Influence of Ethylene Ionomers on the Electrical Properties of Crosslinked Polyethylene

Summary: Water treeing is a deterioration mechanism observed in the polymeric insulation of extruded cables, which can affect the service life of the transmission and distribution XLPE power cables. To improve the water‐tree resistance of XLPE, it was blended with sodium‐neutralized EAA‐Na ionomers which were formed by neutralization of EAA with NaOH. A series of XLPE/EAA‐Na ionomer blends were investigated for their electrical properties, such as water treeing, electrical breakdown strength, dielectric constant, and dissipation factor. The results strongly suggest that EAA‐Na ionomers can improve the water‐tree resistance of XLPE, and the XLPE/EAA‐Na blends retain excellent dielectric properties. Characterization of XLPE/EAA‐Na blends by using FTIR indicates that the neutralization reaction is effectively achieved. In addition, it can be found that XLPE/EAA‐Na blends are partially compatible from observing morphology observations made by SEM and, therefore, EAA‐Na ionomers can be well dispersed in the matrix.

Water tree length of the XLPE/EAA‐0.5Na blends.     

Effect of styrene–ethylene–butadiene–styrene and its synergetic effect with ethylene vinyl acetate on the mechanical,thermal, dielectric,and water‐treeing behaviors of crosslinked polyethylene

In this study, we investigated the effect of an aromatic polymer, styrene–ethylene–butadiene–styrene (SEBS), on the water‐tree resistance of crosslinked polyethylene (XLPE), and the synergetic effect of SEBS and ethylene vinyl acetate (EVA) was also investigated. The XLPE/SEBS and XLPE/SEBS/EVA samples were characterized by means of differential scanning calorimetry, scanning electron microscopy, mechanical measurements, and an accelerated water‐treeing experiment, and the obtained results clearly show the relevant influence of SEBS and EVA, and as expected, the addition of SEBS and EVA was found to synergistically influence the water‐tree resistance of XLPE more positively in comparison with that without the addition of EVA. In addition, it also indicated that the blends possessed excellent dielectric behaviors, such as the dielectric constant and dissipation factor. The crystallization of the blends decreased with increasing SEBS content and addition of EVA. However, the melting temperature of the blends increased with the addition of SEBS and EVA, but the melting temperature of the blends decreased with increasing SEBS content. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Crystallization,morphology, and electrical properties of bio‐based poly(trimethylene terephthalate)/poly(ether esteramide)/ionomer blends

Bio‐based poly(trimethylene terephthalate) (PTT) and poly(ether esteramide) (PEEA) blends were prepared by melt processing with varying weight ratios (0–20 wt %) of ionomers such as lithium‐neutralized poly(ethylene‐co‐methacrylic acid) copolymer (EMAA‐Li) and sodium‐neutralized poly(ethylene‐co‐methacrylic acid) copolymer (EMAA‐Na). The blends were characterized by differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), polarized light microscopy (PLM), and transmission electron microscopy (TEM). DSC and PLM results showed that EMAA‐Na increased the crystallization rate for PTT significantly, whereas EMAA‐Li did not enhance the crystallization rate at all. Specific interactions between PEEA and ionomers were confirmed by DSC and TEM. Electrostatic performance was also investigated for those PTT blends because PEEA is known as an ion‐conductive polymer. Here, we confirmed that both sodium and lithium ionomers work as a synergist to enhance the static decay performance of PTT/PEEA blends. Morphological study of these ternary blends systems was conducted by TEM. Dispersed ionomer domains were encapsulated by PEEA, which increases the interfacial surface area between PEEA and the PTT matrix. This encapsulation effect explains the unexpected synergy for the static dissipation performance on addition of ionomers to PTT/PEEA blends. This core–shell morphology can be predicted by calculating spreading coefficient for the ternary blends. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Effect of silane‐grafting on water tree resistance of XLPE cable insulation

Water treeing is one of the main deterioration phenomena observed in the polymeric insulation of extruded crosslinked polyethylene (XLPE) cables, which can affect the service life of power cables. In this work, we investigated the effect of grafting of a silane (vinyl trimethoxysilane, VTMS) on the resistance of XLPE to water treeing. A series of water‐treeing tests, the mechanical and dielectric measurements indicated that the silane‐grafting could significantly improve the water tree resistance of the conventional XLPE cable insulation with little influences on its dielectric properties, e.g., the dielectric breakdown strength, dielectric constant and loss tangent, and its mechanical performance. It was found that there exists an optimum value of VTMS concentration (about 0.6 phr) corresponding to the minimum water tree length. The water tree resistance mechanism of silane‐grafted XLPE was proposed on the basis of the process of silane hydrolysis and crosslinking. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Antistatic performance and morphological observation of ternary blends of poly(ethylene terephthalate), poly(ether esteramide), and ionomers

Blends of poly(ethylene terephthalate) (PET) and poly (ether esteramide) (PEEA), which is known as an ion conductive polymer, were prepared by melt mixing using a twin screw extruder. Antistatic performance of the molded plaques and the effects of adding ionomers such as lithium neutralized poly(ethylene‐co‐methacrylic acid) copolymer(E/MAA‐Li), magnesium neutralized poly(ethylene‐co‐methacrylic acid) copolymer(E/MAA‐Mg), and zinc neutralized poly(ethylene‐co‐methacrylic acid) copolymer (E/MAA‐Zn) were investigated. Antistatic effect of adding poly(ethylene‐co‐methacrylic acid) copolymer(E/MAA) and polystyrene, and poly(ethylene naphthalate) (PEN) into PET/PEEA blends were also investigated. Here we confirmed that lithium ionomer worked the most effectively in those blend systems. We also confirmed that E/MAA worked to enhance the antistatic performance of PET/PEEA blends. Morphological study of these ternary blends system was conducted by TEM. Specific interaction between PEEA and E/MAA‐Li, and E/MAA were observed. Those ionomers and copolymer domains were encapsulated by PEEA, which could increase the surface area of PEEA in PET matrix. This encapsulation effect explains the unexpected synergy for the static dissipation performance on addition of ionomers and E/MAA to PET/PEEA blends. POLYM. ENG. SCI., 2008. © 2008 Society of Plastics Engineers     

Compatibilizers for thermotropic liquid crystalline polymer/polyethylene blends prepared by reactive mixing

This paper describes the effects of composition and processing conditions on the efficiency of the compatibilizer prepared from a thermotropic liquid crystalline polymer (TLCP) and the sodium salt of a poly(ethylene‐co‐r‐acrylic acid) ionomer (EAA‐Na) in TLCP/low‐density polyethylene (LDPE) blends and TLCP/high‐density polyethylene (HDPE) blends. The TLCP‐ionomer graft copolymer formed by a melt acidolysis reaction effectively reduced the interfacial tension between TLCP and polyethylene, which improved impact strength and toughness of the compatibilized blends. Higher processing temperatures for the reactive extrusion produced a more efficient compatibilizer, presumably due to increased graft‐copolymer formation, but the reaction temperature had little effect on the impact strength of compatibilized blends for temperatures above 300°C. The addition of the compatibilizer to TLCP/LDPE blends significantly increased the melt viscosity due to increased interfacial adhesion. The TLCP/EAA‐Na ratio used to prepare the compatibilizer had little effect on the performance of the compatibilizer. Although the compatibilizer can be prepared in situ by blending and extruding a ternary blend of TLCP/EAA‐Na/polyethylene, pre‐reacting the compatibilizer resulted in blends with improved toughness and elongation.     

Preparation,morphology, and properties of multilamellar barrier materials based on blends of high‐density polyethylene and copolyester

The multilamellar barrier materials based on the blends of high‐density polyethylene (HDPE) and copolyester (PETG) were prepared via melt extrusion, and poly(ethylene‐co‐acrylic acid) (EAA) as a compatibilizer was incorporated into the blends. A systematic investigation was carried out, with regard to morphology and properties. Scanning electron microscopy observation displayed the laminar morphology for the blends with the whole compositions, and the thinner laminas of the PETG phase formed in the HDPE matrix by incorporating EAA into the blends. In addition, the number and the size of the laminas of the dispersed phases were also dependant on the die temperature and screw speed, respectively. Evaluation of the mechanical properties demonstrated that incorporation of the EAA resulted in an improvement of the mechanical properties. These behaviors are attributed mainly to better adhesion and compatibility between HDPE and PETG, which has been confirmed by thermal analysis and the rheological properties. On the basis of these premises, it is reasonable to suggest that the improved barrier properties of the ternary blends with increasing concentration of the EAA be attributed to both the increase in the number of the laminas of the PETG and the decrease in their thickness, which prohibits the organic solvent molecules from entering into and permeating through the amorphous regions of the blends. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 3791–3799, 2006     

Physicomechanical studies and solvent resistance analysis of melt‐blended novel ethylene‐1‐octene elastomer and ethylene‐co‐acrylic acid interpenetrating network hybrids

Polar modification of poly(ethylene‐co‐octene) (POE) elastomer was carried out with a relatively new approach. Poly(ethylene‐co‐acrylic acid) (EAA) was taken as the modifier and POE with a calculated amount of EAA were coextruded with dicumyl peroxide (DCP; used as a crosslinker). The majority of the compositions showed the existence of a crosslinked EAA phase inside POE, although increasing DCP concentrations and extrusion temperatures were possibly capable of crosslinking either of the phases, as observed with a model composition. All of the samples were soft and light in nature. The best composition was the one that contained 13.3 wt % EAA; that composition showed excellent surface polarity and superior mechanical properties. Detailed solvent swelling experiments also yielded the best results for that particular composition. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Oxygen and carbon dioxide permeability of EAA/PEO blends and microlayers

The goal of this study was to broaden the spectrum of gas permeability and selectivity characteristics of poly(ethylene‐co‐acrylic acid) (EAA) by combining it with poly(ethylene oxide) (PEO), which has a high selectivity for CO₂. To obtain films that differed substantially in their solid state morphologies, EAA was combined with PEO as melt blends and as coextruded films with many alternating, continuous microlayers of EAA and PEO. The solid state structure and thermal behavior were characterized and the permeability to O₂ and CO₂ was measured at 23°C. When the PEO was dispersed as small domains, the particles were too numerous for most of them to contain a heterogeneity that was sufficiently active to nucleate crystallization at the normal T_c. The rubbery, amorphous nature of the PEO domains enhanced the gas permeability of the melt blends. In contrast, the constituent polymers maintained the bulk properties in 5–20 μm‐thick microlayers. The series model accurately described the gas transport properties of microlayered films. Comparison of blends and microlayers revealed that the high CO₂ selectivity of PEO was most effectively captured when the PEO phase was continuous, as in the microlayers or in the cocontinuous 50/50 (wt/wt) melt blend. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008.     

Novel ionomers based on blends of ethylene-acrylic acid copolymers with poly(vinyl amine)

The polymerization of N-vinyl formamide followed by hydrolysis yields a linear, water-soluble poly(vinyl amine). The high concentration of pendant primary amine groups leads to a polymer with an interesting set of properties. Complexation with water-soluble anionic polyelectrolytes in water solutions leads to a highly water-insoluble material. The study described herein investigated the phase behavior/properties of melt blends of poly(vinyl amine) with ethylene-acrylic acid (EAA) copolymers of less than 10 wt % acrylic acid. The calorimetric and dynamic mechanical analyses of the resultant blends show that the vinyl amine groups are accessible to the acrylic acid groups of the copolymers and the major property changes occur up to the stoichiometric addition of vinyl amine/acrylic acid. At higher levels of vinyl amine (vinyl amine/acrylic acid mol ratio > 4), additional poly(vinyl amine) forms a separate phase. The mechanical, dynamic mechanical, and calorimetric properties of these blends below the stoichiometric ratio show analogous trends as with typical alkali/alkaline metal neutralization. These characteristics relative to the base EAA include improved transparency, lower melting and crystallization temperature, lower level of crystallinity, and increased modulus and strength. The emergence of the β transition in dynamic mechanical testing is pronounced with these blends (as with alkali/alkaline metal neutralization), indicative of microphase separation of the amorphous phase into ionic-rich and ionic-depleted regions. A rubbery modulus plateau for the blends exists above the polyethylene melting point, demonstrating ionic crosslinking. Above 150°C exposure, further modulus increases occur presumably due to amide formation. This study demonstrates that the highly polar poly(vinyl amine) can interact with acrylic acid units in an EAA copolymer comprised predominately of polyethylene (>90 wt %). The thermodynamic driving force favoring ionic association overrides the highly unfavorable difference in composition. © 1996 John Wiley & Sons, Inc.     

Polypropylene/polypropylene‐grafted acrylic acid copolymer/ethylene–Acrylic acid copolymer ternary blends for hydrophilic polypropylene

Ternary blends of polypropylene (PP), a polypropylene‐grafted acrylic acid copolymer (PP‐g‐AA), and an ethylene–acrylic acid copolymer (EAA) were prepared by melt blending. The surfaces of films with different contents of these three components were characterized with contact‐angle measurements. Scanning electron microscopy, Fourier transform infrared spectroscopy, differential scanning calorimetry, and thermogravimetric analysis were used to characterize the microstructure, melting and crystalline behavior, and thermal stability of the blends. The contact angles of the PP/PP‐g‐AA blends decreased monotonically with increasing PP‐g‐AA content. With the incorporation of EAA, the contact angles of the PP/PP‐g‐AA/EAA ternary blends decreased with increasing EAA content. When the concentration of EAA was higher than 15 wt %, the contact angles of the ternary blends began to increase. Scanning electron microscopy observations confirmed that PP‐g‐AA acted as a compatibilizer and improved the compatibility between PP and EAA in the ternary blends. Differential scanning calorimetry analysis suggested that acrylic acid moieties could act as nucleating agents for PP in the polymer blends. Thermogravimetric analysis and differential thermogravimetry confirmed the optimal blend ratio for the PP/PP‐g‐AA/EAA ternary blends was 70/15/15. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 436–442, 2006     

Melt processable conducting poly(aniline‐co‐o‐anisidine)/linear low‐density polyethylene composites with ethylene‐acrylic acid copolymer as compatibilizer

Conducting composites of aniline/o‐anisidine copolymer doped by dodecylbenzenesulfonic acid (P(An‐co‐oAs)‐DBSA), linear low‐density polyethylene (LLDPE), and ethylene–acrylic acid copolymer (EAA) as compatibilizer were prepared by melt processing. The effects of composition on electrical conductivity, resistivity‐temperature characteristic, and mechanical properties were also investigated. The electrical conductivity of ternary composites markedly increased due to compatibilizition and protonation effect of the EAA. The SEM micrograph shows that the compatibility between the P(An‐co‐oAs)‐DBSA and the LLDPE matrix is enhanced after the introduction of EAA. The positive temperature coefficient of resistivity characteristic is observed. Tensile strength of P(An‐co‐oAs)‐DBSA/LLDPE/EAA composites is improved, compared with P(An‐co‐oAs)‐DBSA/LLDPE composites. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 1511–1516, 2005     

Mechanical properties–morphology relationships in nano‐/microstructured epoxy matrices modified with PEO–PPO–PEO block copolymers

Epoxy‐based blends containing poly(ethylene oxide)‐co‐poly(propylene oxide)‐co‐poly(ethylene oxide) (PEO–PPO–PEO) block copolymers with different PEO/PPO molar ratios have been investigated in order to analyze the effect of the generated morphologies and interactions between components on the mechanical properties of the blends. Mechanical, morphological and dynamic mechanical analyses indicate that the observed increase of flexural modulus can be related to the decrease of free volume. In modified systems that remain miscible, an increase of flexural modulus, strength and fracture toughness can be observed. Also, macrophase‐ and microphase‐separated systems show an increase of fracture toughness but not of flexural modulus and strength at low contents of block copolymers. Copyright © 2007 Society of Chemical Industry     

Preparation of poly(acrylic acid‐co‐acrylamide)/kaolin and release kinetics of urea from it

A series of poly(acrylic acid‐co‐acrylamide)/kaolin [poly(AA‐co‐Am)/kaolin] composites were prepared by aqueous solution copolymerization of partially neutralized acrylic acid and acrylamide in the presence of kaolin nanopowder, which was synthesized to act as a release carrier of urea fertilizer. The superabsorbent composite was swollen in aqueous solution of urea to load urea, and the effect of urea concentration on the swelling was investigated. Furthermore, the effects of the contents of crosslinker, kaolin, and acrylamide, the neutralization degree of acrylic acid, and temperature, pH, and ionic strength of release medium on water absorbency and diffusion coefficient of urea release from poly(AA‐co‐Am)/kaolin were studied systematically. It was found that urea loading percentage could be adjusted by urea concentration of swelling medium, and urea diffusion coefficient could be regulated through the contents of crosslinker, kaolin, and acrylamide, and the neutralization degree of acrylic acid. Additionally, temperature and ionic strength of release medium may also affect the urea release process. The conclusions obtained could provide theoretical basis for urea diffusion behavior in superabsorbent used in agriculture. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Compatibilization of polypropylene/ poly(3‐hydroxybutyrate) blends

Blending polypropylene (PP) with biodegradable poly(3‐hydroxybutyrate) (PHB) can be a nice alternative to minimize the disposal problem of PP and the intrinsic brittleness that restricts PHB applications. However, to achieve acceptable engineering properties, the blend needs to be compatibilized because of the immiscibility between PP and PHB. In this work, PP/PHB blends were prepared with different types of copolymers as possible compatibilizers: poly(propylene‐g‐maleic anhydride) (PP–MAH), poly (ethylene‐co‐methyl acrylate) [P(E–MA)], poly(ethylene‐co‐glycidyl methacrylate) [P(E–GMA)], and poly(ethylene‐co‐methyl acrylate‐co‐glycidyl methacrylate) [P(E–MA–GMA)]. The effect of each copolymer on the morphology and mechanical properties of the blends was investigated. The results show that the compatibilizers efficiency decreased in this order: P(E–MA–GMA) > P(E–MA) > P(E–GMA) > PP–MAH; we explained this by taking into consideration the affinity degree of the compatibilizers with the PP matrix, the compatibilizers properties, and their ability to provide physical and/or reactive compatibilization with PHB. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Polymer nanocomposites containing carbon nanotubes and miscible polymer blends based on poly[ethylene‐co‐(acrylic acid)]

Four binary polymer blends containing poly [ethylene‐co‐(acrylic acid)] (PEAA) as one component, and poly(4‐vinyl phenol‐co‐2‐hydroxy ethyl methacrylate) (P4VPh‐co‐2HEMA) or poly(2‐ethyl‐2‐oxazoline) (PEOx) or poly(vinyl acetate‐co‐vinyl alcohol) (PVAc‐co‐VA) or poly (vinylpyrrolidone‐co‐vinyl acetate) (PVP‐co‐VAc) as the other component were prepared and used as a matrix of a series of composite materials. These binary mixtures were either partially or completely miscible within the composition range studied and were characterized by differential scanning calorimetry (DSC) and Fourier transformed infrared spectroscopy (FTIR). Carbon nanotubes (CNTs) were prepared by a thermal treatment of polyester synthesized through the chemical reaction between ethylene glycol and citric acid over an alumina boat. High resolution transmission electron microscopy (HRTEM) was used to characterize the synthesized CNTs. Films of composite materials containing CNTs were obtained after evaporation of the solvent used to prepare solutions of the four types of binary polymer blends. Young's moduli of the composites were obtained by thermomechanical analysis at room temperature. Only one glass transition temperature was detected for several compositions on both binary blends and the composite material matrices. Evidence of hydrogen bond formation was recorded for both miscible blends and composite materials. The degree of crystallinity and Young's moduli of the CNT‐polymer composites increased compared to the single polymer blends. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci 2008     

Impact modification of waste PET by polyolefinic elastomer

Waste poly(ethylene terephthalate) [PET] and a polyolefinic elastomer (POE), Engage? 8150, were melt blended in a co‐rotating twin screw extruder having initial distributive mixing followed by high shearing/stretching. Compositions having POE up to 10% with and without poly(ethylene‐co‐acrylic acid), as a compatibilizer were studied. The blends were characterized for mechanical, thermal and rheological properties as well as for morphological characteristics. Incorporation of POE improved the impact properties of PET very significantly. © 2003 Society of Chemical Industry     

Surface modification of LDPE with PE‐PEO graft copolymer

Films of LDPE containing 1–10 wt % of various polymeric additives were prepared by different techniques. Three poly(ethylene‐graft‐ethylene oxide)s synthesized by grafting poly(ethylene‐co‐acrylic acid) with poly(ethylene oxide) monomethyl ether (MPEO), and two pure MPEOs having molecular weights 750 and 2000 were used as additives. The additives were mixed with LDPE both by blending in a common solvent and by melt mixing. The blends were then solvent cast from xylene onto glass Petri dishes or compression molded between glass plates. The film surfaces were studied by water contact angle measurements and by X‐ray photoelectron spectroscopy (XPS), and melting points and heats of melting were recorded by differential scanning calorimetry (DSC). The blends had a two‐phase morphology, with enrichment of the graft copolymers at the glass–polymer interface, as shown by contact angle values and XPS spectra. Large differences in the interface accumulation between the different film samples were observed. Films prepared by compression molding of solution‐mixed blends exhibited much lower surface accumulation of graft copolymer at the glass–polymer interface than did the solvent cast or melt‐mixed/compression‐molded samples. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 75: 316–326, 2000     

Cellulose/acrylic acid copolymer blends for films and coating applications

Enzymatically treated cellulose was dissolved in a NaOH/ZnO solvent system and mixed together with poly(ethylene‐co‐acrylic acid) (PE‐co‐AA) or poly(acrylamide‐co‐acrylic acid) (PAA‐co‐AA) polymers, in order to improve the properties of dissolved cellulose and to prepare homogeneous cellulose‐based blends for films and coatings. The solution stage properties of the blends were evaluated by rheological methods and the precipitated dry blends were characterized by dynamic mechanical analysis, differential scanning calorimetry, and scanning electron microscopy. Paperboard coating tests done at laboratory scale showed dissolved cellulose/acrylic acid copolymer‐based blends function well as coating materials. All of the tested blends showed a good resistance against grease in the coating trials, having grease resistance from 60 to 69 days despite a very thin (～2 µm) coating layer. In addition, cellulose/PE‐co‐AA coating showed improved water vapor and oxygen barrier properties when compared with neat dissolved cellulose‐coated paperboard. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40286.     

Relationship between interfacial tension and dispersed‐phase particle size in polymer blends. II. PP/PA6

Simple blends with different viscosity ratios of the components as well as compatibilized blends varying both in type and content of the compatibilizers were used to study the relation between the interfacial tension and the dispersed‐phase particle size for PP/PA6 (80/20 wt %) blends in this work. Four compatibilizing systems including poly(ethylene‐co‐methacrylic acid) ionomers, a maleic anhydride‐grafted propylene copolymer, maleic anhydride‐grafted polypropylene, and a maleic anhydride‐grafted styrene ethylene butylene copolymer were used. For blends prepared in an internal mixer, a power‐law relation was found between the capillary number and the torque ratio of the blends' components. This relation was used to estimate the interfacial tension for the compatibilized blends. The relation between the steady‐state torque of the blends as a measure of viscosity and the estimated values of interfacial tension were also investigated. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 54–63, 2003