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.     

Adhesion of propylene–ethylene copolymers to high‐density polyethylene

The adhesion of some propylene–ethylene (P/E) copolymers to polypropylene (PP) and high density polyethylene (HDPE) was studied in order to compare them with other olefin copolymers as compatibilizers for PP/HDPE blends. A one‐dimensional model of the compatibilized blends was fabricated by layer‐multiplying coextrusion. The microlayered tapes consisted of many alternating layers of PP and HDPE with a thin tie‐layer inserted at each interface. The thickness of the tie‐layer varied from 0.1 to 15 μm, which included thicknesses comparable to those of the interfacial layer in a compatibilized blend. In the T‐peel test, the P/E copolymers delaminated at the HDPE interface. An elastomeric P/E with higher ethylene content exhibited substantially higher delamination toughness than a more thermoplastic P/E with lower ethylene content. Inspection of the crack‐tip damage zone revealed that a change from deformation of the entire tie‐layer to formation of a localized yielded zone was responsible. By treating the damage zone as an Irwin plastic zone, it was demonstrated that a critical stress controlled the delamination toughness. The temperature dependence of the delamination toughness was also measured. POLYM. ENG. SCI., 2010. © 2009 Society of Plastics Engineers     

Effect of ethylene-propylene copolymer with residual PE crystallinity on mechanical properties and morphology of PP/HDPE blends

Morphology and mechanical properties of polypropylene (PP)/high density polyethylene (HDPE) blends modified by ethylene-propylene copolymers (EPC) with residual PE crystallinity were investigated. The EPC showed different interfacial behavior in PP/HDPE blends of different compositions. A 25/75 blend of PP/HDPE (weight ratio) showed improved tensile strength and elongation at break at low EPC content (5 wt %). For the PP/HDPE = 50/50 blend, the presence of the EPC component tended to make the PP dispresed phase structure transform into a cocontinuous one, probably caused by improved viscosity matching of the two components. Both tensile strength and elongation at break were improved at EPC content of 5 wt %. For PP/HDPE 75/25 blends, the much smaller dispersed HDPE phase and significantly improved elongation at break resulted from compatibilization by EPC copolymers. © 1995 John Wiley & Sons, Inc.     

Effect of molding temperature on crystalline and phase morphologies of HDPE composites containing PP nano-fibers

A high-density polyethylene (HDPE)/isotactic polypropylene (PP) (75/25) blend containing 25 wt% of PP was fibrillated by roller drawing at 138 °C. The fibrillated blend was processed again at temperatures ranging from 155 to 200 °C by compression molding or extrusion. The effects of molding temperature on the morphology and mechanical properties of the blend were investigated. Wide angle X-ray scattering (WAXS) and transmission electron microscopy (TEM) were used to study the morphology of the samples. The roller-drawn blend exhibited a fibrous structure with the chain direction aligned parallel to the drawing direction. After molding at 155 °C, the HDPE formed parallel-stacked lamellae retaining the parallel orientation after the melting of the PE crystals. As the molding temperature increased the parallel orientation gradually vanished and some of the parallel-stacked lamellae changed into twisted lamellae. The PP phase existed as fibrils in the PE matrix and the crystals stayed with their molecular chain aligned parallel to the fibrillation direction even when the molding temperature was far above the melting temperature of PP. Nevertheless, the orientation of the crystals did not change as the molding temperature increased from 155 to 165 °C. The internal structure of the PP fibrils changed from a needle structure to a parallel-stacked one. The PP fibrils induced the crystallization of the PE melt, leading to the formation of a trans-crystalline layer at their surface. As the molding temperature increased, more PE lamellae protruded into the PP fibrils and the interface between the PP fibrils and the PE matrix became diffuse.     

Improvement of adhesion between poly(ethylene terephthalate) and polyethylene

Three-layer films were prepared with polyethylene (PE) and poly(ethylene terephthalate) (PET) films as the outer layers and a film of high-density polyethylene (HDPE)/ethylene-methyl acrylate-glycidyl methacrylate (E-MA-GMA) terpolymer blend as the inner layer using compression molding. E-MA-GMA, an elastomer containing an epoxy functional group, was used as the adhesion promoting agent in the multilayer films. The effects of processing temperature, pressure application time and elastomer concentration on adhesion were investigated. The adhesion strength between PE and PET films increased with increasing bonding temperature, bonding time and elastomer concentration. From contact angle measurements, it was observed that the work of adhesion between the polymers increased with increasing amount of elastomer. Improved adhesion between PET and HDPE with 30% elastomer films was confirmed by SEM analyses of the film layers. Using FT-IR analysis of PE/HDPE-30% elastomer/PET delaminated film, the decrease in peak intensity of the epoxy groups tends to indicate reaction of epoxy functionality with functional groups in PET.     

塑料输液容器用聚丙烯组合盖外盖材料增韧研究

采用聚乙烯（PE）、弹性体及其他助剂增韧改性聚丙烯（PP）,熔融共混挤出造粒制备塑料输液容器用PP组合盖（拉环式）外盖材料。通过正交试验优化了各组分之间的配比,考察了弹性体、PE对PP组合盖（拉环式）外盖材料力学性能及外盖拉环开启力的影响。结果表明,弹性体用量对复合材料的性能影响最显著,当弹性体用量从15份（质量份,下同）增加到30份时,材料的冲击强度先增大后减小,最高达35 kJ/m2,拉伸强度减小,外盖拉环开启力减小,最小达64 N;扫描电子显微镜观察显示,当弹性体的用量小于25份时,弹性体在体系中分散均匀;综合考虑,满足外盖拉环开启力小、拉伸强度大和冲击强度大的最佳配方为PP 65份, PE 20份,弹性体25份,抗氧剂及其他助剂共5份。     

Effect of tie-layer thickness on the adhesion of ethylene-octene copolymers to polypropylene

The adhesion of some ethylene-octene copolymers to polypropylene (PP) and high density polyethylene (HDPE) was studied in order to evaluate their suitability as compatibilizers for PP/HDPE blends. A one-dimensional model of the compatibilized blend was fabricated by layer-multiplying coextrusion. The microlayered tapes consisted of many alternating layers of PP and HDPE with a thin tie-layer inserted at each interface. The thickness of the tie-layer varied from 0.1 to 15 μm, which included thicknesses comparable to those of the interfacial layer in a compatibilized blend. The delamination toughness was measured in the T-peel test. Generally, delamination toughness decreased as the tie-layer became thinner with a stronger dependence for tie layers thinner than 2 μm. Inspection of the crack-tip damage zone revealed a change from a continuous yielded zone in thicker tie layers to a highly fibrillated zone in thinner tie layers. By treating the damage zone as an Irwin plastic zone, it was demonstrated that a critical stress controlled the delamination toughness. The temperature dependence of the delamination toughness was also measured. A blocky copolymer (OBC) consistently exhibited better adhesion to PP than statistical copolymers (EO). A one-to-one correlation between the delamination toughness and the reported performance of the copolymers as compatibilizers for PP/HDPE blends confirmed the key role of interfacial adhesion in blend compatibilization.     

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.     

Surface modification of single‐walled carbon nanotubes with polyethylene via in situ Ziegler–Natta polymerization

Single‐walled carbon nanotubes (SWNTs) were modified with polyethylene (PE) prepared by in situ Ziegler–Natta polymerization. Because of the catalyst pretreated on the surface of the SWNTs, the ethylene was expected to polymerize there. Scanning electron microscopy images and solubility measurements showed that the surface of the SWNTs was covered with a PE layer, and a crosslink may have formed between the SWNTs and PE. When the SWNTs covered with a PE layer were mixed with commercialized PE by melt blending, the resulting composite had better mechanical properties than the composite from the SWNTs without a PE layer. The yield strength, the tensile strength and modulus, the strain at break, and the fracture energy of the modified‐SWNT/PE composites were improved by 25, 15.2, 25.4, 21, and 38% in comparison with those of the raw‐SWNT/PE composites. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 3697–3700, 2004     

输液容器用PP组合盖内盖材料制备及性能研究

采用聚乙烯、弹性体及其他助剂增韧改性聚丙烯（PP）,熔融共混挤出造粒制备输液容器用PP组合盖内盖材料。通过正交试验优化了各组分之间的配比,考察了聚乙烯、弹性体对PP组合盖内盖材料机械性能及内盖穿刺力的影响,并测试了内盖材料的溶出物性能。结果表明弹性体用量对内盖材料的机械性能影响最显著,当弹性体用量从15份增加到30份,材料的冲击强度先增大后减小,最高达40 kJ/m2,拉伸强度减小,内盖穿刺力减小,最小达45 N。溶出物测试显示内盖材料溶出物紫外吸收最高为0.011,易氧化物含量为0.4 mL,均低于国标限定值。     

Structure and properties of PP/POE/HDPE blends

This work was aimed to counteract the effect of ethylene‐α‐olefin copolymers (POE) by reinforcing the polypropylene (PP)/POE blends with high density polyethylene (HDPE) particles and, thus, achieved a balance between toughness and strength for the PP/POE/HDPE blends. The results showed that addition of HDPE resulted in an increasing wide stress plateau and more ductile fracture behavior. With the increase of HDPE content, the elongation at break of the blends increased rapidly without obvious decrease of yield strength and Young's modulus, and the notched izod impact strength of the blends can reach as high as 63 kJ/m² at 20 wt % HDPE loading. The storage modulus of PP blends increased and the glass transition temperature of each component of the blends shifted close to each other when HDPE was added. The crystallization of HDPE phase led to an increase of the total crystallinity of the blend. With increasing HDPE content, the dispersed POE particle size was obviously decreased, and the interparticle distance was effectively reduced and the blend rearranged into much more and obvious core‐shell structure. The fracture surface also changed from irregular striation to the regularly distant striations, displaying much obvious character of tough fracture. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Preparation and properties of polyurethane‐coated talcum/polypropylene composite materials

In order to improve the toughness of polypropylene (PP) and expand its applications, a layer of polyurethane (PU) elastomer was coated on the surface of ultrafine talcum powder by an in‐situ synthesis method. In this way, an organic‐inorganic composite particle was formed. Then the surface‐treated talcum powder was mixed with melted PP to prepare PP composite materials through extrusion, granulation, and injection molding. Infrared spectral characterization and energy‐dispersive X‐ray analysis showed that there was a layer of PU elastomer on the surface of the talcum powder. Impact fracture analysis indicated that there was good compatibility between the talcum powder and the PP matrix. With the incorporation of PU elastomer coated on the surface of talcum powder, the toughness of PP was significantly improved, while the tensile strength decreased slightly. The optimum properties of the composite material were obtained when the weight fraction of talcum powder was 20% and the PU coating coverage was 25%. J. VINYL ADDIT. TECHNOL., 2010. © 2010 Society of Plastics Engineers     

Investigations on weld joining of sisal CSM‐thermoplastic composites

An experimental study was conducted to investigate joint efficiency of both, butt, and lap joints of sisal CSM reinforced polymer composites. The thermoplastics, HDPE, and polypropylene (PP) were used separately as matrices in composites. Sisal‐HDPE composites exhibited excellent improvement in tensile strength that reached up to 47.5 MPa at 30 phr loading of sisal CSM as compared with 17.7 MPa of HDPE. Significant improvement in HDT was also observed that increased from 60.2 to 75°C on 0 to 30 phr reinforcement of sisal CSM in HDPE. Similar improvement was noticed with PP where in HDT improved from 69 to 87.6°C on incorporation of 0 to 30 phr sisal CSM. Hot tool welding process was employed for joining the composite materials. The joint efficiency of butt joint of HDPE was observed as 30%. It varied from 48 to 59% for lap joints of different sizes. The joint efficiencies of 20 mm lap joints of different compositions were observed as 59, 98, 75, and 58% in 0, 10, 20, and 30 phr Sisal CSM‐HDPE composites, respectively. Welded joint strengthening is attributed to partial reinforcement of interface that occurs during softening of matrix material which allowed spring back of originally pressed fibers followed by their repositioning in the welded part. POLYM. COMPOS., 36:214–220, 2015. © 2014 Society of Plastics Engineers     

Processing of wood plastic composites: The influence of feeding method and polymer melt flow rate on particle degradation

Spruce wood particle (WP)/polypropylene (PP) compounds were prepared in an internal mixer using different rotor speeds. To analyze the effect of feeding method on particle degradation, WP and PP were either fed as dry‐blend or WP was fed into the PP melt. To prevent melt freezing, pre‐heated WP were used as comparison to cold WP. In addition, WPs were compounded with different grades of PP or high‐density polyethylene (HDPE) to analyze the effect of polymer matrix melt flow rate (MFR) on particle degradation. Mixing behavior of compounds containing 30% and 70% (w/w) WP depended on feeding method, represented by a changing relation of final torque values. Feeding as dry‐blend and using pre‐heated particles led to stronger WP degradation. Degradation decreased with increasing polymer MFR. For PP compounds, particle degradation was stronger when containing 70% WP, for HDPE the difference due to WP content was only marginal. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43231.     

Amine modified polyethylenes,prepared in near critical propane,as adhesion promoting agents in multilayered HDPE/PET films

High density polyethylene [HDPE] grafted with 0.13, 0.04 and 1.04 wt% maleic anhydride (abbr.: PEMA) was modified with an excess of a variety of diamines in near critical propane. The resulting amic acid groups were quatitatively imidized to the corresponding imide (PEMI) in the melt. Increasing the percentage maleic anhydride grafted on the HDPE resulted, upon reaction with the diamines, in an increased gel content, due to crosslinking. Three‐layered films were prepared using HDPE film and polyethylene dterephathalate (PET) film as the outer layers and the PEMAs and PEMIs as the inner layer. Adhesion strengths were measured using a T‐peel test. Increasing the bonding temperature resulted in an improved adhesion. The most optimal system for adhesion proved to be HDPE grafted with 0.40 wt% MA and modified with a pendent secondary amine group. For this system the lowest number of reactive amine groups was lost owing to crosslinking reactions, so the highest concentration of amines is available for interactions with the PET film. The absence of extensive HDPE crosslinking in addition implies a better flow of the adhesive layer during lamination. From contact angle measurements, it was observed for all samples that after delamination of the three‐layered system, PET was present on the PE‐surface and PE was present on the PET‐surface.     

Toughened polyoxymethylene by polyolefin elastomer and glycidyl methacrylate grafted high‐density polyethylene

Ternary blends of polyoxymethylene (POM), polyolefin elastomer (POE), and glycidyl methacrylate grafted high density polyethylene (GMA‐g‐HDPE) with various component ratios were studied for their mechanical and thermal properties. The size of POE dispersed phase increased with increasing the elastomer content due to the observed agglomeration. The notched impact strength demonstrated a parabolic tendency with increasing the elastomer content and reached the peak value of 10.81 kJ/m² when the elastomer addition was 7.5 wt%. The disappearance of epoxy functional groups in the POM/POE/GMA‐g‐HDPE blends indicated that GMA‐g‐HDPE reacted with the terminal hydroxyl groups of POM and formed a new graft copolymer. Higher thermal stability was observed in the modified POM. Both storage modulus and loss modulus decreased from dynamic mechanical analysis tests while the loss factor increased with increasing the elastomer content. GMA‐g‐HDPE showed good compatibility between the POM matrix and the POE dispersed phase due to the reactive compatibilization of the epoxy groups of GMA and the terminal hydroxyl groups of POM. A POM/POE blend without compatibilizer was researched for comparison, it was found that the properties of P‐7.5(POM/POE 92.5 wt%/7.5 wt%) were worse than those of the blend with the GMA‐g‐HDPE compatibilizer. POLYM. ENG. SCI., 57:1119–1126, 2017. © 2017 Society of Plastics Engineers     

Improving polypropylene microcellular foaming through blending and the addition of nano‐calcium carbonate

This article reports an attempt to improve polypropylene (PP) microcellular foaming through the blending of PP with high‐density polyethylene (HDPE) as a minor component and the incorporation of nano‐calcium carbonate (nano‐CaCO₃) into PP and its blends with HDPE. Three HDPEs were selected to form three blends with a viscosity ratio less than, close to, or greater than unity. Two concentrations of nano‐CaCO₃, 5 and 20 wt %, were used. The blends and nanocomposites were prepared with a twin‐screw extruder. The foaming was carried out by a batch process with supercritical carbon dioxide as a blowing agent. The online shear viscosity during compounding and the dynamic rheological properties of some samples used for foaming were measured. The cell structure of the foams was examined with scanning electron microscopy (SEM), and the morphological parameters of some foams were calculated from SEM micrographs. The rheological properties of samples were used to explain the resulting cell structure. The results showed that the blend with a viscosity ratio close to unity produced a microcellular foam with the minimum mean cell diameter (0.7 μm) and maximum cell density (1.17 × 10¹¹ cells/cm³) among the three blends. A foamed PP/nano‐CaCO₃ composite with 5 wt % nano‐CaCO₃ exhibited the largest cell density (8.4 × 10¹¹ cells/cm³). © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

PP/HDPE/滑石粉复合材料微孔发泡实验研究

为了改善聚丙烯(PP)的微孔发泡性能,将PP与高密度聚乙烯(HDPE)共混,提高其熔体强度;然后在PP/HDPE共混体系中加入少量滑石粉,研究滑石粉的用量对共混体系熔体强度及微孔发泡过程的影响。研究结果表明,滑石粉的加入使体系的熔体强度提高,发泡样品的泡孔结构变得更均匀。而且,随着滑石粉用量的增加,泡孔尺寸减小,泡孔密度增加。     

PFG‐NMR measurement of self‐diffusion coefficients of long‐chain α‐olefins and their mixtures in semi‐crystalline polyethylene

The self‐diffusion coefficients of C6–C16 long‐chain α‐olefins and their mixtures in semi‐crystalline polyethylene were measured through the pulsed field gradient nuclear magnetic resonance (PFG‐NMR). The effects of chain length, polyethylene (PE) type, and co‐monomer type in PE on the diffusion coefficients were investigated. Moreover, the influence of halohydrocarbon, cycloalkanes, and arene solvents on the diffusion coefficients of C12 α‐olefin in PE was characterized. The results have demonstrated that the diffusion coefficient of the single‐component α‐olefin in PE decreases exponentially with the increase of the carbon number of α‐olefin, and the crystallinity and crystal morphology of PE play a more important role than the co‐monomer type in determining the diffusion coefficients of α‐olefins. In addition, the apparent diffusion coefficients were used to represent the diffusion behaviors of the α‐olefin mixtures in PE. Owing to the presence of other hydrocarbon solvents, namely trichloromethane, cyclohexane, and benzene, the diffusion coefficients of C12 long‐chain α‐olefin in PE are significantly enhanced, and such promoting effect of the hydrocarbon solvents in polyolefin elastomer (POE) is much stronger than those in high‐density polyethylene (HDPE) and linear low‐density polyethylene (LLDPE). © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44143.     

Binary blends of metallocene polyethylene with conventional polyolefins: Rheological and morphological properties

The rheology and morphology of four sets of binary blends of polyethylene synthesized with metallocene catalysis (metallocene polyethylene: MCPE) with polyolefins prepared using Ziegler‐Natta catalysts have been investigated. The blend systems are MCPE with high density polyethylene (MCPE‐HDPE), polypropylene (MCPE‐PP), poly(propylene‐co‐ethylene) (MCPE‐CoPP), and poly(propylene‐co‐ethylene‐co‐1‐butylene) (MCPE‐TerPP). Cole‐Cole plots [storage melt viscosity (η′) versus loss melt viscosity (η″)], plots of the dynamic storage modulus (G′) versus the dynamic loss modulus (G″), and plots of the log melt viscosity (η*, η′, and η″) versus blend compositions were constructed. The morphology of the blends after microtoming and etching was studied. The phase morphology of MCPE‐HDPE appeared homogeneous, whereas the other three blends were heterogeneous. Rheological and morphological investigations indicated that the MCPE‐HDPE blend was miscible, but the other three blends were immiscible in the melt as well as in the solid state. These observations can be rationalized in terms of the similarity of the chemical structures of the polyolefins.