聚合物基复合材料介电性能研究综诉.pdf

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1、Fundamentals,processes and applicationsof high-permittivity polymermatrix compositesZhi-Min Danga,b,c,Jin-Kai Yuanb,Jun-Wei Zhaa,Tao Zhoub,Sheng-Tao Lic,Guo-Hua Hud,e,aDepartment of Polymer Science and Engineering,School of Chemical and Biological Engineering,University of Science&Technology Beijing

2、,Beijing 100083,ChinabState Key Laboratory of Chemical Resource Engineering,Beijing University of Chemical Technology,Beijing 100029,ChinacState Key Laboratory of Electrical Insulation and Power Equipment,Xian Jiaotong University,Xian 710049,ChinadLaboratory of Reactions and Process Engineering,Nanc

3、y University,CNRS-ENSIC-INPL,1 rue Grandville,B.P.451,54001 Nancy Cedex,FranceeInstitut Universitaire de France,Maison des Universits,103 Boulevard Saint-Michel,75005 Paris,Francea r t i c l ei n f oArticle history:Received 21 April 2011Received in revised form 27 May 2011Accepted 14 August 2011Avai

4、lable online 25 August 2011a b s t r a c tThere is an increasing need for high-permittivity(high-k)materialsdue to rapid development of electrical/electronic industry.It iswell-known that single composition materials cannot meet thehigh-k need.The combination of dissimilar materials is expectedto be

5、 an effective way to fabricate composites with high-k,especial0079-6425/$-see front matter?2011 Elsevier Ltd.All rights reserved.doi:10.1016/j.pmatsci.2011.08.001Abbreviations:Al2O3,alumina;BaTiO3,barium titanate;CB,carbon black;CCTO,calcium copper titanate;CF,carbon fiber;CH2Cl2,dichlodo methylene

6、chloride;CNF,carbon nanofiber;CNT,carbon nanotubes;CuPc,copper-phthalocyanine;DBSA,dodecylbenzene sulfonic acid;DMF,dimethyl formamide;HA,hydroxyapatite;HDPE,high-density polyethylene;LDPE,low-density polyethylene;LTNO,Li and Ti codoped NiO;MNCB,modified nanoscale carbon black;MWNT,multi-wall carbon

7、nanotubes;NMP,N-methyl-pyrrolidone;ODA,4,40-oxydianiline;PA,polyamide;PAA,poly(amic acid);PANI,polyaniline;PbTiO3,lead titanate;PC,polycarbonate;PCMS,poly(p-chloromethyl styrene);PE,polyethylene;PEEK,polyetheretherketone;PFSA,perfluorosulfonic acid;PHAE,polyhydroxyaminoether;PI,polyimide;PLZT,lead l

8、anthanum zirconium titanate;PMDA,pyromellitic dianhydride;PMeT,poly(3-methylthiophene);PMMA,polymethylmethacrylate;PMNPT,lead magnesiumniobatelead titanate;POM,polyoxymethylene or polyformaldehyde;PP,polypropylene;PPY,polypyrrole;PS,polystyrene;PU,polyurethane;PVA,polyvinyl alcohol;PVDF,polyvinylide

9、ne fluoride;P(VDFTrFE),poly(vinylidene fluoridetrifluoroeth-ylene);P(VDFTrFECFE),poly(vinylidene fluoridetrifluoroethylenechlorofluoroethylene);P(VDFTrFECTFE),poly(vinyli-dene fluoridetrifluoroethylenechlorotrifluoroethylene);PVP,polyvinyl pyrrolidone;PZT,lead zirconium titanate;SiO2,silicon dioxide

10、;SPAI,siloxanemodified polyamideimide;SrTiO3,zirconium titanate;SWNT,single-wall carbon nanotubes;TFBB,3,4,5-trifluorobromobenzene;TFP-MWNT,trifluorophenyl(TFP)-functionalized MWNTs;THF,tetrahydrofurane;TiO2,titaniumdioxide;TMPTA,trimethylolpropane triacrylate;UHMWPE,ultrahigh molecular weight polye

11、thylene;xGnP,exfoliated graphitenanoplates.Corresponding authors.Addresses:Department of Polymer Science and Engineering,School of Chemical and BiologicalEngineering,University of Science&Technology Beijing,Beijing 100083,China.Tel./Fax:+86 10 6233 2599(Z.-M.Dang),Laboratory of Reactions and Process

12、 Engineering,Nancy University,CNRS-ENSIC-INPL,1 rue Grandville,B.P.451,54001 NancyCedex,France.Tel.:+33 383 17 53 39;fax:+33 383 32 29 75(G.-H.Hu).E-mail addresses:(Z.-M.Dang),guo-hua.huensic.inpl-nancy.fr(G.-H.Hu).Progress in Materials Science 57(2012)660723Contents lists available at SciVerse Scie

13、nceDirectProgress in Materials Sciencejournal homepage: high-k polymermatrix composites(PMC).This review paperfocuses on the important role and challenges of high-k PMC innew technologies.The use of different materials in the PMC createsinterfaces which have a crucial effect on final dielectric prop

14、erties.Therefore it is necessary to understand dielectric properties andprocessing need before the high-k PMC can be made and appliedcommercially.Theoretical models for increasing dielectric permit-tivity are summarized and are used to explain the behavior ofdielectric properties.The effects of fill

15、ers,fabrication processesand the nature of the interfaces between fillers and polymers arediscussed.Potential applications of high-k PMC are also discussed.?2011 Elsevier Ltd.All rights reserved.Contents1.Introduction.6622.Fundamental aspects of high-k composites.6652.1.Definition of high permittivi

16、ty(high-k).6652.2.Capacitance and electric energy storage of materials.6662.3.Polarization and relaxation of dielectric materials.6662.4.Dielectric strength of random polymermatrix composites.6682.5.Theoretical models for dielectric properties of polymermatrix composites.6692.5.1.MaxwellGarnett equa

17、tion.6692.5.2.Bruggeman self-consistent effective medium approximation.6702.5.3.JaysundereSmith equation.6702.5.4.Lichtenker rule.6712.5.5.Percolation model.6712.6.Connection type of PMC.6743.Processes for the fabrication of high-k PMC.6743.1.Solid phase processes.6743.1.1.Direct compounding.6743.1.

18、2.Melt compounding.6753.2.Liquid phase processes.6753.2.1.Liquid-phase assisted dispersion.6753.2.2.Solution route.6763.3.In situ polymerization processes.6764.Microstructure and interfaces of high-k PMC.6774.1.Two-phase high-k PMC.6774.2.Three-phase high-k PMC.6815.Effect of fillers on dielectric p

19、roperties of high-k PMC.6835.1.Concentration effect of fillers on dielectric properties.6845.1.1.Effect of ceramic fillers.6845.1.2.Effect of electrical conducting fillers.6875.2.Size effect of fillers on dielectric properties of PMC.6895.2.1.Change in physical properties of fillers with size reduct

20、ion.6895.2.2.Dependence of dielectric properties of PMC on size of fillers.6905.2.3.Effect of micronanosize cofillers on dielectric properties of PMC.6925.3.Shape effect of fillers on dielectric properties.6945.3.1.Shape of fillers and fillerpolymer connectivity.6945.3.2.Effect of 1-dimensional fibe

21、r-shape fillers on dielectric properties.6955.3.3.Effect of 2-demension plate-shape fillers on dielectric properties.6985.3.4.Effect of coreshell fillers on dielectric properties.6986.Effects of measurement conditions on dielectric properties.7006.1.Temperature dependence of dielectric properties.70

22、06.1.1.Organic fillers/polymer composites.7006.1.2.Insulating ceramic fillers/polymer composites.701Z.-M.Dang et al./Progress in Materials Science 57(2012)6607236616.1.3.Semiconducting ceramic fillers/polymer composites.7026.1.4.Conducting fillers/polymer composites.7036.2.Frequency dependence of di

23、electric properties.7036.2.1.Organic fillers/polymer composites.7036.2.2.Ceramic fillers/polymer composites.7056.2.3.Conducting fillers/polymer composites.7076.3.Electrical field dependence of dielectric properties.7077.Applications for high-k PMCs.7097.1.Applications in microelectronic field.7097.2

24、.Applications in electrical engineering field.7127.3.Applications in biomedical fields.7138.Concluding remarks and future perspective.714Acknowledgements.715References.7151.IntroductionAs predicted by Moores law,the efficiency of electronic products is improving in an exponentialmanner 1,2.This rapi

25、d improvement in efficiency is concomitant with the creation of new materialswith high permittivity(called high-k dielectric materials).A higher-k dielectric material can storemore electric energy than a lower one.As a result,its use in electronic devices allows improving theirefficiency.Electronic

26、systems are often composed of active components such as integrate circuits(ICs)and passive components.Passive components have become of an increasing interest because they aresteadily growing in number as the electronics industry is progressing toward higher functionality 1.For example,the ratio of

27、the passive to active components in a mobile cellular phone is over 20 2.Inthe next generation packaging technology,the passive components such as capacitors(C),resistors(R)and inductors(L)will be integrated into the substrate as a thin film layer instead of being surfacemounted on the top of the su

28、bstrate as discrete components.The passive components buried insidethe substrate are called integral passives or embedded ones.Embedded passives provide many advan-tages over discrete components and play an important role in microelectronic field,as shown in Fig.13.Among all passive components,capac

29、itors call for special attention.Fig.2 shows the market sharesof capacitors,resistors,and inductors in the United States.Because of the large amount of capacitorsemployed in electronic systems,integration of capacitors is of much importance.Capacitors havemany applications,as shown in Table 1.They c

30、an be used for filtering,timing,alternating/direct(A/D)current conversion,termination,decoupling,and energy storage.Particularly,the developmentof microelectronics requires decoupling capacitors with higher capacitance and shorter distance fromits serving devices 4.Apart from electronic industry,hig

31、h-k materials are widely used in many civilian and militaryapplications including active vibration control,aerospace,underwater navigation and surveillance,hydrophones,biomedical imaging,non-destructive testing and air imaging microphones 5,6.Forexample,high-k elastic rubbermatrix composites could b

32、e used as potential functional materialsfor cable accessories in electrical engineering because they could balance the distribution of electricfield of cable terminal to prevent the cable from failure.Fig.3 shows a clear field distribution of cableterminal before and after the use of high-k rubberma

33、trix materials.In fact,ceramics and metals with high stiffness and excellent thermal stability have also a high-k.However,their high density,brittleness and challenging processing conditions impede their use ashigh-k materials.On the other hand,polymers have the advantage of easy processing and mech

34、anicalflexibility and low cost.Moreover,integration of resistors and capacitors into the internal structure ofprinted wiring boards(PWB),or,directly into integrated circuits packaging requires materials compat-ible with polymers used as support of electronic circuits 710.Mechanical flexibility and t

35、unableproperties of polymer matrix composites(PMC)make them attractive.In addition,polymer materials662Z.-M.Dang et al./Progress in Materials Science 57(2012)660723have found many applications for electromechanical devices to perform energy conversion betweenthe electric and mechanical forms.These d

36、evices could be served as artificial muscles,smart skinsfor drag reduction,actuators for active noise and vibration controls,and microfluidic systems for drugdelivery and micro-reactors 1114.However compared with inorganic materials,organic polymermaterials have often low dielectric permittivity,in

37、the range of 25 15.In exceptional cases thedielectric permittivity of a pure polymer can go beyond 10,but is still very low,impeding their usefor high-k applications,despite their excellent physical properties.Thus a key issue is to substantiallyraise the dielectric permittivity of polymers while re

38、taining their excellent mechanical properties.Very recently,polymer composites with high-k and low dielectric loss and good process compatibilityFig.1.(a)Technology trend and market for organic substrates,(b)a schematic image of embedded passive substrate,the arrowshowing position of passives 3.Fig.

39、2.Market share of capacitors,resistors,and inductors 4.Table 1Applications and properties of capacitors.ApplicationValue rangeStability requiredTolerance requiredFiltering,timing1 pF to 100 nFModerateModerateA/D Conversion1 pF to 10 nFVery highVery highTermination50200 pFLowLowDecoupling1100 nFLowLo

40、wEnergy storage1lFLowLowZ.-M.Dang et al./Progress in Materials Science 57(2012)660723663with printed circuit boards(PCBs)have been recognized as promising candidate dielectric materialsfor embedded capacitors.This is because high-k polymer composites provide an ideal solution to com-bine the dielect

41、ric and electrical properties of the ceramic or metal fillers and the low-temperatureprocessability and mechanical properties of the polymer matrix 1645.Furthermore,their goodadhesive properties are additional advantage for their use in embedded capacitor technology,whichpure ceramics or other diele

42、ctric materials lack.Recently,a few strategies,including random composites of polymers,field structured compositesand synthesis of new polymers,have been developed to improve the dielectric permittivity of PMC.The most common one is addition of fillers in polymers to make composites.These fillers in

43、cludesmetals 1625,ceramics 2645,carbon based materials 4662 and organic fillers such as semi-conductive olligomer 6371 and conducting polymers 7276.In general,ceramicpolymer com-posites are prepared by adding high-k ceramic fillers in polymer matrices 2645.The advantagesof these composites include p

44、redictable dielectric properties,relatively low dielectric loss and easyfabrication 20,28,29,43.However,remarkable issues for use of the ceramicpolymer compositesare related to the deterioration of mechanical and processing properties due to the high concentrationof rigid ceramic particles in the fl

45、exible polymer matrix.By replacing ceramic particles with conduc-tive particles,percolative polymer composites can be made with a drastic increase in dielectric per-mittivity in the vicinity of the percolation threshold of the conductive particles.For example,high-kdielectric composites with highly

46、conducting fillers such as metals and carbon nanotubes have beendeveloped on the basis of percolation 1625,6376.A permittivity value of 2000 has been reportedfor silver flakes-doped epoxy systems 77.Dang et al.reported a value of 400 in Ni/PVDF composites19,20.These remarkable increases in dielectri

47、c permittivity,however,are always concomitant withsignificant increases in electrical conductivity and dielectric loss due to the insulatorconductor tran-sition occurring at the percolation threshold.This transition also leads to extreme sensitivity of thedielectric permittivity to the content of th

48、e conductive fillers.In other words,a small deviation fromthe percolation threshold could result in serious drop of the dielectric permittivity,making it ratherdifficult to control the parameters of the preparation process.The issues mentioned above are consid-ered as drawbacks for conducting filler

49、s/polymer composite systems.As a milestone,superior electrical properties of nanotubes offer excitingopportunitiesfor newhigh-k polymer composites.Apart from electrical properties,nanotubes also impart better mechanical prop-erties to composites at relatively low filler content 52.Higher surface are

50、a and larger aspect ratios areresponsible for superior dielectric properties of nanotube composites 50,51.At the same time,agglomeration of nanotubes and their compatibility to polymer matrices are prime concern ofresearchers in this field.Although different strategies including modifications of nan