Morphology and mechanical properties of binary triblock copolymer blends

The influence of the morphology on the mechanical properties of binary styrene–butadiene (SB) triblock copolymer blends of a thermoplastic block copolymer and a thermoplastic elastomer (TPE) with different molecular architectures was studied with bulk samples prepared from toluene. Both block copolymers contained SB random copolymer middle blocks, that is, the block sequence S–SB–S. The two miscible triblock copolymers were combined to create a TPE with increased tensile strength without a change in their elasticity. The changes in the equilibrium morphology of the miscible triblock copolymer blends as a function of the TPE content (lamellae, bicontinuous morphology, hexagonal cylinders, and worms) resulted in a novel morphology–property correlation: (1) the strain at break and Young's modulus of blends with about 20 wt % TPE were larger than those of the pure thermoplastic triblock copolymer; (2) at the transition from bicontinuous structures to hexagonal structures (～35 wt % TPE), a change in the mechanical properties from thermoplastic to elastomeric was observed; and (3) in the full range of wormlike and hexagonal morphology (60–100 wt % TPE), elastomeric properties were observed, the strength greatly increasing and high‐strength elastomers resulting. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 429–438, 2005     

Influence of different alkyl‐methylimidazolium tetrafluoroborate ionic liquids on the structure of pebax® films. Consequences on thermal,mechanical, and water sorption and diffusion properties

In this work, three ionic liquids (ILs) differing by the length of the alkyl chain linked to their cation were incorporated in a Pebax^® copolymer matrix through a solvent cast process for composition from 0 to 70 wt % IL. The copolymer/IL miscibility was investigated via IR Spectroscopy, Differential Scanning Calorimetry and Scanning Electron Microscopy. The three ILs dissolved in the copolymer soft phase for ILs content below 30 wt % whereas they formed segregated dispersed domains at higher loadings. The plasticizing effect of the ILs was examined through DSC and thermomechanical analyses. In the range of IL amount from 0 to 30 wt %, no significant differences were observed in the thermomechanical properties as a function of the IL structure. At higher IL content, the films based on 1‐ethyl‐methylimidazolium tetrafluoroborate sustained better properties. All films exhibited a good thermal stability up to 300 °C. The water sorption isotherms were modeled with GAB equation and both the kinetic and thermodynamic parameters of the sorption mechanism were investigated. A non‐monotonic evolution of the GAB parameters and diffusion coefficient as a function of the IL content was evidenced. Moreover, different behaviors were observed as a function of the IL nature and structuration within the copolymer matrix. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 811–824     

Water sorption and electrical/dielectric properties of organic-inorganic polymer blends

Organic-inorganic polymer blends (OIPB) were obtained by reaction of organic and inorganic oligomers. The organic oligomer was synthesized with 2,4-toluene diisocyanate (TDI) and oligooxypropylene glycols (OPG) with various molecular weights (MW). The inorganic component was a water solution of sodium silicate. The OIPB obtained are hydrophilic and have great water sorption ability (the relative weight of sorbed water reaches 2000 %). The kinetics of water sorption and the changes of electrical conductivity during sorption were studied. Sorption ability, and mechanical, electrical and dielectric properties of OIPB depend on molecular weight of OPG: conductivity increases with increasing MW, whereas the sorption ability correlates with the mechanical properties. The influence of the inorganic phase content on the electrical and dielectric properties was studied as well.     

Influence of the PVOH molar mass on the morphology and functional properties of EVOH/PVOH films prepared by melt blending

The influences of the molar mass (low, medium, and high) and content of poly(vinyl alcohol) (PVOH) dispersed by melt-blending in an ethylene vinyl alcohol (EVOH) copolymer on the morphology, microstructure, thermal, mechanical, and oxygen barrier properties were investigated. Multilayer films with external low-density polyethylene layers and inner EVOH/PVOH blend layer and respective monolayer films were elaborated and characterized. EVOH/PVOH blends exhibited a good compatibility because of the initial presence of PVOH segments in EVOH. The detailed quantitative analysis of the morphology performed for all blends showed that the finest dispersion was obtained with the PVOH with the lowest molar mass. The properties of the films as a function of the PVOH content and its molar mass were determined herein. Significant improvement of barrier properties was obtained at moderated water activities (up to a_w = 0.6) by using the PVOH with the lowest molar mass. Compared to the neat EVOH material, the oxygen permeability coefficients decreased by a factor 2 by adding 15 vol% PVOH while the thermal and mechanical properties remained similar.     

Water transport properties of thermoplastic polyurethane films

Two linear segmented polyurethanes, based on poly(oxyethylene) (POE) as a soft segment and 4,4′‐diphenylmethane diisocyanate and 1,4‐butanediol as hard segments and differing in their soft segment length, have been studied from a water vapor transport point of view. For both polyurethanes, the water sorption is governed by a Fickian process, and the thermoplastic polyurethane with the longer POE segments displays the higher water diffusion rate. The water sorption isotherms are Brunauer Emmet Teller (BET) type III for both thermoplastic polyurethanes, and the water uptakes are directly related to the polymer POE content. The Flory–Huggins theory cannot correctly describe the sorption isotherms. More sophisticated approaches (Koningsveld–Kleinjtens or Guggenheim‐Anderson‐de Boer (GAB) models) are needed to fit the experimental water uptakes. The positive deviation from Henry's law and the decrease in the apparent diffusion coefficient observed at a high activity have been particularly studied. In this activity range, an isotherm analysis based on the cluster integral of Zimm and Lundberg suggests some clustering phenomenon, which seems consistent with the diffusion coefficient variation. In agreement with the sorption results, the water permeability coefficients are small at low activities, and they increase greatly with the relative pressure of water. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 473–492, 2004     

Phase morphology and mechanical properties of iPP/SEP blends

The effects of the addition of diblock copolymer poly(styrene‐b‐ethylene‐co‐propylene) (SEP) to isotactic polypropylene (iPP) on the morphology and mechanical properties were investigated. Phase morphologies of iPP/SEP blends up to a 70/30 weight ratio, prepared in Brabender Plasticoder, were studied with optical microscopy, scanning electron microscopy, transmission electron microscopy, and wide‐angle X‐ray diffraction. The addition of 2.5 wt % SEP caused a nucleation effect (by decreasing the crystallite and spherulite size) and randomization of the crystallites. With further SEP addition, the crystallite and spherulite size increased because of prolonged solidification and crystallization and achieved the maximum in the 80/20 iPP/SEP blend. This maximum was a result of the appearance of β spherulites and the presence of mixed α spherulites in the 80/20 iPP/SEP blend. Dispersed SEP particles were irregular and elongated clusters consisting of oval and spherical core–shell microdomains or SEP micelles. SEP clusters accommodated their shapes to interlamellar and interspherulitic regions, which enabled a well‐developed spherulitization even in the 70/30 iPP/SEP blend. The addition of SEP decreased the yield stress, elongation at yield, and Young's modulus but significantly improved the notched impact strength with respect to the strength of pure iPP at room temperature. Some theoretical models for the determination of Young's modulus of iPP/SEP blends were applied for a comparison with the experimental results. The experimental line was closest to the Takayanagi series model. © 2001 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 39: 566–580, 2001     

Thermal oxidative stability and effect of water on gas transport and mechanical properties in PA6‐EVOH films

The thermal oxidative stability and the effect of water on gas transport and mechanical properties of blends of polyamide 6 (PA6) with ethylene‐co‐vinyl alcohol (EVOH) and EVOH modified with carboxyl groups (EVOH‐COOH) have been investigated. The presence of EVOH reduces water vapor and oxygen gas permeability of polyamide, as well as small amounts of EVOH‐COOH further improve barrier properties, especially to oxygen. This has been explained in terms of improved interactions of the blend constituents in the amorphous phase, due to ionic linkages between the polyamide amino groups and the carboxyls of modified EVOH. The permeation to gases was found to increase with the amount of sorbed water. The morphology of the samples was found to have an effect on barrier properties, as the presence of EVOH causes the PA6 α crystalline form to increase, lowering the permeability to oxygen and water vapor. Mechanical properties are strongly affected by water sorption, as tensile modulus and strength decrease with increasing water content. Chemiluminescence (CL), infrared spectroscopy (FTIR), and tensile test were employed in order to assess the correlation between chemical composition and the thermal oxidative stability of the films aged at 110 °C in air. CL experiments suggest that the presence of EVOH and EVOH‐COOH efficiently inhibits the formation of peroxidized species during the processing, and increases the thermal oxidative stability of the films. Infrared spectroscopy showed a build‐up of carbonyl absorption in the range 1700–1780 cm^?1, due to the formation of oxidation products, which is greater in the case of the pure polymer. Tensile tests on films revealed a reduction in ductility as a result of ageing for neat PA6, whereas in comparison the blends exhibit a far better long‐term stability. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 840–849, 2007     

Mechanical properties of Nafion and titania/Nafion composite membranes for polymer electrolyte membrane fuel cells

Measurements of the mechanical and electrical properties of Nafion and Nafion/titania composite membranes in constrained environments are reported. The elastic and plastic deformation of Nafion‐based materials decreases with both the temperature and water content. Nafion/titania composites have slightly higher elastic moduli. Thecomposite membranes exhibit less strain hardening than Nafion. Composite membranes also show a reduction in the long‐time creep of ～40% in comparison with Nafion. Water uptake is faster in Nafion membranes recast from solution in comparison with extruded Nafion. The addition of 3–20 wt % titania particles has minimal effect on the rate of water uptake. Water sorption by Nafion membranes generates a swelling pressure of ～0.55 MPa in 125‐μm membranes. The resistivity of Nafion increases when the membrane is placed under a load. At 23 °C and 100% relative humidity, the resistivity of Nafion increases by ～15% under an applied stress of 7.5 MPa. There is a substantial hysteresis in the membrane resistivity as a function of the applied stress depending on whether the pressure is increasing or decreasing. The results demonstrate how the dynamics of water uptake and loss from membranes are dependent on physical constraints, and these constraints can impact fuel cell performance. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 2327–2345, 2006     

Synthesis,characterization, and water sorption properties of new aromatic polyamides containing benzimidazole and ethylene oxide moieties

New polyamides, containing a benzimidazole side group and ethylene oxide moieties in the structural repeat unit, were synthesized by low‐temperature polycondensation. The aim of this design was to obtain polyamides that were more soluble in common organic solvents and hence had better processability than benzimidazole polyamides while maintaining the water sorption properties characteristic of the latter. The results showed that the number of ether linkages of the repeat unit played an important role in the glass‐transition temperature and in the water sorption properties, the polyamides with one or two ethylene oxide units being more hydrophilic than benzimidazole polyamides. However, the length of the ethylene oxide chain played a minor role in the solubility because the second member of the series, with two ether linkages (i.e., one ethylene oxide unit), reached the same level of solubility as those polyamides with more ethylene oxide moieties. No crystallinity was observed by X‐ray and calorimetric measurements for the new polymers. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 112–121, 2005     

Effect of dispersed phase composition on morphological and mechanical properties of PET/EVA/PP ternary blends

Immiscible ternary blends of PET/EVA/PP (PET as the matrix and (PP/EVA) composition ratio = 1/1) were prepared by melt mixing. Scanning electron microscope results showed core‐shell type morphology for this ternary blend. Binary blends of PET/PP and PET/EVA were also prepared as control samples. Two grades of EVA with various viscosities, one higher and the other one lower than that of PP, were used to investigate the effect of components' viscosity on the droplet size of disperse phase. The effect of interfacial tension, elasticity, and viscosity on the disperse phase size of both binary and ternary blends was investigated. Variation of tensile modulus of both binary and ternary blends with dispersed phase content was also studied. Experimental results obtained for modulus of PET/EVA binary blends, showed no significant deviations from Takayanagi model, where considerable deviations were observed for PET/PP binary blends. Here, this model that has been originally proposed for binary blends was improved to become applicable for the prediction of the tensile modulus of ternary blends. The new modified model showed good agreement with the experimental data obtained in this study. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 251–259, 2010     

Thermal,mechanical, and morphological properties of novolac‐type phenolic resin blended with fullerenol polyurethane and linear polyurethane

Fullerenol polyurethane (C₆₀‐PU) and linear polyurethane (linear‐PU) modified phenolic resins were prepared in this study. Phenolic resin/C₆₀‐PU and phenolic resin/linear‐PU blends show good miscibility as a result of the intermolecular hydrogen bonding existing between phenolic resin and PU modifiers. DSC and thermogravimetric analysis methods were used to study the thermal properties of phenolic resin blended with different types of PUs. The intermolecular hydrogen bonding that existed between phenolic resin and C₆₀‐PU was investigated by Fourier transform infrared spectroscopy. The morphology and mechanical properties of phenolic resin/C₆₀‐PU and phenolic resin/linear‐PU blends were also investigated. The char yield of the modified phenolic resins decreased with increasing PU modifier content. Significant improvement in the toughness of the modified phenolic resins was observed. The improvements of impact strength were 27.4% for the phenolic resin/linear‐PU system and 54.3% for the phenolic resin/C₆₀‐PU system, respectively, both with 3 phr linear‐PU and C₆₀‐PU content. © 2001 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 39: 2436–2443, 2001     

Selective localization of organoclay and effects on the morphology and mechanical properties of LDPE/PA11 blends with distributed and co‐continuous morphology

A study was made on the effect of small amounts of organically modified clay on the morphology and mechanical properties of blends of low‐density polyethylene and polyamide 11 at different compositions. The influence of the filler on the blend morphology was investigated using wide angle X‐ray diffractometry, scanning and transmission electron microscopy and selective extraction experiments. The filler was found to locate predominantly in the more hydrophilic polyamide phase. Although such uneven distribution does not have a significant effect on the onset of phase co‐continuity of the polymer components, it brings about a drastic refinement of the microstructure for the blends both with droplets/matrix and co‐continuous morphologies. In addition to the expected reinforcing action of the filler, the resulting fine microstructure plays an important role in enhancing the mechanical properties of the blends. This is essentially because of a good quality of stress transfer across the interface between the constituents, which also seems to benefit for a good interfacial adhesion promoted by the filler. Our results provide the experimental evidence for the capabilities of nanoparticles added to multiphase polymer systems to act selectively as a reinforcing agent for specific domains of the material and as a medium able to assist the refinement of the polymer phases during mixing. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 600–609, 2010     

Morphology and mechanical properties of blown films of a low‐density polyethylene/linear low‐density polyethylene blend

The morphologies of films blown from a low‐density polyethylene (LDPE), a linear low‐density polyethylene (LLDPE), and their blend have been characterized and compared using transmission electron microscopy, small‐angle X‐ray scattering, infrared dichroism, and thermal shrinkage techniques. The blending has a significant effect on film morphology. Under similar processing conditions, the LLDPE film has a relatively random crystal orientation. The film made from the LDPE/LLDPE blend possesses the highest degree of crystal orientation. However, the LDPE film has the greatest amorphous phase orientation. A mechanism is proposed to account for this unusual phenomenon. Cocrystallization between LDPE and LLDPE occurs in the blowing process of the LDPE and LLDPE blend. The structure–property relationship is also discussed. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 507–518, 2002; DOI 10.1002/polb.10115     

Effect of solvent–matrix interactions on structures and mechanical properties of micelle‐crosslinked gels

Previous studies on hydrogels crosslinked by acrylated PEO₉₉–PPO₆₅–PEO₉₉ triblock copolymer (F127DA) micelles demonstrate outstanding strength and toughness, which is attributed to the efficient energy dissipation through the hydrophobic association in the micelles. The current study further focuses on how the solvent property affects the structures and the mechanical properties of F127DA micelle crosslinked polyacrylamide gels. Binary solvents comprised of dimethyl sulfoxide (DMSO) and water are used to adjust the polymer/solvent interactions, which consequently tune the conformations of the polymer chains in the network. The presence of DMSO significantly decreases the strength but increased the stretchability of the gels, whereas the overall tensile toughness remained unchanged. In situ small‐angle X‐ray scattering measurements reveal the deformation of micelles along with the stretching direction. A structure evolution mechanism upon solvent change is proposed, according to the experimental observations, to explain influence of solvent quality on the mechanical properties of the micelle‐crosslinked gels. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2019 , 57, 473–483     

Morphology and mechanical properties of a novel amorphous polyamide/nanoclay nanocomposite

A novel amorphous polyamide/montmorillonite nanocomposite based on poly(hexamethylene isophthalamide) was successfully prepared by melt intercalation. Wide angle X-ray diffraction and transmission electron microscopy showed that organoclay containing quaternary amine surfactants with phenyl and hydroxyl groups was delaminated in the polymer matrix resulting in well-exfoliated morphologies even at high montmorillonite content. Differential scanning calorimetry results indicated that clay platelets did not induce the formation of a crystalline phase in this amorphous polymer. Tensile tests demonstrated that the addition of nanoclay caused a dramatic increase in Young's modulus (almost twofold) and yield strength of the nanocomposites compared with the homopolymer. The nanocomposites exhibited ductile behavior up to 5 wt % of nanoclay. The improvement in Young's modulus is comparable with semicrystalline aliphatic nylon 6 nanocomposites. Both the main chain amide groups and the amorphous nature of the polyamide are responsible for enhancing the dispersion of the nanofillers, thereby, leading to improved properties of the nanocomposites. The structure-property relationship for these nanocomposites was also explored. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 2605–2617, 2008     

Compatibilizing effect of functionalized polystyrene blends: a study of morphology,thermal, and mechanical properties

Polystyrene (PS), being an amorphous polymer is immiscible with other polymers. To engender miscible blends, PS has been functionalized with an active amino‐functional group on the molecular chains of PS to yield amino‐substituted polystyrene (APS), which serves as a reactive compatibilizer. The compatibilization effect of amino functionalized polystyrene on the rubber toughening was explored and results were compared in terms of morphology, thermal, and mechanical properties of PS/SEBS‐g‐MA versus APS/SEBS‐g‐MA blends. In addition, the effect of rubber content on the blend morphology and mechanical properties were investigated. An appreciable change in the thermal stability of APS blends in comparison with PS blend has been probed. A marked correlation has been observed between phase morphology and thermal stability. Use of APS produced the compatibilized blends which render improved blend morphology, enhanced thermal and mechanical properties. Optimal thermal, morphological and mechanical profiles were depicted by 20‐wt% APS blend. Copyright © 2008 John Wiley & Sons, Ltd.     

Mechanical,thermomechanical, and thermal properties of polystyrene crosslinked with a multifunctional zirconium oxo cluster

Inorganic–organic hybrid materials were prepared by free radical polymerization of styrene in the presence of varying amounts of the cluster Zr₆O₄(OH)₄ (methacrylate)₁₂. Stepwise polymerization allowed the preparation of bubble‐ and crack‐free, transparent bulk samples on a 30 g scale with dimensions required for mechanical testing. Small‐angle X‐ray scattering investigations and transmission electron micrographs revealed that the clusters formed randomly distributed aggregates of random size. Solvent uptake in swelling experiments was related to the cluster proportion. Storage moduli in the glassy state were slightly increased when compared with neat polystyrene, but pronounced plateau moduli were observed above the glass transition temperature, which correlated to the cluster proportion. Plateau moduli were used to calculate network parameters such as network density. Onset temperatures of thermal decomposition and the glass transition temperatures of the cluster‐crosslinked polymers were higher than that of neat polystyrene. Thermal expansion coefficients were unaffected in the glassy state, but were gradually reduced above the glass transition temperature with increasing cluster proportion. Both the tensile moduli at room temperature and the yield points increased when polystyrene was doped with the cluster. The strain hardening moduli, as determined in compression tests at large deformations, increased linearly with the cluster proportion. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 2215–2231, 2007     

Nanostructure and mechanical properties studied during dynamical straining of microfibrillar reinforced HDPE/PA blends

Oriented polymer blends whose major component is high‐density polyethylene (HDPE) are strained until failure. Two‐dimensional (2D) small‐angle X‐ray scattering (SAXS) patterns monitor the nanostructure evolution, which is related to the macroscopic mechanical evolution. Data evaluation methods for high‐precision determination of macroscopic and nanoscopic parameters are presented. The hardest materials exhibit a very inhomogeneous nanodomain structure. During straining, their domains appear to be wedged and inhibit transverse contraction on the nanometer scale. Further components of the blends are polyamide 6 (PA6) or polyamide 12 (PA12) (20–30%) and Yparex® 8102 (YP) as compatibilizer (0–10%). Some HDPE/PA6 blends are additionally loaded with commercial nanoclays (Nanomer® or Cloisite®), the respective amounts being 7.5% and 5% with respect to PA. Blending of HDPE with PA12 causes no synergistic effect. In the absence of nanoclay, PA6 and HDPE form a heterogeneous nanostructure with high macroscopic Young's modulus. After addition of YP a rather homogeneous scaffold structure is observed in which some of the PA6 microfibrils and HDPE crystallites appear to be rigidly connected, but the modulus has decreased. Both kinds of nanoclay induce a transition in the HDPE/PA6 blends from a structure without transverse correlation among the microfibrils into a macrolattice with 3D correlations among the HDPE domains from neighboring microfibrils. In the range of extensions between 0.7 and 3.5%, the scattering entities with 3D correlation show transverse elongation instead of transverse contraction. The process is interpreted as overcoming a correlation barrier executed by the crystallites in an evasion‐upon‐approaching mechanism. During continued straining, the 3D correlation is reduced or completely removed. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 237–250, 2010     

Influence of composition on properties of nylon 6/EVOH blends

In this work, the relationships between composition and properties of Ny6/EVOH system were examined by means of several techniques and the results were interpreted in terms of level of compatibility. Blends of different ratio of Ny6 and EVOH have been processed in a laboratory‐based film blowing extrusion apparatus. Rheological measurements, FTIR and morphological analysis, and thermal and mechanical properties were carried out. Peculiar rheological, thermal, and mechanical behaviors were observed for the blend containing 25% by weight of EVOH. At this composition, FTIR analysis has pointed out that a minimum in molecular motion is achieved as a consequence of a maximum interaction of the polar groups (amide groups of Ny6 and hydroxyl groups of EVOH) involved. Moreover, gas permeability measurements on the blown films have been performed at T = 30°C. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 2445–2455, 1999     

Morphology and mechanical properties of extruded ribbons of LDPE/PA6 blends compatibilized with an ethylene-acrylic acid copolymer

Two grades of low density polyethylene (LDPE) were blended with polyamide-6 (PA) in the 75/25 and 25/75 wt/wt ratios and shaped into ribbons with a Brabender single screw extruder. An ethylene-acrylic acid copolymer (EAA) was used in the 2 phr concentration as a compatibilizer precursor (CP). The morphology of the ribbons and its evolution during high temperature annealing were investigated by scanning electron microscopy (SEM). The results confirmed that EAA does actually behave as a reactive compatibilizer for the LDPE/PA blends. In fact, in the presence of EAA, the interfacial adhesion is improved, the dispersion of the minor phase particles is enhanced and their tendency toward fibrillation is increased, especially for the blends with the higher molar mass LDPE grade. The mechanical properties of the latter blends were found to be considerably enhanced by the addition of EAA, whereas the improvement was relatively modest for the blends with the lower molar mass LDPE. The fracture properties of double end notched samples of the ribbons prepared with the blends containing the lower molar mass LDPE grade were also studied. It was shown that, despite of the increased interfacial adhesion caused by the presence of EAA, the latter plays a measurable positive effect on the fracture properties only for the blends with LDPE as the matrix.