磁性纳米流体及其终端技术应用.pdf

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磁性纳米流体及其终端技术应用1 磁性纳米流体及其终端技术应用2 磁性纳米流体及其终端技术应用3 磁性纳米流体及其终端技术应用4 磁性纳米流体及其终端技术应用5 磁性纳米流体及其终端技术应用6 磁性纳米流体及其终端技术应用7 磁性纳米流体及其终端技术应用8 磁性纳米流体及其终端技术应用9 磁性纳米流体及其终端技术应用10
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第43卷第9期—2015年9月第103112页材料工程JournalofMaterialsEngineeringVo1.43No.9Sep.2015PP.103~112磁性纳米流体及其终端技术应用—MagneticNanofluidandItsTerminalTechnologyApplication孙爱娟,方芬(宁夏大学化学化工学院,银川750021)SUNM-juan,FANGFen(SchoolofChemistryandChemicalEngineering,NingxiaUniversity,Yinchuan750021,China)摘要:综述了磁性纳米粒子制备技术的发展,重点讨论了磁性纳米粒子形成磁流体过程在极性或非极性载液中稳定悬浮的机理和磁性纳米流体的终端技术及其应用进展,并指出今后磁性纳米流体技术的研究工作应包括磁性纳米流体性能的主要影响因素、磁性纳米粒子与基液间的相容性、高温和长期使用条件下磁性纳米流体的稳定性以及添加剂的形状和属性对磁性纳米流体性能的影响等方面。关键词:磁性纳米流体;制备方法;分散机理;终端技术—doi:10.11868/i.issn.10014381.2015.09.016中图分类号:TQ584.9文献标识码:A———文章编号:10014381(2015)09010310Abstract:Thedevelopmentofmagneticnanoparticlespreparationtechnologywassummarized.Themechanismofstablesuspensioninthepolarornonpolarcarrierliquidduringtheformationofmagnetic—nanofluidandtheapplicationprogressofitsterminaltechnologywerediscussed.Itispointedoutthat——furtherresearchworkonmagneticnanofluidshouldinclude:themajorfactorsinfluencingtheperformanceofnano-fluid,thecompatibilitybetweennanoparticlesandthebasefluids,theeffectofthe——shapeandpropertyoftheadditive,stabilityofnanofluidontheperformanceofmagneticnanofluidathightemperatureandunderlongtermuseconditions.Keywords:magneticnano~fluid;preparationmethod;dispersionmechanism;terminaltechnology磁性纳米流体是兼具液体属性和磁性的新型智能纳米流体,同时也是一种三组分的胶体稳定体系。该体系通常由超顺磁性纳米粒子、载液及表面活性剂组成。载液是磁性纳米流体的主要组成部分,体系的黏度主要取决于载液的类型。磁性纳米粒子决定磁流体的饱和磁化强度。而磁性纳米粒子能否稳定分散在载液中取决于表面活性剂的分子结构、粒子表面电荷及其与流液的匹配性。此外,制备磁性纳米流体主要步骤包括:(1)制备超顺磁性纳米粒子;(2)表面活性剂修饰纳米粒子并将其分散在非极性或极性载液中。一些特殊的磁性纳米流体也可由合成高分子口]、二氧化硅口]、生物大分子等将磁性纳米粒子改性后分散在载液中获得。水基磁性纳米流体无需表面活性剂,只需将磁性纳米粒子进行离子化处理],使其表面带电荷,然后分散在水基载液中。磁性纳米流体具备固体磁铁所没有的流动性,这为磁性材料的应用开辟了新的篇章。其潜在的应用领域涵盖机械、生物医学和光学行业。目前磁性纳米流体的终端应用技术包括无泄漏密封、智能冷却、微型机器人、微机械传感器、传感器、可调光学无损缺陷过滤器、致动器、光学光栅、磁光波导、磁光波长滤波器、光开关、生物传感器、热疗治疗、肿瘤治疗、细胞分离、磁共振成像、药物靶向等技术_6]。本文将详细介绍磁性纳米粒子的制备方法,磁性纳米流体的稳定机理及其部分终端应用技术。1磁性纳米粒子的制备1.1机械化学合成法在表面活性剂的存在下通过球磨机研磨是制备磁性纳米粒子ll7]最早的方法。采用该方法获得的磁性粒子粒度分布较宽,通常需要离心分离去除大颗粒,否则可能导致磁流体凝聚和沉淀。该方法的缺点还在于研磨时间太长(1000h)。目前,机械化学合成法经改进后仍被用来制备磁性纳米粒子。Bellusci等r8使用高能球磨机在柠檬酸存在下制备锰铁氧体纳米粒子。经1h研磨便可产生直径约8nm的单晶体磁性纳米粒子。该纳米粒子呈超顺磁性且因均匀包覆柠檬酸而具104材料工程2015年9月有生物相容性。1.2共沉淀法共沉淀法是制备氧化铁磁性纳米粒子最常用的方法。该方法的优点是可通过控制实验条件来制备不同粒径(3~20nm)的磁性纳米粒子。大量研究证明l”_g.1o_,Fe和Fe抖的浓度与摩尔比,碱及其浓度是决定粒子大小的关键因素。沉淀温度,在碱性介质中加热沉淀以及在反应混合物中添加表面活性剂对粒径也会产生影响¨1。当未改性的磁性纳米粒子在碱性介质中加热,其粒径增加,增加的程度取决于粒子加热℃温度。在不加碱的情况下提高沉淀温度(2~90),粒”子粒径也会增加。在Fe和Fe摩尔比约为2:1的水溶液中加碱可制备Fe。o纳米粒子。Danescu等。将FeC1。・6HO和FeSO・7HO两种盐以摩尔比Fe:Fe。一1:2混合后溶于300ml水中,加入质量分数为1O的NaOH溶液并加热到80 ̄C。生成的Fe。O沉淀用0.1mol/L的盐酸反复清洗后分散在油酸中形成混合液,将混合液加入到绝缘油中制成磁流体。Fe。O纳米粒子,油酸,绝缘油的体积分数分别为5,10,85。而制备7一Fe。O。的方法相对简单,在Fe。O纳米粒子中加入0.34mol/L硝酸铁并加℃热到90保持30min便可将Fe。0纳米粒子口氧化制得纳米7-Fe0。。用一种或几种二价金属离子如Co,Mn抖,Ni,zn等全部或部分取代Fe抖可制备取代的铁氧体纳米粒子。Li也可以用来制备取代铁氧体。部分采用共沉淀法制备的取代铁氧体纳米粒子如表1所示。表1部分取代的铁氧体纳米粒子Table1SomekindsofreplacedferritenanoparticlesMagneticnanoparticleReferenceMagneticnanoparticleReferenceCoZnFe2O4(_丁一0,0.2,0.4,O.6,0.8,1.o)[15]Mn。5Zn05GdFe2O4(z一0.1,0.2,0.3,0.4)[23]…Co1ZnFe2O4(z一00.7)[16]…Mno5Cuo5NiFe2O4(一0,0.I,0.2,0.3,0.4,0.5)[24]Co1一ZnFe2O4(z一0,25,0.50,0.75)[17]Mno5Zna5Fe2O4[25]Mno5Fe【1_5FezO4[18]—FeBFe2O4(z一01;BMn,Co)[26]NiFelFe2O4(z0,0.1,0.2,0.3,0.4,0.5,0.6)L19,20]CoFe2O4,MnFe2O4[27]CoFe3--xO4(z=0,0.03,0.05,0.1)[21]Mno78Zno22Fe2O4[28]…ColMnZnFe2O4(z一0.9,0.5,0.1;-一0.45,0.25,0.05)[22]NiZn1Fe2O4(z=0.I,0.3,0.5)[29]采用共沉淀法制备Fe。o纳米粒子与取代铁氧体纳米粒子在原理上是相同的。但二者的磁性能差异较大__3。因此,通过共沉淀法可以定制不同性质的磁性纳米粒子,以满足不同的应用需求。例如,需要高磁晶各向异性的粒子,钴铁氧体口是最佳选择;若在热磁对流和热传导。。、热电转换_2方面应用,可制备具有强烈热磁效应和较低居里温度的取代铁氧体。1.3水热法水热还原法口制备水分散型Fe。O纳米粒子大小可控,而且具有成本低、环境友好等特点。在水热合成磁性纳米粒子的过程中可以加入表面活性剂进行粒子表面改性,特别适合制备生物相容性的磁性纳米粒子]。Behdadfar等利用一步水热合成法制备了平均粒径为10nm柠檬酸修饰的锌取代铁氧体纳米粒子(ZnFe3:rO)(一0,0.25,0.3,0.37,0.4)。结果表明:一定量的柠檬酸有助于获得单晶型锌取代Fe。0纳米粒子。柠檬酸作为调节剂和还原剂可以控制粒子大小并促进尖晶石晶体结构的形成。1.4微乳液法Fe。0或7一Fe:o。纳米粒子也可由微乳液法制备口。该方法需要借助表面活性剂制备两种微乳液:~种含有金属盐溶液,另一种含有碱溶液l3。;以适当的比例将这两种微乳液混合并反应得到磁性纳米粒子。微乳液法的缺点是用于合成的表面活性剂与流液可能不匹配。1.5有机金属化合物热分解法有机金属化合物热分解法是制备铁、钴纳米粒子等高磁化率磁性纳米粒子的重要方法。通过改变反应混合物及合成条件,能够对纳米粒子的组成、尺寸及尺寸分布进行精确控制c3。羰基铁/钴、乙酰丙酮铁/钴以及铁和钴的羧酸盐络合物都可作为前驱体制备铁、钴及其氧化物的单分散纳米粒子。在油酸的存在下通过分解溶解在辛醚中的五羰基铁可获得高度单分散的7-Fe03纳米颗粒。粒子的平均粒径为(4.9±0.7)nm。其中94的粒子尺寸为3.5~5.75nm,所有粒子均小℃于8nm。80~90时,在3000mL甲苯中加入171g℃Co(CO)。和88mLAI(csH)。并加热到110反应18h。将反应混合物冷却至室温,由一个小的毛细管导入空气对粒子进行钝化处理,可得到Co纳米粒子,该粒子可制备磁化强度较高的磁流体。1lO材料工程2015年9月决定。表面离子化和表面活性剂改性可增加纳米粒子间斥力促进胶体体系的稳定。通过改变合成方法和原料可为特定的技术应用量身定做磁性纳米粒子。磁性纳米流体现已用于微流控、传感器、致动器等纳米电动机械系统的设计和制造。而在目前开展的研究工作中仍然存在不确切、不完善、不全面的部分。若能解决上述技术问题,将使磁性纳米流体向更高性能、更多应用以及智能化方向发展。参考文献—[1]BRULLOTW,REDDYNK,WOUTERSJ,eta1.Versatilefer—rofluidsbasedonpolyethyleneglycolcoatedironoxidenanoparticles[J].JournalofMagnetismandMagneticMaterials,2012,324—(11):19191925.—[23SONIAGJ,JOANE.Ferrofluidbasedonpolyethyleneglycolcoatedironoxidenanoparticles:characterizationandproperties[J].ColloidsandSurfacesA:PhysicochemEngAspects,2013,—420:7481.—[3]CHENHJ,WANGYM,QUJM,eta1.Preparationandchar—acterizationofsiliconoilbasedferrofluid[J].AppliedSurfaceSci—enee,2011,257(24):1080210807.r4]SAFARIKOVAM,MADEROVAZ,SAFARIKI.FerrofluidmodifiedSaccharomycescerevisiaecellsforbiocatalysis[J].FoodResearchInternationa1,2009,42(4):521524.—[5]LIJ,QtUXY,I.INYQ,eta1.AstudyofmodifiedFenO4nanoparticlesforthesynthesisofionicferrofluids[J].AppliedSurface—Science,2010,256(23):69776981.[6]PHIIIPJ,LASKARJM.Opticalpropertiesandapplicationsof——ferrofluidsareview[J].JournalofNanofluids,2012,1(1):320.[7]PAPELISS.Lowviscositymagneticfluidobtainedbythecolloidalsuspensionofmagneticparticles[P].USPatent:3215572,—1965-0211.r8]BEILUSCIM,ALIOTTAC,FIORANID,eta1.Manganese—ironoxidesuperparamagneticpowderbymechanochemicalprocessing.Nanoparticles{unctionalizationanddispersionina—nanofluid[J].JNanopartRes,2012,14:904915.[9]CABUILV,NEVEUS,ROSENSWEIGRE.Magneticfluids—b|bliography[J].JMagnMagnMat,1993,122:437482.[1O3MASSARTR.Preparationofaqueousmagneticliquidsinalkalineandacidicmedia[J].IEEETransMagMag,1981,17(2):—12471248.[11]DAVIESKJ,WEIISS,CHARLESSW.Theeffectoftern—peratureandoleateadsorptiononthegrowthofmaghemiteparti——cles[J].JMagnMagnMat,1993,122(13):2428.[12]KHAIAFAILAS,REIMERSG.Magnetofluidsandtheirman—ufacture[P].USPatent:3764540,1973-1009.—r13]PISLARUDANESCUL,MOREGAA,TE1IPANG,eta1.NanoparticlesofferrofluidFen04synthetisedbycoprecipitationmethodusedinmicroactuationprocess[J].Opt。electronicsand——AdvancedMaterialsRapidCommunications,2010,4(8):11821186[14]BEEA,MASSARTR,NEVEUS.Synthesisofveryfine—maghemiteparticles[J].JMagnMagnMat,1995,149(12):——69.—r15]VAIDYANATHANG,SENDHIINATHANS.Characteriza——tionofCOlZnFe204nanoparticlessynthesizedbycoprecipita—tionmethod[J].PhysicaB:CondensedMatter,2008,403(13—16):21572167.[16]VAIDYANATHANG,SENDHILNATHANS.SynthesisandmagneticpropertiesofCo-Znmagneticfluid[J].JournalofMag—netismandMagneticMaterials,2008,320(6):803805.—[17]LOPEZJ,GONZAIEZBAHAMONLF,PRADOJ,eta1.Studyofmagneticandstructuralpropertiesofferrofluidsbased—oncobaltzincferritenan。particles[J].JournalofMagnetismand—MagneticMaterials,2012,324(4):394402.—[18]UPADHYAYRV,MEHTARV.MagneticpropertiesofultrafineparticlesofMnFeFe2O4spinelsystem[j].Journalof—Physics,1993,41(5):429442.[19]ABRAHAMVS,NAIRSS,RAJESHS,eta1.MagneticfieldinducedassemblingofnanoparticlesinferrofluidicliquidthinfilmsbasedonNiFe1-xFe2O4[J].BullMaterSci,2004,27(2):—155161.[2O]NAIRSS,XAVIARF,JOYPA,eta1.Enhancedshapeani—sotropyandmagnetoopticalbirefringencebyhighenergyballmillinginNiFe:一Fe204ferrofluids[J].JournalofMagnetism—andMagneticMaterials,2008,320(6):815820.[21]TACKETTR,SUDAKARC,NAIKG,eta1.Magneticandopticalresponseoftuningthemagnetocrystallineanisotropyin—Fe3O4nanoparticleferrofluidsbyCodoping[J 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