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Corrosion protection of AA 2024-T3 aluminium alloys using 3, 4-diaminobenzoic acid

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CorrosionprotectionofAA2024-T3aluminiumalloysusing3,4-diaminobenzoicacidchelatedzirconium–silanehybridsol–gels

P.C.RajathVarmaa,JohnColreavya,JohnCassidyb,MohamedOubahac,ColetteMcDonaghc,BrendanDuffya,⁎aCentreforResearchonEngineeringSurfaceTechnology(CREST),FOCASInstitute,DublinInstituteofTechnology,13CamdenRow,Dublin8,IrelandbSchoolofChemicalandPharmaceuticalSciences,DublinInstituteofTechnology,KevinSt.,Dublin8,IrelandcNationalCentreforSensorResearch(NCSR),DublinCityUniversity,Dublin9,Ireland

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Articlehistory:Received29May2009Receivedinrevisedform26April2010Accepted20May2010Availableonline26May2010Keywords:OrmosilZirconiumChelateCoatingNanoparticlesOrganic–inorganicpolymersformedbyhydrolysis/condensationreactionsofalkoxideprecursors,suchasorganicallymodifiedsilanes(Ormosils)areusedforseveralindustrialapplicationssuchaselectronic,opticalandprotectiveanticorrosioncoatings.Suchmaterialspossesssuperiorchemicalstability,physicalstrengthandscratchresistancecharacteristicswhencomparedtoorganicpolymers.Furtherperformanceimprovementcanbeachievedthroughtheincorporationofzirconiumandtitaniumbasednanoparticles,alsoformedthroughfromprecursorsviathesol–gelprocess.Howeverduetotheinherentreactivitydifferencesoftheaboveprecursors,theymustbehydrolysedseparatelybeforebeingcombinedforfinalcondensation.Zirconiumprecursorsarecommonlychelatedusingaceticacidoracetylacetonatepriortohydrolysis,tolowerthehydrolysisrate.Inthisbodyofwork,3,4-diaminobenzoicacid(DABA)andacetylacetonate(acac)werecomparedaschelatingligandsforcontrollingthehydrolysisreactionsofzirconiumn-propoxidetoformnanoparticleswithinasilanesolmatrix.ThesolswereappliedascoatingsonaerospacegradealuminiumalloyAA2024-T3andcharacterisedbyphysical,spectroscopical,microscopical,electrochemicalandcalorimetrictechniques.Theelectrochemicalpropertiesofthecoatings,ascharacterisedbyEISandPDS,correlatedwithneutralsaltsprayevaluationsconfirmingthattheuseofDABAasachelatingligandsignificantlyimprovedthecoatingperformancewhencomparedtothetraditionaldiketoneligand.Thedataindicatestheanticorrosionpropertiesofthenitrogenrichchelatehaveakeyroleinprotectingthealloythroughtheformationofsmallerzirconiumnanoparticles,thusimprovingthepolymernetworkstability.©2010ElsevierB.V.Allrightsreserved.

1.Introduction

Asthemostabundantmetalintheearth'scrust(8.1%bymass),aluminiumisusedextensivelyinalloysforproductsrangingfromkitchenutensilsanddrinkcanstoengineering,architecturalandautomotivecomponents.Howeveraluminiumisnotfoundfreeinnature,butchieflyinbauxiteduetoitsreactivityandmustbealloyedforengineeringpurposes,usuallywithcopperandmagnesium.Consequentlyproductsofaluminiumanditsalloysneedtobeprotectedfromatmosphericconditionsinordertomaintaintheirappearanceandperformance.Thisisimportantifthealloycontainshighlevelsofsecondaryphaseparticles,suchascopperintermetallics,whichmaypromotegalvanicactivity.Thecurrentstateoftheartforprotectingaluminiumalloysinvolvestheuseofhexavalentchromiumtechnologyintheformofconversioncoatingsandpigmentedanticorrosionprimers[1].Howeverintheinterestofhumanhealth[2,3]andenvironmentalconcerns,alternativesolutionsarebeingpursued.Forengineeringapplicationsorganicpolymers(polyesters,polyamides,alkyds,andpolyurethane)[4],conductivepolymers(polyanilineandpolypyrrole)[5]andsol–gelderivedorganic–inorganichybridmaterialshaveemergedaspromisingCr6+alter-natives[6].Thesol–gelprocesscanbeusedtoformnanostructuredinorganicfilms(typically200nmto10µminoverallthickness)thataremoreresistantthanmetalstooxidation,corrosion,erosionandwearwhilealsopossessinggoodthermalandelectricalproperties.Thechemistryofthesol–gelprocessiswellknown[7–9]withexcellentreviews[6,10,11]andbooks[12]available.Themostcommonsol–gelmaterialsusedascoatingsarebasedonorganicallymodifiedsilicates(Ormosils),whichareformedbythehydrolysisandcondensationoftrialkoxysilanesprecursors[13,14].AlthoughinitialstudiesofOrmosilsasprotectivecoatingsonaluminiumfoundthattheylackedchromium'sself-healingproperties[15,16],theinclusionofzirconiumchemistrieswasfoundto

improveThinSolidFilms518(2010)5753–5761

⁎Correspondingauthor.Tel.:+35314027964;fax:+35314027941.E-mailaddress:bduffy@dit.ie(B.

Duffy).0040-6090/$–seefrontmatter©2010ElsevierB.V.Allrightsreserved.doi:

10.1016/j.tsf.2010.05.088ContentslistsavailableatScienceDirect

ThinSolidFilms

journalhomepage:www.elsevier.com/locate/tsfthecoatings'performanceconsiderably[17],especiallyalkaliresis-tance.SomeUnitedStatesAirForcestudiesinvestigatedvariousroutestowardsimprovingcoatingperformanceincludingtheuseofrare-earthmetalsalts[18],aminecross-linkers[19–21],supramolec-ularinclusionandorganiccorrosioninhibitors[22,23].SimilarapproacheswereinvestigatedbyEuropeanresearchgroupswhichconcentratedonepoxyfunctionalisedsilane–zirconiumsystemsbyaddingcerium[24],azolebasedorganicinhibitorsinhostmolecules[25,26]andbis-silanes[27].Furtherpublisheddatasuggeststhattherouteofzirconiuminclusionisimportant,asthechoiceofchelatingligandmayhaveaneffectofthefinalcoatingperformance[28].Thiswouldbeinagreementwithpreviousstudieswhichfoundthathydrolysisofzirconiumalkoxidescanbecontrolledtodelivernanoparticlesofvaryingsizes[29,30].Inthepresentworkzirconiumn-propoxidewaschelatedseparatelywithtwoligands,3,4-diaminobenzoicacid(DABA)andwithacetylacetonate(acac),hydrolysedandcombinedwithpre-hydrolysed3-(trimethoxysilyl)propylmethacrylate(MAPTMS)toobtaintwohybridsol–gels.ThesolswerethenspincoatedontoaerospaceAA2024-T3aluminiumalloypanelstocomparetheirstructuralpropertiesandanticorrosionperformance.Thestructuralpropertiesofthesolwerecharacterisedby29Sinuclearmagneticresonance(NMR)andFouriertransforminfrared(FTIR)spectrosco-py.Thesol–gelnetworkstabilitywasdeterminedbydifferentialscanningcalorimetry(DSC),whilethesurfacemorphologyofthecoatingswasstudiedbyatomicforcemicroscopy(AFM).Thecorrosionpropertieswerecomparedusingelectrochemicalimped-ancespectroscopy(EIS),potentiodynamicscanning(PDS)andneutralsaltspray(NSS)techniques.TheDABAmodifiedcoatingdisplayssuperiorperformancetotheacacequivalent,whichweproposeisduetobothimprovementsinpolymericnetworkstabilityandthecorrosioninhibitionpropertiesoftheDABAspecies.ThisdualfunctionalityofDABAwithinthehybridcoatingsissignificant,especiallyinharshenvironmentswherealuminiumalloysaredependentonprotectivecoatingsforlongtermusage.

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jed-259

jed-259

Specification 2006-10

Class: Surface protection Class No.:50

WABCO

Passivation of aluminium alloys JED

259

Previous Edition Abbreviated Title

2004-10 Passivation of Al alloys 852 002 590 4

Continuation page 2 Approved Group Standards Responsible for the Contents TRI: 002

by Doc. Code Rev.

408 C

Replacement for JED-128 P

1 Scope

The specification refers to corrosion protection coatings for

aluminium alloys which are exposed to severe corrosive conditions

(direct outdoor weathering or condensing water in interiors). The coatings shall be applied by

passivation without subsequent sealing.

The coatings according to type JED-259-0 incorporate hexavalent chromium ions (Chromium

VI). Their use will be prohibited at WABCO from 1st July 2007 on and this specification then

changed accordingly. For parts with drawing requirement JED-259 or JED-259-0 passivations

3003A1-H14薄壁微小通道扁管波形冲压成形尺寸对截面变形的作用规律

3003A1-H14薄壁微小通道扁管波形冲压成形尺寸对截面变形的作用规律

第43卷　第3期2024年3月中国材料进展MATERIALSCHINAVol.43　No.3Mar.2024

收稿日期:2021-11-05 修回日期:2022-06-17基金项目:国家自然科学基金项目(51601070,51875263);江苏省自然科学基金项目(BK20181447)第一作者:程传峰,男,1974年生,高级工程师通讯作者:朱英霞,女,1986年生,副教授,硕士生导师,Email:xia166109@DOI:10.7502/j.issn.1674-3962.2021110053003Al-H14薄壁微小通道扁管波形冲压成

形尺寸对截面变形的作用规律

程传峰1,金　明2,王项如1,朱英霞3,程一峰3,盘朝奉4,王　园3

(1.安徽新富新能源科技股份有限公司,安徽安庆246001)(2.安徽环新集团股份有限公司,安徽安庆246001)(3.江苏大学机械工程学院,江苏镇江212013)(4.江苏大学汽车工程研究院,江苏镇江212013)

摘　要:薄壁微小通道波形扁管是建设新能源汽车锂电池组恒温系统的绝佳材料,成形尺寸是影响其冲压成形截面变形的关键因素。建立了实验验证的3003Al-H14微小通道薄壁扁管的波形冲压-回弹有限元模型。基于所建模型,研究了截面高度、管坯壁厚、内外面相对弯曲半径缩放系数等成形尺寸,对截面变形率和平均截面变形率的作用规律。研究发现:①横截面上边缘孔的截面变形率通常较大,其余孔的截面变形率相对较小且大小一致;纵截面上孔的截面变形率呈现波峰波谷高、中间段低的分布特点。②扁管的截面变形率随着截面高度增大而增大,当截面高度超过4mm时,扁管内的筋显著弯折,横截面

塌陷严重。③扁管的平均截面变形率随着壁厚增大呈指数函数下降;当壁厚等于0.1mm时,所有截面都畸变严重,而当壁

厚超过0.3mm时,最大截面畸变率下降至24.71%。④内外面相对弯曲半径的缩放系数越大,则内外面的实际弯曲程度越小,平均截面变形率也越小。研究成果对薄壁微小通道波形扁管的精确成形具有科学意义和工程价值。关键词:微小通道管;冲压;薄壁件;成形尺寸;截面变形中图分类号:TG386 文献标识码:A 文章编号:1674-3962(2024)03-0265-08引用格式:程传峰,金明,王项如,等.3003Al-H14薄壁微小通道扁管波形冲压成形尺寸对截面变形的作用规律[J].中国材料进展,2024,43(3):265-272.CHENGCF,JINM,WANGXR,etal.EffectofFormingSizeonSectionalDeformationofWaveStampingof3003Al-H14MicroChannelFlatTube[J].MaterialsChina,2024,43(3):265-272.

6000系铝合金晶间腐蚀研究进展

6000系铝合金晶间腐蚀研究进展

6000系铝合金晶间腐蚀研究进展

贺春林;孟小丹;马国峰;王建明

【摘 要】介绍了与晶界直接相关的铝合金腐蚀类型,概述了合金元素和稀土元素对6000系铝合金晶间腐蚀的影响,重点介绍了热处理条件对6000系铝合金晶间腐蚀敏感性的影响.大量实验显示,热处理影响腐蚀模式,且晶间腐蚀向点蚀的转变与固溶处理温度、冷却速度,以及随后的人工时效温度和时效时间等诸多因素有关,发现经适当条件热处理的6000系铝合金可免受局部腐蚀影响.展望了铝合金晶间腐蚀研究的发展方向.

【期刊名称】《沈阳大学学报》

【年(卷),期】2014(026)001

【总页数】7页(P18-23,34)

【关键词】6000系铝合金;晶间腐蚀;合金元素;热处理;稀土元素

【作 者】贺春林;孟小丹;马国峰;王建明

【作者单位】沈阳大学辽宁省先进材料制备技术重点实验室,辽宁沈阳 110044;沈阳大学辽宁省先进材料制备技术重点实验室,辽宁沈阳 110044;沈阳大学辽宁省先进材料制备技术重点实验室,辽宁沈阳 110044;沈阳大学辽宁省先进材料制备技术重点实验室,辽宁沈阳 110044

【正文语种】中 文

【中图分类】TG17 铝是地球上蕴藏最丰富的金属,铝及铝合金应用广泛.和其他金属材料相比,铝合金具有一系列的优良特性[1].其中,6000系列铝合金是可热处理强化的变形铝合金,具有中等强度、良好的焊接性和耐蚀性等,使用范围广,特别在航天航空、交通运输和建筑等领域已得到广泛应用[2].多年来,国内外一直重视6000系铝合金耐蚀性的研究.

大量的实验结果显示,不适当的热处理或合金化处理会导致6000系列铝合金具有晶间腐蚀(IGC)敏感性[3].因此,近年来的研究主要集中于新型热处理工艺和合金成分设计等方面.本文将主要介绍与晶界直接相关的铝合金腐蚀类型、合金元素对6000系铝合金晶间腐蚀的影响以及6000系铝合金晶间腐蚀的研究现状,并对铝合金晶间腐蚀的研究方向进行了展望.

腐蚀01

腐蚀01

Brazeabilityofa3003AluminumAlloyWithAl-Si-Cu-BasedFillerMetalsL.C.Tsao,W.P.Weng,M.D.Cheng,C.W.Tsao,andT.H.Chuang(Submitted14November2001;inrevisedform4January2002)Al-Si-Cu-basedfillermetalshavebeenusedsuccessfullyforbrazing6061aluminumalloyasreportedintheauthors’previousstudies.Forapplicationinheatexchangersduringmanufacturing,thebrazeabilityof3003aluminumalloywiththesefillermetalsishereinfurtherevaluated.Experimentalresultsshowthatevenatsuchalowtemperatureas550°C,the3003alloyscanbebrazedwiththeAl-Si-Cufillersanddisplaybondingstrengthsthatarehigherthan77MPaaswell.Anoptimized3003jointisattainedinthebrazementswiththeinnovativeAl-7Si-20Cu-2Sn-1Mgfillermetalat575°Cfor30min,whichrevealsabondingstrengthcappingthe3003Almatrix.KeywordsAl-Si-Cufillers,3003aluminumalloy,brazeability1.Introduction3003aluminumalloypossessestheadvantagesofhighther-malconductivity,goodworkability,lowcost,andsuperiorcor-rosionresistance.Therefore,ithasplayedamajorroleinthemanufacturingofheatexchangers,merciallyavailablefillermetalsforthispurposeareusu-allytargetedattheAl-12Sialloy,whichhasaeutecticpointatabout577°C.However,brazingwiththetraditionalfillermetalatsuchahighmeltingtemperaturerequirestheprocesstobeperformedatarelativelyhightemperature(i.e.,above600°C).Asaresult,thealuminumworkpiecescanbepartiallymoltenintheindustrialfurnaceduringthebrazingprocess.Inthepastfewyears,tremendouseffortshavebeenmadeforthedevelopmentofalow-melting-pointfillermetaltobrazewithaluminumalloysthatwouldhavesatisfactorybondingstrength.Suzukietal.[1]hadintroducedaeutecticAl-4.2Si-40Znfillermetalwitha535°Cmeltingpoint,butitsdisad-vantagewouldlieintheveryhighvaporpressureofzinc,whichcouldconstitutequiteanimpedimenttothevacuumbrazingprocess.Kayamotoetal.[2]reportedonaseriesofAl-Ge-Si-Mgfillermetals,amongwhichthethreealloyswithhighergermaniumcontents(25,35,and45wt.%)possessedquitelowmeltingtemperatureranges(solidustoliquidus,435-480°C,448-510°C,and466-539°C,respectively).Whenthesefillermetalswereappliedtothebrazingofa6061alu-minumalloyat575°C,thebrazedjointsprovidedsufficientjointstrengthsabove200MPa.However,forbrazinga5052aluminumalloy,thebondingstrengthdecreasedtovalueslowerthan100MPa.Inaddition,germaniumisapproximately400timesthepriceofaluminum,makingthealloyexcessivelyexpensiveformostapplications.Humpstonetal.[3]andJacob-sonetal.[6]furtherdevelopedanAl-5Si-20Cu-2Nifillermetalwithameltingrangebetween518°Cand538°C.Whenthisfillermetalwasusedforbrazinga3001aluminumalloy,ashearstrengthover75MPawasobtained.Inthepreviousstudiesoftheauthors,thebrazeabilityofa6061-T6aluminumalloyusingaseriesofAl-Si-20Cu-basedfillermetalswasevaluated.[4,5]Forapplicationinthemanufac-turingofheatexchangers,thebrazeabilityofa3003aluminumalloywiththesefillermetalswasfurtherinvestigated.TheresultsarecomparedwiththoseusingthetraditionalAl-12Sifillermetal.2.ExperimentalThepreparationsofvariousfillermetals(Al-9.6Si-20Cu,Al-7Si-20Cu-2Sn,andAl-7Si-20Cu-2Sn-1Mg)werethesameasthosereportedinapreviousstudy.[1]Themicrostructuresofthefillermetalswereobservedbyopticalmicroscopy(OM)afteretchingina10vol.%H3PO4solutionat50°Cfor60s.L.C.Tso,W.P.Weng,M.D.Cheng,C.W.Tsao,andT.H.Chuang,InstituteofMaterialsScienceandEngineering,NationalTaiwanUni-versity,Taipei106,Taiwan.Contacte-mail:tunghan@.tw.Table1ChemicalComposition,SolidusandLiquidus,andtheUltimateTensileStrengthofthe3003AluminumAlloy(a)AlloyChemicalCompositionTS,°CTL,°C␴UTS,MPaMnSiCuZnFeAl3003-O1.070.280.120.010.48Bal.592654112(a)TS:solidus;TL:liquidus;␴UTS:ultimatetensilestrength;3003-O:annealingheattreatment.JMEPEG(2002)11:360-364©ASMInternational