A new process of fabricating electrically conducting nylon 6/graphite nanocomposites via intercalation polymerization

A new process was developed to fabricate electrically conducting nylon 6/graphite nanocomposites via intercalation polymerization of ϵ‐caprolactam in the presence of expanded graphite. The transition from an electrical insulator to an electrical semiconductor for nylon 6 occurred when the graphite volume content was 0.75, which was much lower than that of conventional conducting polymer composites. The electrical conductivity reached 10⁻⁴ S/cm when the graphite content was 2.0 vol %. The TEM microphotographs suggested that the low percolation threshold and the great improvement of electrical conductivity could be attributed to the high aspect ratio (width‐to‐thickness), the high expansion ratio in c axis of the graphite sheets and the homogeneous dispersion of the nanoscale graphite particles in the nylon 6 matrix. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 1626–1633, 2000     

Effect of silver nanoparticles on the dynamic crystallization behavior of nylon‐6

The effect of introducing silver nanoparticles on the rheological properties and dynamic crystallization behavior of nylon‐6 was investigated. The nanocomposites showed slightly higher viscosity than pure nylon‐6 in the low‐frequency range even at an extremely low loading level of the silver particles (0.5–1.0 wt %). The nanoparticles had a more noticeable effect on the storage modulus than on the loss modulus of a nylon‐6 melt and reduced its loss tangent. They increased the crystallization temperature of nylon‐6 by about 14 °C and produced a sharper crystalline peak. The silver nanoparticles promoted the crystallization of nylon‐6, and their effect on the dynamic crystallization of nylon‐6 at 200 °C was more notable at a lower shear rate and at 190 °C at a higher frequency. Nylon‐6 produced large spherulitic crystals, but the nanocomposites showed a grainy structure. In addition, the silver nanoparticles reduced the fraction of the α‐form crystal but increased that of the γ‐form crystal. The nanocomposites crystallized at 190 °C showed a lower melting temperature than nylon‐6 by about 3 °C, whereas the nanocomposites crystallized at 200 °C showed almost the same melting temperature. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 790–799, 2004     

Multiple melting and crystallization of nylon‐66/montmorillonite nanocomposites

Nylon‐66 nanocomposites were prepared by melt‐compounding nylon‐66 with organically modified montmorillonite (MMT). The organic MMT layers were exfoliated in a nylon‐66 matrix as confirmed by wide‐angle X‐ray diffraction (WAXD) and transmission electron microscopy. The presence of MMT layers increased the crystallization temperature of nylon‐66 because of the heterogeneous nucleation of MMT. Multiple melting behavior was observed in the nylon‐66/MMT nanocomposites, and the MMT layers induced the formation of form II spherulites of nylon‐66. The crystallite sizes L₁₀₀ and L₀₁₀ of nylon‐66, determined by WAXD, decreased with an increasing MMT content. High‐temperature WAXD was performed to determine the Brill transition in the nylon‐66/MMT nanocomposites. Polarized optical microscopy demonstrated that the dimension of nylon‐66 spherulites decreased because of the effect of the MMT layers. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 2861–2869, 2003     

Water‐assisted melt compounding of nylon‐6/pristine montmorillonite nanocomposites

An exploratory pioneering study on the fabrication of nylon‐6/montmorillonite (MMT) nanocomposites with the aid of water as an intercalating/exfoliating agent via melt compounding in a twin‐screw extruder was conducted. Commercial nylon‐6 pellets and pristine MMT powder were directly fed into the hopper of the extruder. Water was then injected into the extruder downstream. After interactions with the nylon‐6 melt/pristine MMT system, water was removed from the extruder further downstream via a venting gate. As such, no third‐component residual was left within the extrudates. Transmission electron microscopy micrographs showed that pristine MMT was uniformly dispersed in the nylon‐6 matrix. The contact time between water and the nylon‐6/pristine MMT system inside the extruder was so short that nylon‐6 was subjected to very little hydrolysis, if any. The resultant nanocomposites showed higher stiffness, superior tensile strength, and improved thermal stability in comparison with their counterparts obtained without water assistance and the nylon‐6/organic MMT nanocomposites. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 1100–1112, 2005     

Structure‐property relationships in exfoliated polyisoprene/clay nanocomposites

Structure‐property relationships in exfoliated polyisoprene (PI)/clay nanocomposites have been studied as a function of the clay concentration with rheometry, X‐ray diffraction, small‐angle X‐ray scattering, and transmission electron microscopy. The results presented here indicate that the interlayer spacing of layered silicates increases from 2 to at least approximately 14 nm because of the penetration of polymer molecules into the spacing between the silicate layers. The average aspect ratio (width/thickness) of the dispersed nanoplates is also estimated to be at least approximately 80. Additionally, the storage modulus of the nanocomposite exhibits frequency‐independent pseudo‐solidlike behavior above the percolation threshold [volume fraction of clay at the percolation threshold (?_p) = 0.02] and shows large enhancements (up to approximately six orders of magnitude) in comparison with the storage modulus of PI when the volume fraction of clay (?) is greater than ?_p. For the shear‐aligned PI/clay nanocomposites, an increase in the storage modulus with shear alignment is observed at ? < ?_p, whereas a decrease in the storage modulus is observed for ? > ?_p. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 1000–1009, 2004     

Synthesis,rheology, and morphology of nylon‐11/layered silicate nanocomposite

Exfoliated nylon‐11/layered silicate nanocomposites were prepared via in situ polymerization by dispersing organoclay in 11‐aminoundecanoic acid monomer. The original clay was modified by a novel method with 11‐aminoundecanoic acid. In situ Fourier transform infrared spectroscopy results show that stronger hydrogen bonds exist between nylon‐11 and organoclay than that of between nylon‐11 and original clay. The linear dynamic viscoelasticity of organoclay nanocomposites was investigated. Before taking rheological measurements, the exfoliated and intercalating structures and the thermal properties were characterized using X‐ray diffraction, transmission electron microscopy, differential scanning calorimetry, and thermogravimetric analysis. The results show that the clay was uniformly distributed in nylon‐11 matrix during in situ polymerization of clay with 4 wt % or less. The presence of clay in nylon‐11 matrix increased the crystallization temperature and the thermal stability of nanocomposites prepared. Rheological properties such as storage modulus, loss modulus, and relative viscosity have close relationship with the dispersion favorably compatible with the organically modified clay. Comparing with neat nylon‐11, the nanocomposites show much higher dynamic modulus and stronger shear thinning behavior. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 2161–2172, 2006     

Conductive mechanism of polymer/graphite conducting composites with low percolation threshold

Preparation of the conducting composites of polystyrene/expanded graphite via in situ polymerization and investigation of the conductive mechanism were carried out. They are characterized by high conductivity and a low percolation threshold. The electrical conductivity reached 10^?2 S/cm with 3.0 vol % expanded graphite content, whereas the percolation threshold was 1.0 vol %. Optical micrographs revealed the heterogeneous distribution of the graphite particles and the formation of a conductive network in the polymer matrix. A model of primary particle was proposed to interpret the conductive phenomena. The primary particle is the basic conductive unit in the composites that comprises three of the following parts: the graphite particle, the compact‐adsorbed layer, and the wrapping shell. Our model was also used to explain the experimental data in our previous studies on nylon‐6/expanded graphite composites. A low percolation threshold of conducting composites can be also explained according to the model of the primary particle. Furthermore, the theoretical line of conductivity versus primary particle content calculated from the revised Flory's theory fits the experimental data well. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 954–963, 2002     

Electrical conductivity of poly(ethylene terephthalate)/expanded graphite nanocomposites prepared by in situ polymerization

Nanocomposites based on poly(ethylene terephthalate) (PET) and expanded graphite (EG) have been prepared by in situ polymerization. Morphology of the nanocomposites has been examined by electronic microscopy. The relationship between the preparation method, morphology, and electrical conductivity was studied. Electronic microscopy images reveal that the nanocomposites exhibit well dispersed graphene platelets. The incorporation of EG to the PET results in a sharp insulator‐to‐conductor transition with a percolation threshold (?_c) as low as 0.05 wt %. An electrical conductivity of 10^?3 S/cm was achieved for 0.4 wt % of EG. The low percolation threshold and relatively high electrical conductivity are attributed to the high aspect ratio, large surface area, and uniform dispersion of the EG sheets in PET matrix. © 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2012     

A new conception on the toughness of nylon 6/silica nanocomposite prepared via in situ polymerization

A novel method, in situ polymerization, was used for the preparation of nylon 6/silica nanocomposites, and the mechanical properties of the nanocomposites were examined. The results showed that the tensile strength, elongation at break, and impact strength of silica-modified nanocomposites exhibited a tendency of up and down with the silica content increasing, while those of silica-unmodified nanocomposites decreased gradually. It also exhibited that the mechanical properties of silica-modified nanocomposites have maximum values only when 5% silica particles were filled. Based on the relationship between impact strength of the nanocomposites and the matrix ligament thickness τ, a new criterion was proposed to explain the unique mechanical properties of nylon 6/silica nanocomposites. The nylon 6/silica nanocomposites can be toughened only when the matrix ligament thickness is less than τ_c and greater than τ_a, where τ_a is the matrix ligament thickness when silica particles begin to aggregate, and τ_c is the critical matrix ligament thickness when silica particles begin to toughen the nylon 6 matrix. The matrix ligament thickness, τ, is not independent, which related with the volume fraction of the inorganic component because the diameter of inorganic particles remains constant during processing. According to the observation of Electron Scanning Microscope (SEM), the process of dispersion to aggregation of silica particles in the nylon 6 matrix with increasing of the silica content was observed, and this result strongly supported our proposal. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 789–795, 1998     

Isothermal and nonisothermal crystallization kinetics of nylon 6/functionalized multi‐walled carbon nanotube composites

The well dispersion of functionalized multi‐walled carbon nanotube (f‐MWCNT) in nylon 6 matrix was prepared by solution mixing techniques. The isothermal and nonisothermal crystallization kinetics of nylon 6 and nylon 6/f‐MWCNT nanocomposites were studied by differential scanning calorimetry (DSC), X‐ray diffraction and polarized optical microscopy analysis. DSC isothermal results revealed that the activation energy of nylon 6 extensively decreased by adding 1 wt % f‐MWCNT into nylon 6, suggesting that the addition of small amount of f‐MWCNT probably induces the heterogeneous nucleation. Nevertheless, the addition of more f‐MWCNT into nylon 6 matrix reduced the transportation ability of polymer chains during crystallization process and thus increased the activation energy. The nonisothermal crystallization of nylon 6/f‐MWCNT nanocomposites was also discussed. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 158–169, 2008     

Mutual influence of the morphology and capillary rheological properties in nylon/glass‐fiber/liquid‐crystalline‐polymer blends

Nylon‐6/glass‐fiber (GF)/liquid‐crystalline‐polymer (LCP) ternary blends with different viscosity ratios were prepared with three kinds of nylon‐6 with different viscosities as matrices. The rheological behaviors of these blends were characterized with capillary rheometry. The morphology was observed with scanning electron microscopy and polarizing optical microscopy. This study showed that although LCP did not fibrillate in binary nylon‐6/LCP blends, LCP fibrillated to a large aspect ratio in some ternary blends after GF was added. The addition of 5 wt % LCP significantly reduced the melt viscosity of nylon‐6/GF blends to such an extent that some nylon‐6/GF/LCP blends had quite low viscosities, not only lower than those of neat resins and nylon‐6/GF blends but also lower than those of corresponding nylon‐6/LCP blends. The mutual influence of the morphology and rheological properties was examined. The great reduction of the melt viscosity was considered the result of LCP fibrillation. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 1619–1627, 2004     

Toughening of nylon‐6 with epoxy‐functionalized acrylonitrile‐butadiene‐styrene copolymer

Glycidyl methacrylate (GMA) functionalized acrylonitrile‐butadiene‐styrene (ABS) copolymers have been prepared via an emulsion polymerization process. The epoxy‐functionalized ABS (e‐ABS) particles were used to toughen nylon‐6. Molau tests and FTIR results showed the reactions between nylon‐6 and e‐ABS have taken place. Scanning electron microscopy (SEM) displayed the compatibilization reaction between epoxy groups of e‐ABS and nylon‐6 chain ends (amine or carboxyl groups), which improve disperse morphology of e‐ABS in the nylon‐6 matrix. The presence of only a small amount of GMA (1 wt %) within the e‐ABS copolymer was sufficient to induce a pronounced improvement of the impact strength of nylon‐6 blends; whereas further increase of the GMA contents in e‐ABS resulted in lower impact strength because of the crosslinking reaction between nylon‐6 and e‐ABS, resulting in agglomeration of the ABS particles. SEM results showed shear yielding of the nylon‐6 matrix and cavitation of rubber particles were the major toughening mechanisms. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 2170–2180, 2005     

Exploitation of introducing of catalytic centers into layer galleries of layered silicates and related epoxy nanocomposites. I. Epoxy nanocomposites derived from montmorillonite modified with catalytic surfactant‐bearing carboxyl groups

Montmorillonite (MMT) was modified with the acidified cocamidopropyl betaine (CAB) and the resulting organo‐montmorillonite (O‐MMT) was dispersed in an epoxy/methyl tetrahydrophthalic anhydride system to form epoxy nanocomposites. The intercalation and exfoliation behavior of the epoxy nanocomposites were examined by X‐ray diffraction and transmission electron microscopy. The curing behavior and thermal property were investigated by in situ Fourier transform infrared spectroscopy and DSC, respectively. The results showed that MMT could be highly intercalated by acidified CAB, and O‐MMT could be easily dispersed in epoxy resin to form intercalated/exfoliated epoxy nanocomposites. When the O‐MMT loading was lower than 8 phr (relative to 100 phr resin), exfoliated nanocomposites were achieved. The glass‐transition temperatures (T_g's) of the exfoliated nanocomposite were 20 °C higher than that of the neat resin. At higher O‐MMT loading, partial exfoliation was achieved, and those samples possessed moderately higher T_g's as compared with the neat resin. O‐MMT showed an obviously catalytic nature toward the curing of epoxy resin. The curing rate of the epoxy compound increased with O‐MMT loading. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 1192–1198, 2004     

Electrical and optical properties of ceramic–polymer nanocomposite coatings

Transparent, conductive composite coatings were fabricated from suspensions of poly(vinyl acetate‐acrylic) (PVAc‐co‐acrylic) copolymer latices (50–600 nm) and nanosized antimony‐doped tin oxide (ATO) particles (～15 nm). The suspensions were deposited as coatings onto poly(ethylene terephthalate) substrates and dried at 50 °C. Microstructure studies using field emission scanning electron microscopy and tapping‐mode atomic force microscopy (TMAFM) indicated that the latex particles coalesced during drying and forced the ATO particles to segregate into the boundaries between the latex particles. Low phase contrast was observed with TMAFM; this result was consistent with the presence of PVAc‐co‐acrylic in the ATO‐rich phase of the composite. The conductivity of the composite coatings followed a percolation power‐law equation, with the percolation threshold between 0.05 and 0.075 volume fractions of ATO and the critical conductivity exponent ranging from 1.34 to 2.32. The highest direct‐current conductivity of the composite coatings was around 10^?2 S/cm. The optical transmittance and scattering behavior of the coatings were also investigated. Compared with the PVAc‐co‐acrylic coating, the composite coatings had lower transparency because of the Rayleigh scattering. The transparency of the composite coatings was improved by a reduction in the coating thickness. The best transparency for the coatings with a direct‐current conductivity of approximately 10^?2 S/cm was around 85% at a wavelength of 600 nm. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 1744–1761, 2003     

Hollow latex particles as submicrometer reactors for polymerization in confined geometries

A method was developed for free‐radical polymerization in the confines of a hollow latex particle. Hollow particles were prepared via the dynamic swelling method from polystyrene seed and divinylbenzene and had hollows of 500–1000 nm. So that these hollow poly(divinylbenzene) particles could function as submicrometer reactors, the particles were filled with a monomer (N‐isopropylacrylamide) via the dispersion of the dried particles in the molten monomer. The monomer that was not contained in the hollows was removed by washing and gentle abrasion. Free‐radical polymerization was then initiated by γ radiolysis in the solid state. Transmission electron microscopy showed that poly(N‐isopropylacrylamide) formed in the hollow interior of the particles, which functioned as submicrometer reactors. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 5706–5713, 2004     

Enhancing dispersion of copper nanowires in melt‐mixed polystyrene composites

Copper nanowire (CuNWs)/polystyrene (PS) composites were prepared by melt mixing using unfunctionalized and functionalized nanowires. Alkanethiols were utilized to modify the surface of CuNWs postsynthesis and enable their dispersion in a polymer melt. Unfunctionalized nanowires decreased the electrical resistivity of PS by nine orders of magnitude with 2.0 vol % Cu, and resulted in composites with a viscoelastic behavior dominated by polymer–polymer networks indicating that electrical percolation occurred without a transition from liquid‐like to solid‐like behavior (i.e., rheological percolation). Results from transmission electron microscopy (TEM), scanning electron microscopy (SEM), and melt rheology characterization indicated that surface modification of CuNWs contributed to the dispersion of the nanofiller in the polymer matrix. CuNWs functionalized with 1‐octanethiol and 1‐butanethiol produced rheological percolation and a gradual decrease in the electrical resistivity of the PS nanocomposites with increasing concentration of nanowires. Polymer nanocomposites with low concentrations of functionalized nanowires showed lower complex viscosities than pure PS; this was attributed to a plasticizing effect introduced by the alkanethiols. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 2064–2078, 2008     

Morphological study on water‐borne conducting polyaniline‐poly(ethylene oxide) blends

Conducting polyaniline‐poly(ethylene oxide) blends were prepared from their aqueous solutions. The blends displayed an electrical conductivity percolation threshold as low as 1.83 wt % of polyaniline loading. As demonstrated by scanning electron microscopy, polarized optical microscopy, and wide‐angle X‐ray diffraction studies, the conducting polyaniline took a fibrillar morphology in the blend, and it existed only in the amorphous phase of poly(ethylene oxide). A three‐phase model combining morphological factors instead of a two‐phase model was proposed to explain the low‐conductivity percolation threshold. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 605–612, 2002; DOI 10.1002/polb.10114     

Molecular composites prepared by in situ direct synthesis of wholly aromatic rigid‐rod polyamides via the phosphorylation reaction in a dissolved nylon‐6 matrix

Wholly aromatic rigid‐rod polyamides such as poly(p‐phenyleneterephthalamide) (PPD‐T) were synthesized in situ in a solution of nylon‐6 via the phosphorylation polycondensation method to form nanocomposites or so‐called “molecular composites.” The incorporation of PPD‐T into a nylon‐6 matrix was achieved by this approach in a more compatibilized form than that obtained by the conventional coagulation method that entails precipitation of a blend of PPD‐T and nylon‐6 in a solvent, for example, concentrated sulfuric acid. Gelation occurred during the synthesis, presumably because of the formation of interpenetrating networks accompanied by some block‐copolymer formation. The transparency and tensile properties of the resultant composite films from the rigid‐rod aromatic polyamide/nylon‐6 combination were improved over those of nylon‐6 film alone. Rainbow‐colored intense birefringence was observed for the composite films under crossed polarizers. These properties are discussed in context with the in situ synthesized rigid‐rod polyamides uniformly incorporated in nylon‐6. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 1014–1026, 2003     

Brominated poly(isobutylene‐co‐para‐methylstyrene) (BIMS)‐clay nanocomposites: Synthesis and characterization

In this work, preparation and properties of different nanoclays modified by organic amines (octadecyl amine, a primary amine, and hexadecyltrimethylammonium bromide, a tertiary amine) and brominated polyisobutylene‐co‐paramethylstyrene (BIMS)‐clay nanocomposites are reported. The clays and the rubber nanocomposites have been characterized with the help of Fourier transform infrared spectroscopy (FTIR), transmission electron microscopy (TEM), and X‐ray diffraction (XRD). The X‐ray diffraction peaks observed in the range of 3 °–10 ° for the modified clays disappear in the rubber nanocomposites. TEM photographs show predominantly exfoliation of the clays in the range of 12 ± 4 nm in the BIMS. In the FTIR spectra of the nanocomposites, there are common peaks of virgin rubber as well as those of the clays. Excellent improvement in mechanical properties like tensile strength, elongation at break, and modulus is observed on incorporation of the nanoclays in the BIMS. Structure‐property correlation in the above nanocomposites is attempted. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 4489–4502, 2004     

Synthesis and characterization of polyaniline/graphite conducting nanocomposites

A new method for the synthesis of exfoliated graphite and polyaniline (PANI)/graphite nanocomposites was developed. Exfoliated graphite nanosheets were prepared through the microwave irradiation and sonication of synthesized expandable graphite. The nanocomposites were fabricated via the in situ polymerization of the monomer at the presence of graphite nanosheets. The as-synthesized graphite nanosheets and PANI/graphite nanocomposite materials were characterized with Fourier transform infrared spectroscopy, scanning electron microscopy, transmission electron microscopy, and thermogravimetric analysis (TGA). The conductivity of the PANI/graphite nanocomposites was dramatically increased over that of pure PANI. TGA indicated that the incorporation of graphite greatly improved the thermal stability of PANI. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 1972–1978, 2004