Thermal and mechanical properties of uncrosslinked and chemically crosslinked polyethylene/ethylene vinyl acetate copolymer blends

Uncrosslinked and chemically crosslinked binary blends of low‐ and high‐density polyethylene (PE), with ethylene vinyl acetate copolymer (EVA), were prepared by a melt‐mixing process using 0–3 wt % tert‐butyl cumyl peroxide (BCUP). The uncrosslinked blends revealed two distinct unchanged melting peaks corresponding to the individual components of the blends, but with a reduced overall degree of crystallinity. The crosslinking further reduced crystallinity, but enhanced compatibility between EVA and polyethylene, with LDPE being more compatible than HDPE. Blended with 20 wt % EVA, the EVA melting peak was almost disappeared after the addition of BCUP, and only the corresponding PE melting point was observed at a lowered temperature. But blended with 40% EVA, two peaks still existed with a slight shift toward lower temperatures. Changes of mechanical properties with blending ratio, crosslinking, and temperature had been dominated by the extent of crystallinity, crosslinking degree, and morphology of the blend. A good correlation was observed between elongation‐at‐break and morphological properties. The blends with higher level of compatibility showed less deviation from the additive rule of mixtures. The deviation became more pronounced for HDPE/EVA blends in the phase inversion region, while an opposite trend was observed for LDPE/EVA blends with co‐continuous morphology. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 3261–3270, 2007     

γ-Radiation (0–150 kGy) Effects on Slow and Fast Cooled HDPE/LDPE Blends

Summary The influence of gamma radiation on the morphology, thermal, mechanical and rheological properties of blends of high density polyethylene/low density polyethylene (HDPE/LDPE) was investigated. Prior to irradiation blends of different thermal history were prepared by fast cooling and slow cooling from the melt. Results showed that there were not significant changes in the degree of crystallinity of the blends with radiation. Higher values of degree of crystallinity and melting peak temperature were obtained for the slowly cooled blends. A small increase in the Young modulus and the yield stress were observed by irradiating the blends, and the elongation at break was reduced about 70% when compared to non-irradiated blends. High degree of crosslinking is expected to occur due to the decrease in melt flow rate of the blends irradiated to 50 kGy, and no flow was detected at 150 kGy. Transmission electron microscopy observations failed to show important changes in morphology with radiation.     

m-PE-LLD／PE-LD共混物结晶结构的研究

采用DSC、WAXD和SAXS相结合的方法研究了共混物的相分离、结晶度、片晶厚度等结晶结构参数。研究结果表明，在m-PE-LLD／PE-LD共混物中，当PE-LD含量较大时无论是熔融曲线还是降温曲线都只出现一个峰，说明两者存在共结晶，有很好的相容性。当PE-LD含量减小时，共混物出现相分离，升、降温曲线均出现双峰，但两峰值呈现靠近趋势，预示m-PE-LLD／PE-LD共混物中仍存在少量共结晶。WAXD数据显示，PE-LD添加到m-PE-LLD中，没有改变茂金属聚乙烯固有的晶体结构，共混物仍然保持了聚乙烯的正交晶系结构。并随着PE-LD在m-PE-LLD中添加比例的增加，共混物正交晶系增强的同时晶粒尺寸变小。     

Preparation,Characterization, and Evaluation of Poly(p-azidoaniline) as Thermal Stabilizer for Low Density Polyethylene Films

A series of electrically conducting low density polyethylene/poly(p-azidoaniline) blends containing different loadings of poly(p-azidoaniline) was prepared. The resistance of these blends to accelerated thermal oxidation at 90°C for different time intervals was investigated. The thermal degradation mechanism was determined by attenuated total reflection-Fourier transform infrared technique. The values of melting temperature (T_m), enthalpy of fusion (ΔH_m), and degree of crystallinity showed significant increase upon poly(p-azidoaniline) addition. X-ray diffraction patterns also confirmed increase in degree of crystallinity upon blend formation. Furthermore, scanning electron microscopy observations showed efficient thermal stabilization of low density polyethylene/poly(p-azidoaniline) blends. The mechanical properties showed significant role of poly(p-azidoaniline) as thermal stabilizer for low density polyethylene.     

Tensile properties of polyethylene blends

Binary and ternary blends were prepared from low, medium, and high density polyethylene. The tensile properties of these materials indicated that the blends formed either compatible or semi-compatible mixtures. One of the ternary blends exhibited a slight synergism in properties which could be partially attributed to an enhancement in crystallinity. Such blends may have practical utility by yielding materials having a combination of strength, stiffness, and toughness.     

LLDPE／EPO共混体系相容性及结晶结构的研究

利用DSC、WAXD两种方法系统研究了LIDPE／EPO（线型低密度聚乙烯／乙烯丙烯辛烯－1共聚物）共混体系的相容性及结晶结构，通过DSC上（熔融峰，结晶峰）呈现单峰确定了此共混体系在水晶水平上共晶；用WAXD方法，计算了共混体系的结晶度，晶胞参数及微晶大小随组成不同而变化的关系，进一步证实了LLDPE／EPO共混体系的相容性。     

Rheological and mechanical properties in polyethylene blends

Melt rheology and mechanical properties in linear low density polyethylene (LLDPE)/low density polyethylene (LDPE), LLDPE/high density polyethylene (HDPE), and HDPE/LDPE blends were investigated. All three blends were miscible in the melt, but the LLDPE/LDPE and HDPE/LDPE blends exibiled two crystallization and melting temperatures, indicating that those blends phase separated upon cooling from the melt. The melt strength of the blends increased with increasing molecular weight of the LDPE that was used. The mechanical properties of the LLDPE/LDPE blend were higher than claculated from a simple rule of mixtures, whiele those of the LLDPE/HDPE blend conformed to the rule of mixtures, but the properties of HDPE/LDPE were less than the rule of mixtures prediction.     

Comparison of structure and properties of conventional and “high‐crystallinity” isotactic polypropylenes and their blends with metallocene‐catalyzed linear low‐density polyethylene. I. Relationships between rheological behavior and thermal and physical properties

The present study was conducted to compare the structure and properties of conventional and so‐called “high‐crystallinity” (hcr) polypropylene (PP) and to establish characteristic features of the latter that are responsible for its superior thermal and mechanical performance. Moreover, structure–properties relationships of hcr PP blends with metallocene‐catalyzed, linear low‐density polyethylene (mLLDPE) were compared with those of conventional PP/mLLDPE blends. In Part 1, relationships between rheological behavior (viscosity and melt density) and thermal (transition temperatures and level of crystallinity) and mechanical properties (impact strength and Young's modulus) were analyzed with reference to composition. The rheological and MDSC tests showed that both types of the blends were miscible at the processing temperatures, whereas immiscible in the solid state and in vicinity of the PP melting point. It was found that the improved mechanical properties and the extraordinary high crystallization temperature of hcr PP (and, correspondingly, hcr PP/mLLDPE blends) are not due to the assumed high level of crystallinity but due to alteration of internal structure of this polypropylene. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 1591–1599, 2000     

The effect of paraffin on fiber dispersion and mechanical properties of polyolefin–sawdust composites

This article reports on the influence of the paraffin (PAR) on the wood fiber (WF) dispersion in different polyethylene (low‐density polyethylene, high‐density polyethylene, recycled polyethylene) matrices, as well as on the melt flow behavior and mechanical properties of WF‐reinforced polyethylene (PE) composites. In the presence of paraffin, the composites showed improved tensile and flexural strength and modulus, but lower impact strength and elongation at break. The extent of improvement in mechanical properties depends on paraffin content and type of polyethylene; the most effective paraffin was in LDPE‐based composites. Paraffin‐treated WF showed lower moisture absorption ability in comparison with unmodified wood fiber. The phase segregation process was investigated for PE/PAR blends by DSC method. It was shown that an increase of paraffin concentration in the PE/PAR blend leads to a decrease of PE melting temperature and an increase of paraffin melting temperature; it indicates a net exchange of material from paraffin towards polyethylene. However, generally both components of PE/PAR blends remain immiscible. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 2385–2393, 2004     

Elongational rheology of LLDPE / LDPE blends

The objective of this study is to investigate the effect of low density polyethylene (LDPE) content in linear low density polyethylene (LLDPE) on the crystallinity and strain hardening of LDPE / LLDPE blends. Three different linear low density polyethylenes (LL‐1, LL‐2 and LL‐3) and low density polyethylenes (LD‐1, LD‐2 and LD‐3) were investigated. Eight blends of LL‐1 with 10, 20, 30 and 70 wt % of LD‐1 and LD‐3, respectively, were prepared using a single screw extruder. The elongational behavior of the blends and their constituents were measured at 150°C using an RME rheometer. For the blends of LL‐1 with LD‐1, the low shear rate viscosity indicated a synergistic effect over the whole range of concentrations, whereas for the blends of LL‐1 with LD‐3, a different behavior was observed. For the elongational viscosity behavior, no significant differences were observed for the strain hardening of the 10–30% LDPE blends. Thermal analysis indicated that at concentrations up to 20%, LDPE does not significantly affect the melting and crystallization temperatures of LLDPE blends. In conclusion, the crystallinity and rheological results indicate that 10–20% LDPE is sufficient to provide improved strain hardening in LLDPE. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 3070–3077, 2003     

HDPE/ROSIN blends: I-Morphology, thermal and dynamic-mechanical behavior

SUMMARY Morphological and thermal studies on high density polyethylene (HDPE) / glycerol ester of partially hydrogenated rosin (ester gum) blends reveal phase separation. Both thermal and dynamic-mechanical tests showed no shift of the HDPE glass transition temperature while the HDPE α_c transition appeared. The presence of an additional transition was also noticed as the second component increased in blends; this was attributed to a rosin component. The peak ascribed to this transition became broader in blends enriched with oligomer; it moved toward lower temperatures due to the dissolution of low molecular weight HDPE. The melting temperature and crystallinity of HDPE varied slightly with the amount of amorphous oligomeric component in the blends. Received: 7 May 1997/Revised version: 20 March 1998/Accepted: 14 April 1998     

Surface segregation of polyethylene in low‐density polyethylene/ethylene–propylene–diene rubber blends: Aspects of component structure

Aspects of the molecular weight and its distribution, the branching of low‐density polyethylene (LDPE), and the molecular composition of the ethylene–propylene–diene rubber (EPDM) matrix are presented in this article in terms of their influence on the surface segregation of polyethylene (PE) in elastomer/plastomer blends. All of the PEs studied, despite different weight‐average molecular weights and degrees of branching, segregated to the surface of the LDPE/EPDM blends. Atomic force microscopy pictures demonstrated defective crystalline structures on the surface of the blends, which together with a decrease in the degrees of their bulk crystallinity and a simultaneous increase in their melting temperatures, pointed to a low molecular weight and a defective fraction of PE taking part in the surface segregation. The extent of segregation depended on the molecular structure of the EPDM matrix, which determined the miscibility of the components on a segmental level. The higher the ethylene monomer content in EPDM was, the lower was the PE content in the surface layer of the blends. The composition and structure of the surface layer was responsible for its lower hardness in comparison with the bulk of the blends studied. The surface gradient of the mechanical properties depended on the physicochemical characteristics of the components and the blend composition, which created the possibility of tailoring the LDPE/EPDM blends to dedicated applications. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 625–633, 2006     

大型中空容器级HDPE树脂的中试聚合研究

采用两段淤浆聚合工艺合成了由低摩尔质量的均聚物和高摩尔质量的共聚物组成的、具有宽峰或双峰摩尔质量分布的高密度聚乙烯大型中空容器级树脂。通过调节第一段和第二段聚合过程中聚合物的熔体质量流动速率来控制摩尔质量的大小及其分布；采用控制第二段共聚物中共聚单体数量来调节聚合物密度；控制第一段小分子数目，增加第二段摩尔质量或调整密度获得最大耐环境应力开裂性（ESCR）。随着共聚单体丁烯-1加入量的增加，反应釜共混物的密度、熔点、结晶度、拉伸屈服应力、断裂伸长率减少。随着高摩尔质量共聚物的含量增加，屈服应力、熔点、密度、结晶度减少，摩尔质量分布的双峰特性也增加，反应釜共混物的均聚物峰的高度减少，共聚物峰的高度增加。流变性能结果表明，通过改变共混物的组分可以获得力学性能和加工性能的平衡。     

Liquid-liquid phase separation in a polyethylene blend monitored by crystallization kinetics and crystal-decorated phase morphologies

A series of polyethylene (PE) blends consisting of a linear high density polyethylene (HDPE) and a linear low density polyethylene (LLDPE) with an octane-chain branch density of 120/1000 carbon was prepared at different concentrations. The two components of this set of blends possessed isorefractive indices, thus, making it difficult to detect their liquid-liquid phase separation via scattering techniques. Above the experimentally observed melting temperature of HDPE, T_m = 133 °C, this series of blends can be considered to be in the liquid state. The LLDPE crystallization temperature was below 50 °C; therefore, above 80 °C and below the melting temperature of HDPE, a series of crystalline-amorphous PE blends could be created. A specifically designed two-step isothermal experimental procedure was utilized to monitor the liquid-liquid phase separation of this set of blends. The first step was to quench the system from temperatures of known miscibility and isothermally anneal them at a temperature higher than the equilibrium melting temperature of the HDPE for the purpose of allowing the phase morphology to develop from liquid-liquid phase separation. The second step was to quench the system to a temperature at which the HDPE could rapidly crystallize. The time for developing 50% of the total crystallinity (t_1/2) was used to monitor the crystallization kinetics. Because phase separation results in HDPE-rich domains where the crystallization rates are increased, this technique provided an experimental measure to identify the binodal curve of the liquid-liquid phase separation for the system indicated by faster t_1/2. The annealing temperature in the first step that exhibits an onset of the decrease in t_1/2 is the temperature of the binodal point for that blend composition. In addition, the HDPE-rich domains crystallized to form spherulites which decorate the phase-separated morphology. Therefore, the crystal dispersion indicates whether the phase separation followed a nucleation-and-growth process or a spinodal decomposition process. These crystal-decorated morphologies enabled the spinodal curve to be experimentally determined for the first time in this set of blends.     

BMDPE／LDPE／LLDPE共混熔体的流变行为与力学性能

研究了双峰中密度聚乙烯（BMDPE），低密度聚乙烯（LDPE）与线型低密度聚乙烯（LLDPE）共混熔体的流变行为和力学性能，讨论了共混物的组成，剪切应力和剪切速率以及温度对熔体流变行为，熔体粘度和膨胀比的影响，测定了不同配比熔体的非牛顿指数，熔体流动速率，粘流活性能及屈服应力，断裂应力和断裂伸长率，为BMDPE的加工和使用以及开发高性能价格比的PE材料提供了依据。     

烯基双酚A醚接枝LDPE对HDPE／PC相容性和结晶速率的影响

本文通过热力学曲线,对HDPE/PC体系中HDPE的熔融温度(T_m)和PC的玻璃化转变温度(T_g)的测试,考察了增容剂烯基双酚A醚接枝LDPE(LDPE-g-DBAE)对共混体系相容性的影响,同时还研究了体系中HDPE的结晶速率。     

Microhardness of ternary blends of polyolefins with recycled polymer components

Microhardness tests, Fourier transform infrared spectroscopy (FTIR), and differential scanning calorimetry (DSC) measurements were performed on melt‐pressed films of multicomponent blends based on low‐density polyethylene (LDPE), linear LDPE (LLDPE), high‐density polyethylene (HDPE), and polypropylene (PP), and their recycled homologues. Some of the PE blends also contained ethylene‐propylene‐diene monomer (EPDM) as compatibilizer. In all cases, the variation of microhardness as a function of content of the recycled component follows the additivity law of components. Thus, the range of hardness values of polyolefin blends can be controlled by choice of both components and their relative content in the blend. The hardness of the components increases from LDPE, to LLDPE, to HDPE, to PP and increases from 20 to 84 MPa. For recycled components, the hardness values are reduced by ～15%. According to DSC results, all the blends are immiscible. Results are discussed in terms of the levels of crystallinity reached for the different blends. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 2046–2050, 2003     

Studies on high density polyethylene/polycarbonate blend system compatibilized with low density polyethylene grafted diallyl bisphenol A ether

Blends of a high density polyethylene (HDPE) matrix and a polycarbonate (PC) minor phase were investigated through their morphology, heat resistance, mechanical properties, crystallizing behavior, rheological measurement and especially the compatible effect of a compatibilizer: low density polyethylene grafted diallyl bisphenol A ether (LDPE-g-DBAE). The blends without compatibilizer exhibited a phase growth and no adhesive between the HDPE matrix and the dispersed phase. In the presence of 10% by weight of LDPE-g-DBAE as a compatibilizer, more fine particles and a dim phase interface were observed, and the blends showed a remarkable increase in heat distortion temperature and mechanical properties. The compatibilized blends possessed a high apparent viscosity as compared with the noncompatibilized ones. However, the apparent viscosity of the blends, with or without the compatibilizer, was lower than that of the neat HDPE and PC. Exploration by DSC found that the melting point and the crystallinity of HDPE in the blends decreased, and especially for the blends with the compatibilizer. These facts could be interpreted in terms of the efficient compatible effect of the LDPE-g-DBAE, which resulted from the interaction between the diallyl bisphenol A ether unit of LDPE-g-DBAE and polycarbonate, and the miscibility of the LDPE unit and HDPE.     

X‐ray diffraction studies on reverse‐annealed polyethylenes

Linear low and high density polyethylene sheets were compression molded and crystallized at a 5–10°C/min cooling rate. Parts of the sheets were annealed at different temperatures up to 2°C below the melting temperature. The small angle X‐ray scattering (SAXS) and the wide angle X‐ray scattering intensities of the annealed samples were studied. SAXS intensities showed particle scattering with a bimodal size distribution. The estimated radii of gyration were 15–17 nm and 5–7 nm, respectively. The crystallinity and the radius of gyration increased slightly with increasing annealing temperature for some samples; others did not show any change. No peaks characteristic of intercorrelated lamellar crystallinity in the SAXS intensities developed during the annealing. The original broad peak of high density polyethylene disappeared from the SAXS recordings on annealing. The length of the perfect chain versus melting temperature was calculated by the Thomson‐Gibbs formula and Flory's concept of melting temperature depression where methyl groups and tertiary carbon atoms at the branches were regarded as second components (solvent). Linear relationships were found for both cases. Experimental data for a linear low density polyethylene obtained from the literature were in between the two functions. A lamellar model of crystallization corresponding to the data is proposed. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 340–349, 2001     

Mechanical properties and morphology of polyethylene–polypropylene blends with controlled thermal history

The effect of time–temperature treatment on the mechanical properties and morphology of polyethylene–polypropylene (PE–PP) blends was studied to establish a relationship among the thermal treatment, morphology, and mechanical properties. The experimental techniques used were polarized optical microscopy with hot‐stage, scanning electron microscopy (SEM), differential scanning calorimetry (DSC), and tensile testing. A PP homopolymer was used to blend with various PEs, including high‐density polyethylene (HDPE), low‐density polyethylene (LDPE), linear low‐density polyethylene (LLDPE), and very low density polyethylene (VLDPE). All the blends were made at a ratio of PE:PP = 80:20. Thermal treatment was carried out at temperatures between the crystallization temperatures of PP and PEs to allow PP to crystallize first from the blends. A very diffuse PP spherulite morphology in the PE matrix was formed in partially miscible blends of LLDPE–PP even though PP was present at only 20% by mass. Droplet‐matrix structures were developed in other blends with PP as dispersed domains in a continuous PE matrix. The SEM images displayed a fibrillar structure of PP spherulite in the LLDPE–PP blends and large droplets of PP in the HDPE–PP blend. The DSC results showed that the crystallinity of PP was increased in thermally treated samples. This special time–temperature treatment improved tensile properties for all PE–PP blends by improving the adhesion between PP and PE and increasing the overall crystallinity. In particular, in the LLDPE–PP blends, tensile properties were improved enormously because of a greater increase in the interfacial adhesion induced by the diffuse spherulite and fibrillar structure. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 1151–1164, 2000