Studies on the blends of modified epoxy resin and carboxyl-terminated polybutadiene (CTPB)—II: thermal and mechanical characteristics

Blend samples were prepared by physical mixing of resole–epoxy blend with carboxyl-terminated polybutadiene (CTPB) liquid rubber ranging between 0 and 25 wt% in the interval of 5 wt%. Resoles were synthesized with phenol and various alkyl phenols. The blends were cured with 40 wt% polyamide. The structural changes during the curing were investigated by infra-red spectroscopic analysis. The presence of CTPB in resole-epoxy blends did not affected the values of cure times and ΔH whereas the gel time decreased up to 15 wt% addition of CTPB in the blends. The blend systems containing p-cresolic resole, epoxy and CTPB showed minimum gel time amongst all other blend samples. A clear-cut two-step mass loss in thermogravimetric (TG) trace of unmodified and CTPB-modified systems was observed. The mechanical properties of the blend samples were found to be affected by the CTPB addition. The plane strain fracture toughness (K _IC) values of CTPB-modified matrix resins were greater that that for the unmodified resole/epoxy blends. This was further verified by scanning electron microscopic (SEM) analysis.     

Co-crosslinking blend of incompatible polymers VI: Poly(vinyl chloride) toughened with polyethylene via a co-crosslinking technique

A binary blend which consists of two incompatible polymers such as poly(vinyl chloride) and polyethylene has been performed through a partial co-crosslinking reaction with peroxide to give a co-crosslinked blend with a uniform dispersion of small polyethylene particles and with an improved mechanical property. The results are obtained through the formation of a co-crosslinked product which acts as a potential solid phase dispersant as well as a well-bonded reinforcing interlayer on polyethylene particles uniformly dispersed in poly(vinyl chloride) matrix. The resulting blends (PVC/PE=10/90 wt) give carbon spherules of 0.5 to 1m diameter through pressure-carbonization at 650° C for 1 h.     

UV固化型丙烯酸酯压敏胶的制备及表征

介绍了用BPO为引发剂、乙酸乙酯为溶剂、丙烯酸丁酯(BA)为粘性单体、乙酸乙烯酯(VAc)为内聚单体、丙烯酸(AA)为改性单体三元共聚合成UV固化型丙烯酸酯压敏胶的方法。研究了该压敏胶中各组分和反应条件对其物理-化学性能的影响,得出较优的制备条件是温度为84℃、反应时间为8h、其中单体加入量比为BA:VAc:AA=9:6:4、引发剂总用量为0.45%(wt),并用红外光谱仪、示差扫描量热仪对其合成的压敏胶进行了表征。     

Tear and wear of thermoplastic elastomers from blends of poly(propylene) and ethylene vinyl acetate rubber

Tear and wear properties of thermoplastic elastomers from blends of poly(propylene) (PP) and ethylene vinyl acetate rubber have been studied with special reference to the effect of blend ratios and dynamic crosslinking of the rubber phase. Both tear and wear resistance of the composites were found to increase with increasing proportion of the PP phase. Dynamic crosslinking of the blends containing higher proportions of the rubber phase (> 60%) increases the wear and tear properties, but blends containing higher proportions of the plastic phase show a decrease in properties due to the degradation of the PP phase. Attempts have been made to correlate the changes in properties with the morphology of system. In order to understand the mechanism of failure, the tear and wear fracture surfaces have been examined by scanning electron microscopy. The fractographs have been correlated with the strength and type of failure of these blends.     

Blending and oxygen permeation properties of the blown films of blends of modified polyamide and ethylene vinyl alcohol copolymer with varying vinyl alcohol contents

The oxygen permeation and blending properties of the MPAEVOH blends of modified polyamide (MPA) and ethylene vinyl alcohol copolymer (EVOH) with varying vinyl alcohol contents were systematically investigated in this study. The oxygen permeation rates of EVOH film specimens are dramatically slower than that of the PE specimen and reduce significantly as their vinyl alcohol contents increase. After blending EVOH in MPA resin, the oxygen permeation rates of each MPAEVOH series film specimens reduce significantly as their EVOH and/or vinyl alcohol contents increase, respectively. At some optimum compositions, the oxygen permeation rates of the MPAEVOH film specimens are even lower than that of the pure EVOH film specimen with a vinyl alcohol content of 52 wt%. On the other hand, the average radius (R _f), volume (V _f) of the free-volume-cavities and fractional free-volume (F _v) values of each MPAEVOH series specimens reduce significantly as their EVOH and/or vinyl alcohol contents increase. These interesting barrier and free-volume properties of the EVOH and MPAEVOH specimens with varying vinyl alcohol contents were investigated in terms of the intermolecular interaction and/or free-volume properties in the amorphous phases of the EVOH and MPAEVOH specimens obtained in this study.     

Miscible blends from rigid poly(vinyl chloride) and epoxidized natural rubber

Miscible blends of rigid poly(vinyl chloride), PVC, and epoxidized natural rubber (ENR) having 50 mol % epoxidation level, are prepared in a Brabender Plasticorder by the melt-mixing technique. Changes in Brabender torque and temperature, density, dynamic mechanical properties and DSC thermograms of the samples are studied as a function of blend composition. The PVC-ENR blends behave as a compatible system as is evident from the singleT _g observed both in dynamic mechanical analysis (DMA) and differential scanning calorimetry (DSC). The moderate level broadening of theT _g zone in blends is due to microinhomogeneity, which may arise from the particle structures of PVC perturbing the molecular level mixing of PVC and ENR. Scanning electron microscopic studies were conducted on nitric acid-etched samples and the results showed continuous structures of blend components as well as the occurrence of solvent-induced cracks in high PVC blends.     

Crystallisation and miscibility of poly(ethylene oxide)/poly(vinyl chloride) blends

Isothermal crystallisation of blends of Poly(ethylene oxide) and Poly(vinyl chloride), PEO/PVC, was analysed by differential scanning calorimetry (DSC). The influence of the amorphous polymer, PVC, on crystallisation rate of PEO was investigated using pure PEO as reference. Pure PEO and PEO/PVC blends were submitted to different crystallisation temperatures (from 40 to 58°C) and crystallisation times (from 1 to 72 h). Using the Hoffman-Weeks plot procedure, the equilibrium melting temperature, T _m°, was determined for pure PEO and for PEO/PVC blends with compositions (in wt%): 90/10, 80/20, 70/30, 60/40, 50/50, 40/60, 30/70 and 20/80. The lamellar thickness factor of PEO crystals for pure PEO and for the blends showed a strong decrease when the PVC content was higher than 60 wt%. A small depression in T _m° was verified as the composition of PVC was increased. From the depression in T _m° the polymer-polymer interaction parameter, ₁₂, was evaluated using the Nishi-Wang equation. The results indicate that the miscibility between PEO and PVC in the molten state depends on the blend composition. The crystallisation rate also depends on the blend composition: the richer in PVC is the blend, the slower the crystallisation process.     

Physical and biological stability of dehydro-thermally crosslinked collagen—poly(vinyl alcohol) blends

Dehydro-thermal treatments for 3, 24 and 72 h were used to crosslink blends of collagen and poly(vinyl alcohol) with various compositions. This crosslinking method increases the biological stabilityin vitro of collagen, as was established by an enzymatic test. When the poly(vinyl alcohol) content is not more than 20% the resistance of collagen to enzymatic digestion is not affected by the presence of the synthetic component. A higher content of poly(vinyl alcohol) produces a steric hindrance screening that enhances the resistance of collagen to the collagenase. Dehydro-thermal treatment performed for 24 and 72 h increases the crystallinity of poly(vinyl alcohol), thus reducing the solubility of this component of the blend. Calorimetric analysis was carried out by differential scanning calorimetry to investigate the structure and the thermal stability of the blends. Dehydro-thermal treatments carried out for 24 and 72 h induce high degrees of crosslinking in collagen and high crystallinity in poly(vinyl alcohol). The two components of the blend seem to create independent structures and the blend can show interpenetrating-network-like behaviour.     

Characterization of hydrogel blends of poly(vinyl pyrrolidone) and poly(vinyl alcohol-vinyl acetate)

Hydrogel blends were prepared from water-soluble polymers of poly(vinyl alcohol-vinyl acetate) and poly(vinyl pyrrolidone). The method of preparation was optimized and different compositions of blends were characterized. The effect of thermal treatment and the introduction of an aldehydic crosslinking agent in the blend was also studied. The swelling characteristics of the various compositions, their thermal behaviour and the state of water was examined. Mechanical properties of the hydrogels were determined and it was observed that blends containing glutaraldehyde produced materials with good mechanical integrity and high water contents.     

Extruded Blends of Chitosan and Ethylene Copolymers for Antimicrobial Packaging

Chitosan was melt‐processed with an ethylene methyl acrylate copolymer ionomer and with an ethylene vinyl acetate copolymer to create antimicrobial extruded films. The key to obtaining a successful antimicrobial blend was the use of solid chitosonium acetate that remained after evaporation of water from the chitosan solution. When solid free‐flowing powders of chitosonium acetate were formed by spray drying chitosan solutions, blended in an extruder (at 2.5% and 4% chitosan) with Elvax® 3175 ethylene vinyl acetate copolymer, and extruded through a film die onto a chill roll to form films, the films exhibited antimicrobial activity against Escherichia coli 25922, Salmonella enterica serovar Enteritidis Nal^R, and Listeria monocytogenes Scott A. The log₁₀ reductions in CFU/ml after 24 h in a shake‐flask test were near 2 for films containing 4% chitosan. This melt‐blending/extrusion approach is expected to open applications for chitosan‐based antimicrobial packages and articles that were impossible or impractical with chitosan coatings. Copyright © 2011 John Wiley & Sons, Ltd.     

Low temperature fracture properties of polymer-modified asphalts relationships with the morphology

A methodology for studying the relationships between fracture behavior and morphology of polymer-modified asphalts used as binders was developed by using the linear elastic fracture mechanics (LEFM) method and confocal laser scanning and environmental and cryo-scanning electron microscopies. Different types of polymers were used as modifiers: (i) copolymers from ethylene and methyl acrylate (EMA), butyl acrylate (EBA) or, vinyl acetate (EVA); (ii) diblock or star-shape triblock styrene-butadiene copolymers (SB or SBS^*). The 4 to 6 wt. % blends display an heterogeneous structure with a polymer-rich dispersed phase based on the initial polymer swollen by the aromatic fractions of the asphalt. The fracture toughness of the blends is higher than for the neat asphalt even if KIc of blends remains low compared to usual polymer blends due to the brittleness of the asphalt matrix. The fracture behavior which is strongly dependent on the nature of the polymer is discussed from the toughening mechanisms given for the filled polymers and the polymer blends. The EBA, SB, and SBS-based blends compared to the EMA and EVA-based ones display a higher KIc due to the elastomeric behavior of the polymer phase leading to a more efficient energy dissipation during crack propagation. The sample prepared with 4% crosslinked SB (Styrelf) and the corresponding physical blend (non-crosslinked) display the better fracture properties.     

PVA/PBA乳胶互穿聚合物网络阻尼材料的研究

用种子乳液聚合的方法合成了一系列PVA／PBA乳胶互穿聚合物网络，提出了用相容程度来定量表征聚合物共混物中两组分的相容性，动态力学谱结果表明，乳胶双向互穿以及BA同AN共聚可极大地改善PBA与PVS的相容性和乳胶IPN的阻尼性能。     

Performance characteristics of compatibilized ternary Nylon 6/ABS/LCP in-situ composites

Ternary Nylon 6/poly(acrylonitrile-butadiene-styrene)(ABS)/liquid crystalline polymer (LCP) blends compatibilized by the maleic anhydride-grafted polypropylene (MAP) and solid epoxy resin (bisphenol type-A) were injection molded. Thermoplastic matrix consisting of Nylon 6/ABS (60/40) (wt%) was melt blended with various LCP (Vectra A950) contents. The effects of compatibilizer additions on the structure-mechanical property relationship of the in-situ composites reinforced with LCP were investigated. SEM observation revealed that the additions of epoxy and MAP compatibilizers to the Nylon 6/ABS/LCP blend were very effective to enhance the interfacial adhesion of its phase components. Consequently, extended long and fine LCP fibrils were formed in the skin section of in-situ composites. Tensile measurements revealed that uncompatibilized Nylon 6/ABS/LCP blend exhibited lower strength, stiffness and impact toughness. However, the incorporation of MAP and epoxy resin compatibilizers into Nylon 6/ABS/LCP blend improved its tensile strength, stiffness and impact toughness considerably. This was due to the compatibilizers effectively promoted stress transfer at the interfacial phase regions of ternary in-situ composites. The compatibilized composites exhibited mechanical anisotropy, especially for the tensile strength. Thermogravimetric measurements showed that the heat resistance and heat stability of the in-situ composites tended to increase with increasing LCP content.     

Latex derived blends of poly(vinyl acetate) and natural rubber: thermal and mechanical properties

Poly(vinyl acetate) (PVAc) and natural rubber blends (NR) were prepared by low shear blending of the corresponding lattices. Thin films were cast using a doctor blade technique. SEM and DMA confirmed the essential immiscibility of the two polymers. Even when the poly(vinyl acetate) forms the matrix phase, it still contains domains encapsulated by a rubber phase where particles that resemble the original latex are visible. This incomplete droplet coalescence of the poly(vinyl acetate) is attributed to the fact that the rubber latex droplets were an order of magnitude smaller than the poly(vinyl acetate) latex droplets. Tensile testing revealed a nonlinear dependence of tensile strength and elongation on blend composition. Surprisingly good tensile yield strengths were obtained at intermediate to high PVAc contents. Thermogravimetric analysis of degradation in air and nitrogen atmospheres indicated independent degradation of the parent polymers.     

The effect of matrix polarity on the properties of poly(o-methoxyaniline)–EVA blends

Poly(o-methoxyaniline) (POMA) doped with p-toluene sulfonic acid (TSA) was successfully melt blended with ethylene vinyl acetate copolymer (EVA). The effect of the matrix polarity as well as the blend composition on the properties of the blends was investigated using two grades of EVA as matrix. The lower polarity EVA contains 8% vinyl acetate (VA) (EVA₈) and the higher polarity EVA contains 33% VA (EVA₃₃). The surface resistivity of the POMA-EVA blends was found to decrease with an increase of POMA loading. The POMA-EVA₈ blends had a lower surface resistivity than POMA-EVA₃₃ blends which is attributed to the presence of a higher proportion of conductive POMA particles in the surface region resulting from the larger polarity difference between the POMA and the EVA₈ matrix. More uniform dispersion is observed from scanning electron microscopy (energy-dispersive X-ray spectroscopy) for POMA in EVA₃₃ compared to POMA in EVA₈ and this has been interpreted as being a consequence of the similar polarities between POMA and EVA₃₃. The mechanical properties of the blends were found to be affected by both POMA loading and matrix polarity. The oxygen barrier property of the POMA-EVA blends was found to increase with POMA loading in both high and low polarity EVA matrices.     

以两亲聚合物为乳化剂研制高固含量乳液

合成了聚（醋酸乙烯酯／丙烯酸钠）Ｐ（ＶＡＣ／ＡＡＮａ）两亲聚合物,并以此为乳化剂合成了新型无皂聚（醋酸乙烯酯／丙烯酸丁酯）Ｐ（ＶＡＣ／ＢＡ）共聚乳液。结果表明,该乳液固含量高,稳定性好,为接性能强,其综合性能明显优于常规乳液。     

Kinetic and structural interpretations of post-yield crack resistance behavior of polyamide-6/polyolefin-g-maleic anhydride blends

Binary blends of polyamide-6 (PA-6)/polypropylene-grafted-maleic anhydride (PP-g-MA) and PA-6/low density polyethylene-grafted-maleic anhydride (LDPE-g-MA) were prepared with varied concentration (0–30 wt%) of maleic anhydride-grafted polyolefinic (PP) moiety as the impact modifier. The microstructural attributes and thermal properties of the blends were characterized by WAXD, FTIR, SEM, DSC, and TGA. The WAXD/DSC studies have revealed that the crystallinity of the blends decreased with the increase in the PP modifier whereas the onset of degradation temperature remained nearly unaffected. Comparative assessment of the crack toughness behavior of the blends has been carried out following the essential work of fracture (EWF) approach based on post-yield fracture mechanics (PYFM) concept. The kinetics of crack propagation of the blends has been discussed in the realms of structural and compositional parameters. An enhancement in the toughness (resistance to stable crack propagation) as indicated by a maximum in the non-EWF (βw _p) values have been observed at 10 and 20 wt% followed by a sharp and consistent drop in the composition regime of 10–20 and 20–30 wt% of PP-g-MA and LDPE-g-MA, respectively; conceptually implying possible ductile-to-semiductile transitions in the blend systems. The equivalence of PYFM–EPFM fracture parameters have been discussed following inequality criterion. Fractured surface morphology investigations revealed that the failure mode of the blends undergo a systematic transition from matrix-controlled homogeneous flow/deformation in the PP/polyamide phase to blend composition-dependent changes in the modes and extent of fibrillation via cavitation and shear-banding mechanisms.     

Effects of compatibilization on the essential work of fracture parameters of in situ microfiber reinforced poly(ethylene terephtahalate)/polyethylene blend

A novel in situ microfiber reinforced blend (MRB) based on poly(ethylene terephthalate) (PET) and polyethylene (PE) was prepared by extrusion-hot stretching-quenching process, and was compatibilized with ethylene vinyl acetate copolymer (EVA) in the presence of the transesterification reaction catalyst, dibutyltin oxide (DBTO). The effects of compatibilization on the essential work of fracture parameters in PET/PE MRB were examined. It is found that the specific essential work of fracture (w_e) and the specific non-essential work of fracture (w_p) were significantly increased, when adding 1 and 2.5 phr of EVA to PET/PE MRB and it was further increased with the addition of 0.5 phr of DBTO as the catalyst of the transesterification reaction. The fracture surfaces study by scanning electron microscope (SEM) further proved that EVA is a successful compatibilizer for PET/PP blend. The morphology study of the blends shows that the well-defined fibers with the diameter of several microns were generated in situ during melt extrusion-hot stretch-quenching processing.     

分散剂对聚醋酸乙烯酯共混乳液的影响

对聚醋酸乙烯酯乳液改性进行了研究,通过与丙烯酸丁酯共聚来提高粘接强度,加入分散剂来调节乳液的黏度,改善雾化效果。具体讨论了分散剂的作用以及分散剂的用量对粘接强度和乳液性能的影响,通过透射电镜照片,比较了分散剂加入前后乳液的分散情况。结果表明,当加入适量的丙烯酸丁酯后,分散剂用量为0.05%时,具有较好的粘接效果,乳液的分散效果较好,稀释稳定性也比较好。     

Mechanical and thermal properties of poly(butylene terephthalate)/poly(ethylene naphthalate), and Nylon66/poly(ethylene naphthalate) blends

The tensile modulus, tensile strength and impact strength of melt blends of (a) poly(ethylene naphthalate) (PEN) and poly(butylene terephalate) (PBT) with 30, 40, 50, 60 and 70 wt% PEN, (b) Nylon66 and PEN with 30, 50 and 70 wt% Nylon66 were measured, and thermal/thermomechanical properties were analysed by differential scanning calorimetry and dynamic mechanical thermal analysis. Scanning electron microscopy was used for examination of the fracture surfaces of the blends.All PBT/PEN blends show two glass transitions corresponding to the presence of two phases: the glass transition temperature, T _g, of the phase with the lower T _g increases with increasing PEN content, and T _g for the phase with higher T _g decreases with increasing PBT content. The implication is that the two polymers are partially miscible, and scanning electron microscopy of fracture surfaces reveals a very small (sub-micron) domain size. Nylon66/PEN blends also show two phases, but the domain size is of the order of m and there is no evidence of partial miscibility.Up to 50 weight proportions PBT does not lower the tensile strength of PBT/PEN blends, and the tensile strength lies between values predicted by the rule of mixtures and a modified rule of mixtures. Incorporation of at least 40% PEN in PBT increases impact strength, but blending with smaller proportions of PEN decreases impact strength. By contrast, blending of Ny66 and PEN results in reduction of tensile strength for all blend compositions.