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热镀锌板复合钛盐钝化膜的耐腐蚀性能

周杰 , 姜效军 , , 崔玲 , 李瑞芬

材料保护

为进一步提高热镀锌板无铬钝化膜的耐蚀性能,以钛盐为主盐,加入双氧水、六偏磷酸钠、酸性硅溶胶、聚氟微粉乳液等配制无铬钝化液,对热镀锌板进行钝化,钛盐和双氧水发生配位化合反应,由二氧化钛水合物胶体粒子、氢氧化锌及硅溶胶吸附沉积于镀锌层表面,同时聚氟微粉乳液、六偏磷酸钠等起辅助作用形成钝化膜,在镀锌层表面获得一层均匀的钛溶胶钝化膜.通过正交试验优化钝化液的组成,采用中性盐雾腐蚀试验、极化曲线、光学显微镜、扫描电镜等方式表征钝化膜的耐蚀性能.结果表明:钝化液最优组成为1.0%钛盐,8.0%双氧水,0.4%六偏磷酸钠,1.5%聚氟微粉乳液,3.0%酸性硅溶胶;最优钝化工艺效果理想,具有无毒、无污染特点;最优工艺制备的钝化膜的耐腐蚀性能明显优于未钝化热镀锌钢板,同时优于欧洲某品牌钝化膜.

关键词: 热镀锌板 , 无铬钝化 , 钛盐 , 耐蚀性能

辽宁小家堡子金矿床地质特征及成因研究

刘红霞 , 孔含泉 , 杨言辰

黄金 doi:10.3969/j.issn.1001-1277.2006.05.004

家堡子金矿床位于辽吉古元古代裂谷中部的青城子矿集区内,矿体赋存于辽河群大石桥组上部碳酸岩与片岩的过渡带,容矿岩石为黑云变粒岩和硅质岩,矿体受层位控制,呈层状、似层状产出;矿石中的金以不可见金为主,含量与黄铁矿、毒砂关系密切.对矿石组构特征研究表明,该矿床形成既与沉积作用有关,又遭受后期变质变形及热液的叠加改造,矿床为热水沉积-变质热液改造成因.

关键词: 热水沉积-变质热液改造型金矿床 , 地质特征 , 家堡子金矿床

辽宁小家堡子金矿床主要硫化物矿物特征及其成因意义

王宝林 , 代军治 , 秦丹鹤 , 王可勇

黄金 doi:10.3969/j.issn.1001-1277.2012.02.005

辽东小家堡子金矿床为一产于元古代辽河群大石桥组变质地层中大型蚀变岩型矿床,矿体的产出主要受大石桥组不同岩性地层之间发育的层间破碎带构造控制.金矿化以浸染、细脉浸染状产出方式为主.矿石中主要金属硫化物矿物为黄铁矿,次为毒砂、方铅矿及闪锌矿.不同时期形成的矿物其产状有一定区别.电子探针分析结果表明,黄铁矿、毒砂为主要的载金矿物,根据硫化物矿物产状及含金性特点,提出了矿床为沉积-变质并经后期热液叠加改造成因的认识.

关键词: 硫化物矿物 , 矿床成因 , 家堡子金矿床 , 辽宁

辽宁青城子地区金、银矿床地质特征及其成因

郝通顺 , 王可勇 , 朴星海 , 万多 , 杨言辰 , 边红业

黄金 doi:10.3969/j.issn.1001-1277.2011.01.006

对辽宁青城子地区近年来发现的高家堡子银矿床及小家堡子金矿床地质特征及矿床成因进行了对比研究,结果表明两类矿床是在早期沉积-变质基础上,经历了后期热液叠加改造作用的结果,其中印支期岩浆热液活动导致了小家堡子等金矿床形成,而其后的大气降水活动是导致高家堡子银矿床富集成矿的主要机制.

关键词: 青城子地区 , 高家堡子银矿床 , 家堡子金矿床 , 地质特征 , 矿床成因

辽宁尖山沟金矿床地质特征及成因探讨

刘培栋 , 杨言辰 , 王秀福 , 董立军 , 刘德军

黄金 doi:10.3969/j.issn.1001-1277.2007.08.005

尖山沟金矿是辽宁省有色地质局在近期评价的大型金矿床,是继找到小家堡子金矿后的又一个重大找矿成果.本文阐述了尖山沟金矿床地质特征及地球化学特征,并探讨了矿床成因.

关键词: 矿床地质特征 , 地球化学特征 , 矿床成因 , 尖山沟金矿床

皖南鹤城科马提质变玄武岩地球化学特征及大地构造意义

汪龙 , 刘春明 , 胡召齐 , 江来利 , 黄德志

中国有色金属学报

江南造山带新元古变基性岩为区域构造事件和演化模型的建立提供地质依据.对江南造山带东段皖南鹤城地区变玄武质岩的地球化学及岩石成因进行研究.鹤城变玄武岩呈北东—南西向沿里—鹤城—江潭—带分布.元素地球化学的研究表明:休宁鹤城变玄武岩同科马提质玄武岩及岛弧玄武岩相类似;富集Rb、Ba、Th、U等强不相容元素,亏损高场强元素Nb和Ta,指示其成因可能与富集地幔的部分熔融有关,同时有地壳物质的混染,其可能属于皖南伏川蛇绿岩西延组成部分,与伏川蛇绿岩组成一个弧后杂岩带,形成于与俯冲有关的弧后小洋盆环境.结合区域资料,表明新元古代板块俯冲、岛弧岩浆活动以及拼合是江南造山带形成的比较合理的构造演化过程.

关键词: 江南造山带东段 , 鹤城 , 变玄武岩 , 科马提质玄武岩 , 岛弧玄武岩

ATOMIC FORCE MICROSCOPY OBSERVATION OF MAGNETRON SPUTTERED ALUMINUM-SILICON ALLOY FILMS

金属学报(英文版)

粒裕希停桑谩。疲希遥茫拧。停桑茫遥希樱茫希校。希拢樱牛遥郑粒裕桑希巍。希啤。停粒牵危牛裕遥希巍。樱校眨裕裕牛遥牛摹。粒蹋眨停桑危眨停樱桑蹋桑茫希巍。粒蹋蹋希。疲桑蹋停?##2##3##4##5ATOMICFORCEMICROSCOPYOBSERVATIONOFMAGNETRONSPUTTEREDALUMINUM-SILICONALLOYFILMSJ.W.Wu,J.H.FangandZ.H.Lu(NationalLaboratoryofMoleculeandBiomoleculeElectronics,SoutheastUniversity,Nanjing210096,ChinaManuscriptreceived27October1995)Abstrcat:Twodifferentsurfacemorphologycharacteristicsofmagnetronsputteredaluminumsilicon(Al-Si)alloyfilmsdepositedat0and200℃wereobservedbyatomicforcemicroscopy(AFM).Oneisirregularlyshapedgrainsputtogtheronaplane.TheotherisirregularlyshapedgrainsPiledupinspace.Nanometer-sizedparticleswithheightsfrom1.6to2.9nmwerefirstobserved.Onthebasisoftheseobservationsthegrowthmechanismofmagnetronsputteredfilmsisdiscussed.Keywords:magnetronsputtering,Al-Sialloy,surfacemorphology,atomicforcemicroscopy,filmgrowthmechanism1.IntroductionTheuseofaluminumalloys[1,2],inparticularAl-Si,isacommonfeatureinmanysinglelevelandmultilevelinterconnectionschemesadoptedinthemanufactureofmicroelectronicdevicesbecauseofseveraldesirableproperties.TheAl-Sigrainmorphology(size.geometryanddistributionofgrainsisassociatedwithstepcoverage[3],electromigration[4]andinterconnectsresistivity[5]etc..Thus,characterizationofAl-Sialloysurfacemorphologyisveryimportant,especiallywhenintegratedintensityincreasesandlinewidthsof0.3to0.5μmbecomecommon.Inthepasttwentyyears,theAl-Sialloysurfacemorphologywhichaffectsthereliabilityofmicroelectronicdeviceshasbeenwidelyinvestigatedbyscanningelectronmicroscopy(SEM),transmissionelectronmicroscopy(TEM)etc.[5-7].However,SEMandTEMhavetheirlimitationorinconvenience,forexample,theverticalresolutionofSEMisnothighandTEMneedscomplexsamplepreparation.Recently,anewgrainboundaryetchingmethodwasproposed ̄[8]whichalsoneedstroublesomechemicaletching.Atomicforcemicroscopy(AFM),sinceitsemerging,hasbecomemoreandmoreusefulinphysics,chemistry,materialsscienceandsurfacescience,becauseofitshighresolution,easeofsamplepreparationandrealsurfacetopography.Recently,discussion[9,10]waspresentedonhowAFMwillplayaroleinsemiconductorindustry.Asaresponsetothisdiscussion,weusedAFMtoinvestigateAl-SialloysurfacemorphologyandhaveobtainedsomeresultswhichcannotberevealedbySEMorTEM.ThisindicatesthatAFMisagoodcharacterizationtoolinsemiconductorindustry.2.SamplePreparationInourexperiments,aluminumwith30ppmsiliconwassputteredonsiliconsubstrateinbatchdepositionmodeAllthreefilmswiththicknessof1.6μmweredepositedusinganargonsputteringpressureof4.2×10 ̄-3Pa.TheotherdepositionparametersaredescribedinTable1.Thesubstratewascleanedusingstandardpremetallizationcleaningtechniquespriortofilmdeposition.3.ExperimentalResultsandDiscussionTheAFMmeasurementswereperformedonacommercialsystem(NanoscopeIII,DigitalInstruments,SantaBarbara).Thetipismadeofmicrofabricatedsiliconnitride(Si_3N_4)Itisattachedtoa200μmcantileverwithaforceconstantofabout0.12N/m.Beforethesurfaceofsamplewasexamined.agoodtipwithananometer-sizedprotrusionatitsendwasselectedbeforehand,whichcanbeobtainedbyimagingtheatomicstructureofmicasubstrateandagoldgrid.AtypicaloperatingforcebetweenthetipandAl-Sisamplesurfaceisoftheorderof10 ̄-8Nandallimagesweretakenatroomtemperatureinair.AtypicaltopographicviewoftheAl-SifilmsisshowninFig.1(allimagescansizeis5by5μma,bandcarerespectivelyforsample1,2,and3).FromFig.la,itcanbeseenthatirregularlyshapedgrainstiltinginvaryingdegreespileupinspace,andgroovesamongtheirregularlyshapedgrainsaredifficulttodecideatacertainarea(wedefineitascharacteristicA).Toourknowledge,onreportsonthesurfacemorphologyhavebeenpresentedbefore.InFig1b,however,irregularlyshapedgrainsassembleonaPlaneandgroovesamongtheirregularlyshapedgrainsareeasytodecide(wedefineitascharacteristicB),whichisinagreementwithmanypreviousreports[5-7].InFig.1c,bothcharacteristicA(arrowA)andcharacteristicB(arrowB)wereobserved.IndoingAFMexperiments,weselectedfivedifferentscanareastobeimagedforeachsampleandfoundthatallimagesofeachsamplearerespectivelysimilartoFig.1a,bandc.Also,wenotedthatthesurfaceofinFig.1a.WethinkthatdepositionparameterswillinfluenceAl-Sisurfacemorphology,andthetiltedgrainsmaybesusceptibletomicrocracking.Byreducingthescansizeareato2by2μm(Fig.2aandb).Weobtainedmanyidenticalresultsasdescribedabove,suchasirregularlyshapedgrainsetc.Forthefirsttime,wefoundnanometersizedparticlesonirregularlyshapedgrainsurfacewhichcannotberevealedbySEMbecausethediameterofthesenanoparticlesisabout10nmandtheheightofthesenanoparticlesisintherangeof1.6to2.9nm.Inimaging,wenotedthatrotatingthescandirectionandchangingthescanfrequencydidnotaffectthestructureofthesegrainsasshowninFig.2aandb,rulingoutthepossibilitythatscanninginfluencedtheshapeoftheseparticlesorcausedsomesimilarimagingartifacts.Also,wenotedthatthenanoparticleswerenotobservedontheslopesofthegrooves(Fig.2aandb).Thisphenomenoncanbeexplainedasfollows:thepotentialenergyattheslopeislargerthanthatelsewhere,sotheparticlesseemmorelikelytobedepositedontheseareaswithlowerpotentialenergy.Fig.2c,scansize250by250nm,isazoomtopographicimage(whiteoutlineinb).Itshowsunevendistributionofthenanoparticles.Andtheheightdifferenceofthenanoparticlesindicatesdifferentgrowingspeed.Wethinkbasedonthemorphologyofnanoparticles,thattheheightdifferenceandunevendistributionofthesenanoparticlesshowdifferentgrowingadvantageandindicatethatatomshaveenoughenergytomovetoasuitablegrowingspot.Theenergymaybefromthefollowingsources:surfacetemperaturefluctuation,stressdifferenceorcollisionbetweenhighspeedsputteredatoms.Thesenanoparticlesgoongrowingandformmanyirregularlyshapedgrains.AndtheseirregularlyshapedgrainsfurtherconnecteachotheraccordingtocharacteristicAorB,finallyformingtheAl-Sisurfacemorphology.4.ConclusionWecandrawthefollowingconclusionsfromtheabove.First,theexperimentalresultsshowedthatAFMisapowerfultooltoinvestigatethedetailsofAl-Sisurfacemorphologywhichcangreatlyenrichourknowledgeofthefilmgrowthmechanism.Second,depositionconditionsplayanimportantroleindeterminingtheAl-Sisurfacemorphology.Third,thetwoAl-Sisurfacemorphologycharacteristicsarethatirregularlyshapedgrainsassembleonaplaneandirregularlyshapedgrainstiltinginvaryingdegreespileupinspace.Fourth,forthefirsttime,nanoparticleswereobservedonirregularlyshapedgrainsurfacewhichsuggestedthatthefilmgrowthmechanismwasbyinhomogeneousnucleation.Acknowledgements-BeneficialdiscussionswereheldwithDr.ZhenandMr.Zhu.ThisworkwaspartiallysupportedbytheNationalNaturalScienceFoundationofChina.RFFERENCES||1D.pramanikandA.N.Saxena,SolidStateTechnol.26(1983)127.2D.pramanikandA.N.Saxena,SolidStateTechnol.26(1983)131.3D.pramanikandA.N.Saxena,SolidStateTechnol.33(1990)73.4S.S.IyerandC.Y.Worg,J.Appl.phys.57(1985)4594.5J.F.Smith,SolidStateTechnol.27(1984)135.6D.GerthandD.Katzer,ThinSolidFilm208(1992)67.7R.J.WilsonandB.L.Weiss,ThinSolidFilm207(1991)291.8E.G.Solley,J.H.Linn,R.W.BelcherandM.G.Shlepr,SolidStateTechnol33(1990)409I.SmithandRHowland,SolidStateTechnol.33(1990)53.10L.Peters,SemiconductorInternational16(1993)62.##61D.pramanikandA.N.Saxena,SolidStateTechnol.26(1983)127.2D.pramanikandA.N.Saxena,SolidStateTechnol.26(1983)131.3D.pramanikandA.N.Saxena,SolidStateTechnol.33(1990)73.4S.S.IyerandC.Y.Worg,J.Appl.phys.57(1985)4594.5J.F.Smith,SolidStateTechnol.27(1984)135.6D.GerthandD.Katzer,ThinSolidFilm208(1992)67.7R.J.WilsonandB.L.Weiss,ThinSolidFilm207(1991)291.8E.G.Solley,J.H.Linn,R.W.BelcherandM.G.Shlepr,SolidStateTechnol33(1990)409I.SmithandRHowland,SolidStateTechnol.33(1990)53.10L.Peters,SemiconductorInternational16(1993)62.##A##BATOMIC FORCE MICROSCOPY OBSERVATION OF MAGNETRON SPUTTERED ALUMINUM-SILICON ALLOY FILMS$$$$J.W.Wu,J.H. Fang and Z.H.Lu (National Laboratory of Molecule and Biomolecule Electronics,Southeast University,Nanjing 210096, China Manuscript received 27 October 1995)Abstrcat:Two different surface morphology characteristics of magnetron sputtered aluminumsilicon(Al-Si)alloy films deposited at 0 and 200℃ were observed by atomic force microscopy(AFM).One is irregularly shaped grains put togther on a plane.The other is irregularly shaped grains Piled up in space. Nanometer-sized particles with heights from 1.6 to 2.9 nm were first observed. On the basis of these observations the growth mechanism of magnetron sputtered films is discussed.

关键词: :magnetron sputtering , null , null , null , null

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