Sabtu, 03 Juli 2010

Carbon nanotube–polymer composites: Chemistry, processing, mechanical and electrical properties

sumber :

Zdenko Spitalskya, 1, Dimitrios Tasisb, Corresponding Author Contact Information, E-mail The Corresponding Author, Konstantinos Papagelisb and Costas Galiotisa, b

a FORTH/ICE-HT, Stadiou Str., 265 04 Rion Patras, Greece

b Department of Materials Science, University of Patras, 265 04 Rio Patras, Greece
Received 8 January 2009;
revised 9 September 2009;
accepted 15 September 2009.
Available online 25 September 2009.


Carbon nanotubes have long been recognized as the stiffest and strongest man-made material known to date. In addition, their high electrical conductivity has roused interest in the area of electrical appliances and communication related applications. However, due to their miniscule size, the excellent properties of these nanostructures can only be exploited if they are homogeneously embedded into light-weight matrices as those offered by a whole series of engineering polymers. We review the present state of polymer nanocomposites research in which the fillers are carbon nanotubes. In order to enhance their chemical affinity to engineering polymer matrices, chemical modification of the graphitic sidewalls and tips is necessary. In this review, an extended account of the various chemical strategies for grafting polymers onto carbon nanotubes and the manufacturing of carbon nanotube/polymer nanocomposites is given. The mechanical and electrical properties to date of a whole range of nanocomposites of various carbon nanotube contents are also reviewed in an attempt to facilitate progress in this emerging area.

Keywords: Carbon nanotubes; Polymers; Composites; Processing; Mechanical properties; Electrical properties

Abbreviations: ABS, acrylonitrile–butadiene–styrene copolymer; ACMA, acrylonitrile–methyl acrylate copolymer; AIBN, 2,2′-azobisisobutyronitrile; ATRP, atom transfer radical polymerization; CNT, carbon nanotube; CPP, chlorinated polypropylene; DWCNT, double-walled carbon nanotube; EDS, energy-dispersive X-ray spectroscopy; EMMA, ethyl–methyl methacrylate copolymer; EPDM, ethylene–propylene–diene rubber; EVA, ethylene–vinyl acetate copolymer; EVOH, ethylene–vinyl alcohol copolymer; HDPE, high-density polyethylene; HMW, high molecular weight; LDPE, low density polyethylene; LMW, low molecular weight; MA, maleic anhydride; MBMA, methyl–butyl methacrylate copolymer; MDPE, medium density polyethylene; MEMA, methyl–ethyl methacrylate copolymer; MPTS, methacryloxypropyltrimethoxysilane; MWCNT, multi-walled carbon nanotube; NMP, nitroxide-mediated polymerization; NMR, nuclear magnetic resonance; P3HT, poly(3-hexylthiophene); P3OT, poly(3-octylthiophene); PA, poly-acetylene; PAA, poly(acrylic acid); PABS, poly(m-aminobenzene sulfonic acid); PAM, polyacrylamide; PAMAM, poly(amidoamine); PAN, polyacrylonitrile; PANI, polyaniline; Parmax, poly(benzoyl-1,4-phenylene)-co-(1,3-phenylene); PBA, polybutyl acrylate; PtBA, poly(tert-butyl acrylate); PBMA, poly(butyl methacrylate); PBO, poly(phenylenebenzobisoxazole); PBT, poly(butyl terephthalate); PC, polycarbonate; PCL, polycaprolactone; PDEAEMA, poly[2-(diethylamino)ethyl methacrylate]; PDI, polydispersity index; PDMEMA, poly[2-(dimethylamino)ethyl methacrylate]; PDMS, polydimethylsiloxane; PDPA, polydiphenylamime; PE, polyethylene; PEG, polyethyleneglycol; PEI, polyethyleneimine; PEMA, poly(ethyl methacrylate); PEO, polyethyleneoxide; PET, poly(ethyl terephthalate); PETI, phenylethynyl-terminated imide; PGMA, poly(glycerol monomethacrylate); PHEMA, poly(2-hydroxyethyl methacrylate); PHET, poly[3-(2-hydroxyethyl)-2,5-thienylene]; PHPMA, poly[N-(2-hydroxypropyl)methacrylamide]; PI, polyimide; PIMA, poly(imidazolium methacrylate); PLLA, poly(l-lactic acid); PLLA-g-AA, poly(l-lactic acid) grafted with poly(acrylic acid) chains; PMDMAS, poly[3-(N-(3-methacrylamidopropyl)-N,N-dimethyl)ammoniopropanatesulfonate]; PMMA, poly(methyl methacrylate); PMMAHEMA, poly[(methyl methacrylate)-co-(2-hydroxyethyl methacrylate)]; PmPV, poly(m-phenylenevinylene-co-2,5-dioctoxy-p-phenylenevinylene); PNIPAAm, poly(N-isopropylacrylamide); PP, polypropylene; PPE, poly(p-phenylene ethynylene); PPEI-EI, poly(propionylethylenimine-co-ethylimine); PPS, poly(phenylene sulfide); PPY, polypyrrole; PS, polystyrene; PSS, poly(sodium 4-styrenesulfonate); PSV, poly(styrene-co-p-(4-(4′-vinylphenyl)-3-oxobutanol)); PTH, polythiophene; PU, polyurethane; PVA, poly(vinyl alcohol); PVAc, poly(vinyl acetate); PVAc-VA, poly(vinyl acetate-co-vinyl alcohol); PVC, poly(vinyl chloride); PVDF, poly(vinylidene fluoride); PVK, poly(N-vinyl carbazole); PVKV, poly(N-vinyl carbazole-co-p-(4-(4′-vinylphenyl)-3-oxobutanol)); PVP, polyvinylpyrrolidone; P2VP, poly(2-vinylpyridine); P4VP, poly(4-vinylpyridine); RAFT, reversible addition-fragmentation chain transfer polymerization; ROP, ring opening polymerization; SAN, styrene–acrylonitrile copolymer; SBA, styrene–butyl acrylate copolymer; SBBS, styrene–butadiene–butylene–styrene copolymer; SBR, styrene–butadiene rubber; SCMS, styrene-p-chloromethylstyrene copolymer; SE, silicone elastomer; SEC, size exclusion chromatography; SIBS, poly(styrene-b-isobutylene-b-styrene); SMA, styrene maleic anhydride copolymer; STM, scanning tunneling microscopy; SWCNT, single-walled carbon nanotube; TDI, toluene diisocyanate; TEMPO, 2,2,6,6-tetramethylpiperidinyl-1-oxy; TGA, thermogravimetric analysis; THF, tetrahydrofuran; UHMWPE, ultra high molecular weight polyethylene; WBPU, waterborne polyurethane
Article Outline

1. Introduction
2. Modification of carbon nanotubes with polymers

2.1. Method “grafting to”

2.1.1. Ester linkage between oxidized CNTs and polymers
2.1.2. Amide linkage between oxidized CNTs and polymers
2.1.3. Grafting by a radical mechanism
2.1.4. Nucleophilic addition/coupling reactions
2.1.5. Cycloaddition
2.1.6. Condensation
2.1.7. Sonochemical reaction

2.2. Method “grafting from”

2.2.1. Atom transfer radical polymerization (ATRP)
2.2.2. Reversible addition-fragmentation chain transfer (RAFT)
2.2.3. Ring opening polymerization (ROP)
2.2.4. Free radical polymerization
2.2.5. Cationic/anionic polymerization
2.2.6. Condensation polymerization
2.2.7. Reduction/oxidation polymerization
2.2.8. Metallocene catalysis polymerization
2.2.9. Electrochemical grafting
2.2.10. Nitroxide-mediated radical polymerization

2.3. Mixed mechanism
2.4. Endohedral filling

3. Composite processing

3.1. Solution processing of CNTs and polymer
3.2. Bulk mixing
3.3. Melt mixing
3.4. In situ polymerization
3.5. CNT-based fibers and films

3.5.1. Composite fibers
3.5.2. Composite films

4. Mechanical properties of carbon nanotube/polymer composites

4.1. Literature data
4.2. General conclusions-remarks

5. Electrical properties of carbon nanotube/polymer composites

5.1. Literature data
5.2. General conclusions-remarks


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