Phase behavior of blends of linear low density polyethylene and poly(ethene-propene-1-butene)

The aim of this work was the study of blends of linear low density polyethylene (LLDPE) and an ethene-propene-1-butene terpolymer (t-PP). Two types of polyethylene were used to prepare the blends: an ethene-co-1-hexene (LLDPE(H)) copolymer and an ethene-co-1-octene (LLDPE(O)) copolymer. These copolymers present similar comonomer contents, molar mass, molar mass distribution and catalyst systems, but differ in their comonomer distribution. The blends were obtained through mechanical mixing using a single screw extruder at different compositions: 20, 40, 50, 60 and 80 wt.% of LLDPE. From DSC measurements two separated melting and crystallization peaks were observed and dynamic mechanical analysis showed two glass transitions indicating that LLDPE/t-PP blends are immiscible in amorphous and crystalline phases in the solid state. X-ray diffraction showed that the unit cell parameters of both polymers in the blends remain unchanged independent of the composition of the blend.     

Thermal, ozone and gamma ageing of styrene butadiene rubber and poly(ethylene-co-vinyl acetate) blends

Ageing behaviour of SBR/EVA blends due to the effects of heat, ozone, and gamma radiation was studied with reference to blend ratio, three crosslinking systems (sulfur, peroxide and mixed) and a compatibiliser (SEBS-g-MA). It was found that an increase in the EVA content of the blends enhanced the ageing characteristics. Among the different crosslinking systems, a peroxide cured system exhibited the best retention of properties even after severe ageing. Tensile strength of peroxide cured SBR/EVA blends increased slightly after ageing for three days at 70 °C due to continued crosslinking, whereas tensile strength of all blends decreased on ageing at 100 °C. Compatibilisation with SEBS-g-MA improved the thermal, gamma and water ageing resistance of SBR/EVA blends.     

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     

Photocrosslinking and related properties of intumescent flame‐retardant LLDPE/EVA/IFR blends

The photoinitiated crosslinking of halogen‐free flame retarded linear low density polyethylene/poly(ethylene‐co‐vinyl acetate) blends (LLDPE/EVA) with the intumescent flame retardant (IFR) of phosphorous‐nitrogen compound (NP) in the presence of photoinitiator and crosslinker and their characterization of related properties have been investigated by gel determination, heat extension test, cone calorimeter test (CCT), thermogravimetric analysis (TGA), Fourier transfer infrared (FTIR) spectroscopy, scanning electron microscopy (SEM), mechanical properties measurements, limiting oxygen index (LOI), UL‐94, and water resistance test. The data from the gel content and heat extension rate (HER) show that the LLDPE/EVA/IFR blends filled with NP are readily crosslinked to a gel content of above 75% and the HER values reach about 50% by UV‐irradiation of 5 sec under suitable amount of photoinitiator and crosslinker. The data obtained from the CCT and LOI indicate that photocrosslinking can considerably decrease the heat release rates (HRR) by 10–15%, prolongate the combustion time, and increase two LOI values for the LLDPE/EVA/NP blends UV irradiated for 5 sec. The results from TGA and the dynamic FTIR spectra give the evidence that the photocrosslinked LLDPE/EVA/NP samples show slower thermal degradation rate and higher thermo‐oxidative degradation temperature than the uncrosslinked LLDPE/EVA/NP samples. The morphological structures of charred residues observed by SEM give the positive evidence that the compact charred layers formed from the photocrosslinked LLDPE/EVA/NP samples play an important role in the enhancement of flame retardant and thermal properties. The data from the mechanical tests and water‐resistant measurements show that photocrosslinking can considerably improve the mechanical and water‐resistant properties of LLDPE/EVA/NP samples. Copyright © 2011 John Wiley & Sons, Ltd.     

Effect of electron beam irradiation on dynamic mechanical,thermal and morphological properties of LLDPE and PDMS rubber blends

The effect of electron beam irradiation on the blends of linear low-density polyethylene (LLDPE) and poly dimethyl siloxane rubber (PDMS) prepared over a wide range of compositions starting from 70:30 to 30:70 (LLDPE: PDMS) by varying the radiation doses from 50 to 300 kGy has been studied. The dynamic modulii and dielectric strength of the blends increase on irradiation at 100 kGy as compared to that for the unirradiated blends. Degree of crystallinity and melting behaviour remain unchanged upon irradiation upto a dose of 100 kGy, beyond which it decreases. Thermal stability increases with increase in the proportion of PDMS rubber in the blend as well as on irradiation at 100 kGy. The phase morphology of the blends examined under the SEM exhibit two phase morphology before electron beam irradiation, whereas single phase morphology is observed after electron beam irradiation due to intra- as well as inter-molecular crosslinking leading to a miscible system.     

Poly(hydroxybutyrate) and epichlorohydrin elastomers blends: Phase behavior and morphology

This work studied blends of PHB with epichlorohydrin elastomers, the PEP homopolymer and its copolymer with ethylene oxide, ECO. PHB is a microbial polyester, which is accumulated intracellularly by a large number of microorganisms, presenting characteristics of biodegradability and biocompatibility. It presents a high degree of crystallinity, so is a quite brittle material, and may undergo degradation when is kept for a relatively short time at a temperature above its melting point, about 180 °C. PEP and ECO are linear and amorphous elastomers, exhibit miscibility with many aliphatic polyesters and these elastomers have been used in various branches of technology, such as the automotive industry. The proposed systems combine a polymer with high crystallinity and biodegradability, PHB, with amorphous epichlorohydrin elastomers. Blends were prepared by casting from chloroform solution at different compositions (0, 20, 40, 50, 60, 80 and 100 wt% of PHB). The phase behavior of PHB/PEP and PHB/ECO blends were studied by differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA) and the morphology of the crystalline phase of PHB had been examined by optical microscopy. Blends of PHB/PEP and PHB/ECO have been described in literature as miscible. However, our results from the DSC and DMA show that PHB/PEP and PHB/ECO blends are immiscible. This behavior should be related to the molecular weight of polymers used in the present work, which is higher than the molecular weight of polymers used in the previous works. The crystallization kinetics of PHB is strongly influenced by the presence of the elastomeric phase. The degree of crystallinity of PHB/PEP blends decreases with an increase in the PEP content. PHB/ECO blends present degrees of crystallinity that can be considered nearly independent of the ECO content. Differences in the morphology of the crystalline phase were also observed, and these are attributed to the presence of elastomeric phase in the intraspherulitic zone.     

Two‐way multi‐shape memory properties of peroxide crosslinked ethylene vinyl‐acetate copolymer (EVA)/polycaprolactone (PCL) blends

Rare studies have investigated on the 2‐way shape memory crosslinked blends with multiple shape memory behavior up to date. To consider the merit of commercial cost‐competitive crystalline polymers, ethylene vinyl‐acetate copolymer (EVA) / polycaprolactone (PCL) blends (60/40 and 30/70) were peroxide‐cured to form the 2‐way multi‐shape memory crosslinked blends using a melt‐blending method. Both resins were selected to have a similar controlled crosslinking degree, which allowed us to distinctly evaluate their actuation contributions from the cooling‐induced elongation (crystallization) and from the entropy‐driven elongation during cooling process, respectively. In the 2‐way process for the 60/40 system, 2 respective peaks contributed from the cooling‐induced crystallization of EVA and PCL in the cooling curves based on the strain derivate rates at various temperatures were observed. After the cooling process under the loading stress of 150 kPa, the 2‐step heating‐induced contraction process with increasing temperature started at 54.1°C above the melting temperature of PCL at 52.3°C and EVA at 78.3°C, demonstrating 2‐way multi‐shape memory behavior. The multi‐step behavior was more prominent at higher PCL composition and higher load for the 30/70 system. It was found that the entropy‐driven contribution to the overall actuation magnitude increased with increasing nominal loads due to the increased orientation of molecular networks in the blends. The current approach offers numerous possibilities in preparing 2‐way multi‐shape memory crosslinked blends.     

Solid-state relaxations in linear low-density (1-octene comonomer), low-density,and high-density polyethylene blends

Extensive thermal and relaxational behavior in the blends of linear low-density polyethylene (LLDPE) (1-octene comonomer) with low-density polyethylene (LDPE) and high-density polyethylene (HDPE) have been investigated to elucidate miscibility and molecular relaxations in the crystalline and amorphous phases by using a differential scanning calorimeter (DSC) and a dynamic mechanical thermal analyzer (DMTA). In the LLDPE/LDPE blends, two distinct endotherms during melting and crystallization by DSC were observed supporting the belief that LLDPE and LDPE exclude one another during crystallization. However, the dynamic mechanical β and γ relaxations of the blends indicate that the two constituents are miscible in the amorphous phase, while LLDPE dominates α relaxation. In the LLDPE/HDPE system, there was a single composition-dependent peak during melting and crystallization, and the heat of fusion varied linearly with composition supporting the incorporation of HDPE into the LLDPE crystals. The dynamic mechanical α, β, and γ relaxations of the blends display an intermediate behavior that indicates miscibility in both the crystalline and amorphous phases. In the LDPE/HDPE blend, the melting or crystallization peaks of LDPE were strongly influenced by HDPE. The behavior of the α relaxation was dominated by HDPE, while those of β and γ relaxations were intermediate of the constituents, which were similar to those of the LLDPE/HDPE blends. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35 : 1633–1642, 1997     

Chemical modification of polyolefin blends

The effect of crosslinking on the properties of low density polyethylene / polypropylene blends was investigated. It was found that crosslinking results in much higher deformability of the blends compared to uncrosslinked materials. A decrease in crystalline portion determined by DSC leads to lower modulus in crosslinked samples. High drawability of crosslinked samples is mainly attributed to peculiar behaviour of PE part of the crosslinked blend where thicker lamellae are formed during drawing.     

Influence of chain extension on the compatibilization and properties of recycled poly(ethylene terephthalate)/linear low density polyethylene blends

Polymeric methylene diphenyl diisocyanate (PMDI) was added as chain extender to a blend of recycled poly(ethylene terephthalate) (R-PET) and linear low density polyethylene (LLDPE) with compatibilizer of maleic anhydride-grafted poly(styrene-ethylene/butadiene-styrene) (SEBS-g-MA). Hydroxyl end groups of PET can react with both isocyanate groups of PMDI and maleic anhydride groups of SEBS-g-MA, which are competing reactions during reactive extrusion. The compatibility and properties of the blends with various contents of PMDI were systemically evaluated and investigated. WAXD results and SEM observations indicated that chain extension inhibits the reaction between PET and SEBS-g-MA. As the PMDI content increased, the morphology of dispersed phase changed from droplet dispersion to rodlike shape and then to an irregular structure. The DSC results showed that the crystallinity of PET decreased in the presence of PMDI, and the glass transition temperature (T_g) of PET increased with addition of 0-0.7 w% PMDI. The impact strength of the blend with 1.1 w% PMDI increased by 120% with respect to the blend without PMDI, accompanied by only an 8% tensile strength decrease. It was demonstrated that the chain extension of PET with PMDI in R-PET/LLDPE/SEBS-g-MA blends not only decreased the compatibilization effect of SEBS-g-MA but also hindered the crystallization of PET.     

The morphology and thermal properties of liquid natural rubber (LNR)-compatibilized 60/40 NR/LLDPE blends

The effects of LNR as a compatibilizer in binary blends of 60/40 NR/LLDPE have been investigated by means of differential scanning calorimetry, dynamic mechanical analysis and scanning electron microscopy. Special emphasis was given to the role of LNR in inducing interactions between NR and LLDPE. It has been observed that increasing LNR content decreases T_m and ΔH_f which are indicators of the crystalline part of the blends. The decrease reflects a reduction in the degree of crystallinity which is due to the interference in the form of NR dissolution into the LLDPE phase. The phenomenon leads to a shift in T_g of the amorphous part of LLDPE to higher temperatures as observed by DMA thermograms. The dissolution effect creates better interactions between the phases leading to improvements in the compatibility of the blends. Further confirmation was obtained through SEM examination.     

Solid‐state NMR characterizations on phase structures and molecular dynamics of poly(ethylene‐co‐vinyl acetate)

Solid‐state nuclear magnetic resonance spectroscopy and relaxation measurements, together with DSC, have been used to elucidate the structures and molecular dynamics in poly(ethylene‐co‐vinyl acetate) (EVA). It has been found that besides immobile orthorhombic and monoclinic crystalline phases, the third mobile crystalline phase (possibly the phase) of a considerable amount (36% of total crystalline phases) appears in the EVA samples, which forms during room‐temperature aging as a result of the secondary crystallization and melts at temperature somewhat higher than room temperature. Such a mobile crystalline phase has not only the well‐defined chemical shift of its own, but also has different molecular mobility from the orthorhombic phase. The mobile crystalline phase is characterized by the rapid relaxation of the longitudinal magnetization, which is caused by conventional spin‐lattice relaxation, while the slow relaxation of the longitudinal magnetization occurring in the orthorhombic phase is originated from the chain diffusion. In addition, the amorphous phase also contains two components: an interfacial amorphous phase and a melt‐like amorphous phase. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 2864–2879, 2006     

Structure and properties of compatibilized recycled poly(ethylene terephthalate)/linear low density polyethylene blends

Blends of recycled poly(ethylene terephthalate) (R-PET) and linear low density polyethylene (LLDPE) were compatibilized with poly(styrene-ethylene/butyldiene-styrene) (SEBS) and maleic anhydride-grafted poly(styrene-ethylene/butyldiene-styrene) (SEBS-g-MA). Effects of compatilizer were evaluated systematically by study of mechanical, thermal and morphology properties together with crystallization behavior of PET. Tensile properties of the blends were improved effectively by the addition of 10 wt% SEBS-g-MA, elongation at break and charpy impact strength were increased with the increasing content of compatilizer. SEBS-g-MA is more effectual on mechanical properties of R-PET/LLDPE blends than SEBS. DSC analysis illustrates crystallinities of PET and LLDPE were increased by compatilizer at annealing condition. WAXD and FT-IR spectra show that annealing influences crystallization behavior of PET. Different compatilizer content results in different morphology structure, in particular, higher SEBS-g-MA content can induce the formation of a salami microstructure.     

Blends of propylene-ran-ethylene and propylene-ran-(1-butene) copolymers: Crystal superstructure and mechanical properties

Blends of isotactic propylene-ran-ethylene (EP) and propylene-ran-(1-butene) (BP) copolymers with various comonomer content (2-3.1 wt.% ethylene, 9.9 wt.% 1-butene), were prepared in Brabender internal mixer at various compositions (25/75, 50/50, 75/25). Static, impact and dynamic mechanical behavior of copolymers and their blends was investigated. The crystalline structure was studied by DSC and SAXS analysis. For all copolymers the lamellar thickness, crystallinity degree and glass transition temperature are lower than those of iPP homopolymer, depending on the comonomer content. It was found that the copolymers exhibit improved impact strength as compared to plain iPP, due to lower crystallinity and higher mobility of chains within amorphous component. Moreover, the elastic modulus as well as the yield behavior of the examined samples resulted to depend primarily on the amount of the crystalline phase and the thickness of the lamellar crystals, respectively. A linear dependence of yield stress on the logarithm of reciprocal lamellar thickness was observed for blends and copolymers, supporting the concept of thermal nucleation of dislocations which control the crystallographic slip processes initiated at the yield point. The blends of BPS with either EPS or EP2 display complete miscibility in the entire range of composition and their mechanical properties are intermediate between those of plain components, changing gradually with the composition.     

Poly(ε-caprolactone) + unsaturated isophtalic polyester blends: Thermal properties and morphology

Miscibility of blends composed by a linear unsaturated polyester (LUP) with poly(ε-caprolactone) (PCL) of different molecular weights (M_w = 50 × 10³, 18 × 10³ and 2 × 10³) has been studied. The blends were subjected to different thermal treatments and have been studied by FT-IR spectroscopy, differential scanning calorimetry (DSC) and scanning electronic microscopy (ESEM). FT-IR results allow proving the miscibility of the blends at temperatures above the melting temperature of neat PCL. DSC measurements confirm the existence of a crystalline phase corresponding to neat PCL. The crystallization of PCL is observed in a wide range of blends composition, being detected in all the blend compositions when the crystallization time increases. Thermograms show clearly the glass transition temperatures of samples that have been rapidly quenched from the melt. However, the change in the heat flow corresponding to the glass transition temperatures is difficult to detect in samples with high PCL crystallization degree. The analysis of the results indicates that the morphology of the amorphous phase is heterogeneous for LUP + PCL blends and changes depending on the thermal treatment. The ESEM measurements, confirm the heterogeneity of the amorphous phase. The decrease of the molecular weight of the PCL favours the miscibility of the blends.     

Morphology and crystallization of blends of linear low density polyethylene with a semiflexible liquid crystalline polymer

The morphology and the crystallization behavior of blends of linear low density polyethylene (LLDPE) with an experimental sample of a semiflexible liquid crystalline polymer (SBH 112 by Eniricerche, Italy) have been studied by differential scanning calorimetry (DSC), polarized optical microscopy (POM) and scanning electron microscopy (SEM). The blends possess a two-phase morphology, due to immiscibility of the two components. SEM observations show that dispersion of the minor SBH phase is favored at low (相似文献   

Characterization of irradiation-induced crosslink of epoxidised natural rubber/ethylene vinyl acetate (ENR-50/EVA) blend

The effect of irradiation on tensile, dynamic mechanical properties, thermal properties and morphology of ENR-50, EVA and ENR-50/EVA blend was investigated. All the samples were irradiated using a 3.0 MeV electron beam (EB) machine with doses ranging from 20 to 100 kGy. Results indicate that the gel fraction of ENR-50, EVA and ENR-50/EVA blend increases with irradiation dose. Concerning tensile properties, it can be seen that EB radiation increases the tensile strength of all the samples, increases the elongation at break of ENR-50 and ENR-50/EVA blend, reduces the elongation at break of EVA, increases M200 (modulus at 200% strain) of ENR-50 and EVA, while decreases M200 of the ENR-50/EVA blend. For dynamic mechanical studies, it was found that EB radiation increases the T_g of all the samples due to the effect of irradiation-induced crosslinking. The compatibility of ENR-50/EVA blend also found to be improving upon irradiation. In the case of thermal properties, it was detected that T_m, T_c and the degree of crystallinity of ENR-50/EVA blend increase with an increase in irradiation dose. This was due to the perfection in the crystal growth occurring upon radiation. Morphology changes play a major role in the changes of the properties of ENR-50/EVA blend. Finally, it can be concluded that ENR-50/EVA blend can be vulcanized by EB radiation.     

Studies on dynamic mechanical and mechanical properties of vinyloxyaminosilane grafted ethylene propylene diene terpolymer/linear low density polyethylene (EPDM-g-VOS/LLDPE) blends

The dynamic mechanical properties of vinyloxyaminosilane grafted ethylene propylene diene terpolymer/linear low density polyethylene (EPDM-g-VOS/LLDPE) blends have been evaluated with special reference to the effect of blend ratio. It has been found that increasing the proportion of LLDPE in the blends decreases the T_g values and increases the storage modulus (E^′) and loss modulus (E^′′) due to increase in crystallinity. A gradual increase in the values of tanδ_max is observed for the blends with increase in EPDM-g-VOS concentration, which indicates that no phase inversion occurs. But however the higher increase in tanδ_max after 50 wt.% of EPDM-g-VOS composition is due to small change in crystallinity and is ascertained by SEM micrographs. Mechanical properties such as tensile strength, Young’s modulus and hardness increase with increases in LLDPE concentration in the blends and with dicumyl peroxide (DCP) concentration whereas the values of elongation at break are decreased with increase in LLDPE and DCP concentration.     

Non-isothermal crystallization behavior of Styrene butadiene rubber/high density polyethylene binary blends

The thermal and crystallization behavior of the blends are studied by differential scanning calorimetry and XRD. The presence of the amorphous component in the blend is found to influence the non-isothermal crystallization of HDPE. The addition of small quantities of SBR resulted in an increase in the rate of crystallization whereas nucleation is delayed. As compared to HDPE, larger crystallite size, a narrower size distribution, were observed in low SBR (~up to 30?wt%) content blends. The half time of crystallization also found to reduce as the SBR content in the blend increased. However, a lower degree of crystallinity was observed in these blends. The results thus show that incorporation of SBR in HDPE, while accelerating the rate of crystallization, lower the degree of crystallization. The reduction in the overall crystallization rate at high-SBR content is attributed to a decrease in the growth rate in the later stages of crystallization. It is observed that in dynamically cross-linked blends, the presence of crosslinked SBR that can acts as heterogeneous nuclei facilitated the nucleation of HDPE. However, the crystal growth may be impeded. As a result the overall crystallinity of the crosslinked blends found to decrease. From XRD profiles it had seen that addition of SBR and dynamic crosslinking does not exert an effect on the crystalline structure of HDPE. The dynamic vulcanization of SBR/HDPE blends enhanced the process of crystallization of HDPE phase. These conclusions are supported by the thermal characterization (DSC) results also.     

Effect of organoclay loading and electron beam irradiation on the physico‐mechanical properties of low‐density polyethylene/ethylene‐vinyl acetate blend

The influence of electron beam (EB) irradiation and organoclay (OC) loading on the properties of low‐density polyethylene (LDPE)/ethylene‐vinyl acetate (EVA) blends was investigated. The samples were subjected to the EB irradiation with the dose values of 50 and 250 kGy. X‐ray diffraction (XRD), gel content, mechanical, thermal, and electrical properties were utilized to analyze the characteristics of the LDPE/EVA blends with and without OC at different irradiation dosages. Gel content analysis showed that the OC promotes considerably the insoluble part so that the LDPE/EVA blends filled with OC become fully crosslinked at 250 kGy; possibly through the formation of further crosslinks between OC and polymer chains. The samples irradiated by EB showed enhanced mechanical properties due to the formation of three‐dimensional networks. In addition, thermogravimetric analysis indicated that combined OC loading and radiation‐induced crosslinking improved thermal stability of LDPE/EVA blends considerably. Copyright © 2011 John Wiley & Sons, Ltd.