Thermal,mechanical, and gas barrier properties of ethylene–vinyl alcohol copolymer‐based nanocomposites for food packaging films: Effects of nanoclay loading

For the application of single‐layer food packaging films with improved barrier properties, an attempt was made to prepare ethylene‐vinyl alcohol (EVOH) copolymer‐based nanocomposite films by incorporation of organically modified montmorillonite nanoclays via a two‐step mixing process and solvent cast method. The highly intercalated tactoids coexisted with exfoliated clay nanosheets, and the extent of intercalation and exfoliation depended significantly on the level of clay loadings, which were confirmed from both XRD measurements and TEM observations. It was revealed that the inclusion of nanoclay up to an appropriate level of content resulted in a remarkable enhancement in the thermal, mechanical (tensile strength/modulus), optical, and barrier properties of the prepared EVOH/clay nanocomposite films. However, excess clay loadings gave rise to a reduction in the tensile properties (strength/modulus/elongation) and optical transparency due to the formation of clay tactoids with a larger domain size. With the addition of only 3 wt % clay, the oxygen and water vapor barrier performances of the nanocomposite films were substantially improved by 59 and 90%, respectively, compared to the performances of the neat EVOH film. In addition, the presence of clay nanosheets in the EVOH matrix was found to significantly suppress the moisture‐derived deterioration in the oxygen barrier performance, implying the feasibility of applying the nanocomposite films to single‐layer food packaging films. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40289.     

EVA nanocomposites based on South African Koppies clay

South African Koppies bentonite was organomodified with single‐tail and double‐tail alkyl ammonium cationic surfactants with the latter intercalated both below and above the clay cationic exchange capacity. Corresponding poly(ethylene‐co‐vinylacetate) nanocomposites were prepared by twin‐screw melt compounding. Transmission electron microscopy indicated the presence of mixed nano‐sized and micron‐sized clay morphologies. X‐ray diffraction studies revealed that the crystallinity of the particles improved and that the d‐spacing values increased on incorporating the clays in the polymer matrix. It is postulated that, rather than indicating polymer co‐intercalation, this is caused by further intercalation of either excess surfactants or surfactant residues that were released by shear delamination of the clays during compounding. Improved mechanical properties were realized especially when using the clay containing the longer double‐tail surfactant intercalated at levels in excess of the cation exchange capacity of the clay. The nanocomposites showed improved tensile modulus and elongation‐at‐break values at the expense of a reduction in impact strength, whereas tensile strength was about the same as for the neat polymer. J. VINYL ADDIT. TECHNOL., 20:143–151, 2014. © 2014 Society of Plastics Engineers     

Poly(vinyl alcohol) nanocomposites with different clays: Pristine clays and organoclays

Poly(vinyl alcohol) (PVA)/clay nanocomposites were synthesized using the solution intercalation method. Na ion‐exchanged clays [Na⁺–saponite (SPT) and Na⁺–montmorillonite (MMT)] and alkyl ammonium ion‐exchanged clays (C₁₂–MMT and C₁₂OOH–MMT) were used for the PVA nanocomposites. From the morphological studies, the Na ion‐exchanged clay is more easily dispersed in a PVA matrix than is the alkyl ammonium ion‐exchanged clay. Attempts were also made to improve both the thermal stabilities and the tensile properties of PVA/clay nanocomposite films, and it was found that the addition of only a small amount of clay was sufficient for that purpose. Both the ultimate tensile strength and the initial modulus for the nanocomposites increased gradually with clay loading up to 8 wt %. In C₁₂OOH–MMT, the maximum enhancement of the ultimate tensile strength and the initial modulus for the nanocomposites was observed for blends containing 6 wt % organoclay. Na ion‐exchanged clays have higher tensile strengths than those of organic alkyl‐exchanged clays in PVA nanocomposites films. On the other hand, organic alkyl‐exchanged clays have initial moduli that are better than those of Na ion‐exchanged clays. Overall, the content of clay particles in the polymer matrix affect both the thermal stability and the tensile properties of the polymer/clay nanocomposites. However, a change in thermal stability with clay was not significant. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 3208–3214, 2003     

Room temperature spontaneous exfoliation of organo-clay in liquid polybutadiene: Effect of polymer end-groups and the alkyl tail number of organic modifier

Disorderly exfoliated telechelic liquid polybutadiene/organo-clay nanocomposite gel was, for the first time, successfully prepared at room temperature of 26 °C by simply compounding of carboxyl-terminated polybutadiene (CTPB) with organo-clay containing surfactant modifier with two alkyl tails. The dispersion behavior of organo-clay in liquid polybutadiene/organo-clay nanocomposite gels were systematically investigated using X-ray diffraction (XRD), transmission electron microscopy (TEM), rheology and compatibility experiments, focusing on the influence of the functional end-groups of the liquid rubber and the alkyl tails number of the organic modifier on the clay exfoliation. A unique liquid-like reversible rheological behavior was observed for CTPB/exfoliated clay nanocomposite gels with organic modifier having two alkyl tails, which is totally different with that of other samples (HTPB/C18-clay, HTPB/D18-clay and CTPB/C18-clay). And it is noteworthy that CTPB exhibits a higher level of dispersion with an organo-clay with two alkyl tailed surfactant than that with one alkyl tail.     

Photopolymerization kinetics of poly(acrylate)-clay composites using polymerizable surfactants

Photopolymerization kinetics of polymer-clay nanocomposite systems utilizing polymerizable quaternary ammonium surfactants as dispersants were systematically investigated to determine the effects of surfactant type and clay morphology on polymerization behavior. For these studies, either polymerizable surfactants were mixed into a clay-monomer system or the surfactants were ionically anchored to clay surfaces and added to the monomer for in situ photopolymerization. Higher photopolymerization rates are observed with increasing polymerizable surfactant concentration, while no significant change or decreases in polymerization rate occur with incorporation of non-polymerizable surfactants. The higher rates observed for polymerizable surfactant systems are due to lower apparent termination rate parameters stemming from immobilization of the surfactants. For clay that is modified with ionically bonded quaternary ammonium surfactants, polymerization rates decrease in both polymerizable and non-polymerizable organoclay systems with increasing concentration, but this decrease is much smaller when polymerizable organoclays are utilized. For the same organoclay concentration, higher polymerization rates and double bond conversions result with increasing polymerizable surfactant concentration via cation exchange. Significant increases in polymerization rate also occur with increasing degree of clay exfoliation.     

Experimental and MD simulation study on the physical and mechanical properties of organically modified montmorillonite clay and compatibilized linear low density polyethylene nanocomposites

Understanding the interfacial interactions plays a key role in controlling mechanical and physical properties of polymer/clay nanocomposites (PCNs). In this work, the surface interactions between constituents of experimentally prepared PCNs which are the pristine linear low density polyethylene (PE) chains, PE compatibilizers, montmorillonite clay surface layer, and surfactants were studied quantitatively by employing molecular dynamics simulation technique. The interaction energy between the polymer and the clay was found to be inversely proportional with the volume of the surfactant which decreases the electrostatic interactions between the compatibilizer and the hydrophilic clay surface. However, the van der Waals (vdW) interactions between alkyl tails of surfactants and the PE chains increase with the tail length of the surfactants. The most attractive interaction was between the surfactant's head group and the clay surface. We showed that there existed fine balance between the electrostatic and vdW type forces on the stability and the enhanced properties of the PE–organoclay nanocomposites. Calculated interaction energies were then correlated to the experimentally measured mechanical properties. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45817.     

Organoclay degradation in melt processed polyethylene nanocomposites

Melt processed nanocomposites were formed from low-density polyethylene, LDPE, and organoclays over a wide range of processing temperatures. These composites show limited exfoliation, and hence, their X-ray analysis reveals a distinct peak corresponding to the interplatelet distances in the unexfoliated clay galleries. The degradation of the quaternary ammonium surfactant of the organoclay in these systems was characterized by examining the change in the position of these peaks as a function of the melt processing temperature. Upon degradation, the mass of the surfactant within the clay galleries decreases, which causes the platelets to collapse and shifts the WAXS peak to lower d-spacings. The results of the WAXS analysis suggest that a significant portion of the surfactant is lost from the organoclays when the melt processing temperature is increased from 180 to 200 °C or higher. The extent of surfactant degradation in these composites was determined to be independent of the organoclay content. Organoclay degradation appears to limit the extent of exfoliation or dispersion in LDPE as revealed by stress-strain analyses of nanocomposites processed at different temperatures. The amount of surfactant lost during thermogravimetric analysis of various organoclays indicates that surfactants with multiple alkyl tails have greater thermal stability than those with a single alkyl tail. A comparison of the mass of surfactant lost during melt processing of nanocomposites and during thermogravimetric analysis of organoclays (in the absence of polymer) indicated that at a given time, a larger surfactant loss from the clay galleries occurs during extrusion than during the TGA experiment. This is attributed to the greater ease with which the degradation products (predominantly α-olefins) are solubilized in polyethylene for the composites as opposed to evaporated from the organoclay during TGA.     

Limonene transport and mechanical properties of EVOH and nylon 6,6 films as influenced by RH

The transport properties of d‐limonene through ethylene vinyl alcohol copolymers (EVOH) and nylon 6,6 films as functions of relative humidity (RH) and temperature were studied. Permeation properties of these polymers were strongly influenced by temperature and RH. Compared to the EVOH films, the nylon 6,6 film had much greater limonene permeability. Mechanical property studies indicated that both the tensile modulus and yield strength of the EVOH films decreased with an increase in RH. The polymer changed from being stiff and brittle at low RH to being soft and ductile at high RH. In addition, ethylene content and orientation were found to affect the transport and mechanical properties of limonene through EVOH polymers. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 79: 1949–1957, 2001     

Effect of interfacial attraction on intercalation in polymer/clay nanocomposites

In order to examine the adhesive behavior of a polar polymer between hydrophilic clay layers, the so‐called glue effect, a clay intercalation by an ethylene–vinyl alcohol (EVOH) copolymer, which was capable of strong hydrogen bonding with the silicate surface of clay, was prepared by the melt intercalation technique and compared with a clay nanocomposite containing styrene–acrylonitrile (SAN) copolymer of less polar interaction energy in terms of the morphology and mechanical properties. Although initial penetration of the guest polymer into the gallery of the host clay occurred more rapidly for EVOH because of its strong hydrophilic nature, the dissociation of clay nanoplatelets was better developed for SAN with less polar interaction with clay, well evidencing the fact that the glue effect effectively affects the intercalation behavior of polymer/clay nanocomposites. However, the mechanical properties of the EVOH/clay nanocomposite were superior to those of SAN/clay nanocomposites. Although dissociation of respective silicate layers was poor for EVOH/clay nanocomposites, strong attractive energy stabilizes the interface between inorganic nanoparticles and the polymer matrix much more effectively, resulting in higher mechanical properties. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 2749–2753, 2006     

The critical organic modifier aliphatic tail length for the formation of poly(methyl methacrylate)-montmorillonite nanocomposites

In this article, we report the influence of organic modifier structure (alkyl chain length C8-C20, single vs ditallow) and thereby, the effect of hydrophobicity on the structure, thermal and mechanical properties of poly(methyl methacrylate) (PMMA)-clay hybrids. Melt processed PMMA-clay hybrids were characterized using wide-angle X-ray diffraction, transmission electron microscopy, and differential scanning calorimetry. The organoclays having an alkyl chain length of more than 12 CH₂ groups resulted in the formation of nanocomposites. The glass transition temperature (T_g) of PMMA increased in the presence of clay. The mean-field lattice model was used to predict the free energy for nanocomposite formation, which showed a reasonable match with the experimental results and provided a general guideline for the proper selection of polymer and organoclay (ie, organic modifier) to obtain nanocomposite. Tensile modulus showed maximum improvement of 58% for the nanocomposites compared to 9% improvement for the composites. Tensile modulus increased with increases in the alkyl chain length of the organic modifier and clay loading. The level of improvement for the tensile properties of nanocomposites prepared from primary and secondary ammonium-modified clay is the same as that obtained with the commercial organoclays.     

Transparent low‐density polyethylene/starch nanocomposite films

Low‐density polyethylene (LDPE)/starch nanocomposite films were prepared by melt extrusion process. The first step includes the preparation of starch–clay nanocomposite by solution intercalation method. The resultant product was then melt mixed with the main matrix, which is LDPE. Maleic anhydride‐grafted polyethylene (MAgPE), produced by reactive extrusion, was used as a compatibilizer between starch and LDPE phases. The effects of using compatibilizer, clay, and plasticizers on physico‐mechanical properties were investigated. The results indicated that the initial intercalation reaction of clay layers with starch molecules, the conversion of starch into thermoplastic starch (TPS) by plasticizers, and using MAgPE as a compatibilizer provided uniform distribution of both starch particles and clay layers, without any need of alkyl ammonium treatment, in LDPE matrix. The nanocomposite films exhibited better tensile properties compared to clay‐free ones. In addition, the transparency of LDPE film did not significantly change in the presence of TPS and clay particles. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Effects of dispersion and arrangement of clay on thermal diffusivity of polyimide‐clay nanocomposite film

Polymer‐clay nanocomposites are well‐known high‐performance materials with a superior tensile modulus. However, in the case of composites with polyimide (PI), additional functions require study because PI is a high‐performance material in itself. Significant enhancement of thermal conductivity, which is closely related to the state of clay dispersion, is expected for a polymer‐clay nanocomposite. In this study, variations in the thermal diffusivity of PI‐clay nanocomposite films prepared by different methods were investigated. The thermal diffusivity of PI‐clay nanocomposite film increased at low clay content only when unmodified clay was used, where the clay morphology was a layered structure dispersed on a nanometer scale. Moreover, the thermal diffusivity could be enhanced by controlling the tensile stress induced by spontaneous shrinkage of the film during thermal imidization. These results demonstrated that the thermal diffusivity of PI‐clay nanocomposite films is significantly affected by the dispersion and/or arrangement states of the clay. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

EVOH nanocomposite films with enhanced barrier properties under high humidity conditions

To improve the oxygen and water vapor barrier properties of ethylene vinyl alcohol, EVOH/EFG nanocomposite films under high humidity conditions, we successfully prepared highly exfoliated graphite (EFG) containing a monolayer or a few layers of graphene via rapid heating treatment and ultrasonication as confirmed by Fourier transform infrared spectroscopy (FTIR), scanning electron microscope (SEM), elemental analysis (EA), and nitrogen adsorption–desorption analysis. Six different EVOH/EFG nanocomposite films containing as‐prepared EFG were prepared via a solvent blend method and their physical and barrier properties at different relative humidities were investigated as a function of EFG content. Depending on the EFG content, oxygen transmission rate (OTR) decreased from 3.7 to 0.1 cc/m²/day at dry condition, and the difference in OTR between dry condition and humid condition decreased from 6.5 to 2.3 cc/m²/day. Barrier properties of the EVOH/EFG nanocomposite films were strongly dependent on their chemical structure and morphology. Crystallinity, tortuous path length, and hydrophobicity of EVOH/EFG nanocomposite films were enhanced by the addition of EFG. However, the thermal stability and glass transition temperature of the nanocomposite films were not improved by incorporation of EFG due to the weak interaction between EVOH and EFG. To maximize the performance of EVOH/EFG nanocomposite films, the compatibility of the polymer matrix and fillers needs to be improved. POLYM. COMPOS., 35:644–654, 2014. © 2013 Society of Plastics Engineers     

Studies on properties of softwood (Ficus hispida)/PMMA nanocomposites reinforced with polymerizable surfactant-modified nanoclay

Soft wood (Ficus hispida) was chemically modified by impregnation of methyl methacrylate monomer, glycidyl methacrylate (GMA), a cross-linking agent, and montmorillonite (MMT) using catalyst heat treatment. MMT was modified by using a polymerizable surfactant 2-acryloloxy ethyl trimethyl ammonium chloride (ATAC) and a mixture of surfactants ATAC and cetyl trimethyl ammonium bromide (CTAB) in a molar ratio of (1:1). A comparative study on different properties of the prepared wood polymer nanocomposite (WPNC) based on impregnation of intercalating mixture containing MMA/GMA/clay modified by both the surfactants (ATAC and CTAB) and MMA/GMA/clay modified by only surfactant ATAC were done. FTIR, XRD, and TGA studies were employed for the characterization of clay and WPNC. WPNC prepared by using combined surfactant-modified clay along with MMA/GMA exhibited improved dimensional stability, chemical resistance, thermal stability, mechanical properties, and lower water uptake than that of WPNC prepared by using single surfactant-modified clay and MMA/GMA system.     

Surfactant‐dispersed carbon black in polyimide nanocomposites: Spectroscopic monitoring of the dispersion state in the polymer matrix

The effects of an anionic surfactant on the dispersion of carbon black (CB) for the purpose of forming conducting composite films were examined with ultraviolet–visible (UV–vis) absorption spectroscopy. To obtain a good dispersion and size reduction of aggregated CB in a polymer matrix, sodium dodecyl sulfate (SDS), used as a surfactant, was introduced into a CB suspension. A set of concentrations with various ratios of CB to SDS (ranging from 1 : 0.4 to 1 : 10) was established before mixing with poly(amic acid) (PAA), a precursor of pyromellitic dianhydride and oxydianiline, was performed. The CB/PAA solution mixtures were submerged under an ultrasonic bath for several hours, then cast onto dry plate glasses, and finally subjected to thermal imidization to produce CB/polyimide (PI) nanocomposite films with various CB weight fractions ranging from 0.025 to 0.50 wt %. A method for evaluating the absorbance at 500 nm of the CB/PI nanocomposite films was established. The absorbance of CB/PI nanocomposite samples of various thicknesses was also normalized to get rid of the effects of the different thicknesses. UV–vis spectra showed that the minimum weight ratio of CB to SDS in the nanocomposite films that achieved well‐dispersed CB and still had transparent properties was 1 : 2.0. Transmission electron microscopy demonstrated that CB was dispersed homogeneously in the PI matrix, and the size of the aggregated CB was affected by the amount of the surfactant. The dielectric properties of the nanocomposite films without the surfactant increased by approximately 2 orders of magnitude with an increasing mass weight fraction of CB and decreased when the surfactant was added. The surfactant also reduced the tensile strength of the CB/PI nanocomposites when the CB/SDS ratio was higher than 1 : 2.0. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Polymer–surfactant interactions in graft copolymer solutions

Graft copolymers composed of water-soluble cellulosic backbones and > 0.4% (by weight) alkyl grafts are insoluble in water but soluble in surfactant solutions. Studies of the bulk viscosity and stability of polymer-surfactant solutions at 49°C indicate that the mechanism for solubilization of the polymer is the incorporation of the alkyl side chains into surfactant micelles. The tendency for side chains to combine with micelles appears to depend at least in part on the geometry of the surfactant tail group such that surfactants containing straight-chain tail groups solubilize alkyl side chains more readily than olefinic surfactants. The presence of small solutes near the surface of the micelle also inhibits incorporation of side chains from the polymer. Unsolubilized side chains remain in the aqueous phase of the solution, where they form thermally unstable intermolecular aggregates.     

Self-Assembly of Polyethylene Glycol Ether Surfactants in Aqueous Solutions: The Effect of Linker between Alkyl and Ethoxylate

The aqueous self-assembly behavior of two homologous series of poly(ethylene oxide) (PEO)-containing nonionic surfactants based on a C₁₀-Guerbet hydrophobe is reported. The two families of surfactants, alkyl ethoxylates and alkyl alkoxylates, are commercially available from BASF under the trade name Lutensol® XP-series and XL-series, respectively. The latter incorporate propylene oxide (PO) units in the surfactant chain. Dye solubilization was used to determine the critical micellization concentration (CMC) of each surfactant at 22 and 50 °C. The PO-containing alkyl alkoxylates displayed lower CMC values, which were also more sensitive to temperature. The Gibbs free energy, enthalpy, and entropy of micellization were computed from the CMC data and used to identify the contribution of each surfactant moiety (alkyl chain, PO unit, and PEO block) in controlling the CMC. The micellization properties are compared with compositionally similar surfactants with linear alkyl chains, yielding information about the effects of the Guerbet alkyl chain on micellization. Isothermal titration calorimetry was also used to characterize the CMC and enthalpy of micellization which generally compare well with the dye solubilization results. Cloud point data reveal nonmonotonic relationships for the Lutensol® surfactants with respect to composition, unlike linear alkyl chain surfactants. Finally, dilute solution viscosity measurements performed on some Lutensol® surfactants show a change in the slope, suggesting a structural change that tends to be more pronounced for surfactants with longer PEO blocks. The data presented herein enhance the understanding of surfactant structure–property relationships required for industrial formulation.     

Thermal and barrier properties of EVOH/EFG nanocomposite films for packaging applications: Effect of the mixing method

Ethylene‐vinyl alcohol copolymer (EVOH)/exfoliated graphite (EFG) nanocomposite films were prepared by precoating EFG on the EVOH surface and conducting a successive melt‐extrusion process. Their physical properties were strongly dependent on the EFG content and the mixing method, which strongly affected the morphology and surface properties of the nanocomposite films. The hydrophobicity and water resistance property of EVOH increased by incorporating hydrophobic EFG and their effects were more pronounced in the precoating method, which is related to good dispersion of EFG in EVOH and an enhanced crystalline structure. The incorporation of EFG into EVOH by the precoating method more effectively diminished the dependence of the relative humidity on the oxygen transmission rate of pure EVOH and increased the oxygen barrier properties of EVOH at a high relative humidity. The incorporation of EFG into EVOH by the precoating method also induced relatively more enhanced thermal stability. These results suggest the feasibility of the application of moisture‐sensitive EVOH resin for food packaging films. POLYM. COMPOS., 37:1744–1753, 2016. © 2014 Society of Plastics Engineers     

Influence of the ethylene–(methacrylic acid)–Zn2+ ionomer on the thermal and mechanical properties of blends of poly(propylene) (PP)/ethylene–(vinyl alcohol) copolymer (EVOH)

The thermal and mechanical properties and the morphologies of blends of poly(propylene) (PP) and an ethylene–(vinyl alcohol) copolymer (EVOH) and of blends of PP/EVOH/ethylene–(methacrylic acid)–Zn²⁺ ionomer were studied to establish the influence of the ionomer addition on the compatibilization of PP/EVOH blends and on their properties. The oxygen transmission rate (O₂TR) values of the blends were measured as well. PP and EVOH are initially incompatible as was determined by tensile tests and scanning electronic microscopy. Addition of the ionomer Zn²⁺ led to good compatibility and mechanical behaviour was improved in all blends. The mechanical properties on extruded films were studied for 90/10 and 80/20 w/w PP/EVOH blends compatibilized with 10 % of ionomer Zn²⁺. These experiments have shown that the tensile properties are better than in the injection‐moulded samples. The stretching during the extrusion improved the compatibility of the blends, diminishing the size of EVOH domains and enhancing their distribution in the PP matrix. As was to be expected, the EVOH improved the oxygen permeation of the films, even in compatibilized blends. Copyright © 2004 Society of Chemical Industry     

Reactive surfactants in heterophase polymerization. XVII. Influence of the surfactant on the mechanical properties and hydration of the films

In the context of a European union‐supported network on “Reactive Surfactants for Heterophase Polymerization,” different polymerizable surfactants (surfmers) have been synthesized and engaged in the emulsion polymerization of styrene, butyl acrylate, and acrylic acid. The thermomechanical properties of films cast from these different latices are reported in this article. The evolution of the mechanical properties with temperature and the effect of water molecules on these properties are studied. We observed that the studied surfactants do not influence the properties of the dry films. However, some differences due to grafting of reactive surfactants appeared when the films were wet. The amount of water uptake is drastically decreased when only reactive surfactants are present in the film. Concerning the mechanical behavior of the wet films, a decrease of the plastic flow stress is observed for all the samples whatever the nature of the surfactant (reactive or conventional). Hence, calorimetric measurements and dynamic mechanical analysis are used to identify the possible mechanisms that induce the change in the mechanical behavior of the latex films. In the case of reactive surfactant grafted to the polymer, the very low value of water uptake is accompanied by a plasticization of the polymer. In contrast, no plasticizing effect is observed in the case of nonreactive surfactant, even if the amount of water is very large. Finally, the tensile behavior of the styrene–butyl acrylate copolymer versus temperature is analyzed in the frame of the quasi point defects (qpd) model. Both rubber elasticity and chain orientation effects are taken into account to describe the behavior laws at large extensions (i.e., ? ≈ 1.2). © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 1686–1700, 2002; DOI 10.1002/app.10548