Effects of matrix molecular weight on structure and reinforcement of high density polyethylene/mica composites

Three types of high-density polyethylene(HDPE)with different molecular weights(high,medium and low)were adopted to evaluate the influence of matrix molecular weight on the structure-property relation of injection-molded HDPE/mica composites through a combination of SEM,2d-WAXS,DSC,DMA and tensile testing.Various structural factors including orientation,filler dispersion,interfacial interaction between HDPE and mica,etc.,which can impact the macroscopic mechanics,were compared in detail among the three HDPE/mica composites.The transcrystallization of HDPE on the mica surface was observed and it exhibited strong matrix molecular weight dependence.Obvious transcrystalline structure was found in the composite with low molecular weight HDPE,whereas it was hard to be detected in the composites with increased HDPE molecular weight.The best reinforcement effect in the composite with low molecular weight HDPE can be understood as mainly due to substantially improved interfacial adhesion between matrix and mica filler,which arises from the transcrystallization mechanism.     

Evolution of products during the degradation of polyethylene in a batch reactor

The thermal degradation of two polyethylene samples (LDPE and HDPE) has been carried out in a batch reactor under dynamic conditions. The evolution of products generated after regular intervals of 5 min (temperature increments of approximately 25 °C) has been analyzed. The behaviour of LDPE and HDPE has been compared, and no differences in the quantity and weight fraction of the gaseous products obtained have been found. For both polymers, n-paraffins are the major products at the very beginning of the process, while as the decomposition proceeds 1-olefins are more abundant. The condensed fraction is much larger than the gaseous fraction and its analysis reveals some differences between the behaviour of LDPE and HDPE at the beginning of the degradation process. These differences disappear at higher temperatures where more similar trends are observed. 1-Olefins, n-paraffins, dienes and olefins with wide carbon number distributions are the most important condensed compounds obtained in the thermal degradation of both polyethylenes. The formation of 1-olefins and n-paraffins begins at slightly lower temperatures than for dienes and olefins. On the other hand, as the temperature increases, the amount of low and high molecular weight compounds increases at the expense of intermediate molecular weight products and the former become the most important by the end of the degradation process. This behaviour could be related to the thermal cracking of waxes through secondary reactions.     

FRACTIONATED CRYSTALLIZATION OF HDPE IN PS/POE/HDPE/SBS BLENDS

The fractionated crystallization behavior of the minor dispersed HDPE phase in PS/POE/HDPE/SBS quaternary blends was investigated by differential scanning calorimetry (DSC).Interestingly,we found that the fractionated crystallization behavior of HDPE was molecular weight dependent.At a fixed composition,HDPE with lower molecular weight showed more obvious fractionated crystallization behavior than HDPE with higher molecular weight.This was ascribed to a finer dispersion of HDPE with lower molecular weigh...     

环境温度对紫外辐照HDPE结构与性能的影响研究

采用元素、XPS、GPC分析，凝胶和力学性能测定，研究了空气中不同环境温度下紫外辐照官能化HDPE的结构、粘着性以及紫外辐照官能化HDPE对HDPE/聚乙烯醇(PVA)体系的增容作用。实验结果表明，提高环境温度可显著提高引入C-O、C(=O)O和C=O等含氧基团的速度。在相同辐照时间下，随环境温度提高，辐照HDPE的分子量下降、分子量分布变宽以及剥离强度提高的幅度增大，并在70℃时产生凝胶。较高环境温度下辐照的HDPE对HDPE/PVA共混体系有较好增容作用，在HDPE/PVA(83/17)体系中加入10%(质量分数)的70℃环境温度下辐照24h的HDPE，共混物的拉伸屈服强度和缺口冲击强度分别从30.8MPa和110J/m提高到34.9MPa和142J/m。     

Unexpected molecular weight dependence of shish-kebab structure in the oriented linear low density polyethylene/high density polyethylene blends

In this study, highly oriented shish-kebab structure was achieved via imposing oscillatory shear on the melts of linear low density polyethylene (LLDPE)/high density polyethylene (HDPE) blends during the packing stage of injection molding. To investigate the effect of molecular weight of HDPE on the formation of shish-kebab structure, two kinds HDPE with large melt flow index (low molecular weight) and small melt flow index (high molecular weight) were added into LLDPE matrix. The structural characteristics of LLDPE/HDPE blends were systematically elucidated through two-dimensional wide-angle x-ray scattering, scanning electron microscopy, and differential scanning calorimetry. Interestingly, an unexpected molecular weight dependence of shish-kebab structure of the prepared samples was found that the addition of HDPE with low molecular weight resulted in an higher degree of orientation, better regularity of lamellar arrangement, thicker lamellar size, and higher crystal melting temperature than that adding HDPE with high molecular weight. Correspondingly, the blend containing low molecular weight HDPE had better tensile strength. A possible mechanism was suggested to elucidate the role of HDPE molecular weight on the formation of shish-kebab structure in the oriented blends, considering the change of chain mobility and entanglement density with change of molecular weight.     

Characterization of high molecular weight polyethylenes using high temperature asymmetrical flow field-flow fractionation with on-line infrared, light scattering, and viscometry detection

High temperature asymmetrical flow field-flow fractionation (HTAF4) coupled to infrared (IR), multi-angle light scattering (MALS), and viscometry (Visc) detection is introduced as a tool for the characterization of high molecular weight polyethylenes. The high molecular weight fraction strongly affects the rheological behaviour and processability of polyethylene materials and can often not be accurately resolved by current technology such as high temperature size-exclusion chromatography (HTSEC). Molecular weight (M), radius of gyration (Rg), and intrinsic viscosity [eta] of linear high density polyethylene (HDPE) and branched low density polyethylene (LDPE) samples are studied in detail by HTAF4 and are compared to HTSEC. HTAF4 showed a better separation and mass recovery than HTSEC for very high molecular weight fractions in HDPE and LDPE samples. As no stationary phase is present in an HTAF4 channel, the technique does not show the typical drawbacks associated with HTSEC analysis of high molecular weight polyethylenes, such as, exclusion effects, shear degradation, and anomalous late elution of highly branched material. HTAF4 is applied to study the relation between the molecular weight and the zero shear viscosity eta0 for high molecular weight HDPE. It was found that the zero shear viscosity values predicted from HTAF4 results are in good qualitative agreement with measured values obtained from dynamic mechanical spectroscopy (DMS) experiments, whereas eta0 values predicted from HTSEC do not show a strong correlation. The low molecular weight cutoff of HTAF4 is approximately 5x10(4) as a result of relatively large pores in the HTAF4 channel membrane. HTAF4 is, therefore, currently not suited to analyze low molecular weight materials.     

聚合物分子量对热致相分离法制备聚乙烯微孔滤膜的影响

选取不同分子量的聚乙烯/二苯醚作为聚合物稀释剂体系,通过浊点及结晶温度绘制了体系的热力学相图;并在不同淬冷温度下,通过热致相分离法制备了聚乙烯微孔滤膜。讨论了聚合物分子量及淬冷温度对成膜孔结构的影响。结果表明:聚合物的分子量不仅影响微孔滤膜断面的孔径,还影响其形态和结构。     

Effect of diblock copolymers on dynamic mechanical properties of polyethylene/polystyrene blends

A systematic investigation of the dynamic mechanical properties of high-density polyethylene (HDPE)/high-impact polystyrene (HIPS)/copolymer blends was carried out. Blends of 80/20 weight percent of HDPE/HIPS were prepared in the melt state at 180°C in a batch mixer. Synthesized pure diblock (H77) and tapered diblock (H35) copolymers of hydrogenated polybutadiene (HPB) and polystyrene (PS) were added at different concentrations (1, 3, and 5 wt %), and the dynamic mechanical properties were investigated. The results show that: (1) both the tapered and the pure diblock copolymers enhance the phase dispersion and the interphase interactions; (2) structure and molecular weight are both important parameters in the molecular design of copolymers; (3) important effects occur when only small amounts of copolymer are added (up to the interface saturation concentration SC); (4) a micellar structure formation is possible when the copolymer is in excess in the blend; (5) the effect of the copolymer structure on the SC and the critical micellar concentration (CMC) is more pronounced than the effect of molecular weight. These concentrations are found to be lower for the tapered diblock copolymer. The analysis of the dynamic mechanical thermal analysis (DMTA) results obtained for the 20/80 HDPE/HIPS blend leads to the conclusion that the copolymers also enhance the interactions between heterogeneous phases. Similar conclusions based on electron microscopy were reported in the literature. DMTA shows great potential to relate macroscopic observations to the state of a copolymer in an immiscible blend.     

Thermally Robust yet Deconstructable and Chemically Recyclable High-Density Polyethylene (HDPE)-Like Materials Based on Si−O Bonds

Polyethylene (PE) is the most widely produced synthetic polymer. By installing chemically cleavable bonds into the backbone of PE, it is possible to produce chemically deconstructable PE derivatives; to date, however, such designs have primarily relied on carbonyl- and olefin-related functional groups. Bifunctional silyl ethers (BSEs; SiR₂(OR′₂)) could expand the functional scope of PE mimics as they possess strong Si−O bonds and facile chemical tunability. Here, we report BSE-containing high-density polyethylene (HDPE)-like materials synthesized through a one-pot catalytic ring-opening metathesis polymerization (ROMP) and hydrogenation sequence. The crystallinity of these materials can be adjusted by varying the BSE concentration or the steric bulk of the Si-substituents, providing handles to control thermomechanical properties. Two methods for chemical recycling of HDPE mimics are introduced, including a circular approach that leverages acid-catalyzed Si−O bond exchange with 1-propanol. Additionally, despite the fact that the starting HDPE mimics were synthesized by chain-growth polymerization (ROMP), we show that it is possible to recover the molar mass and dispersity of recycled HDPE products using step-growth Si−O bond formation or exchange, generating high molecular weight recycled HDPE products with mechanical properties similar to commercial HDPE.     

High speed injection molding of high density polyethylene �� Effects of injection speed on structure and properties

Thin wall samples of high density polyethylene (HDPE) were prepared via injection molding with different injection speeds ranging from 100 mm/s to 1200 mm/s. A significant decrease in the tensile strength and Young??s modulus was observed with increasing injection speed. In order to investigate the mechanism behind this decrease, the orientation, molecular weight, molecular weight distribution, melt flow rate, crystallinity and crystal morphology of HDPE were characterized using two-dimensional wide-angle X-ray diffraction (2D-WAXD), gel permeation chromatography (GPC), capillary rheometry and differential scanning calorimetry (DSC), respectively. It is demonstrated that the orientation, molecular weight, molecular weight distribution, melt flow rate and crystallinity have no obvious change with increasing injection speed. Nevertheless, the content of extended chain crystals or large folded chain crystals was found to decrease with increasing injection speed. Therefore, it is concluded that the decrease in tensile properties is mainly contributed by the reduced content of extended chain crystals or large folded chain crystals. This study provides industry with valuable information for the application of high speed injection molding.     

Morphological and structural features of heat-treated drawn polypropylene/high-density polyethylene blends

The ion etching technique has been applied to a morphological study of mechanically blended polypropylene (PP) with high-density polyethylene (HDPE). Samples blended to PP/HDPE compositions of 65/35 and 85/15 by weight were highly drawn and then heat treated for 30 min at selected temperatures up to 163°C. When these samples are carefully ion-etched several features are observed in electron micrographs, namely (i) crosshatched, and (ii) twisted or layered textured inclusions of HDPE crystals within arrays of lamellalike PP crystals situated perpendicular to the direction of drawing. X-ray diffraction measurements of the drawn samples heat treated in the range 145–163°C for 30 min shows that oriented HDPE crystallizes with b-axis orientation along the drawing direction. Supporting evidence is obtained from electron diffraction measurements. The molecular weight of the HDPE component is a major factor in the b-axis-oriented growth of HDPE crystals in PP/HDPE blends.     

辊速辊温对高密度聚乙烯拉伸微孔膜及其片晶结构的影响

采用熔融挤出片材—退火—冷拉伸—热拉伸—热定形的方法来制备高密度聚乙烯(HDPE)微孔膜,利用FTIR、SEM和DSC等测试方法来研究辊速辊温对HDPE拉伸微孔膜及其片晶结构的影响.研究结果表明,所选树脂的分子量、分子量分布以及弛豫时间能够满足现有加工条件,形成片晶取向度较高的预制膜;在相同辊温下,随辊速增加,退火前预...     

紫外辐照对高密度聚乙烯分子结构的影响

紫外线;官能化;紫外辐照对高密度聚乙烯分子结构的影响     

Preparing iPP/HDPE/CB functionally gradient materials: influence factors of components and processing

In this work, gradient materials with low electrical resistivity were prepared by compounding isotactic polypropylene (iPP)/high density polyethylene (HDPE) blends with carbon black (CB) through extruding and injection molding. Contact angle measurements and morphology measurements showed that the CB particles were selectively located in HDPE phase and the final composites had a gradient structure that the HDPE/CB phase exhibited different morphologies in the skin layer and core layer of the composites under different processing procedures. The main factors influencing the formation of the functional gradient materials (FGM), including screw speed during extruding, iPP types and CB contents were discussed. They affect the phase morphology by shear stress, the restoration of HDPE phase, and the viscosity ratio of polymer blends, respectively. In conclusion, iPP/HDPE/CB FGM could be formed easily in the composites blending with the iPP type with narrow molecular weight distribution (MWD) and higher CB content extruded at higher screw speed. The electrical properties of iPP/HDPE/CB composites were studied and the results showed that screw speed in extrusion significantly influenced the percolation curve and electrical property of the final composites. Copyright © 2011 John Wiley & Sons, Ltd.     

Tear anisotropy in films blown from polyethylenes of different macromolecular architectures

Blown films of different types of polyethylenes, such as branched low‐density polyethylene (LDPE) and linear high‐density polyethylene (HDPE), are well known to tear easily along particular directions: along the film bubble's transverse direction for LDPE and along the machine direction (MD) for HDPE. Depending on the resin characteristics and processing conditions, different structures can form within the film; it is therefore difficult to separate the effects of the crystal structure and orientation on the film tear behavior from the effects of the macromolecular architecture, such as the molecular weight distribution and long‐chain branching. Here we examine LDPE, HDPE, and linear low‐density polyethylene (LLDPE) blown films with similar crystal orientations, as verified by through‐film X‐ray scattering measurements. With these common orientations, LDPE and HDPE films still follow the usual preferred tear directions, whereas LLDPE tears isotropically despite an oriented crystal structure. These differences are attributed to the number densities of the tie molecules, especially along MD, which are considerably greater for linear‐architecture polymers with a substantial fraction of long chains, capable of significant extension in flow. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 413–420, 2005     

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.     

Influence of extrusion ratio on the thermal properties and morphology of ultradrawn high-density polyethylene

Solid-state extrusion of high-density polyethylene (HDPE) has received considerable attention. It has been shown that extrudate may have high values of optical clarity, tensile modulus (～70 GPa = 7 × 10¹¹ dyn/cm²), and c-axis orientation. The effects of extrusion conditions on the properties of the resultant fibers have, however, not yet been clarified. A systematic study has thus been made here to evaluate extrusion pressure, temperature, and extrusion (draw) ratio, and the molecular weight of extruded HDPE. The effects of extrusion ratio on the degree of crystallinity, melting behavior, crystal orientation, and dimensional change along the extrusion direction are reported.     

Characterization of Polyethylene Nascent Powders Synthesized with TpTiCl2(OR) Catalysts

Summary: Different kinds of polyethylene and ethylene-1-hexene copolymers were synthesized with TpTiCl₂(OR) (Tp = hydrotris(pyrazolyl)borate; R = Et, i-Pr, n-Bu) catalysts with and without H₂. The polymers were characterized by ¹³C NMR, capillary viscosimetry or GPC, and DSC. The homopolymers showed properties characteristic of ultra-high molecular weight polyethylenes (UHMWPE) with linear structure and high density polyethylenes (HDPE) with molecular weights in the range of commercial grades under hydrogen atmosphere. The copolymers showed a 1-hexene incorporation up to 6 mol-%. Important differences in the thermal properties were observed between the first DSC (nascent powders) and the second DSC heatings (melt-crystallized samples), which evidenced the molecular weights influence on the melt-crystallized samples.     

高密度聚乙烯／超高分子量聚乙烯共混物高取向薄膜形态结构与力学性能的研究

高密度聚乙烯／超高分子量聚乙烯共混物高取向薄膜形态结构与力学性能的研究张伟广，赵勇，杨德才中国科学院长春应用化学研究所，高分子物理开放实验室，长春，１３００２２）关键词ＨＤＰＥ、ＵＨＭＷＰＥ、共混物、形态结构、力学性能如何提高高分子材料抗张强度和模量...     

The effect of plasma treatment on the mechanical behavior of UHMWPE fiber–reinforced thermoplastic HDPE composite

Ultra‐high‐molecular‐weight polyethylene (UHMWPE) fibers have been modified by plasma treatment to increase adhesion in high‐density polyethylene (HDPE) matrices. Results showed that surface roughness predominates for modified UHMWPE fibers, indicating that the plasma treatment favors the interaction with HDPE. Unmodified HDPE composite samples gave a lower interlaminar shear strength than did the samples that were incorporated with UHMWPE. The addition of unmodified UHMWPE fibers to the neat HDPE significantly increases interlaminar shear strengths of composites, up to 20 vol%. The oxygen concentration increased from 16.16 %to 21.99%, and the ratio of oxygen to carbon atoms increased significantly from 0.194 to 0.284 after oxygen plasma treatment for 5 minutes with a power of 300 W.