8vo. Paris, 1881.

R S-H Histoire d’Espagne. 14 vols. 8vo. Paris, 1859.

S Notice sur Gerbert. 8vo. Paris, 1850.

S-P—Histoire Littéraire des Troubadours 3 vols 12mo Paris, 1774.

S Essai sur les Écoles Philosophiques chez les Arabes. 8vo Paris, 1842

S Le Bouddhisme et ses Origines. 8vo. Paris, 1874.

S L’Islam et son Fondateur 8vo Neuchatel, 1844

S Histoire Générale des Arabes. 2 vols. 8vo. Paris, 1877.

S Matériaux pour servir à l’Histoire Complète des Sciences Mathématiques chez les Orientaux 2 vols 8vo Paris, 1845

S Mémoire sur les Systèmes Géographiques des Arabes. 8vo. Paris, 1842.

S Prolégomènes des Tables Astronomiques d’Oloug Beg 8vo Paris, 1853

S Traité des Instruments Astronomiques des Arabes. 4to. Paris, 1833.

S—Histoire de la Littérature du Midi de Europe 4 vols 8vo Paris, 1829.

S Républiques Italiennes du Moyen Age. 10 vols. 8vo. Paris, 1840.

S Description du Pays de Magreb. 8vo. Alger, 1839.

T Histoire des Chérifs. 4to. Paris, 1667.

V Histoire Critique de l’École d’Alexandrie. 3 vols. 8vo. Paris, 1846.

V Histoire des Chevaliers Hospitaliers 5 vols 8vo Amsterdam, 1732

V Histoire des Arabes et des Mores d’Espagne. 2 vols. 8vo. Paris, 1857.

V Scènes des Mœurs Arabes 8vo Paris, 1834

V Histoire de Gregoire VII. 8vo. Paris, 1874.

V Tableau de la Littérature au Moyen Age 8vo Paris, 1878

V Études sur la Loi Musulmane Législation Criminelle. 8vo. Paris, 1842.

W—L’Algèbre d’Omar Al-Khayymi 8vo Paris, 1857

W Mémoire sur la Propagation des Chiffres Indiens. 8vo. Paris, 1863.

W—Recherches sur l’Histoire des Sciences Mathématiques chez les Orientaux. 8vo. Paris, 1860.

W Sur l’Introduction de l’Arithmétique en Occident 4to Paris, 1859

Z Les Colliers d’Or. 8vo. Paris, 1876.

Z Entretiens sur l’Histoire du Moyen Age 12mo Paris, 1865

Z Histoire d’Allemagne. 7 vols. 8vo. Paris, 1872.

SPANISH.

A Anales de Aragon 2 vols Folio Salamanca, 1684

A Varias Antigüedades de España. 4to. Amberes, 1614.

A Inscripciones Arabes de Granada 4to Granada, 1877

A S Las Siete Partidas. 3 vols. 4to. Madrid, 1807.

A Tradiciones Vasco-Cántabras 8vo Tolosa, 1866

A M Nobleza de Andalucia. Folio. Sevilla, 1581.

A Nuevos Paseos por Granada 2 vols 12mo Granada, 1820

B Ultimos Sucesos del Reino de Granada. 8vo. Madrid, 1868.

B Historia de los Trovadores 6 vols 8vo Madrid, 1878

B Los Reyes Catolicos. 2 vols. 8vo. Madrid, 1894.

B Historia de los Reyes Catolicos 2 vols 4to Sevilla, 1870

B Coronica de los Moros de España. Folio. Valencia, 1618.

B—Xativa 8vo 1857

C De la Agricultura Española. 16mo. Valladolid, 1868.

C—Antigüedades de Sevilla Folio Sevilla, 1634

C Discursos Historicos sobre Murcia. Folio. Murcia, 1775.

C—Ensayo Historico sobre los diversos generos de Architectura en España. 8vo. Madrid, 1848.

C Cronica de Don Alvaro de Luna. Folio. Madrid, 1784.

C—Historia de los Arabes en Murcia. 8vo. Palma, 1845.

C Z Tratado de Numismatica Arabigo-Española. 4to. Madrid, 1879.

C—Historia de Segovia. Folio. Madrid, 1640.

C Historia de la Dominacion de los Arabes en España. 2 vols. 4to Madrid, 1820

C Monumentos Arabes. 4to. Madrid, 1878. Cronicas de los Reyes de Castilla 3 vols 8vo Madrid, 1875

D Historia del Reyno Balearico. 3 vols. 4to. Palma, 1840.

D C La Expulsion de los Moriscos 8vo Madrid, 1889

D P Anales de Cataluña. 3 vols. Folio. Barcelona, 1709.

D R El Arte Latino-Byzantino 4to Madrid, 1861

D R Historia de los Judios de España. 3 vols. 8vo. Madrid, 1876.

D R Inscripciones Arabes de Cordoba y Sevilla 8vo Madrid, 1879

D R Sevilla Pintoresca. 4to. Sevilla, 1844.

D R—Toledo Pintoresca 4to Madrid, 1845

D V Anales de la Inquisicion. 8vo. Madrid, 1868.

D S—Poesía y Arte de los Arabes en España y Sicilia 3 vols 12mo. Madrid, 1872.

D Historia de los Condes de Barcelona. Folio. Barcelona, 1603.

D—Memorias de Zamora. 4 vols. 8vo. Madrid, 1883.

E Paseos por Granada. 2 vols. 8vo. Granada, 1814.

E—Historia de Valencia. 2 vols. Folio. Valencia, 1610.

F Historia del Cardenal Ximenes. 8vo. Lyons, 1712.

F España Sagrada. 51 vols. 4to. Madrid, 1754.

G Historia de España. 4 vols. 8vo. Madrid, 1844.

G Compendio Historial de las Chronicas. 2 vols. Folio. Barcelona, 1628.

G-M Historia del Rey Don Jayme I de Aragon Folio Valencia, 1584

G Historia de Navarra. 4to. Pamplona, 1628.

G X Memorable Expulsion de los Moriscos de España. 4to. Pamplona, 1613.

H M—Guerra de Granada contra los Moriscos. 4to. 1776.

I-A Descripcion del Reino de Granada 8vo Madrid, 1860

J Condicion Social de los Moriscos de España. 8vo. Madrid, 1857.

J Anales de Jaen y Baeza 4to Matriti, 1654

L-A El Libro del Viajero en Granada. 16mo. Granada, 1843.

L-A Historia de Granada 2 vols 8vo Paris, 1852

L-A Inscripciones Arabes de Granada. 8vo. Madrid, 1859.

L Historia General de España 6 vols 4to Barcelona, 1882

L Los Reyes Nuevos de Toledo. 4to. Valencia, 1698.

M—Cordova 4to Madrid, 1855

M Sevilla y Cadiz. 4to. Madrid, 1856.

M—Historia General de España 2 vols Folio Madrid, 1650

M-C Historia de la Rebelion y Castigo de los Moriscos. 4to. Madrid, 1797.

M R—Obras. 8vo. Paris, 1844.

M Historia Critica de España. 20 vols. 4to. Madrid, 1787.

—— Memorial Histórico Español. 21 vols. 4to. Madrid, 1851–1889.

Memorias de la Real Academia de Historia. 11 vols. 4to. Madrid, 1796–1888.

M-V La Monarchia Asturiana. 4to. Madrid.

M-G Historia de Jerez de la Frontera. 2 vols. 4to. Jerez, 1888

M F De los Trovadores en España. 8vo. Barcelona, 1861.

M Rodrigo el Campeador 4to Madrid, 1857

M Memorias del Rei Alonso el Sabio. Folio. Madrid, 1777.

M Coronica General de España 15 vols 4to Madrid, 1791

M Historia de Ronda. 4to. Ronda, 1867.

M G—Historia del Alzamiento de los Moriscos 12mo Madrid, 1861.

N Chronica de los Reyes Catholicos. Folio. Valladolid, 1565.

N C—Coronica de los Reyes de Castilla. Folio. Madrid, 1665.

O H Tradiciones de Toledo 12mo Madrid, 1880

O-H Granada y sus Monumentos Arabes. 8vo. Malaga, 1875.

O Almeria Ilustrada Folio Almeria, 1699

P Historia Eclesiastica de Granada. Folio. Granada, 1638.

P M Granada 4to Madrid, 1850

R D Museo Español de Antigüedades. 9 vols. Folio. Madrid.

R La Castilla 4to Madrid, 1792

R Historia de Ronda. 16mo. Ronda, 1873.

R Malaga Musulmana 4to Malaga, 1880

R Historia de Toledo. 2 vols. Folio. Madrid, 1659.

S Estudio sobre la Invasion de los Arabes en España 8vo Madrid, 1892

S M Cronica de la Casa de los Ponces de Leon. 4to. 1620.

S M—Cronica del Gran Cardenal de España. Folio. Toledo, 1725.

S Chronica de Don Alonso VII. Folio. Madrid, 1600.

S Historia de los Reyes de Castilla y Leon. Folio. Pamplona, 1634.

S Leyendas Historicas Arabes 8vo Madrid, 1858

T Historia de la Civilizacion Española. 4 vols. 12mo. Madrid, 1840.

T Historia de las Ordenes Militares 4to Madrid 1629

V Monarchia Asturiana. 4to. Madrid.

V Los Euskaros 8vo Barcelona, 1879

V Principios del Reyno de Portugal. 4to. Barcelona.

Z—Anales de Sevilla 5 vols 4to Madrid, 1796

Z Anales de Aragon. 7 vols. Folio. Zaragoza, 1610.

PORTUGUESE.

B—Rainhas de Portugal 2 vols 8vo Lisboa, 1878

B Historia da Poesia Popular Portuguesa. 12mo. Porto, 1867.

B B—Monarchia Lusitana 8 vols Folio Lisboa, 1690

Cancioneirinho de Trovas Antigas. 12mo. Vienna, 1857.

D S—Colecçao de Livros Ineditos de Historia Portuguesa 5 vols. Folio. Lisboa, 1790.

D S Vestigios de la Lingua Arabica em Portugal. 8vo. Lisboa, 1789

E Historia de Portugal. 2 vols. 8vo. Lisboa, 1876.

H Historia da Inquisiçao em Portugal 3 vols 12mo 1874

H Historia de Portugal. 2 vols. 8vo. Lisboa, 1880.

N L Chronicas dos Reis de Portugal 4 vols Lisboa, 1774

ITALIAN

A Italia nel Medio Evo. 8vo. Alba, 1892.

A Codice Diplomatico di Sicilia 6 vols 4to Palermo, 1789

A Biblioteca Arabo-Sicula. 3 vols. 8vo. Torino, 1880.

A I Diplomi Arabi Folio Firenze, 1863

A Ricordi Arabici. 8vo. Genova, 1873.

A Solwan el Mota 12mo Firenze, 1851

A Storia dei Mussulmani di Sicilia. 3 vols. 8vo. Firenze, 1854.

A Un Periode delle Istoriæ Siciliane 8vo Panormo, 1842

B Storia della Letteratura Araba sotto il Califato. 2 vols. 8vo. Firenze, 1846.

B L’Ultimo dei Trovatori in Sicilia 12mo Palermo, 1874

B Gli Arabi in Italia. 8vo. Torino, 1838.

B Opere 2 vols 8vo Lipsiæ, 1830

C Ricerche sui Trovatori. Folio. Modena, 1844.

C—Sardegna e Corsica 8vo Milano, 1877

C I Diplomi Greci ed Arabi. Folio. Palermo, 1868.

D R—Collectio Salernitana 5 vols 8vo Napoli, 1852

F Storia degli Antichi Romanzi di Cavalleria. 4 vols. 8vo. Milano, 1828.

G Opere. 16 vols. 8vo. Firenze, 1853.

G Istoria del Regno di Napoli 8 vols 8vo 1882

G Storia d’ Italia. 6 vols. 8vo. Parigi, 1837.

M Storia di Sardegna 8vo Firenze, 1858

M Storia degli Arabi. 4 vols. 12mo. Venezia, 1753.

M Storia delle Invasioni degli Arabi in Sardegna 8vo Cagliari, 1861

M Descrizione di Palermo Antico. 8vo. Palermo, 1827.

M Annali d’ Italia 17 vols 8vo Milano, 1820

N Il Viaggio Fatto in Spagna et in Francia. 12mo. Venegia, 1563.

N Della Transmutatione Metallica 4to Brescia, 1599

P Usi e Costumi del Popolo Siciliano. 4 vols. 8vo. Palermo, 1889.

T—Il Regime Feudale 8vo Napoli, 1890

T Storia della Letteratura Italiana. 27 vols. 8vo. Venezia, 1824.

V—Dei Primordi della Invasione Araba 8vo 1882

GERMAN

Die Alte Arabische Gedichte. 8vo. Greifswald, 1872.

A—Poësie der Araber 4to Gotha, 1856

A Provenzalische Inedita. 8vo. Leipzig, 1890.

A—Geschichte der Ommaijden in Spanien 2 vols 8vo Wien, 1860.

A Geschichte der Westgothen. 8vo. Franc. am Main, 1827.

A Geschichte Spaniens und Portugals. 2 vols. 8vo. Franc. am Main, 1833.

A—Geschichte des Mittelalters. 4 vols. 8vo. Braunschweig, 1857.

B Grundniss zur Geschichte der Provenzalische Litteratur 8vo Elberfeld, 1872

B Studien zur Semitischen Religionsgeschichte. 8vo. Leipzig, 1876.

B Die Mohammedanische-Arabische Kultur Periode 8vo Stuttgart, 1889

B Chemische Anekdoten. 8vo. Leipzig, 1788.

B Die Medizin der Talmudisten 8vo Leipzig, 1885

B-H Ueber die den Provenzalischen Troubadours Epischen Stoffe. 8vo. Leipzig, 1878.

B—Arabien im VI Jahrhundert 8vo

B Geschichte der Carthager. 8vo. Berlin, 1827.

B—Die Provenzalischen Troubadours 8vo Göttingen, 1882.

C Die Ssabier und der Ssabismus. 2 vols. 8vo. St. Petersburg, 1856.

D Die Araber im Mittelalter. 8vo. Leipzig, 1882.

D Die Philosophie der Araber im X. Jahrhundert. 8 vols. 8vo. Leipzig, 1876

D Die Poësie der Troubadours. 8vo. Zwickau, 1826.

D Leben und Werke der Troubadours 8vo Leipzig, 1882

D Von der Papstfabeln des Mittelalters. 8vo. Stuttgart, 1890.

D Moses ben Ezra aus Granada 8vo Altona, 1839

E Allgemeine Geschichte der Litteratur des Mittelalters. 3 vols. 8vo. Leipzig, 1887.

E Geschichte des Volkes Israel 7 vols 8vo Göttingen, 1843

F Geschichte der Textelkunst. 8vo. Hanau, 1883.

F Die Schulen von Bosra und Kufa 8vo Leipzig, 1862

F Geschichte der Araber. 8vo. Leipzig, 1867.

F—Darstellung der Arabischen Verskunst 8vo Bonn, 1830

F Kaiser Friedrich II. 8vo. Wien, 1817.

G—Was hat Mohammed aus dem Judenthum aufgenommen 8vo. Bonn, 1883.

G Wanderungen in Sicilien. 8vo. Leipzig, 1855.

G Der Mythos bei den Hebraern. 8vo. Leipzig, 1876.

G Die Zahiriten 8vo Halle, 1884

G Mohammedanische Studien. 2 vols. 8vo. Halle, 1889.

G Die Alhambra 16mo Berlin, 1854

G Semiten und Indogermanen. 8vo. Stuttgart, 1867.

G Das Judische Unterrechtswesen wahrend der Spanische-Arabische Periode 8vo Wien, 1873

H-P Gemäldesaal der grossen Mohammedanische Herrscher. 6 vols. 8vo. Leipzig, 1873.

H-P Literaturgeschichte der Araber 7 vols 4to Wien, 1855

H Geschichte der Mathematik. 8vo. Leipzig, 1874.

H Geschichte der Araber in Sicilien 4 vols 8vo Königsberg, 1791

H Beiträge zur Erklarung des Koran. 8vo. Leipzig, 1886.

H—Kaiser Friedrich II 8vo Munich, 1844

I-I Das Leben Mohammeds. 8vo. Stuttgart, 1864.

J—Welche Handsartikel bezogen die Araber en Mittelalter aus den Nordische-Baltischen Ländern. 8vo. Berlin, 1891.

J Geschichte des Judenthums. 8vo. Leipzig, 1857.

K Poësie Andalusischen Dichter. 8vo. Prag, 1858.

K Die Alchemie. 2 vols. 8vo. Heidelburg, 1886.

K Die Judischen Frauen. 8vo. Leipzig, 1879.

K Sephardim. 8vo. Leipzig, 1859.

K Der Kreuzzug Friedrichs II. 8vo. Göttingen, 1873.

K Die Musik der Araber 4to Leipzig, 1842

K Die Anfänge des Konigthums bei den Gothen. 8vo. Berlin, 1859.

K—Die Byzantiner des Mittelalters. 8vo. Halle, 1869.

K Das Leben des Muhammed. 12mo. Leipzig, 1884.

K—Die Religion der Vorislamischen Araber. 8vo. Leipzig, 1863.

K Culturgeschichte des Orients. 2 vols. 8vo. Wien, 1875.

K Geschichte der Baukunst. 8vo. Stuttgart, 1859.

L Geschichte von Spanien 4 vols 8vo Hamburg, 1831

M Gedichte der Troubadours. 3 vols. 12mo. Berlin, 1856.

M Das Phönizische Alterthum 2 vols 8vo Berlin, 1850

M Die Letzten Zeiten von Granada. 8vo. München, 1863.

M Philosophie und Theologie von Averroes 4to München, 1875

M Ueber die Judische Aerzte im Mittelalter. 8vo. Berlin, 1887.

N Versuch einer Geschichte des Algebra 8vo Berlin, 1842

N Beiträge zur Kenntniss der Poësie der Alten Araber. 8vo. Hannover, 1864.

N Das Leben Muhammads 8vo Hannover, 1863

N Vom Kreml bis zur Alhambra. 2 vols. 8vo. Leipzig, 1889.

O—Buddha 8vo Berlin, 1881

P Das Alexandrinische Museum. 8vo. Berlin, 1838.

P—Wanderungen durch Sicilien 2 vols 12mo Berlin, 1834

P Der Einfluss des Islams. 8vo. Leipzig, 1881.

P—Aus Phönizien 8vo Leipzig, 1870

R Geschichte der Hohenstaufen. 4 vols. 8vo. Leipzig, 1878.

R—Geschichte der Baukunst 8vo Leipzig, 1866

R Die Arabische Philosophie. 4to. Göttingen, 1844.

R—Geschichte der Kreuzzuge 2 vols 8vo Berlin, 1874

S Geschichte der Normannen in Sicilien. 8vo. Stuttgart, 1889.

S Geschichte von Portugal. 5 vols. 8vo. Hamburg, 1883.

S Kaiser Friedrich II. 4 vols. 8vo. Göttingen, 1859.

S—Geschichte Aragoniens 8vo Leipzig, 1828

S Geschichte der Alchemie. 8vo. Halle, 1832.

S—Das Höflische Leben zur Zeit der Minnesinger 2 vols 4to Leipzig, 1889.

S Italienische Trobadors. 8vo. Berlin, 1883.

S Die Minnehofe des Mittelalters. 8vo. Leipzig, 1821.

S Zur Geschichte Abul Hasan Ali Asaris 8vo Leipzig, 1876

S Geschichte der Arzneikunde. 6 vols. 8vo. Halle, 1821.

S Das Leben und die Lehre des Muhammed 3 vols 8vo Berlin, 1861

S Die Alte Geographie Arabiens. 8vo. Bern, 1875.

S Bertran de Born 8vo Halle, 1879

S Der Troubadour Jaufre Rudel. 8vo. Kiel, 1873.

S Die Handelszüge der Araber 8vo Berlin, 1836

S Denkmäler der Provenzalische Litteratur. 8vo. Halle, 1883.

U Geschichte der Pflanzenwelt 8vo Wien, 1852

V K Gebiete des Islams. 8vo. Leipzig, 1873.

V K Geschichte der Herrschenden Ideen des Islams 8vo Leipzig, 1868

V L Zeugnisse eines Handels-Verkehrs mit dem Orient. 8vo. Berlin, 1840.

W—Statistik der Araber in Sicilien 8vo

W Die Poetische Literatur der Araber vor Mohammed. 12mo. Stuttgart, 1837.

W—Einleitung in den Koran. 12mo. Bielefeld, 1844.

W Geschichte der Chalifen. 3 vols. 8vo. Mannheim, 1846.

W—Geschichte der Islamischen Völker. 8vo. Stuttgart, 1866.

W Das Alexandrinische Museum. 8vo. Berlin, 1875.

W—Geschichte der Kreuzzuge. 8 vols. 8vo. Leipzig, 1830.

W Geschichte der Kunst des Alterthums. 8vo. Heidelberg, 1882

W Kaiser Friedrich II. 2 vols. 8vo. Leipzig, 1889.

W—Geschichte der Botanik 8vo Frankfort, 1854

W Ueber Ein Arabisches Astrolabium. 4to. Berlin, 1858.

W—Die Academien der Araber 8vo Göttingen, 1837

W Geschichte der Arabischen Aerzte und Naturforscher. 8vo. Göttingen, 1840.

Z Das Kaisertraum des Mittelalters. 8vo. Leipzig, 1877.

Z Geschichte der Hohenstaufen 8vo Stuttgart, 1865

DUTCH.

D—De Israelieten te Mekka. 8vo. Haarlem, 1864.

H De Strijd over het Dogma in den Islam. 8vo. Leiden, 1875.

K De Leerstellingen van de Mohammedaansche Godsdienst. 8vo. Gorinchem, 1854.

K Handboek voor Het Mohammedaansche Regt 8vo 's Gravenhage, 1853

K Het Buddhisme in Indie. 2 vols. 8vo. Haarlem, 1882.

K De Pausin Johanna 8vo Gravenhage, 1845

K Varia, 8vo.

K De Baalsdienst onder Israel 8vo

K De Godsdienst van Israel. 2 vols. 8vo. Haarlem, 1869.

N Mohammed 12mo Amstelodami, 1758

S-H Het Mekkaansche Feest. 8vo. Leiden, 1880.

T De Godsdienst van Zarathustra 8vo Haarlem, 1864

W Legenden der Muselmannen. 8vo. Schiedam, 1853.

W Mohammed de Propheet 2 vols 8vo Amsterdam, 1846

W Geschiedenis der Geneeskunde. 8vo. Tiel, 1861.

DANISH.

F Forbindelserne mellem Norden og den Spanske Halvo, i ældre Tider 8vo Kjobenhavn, 1882

M Europa i Middelalderen. 8vo. Kjobenhavn, 1819.

R Middelalderens Magi 12mo Kjobenhavn, 1873

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