Progress in Polymer Science 37 (2012) 487–513

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Progress in Polymer Science
journal homepage: www.elsevier.com/locate/ppolysci

Polyacrylonitrile-based nanofibers—A state-of-the-art review
S.K. Nataraj a,b,∗ , K.S. Yang b,∗ , T.M. Aminabhavi b
a
Cavendish Laboratory, Department of Physics, University of Cambridge, JJ Thomson Avenue, Cambridge CB3 0HE, United Kingdom
b
Carbon Materials Lab, Alan G. MacDiarmid Energy Research Institute (AMERI), Chonnam National University, Gwangju 500-757, South Korea

a r t i c l e i n f o a b s t r a c t

Article history: Polyacrylonitrile (PAN), a well-known polymer with good stability and mechanical prop-
Available online 18 July 2011 erties, has been widely used in producing carbon nanofibers (CNFs) as these have attracted
much recent attention due to their excellent characteristics, such as spinnability, environ-
Keywords: mentally benign nature and commercial viability. Among the various precursors to produce
Polyacrylonitrile
CNFs, PAN has been extensively studied due to its high carbon yield and flexibility for tai-
Electrospinning
loring the structure of the final CNFs as well as the ease of obtaining stabilized products
Nanofibers
Activation
due to the formation of a ladder structure via nitrile polymerization. In view of this, they
Carbon nanofibers have applications in areas such as electronics, tissue engineering, membrane filtration and
high performance composites. This review presents various combinations of PAN and PAN-
based precursors in producing CNFs from the PAN homopolymer or its modified precursors,
copolymers, blends and various composites. Various modifications of PAN and their future
prospects in different scientific and technological disciplines are addressed.
© 2011 Elsevier Ltd. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 488
2. Polyacrylonitrile as a fiber . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 488
3. Techniques to produce nanofibers and electrospinning . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 488
4. Carbon nanofiber . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 488
4.1. Porous CNFs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 490
4.1.1. PAN homopolymer . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 490
4.1.2. Modifications of PAN as a precursor . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 493

Abbreviations: (NaCo2 O4 ), sodium cobalt oxide; [Pt(acac)2 ], platinum(II) acetylacetonate; AAO, anodic aluminum oxide; ACNFS, activated carbon
nanofibers; AFM, atomic force microscopy; CCVD, catalytic chemical vapor deposition; CNFs, carbon nanofibers; CR, Congo red; DMAc, dimethylacetamide;
DMF, dimethylformamide; DMS, dimethylsulfone; DMSO, dimethylsulfoxide; DWNTs, double walled carbon nanotubes; EB, 1-(o-cyanostyryl)-4-(p-
cyanostyryl)benzene; EDC/NHS, N-(3-dimethylaminopropyl)-N -ethylcarbodiimide hydrochloride and N-hydroxysuccinimide; EDLC, electrochemical
double-layer capacitors; ER, 1,4-bis(o-cyanostyryl)benzene; Fe(Acc)3 , Fe(acetylacetonate)3 ; FE-SEM, Fourier transform scanning electron microscopy; FTIR,
Fourier transform infra-red spectrometer; GNFs, graphite nanofibers; HRXRD, high resolution X-ray diffraction; MB, methylene blue; MWCNTS, multiwalled
carbon nanotubes; NFs, nanofibers; PAN, polyacrylonitrile; PAN-b-PMMA, poly(acrlylonitrile-b-methyl methacrylate); PAN-b-PS, poly(acrylonitrile-b-
polystyrene); PANCAA, poly(acrylonitrile-co-acrylic acid); PANCAA, poly(acrylonitrile-co-acrylic acid); PANCMA, poly(acrylonitrile-co-maleic acid); PANOx,
polyacrylamidoxime; PEO, polyethyleneoxide; PEU, poly(ester urethane); PL, photoluminescence; PMMA, poly(methyl methacrylate); Poly(AN-co-MMA),
poly(acrylonitrile-co-methyl methacrylate); PU, polyurethane; PVdF, poly(vinylidoneflouride); PVP, poly(vinylpyrrilidone); RS, Raman spectroscopy; RSM,
response surface methodology; SERS, surface-enhanced Raman scattering; SiMoA, silicomolybdic acid; SiWA, silicotungstic acid; SWCNTs, single walled
carbon nanotubes; TEM, transmission electron microscopy; THF, tetrahydrofuran; TMS, tetramethylsulfide; VGCNFs, vapor grown carbon nanofibers;
WAXRD, wide angle X-ray diffraction; XRD, X-ray diffraction.
∗ Corresponding authors. Tel.: +82 625301774; fax: +82 625301779.
E-mail addresses: sknata@gmail.com, skn30@cam.ac.uk (S.K. Nataraj), ksyang@chonnam.ac.kr (K.S. Yang), aminabhavi@yahoo.com (T.M. Aminabhavi).

0079-6700/$ – see front matter © 2011 Elsevier Ltd. All rights reserved.
doi:10.1016/j.progpolymsci.2011.07.001

488 S.K. Nataraj et al. / Progress in Polymer Science 37 (2012) 487–513

4.1.3. PAN blends . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 498
4.1.4. Metal oxide incorporated PAN . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 499
4.2. Composite PAN nanofibers containing CNTs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 503
5. PAN-based nanofibers for electronic and energy storage applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 505
6. PAN-based mechanical nanofibers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 505
7. PAN-based nanofibers as filtration membranes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 507
8. Specialized applications and future prospects of PAN-based CNFs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 508
9. Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 508
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 508
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 509

1. Introduction DuPont. PAN is soluble in polar solvents like DMF, DMSO,
DMAc, dimethylsulfone, tetramethylsulfide and aqueous
Polyacrylonitrile (PAN) and copolymers of PAN have solutions of ethylene carbonate, as well as some mineral
been widely studied for almost a century for commer- salts. PAN forms saturated solution with 25% dissolved in
cial/technological exploitations. PAN may be crosslinked, DMF at 50 ◦ C, which is high solubility compared to other
but also may exist without crosslinking. Crosslinking of solvents [9]. PAN and its copolymers are predominantly
PAN will impart some of its important physical properties, white powders up to 250 ◦ C, at which point they become
such as insolubility and resistance to swelling in com- darker due to degradation. Having a relatively high Tg , these
mon organic solvents. Recently, considerable efforts have polymers have low thermal plasticity and cannot be used
been devoted to its processing and fiber forming technolo- as a plastic material. The high crystalline melting point
gies. Among the various precursors for producing carbon (317 ◦ C) of PAN, its limited solubility in certain solvents
nanofibers (CNFs), PAN is the most commonly used poly- coupled with superior mechanical properties of its fibers is
mer, mainly due to its high carbon yield (up to 56%), due to intermolecular forces between the polymer chains.
flexibility for tailoring the structure of the final CNF prod- Appreciable electrostatic forces occur between the dipoles
ucts and the ease of obtaining stabilized products due to of adjacent C N groups and this intramolecular interac-
the formation of a ladder structure via nitrile polymeriza- tion restricts the bond rotation, leading to a stiffer chain
tion [1–5]. The chemistry of PAN is of particular interest [10]. The properties of CNFs are strongly dependent on the
because of its use as a precursor in the formation of CNFs microstructure of the stabilized PAN fiber [11–20].
for different applications, including porous structured CNFs
of high surface area for electronics and energy storage 3. Techniques to produce nanofibers and
applications as well as graphite reinforcement filaments for electrospinning
organic materials in high strength and high stiffness com-
posites. The recent review by Inagaki et al. [6] describes There are a number of methods to produce nanofibers,
the chemistry and applications of CNFs, restricted mainly e.g., vapor growth [21], arc discharge [22], laser ablation
to the research on scientific and technological develop- and chemical vapor deposition [23]. However, these are
ments in Japan. Barhate and Ramakrishna [7] published a very expensive processes due to low product yield and
review on nanofibers as a filtering media for tiny materi- the expensive equipment required. On the other hand, the
als. Li and Xia [8] discussed about the trends in nanofibers electrospinning method, invented in 1934, can generate
with emphasis on electrospinning techniques to produce fibers with diameters from 10 nm to 10 ␮m [24,25] from a
nanofibers. However, to the best of our knowledge, no polymer solution under the application of an electrostatic
review on the overall critical assessment of research activ- force. The applied electric field and solution conductivity
ities on PAN-based CNFs prepared by different techniques are important parameters that influence the fiber diame-
and their numerous applications in a variety of areas as ter during the spinning, in addition to parameters such as
shown in Fig. 1. Various modifications of PAN as an efficient the jet length, solution viscosity, surrounding gas, flow rate,
precursor and their future prospects in different scientific and the geometry of the collector assembly [26–30]. Fig. 2
and technological fields as well as commercial applications displays the electrospinning process; these details can be
are addressed in the following. found in published reports [31–33].

2. Polyacrylonitrile as a fiber 4. Carbon nanofiber

Even though acrylonitrile (AN) was known as far back A carbon nanofiber (CNF) is a long, thin strand of
as 1893, but PAN, because of difficulties in dissolving it material, about 10–1000 nm diameter composed mostly
for spinning, no progress was made in converting into a of carbon atoms bonded together in microscopic crystals
usable fiber until 1925. Acrylonitrile monomer was also and aligned parallel to the long axis of the fiber. The crys-
useful as a copolymer with styrene, especially in a terpoly- tal alignment makes the fiber exceptionally strong for its
mer with styrene and butadiene, known as ABS rubber. The size. The preparation of CNFs from PAN precursor involves
homopolymer of PAN was developed for manufacturing of three main stages; electrospinning, oxidative stabilization
fibers in 1940, after a suitable solvent was discovered by and carbonization. Adequate stabilization of the spun PAN

inducing cyclization of nitrile groups (C N) the stabilized PAN fibers in an inert atmosphere [34–36] and crosslinking of the chain molecules in the form of removes non-carbonized components selectively in the Fig. Stabiliza. carbonizing atmosphere. Nataraj et al. In the second step. / Progress in Polymer Science 37 (2012) 487–513 489 Fig. fiber is necessary in obtaining good quality CNFs. –C N–C N–.K. Schematic diagram of electrospinning apparatus. 1. . Broad spectrum of PAN-based nanofiber applications in various fields. a process that prevents melting during sub- tion involves heating PAN fibers in an oxygen-containing sequent carbonization. S. 2.

evaluated by optical and scanning probe microscopes. NH3 . respectively. viz. CO.K. acrylonitrile within the pores of alumina film. CO2 and N2 . For the same reason. Among many techniques used for the strate was used in place of a collector to accumulate PAN synthesis of CNFs and CNTs. brane as a template and extruding PAN precursor solution ratio of the precursor [57. minum oxide membrane was used as the template (see but since the carbon fiber properties depend upon the pre. By contrast. The length and cross-section area of the pitches [51]. [65] through electrospinning and subsequent pyrolysis. with 600 mg PAN dissolved in structure. to around 490 S/m.1 MPa resulted in the formation of PAN bonized structure of PAN. such as incorporation of cer. Due to their high specific surface areas. When glycerol is used as the of 18 wt. 2 and large-scale production of CNFs are from PAN. leading to the fabrication of sensor of the original PAN. vacuum pyrolysis techniques. PAN homopolymer were pyrolyzed at 1000 ◦ C for 27 h in vacuum (10 Torr). precursor solutions using electrospinning and vacuum bon yields [43–50].62] were the first to prepare The magneto-conductance of these materials was negative PAN nanofibers having diameters typically in the range with a parabolic dependence on the transverse magnetic from 100 nm to a few microns.490 S. resulting in the formation of a network commercial grade PAN. Carbonizing involves the heat treatment of the sta. copolymeriza. were used to calculate the electrical conduc- grade PAN contains 15% comonomers. the conductivity varied less obviously with bution. Carbon polymorphs are field and the conductivity was about 27535 S/m. SantiagoAviles and Wang [71] later bilized PAN fibers to remove non-carbon elements in the performed conductivity and magneto-conductance mea- form of different gases ranging from 700 to 1500 ◦ C in an surements on CNFs prepared by using electrospinning and inert atmosphere. When the PAN fiber is subjected NFs. Nataraj et al. crystallinity. Commer. to a sharp increase in conductivity. post-spinning stretching in super-heated steam and nitro. but the amount of tivity. characteristics. molecular orientation and pyrolysis time at higher pyrolysis temperatures of 900 and impurities [52]. The three precursors that are used in pyrolysis at temperatures from 500 to 1000 ◦ C for 0. the precursor into a liquid for solidification using a pump Fig. increasing considerably with pyrolysis time cially available PAN precursors differ appreciably in their at lower pyrolysis temperatures. 10 mL of DMF.. On the other hand. For this process. ultrafine fibers can be used as high performance filters carbon precursors were developed via polymerization of or scaffolds in tissue engineering. Gib- mechanical and other properties of the final CNFs. The conductivity increased sharply with pyrolysis comonomers in PAN used for CNFs is less than 8%. thick film of silicon oxide were lithographically patterned with a 131-mm gold contact array. Extruding tion. to one may expect that chemisorbed gases may modulate give carbon fibers with a yield of about 50–57% of the mass electrical conductivity. 600. gold coated target of patterned Si-wafer sub- displays [37–42]. diameter.58]. fibers shrink in diameter. A clean and dry template was placed on a com- cursor properties. [72] on [63]. tensile properties are much improved. batteries. After carbonizing at 800 ◦ C. attention in view of their unusual structural and electronic the PAN-based graphite NFs were obtained by Wang et al. denitrogena. Fig. such as molecular weight and its distri. The as-spun PAN fibers 4. mechanical properties are not so important. rayon. A self- the well-known Raman-active groups in these materials lubricating anodic film was developed by Zhao et al. temperature. properties. and field emission that study. while companies prefer to manufacture their own precursors Ryu et al. Since these characteristics will affect the 1000 ◦ C due to thermally activated transformation. NFs were prepared from PAN/DMF shown poor mechanical properties giving very low car. In tors (EDLC).56]. Regular textile respectively. dense ladder-polymer The significance of pyrolysis temperature on carbon structure begins to form above 200 ◦ C by reacting with oxy. tion of PAN [70]. During this process. Porous CNFs with a 20–25 nm thin layer of a conducting polymer with a polypyrrole by immersing PAN-based graphite NFs in Carbon nanotubes (CNTs) and CNFs have attracted much an aqueous solution of polypyrrole. catalyst supports. resin using low temperature nitrogen adsorption methods over coatings to suppress the cyclization exothermicity [54]. to the stabilization temperature. [69] developed a novel and simple method to gen to improve the structure [55. Chun and co-workers [61. many son et al. the pressure range from 10−6 to 1 Pa. efforts have been made to improve the pact polytetrafluroroethylene (PTFE) film and the upper properties of PAN structure by modification. 4). blending as well as in the composite form [59]. using various activation methods that were characterized tain additives to catalyze the cyclization reaction [53]. electrospinning and catalytic spun fibers for subsequent single fiber conductivity mea- chemical vapor deposition (CCVD) are the most promising surements. CNFs were .1. / Progress in Polymer Science 37 (2012) 487–513 form of gases.5.1. [67] explored NFs as filtration membranes. an anodic alu- drawing medium.1. The precursor used was a tion takes place. cavity was filled with PAN precursor solution. Feng et al.% of PAN in DMF. and 5 h. The graphitization of the PAN nanofiber led ones. 700 and 800 ◦ C. 3 displays the schematic route of forming the car. MacDiarmid et al. useful in electrochemical double-layer capaci. HCN. [64] coated the PAN nanofibers evenly 4. devices. The modulus and synthesize PAN NFs using an anodic aluminum oxide mem- strength of the final CNFs are directly related to stretch. electrospun aluminum by re-anodizing in oxalic acid and subsequently. [68] reported the fabrication of PAN-based CNFs using modified procedures. at a pressure of 0. such as H2 O. The polymer precursors used for making CNFs have In another study [66]. Silicon wafer substrates with a 150-nm losing approximately 50% of its weight. fibers at 1000 ◦ C and above was examined to study the gen that prevents melting during subsequent carbonization effect of various intermediate steps involved in carboniza- [60]. while other precursors are generally used if NFs.

The carbonized PAN nanofibers AN. sensors. treatment at 220 ◦ C for 24 h in atmospheric air leading to Low-temperature electronic transport properties of yield sepiolite-PAN nanocomposite. This natural CNFs. [73] used another method to prepare Jang and Bae [74] demonstrated a salt-assisted CNFs consisting of graphitization of previously formed microemulsion polymerization technique to synthesize PAN inside the nanosized pores of sepiolite. Schematics of the formation of carbonized structure from PAN nanofiber. Nataraj et al. polymerization. useful for applications in diverse electro- on aluminum to improve the wear properties of the alu. electrocatalysts. 6. Fig. 1 g of dehydrated sepiolite was added to 3 mL of under inert N2 atmosphere. in which iron(III) chloride coordinates PAN nanopar- microfibrous silicate contains structural pores extending ticles formed as spherical micelles in the microemulsion throughout its volume able to contain acrylonitrile.K. Carbonization to eliminate free water before mixing with the monomer. After uum pyrolysis at temperatures from 500 to 1000 ◦ C by soaking for 24 h. Fernández et al. 5 shows resulting electrospun PAN-based carbonized nanofibers have been solids that constitute a new class of conductive carbon-clay reported [76]. followed by heat were investigated [75]. Further. were used as conducting fillers for polymer composites to lite sample using a syringe inside a glove box to avoid enhance the conductivity. the mixture was heated at 60 ◦ C for 24 h in Wang et al. / Progress in Polymer Science 37 (2012) 487–513 491 Fig. applied in the pores of the porous anodic oxide film (AOF) nanocomposites. CNFs were also produced from contact of any water from the atmospheric air with the PAN/DMF precursor solution by electrospinning and vac- sepiolite and AIBN was used as a radical initiator. was done by heating PAN nanofibers up to 900 ◦ C for 4 h Then. 3. their electrical conductivities sealed bottles to induce polymerization. and the mixture was slowly sprayed onto a sepio. and/or mina film. chemical devices such as lithium batteries. S. followed by fiber formation with addi- olite powder was dehydrated at 140 ◦ C in vacuum for 2 h tional AN polymerization as shown in Fig. Sepi. and their resistance was measured using . [66].

Copyright 2004. Structural model of sepiolite arrangements in the fibers [73]. Reproduced with permission.K. / Progress in Polymer Science 37 (2012) 487–513 Fig. Schematic drawing of the formation of PAN nanofibers [69]. KGaA. . 5. Nataraj et al.492 S. 4. Fig. Wiley-VCH Verlag GmbH & Co.

Also. However. [77] used Raman spectroscopy to characterize charge density of 30–50 C/m3 for the electrospun PAN CNFs of PAN prepared from PAN/DMF precursor solution fibers and their theoretical charge density calculations following the pyrolysis in vacuum at 600. Kalayci et al.1. designs taking PAN as a model. et al. wherein fibers were formed by the collected PAN fibers were reported. / Progress in Polymer Science 37 (2012) 487–513 493 Fig. Schematics of CNF preparation from PAN [74]. Oxime groups or oximate ions. 1000 and compared well with the experimental observations. KGaA. further spinning on evaporation of DMF. A strong viscosity dependence copolymer of acrylonitrile and styrene on rubber. were reduced onto CNFs temperature of 700 and 1000 ◦ C. a temperatures. Copyright 2004. among 6. electrospun. and temperature effects on cone/jet/fiber new method was developed [85] to obtain delustered morphologies as well as birefringence and crystallinity of polyacrylonitrile fibers. Nataraj et al.8 × 10−3 and 1. After oxidation and car- displayed in Fig. Chen capacitors. properties at higher temperatures.2. Modifications of PAN as a precursor nanofibers. the copolymer domains were pyrolyzed and .%). Since the polymers were PAN concentration of as low as 2 wt. Acrylonitrile-based homopolymer and its copolymers Yang et al. The viscosity ranging from 10 to 300 nm were produced by electrospin- dependence of fiber (jet) diameter was studied to prepare ning the blend solution of PANOx with PAN (1:1 by weight) uniform electrospun fibers. eters. nonwoven structural properties of PAN solutions in DMF. [78] produced CNFs by electrospinning have been widely used for electrospinning due to their without a catalyst and reported useful electrical proper. such as of fiber diameter was obtained due to enhanced solution butadiene or butadiene–styrene rubber–ABS-copolymer. [83] explored the issues bonization. [86] reported a novel strategy to prepare electrospun spun PAN/DMF solution was studied by Wang and Kumar ultrathin CNFs from a blend consisting of a mixture of PAN [82] to reveal that individual beads may be produced at and poly(AN-co-MMA) in DMF. 6. Wang et al. leading to the formation increase of PAN concentration led to uniform size fibers as of microphase-separated fibers. S. PAN was modified the effect of temperature on cone/jet/fiber morphologies via catalytic conversion of acrylonitrile groups to result in during electrospinning of PAN/DMF solutions by varying PANOx as shown in Fig. higher conductivity and This approach used low blending ratio of copolymers to lower surface tension. 800. 1200 ◦ C. as well as their applications in different fields. 8. dence of the viscosity. Electrical nanofiber mats composed of polyacrylamidoxime (PANOx) conductivity of the carbonized PAN CNF webs ranged from blended with PAN. Yang and co-workers [80] also reported the et al. related to charging of polymer solution viz. Kim and Yang [79] tested the activated PAN as a precursor in its pristine. The PAN NFs of this spinning a solution consisting of two copolymer solutions. self-detoxifying protective clothing. This study concluded with precise estimation of temperature dependent carbon and graphic disorder in the 4.K. charge quan- The semiconducting nature of CNFs was revealed by the tification of electrospun fibers and different charge delivery positive temperature coefficient of conductance. study have a 65 nm diameter and were readily obtained one being polyacrylonitrile and the other a grafted ter- by electrospinning at 89 ◦ C. Table 1 gives details of ties of the web. Peng Effect of concentration on the morphology of electro. 7. act as dopant to yield different texture to nanofibers. a four-point probe method from 22 ◦ C down to −260 ◦ C. superior fiber-forming properties. PANOx fibers with diameters solution properties and processing variables. forms. For example. Reproduced with permission.96 S/cm by increasing the carbonization the most powerful nucleophiles. blend and composite CNFs of PAN that showed excellent performance as super. The beaded fibers incompatible. [84] reported the catalytic. electrospinning was performed at various high There are many other developments.%. in a mixture of DMF and DMSO in 85:15 ratios by weight.. phase separation occurred during electro- were electrospun from a solution of PAN (3–6 wt. conductivity and surface tension was Such PANOx fibers have shown potential applications in investigated to obtain the corresponding activation param. Wiley-VCH Verlag GmbH & Co. and the temperature depen. The authors reported a Wang et al. [81] studied to obtain a stabilized transition state.

165.000 LiCl Composite NFs Electrospinning – 555–880 nm Composite applications [109. Nataraj et al. NaNO3 .200 Tin dioxide and titanium Porous substrate Electrospinning – 100 nm Catalysis.000 LiCl/DMF Modified NFs Electrospinning – 12–15 nm – [111. sensing and [68] dioxide photoelectric conversion applications PAN – Composite NFPorous Electrospinning – 10–500 nm In military/civilian [67] protective clothing systems ◦ PAN On silicon substrate Composite Electrospinning 1000 C – Electronic devices [71] PAN Mw = 125.5–5 ␮m As hollow [95] PMMA-996.000 Triethylbenzylammonium Composite NFs Electrospinning – 100 nm Effect of needle on [81] chloride (TEBAC) diameter PAN Dedecyltrimethylammonium Composite NFs Electrospinning – 100–1000 nm – [82] bromide (DTAB) S.000 – Composite NFs Co-electrospun from – 0. CaCl2 and NaCl Porous composite Electrospinning – 410–473 nm Composite applications [108] PAN Mw = 75. [97.K.206] PAN-15.000 Polyacrylonitrile-co-3-allyl. [102] nanoactuators PAN Mw = 52. and vinyl CNTs Modified NFs Electrospinning – 180 nm Supports for redox enzyme [87] porphyrin such as catalase ter-copolymer immobilization PAN Mw = 86.000 MWCNTs Mechanical nanofibers Electrospinning and – 1000 nm Composites applications [98. biosensor PAN MWCNTs Plain NFs Electrospinning 1000 ◦ C 100–120 nm Nano-electrodes.172] supercapacitors and nano-sensors PAN – Composite NFs Electrospinning – 200 nm Viscoelestic performances [98.000 LiCl.000 – Core-shell fibers Electrospinning 700–1100 ◦ C 220–280 nm Mechanical applications [90.000 ER and EB whitening agents Mechanical nanofibers Electrospinning 800 ◦ C 78–154 nm Nano-photoluminescent [88] fibers PAN Mw = 150. PAN grade and form Filler Type of NF Technique Temperature Fiber diameter Applications Ref.167] PAN Mw = 70.167] vibration-electrospinning PAN Mw = 86. AA.91.155.200 Polyester urethane Blend nanofiber Electrospinning – 200–300 nm As high strength [99] mechanical applications PAN blend Polyurethane Blend fiber Electrospinning – 240 nm As nanotweezers.112] PAN Platinum(II) acetylacetonate Porous NFs Polymerization of 700 ◦ C 80 nm As electrocatalysts for fuel [113] acrylonitrile in a porous cells anodic aluminum oxide template . nano/micro-fibers PAN-co-PANCAA MWCNTs Composite CNFs Electrospinning – 100–300 nm For immobilizing redox [96] Mw = 83.000 and p-nitrophenyl acetate a new generation of (PNPA) protective fabrics and filters PAN blend Poly(AN-co-MMA) Porous nanofiber Electrospinning 600–1000 ◦ C 500 nm Electronic applications [86] AN.200 enzymes.110] PAN Mw = 75. in bioprocess applications. / Progress in Polymer Science 37 (2012) 487–513 ◦ PAN – Modified PAN nanofibers Electrospinning 20 C 600 nm Medical and filtration [83] Modified PAN Hydroxylamine hydrochloride Porous carbon fibers Electrospinning – 300 nm As key functional layers in [84] Mw = 150. 494 Table 1 Details of PAN based precursors used in its different forms for the preparation of nanofibers. PAN – Ultrafine fibers Electrospinning 600–1200 ◦ C 100 nm Electrochemical device [65] PAN Mw = 86.5-dimethylhydantoin process and medical applications copolymer PAN Mw = 75.000 co-annular nozzles. Composite fibers Two-stage wet spinning – – In antibacterial activities [103] 5.

– 30–3000 nm Biomedical applications [183] 700.000 and PdCl2 and AgNO3 C/Co composite nanofibers Electrospinning 1000 ◦ C 100–300 nm Composite electronic [130] 150. – 150–500 nm High strength [175] PAN – Composite NFs Electrospinning – 130–280 nm Composite applications [177] PAN ZnCl2 and KOH activation Composite NFs Electrospinning 1050 ◦ C 200–300 nm Hydrogen adsorption [180] storage media PAN Mw = 250. Nataraj et al.7 nm Composite applications [126] extrusion in to solidifying solution method PAN Mw = 120.000 – Porous nanofibers Electrospinning 500–1100 ◦ C 149 nm Electronic devices [159] Commercial Graphite felts CNF/graphite-felt Catalytic chemical vapor 500 ◦ C 100 nm Catalytic applications [162] PAN-based CNFs composite deposition (CCVD) PAN Mw = 100.205] applications PAN Mw = 100.600 (NaCo2 O4 ) nanodevices Metal composite NFs PAN Mw = 60.000 – Mechanical nanofibers Electrospinning 750–1600 ◦ C 131 nm Composite applications [144. / Progress in Polymer Science 37 (2012) 487–513 anodic Al2 O3 membrane as applications the template PAN Porous anodic alumina Composite NFs Electrospinning/self 200–700 ◦ C 80 nm Aerospace and automobile [72.K.000 acrylate) copolymer Mw = 100.PAN DMAc/iron(III) Composite NFs Electrospinning 900–1500 ◦ C 150 nm Gas diffusion electrodes [114] acetylacetonate (AAI) and supercapacitor electrodes PAN NaY zeolite Porous NFs Electrospinning 700 ◦ C – As composite material [116] PAN Fe(acetylacetonate)3 Fe(Acc)3 Porous NFs Electrospinning 700 ◦ C 100–300 nm Redox reaction electrodes [117] and in nanoscale engineering PAN Mw = 160.000 495 .600 MWCNTs Composite NFs Electrospinning 700–750 ◦ C 100–300 nm High strength applications [156] Mw = 86.200 Sodium cobalt oxide Composite NFs Electrospinning 800 ◦ C 20–200 nm In thermoelectric [129] Mn = 22.000 Cobalt acetate Co(CH3 COO)2 – Electrospinning 600 C 100–300 nm Anode material for [133] high-power Li-ion batteries PAN Manganese acetate Composite NFs Electrospinning-activation 800 ◦ C 250 nm Toluene adsorption [136] PAN Mw = 80.000 DMF Porous NFs Extrusion process with an – 104.6 nm Super hydrophobic surface [127] S.000 Silver nitrate Composite NFs Electrospinning 2000 ◦ C 100 nm Catalytic applications [138] PAN – Ultrafine nanofibers Electrospinning – 200–1200 nm Electrochemical [142.000 PTFE substrate – Anodic Al2 O3 membrane – 206.000 Zinc chloride Composite NFs Electrospinning 800 ◦ C 200–350 nm Electrode in electrically [125] double layered supercapacitor PAN Mw = 120.000 and Poly(acrylonitrile-co-methyl Blend NFs Electrospinning.145] PAN Mw = 22.128] lubrication products PAN Mw = 86.000 SWNT Composite NFs Electrospinning – 100–2000 nm In nanodevices and as AFM [164] tips ◦ PAN MWCNTs Anisotropic porous Chemically vapor grown 800–1000 C – Electrodes in [169] (CVD) supercapacitors and fuel cells PAN Silica composite NFs Ultrafine composite NFs Electrospinning – 200–300 nm Composite applications [173] Composite nanofibers PAN Graphite nanoplatelets Composite NFs Electrospinning – 5–500 nm Composite applications [174] PAN Ceramic Composite NFs Electrospinning.000 applications ◦ PAN Mw = 86.000 PAN Mw = 150.

PAN Mw = 180.000 – PAN/CdS composite Electrospinning – 270–290 nm Composite reinforcement.000 – Porous nanofibers Electrospinning 800 ◦ C 200–300 nm Adsorbents for removing [184] toxic compounds PAN Mn = 80. [198] membrane-based separation.000 CNTs/DMAc Composite NFs Dry-jet-wet fiber spinning – 60 nm In composite applications [200] PAN Mw = 100. Nataraj et al.K.000 Silver nitrate Porous fibers composite – 150–200 nm As filters to protect the [222] NFs wearer from bacterial contaminants PAN – Porous NFs Electrospinning following – 100 nm Medical applications [223] UV-irradiation ◦ PAN IM7 fiber CNTs Composite fibers Electrospinning and the 500–1500 C pyrolysis of carbon-containing gases on an iron catalyst PAN Mw = 150. sensing and tissue engineering PAN Mw = 100.000 – Porous nanofibrous Electrospinning followed – 124–720 nm As membrane filtration [214] scaffolds by phase inversion media technique PAN – Hollow fibers Electrospinning and phase 500–800 ◦ C 300 nm–6 ␮m As gas and liquid [217] inversion method separation membranes PAN 150.000 Cadmium acetate – Electrospinning and 600 ◦ C 100–800 nm Optoelectronic and [190] S.000 – Porous filtration fiber Electrospinning – 270–400 nm As a filter media [220] Lipase Electrospinning – 150–300 nm For lipase immobilization PAN Mw = 150.000 – Composite NFs – 150–200 nm Mechanical applications [202] – Composite NFs [206] – Mechanical nanofibers Electrospinning PAN blend PMMA Hollow NFs Two stage 750–1100 ◦ C 200 nm-7 ␮m For hydrogen storage [211] co-electrospinning PAN Mw = 150. 496 Table 1 (Continued) PAN grade and form Filler Type of NF Technique Temperature Fiber diameter Applications Ref.000 – Porous nanofibers Electrospinning – 500 nm As filtration membranes [224] . / Progress in Polymer Science 37 (2012) 487–513 (Cd(Ac)2 ·2H2 O gas–solid reaction photonic devices PAN Mw = 200.

A copolymer of PAN and methyl methacrylate (MMA) truded parts induced by blending of CNTs were observed was used instead of poly(methyl methacrylate) (PMMA) from the CNFs. and (l) 20.1. The variations in photoluminescence (PL) peak inten- domains produced a porous structure in the fibers that sities between ER/PAN and EB/PAN nanofibers were related were preserved even after carbonization.1. On the contrary. Rough surfaces as well as pro- rior.5.1. (f) 9.7.5. Reproduced with permission residual carbon fibers were interconnected with nanoscale trospun into nanofibers on which redox enzyme catalase dimensions throughout the surface as well as the inte. pyrolysis of copolymer Fig. process modification were attempted in a series of papers Wan et al.0. However. which were blended and elec.% [voltage = 22 kV.. during oxidation. suggesting duce the desired properties of PAN-based system by their potential in electrochemical applications.%. Results indi- bility during electrospinning. (g) 13. was covalently immobilized. Doshi and Reneker [89] showed that as- bearing porphyrin pendants. Nataraj et al. 7. The pores Along with precursor modification. [88] also prepared the PAN-based regardless of the PAN/copolymer ratio. It was found that PAN and cated that both the introduction of porphyrin pendants and poly(MMA-co-AN) formed transparent and homogeneous CNTs improved the activity and stability of the immobilized solution in DMF at a polymer concentration of <15 wt. ride and N-hydroxysuccinimide (EDC/NHS). nanofibers composed of two kinds of fluorescent whitening when PMMA was used as the second component the blend agents viz. catalases. 8. ultrathin to their different structures and method of producing CNFs were obtained with high nanopore content through. out the surface as well as in the interior of fibers. (i) 17.3 wt.4-bis(o-cyanostyryl)benzene (ER) and 1-(o- solution in the syringe phase separated during electrospin. SEM micrographs of the electrospun PAN copolymer fibers prepared in various concentrations: (a) 0. (j) 19. Modification schematics of Polyacrylonitrile to polyacrylamidoxime [84]. (k) 19. (b) 1. / Progress in Polymer Science 37 (2012) 487–513 497 Fig. Catalase was immobilized onto nanofiber homopolymer as a second component in the polymer mix. Of these. Q = 1 mL/h. 9. distance between tip and the target was kept constant at 10 cm] [82]. cyanostyryl)-4-(p-cyanostyryl)benzene (EB) as shown in ning. (c) 2. .1. Wang et al. new routes to pro- have diameter of 10 nm and were continuous. (h) 16. surface through activation of carboxyl groups by N-(3- ture to improve the compatibility of the second component dimethylaminopropyl)-N -ethylcarbodiimide hydrochlo- with PAN in DMF solvent as well as the solution sta. Copyright 2006. fibers. Thus.1. spun fibers could be aligned parallel to each other when a Fig. (d) 3.8. [87] explored acrylonitrile-based copolymers [89–94].K.6. John Wiley & Sons. S. 1. (e) 5.

assuming that the incorporated MWCNTs would act as microfluidic device was prepared using three stainless- electron transfer agents during enzyme catalysis. PAN blends blends. electrical con. mers with less polar polymers facilitated phase-separation electrospinning technique to prepare CNFs from MMA/PAN in bulk and micellization in block-selective solvents. The tion. while PAN/MWCNTs silica/polyvinylpyrolidone (PVP)–PAN coaxial composite composite mesh without carbonization had a conductivity NFs. PMMA/PAN polymers mixtures to produce PAN-based composite silica blend nanofibers were electrospun with PAN as the core nanofibers [104]. which follows the co-electrospinning of two or more of 0. were all improved. PANCAA steel rods held together with a commercial cyanoacrylate was blended with MWCNTs for electrospinning to facili. On A crosslinkable elastomeric polyester urethane (PEU) the other hand. as-spun bicomponent PAN/PU nanofiber was removed by cal conductivity of the composite nanofiber mesh as well extracting the fibers with THF in an extractor for four days. Zussman and co-workers [90. In case of PAN nanofiber. [102] reported a different approach for electro- This concept was demonstrated by producing multichan. obtained yarns of aligned poly(ethylene oxide) fibers by At a polymer concentration of 9 wt. sensor. as the collector to generate parallel arrays of polyamide Lazzari et al.0 S/cm at ambient temperature [97]. . and thermoplastic PAN. Lin et al. [100] described a facile and low-cost nanofibers with an average diameter of 50 nm. The method was attractive for CNFs due to a combination of potentially superconducting technological applications involving macroscopically long phases dispersed in CNFs microstructure. The crosslinked sharp. Nataraj et al. Structure of 1.3. Jang and Zhao [101] trapped at the base of the Taylor cone issuing the PAN discovered several electrical phenomena associated with solution jet from its tip. This technique provided even [96] from solutions containing poly(acrylonitrile-co-acrylic smaller nanofibers useful as a nano-mechanical chemical acid) (PANCAA) and MWCNTs for redoxase immobiliza.5–1.K. method to prepare the CNFs from tunable wormlike micel- lar aggregates of PAN-based block copolymers and PAN 4. These tensile properties were further cussions were provided in their work. leading to enhanced electri. This technique was (PAN-b-PMMA) micelles were prepared by dissolution in a based on the precipitation of PMMA solution droplets selective solvent for the second block. as shown poly(AN-co-MMA) in DMF solution. glue to form the desired capillary channel structure. the nanofiber con- introducing an electrostatic lens element to stabilize the taining higher composition of PEU showed a slight decrease liquid jet. fibers were prepared from elastomeric polyurethane (PU) ing the reactive groups was electrospun by Wang et al. / Progress in Polymer Science 37 (2012) 487–513 Fig. drum rotating at a high speed was used as the collector. High incompatibility of PAN in block copoly- Bazilevsky et al. Wendorff improved by a slight crosslinking of PEU component within and co-workers [94] reported the use of a metal frame the nanofibers. Deitzel et al. was blended with a thermoplastic PAN and electrospun strated a wheel-like bobbin as the collector to position and into nanofibers [99] to investigate the effects of PEU/PAN align the individual polymer nanofibers into parallel arrays. [92] and catalyst to PEU/PAN solutions prior to electrospinning. Recently. blends dissolved in DMF. this technique is not feasible to form well-aligned PEU/PAN fibers were prepared by adding the crosslinker nanofibers over large areas. Recent studies [103] have reported the ductivity was of the order of 1 mS/cm. elonga- of nylon-6 nanofibers by rapidly oscillating a grounded tion at break and tensile modulus of the nanofiber mats frame within the jet. but no detailed description and dis. Self-crimping nanofibers were obtained when Novel conductive composite nanofiber mesh possess. but tensile strength. and radially inhomogeneous or hollow nano/micro-fibers.91] demon.498 S. similar to micromechanical chemical sensors. ratio and crosslinking reaction on the morphology and ten- Because the edge of such a bobbin had to be relatively sile properties of the as-spun fiber mats. temperature for 6 h. Subsequently.%. poly[(acrylonitrile-b-polystyrene)] (PAN-b- of 0. nel porous nanofibers via co-electrospinning of PAN and using a microfluidic device as the spinneret.1. as the interfacial interaction between MWCNTs and the The residual fiber mat was dried in a vacuum at ambient polymer chains. Two tate the formation of charge transfer complexes between different polymer solutions were supplied separately from the negatively charged functional groups (–C N–) and the syringes through the side channels. spinning side-by-side bicomponent polymer nanofibers.5–5 ␮m and a core-shell structure. [95] developed a single-nozzle co. In a modified electrospinning set-up com- and PMMA as the shell wall by Yang and co-workers [98] for prising two syringes having immiscible and miscible pairs processing PAN as the continuous core and PMMA covering of polymer solutions directed through a single needle to the nanofibers. 9. in Fig. 10.4-bis(o-cyanostyryl)benzene (ER) and 1-(o-cyanostyryl)-4-(p-cyanostyryl)benzene (EB) [88]. similar to that PS) and poly(acrylonitrile-b-poly-(methyl methacrylate)) obtained using co-annular nozzles. The PU half of the surface-oxidized MWCNTs. producing an outer diameter For instance. Vaia and co-workers [93] fabricated aligned yarns in average fiber diameter.

using LiCl in controlling 4. These experiments showed composed of nanoparticles of metal oxide. an additional sintering ning solution. [110] in situ to elemental Pt. This study elaborated the carbon con. Anodic aluminum oxide templates were immersed The effect of salts such as LiCl. KGaA. 100 nm diameter fibers with a 20–80 nm thick coating. proposed allometric scaling laws for partial to fully charged ing PAN as shell and conductive polymer species in the core. 10. thus causing the jet instability to occur at initial apply a metal oxide coating. the interior structure of electrospun PAN nanofibers with Similarly. Fig. / Progress in Polymer Science 37 (2012) 487–513 499 Fig.4. gated by Qin et al. [111] ity between the metal oxide particles [105. Tin dioxide and titanium diox. to assess the applicability of scaling laws. [113] prepared densely packed PAN nanofibers produce composite or porous CNFs through carbonization containing platinum(II) acetylacetonate by polymerizing and/or silica removal. tocol. The interface is often larger during electrospinning. The decrease of the electrical poten- electrospun into a nonwoven fiber web. well with the experimental observations. ning method in DMF. In the case of that the radius of the jet depends on salt content in the spin- dye-sensitized photovoltaic cells. r of the jet and the axial community due to their interesting chemical and elec. wherein PAN fibers were the spinning solution. 11 displays the schematics of the fabrication pro- composites with a maximum PAN loading. generate. NaNO3 . acrylonitrile in porous anodic aluminum oxide (AAO) tem- tent in silica/carbon composites obtained from silica/PAN plate. trical properties as well as their large interfacial area In case of fully charged surface. The predictions of theoretical analysis agreed step is required to ensure maximum electrical connectiv. ing AIBN and platinum(II) acetylacetonate [Pt(acac)2 ].106]. also used PAN to study instability in fiber formation during [107] reported the fabrication of novel metal oxide-coated electrospinning with varying amounts of LiCl precursors in polymeric NFs by electrospinning. These PAN/silica NFs were used to Lei et al. ultrafine PAN/silica nanofibers were prepared LiCl was investigated to observe that diameter of CNF was by Ji and Zhang [108] following a one-step electrospin. increased by adding LiCl into the PAN matrix [112].K. [109]. High-resolution TEM showed that . distance. Schematics of microfluidic electrospinning device [102]. NaCl and CaCl2 on in distilled acrylonitrile monomer (CH3 CH2 CN) contain- the electrospinning of PAN polymer solution was investi. The formed for 10 h in air. Metal oxide incorporated PAN the surface charge. Their ide were applied as coatings by this method to obtain data agreed well with the theoretical analysis. S. wherein Pt(II) salt was reduced the conductivity of the spinning solution. Drew et al. Qin et al.1. fibers in electrospinning for PAN/DMF solutions. tial of the fiber with increasing distance from the jet orifice quently immersed in an aqueous solution of metal halide was sharper with high content of LiCl than with of low con- salts and halogen scavengers at ambient temperature to centrations. stage of jet formation with the higher LICl content. which was subse. scaling exponent became to enhance the desired properties. Nataraj et al. NFs with core/shell structures primarily compris. Recently. Copyright 2005. This theoretical analysis showed that Metal oxides are of immense interest to the scientific the relationship between radius. Reproduced with permission. Z from the nozzle followed the relation: r ∼ Z−0. The PAN nanofibers were pyrolyzed conductivity of salt/CNFs varied in the order of added salt: at 700 ◦ C under high vacuum for 6 h. Qin et al. Wiley-VCH Verlag GmbH & Co. Subsequent pyrol- LiCl > NaNO3 > CaCl2 > NaCl > pristine PAN as measured by ysis resulted in CNFs. showing that the diameter and Polymerization at 50 ◦ C and cyclization at 220 ◦ C were per- length of NFs depend on the amount of added salt.5 .

the carbonization of PAN electrical conductivity. netic suspension balance (MSB) at room temperature and Introduction of AAI promoted the formation of crystalline at 100 bar pressure. The electrical capacities in the range of 0.16–0. 11. Pt nanoparticles were highly dispersed throughout the resulting in ultrafine 90–300 nm diameter carbon fibers. Hydrogen storage capacities of these CNF and GNF NFs using iron(III) acetylacetonate (AAI) and DMAc in the materials were also evaluated gravimetrically using mag- temperature range 900–1500 ◦ C in nitrogen atmosphere. The authors of GNFs with low surface areas of 60–253 m2 /g were claimed these materials as potential candidates for gas dif. Schematics of the fabrication process of Pt-CNFs using an anodic aluminum oxide (AAO) membrane template [113]. [114] investigated the effect of iron complex in the presence of a catalyst produced graphitic nanofiber on the carbonization behavior of PAN-based electrospun (GNF). / Progress in Polymer Science 37 (2012) 487–513 Fig.01 wt.50 wt. 0. very low surface areas of 22–31 m2 /g. carbonization temperature. Hou and . lization of the precursor nanofibers at 250 ◦ C in air. Nataraj et al. CNFs produced similar materials fabricated via more complicated proce. electrospun PAN nanofibers nanofibers and reduction of Fe3+ were performed in a were carbonized with or without iron(III) acetylacetonate tubular high-temperature furnace through oxidative stabi- to induce catalytic graphitization in the range 900–1500 ◦ C. Also.14–1. It CNFs as single crystal sizes range from 1 to 4 nm. was established that the structure and diameter of CNFs ing disc electrode voltammetry of these new composite can be controlled by selection of the catalyst.K. but carbonization Park et al. without a catalyst showed amorphous structures with dures. Hydrogen storage capacities bonization temperature and catalyst content.500 S. the carbon materials has shown better electrocatalytic activity than sources and the synthetic conditions [115]. The CNFs showed hydrogen storage domains during catalytic carbonization. Rotat. These materials were tested for fuel cell applications. fusion and supercapacitor electrodes because of their high In a recent study [116].%.% with increasing conductivity of CNF webs increased with increasing car.

In another study to produce CNFs using PAN the secondary NFs [123]. particles ranged from 10 to 30 nm. Ru particles (size distribution of come delamination problems in composites by Milewski 2–15 nm) were embedded randomly into CNFs to increase [119]. and PAN in DMF [124]. was used as a catalyst solution was successfully electrospun into thin white webs . The zinc chloride-incorporated PAN which is soluble in organic solvents. Car.5 nm. Yang and co-workers incipient wetness method to grow branches under mild [125] prepared a flexible. while that with 7. Fe(acetylacetonate)3 . The iron catalyst used for nanofiber the Fe(Acc)3 concentration in the spinning solution. This method resulted in obtaining CNFs/CNTs the secondary nanofibers was around 40 nm. the Ruthenium-embedded CNFs were prepared by stabi- authors suggested their applications as electrodes in elec. and the diameter of ite CNFs. 12). McAllister and pore diameter as well as pseudo-capacitance by the well- Wolf [122] impregnated Ni on rayon fibers by using an dispersed Ru nanoparticles. pitch-based carbon fibers were employed as substrates for age devices. Processing steps for fabrication of porous carbon nanofiber embedded with iron oxide (left) and FE-SEM images of CNFs carbonized at 1000 ◦ C showing porous surface. lization. Nataraj et al. This pyrolysis of C2 H4 . the composite solution of ruthenium(III) acetylacetonate Branching of carbon fibers was first introduced to over.K. thin web consisting of intermin- conditions. The size of the iron were then used as catalysts to grow CNTs on compos. Activated dense mats with unique properties useful for energy stor. The metallic that contained Fe(Acc)3 nanofibers ranging in diameter particle size in resulting CNFs was controlled by varying from 100 to 300 nm. S. Later. The specific capacitance of CNF process by growing carbon filaments on the surface of without Ru loading was 140 F/g. which bonized nanofibers having reduced metal nanoparticles was produced by electrospinning.31 wt. growth was mixed with the precursor of PAN fibers. but a recent study by Hou and Reneker [117] gled long nanofibers by electrospinning of PAN solution reported homogeneously distributed nanofibers grown on containing zinc chloride. PAN and Fe(Acc)3 were both dissolved in DMF PAN/Fe using PAN and Fe(Acc)3 precursors with varying and the solution was spun into PAN precursor nanofibers concentrations of Fe(Acc)3 in PAN solution. followed by high-temperature PAN-based nanofibers.121] improved the the size from 2. carbonation and activation after electrospinning trical double layer supercapacitors [118]. / Progress in Polymer Science 37 (2012) 487–513 501 Fig. Recently. resulting in enhanced interfacial layer capacitance as a result of the expansion of average bonding between the fibers and the matrix. thermal treatment. (Fe(Acc)3 ). incorporated with iron oxide particles (see Fig. 12.0 to 2. Specific surface area was significantly was due to the synergistic effect of electrical double- increased by branching.% PAN and pitch-based carbon fibers via Cu/Ni catalyzed Ru–carbon nanofibers increased to 280% for 391 F/g. Reneker [117] prepared self-supported nanofiber sheets of precursor. Downs and Baker [120.

CNFs prepared [128] to achieve controlled morphology with fiber diameter by pyrolysis of PAN precursors in the interlayer space of required in medical applications. [142] produced PAN NFs using a stainless NFs.132] in ElHamid [145] studied the electrospinning of PAN/DMF in the electrospun nanofibers to enhance the electronic prop. Thus. metal precursors in the PAN solution. ter. this method was much simpler. Nataraj et al. It in PAN. taeniolite were used as electrode materials in lithium bat. A flat metal plate covered with Ag(NO)3 and PdCl2 and PAN using microwave irradiation aluminum foil placed below the electrode served as the and electrospinning techniques.127] reported a novel method Wang et al. face [146]. The pores of the silica templates were [137] adapted a new route to incorporate Mg into PAN infiltrated with PAN via polymerization of acrylonitrile to produce porous CNF following two steps: the first one from initiation sites chemically bonded to the template .K. This method offered a The molecular chains were oriented within the electro- powerful platform to design and fabricate functional poly.502 S. The nanoporous ultrahigh phological and physico-chemical properties. ports in fuel cells and energy storage devices. Similarly. Ali and fabrication of CNFs containing metal oxides [107. [138] studied the dispersion of Ag to prepare PAN nanofibers using anodic aluminum oxide nanoparticles (10 nm diameter) in PAN nanofiber film by membrane as a template. The fibers were dried in flight ticles (Ag and Pd) was adjusted by varying the molar ratio of and collected on the aluminum foil as nonwoven fabric. give cubic carbides [148]. These Maensiri and Nuansing [129] were the first to use CNFs exhibited enhanced physico-chemical properties. giving a short high surface area CNFs. ranging hundreds of nanometers with the pore diameter of Composites of PAN with layered oxides undergo carbo- 8–24 nm. The size of metal nanopar. mesoporous amount of manganese salt for toluene adsorption to get carbons were synthesized from PAN using mesoporous higher toluene storage efficiency. of CNFs. applications as sensors. Oh et al. initiated at lower temperature due to cyclization exother- Other similar studies reported in the literature involved the mic peak shift to lower temperature [143. Yang and co-workers templates [149]. the template can matrix. nickel nitrate was diameters ranging from 20 to 200 nm by electrospinning a loaded into PAN to enhance the electrical and physico- precursor mixture of sodium acetate/cobalt acetate/PAN. NaCo2 O4 in sodium acetate/cobalt acetate/PAN composite Gu et al. changing its color from magnesium acetate to increase the surface area. Recently. In sodium cobalt oxide (NaCo2 O4 ) to prepare nanofibers of a further study by Nataraj et al. surface porosity and thermal degradation of the phase separation and electrospinning with the diameters PAN nanofibers. Controlled deposition of silver oxide nanoparti- be recycled after washing. deposit a continuous film of titanium dioxide on the sur- ning and subsequent low temperature thermal treatment. This novel method served a dual stabilization time. spun fibers during electrospinning.144]. such as the surface of the PAN fibers was fabricated by combining diameter. Yang and co-workers [147] recently developed the electrical conductivity for applications in Li-ion bat. which enhanced the oxidation rate.. [140] fabricated long and continuous composite nanofiber teries. Microscopic studies confirmed cylindrical mor- was later demonstrated by Zhang and Hsieh [135] that phologies of CNFs with diameters of 100–300 nm after such porous CNFs and metal oxide fibers can be readily carbonization at 1000 ◦ C. [141]. and the white to dark brown. sheets of PAN incorporated with zinc oxide (ZnO). cyclization of PAN was mer/metal nanocomposite fibers with desirable properties. Zinc chloride acted as a dehydrating second step includes the coating of manganese oxide onto agent.131] fabricated steel electrode immersed in a solution connected to a high PAN nanofibers from a precursor solution comprising voltage power supply. Surface-enhanced Raman scat- nanofiber via extrusion of a PAN precursor solution into tering (SERS) indicated that the structure of PAN was a solution of DI water under pressure where it solidified altered after Ag nanoparticles were dispersed in the PAN and polymerized as closely packed fibers. chemical properties of the CNFs and these materials were followed by a calcination treatment of the electrospun proposed for their potential applications as catalyst sup- composite nanofibers. in addition to enhanced mor- synthesized via electrospinning. Aligned CNF membranes with cles on PAN/TiO2 composite nanofibers was also achieved different diameters and densities were obtained by using through photocatalytic reduction [139] by a simple method templates of different pore diameters. grounded counter electrode. Wang and co-workers [130. a coagulating bath to produce CNFs with <100 nm diame- erties of the composite CNFs. Electrospun PAN fibers with diameters of 50–200 nm In another study. sili- the nanocomposite fiber mats of PAN containing SnO2 cotungstic acid (SiWA) and silicomolybdic acid (SiMoA) nanoparticles as an optical sensor to detect CO2 gas. Formation of carbide begins dispersed PAN-based composite CNFs by loading various at 800 ◦ C and completes at 1000 ◦ C. the PAN-based carbon–cobalt (C/Co) were also produced in an aqueous coating solution to composite nanofiber was fabricated [133] via electrospin. Nataraj et al. Such PAN–metal oxide nanocomposites have The incorporation of cobalt increased the interfacial sur. electrically conducting CNFs obtained by incorporating teries. Feng and co-workers [69. PAN-based composite nanofibers purpose of producing high surface area and the coating of containing magnetic nanoparticles have been studied using electrochemically active MnO2 thin layer onto the surface PAN solutions [126]. Compared to conventional tem. to obtain N2 H5 OH aqueous solution. This resulted in the formation of ␥. photovoltaic cells and catalytic face area between carbon and liquid electrolyte to enhance surfaces. includes the preparation of porous CNFs by incorporating The web was stabilized in air. [136] prepared the manganese (Mn). electrospinning and by in situ reduction of silver ions in plate syntheses. Luoh and Hahn [134] also successfully electrospun different amounts of heteropolyacids (HPAs) viz. Also. / Progress in Polymer Science 37 (2012) 487–513 consisting of long nanofibers 350–200 nm in diameter. thermal reduction in an argon atmosphere at 1000 ◦ C to Recently.

13 suggests an interac. The extensive fine absorption structure detected via diameter of the nanofibers decreased with increasing UV–vis spectroscopy indicated that charge transfer com. but coated onto ACFs. Thus. [97] prepared highly oriented. [83] observed a in PAN–DMF solution was ejected from a spinneret con. in the direction of the nanofiber alignment and about 11% SEM and TEM revealed that GNFs were homogeneously in the direction perpendicular to nanofiber alignment. Kim and Park [160] described a sim- MWCNTs are nearly parallel to the nanofiber axis. The MWCNT suspension ing electrode materials. [159] measured the electrical conductiv- and ductile behavior than the nascent PAN. ity of PAN CNFs web to show that the conductivity of The molecular orientation and microstructure of PAN CNFs increased with increasing the pyrolysis temperature. S. with PAN-based graphitized nanofibers (GNFs). between CNTs and the surrounding polymer chains. However. CNFs without CNTs did not reveal anisotropy in electrical mal deformation temperature increased with increasing conductivity measurements. It was found that the effectiveness of CNT in reinforcing PAN precursor is highly dependent on the dispersion and alignment of CNT [150–153]. MWCNTs-embedded PAN nanofiber paper. PAN-based CNF papers are used as supercapacitor elec- trodes. considerable increase in the accumulation of charge on nected with a solution reservoir under the driving force electrospun PAN fibers at increased electric voltage result- of high voltage. tensile strength and modulus of the not sharply decrease even after GNF coating. conductivities up to 0. Composite papers of MWC. Such . CNT concentration. Schematics describing the interaction of CNT surfaces with sol- of high performance CNFs. American Chemical Society.K. The electrical conductivity of the CNF plexes formed between surface-oxidized nanotubes and web spun on aligned charged collector along the spin- the negatively charged functional groups in PAN dur.2. the sample shrank only 3% ment of ACFs led to the growth of GNFs on the surface. Thus. Hou et al.% MWCNTs loading. lightweight and controlled pore structure as well as inter- facial properties are desired. a study [155] revealed the preferentially aligned along the nanofiber axis are in excel- mechanical examination of hot pressed CNTs induced elec. double wall (DWCNT) and multi- wall carbon nanotubes (MWCNT) can be electrostatically assembled into nanofibers by electrospinning to increase the electrical property. These results have technological interest as the porous metal oxide–CNFs are promising candidates for a wide range of applications in which fiber morphology. Kalayci et al. strength and toughness of PAN- derived CNFs. The pre. precursors are strongly affected by incorporation of CNTs concluding that at high temperature. 4. decrease in the void space and increase nanofibers containing well-aligned MWCNT in concentra. and that porous structures of ACFs did electrical resistance. In their ing carbonization was altered in the presence of the CNTs. in enhanced repulsion between individual fibers. for which the tion. by 75% at 5 wt. CNTs in PAN nanofiber MWNT loading. MWCNTs rein- obtained. These results promise to produce the next generation Fig. the thermal conductivity.% as thick sheets of well-aligned favorable microstructure to give increased electrical and nanofibers to demonstrate that at higher concentration. 13. lent agreement with TEM observations. where high capacitance of 173 F/g at 10 mA/g can be were formed by evaporating the solvent. by 144% at 20 wt. The PAN–MWCNT composite nanofibers ing. while tensile strength Ge et al. ning direction was about three times greater than that ing electrospinning led to a strong interfacial bonding of the randomly collected nanofiber mats. trospun PAN nanofiber mat that showed better flexibility Agend et al. ple method to prepare activated carbon fibers (ACFs) coated the heat shrinkage of the composite nanofiber sheet dur. The morphology and shape of uous composite nanofiber sheets made of surface-oxidized the PAN–MWCNT composite nanofibers were maintained MWNTs and PAN by the electrospinning method. the GNF-coated ACFs are promis- attached to the MWCNT surface. Nataraj et al.5–1. than that of as-received ACF sample. NTs/PAN (20/80) without carbonization have electrical Copyright 2005. Ther.0 S/cm at ambient temperature. [157] prepared PAN layer spacing. the low-pressure plasma mixed-gas (Ar/O2 ) treat- For a CNT concentration of 35%. but power density will be poor due to the large forced the PAN nanofibers to improve the tensile modulus electrical resistivity of PAN-based CNFs [79. by contrast. / Progress in Polymer Science 37 (2012) 487–513 503 surface. The electri- nanofiber sheets were improved after the carbonization cal resistivity of GNF-coated samples was slightly lower process. large area contin. In one such a study. The model shown in Fig. even after carbonization. Composite PAN nanofibers containing CNTs Single wall (SWCNT). reduction of the inter- [156]. study. Alignment was achieved during electrospinning by controlling the flow of polymer. Reproduced with permission. vent molecules [157].% MWCNTs. but was higher than tion between the DMF solvent and the carboxylic groups commercial GNF. In this aspect. in the preferred orientation would facilitate compact and tions from 0 to 35 wt. ferred orientation of surface-oxidized MWNTs along the Lee and co-workers [158] successfully fabricated fiber axis was determined with TEM and electron diffrac. electrostatic charge and diameter confine- ment.154].

trical conductivity of the carbonized NF paper along the [177]. Due to 2800 ◦ C were examined for structural characterization the highly anisotropic orientation and formation of com- [163]. hot-stretched PAN/SWNT composite An improved method was developed [165] based nanofibers were prepared in an oven to enhance the ori- on X-ray diffraction studies for structural measurement entation and crystallinity. The graphite felt was cut to pre-defined higher than that of PAN. thermal and dimensional stabil- as a shell in a continuous nanofiber filaments. jet elongation and spin resonance characteristics of fibers derived from a slow relaxation of CNTs in PAN nanofibers were the PAN-based precursor. It was suggested that concentration of the and high surface area. offering rheological properties of composite PAN precursor solu- increased permeability with uniform pore size distribution. A sys- nanofiber paper without CNTs did not reveal anisotropy tematic understanding of process parameters was achieved in electrical conductivity. [97] growth of CNFs by catalytic a chemical vapor deposition observed that orientation of CNTs within NFs was much (CCVD) technique. suggesting that CNTs in PAN by establishing a quantitative relationship between elec- nanofiber are preferentially aligned along the nanofiber trospinning parameters and average fiber diameter using axis. which was vibration. In another study [167]. In an attempt [169] to get high surface area CNFs response surface methodology to conclude that concentra- suitable for energy storage applications. Kaner and co-workers [174] used 7 wt. electrical conductivity. The composite CNTs/NFs of shapes and sizes. in poly(acrylonitrile-co-acrylic acid) (PAN-co-PAA) were which information could be obtained about rheological developed with charged [Ru(bpy)3 ]+2 immobilization in a properties with respect to slow forces under the action of controlled procedure to modify an electrode. ceram- alignment was observed in PAN fibers obtained by ics and polymer/ceramic composites.% PAN larger with gel-spun fibers than the solution spun fibers. In a theoretical and experimental approach by Gu et al. tested using CV for range of scan rate (5–2000 mV/s) in In another study [171]. to achieve high capacitance. Ge et al. of micrometers to several centimeters. of this method was the use of a collector consisting of ther supported by Yang and co-workers [168]. of well-aligned PAN containing CNTs were prepared Li et al.K. Kumar and co-workers [164] developed a novel plexes (PAN/CNTs). Materials used in MWCNTs-embedded PAN nanofiber paper was pre. In a systematic approach from pre. who two pieces of electrically conductive substrates separated suggested that using CNTs as fillers would offer property by a gap whose width could be varied from hundreds improvement in the derived CNFs. which fibers. including helix-zigzag conformational changes conductivity and mechanical properties of the composite in the alignment of CNTs in CNFs [166]. Wan et al. thereby resulting in enhanced and evaluation to obtain detailed information on fiber electrical conductivity. tion as well as the effect on electrospinning under the In another study [161]. [162] prepared graphite-felt composite CNFs by electrospinning.% CNTs was enhanced to 1 S/cm. but elec. wherein carbonization showed that using the commercially available graphite felt composed higher concentration of CNTs effectively resisted the heat of PAN-based graphite fibers as the substrate for in situ shrinkage of composite nanofiber sheet. ing surface-oxidized MWCNTs and PAN were developed drogenation of ethyl benzene to styrene. in DMF containing 1–4 wt. These graphite–felt CNF composites were highly oriented. The authors used CNTs as tures. Li et al. It was shown that trospinning and vibration-electrospinning methods. [173] on the physically mixed CNTs/PAN nanofibers structures confirmed the absence of two-phase struc. tive to the weight of PAN to produce composite NFs that ing. while a good distribution and uniaxially aligned nanofibers of organic polymers. CNFs paper was tion of the solution was important to the diameter of the prepared from PAN/camphor composite solutions. Surface tension. MWCNTs were directly demonstrated a modest increase in thermal stability with electrospun into PAN nanofibers by the traditional elec. carbonized PAN diameters from 200 nm to 1200 nm were obtained. thermal trospinning using CNTs in the core surrounded with PAN deformation temperature. The applied voltage had no significant impact on the upon carbonization resulted in submicron pore structures fiber diameter. Structural changes due to the addition of CNTs were minor electrode components to improve the electrical studied. Changes were nanofiber. CNTs nanoplatelets can serve as alternative reinforcement mate- aggregated extensively in the fibers obtained by tra. increasing wt. In a nanodevices as well as AFM tips. The electron by electrospinning. . Nataraj et al. Fibers with mal to the spinning direction. rheology and nonlinear mechanics. [170] studied the diameter of the fibers. composite NF sheets showed enhanced approach to prepare SWNT/PAN composite CNFs by elec. mechanical properties. new approach [172]. these protocols include conventional organic polymers. heat-treated between 1000 ◦ C and determining factors in the orientation of CNTs. ultrafine fibers were spun from PAN/DMF solution spinning direction was three times higher than that nor.% graphite nanoplatelets. composite nanofiber sheets electrochemical and electrochemiluminescent sensors. blend nanofibers of action of vibration. However. Insights on ordered and disordered domain et al. Electrical conductivity of PAN/MWNT composite NFs composite materials are expected to find applications in containing 20 wt. These observations were fur. Key to the success vibration-electrospinning. These ity. decreased with increasing CNT concentration. solution played the most significant factor in affecting the cursor to final fiber formation. structure along with the evaluation of disordered fiber A simple one step pyrolysis was carried out by Beguin structures. rials. / Progress in Polymer Science 37 (2012) 487–513 fibers were later arranged in an orderly manner. large area continuous sheets compris- used as catalysts in a probe reaction of oxidative dehy. pared [158] in which the diameters of PAN nanofibers graphite carbon and metal oxides [176]. [175] developed a new method to prepare ditional electrospinning.% graphite nanoplatelets rela- mainly due to a decrease in PAN inter-chain spac. as a precursor of CNTs by electrospinning.504 S.

PAN-based nanofibers for electronic and energy kinetics of organic compounds using PAN-based CNFs to storage applications assess their possibility as alternative adsorbent to com- mercial ACFs. Im et al. Hydrogen several min. resulting in a low of 200–300 nm produced microporous CNFs with much surface area. by immersing the as-spun PAN were 310. [180] prepared PAN-based heterogeneities of CNFs. Specific surface areas obtained for sam. PAN-based mechanical nanofibers the original value. sion balance. Furthermore. i. while others [186. whereas beyond this diameter. Yang et al. even though specific surface area was reduced by the deposition of RuO2 down to 1/3 of 6. catalyst sup. catalysis slipping from or breaking at the grips. controlled atmosphere N2 flow to increase the specific sur. and carbonization at 200 and 700 ◦ C. Their unusual structural and electronic properties between 90 and 300 nm. PAN nanofibers with or without iron(III) acctylacetonate to nanofibers attract much attention as these bear many induce catalytic graphitization in the range of 900–1500 ◦ C.. potential applications in different fields of commercial resulting in ultrafine carbon fibers with diameters ranging interest. and 550 m2 /g. ionic char- trochemical behavior of PAN nanofibers. Ko and co-workers [192.% loaded MWCNT with a concentration of stacking faults. resulting in high porosity. photoluminescence character as observed by Jang et al. since they carry high power were 0. MWCNT/PAN. using zinc chloride.14–1. There are at beads. In addition. desired PAN-based GNFs [188]. S. chain length. Yang and co-workers cursors to prepare carbon/CdS coaxial nanofibers. CNFs were treated in CO2 at 880 ◦ C for higher surface areas than the PAN-based GNFs. 180. solution flow rate and polymer concen. et al. of CNFs are the most challenging ones to perform because tration. PAN was electrospun in DMF solvent as a function Of all the mechanical tests. [190] used PAN/CdS composite NFs as pre- face area and pore volume of CNFs. Fibers less than 350 nm in diameter contained direct manipulation of a fiber is required. carbonization of these composites into car- ples prepared from PAN containing 1. Subsequently.125] reported a solution method to prepare porous synthetic strategy involved the preparation of CdS/PAN and smaller-sized fibrous carbon in the form of thin webs composite NFs via electrospinning and gas–solid reaction.187] reported the and have long lifecycles. The capacitances of pristine PAN. Their double-layer capacitance effects of iron(III) acetylacetonate (IAA) on the carboniza- strongly depends on the type and form of electrode tion behavior of electrospun polyimide and PAN-based materials. The electrical conductivity of PAN. and RuO2 /MWCNT/PAN-based ACNFs were temperature treatment sequence resulted in a uniform 140. batteries. Their [124. an investigation of CNFs by electrospinning and subsequent heat treatment adsorption equilibrium and kinetics of methylene blue to obtain media for hydrogen adsorption storage. respectively. proper obtained [183]. properties such as concentration. In view of their scientific and technological NFs. [189] on energy distribution functions provided Microporous materials are promising as components significant information on the energetic and structural for hydrogen storage. tensile test measurements of electric field. 390 and 530 F/g. resulting in GNFs. fuel cells and different electronic that increased with increasing carbonization tempera- devices. The from 0. Park et al. Carbonized and activated electrospun PAN specimen gripping is necessary to prevent the fiber from fibers are attractive for supercapacitor electrodes. respectively. Many attempts have been made to produce ture ∼1200 ◦ C. Hydrogen storage supercapacitors that are intensely investigated as backup capacities of GNFs with low surface areas of 100–250 m2 /g energy storage systems. First. the channel between trospun PVDF-based NFs with an average fiber diameter carbon basal planes in PAN will be filled. PAN-based nanofibers exhibited novel and co-workers [182]. the effects of surfactant capacitance (140 F/g). fibers into cadmium acetate aqueous solution. Chemi. In a the largest specific surface area (550 m2 /g) and highest microemulsion polymerization.42 S/cm to 0. energy storage. deposition of 20 wt.e. conventional mechanical grips are gated the adsorption equilibrium. (MB) and Congo red (CR) revealed that adsorption capacity cal agents such as KOH and ZnCl2 activations were done and kinetics of MB were much higher and faster than that during carbonization in a pyrolysis chamber under the of CR. The CNFs showed hydrogen storage capacities ports. thermal desorption and not suitable. but a storage capacity decreased for CNFs PAN-based CNFs of high surface area for applications as prepared at a temperature of 1500 ◦ C. / Progress in Polymer Science 37 (2012) 487–513 505 5. the surface of CNFs was etched and the new storage capacity in SWCNTs was much lower than that of pores formed enhanced the improved surface area. The CNF webs with 5 wt. [181] reported the elec. respectively.% of RuO2 . Then.98 S/cm by the dispersion of 3 wt.01 wt.% ZnCl2 bon/CdS coaxial NFs.% of PAN-based CNFs were of high porosity after stabilization MWCNT. Due to the small and other applications. bead-free fibers were least two difficulties that are to be overcome. A comparative analysis by Pittman in electrochemical applications [178. 420. carbonization of elec- importance at elevated temperature.%.193] used AFM to . Their hydrogen storage capacities make carbon nanostructures applicable in electrochemical were evaluated gravimetrically using a magnetic suspen- double-layer capacitors (EDLC).% ZnCl2 exhibited rials for use in optoelectronic and photonic devices. Nataraj et al. The capacitance cross-section and a well ordered structure with a very low was increased 4 times for 3 wt. 3. Higher sur. The performance acters and polymerization temperature on the structure of hybrid supercapacitor with electrodes of carbon/RuO2 of the resulting polymer nanofibers have been investi- in 6 M of aqueous KOH solution was investigated by Yang gated. size of the samples. Park and co-workers [185] electrospun the Because of their unique tailor-made properties.179].K. Yang and co-workers [184] investi. Importantly. This RuO2 /PAN. based activated carbon nanofibers (ACNFs) was increased [191] using electrospun PAN nanofibers as a template. followed by face areas of fibrous materials exhibited higher specific reaction with H2 S gas and carbonization produced mate- capacitances. and 5 wt.

At faster CNFs are described as a new ultrahigh-strength material. strength at break were 4575 and 178 MPa. MWCNTs and VGCNFs. respectively. [204] introduced a new system and modulus of the twisted yarns increased with increas. These CNFs bundles have shown in high temperature reactions. Multifilament yarns of uniaxi- to mass than carbon fibers ordinarily used in composites. On the contrary. elonga- to weight ratios that are generally not achievable by other tion to break. PAN/CNTs composite fibers were spun from solutions in Nanofibers of PAN–PMMA were prepared in a core-shell DMAc using SWCNTs. Nanopores in carbon fibers were Electrospun PAN nanofibers were subjected to cold produced using nitrogen gas saturated with water vapor. ally aligned nanofibers were obtained by electrospinning of CNFs can also be useful in filters. It is anticipated that NFs will eventu. untreated ones. nanotube length. at an angle of 9. if there is a difference in refractive CNT indicated that VGNFs are more processable than the indices between fiber and matrix. With these properties such as modulus and shrinkage was attributed reinforcements. The post-drawn procedure all cases. with an . drawing in atmospheric conditions and at different strain Mordkovich [197] analyzed the prospects of introduc. first and foremost. In a similar study. Nataraj et al. nanofibers deformed homogeneously.. Chae et al. [199] prepared CNT-PAN composite fibers by the Young’s modulus of a single electrospun PAN fiber using electrospinning using both SWCNT and MWCNTs for the AFM cantilever. Car- size to the AFM tip and that the tip radius (5 nm) was small bonization showed that higher concentration of MWCNTs compared to nanofiber diameter (50–500 nm). large fiber ductilities originated in the formation of superior to both ordinary carbon fibers and other high. [200] observed a maximum increase enhanced the composite tensile strength and modulus of in modulus of 75% and reduction in thermal shrinkage PAN nanofibers by several orders of magnitude. ical diameters of few hundred nm after pyrolysis. Earlier tests nanofiber sheet. DWNT and MWNT in terms of dispersion. allowing for fiber spinning velocity and fiber draw ratio was measured the largest mechanical strengths and extension ratios. Naraghi et al.5 MPa and PAN nanofiber yarns by manipulating the electric field. glass and Kevlar fibers. Mechanical properties of the composite were also conducted on CNFs produced from both PAN nanofibers were reinforced by MWCNT fillers. and work of rupture was correlated with the monolithic materials. strength. capable of producing such continuous uniaxially aligned ing angle of twist to a maximum of 162 ± 8. conductor devices [196]. Thus. changes associated with mechanical properties of CNFs. as a support for catalysts PAN/DMF precursor [202].506 S. ally find important applications in making nanocomposites The feasibility of co-electrospinning of vapor grown because they have even better mechanical properties than nanofiber (VGNF) reinforced PAN a fiber was demonstrated micro-fibers of the same materials and hence. rates. [203] observed ultimate ing NFs into the market of high-strength and heat-resistant strain of PAN nanofibers of 60–130%.9 ± 0. composite materials will provide superior to PAN interaction with the nanotubes. varying monoton- materials and realized the importance of partial replace. Gu et al. Formation of PAN-based nanofibers. fiber tensile ment of PAN-based fibers by nanofibers.8◦ were prepared. and these ble for the determination of the reinforcement effect of were characterized for structures as well as mechanical CNTs in the polymer fibers. The bending modulus of individual nanofibers of well-aligned PAN nanofibers containing MWCNTs were was measured by a mechanical resonance method.3◦ . reinforcement. These nanofibers provide a higher ratio of surface area CNT-reinforced nanofibers. the in the largest ductilities and fiber strengths. with the slowest drawing rate resulting are particularly stringent due to safety reasons. The ultimate strength Recently. [206]. the rate. prepared by electrospinning MWCNT-suspended solution They assumed that indentation depth was of comparable of PAN in DMF using a moving collector [156]. A comparison of the processability structural properties of nanocomposites can be anticipated and properties of the fibers reinforced with VGNF and [195]. ranging between 30 and 130 MPa varied non- in the fields where the requirements for high strength monotonically. [205] measured Ye et al. up to 50% in SWNT-containing composites and maximum One of the most important applications of traditional improvement in tensile strength of about 70%. [201]. The nanotubes contributed to property improvements in forced dental composites [194]. which were and mesophase pitch [61] to examine the morphological observed parallel and oriented along the nanofibers axes. strain to fail- (micron-size) fibers. such as tensile strength. DWCNTs. modulus and tensile mechanical properties or for thermal management in semi. ically with the strain rate. respectively. is to use them as MWNTs containing composites.K. in composites to improve enhanced mechanical properties viz. rates. for PAN solutions with DMF [198]. superior by Lam et al. Dabirian et al. such that effectively resisted the heat shrinkage of the composite the curvature of the fiber may be ignored. resulting in higher mechanical strength properties. / Progress in Polymer Science 37 (2012) 487–513 perform nano-indentation of electrospun PAN nanofibers. especially engineering fibers such ure of 110% and work of rupture of 230% were observed in as carbon. while at the slowest strain strength materials. a cascade of ripples (necks). CNFs were produced CNTs in polymer matrix and interfacial adhesion between by pyrolyzing electrospun nanofibers from PAN having typ- nanotubes and polymers are the major factors responsi. The results showed that distribution of In a study by Zussman et al. confinement and used as-spun as well as post-drawn rein. For instance. Composite nanofiber sheets properties. becomes opaque or nontransparent due to light scattering.3 GPa. while improvement structural properties such as high modulus and strength in high strain properties. Improvement in low strain reinforcements in composite developments. The 5. the resulting composite smaller SWNT.1◦ and 16. The This limitation can be circumvented when fiber diameters better dispersed VGCF has lead to composite fibers having become significantly smaller than the wavelength of visible mechanical properties that are almost double than that of light. Twisted yarns yarns were treated in boiling water under tension and their of highly aligned PAN nanofibers with twist angles between mechanical properties were comparable with those of the 1. In this case.

. ical properties and the capacity of dye adsorption using Drew et al. a major Liu and Hsieh [219] prepared PAN nanofiber mem- challenge is to overcome the apparent 3 ␮m particle fil. Nataraj et al. Gibson et al. The fracture strength [MWCO] applications involving dairy and beverage prod- of the carbonized fibers was analyzed using the Weibull ucts [215]. erties for immobilization of lipase. [206] found that the stiffness [217] prepared the PAN fibers by electrospinning for use as and fracture strength of CNFs improved substantially by a filter media with the mean diameters ranging between optimizing polymer precursor morphology and molecular 270 and 400 nm and their performance was evaluated by orientation through the carbonization process. isms in gas/liquid. of such filtration nanofibers are as the effective barriers its for producing commercially available monofilaments against bacteria of <0. experi. of material. Adsorption and regeneration were carried out over halogen scavengers to apply tin dioxide and titanium diox- several cycles. PAN fibers measuring the penetration of monodisperse NaCl nanopar- modified with cobaltous chloride at 1300 ◦ C gave increased ticles of <80 nm. resulting in an electrospun filter media was minimized by increasing the improved tensile strength by about 15–40% and modulus fiber web thickness. The regeneration process led to a oxide-coated PAN nanofiber nonwoven fiber membrane decrease in weight and loss in mechanical strength due to a using electrospinning. statistical distribution function based on the assumption Musale and Kumar [216] discussed the importance of that variation in strength is caused by the variation in PAN as a filtration media on nanoparticles. retical predictions than the measured penetration through A recent study [208] focused on the changes in phys. nology are in the range of 3–8 ␮m. ide coating.3 ␮m. but fibers retained their mechanical proper. which was achieved by introducing its good solvent resistivity. Thus. fiber reinforced composite materials and while the nonwoven fibers produced by melt blown tech. [67] summarized the informa- high-capture efficiency at an affordable cost. These nano-scaled textiles meet the increasing demand 7.K. Yun et al. poly(acrylonitrile-co-maleic theoretical calculations showed that electrospun fiber mats acid) (PANCMA) containing reactive carboxyl groups was are extremely efficient in trapping airborne particles and synthesized and fabricated into NF membrane for lipase the high filtration efficiency is a direct consequence of the immobilization [221]. Zussman et al. wherein they stress concentration from a critical defect in a given volume produced PAN fiber mats by electrospinning. or even less. [146] reported the fabrication of novel metal the regenerated ACNFs. Filter quality factors and single fiber by 10–20% [207]. [220]. This study was an attempt to enlighten the media represents a unique opportunity to overcome the information on water vapor diffusion and air permeability current threshold of filterable particle size barrier. Simple and effective enzyme immobiliza- like Nylon 6. The penetration of nanoparticles through tion during the stabilization process. branes from hydrophilic acrylic nanofibers by alkaline tration barrier for a fiber-based filter that has desirable hydrolysis. In another structure and their transport properties.3 ␮m. tion related to the transport properties of electrospun fiber ning produces nanofibers of unprecedented and unrivalled membranes. In this situation. This lipase immobilization method submicron-size fibers generated by electrospinning [67]. the surface active nanofiber affinity membranes offer bilized lipase systems using the same source of lipase and better separation properties compared to the traditional substrate when considering protein loading. for protection from chemical and biological warfare agents. PAN and Ultem-1000 on PAN nanofibers filter tion system showing improved enzyme properties over media prepared by electrospinning to capture oil droplets the previous immobilized lipase systems using the same as small as 0. Enzyme immobilization requires inertness and hydropho- nanofiltration [211. Electrospin. PAN electrospun enzyme and substrate were prepared by Li et al. membranes in highly reactive surfaces for improved catal- ysis. crystallinity and orientation. S. showed the best performance among the various immo- Also. The formation of ladder structure in these collection efficiencies were found to be independent on the modified PAN fibers shows slow and gradual transforma. chymotrypsin. . cellulose ments were performed to study the effects of co-precursors and lysozyme. a PAN derivative viz. PAN-based nanofibers as filtration membranes of filter media with high filter efficiency in the sub- micrometer range [218]. activity reten- polymer membranes for high molecular weight cut off tion. The membranes were subsequently change in the orientation of the structure during air reacti. both as single layers and as coatings applied to small diameter with a high surface area. The PAN nanofiber layer was supported low fiber carbon membrane and discussed various factors on the nonwoven microfibrous substrate on which a water influencing the electrospun nonwoven fibrous membrane permeable coating of chitosan was applied. nanofiber mats have been widely used in ultrafiltration.212] and reverse osmosis [213] due to bicity in the backbone. immersed in an aqueous solution of metal halide salts and vation. Integrating such the existing military chemical/biological protective cloth- electrospun polymeric nanofibers with conventional filter ing systems. The penetration of nanoparticles through crystal size. filter thickness. The authors explored the potential of these ties even after the fourth regeneration [209]. a commercial filter. viruses and other microorgan- and are likely to produce fibers in the range of 10–50 ␮m. Other interesting applications Conventional fiber technologies have reached their lim. / Progress in Polymer Science 37 (2012) 487–513 507 average modulus found to be 63 GPa. protective clothing. and kinetic parameters. The resulting CNFs electrospun filters was in better agreement with the theo- have better modulus than the pristine PAN-based CNFs. Experiments and study. acrylonitrile monomer functional groups into the main Saufi and Ismail [214] reported PAN-based carbon hol. polymer backbone. sensing and photoelectric conversion applications. Since electrospinning would produce polymer fibers Electrospun PAN-based NFs have shown excellent prop- with diameters ranging from 3 to 1000 nm [210].

Conclusions PAN-based CNFs. electrocatalysts. that exhibit high breathability. In addition. The accelerating the strongly oxidizing conditions to which these fibers technologies of producing PAN-based nanofibers have were exposed (69–71 wt. the increases were very small considering ering engineering.% of AgNO3 and UV-irradiated for vidual nanofibers that are stiff and strong enough to 30 min was found to be most effective. etc.. The high specific surface area of ultrafine fibers 8.508 S. scaffolds in tissue engineer- PAN-based CNFs ing. Electrospun trospun mat and correlating the conditions of collection of fiber coatings produce exceptionally lightweight multi- the nanofibers with the structural and transport properties functional membranes for protective clothing applications of the mat were found to be important. This work was supported by the covering a wide range of areas such as electrochemical Korea Foundation for International Cooperation of Sci- devices. Grabinski et al. protective clothing. PAN and PVC was done by Lala et al. and many more. elasticity and filtration effi- ciency.to nano-dimension. but the PAN-based fibers exhibited a continu- PAN-based CNFs are seemingly a new class of materi- ally increasing surface area with a continuous weight loss als used in a wide array of applications including filtration by increasing oxidation time. sensors. for financially sup- From the forgoing discussions. barriers. Very few reports are [223] studied the cellular effects of PAN-based CNFs with available in the literature on mechanical nanofibers and diameters ranging from micron. withstand the forces are required. con. one can in the mouse keratinocyte cell line. interconnectivity. 115 ◦ C) and the now matured enough to overcome the drawbacks of much larger surface area increase that occurred when low production rate of few grams per hour in labora- the PAN-based CNFs were oxidized. It is antici- in membrane bioreactors. it is important to know that indi- in DMF containing 5 wt. insulators. their unique properties make them perfect area with oxidation time using nitrogen BET measure- modern materials of choice across many disciplines cov- ments. The orientation of NFs in the elec.K. Such challenges have been isolated in role of dimension in dermal toxicity of CNTs and their use handling individual nanofibers. The authors thank MCIE. [224] investigated the mentation of high strength nanofibers for numerous structural and transport properties of electrospun PAN applications. ence & Technology (KICOS) through a grant provided by ducting nanowires. biomacromolecules or even cells can be attached or Nanofiber membranes comprising sheets of randomly ori- hybridized with the nanofiber membrane for applica- ented nanofibers show an extremely effective removal tions in protein purification and waste water treatment method with a high rejection rate of airborne particles as affinity membranes. Research trends have shown pated that the future will witness many more applications that new ways in chemical analysis and in biosensor of PAN-based nanofibers in a wide variety of scientific applications may be anticipated using the PAN-based disciplines. lithium batteries. However. This study focused on the gle nanofibers. have been envisaged. CNFs. the CNFs can also form an effec- tive size exclusion membrane for particulate removal from wastewater. Pittman tal engineering applications. garments. High porosity. Specialized applications and future prospects of as high performance filters. Ligand molecules.% nitric acid. etc. sensors. In the future. microscale interstitial space. surface-to-volume ratio mean that nonwoven electrospun based CNFs has been rapidly increasing over the past nanofiber meshes are excellent materials for membrane decade in flexible photovoltaic membranes and biomedical preparation. material reinforcements. the future research on Global Partnership Program (GPP). Nataraj et al. it is realized that the porting this research through “Technology Development PAN-based CNFs are increasing in the worldwide market for Future Generation”. CA. / Progress in Polymer Science 37 (2012) 487–513 A comparative study of antimicrobial activity using methods of observing changes in nanostructures of a three different electrospun CNFs incorporated with silver single polymeric nanofiber during stretching and devel- nanoparticles viz. Korea. tory environments to large industrial scale production. et al. Their wettability increased sharply on oxidation. fiber web membrane in relation to processing parameters Other innovations of NFs and nano-structured sur- to understand the distribution. . HEL-30 cells. [189] found that vapor-grown CNFs during nitric acid oxidation have produced high strength materials than the 9. ballistic the Korean Ministry of Science & Technology (MOST) and chem-bio protection. PAN-based CNFs to show a continually increasing surface However. The antimicrobial activity of these single polymeric nanofibers. composites materials. BK21. oping methods of measuring viscoelastic properties of [222] in a DMF solvent. using not many tests have been done to characterize the sin- mouse keratinocytes (HEL-30). deposition and orientation faces are in gas and liquid filtration areas. Lakshminarayanan et al. enzymatic catalysis or synthesis by both physical trapping and adsorption. However. as a model expect more attention to the preparation and docu- for dermal exposure. medicine.226]. Several studies are underway to check Acknowledgements their efficiency in removing particles from polluted air. When using such fibers as functionalized CNFs showed that the combination of PAN an engineering fiber. fiber-reinforced of NFs as filtering media. Barhate et al. atomic force microscopy tips. and a large The pace and development on electrospinning of PAN. project number in this area depends on the development of in situ K20602000009-07E0200-00910. especially in biotechnology and environmen- devices to serve as encapsulating tools [225. [227] studied the oxidation of medical and energy storage devices. and biology.

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