Fabrication of surfactant‐removed polymer composites with single‐walled carbon nanotube networks

Polystyrene (PS) composites with a network of single‐walled carbon nanotubes (SWNTs) were fabricated by using monodispersed PS micospheres. First, PS spheres and surfactant‐dispersed SWNTs were mixed in water, then a hybrid cake was obtained by filtration via a microporous membrane and the SWNTs were filled within the spaces of packed polymer spheres. At this stage, the surfactants for dispersing SWNTs were totally removed from the composites by a thorough washing. Then the composite films with SWNT networks were obtained by compression molding at 160°C. Structure of the composites had been characterized by transmission electron microscopy and scanning electron microscopy. The present SWNT composites showed a low percolation threshold of electrical conductivities. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Electrical and mechanical properties of multi‐walled carbon nanotubes reinforced PMMA and PS composites

The use of multi‐walled carbon nanotubes (MWCNT) as reinforcing material for thermoplastic polymer matrices, polymethyl methacrylate (PMMA), and polystyrene (PS) has been studied. MWCNT were synthesized by chemical vapor deposition (CVD) technique using ferrocene‐toluene mixture. As‐prepared nanotubes were ultrasonically dispersed in toluene and subsequently dispersed in PMMA and PS. Thin polymer composite films were fabricated by solvent casting. The effect of nanotube content on the electrical and mechanical properties of the nanocomposites was investigated. An improvement in electrical conductivity from insulating to conducting with increasing MWCNT content was observed. The carbon nanotube network showed a classical percolating network behavior with a low percolation threshold. Electromagnetic interference (EMI) shielding effectiveness value of about 18 dB was obtained in the frequency range 8.0–12 GHz (X‐band), for a 10 vol% CNT loading. An improved composite fabrication process using casting followed by compression molding and use of functionalized MWCNT resulted in increased composites strength. POLYM. COMPOS., 2008. © 2008 Society of Plastics Engineers     

Characterization of conductive multiwall carbon nanotube/polystyrene composites prepared by latex technology

Conductive multiwall carbon nanotube/polystyrene (MWCNT/PS) composites are prepared based on latex technology. MWCNTs are first dispersed in aqueous solution of sodium dodecyl sulfate (SDS) driven by sonication and then mixed with different amounts of PS latex. From these mixtures MWCNT/PS composites were prepared by freeze-drying and compression molding. The dispersion of MWCNTs in aqueous SDS solution and in the PS matrix is monitored by UV–vis, transmission electron microscopy, electron tomography and scanning electron microscopy. When applying adequate preparation conditions, MWCNTs are well dispersed and homogeneously incorporated in the PS matrix. The percolation threshold for conduction is about 1.5 wt% of MWCNTs in the composites, and a maximum conductivity of about 1 S m⁻¹ can be achieved. The approach presented can be adapted to other MWCNT/polymer latex systems.     

Metalizable Polymer Thin Films in Supercritical Carbon Dioxide

We report an environmentally “green” method to improve adhesion at a polymer/metal interface by using supercritical carbon dioxide (scCO₂). Spun-cast polystyrene (PS) and poly(methyl methacrylate) (PMMA) thin films on cleaned Si wafers were used for this study. Film thicknesses of both polymer films were prepared in the range of 100 Å to 1600 Å. We exposed the films to scCO₂ in the pressure-temperature (P–T) range corresponding to the density-fluctuation ridge, where the excess swelling of both polymer films occurred, and then froze the swollen structures by quick evaporation of CO₂. A chromium (Cr) layer with film thickness of 300–400 Å was deposited onto the exposed film by using an E-beam evaporator. X-ray reflectivity (XR) measurements showed that the interfacial width between the Cr and exposed polymer layers increased by a factor of about two compared with that without exposure to scCO₂. In addition, the large interfacial broadening was found to occur irrespective of the thickness of both polymer films. After the XR measurements, the dewetting structures of the PS/Cr films induced by additional annealing were characterized by using atomic force microscopy, showing improved surface morphology in the exposed films. Contact angle measurements showed that a decrease in interfacial tension with exposure to scCO₂ accompanied the increase in interfacial width.     

The effect of filler type and content and the manufacturing process on the performance of multifunctional carbon/poly-lactide composites

Two nanosized carbonaceous fillers, vapor grown carbon nanofibers and exfoliated graphite nanoplatelets, were used to prepare poly(lactide acid) composites at various concentrations from 0 up to 20 wt.%. The two fillers were also combined in order to explore possible synergistic actions. Two compounding processes, melt mixing and polymer dissolution, and two forming methods, injection and compression molding, were used to manufacture the composites. The flexural properties, impact strength, storage and loss modulus, Vicat softening temperature, and electrical conductivity of neat matrix and composites were determined as a function of the filler type and content, and of the processing method used. The filler dispersion within the polymer matrix, the presence of agglomerates and the existence of voids were studied using field-emission scanning electron microscopy. It is concluded that compounding by polymer dissolution followed by compression molding leads to composites with the lowest percolation threshold and surface conductivity and highest storage modulus whereas extrusion injection molding results in composites with the highest mechanical properties. The results can be used to engineer biodegradable composites with specific properties for targeted applications.     

Understanding the effect of polymer crystallinity on the electrical conductivity of exfoliated graphite nanoplatelet/polylactic acid composite films

Electrically conductive exfoliated graphite nanoplatelet (GNP) / polylactic acid (PLA) nanocomposite films were fabricated using a two-step, scalable melt compounding process. The effect of the polymer’s physical properties, such as crystallinity, on the mechanical and electrical properties of the composites were determined. The crystallization characteristics of PLA were altered significantly by altering the cooling rate during compression molding of the films. The crystallinity and crystal structure were investigated using differential scanning calorimetry (DSC), wide angle X-ray diffraction (WAXD), and polarized optical microscopy (POM). The mechanical and electrical properties were also examined as a function of PLA’s crystallinity dictated by the cooling rate during compression molding. The electrical conductivity was examined using impedance spectroscopy. For the same GNP content, the crystallinity increases by ~40 % and electrical conductivity increases by ~3 orders of magnitude with decreased cooling rate indicating a strong correlation between polymer physical properties and electrical conductivity of the polymer composites. This mechanism can be utilized to tailor the electrical conductivity of a given filler/polymer system by tuning the physical properties of the polymer, without altering the fillers’ characteristics or the processing method, which is the common approach used.     

Cocontinuous morphologies in polystyrene/ethylene–vinyl acetate blends: The influence of the processing temperature

The influence of the compression‐molding temperature on the range of cocontinuity in polystyrene (PS)/ethylene–vinyl acetate (EVA) copolymer blends was studied. The blends presented a broad range of cocontinuity when compression‐molded at 160°C, and they became narrower when compression‐molded at higher temperatures. A coarsening effect was observed in PS/EVA (60:40 vol %) blends upon compression molding at higher temperature with an increase in the phase size of the cocontinuous structure. Concerning PS/EVA (40:60 vol %) blends, an increase in the mixing and molding temperatures resulted in a change from a cocontinuous morphology to a droplet–matrix morphology. This effect was observed by selective extraction experiments and scanning electron microscopy. The changes in the morphology with the molding conditions affected the storage modulus. An increase in the storage modulus in blends compression‐molded at 160°C was observed as a result of dual‐phase continuity. An EVA copolymer with a higher vinyl acetate content (28 wt %) and a higher melt‐flow index resulted in blends with a broader range of cocontinuity. This effect was more pronounced in blends with lower amounts of PS, that is, when EVA formed the matrix. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 386–398, 2003     

Solid-State Compaction of Polyphenylene Sulfide

Polyphenylene sulfide (PPS) is an engineering plastic with excellent thermal, mechanical, and electrical properties, and has received considerable attention during the last few years. There are numerous reports on the crystallization behavior and physical properties of PPS (1-7). This polymer can be processed by conventional melt-processing techniques such as injection molding, compression molding, etc., and also by powder metallurgical technique. However, there are few reports on the powder processing of PPS (8, 9).     

Mechanical,barrier, and interfacial properties of biodegradable composite films made of methylcellulose and poly(caprolactone)

Methylcellulose (MC) films were prepared by casting from its 1% aqueous solution containing 0.5% vegetable oil, 0.25% glycerol, and 0.025% Tween^®80. Poly(caprolactone) (PCL) films were prepared by compression molding from its granules. Biodegradable composite films were fabricated using MC film as reinforcing agent and PCL as the matrix material by compression molding. One layer of MC film was reinforced with two layers of PCL films. The MC content in the composites was varied from 10 to 50% by weight. Mechanical, barrier, and degradation properties of PCL, MC, and composite films were evaluated. The values of puncture strength (PS), puncture deformation (PD), viscoelasticity (Y) coefficient, and water vapor permeability (WVP) of the composites (50% MC content) were found to be 124.3 N/mm, 3.2 mm, 31%, and 2.6 g·mm/m²·day·kPa, respectively. Oxygen transmission rate (OTR) of PCL, MC, and composites (50% MC) were found to be 175, 25, 22 cc/m²/d, respectively, which indicated that composite films showed significantly lower OTR than PCL films. Degradation tests of the composite films (50% MC) were performed for 6 weeks in aqueous medium (at 25°C), and it was found that composites lost its mass slowly with time. After 6 weeks, mass and PS of the composites were decreased to 13.4 and 12%, respectively. Composite interface was studied by scanning electron microscopy (SEM). The MC film had good adhesion with PCL matrix during compression molding and suggested strong interface of the composite system. SEM image after 6 weeks of degradation showed some openings in the interface and revealed slow degradation of the MC films. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Comparative study on the electrical,thermal, and mechanical properties of multiwalled carbon nanotubes filled polypropylene and polyamide 6 micromoldings

In this work, a series of carbon nanotubes filled polypropylene (PP/CNT) and polyamide 6 (PA6/CNT) composites were prepared by melt blending and subsequently molded by compression molding and microinjection molding (μIM), respectively. Electrical conductivity results indicate that the percolation threshold of corresponding microparts shifted to higher filler concentrations when compared with that of compression molded counterparts, suggesting the prevailing shearing conditions in μIM is unfavorable for the construction of conductive pathways. In addition, Raman spectral analysis shows that there is a preferential alignment of CNTs along the flow direction of microparts. Thermal properties of both melt blended samples and subsequent microparts were evaluated using differential scanning calorimetry and thermogravimetric analysis. The mechanical properties of subsequent microparts are greatly affected by filler concentration, which might be related to the structural change that induced by the state of dispersion of CNTs.     

A conducting composite of polypyrrole with ultrahigh molecular weight polyethylene foam

Through a chemical polymerization of pyrrole inside ultrahigh molecular weight polyethylene (UHMWPE) foam, a conducting polymer composite was obtained. To produce conductive polymer foams, successive imbibiting of reactives, FeCl₃ and pyrrole in tetrahydrofuran solutions, were carried out. The conductive polymeric materials were characterized by FTIR, DSC, and SEM. Mechanical property measurements were carried out on the films prepared by the compression molding of the conductive foam polymers. These films showed rather high tensile strength compared to pure UHMWPE. Conductivity determined by a two‐probe technique showed that it increased with the pyrrole content in the UHMWPE foam matrix. The compression molding, however, resulted in a considerable reduction in the conductivities. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 72: 1843–1850, 1999     

Injection and compression molding of polystyrene/high-density polyethylene blends—phase morphology and tensile behavior

Processing and compatibilization effects on the phase morphology and the tensile behavior of blends of polystyrene and high-density polyethylene (PS/HDPE) were investigated. As predicted by theory, high shear rates encountered during extrusion blending led to efficient minor phase emulsification in immiscible PS/HDPE blends for which the viscosity ratio approaches unity. Consequently, the emulsifying effect of a styrene/ethylene-butylene/styrene (SEBS) compatibilizer was found to be negligible. In the subsequent molding process, disintegration, shape relaxation and coarsening of the minor phase domains were found to be responsible for the morphological evolution. In the compression molding process, morphological observations showed that the rate of minor phase coarsening followed the predictions of the Ostwald ripening theory, in agreement with the rheological analysis. In the injection molding process, minor phase coarsening was attributed to shear coalescence. Tensile tests performed on compression molded and injection molded blends showed that the mechanical behavior of PS/HDPE blends depend strongly upon the matrix orientation as well as the dispersed phase morphology and orientation. In both postforming operations, compatibilization effects on the morphological stability and the tensile behavior of PS/HDPE blends were found to be dependent upon the composition and the rheological behavior of the blend. Evidence of adhesion between the PS and HDPE phases was observed in the presence of SEBS in HDPE-rich blends.     

石墨/酚醛树脂复合板与碳纸间接触电阻

应用模压工艺制备了质子交换膜燃料电池（PEMFC）用石墨/酚醛树脂（PF）复合板.通过四电极法测量了复合板与碳纸间的接触电阻.考察了接触压力、PF树脂含量及模压工艺条件对接触电阻的影响.结果表明,接触压力和PF树脂含量是对接触电阻有较大程度影响的两个重要因素.接触压力的增大导致接触电阻迅速减小,而随着PF树脂含量的增加,接触电阻有着非常快的增加趋势.模压压力对接触电阻已有一定程度的影响,但其影响幅度不如接触压力和树脂含量那么大.随着模压压力的增大,接触电阻的增加趋势比较缓慢.模压时间和模压温度对接触电阻基本没有影响.     

Multi‐gating injection molding to enhance the thermal conductivity of carbon fiber/polysulfone composite

Carbon fiber was blended into the polysulfone matrix by twin screw extruder. The polymer composites samples were prepared using four different processing technologies, the compression molding, edge‐gating injection molding, sprue‐gating injection molding, and the multi‐gating injection molding techniques. Among four techniques, the composite samples manufactured by multi‐gating injection molding technique got a higher value of thermal conductivity, which is due to the carbon fibers orientation and distribution. The experimental result indicated that the fiber orientation have a significant influence on the thermal conductivity of polymer composites. The thermal conductivity of sample made by multi‐gating injection molding was 1.82 W/(m·K) when the fiber content was 26 vol%, which was nearly twice than the values obtained by conventional technologies. POLYM. COMPOS., 38:185–191, 2017. © 2015 Society of Plastics Engineers     

Packaging technology for improving shelf‐life of fruits based on a nanoporous–crystalline polymer

The ability of films with an active layer of nanoporous–crystalline syndiotactic polystyrene (s‐PS) to prolong shelf‐life, not only of climacteric but also of non‐climacteric fruits, is discussed. Studies on oxygen and carbon dioxide concentrations in the environment of packaged fruits as well as in s‐PS active layers have been combined. Reported results indicate that prolonged shelf‐life can be associated with large increases and decreases of carbon dioxide and oxygen concentrations inside the package, respectively. These data are consistent with a higher barrier offered to both gases by nanoporous–crystalline s‐PS layers. This barrier phenomenon is due to reduction of gas diffusivity typical of nanoporous–crystalline polymer films, which is further enhanced by orientation, parallel to the film plane, of crystalline planes of closely packed s‐PS helices. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46256.     

Surface modification of polymeric nanocomposite thin films using supercritical carbon dioxide

We report on an efficient and environmentally friendly means to modify surface properties of polymer films supported for nanoparticles. Ultrathin polystyrene (PS) films (<300 Å), in which inorganic nanoparticles were embedded, were exposed to supercritical carbon dioxide (scCO₂). The swollen structure was then preserved by quickly evaporating CO₂. X-ray reflectivity (XR) results showed that this procedure produced polymeric nanocomposite films with a low-density region of about 150Å at the polymer/air interface. The formation of the low-density layer was independent of the nature of the particles, indicating that the surface modification through exposure to scCO₂ may be a universal phenomenon regardless of a choice of nanoparticles.     

An evaluation of the curing characteristics of thermosetting epoxy carbon fiber sheet molding compounds and validation through computer simulations and molding trials

Sheet molding compounds (SMC) are ready-to-mold thermoset composite materials reinforced with discontinuous fibers, usually compression molded. Finite element (FE) based compression molding tools can be employed to optimize this process; FE tools require to define material models using raw material data measured through different characterization techniques. In this study, the cure kinetics of an epoxy-based carbon fiber SMC has been characterized by means of differential scanning calorimetry (DSC) and moving die rheometer (MDR) techniques. Based on these datasets, Claxton-Liska and Kamal-Souror models have been set and the compression molding of a validation plate was performed, both experimentally and virtually. The results indicate that, even if both characterization techniques are valid for SMC curing characterization, MDR technique enables the characterization of the material at real molding temperatures and the model based on MDR leads to more accurate results.     

Electrical and morphological properties of microinjection molded polypropylene/carbon nanocomposites

A series of different carbon (carbon black, carbon nanotubes, and graphite nanoplatelets) filled polypropylene nanocomposites were prepared by melt blending, then followed by compression molding or microinjection molding (µIM). Direct current electrical conductivity measurements and melt rheology tests were utilized to detect the percolated structure for compression molded polypropylene/carbon nanocomposites. For µIM, a rectangular mold insert which has a three‐step decrease in thickness along the flow direction was adopted to study the effect of abrupt changes in mold geometry on the electrical and morphological properties of subsequent micromoldings (µ‐moldings). Results indicated that the µ‐moldings exhibited a higher percolation threshold when compared with their compression molded counterparts. This is largely due to the severe shearing conditions that prevail in the µIM process. The morphology of µ‐moldings containing different carbon fillers was examined using scanning electron microscopy. The development of corresponding microstructure is found to be strongly dependent on the types of carbon fillers used in µIM, which is crucial to the enhancement of electrical conductivity for the resulting µ‐moldings. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45462.     

Electrical conductivity in carbon black-loaded polystyrene-polyisoprene blends. Selective localization of carbon black at the interface

Summary The electrical conductivity of carbon-black loaded polystyrene-polyisoprene blends has been studied. In this ternary system, the filler is at the interface of co-continuous polyblends as confirmed by the very low value of the filler percolation threshold (0.2 vol % for blends compression molded at 250°C) and by optical microscopy. As a result of the selective localization of carbon black at the interface, the percolation threshold is very sensitive to the compression molding temperature.     

Dependence of thin polystyrene films stability on the thickness of grafted polystyrene brushes

We investigate the stability of thin polystyrene (PS) films on chemically identical grafted brushes of various thickness and grafting density. We observe an essential influence of the brush thickness on the stability of the PS films. For brushes with a thickness of 20-35 nm no de-wetting of the PS film occurs, while considerably thicker or thinner PS brushes lead to de-wetting of the PS top layer. We suggest that in the thin brush-like layers, the unfavorable interactions with underlying silica favor de-wetting. The tendency to de-wet is reduced once the brush is sufficiently thick to insulate the free PS layer from the surface. Beyond that point, the de-wetting process speeds up as the brush becomes thicker and has a higher grafting density with a substantial increase of the interfacial tension between the brush and the free polymer.