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Geometric and Electronic Structure of Squaric Acid from DFT Calculation

Xuyan XUE , Chunlei WANG , Weilie ZHONG

材料科学技术(英)

The crystal and electronic structure of antiferroelectric squaric acid is studied using density functional theory method, and the exchange correlation effects are treated by the generalized approximation. In order to understand the ferroelectricity of H2SQ in the molecular plane and the antiferroelectricity in whole crystal, the density of states, charge density distribution and band structure are calculated. The result showed that O2p and C2p play important roles in the interactions between layers. The hybridizations of O2s-H1s and O2p-H1s are responsible for the tendency to ferroelectricity within each layer.

关键词: Antiferroelectricity , null , null

INVESTIGATION OF HYDROGEN INDUCED DUCTILE BRITTLE TRANSITION IN 7175 ALUMINUM ALLOY

金属学报(英文版)

桑危郑牛樱裕桑牵粒裕桑希巍。希啤。龋伲模遥希牵牛巍。桑危模眨茫牛摹。模眨茫裕桑蹋拧。拢遥桑裕裕蹋拧。裕遥粒危樱桑裕桑希巍。桑巍。罚保罚怠。粒蹋眨停桑危眨汀。粒蹋蹋希?##2##3##4##5INVESTIGATIONOFHYDROGENINDUCEDDUCTILEBRITTLETRANSITIONIN7175ALUMINUMALLOY$R.G.Seng:B.JZhong,MG.ZengandP.Geng(DepartmentofMaterialsScierce,ScienceCollege,NorthearsternUniveisity,Shenyang110006,ChinaMaruscriptreceived4September1995inrevisedform20April1996)Abstrac:Effectsofhydrogenonthemechanicalpropertiesofdifferentlyaged7175aluminumalloyswereinvestigatedbyusingcathodicH-permeation,slowstrainratetensionandsoon.Theresultsindicatethatboththeyieldstressandthepercentagereductionofareadecreasewithincreasinghydrogenchargingtime,andthedegreeofreductiondecreasesasagingtimeincreasesforthesamehydrogenchargingtime.Keywords:hydrogeninducedductile-brittletransition,7175aluminumalloy,mechanicalproperty,cathodicH-permeation1.IntroductionForalongtimehydrogenembrittlementproblemwasthoughttobeabsentinhighstrengthaluminiumalloybecausethesolutiondegreeofhydrogeninaluminumatcommontemperatureandpressureisverysmall.However,hydrogenembrittlementphenomenonwasfoundinaluminumalloyduringtheinvestigationofstresscorrosionandcorrosionfatigue[1-5].Therehavebeenonlyafewreportsofhydrogeninducedsofteningandhardening.Inthispaper,theeffectsofhydrogenonmechanicalpropertiesof7175aluminumalloywereinvestigatedbyusingcathodicalchargingwithhydrogenandslowtensiontests.2.ExperimentalProcedureTheexperimentalmaterialwas7175aluminumalloyforgingintheformofa43mminthicknessandwithcomposition(wt%).5.41Zn,2.54Mg.1.49Cu,0.22Cr,0.1Mn.0.1Ti,0.16Fe.0.11Si,balancedbyA1.Alloyplateof1.5mminthicknesswasobtainedbyhot(465℃)andtoldrollingto83%reductioninthickness.Thelongaxisofhydrogenchargedspecimensisalongtherollingdirection.Allspecimensweresolidsolutionedat480℃for70min,followedtyimmediatequenchinginwaterandthenagedat140℃for6h(A),16h(B)and98h(C).Thetreatmentof6hiscorrespondingtotheunderagedstate.16hthefirstpeak-agedstateand98hthesecondpeak-agedstate.Thespecimenswerepolishedsuccessivelyusingemerypaperbeforehydrogencharging.Thetensilespecimenswerecathodicallychargedina2NH_2SO_4solutionwithasmallamountofAs_2O_3forpromotinghydrogenabsorption,andwithacurrentdensityof20±1mA/cm ̄2atroomtemperature.ThehydrogencontentanalysiswascarriedoutonanLT-1Amodelionmassmicroprobeafterthesputteringdepthreached8nm.Theioncurrentsofhydrogenandaluminuminvariousagedstateswererecordedunderthesamecondition.ThetensiletestswereperformedonanAG-10TAmodeltestmachinewhichwascontrolledbycomputer.3.ExperimentalResultsTheratioofioncurrentstrengthofhydrogentoaluminumisrelatedtohydrogenconcentrationinhydrogenchargedspecimen.TheresultswereshowninTable1Thehydrogencontentincreaseswiththeincreaseincharingtime.Ofthethreeagedstates,theunderagedspecimenhasthehighesthydrogencontent.Theratioofyieldstrengthofhydrogenchargedandunchargedspecimenschangeswithhydrogenchargingtime,asshowninFig.1Itcanbeseenthattheyieldstrengthofhydrogenchargedspecimendecreasewithincreasinghydrogenchargingtime.Atthesamechargingtime,theyieldstressdecreasestheleastinthesecondpeak-agedstate,anddecreasesthemostintheunderagedstate.Itindicatesthattheunderagedspecimenismostsensitivetohydrogeninducedsoftening,whichisconsistentwiththeresultsofanotherhighstrengthaluminumalloy[6].TherelativechangesoftheradioofreductionofareawithhydrogenchargingtimearesummarizedinFig.2,whereΨ ̄0andΨ ̄Harethepercentagereductionofareaofthesamplewithoutandwithhydrogenchargingrespectively.Theradioofreductionofareareduceswhenhydrogenchargingtimeincreases,andthedecreasingdegreeofreductionofareaincreaseswithincreasingagingtime,ie,,theunderagedstateisthemostsensitivetohydrogenembrittlement.4.DiscussionItisknownfromtheresultsabovethatcathodicalchargingwithhydrogenleadstotheobviousdecreaseinthetensilestrengthandplasticityThisisbecausealargeamountofsolidsolutionhydrogenentersthespecimenintheprocessofhydrogenchargingSolidsolutionhydrogenisliabletoenterthecentreofdislocationundertheactionofdislocationtrap,henceraisingthemovabilityofdislocation.Thereforethedislocationsinhydrogenchargedspecimenmoveeasierthaninunchargedspecimen.soresultinginthereductionofyieldstrength[7].Whendislocationstartstomove,thecrystallatticeresistance(P-Nforce)whichitmustovercomeisgivenby:whereμismodulusofshear,visPoissonratio,aisspanofslipplane,bisatomspanofslipdirection.Moreover.theotherresistanceofdislocationmotionmayarisefromtheelasticinteractionofdislocation,theactionwithtreedislocationandetc.,itcanbeexpressedasfollows:whereαisconstant,XisdislocationspanSotheresistanceofdislocationmotioncanbewrittenasfollows:Becausehydrogenatomsreducetheatombondingstrengthafterhydrogencharging,shearmodulusμdecreasesandresultsinthereductionoff,therebytheyieldstressdecreases.Asthecentreofdislocationistheseriousdistortionzoneoflattice.thestresscanberelaxedafterhydrogenatomstuffing,andthesystemenergydecreases.Thusthecentreofdislocationisastrongtrapofhydrogen[8].Therefore,amovabledislocationcaptureshydrogenandmigratestograinboundaries.phaseboundariesorsurfaceofthespecimen,promotingthecrackiesformationandgrowth,thuscausingthelossofplasticity.Sincethelocalenrichmentofhydrogenisrealizedbydislocationtransporting(inthestageofdeformation),thelargerthereductionofyieldstress.theearlierarehydrogenatomstransportedtotheplaceofenrichment.Inaddition,thedamageofatombondingstrengthinducedbyhydrogenmakesthefracturestressdecrease[9]:whereCHishydrogenconcentration.σ_thisfracturestrengthbeforehydrogenchargingandisfracturestrengthafterhydrogencharging.Eq.(4)showsthatthematerialsmaybefracturedatalowerstraini.e.,brittlefractureoccurs.5.Conclusions(1)Hydrogencontentofdifferentlyagedspecimensincreaseswithincreasinghydrogenchargingtimethecapabilityofthealloytoabsorbhydrogeninunderagedstateisthestrongest.(2)Theyieldstressaswellasthepercentagereductionofareaof7175aluminumalloydecreaseashydrogenchargingtimeincreasesundervariousagedstates.(3)Underagedstateismostsensitivetohydrogeninducedsofteningandhardening.(4)Anexplanationwasofferedforthephenomenonofhydrogeninducedsofteninginthestageofdeformation,andhardeninginthestageoffracture.REFERENCES||1G.KKock,Corrosion35(1979)73.2M.K.TsengandH.LMarcus,Scr.Metall.15(1981)427.3PSFao.M.GaoandR.P.Wei,Scr.Metall.19(1985)265.4R.G.SongandM.K.TsengJ.NortheasternUniversity15(1994)5(inChinese).5R.K.Viswanadham,T.S.sunandJ.A.S.Green,Metall.Trans.11A(1980)85.6J.Liu,M.KTsengandB.R.Liu.NonferrousMiningandMetallrgy5(1989)33(inChinese).7LChen,WXChen,ZHLiuandZ.Q.Hu,InFrocofthe1stNationalConfonAl-LiAlloys(Sheryang.China,1991)p.328(inChinese).8Z.HLiuL.ChenW.XChenY.X.ShaoandZ.Q.Hu,InProc.ofthe1stNationalConfonAl-LiAlloys(Shenyang,China,1991)p.334(inChinese).9R.A.OrianiandF.H.Josephic,ActaMetall.22(1974)1065.##61G.KKock,Corrosion35(1979)73.2M.K.TsengandH.LMarcus,Scr.Metall.15(1981)427.3PSFao.M.GaoandR.P.Wei,Scr.Metall.19(1985)265.4R.G.SongandM.K.TsengJ.NortheasternUniversity15(1994)5(inChinese).5R.K.Viswanadham,T.S.sunandJ.A.S.Green,Metall.Trans.11A(1980)85.6J.Liu,M.KTsengandB.R.Liu.NonferrousMiningandMetallrgy5(1989)33(inChinese).7LChen,WXChen,ZHLiuandZ.Q.Hu,InFrocofthe1stNationalConfonAl-LiAlloys(Sheryang.China,1991)p.328(inChinese).8Z.HLiuL.ChenW.XChenY.X.ShaoandZ.Q.Hu,InProc.ofthe1stNationalConfonAl-LiAlloys(Shenyang,China,1991)p.334(inChinese).9R.A.OrianiandF.H.Josephic,ActaMetall.22(1974)1065.##A##BINVESTIGATION OF HYDROGEN INDUCED DUCTILE BRITTLE TRANSITION IN 7175 ALUMINUM ALLOY$$$$R.G.Seng: B.J Zhong, MG. Zeng and P. Geng(Department of Materials Scierce, Science College,Northearstern Univeisity, Shenyang 110006, China Maruscript received 4 September 1995 in revised form 20 April 1996)Abstrac:Effects of hydrogen on the mechanical properties of differently aged 7175 aluminum alloys were investigated by using cathodic H-permeation, slow strain rate tension and so on. The results indicate that both the yield stress and the percentage reduction of area decrease with increasing hydrogen charging time, and the degree of reduction decreases as aging time increases for the same hydrogen charging time.

关键词: :hydrogen induced ductile-brittle transition , null , null , null

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