Thermal conductivity models for carbon/liquid crystal polymer composites

Thermally conductive resins are needed for bipolar plates in fuel cells. Currently, the materials used for these bipolar plates often contain a single type of graphite in a thermosetting resin. In this study, varying amounts of four different types of polyacrylonitrile carbon fillers (Ketjenblack carbon black, Thermocarb synthetic graphite, Fortafil 243 carbon fiber, and Panex 30 carbon fiber) were added to a thermoplastic matrix (Vectra A950RX Liquid Crystal Polymer), with the resulting resins tested for through‐plane and in‐plane thermal conductivity. There are two unique contributions of this work. The first contribution is the use of the Nielsen model for the through‐plane thermal conductivity as a function of the single filler volume fraction. The model fits the data for all composites well. The second contribution is the development of a new, accurate, empirical model to predict the in‐plane thermal conductivity for all resins containing synthetic graphite or carbon fiber. Both of these models will form the basis for the development of new thermal conductivity models for composites with multiple fillers for fuel cell bipolar plate applications. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Effect of the ionic conductivity of a polymer matrix on the electrooptical properties of polymer-dispersed liquid crystal films

Summary The influence of ionic conductivity on the electrooptical response was investigated. A new monomer of 2-(poly(ethylene glycol)oxycarbonyl)-bicyclo[2.2.1] hepta-2,5-diene (PEGOC-BCHD) was synthesized and polymerized. Polymer/liquid crystal composite films are composed of poly(PEGOC-BCHD), E8, and alkali metal salts. The ionic conductivities were measured as a function of the ratio of LiClO₄/ethylene oxide for various molecular weights of poly(ethylene glycol). The results indicate that the threshold field and response rise time can be reduced by increasing ionic conductivity of the matrix polymer. Liquid crystal droplets were observed in a continuous matrix phase in the form of ‘Swiss cheese’ morphology. Received: 13 March 1998/Accepted: 19 May 1998     

Thermal conductivity of carbon fiber/liquid crystal polymer composites

Thermally conductive resins are needed for bipolar plates in fuel cells. Currently, the materials used for these bipolar plates often contain a single type of graphite in a thermosetting resin. In this study, varying amounts of two different types of polyacrylonitrile based carbon fibers, Fortafil 243 and Panex 30, were added to a thermoplastic matrix (Vectra A950RX Liquid Crystal Polymer). The resulting single filler composites were tested for thermal conductivity and a simple exponential thermal conductivity model was developed for the square root of the product of the in‐plane and through‐plane thermal conductivity . The experiments showed that the through‐plane thermal conductivity was similar for composites up to 40 vol % fiber. However, at higher loadings, the Panex 30 samples exhibited higher thermal conductivity. The experiments also showed that the in‐plane thermal conductivity of composites containing Panex 30 was higher than those containing Fortafil 243 for all volume fractions studied. Finally, the model agreed very well with experimental data covering a large range of filler volume fraction (from 0 to 55 vol % for both single filler systems). The model can be used with existing through‐plane thermal conductivity models to predict in‐plane thermal conductivity. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 5456–5462, 2006     

Electrical conductivity and rheology of carbon fiber/liquid crystal polymer composites

One emerging market for electrically conductive resins is for bipolar plates for use in fuel cells. Adding carbon fillers to thermoplastic resins increases composite electrical conductivity and viscosity. Current technology often adds as much of a single type of carbon filler as possible to achieve the desired conductivity, while still allowing the material to be extruded and molded into a bipolar plate. In this study, varying amounts of two different types of polyacrylonitrile (PAN) based carbon fiber (Fortafil 243 and Panex 30) were added to Vectra A950RX liquid crystal polymer. The resulting single fiber composites were then tested for electrical conductivity and rheological properties. The electrical conductivity followed the behavior typically seen in composites with a percolation threshold at 5 vol% for Fortafil 243 and at 13 vol% for Panex 30. Viscosity increased with increasing filler volume fraction for all shear rates, but was more rapid for the Fortafil 243 composites. Over the range of shear rates studied, the viscosity followed a shear‐thinning power law model with power‐law exponent (n – 1) = –0.5 for neat Vectra A950RX. Panex 30 had no effect on the power‐law exponent and Fortafil 243 changed (n – 1) to −0.6. POLYM. COMPOS., 28:168–174, 2007. © 2007 Society of Plastics Engineers     

Optical switching behavior of polymer‐dispersed liquid crystal composite films with various novel azobenzene derivatives

Polymer‐dispersed liquid crystal (PDLC) composite films were fabricated by thermal polymerization with E7 liquid crystal, monomers, and novel azobenzene derivatives synthesized in this study. To investigate the effects of azocompounds on the optical switching of PDLC films, a series of novel azobenzene derivatives of 4‐alkyloxy‐4′‐methoxyazobenzene with carbon numbers of 3–6, chiral compounds of amyl‐4‐(4‐hexyloxyphenylazo)benzoate, and bornyl‐4‐(4‐hexyloxyphenylazo)benzoate were synthesized. The compounds synthesized in this investigation were identified using FTIR, NMR, and elemental analysis. The optical texture of the composite films was analyzed under crossed nicols with a polarizing microscope. The morphological observation of the solid polymer in the composite films was performed with a scanning electron microscope (SEM). The optical behavior of the composite films on UV irradiation and the effects of the curing time on the thermal stability of the composite films were investigated. Isomerization of the azobenzene derivatives due to UV irradiation was confirmed by a texture study and image recording method. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 789–799, 2004     

Dual frequency conductivity switching in a carbon nanotube/liquid crystal composite

We report dielectric and conductivity measurements on a composite of carbon nanotubes and a liquid crystal possessing dual frequency switching characteristics. The conductivity increases by two orders of magnitude with respect to that for the host liquid crystal, and achieves negligible temperature dependence. The frequency dependence of the ac conductivity is explained by the extended pair approximation model, although the exponent is slightly higher than generally seen. We demonstrate that the current through the sample can be field-driven between the two anisotropic values (170:1) by simply changing the frequency of the applied voltage, and exhibiting at least a millisecond response.     

Effects of polymer matrix and salt concentration on the ionic conductivity of plasticized polymer electrolytes

Two polar polymers with different dielectric constants, poly(vinylidene fluoride) (PVDF) and poly(ethylene oxide) (PEO), were each blended with a chlorine-terminated poly(ethylene ether) (PEC) and one of the two salts, LiBF₄ and LiCF₃CO₂, to form PEC plasticized polymer electrolytes. The room-temperature ionic conductivity of the PEC plasticized polymer electrolytes reached a value as high as 10^?4 S/cm. The room-temperature ionic conductivity of the PVDF-based polymer electrolytes displayed a stronger dependence on the PEC content than did the PEO-based polymer electrolytes. In PVDF/PEC/LiBF₄ polymer electrolytes, the dynamic ionic conductivity was less dependent on temperature and more dependent on the PEC content than it was in PEO/PEC/LiBF₄ polymer electrolytes. The highly plasticized PVDF-based polymer electrolyte film with a PEC content greater than CF4 (CF4 defined as the molar ratio of the repeat units of PEC to those of PVDF equal to 4) was self-supported and nonsticky, while the corresponding PEO-based polymer electrolyte film was sticky. In these highly plasticized PVDF-based polymer electrolytes, the curves of the room-temperature ionic conductivity vs. the salt concentration were convex because the number of carrier ions and the chain rigidity both increased with increase of the salt content. The maximum ionic conductivity at 30°C was independent of the PEC content, but it depended on the anion species of the lithium salts in these highly plasticized polymer electrolytes. © 1995 John Wiley & Sons, Inc.     

Preparation of composites of polymer liquid crystal/cholesteric liquid crystal and their photochemical switching and memory properties by photoisomerization of a chiral azobenzene molecule

A chiral azobenzene compound was synthesized, and mixing the chiral azobenzene compound in a host nematic liquid crystal (LC) induced a cholesteric phase. The twisting power of the trans‐form of the chiral azobenzene compound was larger than that of its cis‐form produced by ultraviolet irradiation. A low molecular weight compensated nematic LC was then prepared by mixing of the chiral azobenzene and a nonphotochromic chiral compound, thus giving mutual opposite helical sense in the host LC. Reversible optical switching between transparent and opaque was achieved by ultraviolet and visible light irradiation. However, the photochemically switched opaque state was not stable even in the dark. Stability of the opaque state was found to be improved by adding polymer LC to the low molecular weight compensated nematic LC. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 2577–2580, 2004     

Synthesis of poly(benzylmethacrylate)-co-perfluorooctylethylmethacrylate) and electrooptical properties of the resultant polymer/liquid crystal composite films

Methacrylate copolymers of benzylmethacylate (BMA) and perfluorooctylethylmethacrylate (FMA) were synthesized and applied to the polymer/liquid crystal (LC) composite films. The copolymers were prepared by a radical solution polymerization. The high composition of FMA resulted in a precipitation during the polymerization. The contact angle of the LC on the copolymer films decreased with increasing FMA composition. Due to a small interaction between the LC and the copolymers, the copolymer/LC composite films showed low driving voltage in the range of 18–25 V_rms, corresponding to about 1/3 the value of the poly(methyl methacrylate) (PMMA)/LC composite film. © 1995 John Wiley & Sons, Inc.     

Effect of polymer blending on the electrical conductivity of polypyrrole/copolyester composite films

Summary The effect of polymer blending on the electrical conductivity of polypyrrole/copolyester composite film was investigated. Copolyesters containing sodium sulfonate group with various main chain structures were synthesized and blended with PET. The average anionic group contents in the blend samples were controlled to be 3.5 and 6.1 mol%. The polypyrrole composite films were prepared by polymerization of pyrrole through vapor phase absorption onto the copolyester-PET blend films which contained FeCl₃. The conductivity of the blend samples containing 3.5 mol% of DMS was greater than that of the copolyester of the same DMS content when the pyrrole vapor exposure time was longer than 30 min. The blends of 6.1 mol% of DMS showed higher conductivity than the copolyesters of the same DMS amount even when the exposure time was short. The high electrical conductivity of the blend samples was thought to be due to the phase separation between PET and copolyesters in amorphous region. Received: 1 June 1998/Revised version: 5 October 1998/Accepted: 30 October 1998     

Effect of acrylonitrile content of styrene-co-acrylonitrile (SAN) on morphology and electrooptical properties of polymer/liquid crystal composite films

Effects of copolymer composition on morphology and electrooptical properties of polymer/liquid crystal (LC) (40/60 w/w) composite films were studied with styrene-co-acrylonitrile (SAN) of varying acrylonitrile (AN) content (6.3–35 wt %) and a cyanobiphenyl-type liquid crystal (E8). The dimension of the LC domain in the composite film decreased with increase of AN content of SAN up to 30 and increased at 35 wt %. The contact angle of the film with an LC drop showed a similar trend; however, its minimum was obtained at 24% AN. Threshold voltage (V_th) and rise time (τ_R) increased, and decay time (τ_D) decreased with AN content up to 30%, and the tendency is reversed at 35%. The results were interpreted in terms of, possibly, a solubility parameter matching between SAN and LC. © 1993 John Wiley & Sons, Inc.     

Display forming polymer/liquid crystal composite layers and their stability against external mechanical distortions

The liquid crystal display (LCD) technology is confronted with the task to substitute rigid glass plates enclosing the electro‐optically active liquid crystal (LC) material by plastic substrates. In particular, the commercialization of flexible displays requires a sufficient stabilization against external mechanical distortions. To achieve LC layer stabilization, several procedures have been suggested. In this work, the thermal‐induced phase separation (TIPS) technique has been applied to generate composite films consisting of LC compartments which are encased by coherent polymer walls after binodal phase separation. Composite films were prepared from a series of poly(methacrylates) and various commercial nematic LC mixtures. Furthermore, the use of copolymers as well as binary blends from “hard” and “soft” poly(methacrylates) broadens the possibilities to control the film morphology. To compare different polymer/LC composite films regarding their stability under compression load, the samples were investigated by indentation tests using an inverse reflected‐light microscope combined with a digital image acquisition technique. The deformation of the composite layers was evaluated by the uniDAC image analysis which relies on the more general method of Digital Image Correlation (DIC). Some of the fabricated composites show a remarkably high indentation resistance, especially such prepared from poly(1‐tetralyl methacrylate) and poly(4‐tert‐butylcyclohexyl methacrylate). The results facilitate the selection of suitable composite systems for the fabrication of mechanically stabilized flexible LC displays. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Preparation of photoresponsive polymeric adsorbent containing amphiphilic polymer with azobenzene moiety and its application for cell adhesion chromatography

In order to develop a new type column chromatography, a polymeric adsorbent was prepared by grafting a photoresponsive polymer containing an azobenzene moiety on the surface of controlled pore glass beads. The polarity of the surface of the polymeric adsorbent was increased by UV irradiation because of trans–cis isomerization of azobenzene moiety. Adhesion chromatography of erythrocytes was carried out using the photoresponsive polymeric adsorbent. The erythrocytes were adhered to the adsorbent in the dark and separated from the adsorbent by UV irradiation. This behavior appears to be caused by the photoresponse of the polarity change on the surface of the polymeric adsorbent. The morphology of the erythrocytes which adhered on the surface of the photoresponsive polymeric adsorbent remained unchanged both in the dark and after UV irradiation. The amount of erythrocytes which adhered to the adsorbent increased with increasing the molecular weight of the grafted polymer and the hydrophobicity of the surface.     

Thermal and electrical conductivity of carbon–filled liquid crystal polymer composites

The thermal and electrical conductivity of resins can be increased by adding conductive carbon fillers. One emerging market for thermally and electrically conductive resins is for bipolar plates for use in fuel cells. In this study, varying amounts of five different types of carbon, one carbon black, two synthetic graphites, one natural flake graphite, and one calcined needle coke, were added to Vectra A950RX Liquid Crystal Polymer. The resulting composites containing only one type of filler were then tested for thermal and electrical conductivity. The objective of this work was to determine which carbon filler produced a composite with the highest thermal and electrical conductivity. The results showed that composites containing Thermocarb TC‐300 synthetic graphite particles had the highest thermal and electrical conductivity. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99; 1552–1558, 2006     

Electrical conductivity and rheology of carbon‐filled liquid crystal polymer composites

One emerging market for electrically conductive resins is for bipolar plates for use in fuel cells. Adding carbon fillers to thermoplastic resins increases composite electrical conductivity and viscosity. Current technology often adds as much of a single type of carbon filler as possible to achieve the desired conductivity, while still allowing the carbon‐filled thermoplastic matrix material to be extruded and molded into a bipolar plate. In this study, varying amounts of two different types of carbon, one carbon black and one synthetic graphite, were added to Vectra A950RX liquid crystal polymer. The resulting single filler composites were then tested for electrical conductivity and rheological properties. The electrical conductivity followed that typically seen in polymer composites with a percolation threshold at 4 vol % for carbon black and at 15 vol % for synthetic graphite. Over the range of shear rates studied, the viscosity followed a shear‐thinning power law model with power‐law exponent (n ? 1) = ?0.5 for neat Vectra A950RX and (n ? 1) = ?0.7 for highly filled composite materials. Viscosity increased with increasing filler volume fraction for all shear rates. The viscosity–enhancement effect was more rapid for the composites containing carbon black when compared with those containing synthetic graphite. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 2680–2688, 2006     

The compatibility of transition metal oxide/carbon composite anode and ionic liquid electrolyte for the lithium-ion battery

Three types of transition metal oxide/carbon composites including Fe₂O₃/C, NiO/C and CuO/Cu₂O/C synthesized via spray pyrolysis were used as anode for lithium ion battery application in conjunction with two types of ionic liquid: 1 M LiN(SO₂CF₃)₂ (LiTFSI) in 1-ethyl-3-methyl-imidazolium bis(fluorosulfonlyl)imide (EMI-FSI) or 1-methyl-1-propylpyrrolidinium bis(fluorosulfonyl)imide (Py13-FSI). From the electrochemical measurements, the composite electrodes using Py13-FSI as electrolyte show much better electrochemical performance than those using EMI-FSI as electrolyte in terms of reversibility. The Fe₂O₃/C composite shows the highest specific capacity and the best capacity retention (425 mAh g⁻¹) under a current density of 50 mA g⁻¹ for up to 50 cycles, as compared with the NiO/C and CuO/Cu₂O/C composites. The present research demonstrates that Py13-FSI could be used as an electrolyte for transition metal oxides in lithium-ion batteries.     

Fabrication of insulated metal substrates with organic ceramic composite films for high thermal conductivity

Insulated metal substrates (IMSs) were fabricated and characterized using an organic ceramic composite as a coating mixture. Organic‐inorganic sol solutions were prepared by a sol‐gel process using TEOS (tetraethylorthosilicate), MTMS (methyltrimethoxysilane) and PhTMS (phenyltrimethoxysilane). Ceramic fillers were composed of aluminum oxide (1 and 4 µm) and silicon nitride. The optimal ratio of ceramic filler in the coating mixture was found to be 70 wt%. A thermal conductivity of 3.16 W/mK and a breakdown voltage of 4 kV with a leakage current of 0.17 mA/cm² were obtained for the 122 µm-thick film. A well-networked microstructure between the sol resin and filler in the organic ceramic composite films enhanced the properties of the IMS, such as thermal conductivity and electric insulation.     

Thermal expansivity and thermal conductivity of amorphous thermoplastic polyimide and polymer liquid crystal blends

Linear thermal expansivities α_L and thermal conductivities of polyimide (TPI) and polymer liquid crystal (PLC) blends were studied. The glass transition temperatures T_g of our amorphous TPI and the PLC are, respectively, 240 and 220°C. The addition of the PLC induces orientation through the channeling process, as predicted by an extension of the Flory statistical‐mechanical theory of PLCs (27). Channeling was observed at PLC concentrations as low as 5 wt%. Thermal conductivity decreases with the addition of the PLC to the TPI. The anisotropic expansivity of the blends shows a strong dependence on PLC concentration and orientation direction. The pure PLC shows a maximum on the along‐the‐flow expansivity vs. temperature curves and also negative α_L values. TPI addition moves the expansivities to positive values, but the maximum persists, even for 5% PLC only.     

New ionic polymer–metal composite actuators based on PVDF/PSSA/PVP polymer blend membrane

Ionic polymer–metal composite (IPMC) actuators that display continuously large actuation displacements without back relaxation and with large blocking force at low direct current (DC) voltages are used as biomimetic sensors, actuators and biomedical devices. This article reports the preparation and actuation performance of new IPMC actuators based on the polyvinylidene fluoride (PVDF)/polystyrene sulfonic acid (PSSA)/polyvinyl pyrrolidone (PVP) polymer blend membrane, which requires low voltage DC. The performance results of the proposed IPMC actuators are compared with Nafion‐based IPMC actuators. In the blend membrane, PVDF is the hydrophobic polymer, PSSA is the polyelectrolyte, and PVP is the hydrophilic basic polymer. The proposed IPMC actuators based on the PVDF/PSSA/PVP blend membrane of polymer mixture ratios of 60/15/25 and 50/25/25 gave higher actuation displacement and higher blocking force at low DC voltages than the Nafion‐based IPMC actuator. POLYM. ENG. SCI., 2011. © 2011 Society of Plastics Engineers     

Ionic conductivity of polymer gels deriving from alkali metal ionic liquids and negatively charged polyelectrolytes

We have prepared polymer gel electrolytes with alkali metal ionic liquids (AMILs) that inherently contain alkali metal ions. The AMIL consisted of sulfate anion, imidazolium cation, and alkali metal cation. AMILs were mixed directly with poly(3-sulfopropyl acrylate) lithium salt or poly(2-acrylamido-2-methylpropanesulfonic acid) lithium salt to form polymer gels. The ionic conductivity of these gels decreased with increasing polymer fraction, as in general ionic liquid/polymer mixed systems. At low polymer concentrations, these gels displayed excellent ionic conductivity of 10⁻⁴ to 10⁻³ S cm⁻¹ at room temperature. Gelation was found to cause little change in the diffusion coefficient of the ionic liquid, as measured by pulse-field-gradient NMR. These data strongly suggest that the lithium cation migrates in successive pathways provided by the ionic liquids.