Melt transcrystallization of polyethylene on high modulus polyethylene fibers

A polytheylene composite was prepared and tested. It was consisted of a high-density polyethylene (HDPE) matrix and uniaxial gel-spun high-modulus PE fiber. Aided by the similarity between matrix and fiber, transcrystallization of HDPE melt on the PE fiber surface was generated. Nucleating agents were not employed. The transcrystalline growth of HDPE on the PE fiber surface was found to consist of an inner and an outer zone. The inner zone, 2–3 μm thick, is composed of HDPE crystals nucleated on the PE fiber surface. Photomicrographs showed a well-defined region of row-nucleated HDPE on the surface of PE fiber. This means the fibrils of HDPE were found to grow out from the PE fiber axis and HDPE crystallites are oriented in planes perpendicular to the PE fiber axis. The fiber in the composite induced the transcrystalline growth of HDPE on the PE fiber surface at higher temperature than on cooling the melt. For 36 wt% fiber, the increase was 2.5°C, also resulting in ～ 10% more crystals. Crystallization of a composite with 50 wt% fiber at 124°C involved two steps: The first a fast transcrystallization of HDPE on the PE fiber surface followed by the bulk crystallization of the HDPE.     

Nanoclay reinforced polyethylene composites: Effect of different melt compounding methods

Nanoclay (NC) reinforced high‐density polyethylene (HDPE) composites were prepared by different melt compounding methods using (1) a single screw extruder (SSE), (2) twin screw extruder (TSE), (3) a combination of SSE and extensional flow mixer (EFM), and (4) a bowl mixer masterbatch method (MB). PE‐grafted maleic anhydride (PE‐g‐MA) was used as a compatibilizer. EFM increased complex melt viscosity (η*) of the HDPE/NC composites as compared to the neat HDPE and also provided a better interaction between HDPE and NC to create slightly lower melt η* as compared to MB and PE‐g‐MA composites. The low viscosity melt behavior of the pure HDPE changes to more solid like melt behavior in the PE‐g‐MA HDPE/NC composites in the low frequency (ω) region. PE‐g‐MA + EFM method exhibited better impact strength compared to the other HDPE/NC composites. Using the PE‐g‐MA and masterbatch compounding methods had a beneficial role in improving mechanical properties. POLYM. ENG. SCI., 57:324–334, 2017. © 2016 Society of Plastics Engineers     

Processing–Nanostructure–Property Relationships of All‐Polyethylene Composites Reinforced by Flow‐Induced Oriented Crystallization of UHMWPE

All‐polyethylene composites exhibiting substantially improved toughness/stiffness balance are readily produced during conventional injection molding of high density polyethylene (HDPE) in the presence of bimodal polyethylene reactor blends (RB40) containing 40 wt% ultrahigh molar mass polyethylene (UHMWPE) dispersed in HDPE wax. Scanning electron microscopy (SEM) and differential scanning calorimetry (DSC) analyses shows that flow‐induced crystallization affords extended‐chain UHMWPE nanofibers forming shish which nucleates HDPE crystallization producing shish‐kebab structures as reinforcing phases. This is unparalleled by melt compounding micron‐sized UHMWPE. Injection molding of HDPE with 30 wt% RB40 at 165 °C affords thermoplastic all‐PE composites (12 wt% UHMWPE), improved Young's modulus of 3400 MPa, tensile strength of 140 MPa, and impact resistance of 22.0 kJ/m². According to fracture surface analysis, the formation of skin‐intermediate‐core structures accounts for significantly improved impact resistance. At constant RB40 content both morphology and mechanical properties strongly depend upon processing temperature. Upon increasing processing temperature from 165 °C to 250 °C the average shish‐kebab diameter increases from the nanometer to micron range, paralleled by massive loss of self‐reinforcement above 200 °C. The absence of shish‐kebab structure at 250 °C is attributed to relaxation of polymer chains and stretch‐coil transition impairing shish formation.     

Effect of small amount of ultra high molecular weight component on the crystallization behaviors of bimodal high density polyethylene

In order to clarify the effect of high molecular weight component on the crystallization of bimodal high density polyethylene (HDPE), a commercial PE-100 pipe resin was blended with small loading of ultra high molecular weight polyethylene (UHMWPE). The isothermal crystallization kinetics and crystal morphology of HDPE/UHMWPE composites were studied by differential scanning calorimetry (DSC) and polarized optical microscopy (POM), respectively. The presence of UHMWPE results in elevated initial crystallization temperature of HDPE and an accelerating effect on isothermal crystallization. Analysis of growth rate using Lauritzen-Hoffman model shows that the fold surface free energy (σ_e) of polymer chains in HDPE/UHMWPE composites was lower than that in neat HDPE. Morphological development during isothermal crystallization shows that UHMWPE can obviously promote the nucleation rate of HDPE. It should be reasonable to conclude that UHMWPE appeared as an effective nucleating agent in HDPE matrix. Rheological measurements were also performed and it is shown that HDPE/UHMWPE composites are easy to process and own higher melt viscosity at low shear rate. Combining with their faster solidification, gravity-induced sag in practical pipe production is expected to be effectively avoided.     

Influence of nanoclay on properties of HDPE/wood composites

Composites based on high density polyethylene (HDPE), pine flour, and organic clay were made by melt compounding and then injection molding. The influence of clay on crystallization behavior, mechanical properties, water absorption, and thermal stability of HDPE/pine composites was investigated. The HDPE/pine composites containing exfoliated clay were made by a two‐step melt compounding procedure with the aid of a maleated polyethylene (MAPE). The use of 2% clay decreased the crystallization temperature (T_c), crystallization rate, and the crystallinity level of the HDPE/pine composites, but did not change the crystalline thickness. When 2% MAPE was added, the crystallization rate increased, but the crystallinity level was further lowered. The flexural and tensile strength of HDPE/pine composites increased about 20 and 24%, respectively, with addition of 1% clay, but then decreased slightly as the clay content increased to 3%. The tensile modulus and tensile elongation were also increased with the addition of 1% clay. The impact strength was lowered about 7% by 1% clay, but did not decrease further as more clay was added. The MAPE improved the state of dispersion in the composites. Moisture content and thickness swelling of the HDPE/pine composites was reduced by the clay, but the clay did not improve the composite thermal stability. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Properties of bamboo flour/high-density polyethylene composites reinforced with ultrahigh molecular weight polyethylene

In order to improve the properties of bamboo-plastic composites (BPCs), bamboo flour/high-density polyethylene (HDPE) composites were reinforced with ultrahigh molecular weight polyethylene (UHMWPE). The effects of UHMWPE on properties of composites were studied. The crystallinity of composites decreased slightly. Compared with non-UHMWPE added bamboo powder/HDPE composite, the composite with 6 wt % UHMWPE, showed decrease in water absorption to 0.41%, whereas its tensile strength and flexural strength increased to 34.51 and 25.88 MPa, respectively, a corresponding increase of 34.59 and 12.87%. The temperatures corresponding to initial degradation temperature (T_initial) and maximum degradation temperature (T_max) of the composite increased from 282.7 and 467.4 °C to 288.5 and 474.7 °C respectively. Scanning electron microscopic images showed that UHMWPE was well dispersed and fully extended as long fibers in the composite, forming a “three-dimensional physically cross-linked network structure,” which contributed to the improved properties of the composites. © 2020 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48971.     

增容剂对HDPE/UHMWPE/纳米HA生物复合材料性能的影响

通过熔融共混法制备了高密度聚乙烯/超高分子量聚乙烯/纳米羟基磷灰(石HDPE/UHMWPE/纳米HA)生物复合材料,研究了增容剂三元乙丙橡胶接枝马来酸(酐EPDM-g-MAH)和聚烯烃弹性体接枝马来酸酐(POE-g-MAH)对复合材料力学性能的影响,并利用红外光谱、扫描电镜、热重分析仪及熔体流动速率仪表征了复合材料的微观结构、热性能和流动性能。结果表明:EPDM-g-MAH和POE-g-MAH均可提高HDPE/UHMWPE/纳米HA复合材料的相容性,其中EPDM-g-MAH的增容效果更明显;随着增容剂用量的增大,复合材料的熔体流动速率、热变形温度和热稳定性逐渐下降;与添加POE-g-MAH相比,含有EPDM-g-MAH的复合材料的综合性能较好。     

Effect of entangled state of nascent UHMWPE on structural and mechanical properties of HDPE/UHMWPE blends

In this study, a synthesized ultra‐high molecular weight polyethylene (UHMWPE) with a less entangled state and a commercial UHMWPE with a highly entangled state were blended with high‐density polyethylene (HDPE) by melt blending, respectively. Rheology, 2D small‐angle X‐ray scattering (2D‐SAXS), differential scanning calorimetry (DSC), and tensile test were used to study the relationship between the microstructure and the mechanical properties of blends. It was demonstrated that the UHMWPE with the less entangled state was easy to be oriented at a given flow. More mechanical networks were achieved among the HDPE matrix and the UHMWPE chains due to the fewer entanglements of synthesized UHMWPE, improving the melting recovery of blends. Furthermore, notably oriented structures (shish‐kebabs) with increased long‐periods were made in the blends of weakly entangled UHMWPE and HDPE. The tensile strength of this blend was thus enhanced, i.e., the tensile strength raised for neat HDPE from 45.7 to 83.1 MPa for HDPE/UHMWPE blends containing 10 wt % of less entangled UHMWPE. However, the phase separation of blends was characterized when more weakly entangled UHMWPE was incorporated. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44728.     

Transcrystallinity in brominated UHMWPE fiber reinforced HDPE composites: morphology and dielectric properties

Ultra-high-molecular-weight polyethylene (UHMWPE) fibers were treated by photochemical bromination. The analysis of the fibers by XPS and ATR-FTIR showed that this process led to the introduction of C–Br and C–OH moieties and generated CC bonds at the PE fiber surface.Composites were fabricated using either treated or untreated fibers and high-density polyethylene (HDPE) for the matrix. WAXD analysis showed that the treated fibers, through offering a higher concentration of crystallization nuclei, generated a denser transcrystalline layer with higher specific radial orientation with respect to the fiber axis—compared with the untreated fiber. Furthermore, the introduction of polarity onto the fiber surface enabled analysis of the complex relaxation behavior of PE/PE composites by dielectric spectroscopy. It showed the typical α, β and γ-relaxation processes of polyethylene, combined with the effect of the transcrystalline layer, generating—among other changes—a strong β-transition.     

超高相对分子质量聚乙烯对双峰HDPE树脂性能的影响

为了提高双峰高密度聚乙烯（HDPE）的力学性能,采用超高相对分子质量聚乙烯（UHM—WPE）与双峰HDPE以不同比例共混,对共混物的相对分子质量及其分布、热性能、流变性能和力学性能进行了测试。UHMWPE的加入使高相对分子质量部分显著增加,流变性能下降,添加量小于10％（质量分数）时,共混物粘度在高剪切速率下变化不大;UHMWPE可提高共混物的熔融温度和初始结晶温度,结晶度先增加然后迅速降低;随着UHMWPE含量的增加,混合物的拉伸强度也随之增加,呈线性关系;结晶度与冲击强度成反比。     

Effect of polyethylene‐graft‐maleic anhydride as a compatibilizer on the mechanical and tribological behaviors of ultrahigh‐molecular‐weight polyethylene/copper composites

Ultrahigh‐molecular‐weight polyethylene/copper (UHMWPE/Cu) composites compatibilized with polyethylene‐graft‐maleic anhydride (PE‐g‐MAH) were prepared by compression molding. The effects of the compatibilizer on the mechanical, thermal, and tribological properties of the UHMWPE/Cu composites were investigated. These properties of the composites were evaluated at various compositions, and worn steel surfaces and composite surfaces were examined with scanning electron microscopy and X‐ray photoelectron spectroscopy. The incorporation of PE‐g‐MAH reduced the melting points of the composites and increased their crystallinity to some extent. Moreover, the inclusion of the PE‐g‐MAH compatibilizer greatly increased the tensile rupture strength and tensile modulus of the composites, and this improved the wear resistance of the composites. These improvements in the mechanical and tribological behavior of the ultrahigh‐molecular‐weight‐polyethylene‐matrix composites with the PE‐g‐MAH compatibilizer could be closely related to the enhanced crosslinking function of the composites in the presence of the compatibilizer. Moreover, the compatibilizer had an effect on the transfer and oxidation behavior of the filler Cu particulates, which could be critical to the application of metallic‐particulate‐filled polymer composites in engineering. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 948–955, 2004     

Influence of fly ash cenospheres on performance of coir fiber‐reinforced recycled high‐density polyethylene biocomposites

Recycled high‐density polyethylene (RHDPE)/coir fiber (CF)‐reinforced biocomposites were fabricated using melt blending technique in a twin‐screw extruder and the test specimens were prepared in an automatic injection molding machine. Variation in mechanical properties, crystallization behavior, water absorption, and thermal stability with the addition of fly ash cenospheres (FACS) in RHDPE/CF composites were investigated. It was observed that the tensile modulus, flexural strength, flexural modulus, and hardness properties of RHDPE increase with an increase in fiber loading from 10 to 30 wt %. Composites prepared using 30 wt % CF and 1 wt % MA‐g‐HDPE exhibited optimum mechanical performance with an increase in tensile modulus to 217%, flexural strength to 30%, flexural modulus to 97%, and hardness to 27% when compared with the RHDPE matrix. Addition of FACS results in a significant increase in the flexural modulus and hardness of the RHDPE/CF composites. Dynamic mechanical analysis tests of the RHDPE/CF/FACS biocomposites in presence of MA‐g‐HDPE revealed an increase in storage (E′) and loss (E″) modulus with reduction in damping factor (tan δ), confirming a strong influence between the fiber/FACS and MA‐g‐HDPE in the RHDPE matrix. Differential scanning calorimetry, thermogravimetric analysis thermograms also showed improved thermal properties in the composites when compared with RHDPE matrix. The main motivation of this study was to prepare a value added and low‐cost composite material with optimum properties from consumer and industrial wastes as matrix and filler. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42237.     

Development of a new thermoplastic laminate system

In this investigation an all-olefin thermoplastic laminate was developed and characterized. Commingled glass-fiber polypropylene (PP) composite was used as skin and HDPE (PE) foam with closed cells as core. Infra-red heating was used for melting the surfaces of the substrates for surface fusion bonding with a cold press. Two tie-layer films, viz., ethylene-propylene copolymer (EPC) and HDPE/elastomer blend were used as hot-melt adhesives for bonding the substrates. Singlelap shear joints were prepared from PP composite and PE foam adherends with a bonding area of 25.4 mm × 25.4 mm to determine the bond strength. EPC tie-layer adhesive provided higher bond strength (2.68 × 10⁶ N/m²) to the all-olefin laminate than that based on HDPE/elastomer blend (1.93 × 106 N/m²). For EPC tie-layer-based laminates, a mixed mode of failure was observed in the failed lap shear samples: about 40% was cohesive failure through the tie-layer, and the rest of failure was interfacial, either at PP composite or PE foam surfaces. Environmental scanning electron micrographs (ESEM) revealed that in the process of surface fusion bonding, PE foam cells in the vicinity of interphase (800-μm-thick) were coalesced with high temperature and pressure. No macro-level penetration of the tie-layer melt front into the foam cells was observed. As the surface morphology of foam was altered due to IR surface heating and the PP composite bonding side had a resin-rich layer, the bonding situation was closer to that between two polymer film surfaces.     

PE/PE‐g‐MAH/Org‐MMT nanocomposites. II. Nonisothermal crystallization kinetics

The nonisothermal crystallization kinetics of high‐density polyethylene (HDPE) and polyethylene (PE)/PE‐grafted maleic anhydride (PE‐g‐MAH)/organic‐montmorillonite (Org‐MMT) nanocomposite were investigated by differential scanning calorimetry (DSC) at various cooling rates. Avrami analysis modified by Jeziorny, Ozawa analysis, and a method developed by Liu well described the nonisothermal crystallization process of these samples. The difference in the exponent n, m, and a between HDPE and the nanocomposite indicated that nucleation mechanism and dimension of spherulite growth of the nanocomposite were different from that of HDPE to some extent. The values of half‐time (t_1/2), K(T), and F(T) showed that the crystallization rate increased with the increase of cooling rates for HDPE and composite, but the crystallization rate of composite was faster than that of HDPE at a given cooling rate. Moreover, the method proposed by Kissinger was used to evaluate the activation energy of the mentioned samples. It was 223.7 kJ/mol for composite, which was much smaller than that for HDPE (304.6 kJ/mol). Overall, the results indicated that the addition of Org‐MMT and PE‐g‐MAH could accelerate the overall nonisothermal crystallization process of PE. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 91: 3054–3059, 2004     

用PE改进UHMPE流动性的研究

选用不同牌号的高密度聚乙烯(HDPE)和低密度聚乙烯(LDPE)作为超高摩尔质量聚乙烯(UHMWPE)的流动改性剂，通过对共混物流变转矩、熔体质量流动速率及力学性能的分析；探讨了配比对UHMWPE／PE共混物流动性的影响。结果表明：用中等摩尔质量的PE改善UHMWPE的加工流动性效果较好，流动性越好的中等摩尔质量PE对UHMWPE的流动性改善效果也越显著；但对共混物力学性能的不利影响也越大。     

Property transitions in high‐density polyethylene/maleated poly(ethylene–octene)/calcium carbonate ternary composites

Ternary composites of high‐density polyethylene (HDPE)/maleated poly(ethylene–octene) (POE‐g)/calcium carbonate (CaCO₃) were prepared by the melt extrusion process. Crystallization behavior investigation and mechanical properties study showed that there existed a transition in both crystallization temperature (T_c) and impact strength of ternary composites. These transitions were attributed to the development of morphology, with variation of concentration of POE‐g in ternary composites. The strength of interfacial adhesion also influenced the property transitions. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 3361–3366, 2006     

Development and characterization of an all‐olefin thermoplastic sandwich composite system

In this investigation an all‐olefin thermoplastic sandwich system was developed and characterized. Commingled glass fiber polypropylene (PP) composite was used as skin and HDPE (PE) foam with closed cells as core. Infra‐red heating was used for melting the surfaces of the substrates for surface fusion bonding with a cold press. Two tie layer films, viz. ethylene‐propylene copolymer (EPC) and HDPE/elastomer blend, were used as hot melt adhesives for bonding the substrates. Single lap shear joints were prepared from PP composite and PE foam adherends with a bonding area of 25.4 mm × 25.4 mm to determine the interface strength. EPC tie layer provided higher bond strength (27.4 kg/cm²) to the all‐olefin sandwich system than HDPE/elastomer blend based one (19.7 kg/cm²). For EPC tie layer based sandwiches, a mixed mode a failure was observed in the failed lap shear samples; about 40% is cohesive failure through tie layer, and the rest of failure was adhesive either at PP composite or PE surfaces. Environmental scanning electron micrographs (ESEM) reveal that in the process of surface fusion bonding, PE foam cells in the vicinity of 0.80 mm interphase area were coalesced with high temperature and pressure. No macro level penetration of tie layer melt front into foam cells was observed. As the surface morphology of foam was altered on account of IR surface heating and the PP composite bonding side had a resin‐rich layer, the bonding situation was closer to that between two polymer film surface.     

Thermal and mechanical properties of UHMWPE/HDPE/PCL and bioglass filler: Effect of polycaprolactone

Polymeric composites based on polyethylene, high-density polyethylene (HDPE) and ultra-high-molecular-weight polyethylene (UHMWPE) with polycaprolactone (PCL) and a ceramic filler (bioglass type) were studied in terms of their thermal and mechanical behavior. Two polyethylene ratios (10/90 and 30/70% wt/wt of UHMWPE/HDPE) and two PCL content ratios (5% and 10% wt/wt) were used. The obtained composites were characterized by differential scanning calorimetry, melt flow index, Fourier transform infrared spectroscopy, scanning electron microscopy, and X-ray diffraction. The results indicate a nonchemical interaction between polyethylene, especially the UHMWPE, and PCL and that the composites' thermal transitions vary from the parent polymers and depend on the PCL concentration. The PCL's melting temperature in the composite was reduced, showing a new one. Also, the melting enthalpy of polyethylene was reduced when the concentration of PCL increased. The mechanical behavior depends on both the polyethylene ratio and the PCL content. The composite with 30% wt/wt of UHMWPE and 10% wt/wt of PCL showed the highest toughness value due to the good interaction between polymers. These new composites may be attractive for biomedical applications and could be evaluated, for example, as materials for prostheses.     

The effects of hybrid fillers on thermal,mechanical, physical,and antimicrobial properties of ultrahigh‐molecular‐weight polyethylene‐reinforced composites

The effects of hybrid filler of zinc oxide and chitosan (chitosan–ZnO) on thermal, flexural, antimicrobial, chemical resistance, and hardness properties of ultrahigh‐molecular‐weight polyethylene (UHMWPE) composites with varying concentration of zinc oxide (ZnO) and further hybridized by chitosan (CS) were successfully studied. The composites were prepared using mechanical ball milling and followed by hot compression molding. The addition of ZnO to the UHMWPE matrix had lowered the melting temperature (T _m) of the composite but delayed its degradation temperature. Further investigation of dual filler incorporation was done by the addition of chitosan to the UHMWPE/ZnO composite and resulted in the reduction of UHMWPE crystallization. The flexural strength and modulus had a notably high improvement through ZnO addition up to 25 wt% as compared to neat UHMWPE. However, the addition of chitosan had resulted in lower flexural strength than that of 12 wt% ZnO UHMWPE composite but still higher than that of neat UHMWPE. It was experimentally proven that the incorporation of ZnO and chitosan particles within UHMWPE matrix had further enhanced the antimicrobial properties of neat UHMWPE. Chemical resistance was improved with higher ZnO content with a slight reduction of mass change after the incorporation of chitosan. The hardness value increased with ZnO addition but higher incorporation of chitosan had lowered the hardness value. These findings have significant implications for the commercial application of UHMWPE based products. It appears that these hybrid fillers (chitosan–ZnO)‐reinforced UHMWPE composites exhibit superior overall properties than that of conventional neat UHMWPE. POLYM. COMPOS., 38:1689–1697, 2017. © 2015 Society of Plastics Engineers     

碳纳米管/HDPE复合材料的制备及性能研究

将酸化处理以后的碳纳米管（CNTs）与高密度聚乙烯（HDPE）复合，采用机械共混法制备了定向CNTs／HDPE复合材料，并对其力学性能、相态结构、流变性能及热性能进行了研究。结果表明：CNTs的加入，提高了复合材料的屈服强度和拉伸模量，但同时却降低了材料的断裂强度和断裂伸长率；CNTs在HDPE基体中有了较好的分散性和相容性；CNTs的加入对复合材料流变性能产生了较大的影响，加入少量的CNTs可以使复合材料体系的表观粘度降低，有利于HDPE加工性能的改善；CNTs加入后，HDPE的熔融温度和结晶熔融焓均有所下降。