Effect of EVA copolymer containing different VA content on the thermal and rheological properties of bio-based high-density polyethylene/ethylene vinyl acetate blends

The effect of ethylene vinyl acetate (EVA) concentration and vinyl acetate (VA) content of EVA on the mechanical, morphological, and rheological properties of bio-based high-density polyethylene (BioPE)/EVA blends was investigated. The blends were characterized by X-ray diffraction, differential scanning calorimetry, scanning electron microscopy, and rheological measurements under oscillatory shear flow. The degree of crystallinity of BioPE decreased with the increase in the EVA concentration and was unaffected with the increase in the VA content. DMTA results showed a decrease in the storage modulus (E′) with the increase in EVA content and that the BioPE/EVA19 blends showed higher E′ values than BioPE/EVA28 blend. The impact strength substantially increased with the addition of EVA concentration above 5 mass% and was higher for the blends containing the highest VA content. The blends containing a higher content of VA exhibited the higher EVA dispersed phase domain size, which increased with the increase in EVA concentration. The complex viscosity increased with the increase in the EVA content, being higher for the BioPE/EVA blends containing higher VA content. The storage modulus increased, at low frequencies, with the increase in the EVA content and can be ascribed to the increase in the EVA dispersed phase domain size.

     

Toughening of poly(lactic acid) by ethylene-co-vinyl acetate copolymer with different vinyl acetate contents

The well-known bio-based and biocompostable poly(lactic acid), PLA, suffers from brittleness and a low heat distortion temperature. In this paper, we address a possible route to make PLA tough(er) by blending with ethylene-co-vinyl acetate (EVA) with different vinyl acetate contents. The compatibility and phase morphology of the PLA/EVA blends was controlled by the ratio of vinyl acetate and ethylene in the random copolymers. Tough PLA/EVA blends with increased impact toughness, up to a factor of 30, were obtained with a maximum toughness at a vinyl acetate content of approximately 50 wt.%. The local deformation mechanism was well studied by TEM, SAXS and SEM. It revealed that internal rubber cavitation in combination with matrix yielding is the dominant toughening mechanism for the PLA/EVA blends under both impact and tensile testing conditions.     

聚乳酸/乙烯-醋酸乙烯酯共聚物共混物的形态与黏弹行为

熔融共混制备了不同组分比的聚乳酸(PLA)/乙烯-醋酸乙烯酯共聚物(EVA)共混物,采用扫描电子显微镜(SEM)、溶剂选择性蚀刻和旋转流变仪研究了共混物不相容的相形态及其黏弹响应.研究结果表明,PLA/EVA共混物为典型的热力学不相容体系,两基体组分间的界面张力约为2.2 mN/m;因此随组分比的不同,共混物表现出"海-岛"分散和双连续的不相容相形态;体系中EVA的相反转浓度约为50 wt%～60 wt%,这与黏性模型对相反点预测的结果一致;与双连续相形态的体系相比,乳液模型能够更好的描述具有"海-岛"分散形态的体系的线性黏弹响应,共混体系相对较宽的相反转区域主要源于两组分间较大的弹性比以及EVA自身的屈服行为.     

Effect of EVM/EVA‐g‐MAH ratio on the structure and properties of nylon 1010 blends

The nylon 1010/ethylene‐vinyl acetate rubber (EVM)/maleated ethylene‐vinyl acetate copolymers (EVA‐g‐MAH) ternary blends were prepared. The effect of EVM/EVA‐g‐MAH ratio on the toughness of blends was examined. A super tough nylon 1010 blends were obtained by the incorporation of both EVM and EVA‐g‐MAH. Impact essential work of fracture (EWF) model was used to characterize the fracture behavior of the blends. The nylon/EVM/EVA‐g‐MAH (80/15/5) blend had the highest total fracture energy at a given ligament length (5 mm) and the highest dissipative energy density among all the studied blends. Scanning electron microscopy images showed the EVM and EVA‐g‐MAH existed as spherical particles in nylon 1010 matrix and their size decreased gradually with increasing EVA‐g‐MAH content. Large plastic deformation was observed on the impact fracture surface of the nylon/EVM/EVA‐g‐MAH (80/15/5) blend and related to its high impact strength. Then with increasing EVA‐g‐MAH proportion, the matrix shear yielding of nylon/EVM/EVA‐g‐MAH blends became less obvious. EVM and EVA‐g‐MAH greatly increased the apparent viscosity of nylon 1010, especially at low shear rates. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 877–887, 2009     

利用~1H-NMR研究HDPE/PET/EVA共混体系的酯交换反应

本文在选用EVA作为HDPE/PET共混体系增容剂的基础上 ,通过双螺杆反应挤出熔融加工过程 ,促使EVA侧基上的酯基官能团与PET组分主链上的酯基在适当催化剂———有机金属化合物存在的条件下发生酯交换反应 .1H NMR结果表明 ,酯交换反应的产生在共混体系界面原位形成接枝或交联的PET EVA共聚物 ,且主要是以生成接枝共聚物的反应为主 .     

Thermorheological analysis of PVC blends

The effect of temperature on dynamic viscoelastic measurements of miscible poly (vinyl chloride) (PVC)/ethylene‐vinyl acetate–carbon monoxide terpolymer (EVA‐CO) and immiscible PVC/high‐density polyethylene (HDPE) and PVC/chlorinated polyethylene (CPE) molten blends is discussed. PVC plasticized with di(2 ethyl hexyl) phthalate (PVC/DOP) and CaCO₃ filled HDPE (HDPE/CaCO₃) are also considered for comparison purposes. Thermorheological complexity is analyzed using two time–temperature superposition methods: double logarithmic plots of storage modulus, G′, vs. loss modulus, G″, and loss tangent, tan δ, vs. complex modulus, G*, plots. Both methods reveal that miscible PVC/EVA‐CO and PVC/DOP systems are thermorheologically complex, which is explained by the capacity of PVC to form microdomains or crystallites during mixing and following cooling of the blends. For immiscible PVC/HDPE and PVC/CPE blends the results of log G′ vs. log G″ show temperature independence. However, when tan δ vs. log G* plots are used, the immiscible blends are shown to be thermorheologically complex, indicating that the morphology observed by microscopy and constitued by a PVC phase dispersed in a HDPE or CPE matrix, is reflected by this rheological technique. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 469–477, 2000     

Reduced percolation thresholds of immiscible conductive blends

The DC conductivity of polymer blends composed of poly(ethylene‐co‐vinyl acetate) (EVA) and high density polyethylene (HDPE), where a conductive carbon black (CB) had been preferentially blended into the HDPE, were investigated to establish the percolation characteristics. The blends exhibited reduced percolation thresholds and enhanced conductivities above that of the individually carbon filled HDPE and EVA. The percolation threshold of the EVA/HDPE/CB composites was between 3.6 and 4.2 wt % carbon black, where the volume resistivity changed by 8 orders of magnitude. This threshold is at a significantly lower carbon content than the individually filled HDPE or EVA. At a carbon black loading of 4.8 wt %, the EVA/HDPE/CB composite exhibits a volume resistivity which is approximately 14 and 11 orders of magnitude lower than the HDPE/CB and EVA/CB systems, respectively, at the same level of incorporated carbon black. The dielectric response of the ternary composites, at a temperature of 23°C and frequency of 1 kHz, exhibited an abrupt increase of ca. 252% at a carbon concentration of 4.8 wt %, suggesting that the percolation threshold is somewhat higher than the range predicted from DC conductivity measurements. Percolating composites with increasing levels of carbon black exhibit significantly greater relative permittivity and dielectric loss factors, with the composite containing 6 wt % of carbon black having a value of ϵ′ ≈ 79 and ϵ″ ≈ 14. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 1899–1910, 1999     

Electrically conductive,melt‐processed ternary blends of polyaniline/dodecylbenzene sulfonic acid,ethylene/vinyl acetate,and low‐density polyethylene

Although polyaniline (PANI) has high conductivity and relatively good environmental and thermal stability and is easily synthesized, the intractability of this intrinsically conducting polymer with a melting procedure prevents extensive applications. This work was designed to process PANI with a melting blend method with current thermoplastic polymers. PANI in an emeraldine base form was plasticized and doped with dodecylbenzene sulfonic acid (DBSA) to prepare a conductive complex (PANI–DBSA). PANI–DBSA, low‐density polyethylene (LDPE), and an ethylene/vinyl acetate copolymer (EVA) were blended in a twin‐rotor mixer. The blending procedure was monitored, including the changes in the temperature, torque moment, and work. As expected, the conductivity of ternary PANI–DBSA/LDPE/EVA was higher by one order of magnitude than that of binary PANI–DBSA/LDPE, and this was attributed to the PANI–DBSA phase being preferentially located in the EVA phase. An investigation of the morphology of the polymer blends with high‐resolution optical microscopy indicated that PANI–DBSA formed a conducting network at a high concentration of PANI–DBSA. The thermal and crystalline properties of the polymer blends were measured with differential scanning calorimetry. The mechanical properties were also measured. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 3750–3758, 2004     

EFFECT OF VINYL ACETATE CONTENT ON THE MECHANICAL PROPERTIES AND MORPHOLOGICAL STRUCTURES OF POLYPROPYLENE

The effect of vinyl acetate （VA） content in ethylene vinyl acetate （EVA） copolyrner on the mechanical properties of polypropylene was investigated. Three different EVA copolymers with concentrations of 3 wt%, 6 wt%, 9 wt%, 12 wt% and 15 wt%, were blended to polypropylene. The mechanical properties such as yield and tensile strengths, elastic modulus, Izod impact strength, hardness and melt flow index of the blends were investigated. Relationship between type of vinyl acetate and concentrations, mechanical, MFI and morphological properties were explored.     

Selective distribution,reinforcement, and toughening roles of MWCNTs in immiscible polypropylene/ethylene‐co‐vinyl acetate blends

Polypropylene/ethylene‐co‐vinyl acetate (PP/EVA) nanocomposites with functionalized multiwalled carbon nanotubes (FMWCNTs) have been prepared. The dissolution experiment, transmission electronic microscope, and scanning electronic microscope characterizations prove that, in the nanocomposites with sea–island morphology, although some FMWCNTs are observed in both PP and EVA phases, most of FMWCNTs distribute at the interface; however, in the nanocomposites with cocontinuous morphology, FMWCNTs mainly distribute in EVA phase. Further results based on (differential scanning calorimetry) measurements show that the different dispersion states of FMWCNTs, which are resulted by the different melt blending sequences, result in the different crystallization behaviors of PP matrix. The mechanical measurements show that FMWCNTs exhibit apparent reinforcement and toughening effects for immiscible PP/EVA blends, and such effects are greatly dependent upon the blending sequences. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 1882–1892, 2010     

Effect of Electron Beam Irradiation and Ethylene Vinyl Acetate Copolymer on the Properties of NBR/HDPE Blends

The mechanical and physical properties of blends based essentially on nitrile butadiene rubber (NBR) and different ratios of high density polyethylene (HDPE) up to 25 parts per hundred part of rubber (phr) before and after electron beam irradiation were investigated. The values of tensile strength (TS), tensile modulus at 50% elongation (M₅₀), hardness and gel fraction % (GF%) of NBR/HDPE blends were increased with both irradiation dose and by increasing the content of HDPE in the blends. On the other hand, the values of elongation at break (E _b ) were decreased with both irradiation dose and the content of HDPE in the blends. By loading NBR/HDPE (100/25) blend with ethylene vinyl acetate (EVA) copolymer the mechanical and physico-chemical properties were improved. Moreover, the degree of improvement is proportional to the loading content of EVA.     

The effect of various compatibilizers on thermal,mechanical, and morphological properties of polystyrene/polypropylene blends

The effects of various compatibilizers on thermal, mechanical and morphological properties of 50/50 polypropylene/polystyrene blends were investigated. Various compatibilizers, polystyrene-(ethylene/butylenes/ styrene) (SEBS), ethylene vinyl acetate (EVA), polystyrene-butylene rubber (SBR) and blend of compatibilizers SEBS/PP-g-MAH, EVA/PP-g-MAH, and SBR/PP-g-MAH were used. Differential scanning calorimetry, thermogravimetric analysis, wide-angle X-ray scattering, scanning electron microscopy, microhardness, and Izod impact strength were adopted. It was found that the influence of various compatibilizers was appeared on all the properties studied. The properties of the blends compatibilized with SEBS, EVA, and SBR are very distinct from those of blends compatibilized with blend of compatibilizers. Results show that compatibilized blends with the blend of compatibilizers EVA/PP-g-MAH, SBR/PP-g-MAH, and SEBS/PP-g-MAH or SBR were relatively more stable than the uncompatibilized blend and blend compatibilized with SEBS or EVA. The compatibilizer does not only reduce the interfacial tension or increase the phase interfacial adhesion between the immiscible polymers, but greatly affects the degree of crystallinity of blends.

     

A comparative study of UV aging characteristics of poly(ethylene‐co‐vinyl acetate) and poly(ethylene‐co‐vinyl acetate)/carbon black mixture

In this comparative study, the effect of carbon black (CB) on the UV aging characteristics of poly(ethylene‐co‐vinyl acetate) (EVA) was investigated. EVA, containing 13% vinyl acetate (VA), and poly(ethylene‐co‐vinyl acetate)/carbon black mixture (EVA/CB), containing 13% VA and 1% CB, were aged by means of UV light with a wavelength in the vicinity of 259 nm, in air, up to 400 hr. Sol‐gel analyses were made to determine the percentage gelation of both virgin and aged samples. FT‐IR measurements were performed to follow the chemical changes which took place in the samples during aging. Dynamic and isothermal thermogravimetry studies were performed for determination of the thermal stabilities of virgin and aged samples. Sol‐gel analysis results showed that EVA itself has a tendency to form a gel under UV irradiation. EVA/CB, however, becomes a gel to a smaller extent, comparatively, under the same conditions. As a result of FT‐IR measurements, some oxidation products such as ketone, lactone and vinyl species were observed through UV ageing of EVA and EVA/CB. Thermal analysis experiments exhibited that the thermal stabilities of EVA and EVA/CB decreased, to a similar extent through UV aging. Copyright © 2004 John Wiley & Sons, Ltd.     

A comparative study of thermal ageing characteristics of poly(ethylene‐co‐vinyl acetate) and poly(ethylene‐co‐vinyl acetate)/carbon black mixture

In this comparative study, the effect of carbon black (CB) on the thermal ageing characteristics of poly(ethylene‐co‐vinyl acetate) (EVA) was investigated. EVA, containing 13% vinyl acetate (VA), and poly(ethylene‐co‐vinyl acetate)/carbon black mixture (EVA/CB) containing 13% VA and 1% CB were aged at 85°C in air up to 30 weeks. Sol‐gel analysis experiments were made to determine the percentage gelation of both virgin and aged samples. FT‐IR measurements were performed to follow the chemical changes which took place in the samples during ageing. Dynamic and isothermal thermogravimetric studies were performed for determination of the thermal stabilities of virgin and aged samples. Sol‐gel analysis results showed that EVA itself has a tendency to form a gel under thermal treatment, whereas EVA/CB never becomes a gel when being thermally aged under the same conditions. As a result of FT‐IR measurements, some oxidation products such as ketone, lactone and vinyl species were observed through thermal ageing of EVA. It is also clear that these kind of oxidation products did not appear to a considerable extent in EVA/CB. Thermal analysis experiments exhibit that thermal stability of EVA decreased through thermal ageing; whereas that of EVA/CB remained almost unchanged. Copyright © 2004 John Wiley & Sons, Ltd.     

EFFECT OF COMPATIBILITY ON PHASE MORPHOLOGY AND ORIENTATION OF ISOTACTIC POLYPROPYLENE （IPP） BLENDS OBTAINED BY DYNAMIC PACKING INJECTION MOLDING

The effect of compatibility on phase morphology and orientation of isotactic polypropylene （iPP） blends under shear stress was investigated via dynamic packing injection molding （DPIM）. The compatibility of iPP blended with other polymers, namely, atactic polypropylene （aPP）, octane-ethylene copolymer （POE）, ethylene-propylene-diene rubber （EPDM） and poly（ethylene-co-vinyl acetate） （EVA）, have first been studied using dynamic mechanical analysis （DMA）. These blends were subjected to DPIM, which relies on the application of shear stress fields to the melt/solid interfaces during the packing stage by means of hydraulically actuated pistons. The phase morphology, orientation and mechanical properties of the injection-molded samples were characterized by SEM, 2D WAXS and Instron. For incompatible iPP/EVA blends, a much elongated and deformed EVA particles and a higher degree of iPP chain orientation were observed under the effect of shear. However, for compatible iPP/aPP blends, a less deformed and elongated aPP particles and less oriented iPP chains were deduced. It can be concluded that the compatibility between the components decreases the deformation and orientation in the polymer blends. This is most likely due to the hindering effect, resulting from the molecular entanglement and interaction in the compatible system.     

On the wall slip of polymer blends

The slip flow of the polypropylene (PP)/poly[ethylene‐co‐(vinyl acetate)] (EVA) system was studied in a capillary rheometer for shear rates of 40–1000 s^?1 at four temperatures. Three dies made of aluminum with a length/diameter (L/D) ratio of 15 and diameters of 1.59, 1.19, and 0.79 mm provided the flow data. Calculations of the slip velocity by the Mooney method showed power‐law behavior with the stress. Blends were prepared at various proportions of PP and EVA for observation of the variation of the slip velocity for different compositions and temperatures. Direct microscopic observations of the slip layer on extruded samples showed domains of the dispersed phase unevenly distributed between the slip layer and the core and provided estimates of the thickness of the layer adjacent to the capillary wall. Results showed that the viscosity in the slip layer was 10–100 times lower than that in the bulk for the same value of the shear stress. In terms of the extrapolation length, the development of the slip layer was the result of different disentanglement dynamics of the molecules in the slip layer in comparison with those in the bulk. © 2002 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 40: 303–316, 2002     

Effect of the liquid–liquid phase separation on the crystallization behavior and mechanical properties of poly(ethylene‐ran‐vinyl acetate) and paraffin wax blend

The effect of liquid–liquid phase‐separation (LLPS) on the crystallization behavior and mechanical properties of poly(ethylene‐ran‐vinyl acetate) (EVA) with various amounts of vinyl acetate and paraffin wax blend was investigated. The blend of EVA‐H (9.5% vinyl acetate) and the wax became homogeneous at temperatures greater than its upper critical solution temperature (UCST) (98°C), and an LLPS was observed between UCST and the melting point of 88°C for EVA‐H in the blend. The existence of the LLPS is attributed to the relatively large amount of the hydrophilic component of vinyl acetate in EVA, although the molecular weight of the wax was just 560. However, LLPS did not occur for the EVA/wax blend when the content of vinyl acetate in EVA was less than 3%. This behavior was explained by using the Flory–Huggins lattice model with an effective interaction parameter. The degree of crystallinity of EVA‐H in the EVA‐H/wax blend, judged from a melting endothermic peak in differential scanning calorimeter (DSC) thermograms obtained during heating runs, decreased with increasing duration time in the LLPS region. The flexural modulus of the EVA/wax blend became maximum at certain blend composition (about 30 ∼ 40 wt % EVA depending upon the amount of vinyl acetate). This behavior can be explained by the fact that this blend composition has the largest relative degree of crystallinity of EVA measured by DSC and wide‐angle X‐ray scattering method. We found that the flexural modulus of the binder itself is directly related to that of a feedstock consisting of larger amounts of metal powder and the binder, which can help someone to develop a suitable binder system for a powder injection molding process. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 1991–2005, 1999     

Grafting of polycaprolactone onto poly(ethylene‐co‐vinyl alcohol) and application to polyethylene‐based bioerodable blends

Poly(ethylene‐co‐vinyl acetate) (EVA) powders containing 10 and 20 wt % of vinyl acetate (VAc) units was saponified in ethanol/KOH solution in a heterogeneous manner. Intermolecular interaction between vinyl alcohol(VOH) units in the produced poly(ethylene‐co‐vinyl alcohol) (EVOH) promoted the crystallization of intervening segments composed of ethylene units. Ring opening polymerization of caprolactone (CL) in the presence of EVOH gave EVOH‐g‐PCL graft copolymers with relatively short chain branches. Even though the graft copolymerization was carried out in a homogeneous solution, all the VOH units were not equally reactive for the PCL grafting. And the unreacted VOH units decreased very slowly with the graft copolymerization time. EVOH‐g‐PCL decreased the domain size of the dispersed phase in low density polyethylene (PE)/biodegradable master batch (MB) blends, and thus increased their tensile properties significantly. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 2561–2569, 2002     

Dynamic mechanical behavior of acrylonitrile butadiene rubber/poly(ethylene‐co‐vinyl acetate) blends

The dynamic mechanical behavior of uncrosslinked (thermoplastic) and crosslinked (thermosetting) acrylonitrile butadiene rubber/poly(ethylene‐co‐vinyl acetate) (NBR/EVA) blends was studied with reference to the effect of blend ratio, crosslinking systems, frequency, and temperature. Different crosslinked systems were prepared using peroxide (DCP), sulfur, and mixed crosslink systems. The glass‐transition behavior of the blends was affected by the blend ratio, the nature of crosslinking, and frequency. sThe damping properties of the blends increased with NBR content. The variations in tan δ_max were in accordance with morphology changes in the blends. From tan δ values of peroxide‐cured NBR, EVA, and blends the crosslinking effect of DCP was more predominant in NBR. The morphology of the uncrosslinked blends was examined using scanning electron and optical microscopes. Cocontinuous morphology was observed between 40 and 60 wt % of NBR. The particle size distribution curve of the blends was also drawn. The Arrhenius relationship was used to calculate the activation energy for the glass transition of the blends, and it decreased with an increase in the NBR content. Various theoretical models were used to predict the modulus of the blends. From wide‐angle X‐ray scattering studies, the degree of crystallinity of the blends decreased with an increasing NBR content. The thermal behavior of the uncrosslinked and crosslinked systems of NBR/EVA blends was analyzed using a differential scanning calorimeter. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 1556–1570, 2002     

Kinetic Study of the Accelerating Effect of Coal-burning Additives on the Combustion of Graphite

The relationship between copolymer composition and transition temperatures was studied by means of differential scanning calorimetric analysis and dynamic mechanical spectroscopy. Six samples of ethylene vinyl acetate (EVA) copolymers containing from 5 to 40 mass per cent of vinyl acetate (VA) were studied. The differential scanning calorimetric analysis revealed that each EVA copolymer displays two endothermic peaks (T_m1 and T_m2 ) in the melting zone. Dynamic mechanical spectroscopy was used to determine the primary relaxation temperature (T_α ) for EVA copolymers. This latter characteristic is relatively insensitive to the level of vinyl acetate contained in the copolymer and is influenced by the pulsation frequency ω, also named the angular frequency. This revised version was published online in July 2006 with corrections to the Cover Date.