BaTiO3 incorporation effect on the dielectric properties of polymer from aqueous emulsion: An enhanced dispersion technique

An economic and environment friendly process was adapted to synthesize new dielectric composite materials. Using ethylene vinyl acetate (EVA)/vinyl ester of versatic acid (VeoVa) terpolymer as an aqueous emulsion provides a homogenous dispersion of BaTiO₃ (BT) particles, due to the high viscosity and polarity of the vinyl resin (VR). Composites films were obtained from these dispersions by water evaporation. The evolution of the dielectric properties as a function of the BaTiO₃ content, was correctly fitted by a Maxwell‐Garnett model. This fitting of the experimental curve shows a good dispersion of filler in the vinyl resin and the particles separation by a layer of resin as expected for the preparation method used in this study. The VR/BT composites show good synergy between the dielectric properties of the different phases of the composites due to the formation of macrodipoles and to the strong interactions between polar EVA/VeoVa groups and the BaTiO₃ particles surface. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44333.     

Toward green three‐phase composites with enhanced dielectric permittivity

This work aims to investigate the dielectric potential of microcrystalline cellulose, a green biosourced material, as a third constituent in the three‐phase composites based on ethylene vinyl acetate‐vinyl ester of versatic acid (EVA‐VeoVa) terpolymer and BaTiO₃. For that, new green three‐phase composites were prepared using an economic and green process, with simple implementation at room temperature and using water as a solvent. Compared with the binary composite EVA‐VeoVa/BaTiO₃, the three‐phase composite EVA‐VeoVa/BaTiO₃/microcrystalline cellulose showed an improvement of the BaTiO₃ particles dispersion, enhanced relative permittivity, and reduced dielectric loss, which explains the significance of this study. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46147.     

Bulk polymer/solvent interactions for polyethylene and EVA copolymers,below their melting temperatures

In this work, the Flory–Huggins parameters corresponding to the amorphous phase of a polyethylene (PE) and two ethylene–vinyl acetate (EVA) copolymers (with 18 and 33 % vinyl acetate content, respectively) samples, with different solvents have been determined below the melting temperature of the polymers, in order to quantify the bulk interactions of these polymer/solvent systems. The employed solvents were a dispersion solvent (cyclohexane), a polar solvent (vinyl acetate) and an association solvent (methanol). Initially, the inverse gas chromatography measurements allowed obtaining the retention volumes, activity coefficients and overall Flory–Huggins parameters of every polymer/solvent system. According to these parameters, in all cases, the more compatible solvent was cyclohexane, so it was selected as the probe to calculate the percentages of crystallinity at room temperature, whose results were in agreement the literature data (35 % for PE, 29 % for EVA18, and 12 % for EVA33). The percentage of crystallinity allowed determining the amorphous Flory–Huggins parameters which are the ones which take into account just the bulk interactions in a polymer/solvent mixture. The Flory–Huggins parameter results show that, to accurately study the vapor–liquid equilibrium between a polymer and a solvent (bulk interactions), when the range of studied temperatures is below the melting point of the polymer, it is crucial to calculate the amorphous contribution (χ _amorphous) on the overall Flory–Huggins parameter. In the case of this study, the lower the vinyl acetate content (higher crystallinity), the higher the difference between the overall and amorphous Flory–Huggins parameters is. Analyzing the interactions between the three polymeric materials and the solvents it can be noticed that, for the most compatible solvent (cyclohexane), χ _amorphous represents the less contribution, or the highest correction, to the overall Flory–Huggins parameter (around 50 % for PE and EVA18, and 79 % for EVA33, the less crystalline polymer).     

Effect of filler treatment on temperature dependence of resistivity of carbon-black-filled polymer blends

Polyblends prove to be able to provide more possibilities for tailoring conductive polymer composites in comparison with individual polymer systems. Accordingly, ethylene–vinyl acetate—low-density polyethylene (EVA–LDPE) filled with carbon black (CB) was prepared in this study as a candidate for positive temperature coefficient (PTC) material. In consideration of the fact that CB distribution plays the leading role in controlling a composite's conduction behavior, chemical treatment of CB was applied to reveal its influence on percolation and the PTC effect. It was found that titanate coupling agent treatment facilitated sufficient distribution of CB in LDPE phase, leading to lower resistivity and a squarer PTC curve. Composites filled with nitric-acid-treated CB exhibited specific temperature dependence of resistivity as a result of the heterogeneous dispersion of CB at the interface of EVA–LDPE, which might provide the materials with a new function. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 489–494, 1999     

Studies on effect of nanoclay on the properties of thermally sprayable EVA and EVAI coatings

Dispersion of nanoclay (NC) in polymer blend system is governed by the sequence of addition of different ingredients. In the present work nanoclay was added in different sequences to blend composition such as ethylene vinyl acetate (EVA)/low density polyethylene (LDPE) and ethylene vinyl alcohol (EVAl)/LDPE in internal mixer to get nanocomposite. It was found that sequential addition of individual polymers and nanoclay influenced mechanical properties of resulting composites. Blending sequence of PE/NC/EVA and PE/NC/EVAl gave best mechanical properties. After optimization of addition sequence, concentration of nanoclay was varied from 1 to 8% by weight in the polymer blend. The resulting composites were evaluated in terms of their mechanical properties, dispersion characteristics (XRD), water vapor transmission rate (WVTR) and water absorption (Wa). Nanocomposite containing EVA/LDPE blend with 4% nanoclay showed optimum properties. The optimized composition was applied on grit blasted mild steel specimens by flame spray technique. The coated specimens were evaluated for adhesion strength, abrasion resistance and resistance to corrosion properties.     

Preparation and characterization of binary blends composed of poly(dioctylfluorene‐alt‐hexylsulfonylthiophene) and nonconjugated polymers

The solutions and the thin films of poly[9,9‐dioctyl‐2,7‐fluorene‐alt‐2,5–(3‐hexyl‐sulfonylthiophene)] (PFSO₂T) and its binary blends with other nonconjugated polymers such as poly(methyl methacrylate) (PMMA), polycarbonate (PC), and ethylene vinyl acetate copolymer (EVA) can be prepared by different concentrations from a polymer solution. Binary polymer blends can increase the absorbance and photoluminescence intensities in the solid state due to nonconjugated polymers can act as dispersion agents which can reduce the interchain interaction or the aggregation of the conjugated polymers. Photoluminescence intensity of the thin films of fluorescent polymers blending with ethylene vinyl acetate copolymers exhibited six times higher than that of the neat fluorescent polymers. The PFSO₂T/EVA binary blends reveal the least extent of optical degradation of around 20% compared to those binary blends in both absorption and emission intensities after the irradiation under the UV‐light for 20 h. The cross‐sectional morphology of fluorescent polymers blending with ethylene vinyl acetate copolymers reveals little aggregation and better phase separation among the other binary polymer blends. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44969.     

Constructing the core–shell structured island domain in polymer blends to achieve high dielectric constant and low loss

Carbon nanotubes (CNTs) and barium titanate (BaTiO₃) (BT) were simultaneously introduced into the immiscible blend poly(ethylene‐co‐vinyl acetate)/thermoplastic urethane (EVA/TPU), and the EVA/TPU/CNT/BT quaternary polymer composite blends with core–shell structured island TPU domain were successfully prepared, in which CNTs in the TPU domain act as the core and the BT spheres at the interface of the TPU and EVA act as the shell. A core–shell structured island can lead to the formation of micro‐capacitors and further accumulate electron storage owing to the incorporation of CNTs and BT; on the other hand, a BT shell can be assembled along the TPU spheres, reducing the possibility of formation of a conductive CNT network, resulting in suppressed dielectric loss. Therefore, CNTs and BT were tailor‐made into blend composites with a core–shell structured domain, which can achieve an increased dielectric constant by 176% and decreased low dielectric loss by 80% compared with the blend composites with only CNTs in the TPU domain. © 2019 Society of Chemical Industry     

Influence of Polymer Type and Structure on Polymer Modified Asphalt Concrete Mix

Two low‐density polyethylene (LDPE) resins and two ethyl vinyl acetate (EVA) polymers were used to modify asphalt binder, and then mixed with asphalt concrete according to Marshall Method of mix design (ASTM D 1559). Effect of weight average molecular weight (M_w) of LDPE and vinyl acetate (VA) content of EVA was studied by performing Marshall Stability, moisture susceptibility (AASHTO T 283‐89), resilient modulus (M_R) and permanent deformation (rutting) tests. EVA with low VA content showed lower stability loss in Marshall Stability test and improved resistance in moisture susceptibility test in comparison to hot mix asphalt concrete mix (HMA) and other polymer modified asphalt concrete mixes (PMAMs). Higher M_R and better rutting resistance were observed for PMAMs than that of HMA. This elastic behaviour of modified asphalt correlates very well with the M_R and rutting resistance properties of PMAM.     

木质素填充LDPE、EVA对复合物性能的影响

以木质素为填充剂分别与低密度聚乙烯(LDPE)、乙烯-乙酸乙烯酯共聚物(EVA)共混,经双螺杆造粒机共混挤出造粒,再经吹塑成膜。研究了木质素/LDPE、木质素/EVA共混物薄膜的表面形貌、力学性能、热性能和红外光谱。热分析表明木质素与EVA共混物的热稳定性比木质素与LDPE的共混物热稳定性好;红外光谱分析表明木质素与EVA分子间产生了强烈的相互作用,扫描电镜分析表明木质素与EVA共混的相容性较好,力学性能分析表明低于30%的木质素与LDPE、EVA共混力学性能较好。     

Fabrication,characterization, and properties of poly(ethylene‐co‐vinyl acetate)/magnetite nanocomposites

Poly(ethylene‐co‐vinyl acetate) (EVA)/magnetite (Fe₃O₄) nanocomposite was prepared with different loading of Fe₃O₄ nanoparticles. The mixing and compounding were carried out on a two‐roll mixing mill and the sheets were prepared in a compression‐molding machine. The effect of loading of nanoparticles in EVA was investigated thoroughly by different characterization technique such as transmission electron microscopy (TEM), X‐ray diffraction (XRD), differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), limiting oxygen index (LOI), and technological properties. TEM analysis showed the uniform dispersion of filler in the polymer matrix and the dispersion of filler decreased with increase in filler content. XRD of the nanocomposite revealed the more ordered structure of the polymer chain. An appreciable increase in glass transition temperature was observed owing to the restricted mobility of Fe₃O₄‐filled EVA nanocomposite. TGA and flame resistance studies indicated that the composites attain better thermal and flame resistance than EVA owing to the interaction of filler and polymer segments. Mechanical properties such as tensile strength, tear resistance, and modulus were increased for composites up to 7 phr of filler, which is presumably owing to aggregation of Fe₃O₄ nanoparticle at higher loading. The presence of Fe₃O₄ nanoparticles in the polymer matrix reduced the elongation at break and impact strength while improved hardness of the composite than unfilled EVA. The change in technological properties had been correlated with the variation of polymer–filler interaction estimated from the swelling behavior. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40116.     

Dielectric properties of polymer/ceramic composites based on thermosetting polymers

Summary A series of thermosetting polymer/ceramic composites were prepared. Three kinds of thermosetting polymers, i.e. cyanate resin, bismaleimide resin, and epoxy resin, were used as matrixes, and BaTiO₃ particles were as fillers. The dielectric properties of these composites were investigated. Experimental data of the dielectric constants were fitted to several theoretical equations in order to obtain the best-fitting equations of the dielectric constants of these composites. The result indicates that the dielectric constants of composites all increase with the increase of BaTiO₃ content. Using bismaleimide resin and epoxy resin as matrixes, the dielectric losses both increase obviously as the amount of BaTiO₃ particles is increased, but the dielectric loss of cyanate/BaTiO₃ composite decreases. With the increase of the frequency, the variation ranges of the dielectric constant and dielectric loss of cyanate/BaTiO₃ composite are both the smallest. The predications of the effective dielectric constants by Lichterecker mixing rule are in good agreement with experiment data.     

Well dispersion of rGOs in PLLA matrix mediated by incorporation of EVA and its resultant electrical property

In this work, a new method was introduced to improve the dispersion of the reduced graphene oxides (rGOs) in polymer host, and the corresponding electrical properties of the composites were discussed. The method was related to incorporation of the third component ethylene‐co‐vinyl acetate (EVA) into the poly(l ‐lactide) (PLLA)/rGOs composites. Because of a better affinity of the rGOs to the EVA than the PLLA, rGOs were attracted to adsorb on the EVA particles. Consequently, homogeneous dispersion of the EVA particles directed a better dispersion of the rGOs in polymer host. In this case, compared with the PLLA/rGOs binary composite, the ternary composite showed a 10 orders decrease of electrical resistance with a lower electrical percolation threshold than that of the binary composite. This work opens up a viable strategy to the melt blending of polymer/graphene composites with good dispersion and markedly improved properties. POLYM. COMPOS., 35:1051–1059, 2014. © 2013 Society of Plastics Engineers     

Swelling and diffusion characteristics of polar and nonpolar polymers in asphalt

The swelling and diffusion characteristics of a polar polymer [ethylene vinyl acetate (EVA)] and a nonpolar polymer [low-density polyethylene (LDPE)] were studied with swelling experiments of the polymers in asphalt at different temperatures. The study showed that the diffusion mechanisms for LDPE and EVA were different and temperature-dependent. In the case of LDPE, the observed diffusion was anomalous at both swelling temperatures (70 and 90°C). LDPE at 90°C showed sigmoidal solvent-uptake behavior during the initial period of swelling and a sorption overshoot in a later period. EVA showed Fickian transport at 60°C and anomalous diffusion at a higher swelling temperature (70°C) with sigmoidal uptake behavior. An analysis of the diffusion coefficients and the Fourier transform infrared results showed that the diffusing molecules were different in the case of LDPE and EVA, and there were possible polymer–asphalt interactions. Differential scanning calorimetry and swelling studies showed that penetrant-induced crystallization affected the diffusion process in the case of LDPE. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Miscibility studies of polymer blends by viscometry methods

The intrinsic viscosities of blends of poly(vinyl chloride)/poly(ethylene-co-vinyl acetate) (PVC/EVA), poly(vinyl chloride)/poly(styrene-co-acrylonitrile) (PVC/SAN), and poly(ethylene-co-vinyl acetate)/poly(styrene-co-acrylonitrile) (EVA/SAN) have been studied in cyclohexanone as a function of blend composition. In order to predict the compatibility of polymer pairs in solution, the interaction parameter term, Δb, obtained from the modified Krigbaum and Wall theory, and the difference in the intrinsic viscosities of the polymer mixtures and the weight average intrinsic viscosities of the two polymer solutions taken separately are used. © 1994 John Wiley & Sons, Inc.     

Achieving compatibility in blends of low‐density polyethylene/polyamide‐6 with addition of ethylene vinyl acetate

Polymer alloys and blends, whose major advantage is the potential of achieving a range of physical and mechanical properties, have continued to be a subject of interest over recent years. Addition of a block or graft copolymer, with chemically similar segments to those involved in the polymer blend considered, led to a variety of desirable properties. The copolymer added to the blend functioned to promote a homogeneous dispersion of the constituent phases and to enhance their mutual adhesion. Such agents that enable better dispersion in polymer blends are known as compatibilizers. In this study an attempt has been made to improve the compatibility in a polymer blend composed of two normally incompatible constituents, LDPE and PA₆, by addition of a compatibilizer. The compatibilizer agent, ethylene vinyl acetate (EVA), was added to the polymer blend in ratios of 1, 5, and 10% by using a twin‐screw extruder. The effect of EVA on the crystallization of the polymer constituents was observed through DSC examinations. Furthermore, the control sample and all three blends of LDPE/PA₆/EVA were subjected to examinations to obtain their yield and tensile strengths, elasticity modulus, percentage elongation, izod impact strength, hardness, and melt flow index. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 1748–1754, 2001     

The influence of filler particles and polymer structure on the mobility of polymer molecules

The presence of carbon filler has been shown to cause a change in the glass transition temperature of polymers. For poly(vinyl chloride) and two of its copolymers with 10 and 15% vinyl acetate an increase in T_g was observed when Graphon C Carbon was added. The increase was greater when the proportion of vinyl acetate was greater. Polar vinyl acetate units allow stronger adsorption of polymer onto the carbon. Brittle polymers such as polystyrene and poly(methyl methacrylate) showed scattered T_g's when filled with carbon. The changes were not a function of concentration. It is postulated that the thermal stress of these polymers is increased in the presence of filler.     

Electrical behavior of carbon black-filled polymer composites: Effect of interaction between filler and matrix

The effect of interaction between carbon black and polymer on electrical behavior was studied using the ESR method. The polymer matrices used were HDPE, LDPE, and ethylene/vinyl acetate (EVA). Two kinds of carbon blacks (CB), high structure CSF-III and low structure FEF, were used as a conductive filler. Compared to that of the HDPE/FEF compound, the positive temperature coefficient (PTC) intensity is lower and electrical reproducibility is worse for the HDPE/CSF-III compound; however, it can be improved significantly by radiation cross-linking. On the other hand, the cross-linking has no practical effect on the PTC intensity of the LDPE/CSF-III compound while it can be achieved by mixing the compound for a longer time. The great PTC intensity was obtained in the HDPE/EVA/CSF-III compound, and it is greater than that of HDPE/CSF-III or EVA/CSF-III. We explain these results using the concept of interaction between the filler and matrix. The absorption of the polymer on the carbon black surface may be physical or chemical; the latter is caused by the free-radical reaction between the polymer and carbon black, and it can occur during the radiation or preparation process of the compound. These “bound polymers” are essentially important for materials to have a great PTC intensity and good reproducibility. © 1994 John Wiley & Sons, Inc.     

Barrier properties of poly(ethylene‐co‐vinyl acetate)/cellulose composite membranes

Poly(ethylene‐co‐vinyl acetate) (EVA)/cellulose composite membranes were prepared and their vapor permeation characteristics were studied. Two types of EVA [having vinyl acetate contents of 18% (EVA18) and of 40% (EVA40), respectively] were used for the composite fabrication. Cellulose, isolated from banana waste fibers, was used as the filler. It was observed that the EVA40 composites were more permeating than were the EVA18 composites. This observation is explained on the basis of more amorphous nature of EVA40 as compared to EVA18. The extent of vapor permeation decreased with increase in the cellulose content in the composites. The presence of voids in the polymer membranes that were designed to possess controlled behavior for the permeation was confirmed using scanning electron microscopic images to complement the observations made during the permeation studies. The influence of molecular weight, molar size, and polarity of the penetrants, on the permeation process, was also considered. The permeability of the membrane samples was calculated and the values obtained were compared with the theoretical values provided by using the modified Neilson permeability equation. POLYM. ENG. SCI., 2012. © 2012 Society of Plastics Engineers     

Strategies for improving graft degree of urethane derivative of 2‐hydroxymethyl methacrylate grafted onto LDPE

A novel monomer, 2‐methyl‐acrylic acid 2‐(3‐isocyanato‐2‐methyl‐phenyl carbamoyloxy)‐ethyl ester (HT), was synthesized by the reaction of 2‐hydroxymethyl methacrylate with toluene diisocyanate. The influences of solvents, temperature and catalyst, dibutyl tin dilaurate on the total yield of HT were investigated and theoptimum synthesis conditions were obtained. The obtained monomer was then used to modify low density polyethylene (LDPE) in the Haake Rheomix 600P via melt grafting copolymerization. The modified LDPE was characterized by Fourier transform infrared. During the grafting process, single‐step and two‐step procedures were compared and the results showed that the two‐step procedure was more favorable. In a two‐step procedure, the influences of melting temperatures, monomer amount, and ethylene vinyl acetate copolymer (EVA, M_n = 800–1200) on the graft degree were also investigated. The investigation confirmed that EVA acting as a dispersant could enhance the dispersion of the monomer and improve graft degree significantly, and net value of increased graft degree was about 1.5%. The better dispersion of HT in the matrix of LDPE was confirmed via scanning electron microscope after adding EVA to the system. POLYM. ENG. SCI., 2009. © 2009 Society of Plastics Engineers     

Effect of hot air aging on properties of EPDM/SmBO3/EVA and EPDM/ATO/EVA composites

Ethylene–propylene–diene rubber (EPDM)/samarium borate (SmBO₃)/ethylene‐vinyl acetate (EVA) copolymer and EPDM/antimony‐doped tin oxide (ATO)/EVA composites are aged at 150°C for different intervals. Surface modification is used to improve filler to matrix interphase. The main aim is to investigate the effect of filler type and vinyl acetate (VA) content in EVA on stability of EPDM composites. It is found that acidic ATO particles can lower pH level of EPDM composites and then promote the degradation of acetic acid during aging. Moreover, when VA content exceeds 14 wt %, the instable VA content causes more acetic acids escape during aging. With the increasing of aging time, EPDM/SmBO₃ control and EPDM/SmBO₃/EVA composites tend to become darker while EPDM/ATO and EPDM/ATO/EVA composites would become yellow. And the color change is correlated well with the variation of carbonyl index. The chemical crosslink points prevent crystals in EVA from melting at aging temperature (150°C), and the variation of crosslink density influences the crystallinity during aging. The tendency of tensile strength is well consistent with that of swelling ratios, and electric properties are correlated with increased polar groups and crystallinity. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011