Effect of processing conditions on the orientation and properties of polyethylene blown film

The amorphous and crystallite orientation in a number of films produced from characterised grades of high density polyethylene has been examined and some tensile properties measured. The films were produced under commercial production conditions with various blow ratios, freeze line heights and thicknesses. Orientation was assessed using optical and X-ray methods. The relative contributions of the crystallite and amorphous components were calculated for a limited number of the films produced. Amongst the properties measured the ultimate tensile strength and elongation at break appeared to be the most variable. Birefringence was more affected by variation in blow ratio and film thickness than by freeze height changes. Attempts have been made to correlate these variations with crystallite and amorphous orientation as well as the individual behaviour of the polyethylene grades. In carrying out this correlation it became clear that the films could not generally be described by established low or high stress models of crystallite orientation. For these films produced on full-scale commercial equipment it appears that transcrystallisation behaviour is frequently observed, with a tendency towards the low stress model.     

Liquid crystalline copolyester/polyethylene in situ composite film: Rheology,morphology, molecular orientation,and tensile properties

A thermotropic liquid crystalline copolyester (TLCP) was blended with low density polyethylene using a corotating twin screw extruder and then fabricated by extrusion through a miniextruder as cast film. Rheological behavior, morphology, and tensile properties of the blends were investigated. Melt viscosities of neat components and blends measured by using plate‐and‐plate and capillary rheometers at 240°C, in the shear rate range 1–10⁴ s^?1, showed similar shear thinning effect. The viscosity values measured by the two techniques in the overlapping range of shear rate are found to be identical, which is in accord with the Cox–Merz rule. Addition of TLCP slightly reduces the matrix melt viscosity. TLCP dispersed phase in the extruded strand appeared in the form of spherical droplets. These droplets were elongated into fibrils with high aspect ratio (length to width) at the film extrusion step. As a result, the Young's modulus in machine direction (MD) of the composite film was greatly enhanced. At 20 wt % of TLCP, the MD Young's modulus was found to be about 16‐fold increase compared to that of the neat polyethylene film. However, the elongation at break sharply dropped with the increase of TLCP content. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 561–567, 2002; DOI 10.1002/app.10307     

Molecular,rheological, and crystalline properties of low‐density polyethylene in blown film extrusion

The molecular weight and its distribution, degree of long chain branching and cooling rate strongly influence crystallinity during processing, which in turn determines the processability and the ultimate properties of the blown film. Generally a decrease in the number of branches and molecular weight of the polymer and the cooling rate results in an increase of the crystallinity. Length of the main chain and extent of branching in low‐density polyethylene (LDPE) are also factors that affect melt rheology and film crystallinity. Long chain branched polyethylene is suitable in the blown film process due to its better melt strength for bubble stability. The objective of this article is to describe the effect of molecular properties (e.g. molecular weight and its distribution, degree of long chain branching etc) of LDPE on film crystallinity at different cooling rates of blown film extrusion. Two different grades of LDPE were selected to investigate molecular characteristics, crystallinity, and rheology. The resins were processed in a blown film extrusion pilot plant using four different cooling rates. Molecular, rheological, and crystalline properties of the resins were key parameters considered in this study. POLYM. ENG. SCI., 47:1983–1991, 2007. © 2007 Society of Plastics Engineers     

Effect of extrusion screw type on properties of recycled glass fiber reinforced liquid crystalline polymer

In this work, when glass fiber reinforced liquid crystalline polymer (GFLCP) was subjected to injection molding once, the recycled GFLCP (RGFLCP) including the scraps and unqualified injection products was granulated by different extruders with varying screw configurations. The glass fibers were observed by SEM and their lengths were calculated by mathematical statistics. In the case of the samples prepared by a single‐screw extruder, the average glass fiber length ( ) and the percentage of glass fibers whose length was higher than critical length (V_j) gradually decreased with the increase of the screw diameter and the ratio of its length to diameter (L/D). However, a drastic reduction of and V_j was observed for the RGFLCP extruded by a twin‐screw extruder. The mechanical, thermal properties, and the shear viscosity of the extruded RGFLCP decreased with the reduction of and V_j. The extruded RGFLCP prepared with a single screw extruder that was featured with 30 mm screw diameter and 30 L/D obtained the excellent properties with a notched impact strength of 103.4 J/m, tensile strength of 110.2 MPa, and flexural strength of 159.3 MPa. Its initial decomposition temperature (T_−1%) and heat distortion temperature were 483.1°C and 256.4°C, respectively. POLYM. COMPOS., 37:370–378, 2016. © 2014 Society of Plastics Engineers     

Structure and properties of blend fibers from poly(ethylene terephthalate) and liquid crystalline polymer

The structure and properties of the as-spun fibers of poly(ethylene terephthalate) (PET) blends with a thermotropic liquid crystalline polymer (LCP), Vectra A900, were studied in detail. The DSC results indicate that the LCP component may act as a nucleating agent promoting the crystallization of the PET matrix from the glassy state but which inhibits its crystallization from the melt due to the existence of an LCP supercooled mesophase. The effect of the drawdown ratio on the orientation of the as-spun blend fibers is highly composition-dependent, which is mainly associated with the formation of LCP fibrils during melt spinning. The modulus of the as-spun blend fibers has a significant increase as the content of LCP reaches 10%, while the tensile strength has a slightly decreasing tendency. The mechanical properties of the as-spun blend fibers could be well improved by heat treatment because of a striking increase in the crystallinity of the PET matrix. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 66: 217–224, 1997     

An investigation of optical clarity and crystalline orientation in polyethylene tubular film

A study of the crystalline orientation, light transmission, and surface roughness of polyethylene tubular film prepared in our laboratories is presented. The present studies were primarily carried out on low-density (LDPE) and linear-low-density (LLDPE) polyethylene films. The optical properties of a few films of high-density polyethylene (HDPE) prepared for a previous study of morphology were characterized for comparison to the LDPE and LLDPE films. Wide angle X-ray diffraction and birefringence were used to characterize orientation. Both the LDPE and LLDPE films exhibited crystalline texture in which the b-axes tended to be perpendicular to the film surface and the a-axes had some tendency to align with the machine direction. The c-axes tended to be concentrated in the plane of the film with nearly equal biaxial orientation with respect to the machine and transverse directions. Little variation in the crystalline orientation was found with changes of process conditions in the range studied. Birefringence results indicate that the amorphous regions developed an orientation in which the chains tend to be normal to the film surface. The majority of light scattering from these films and a series of HDPE films was from the surface and not from the film interior. The transmission coefficient for the surface contribution was found to be a monotonic decreasing function of the standard deviation of the surface height obtained from surface profiles measured by profilometer. The surface asperites were largest for the HDPE and smallest for the LDPE samples. The intensity of both the surface and interior contributions to the scattering increased with increasing frostline height, i.e., a slower cooling rate. As draw-down ratio and blow-up ratio increase the scattering contribution from the film interior decreases but the contribution from the surface increases somewhat. These effects are discussed in terms of the changes in crystalline morphology and surface roughness produced by flow defects generated during extrusion.     

Atomic force microscopy (AFM) studies of liquid crystalline polymer (LCP) surfaces

An atomic force microscope (AFM) operating in tapping or contact mode was used to study the surface topography and the molecular organization of Vectra‐A and Vectra‐B films. Large‐scale (15 × 15 μm) AFM images revealed that ribbonlike fibrils with a width/height ≫ 1.0 are the dominant surface features of these liquid crystalline polymers (LCPs). The region of local disorder, surface debris, and interfibrillar debris as well as possible amorphous regions were observed in both LCP samples. Large fibrils, 5.0–10.0 μm in width, can be thought of as formed by smaller microfibrils capable of forming ordered structures. Microfibrils can bend upward, forming raised surface features; bend inward, originating cracks 1–2 μm wide on the film surface; or divide and subdivide into smaller units. Longitudinal and lateral stresses are believed responsible for the variation in fibril size, shape, and orientation. AFM images containing molecular‐scale details showed that microfibrils consists of chains of molecules coiled around a central axis and that they can be only about 2.0 nm wide. These submicron surfaces consist of white spots (representing molecules) that can form ordered structures or that can cluster to form agglomerates distributed in a random manner. Submicron fibrils are believed to represent the LCP basic structural unit. AFM results indicate that the surface topography of Vecta‐B is more ordered and uniform than is the one observed for Vectra‐A. Seemingly, amorphous particles form debris on Vectra‐A surfaces. Short rods oriented crosswise on the fibril surface are instead what increases the Vectra‐B roughness. These LCPs can have a surface topography similar to the one observed in AFM images of a spiderweb. However, the spiderweb fibrils are formed by more uniform microfibrils that are oriented parallel to each other. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 2243–2254, 1999     

Effects of shearing conditions on crystalline orientation and relaxation in polyethylene

The effects of shearing conditions (i.e., shear temperature and shear rate) on the degree of orientation of polyethylene (Marlex 6006) and to what extent the induced orientation could be relaxed were examined in this study. Two types of samples were prepared: namely, SIC (shear-induced crystallization) and non-SIC samples. The SIC samples show induction times and possess a high degree of c-axis orientation along the shear direction. The induced orientation of SIC samples can be relaxed to a small extent but does not reach a steady value. Non-SIC samples do not show induction times and they show low degrees of c-axis orientation. The induced orientation of non-SIC samples can be relaxed to a steady state value with an activation energy of 90 kJ/mole. Our results also indicate that, when the shear temperature is at and above 145°C, polyethylene can be sheared up to 200X without introducing any significant molecular orientation even at very high shear rates.     

Tensile properties of linear low density polyethylene (LLDPE) blown films

Various linear low‐density polyethylene (LLDPE; density ～ (0.920 g/cm³)) resins that encompass those polymerized using Ziegler‐Natta, metallocene, and chromium oxide based catalysts were blown into film at similar process conditions, and the tensile properties of the resulting films were investigated in relation to their orientation characteristics. The tensile properties of the subject blown films were observed to be significantly different from those of isotropic/un‐oriented polyethylene specimens of similar density (crystallinity). Further, the tensile properties were different in the machine and transverse directions. These were explained in terms of the orientation and lamellar organization characteristics of the LLDPE blown films. Investigation of the temperature dependence (between ?50°C and +50°C) of these tensile properties indicated an increase in modulus, yield stress and break stress with decreasing temperature pointing to the possible role played by the decreased mobility of the non‐crystalline phase at lower temperatures. Excellent correlation between the Elmendorf tear properties of the LLDPE blown films and their tensile yield characteristics was observed. This added substantial credibility to previous hypotheses that specimen stretching plays a significant role in Elmendorf tear tests and further supported the previously identified structural features and microstructural deformation mechanisms that are deemed responsible for the discernment of LLDPE blown film tear resistance.     

Effect of (3-aminopropyl)trimethoxysilane on mechanical properties of PLA/PBAT blend reinforced kenaf fiber

The composite-based poly(lactic acid) (PLA)/poly(butylene adipate-co-terephthalate) (PBAT)/kenaf fiber has been prepared using melt blending method. A PLA/PBAT blend with the ratio of 90:10 wt%, and the same blend ratio reinforced with various amounts of kenaf fiber have been prepared and characterized. However, the addition of kenaf fiber has reduced the mechanical properties sharply due to the poor interaction between the fiber and polymer matrix. Modification of the composite by (3-aminopropyl)trimethoxysilane (APTMS) showed improvements in mechanical properties, increasing up to 42.46, 62.71 and 22.00 % for tensile strength, flexural strength and impact strength, respectively. The composite treated with 2 % APTMS successfully exhibited optimum tensile strength (52.27 MPa), flexural strength (64.27 MPa) and impact strength (234.21 J/m). Morphological interpretation through scanning electron microscopy (SEM) reveals improved interaction and interfacial adhesion between PLA/PBAT blend and kenaf fiber. The fiber was well distributed and remained in the PLA/PBAT blend evenly. DMA results showed lower storage modulus (E′) for PLA/PBAT/kenaf fiber blend and an increase after modification by 2 wt% APTMS. Conversely, the relative damping properties decreased. Based on overall results, APTMS can be used as coupling agent for the composite since APTMS can improve the interaction between hydrophilic natural fibers and non-polar polymers.     

Effect of short chain branching on the blown film properties of linear low density polyethylene

Three linear low density polyethylene (LLDPE) resins of similar melt index and density were synthesized with different comonomers in the Unipol pilot-plant scale reactor. The molecular structure, blown film morphology, and film strength properties of the resins have been comprehensively characterized. The film dart drop impact strength of the LLDPEs increases in the order of ethylene/1-butene, ethylene/1-octene, and ethylene/1-hexene copolymers; whereas the Elmendorf tear strength of them increases in the order of ethylene/1-butene, ethylene/1-hexene, and ethylene/1-octene copolymers. The mechanical properties seem to be highly associated with the length and distribution of short chain branches and, consequently, the lamellar thickness distribution of the resins. © 1996 John Wiley & Sons, Inc.     

Effects of shear rate,viscosity ratio and liquid crystalline polymer content on morphological and mechanical properties of polycarbonate and LCP blends

Studies were conducted on the effects of shear rate, viscosity ratio and liquid crystalline polymer (LCP) content on the morphological and mechanical properties of polycarbonate (PC) and LCP blends. The LCP (LC5000) used was a thermotropic liquid crystalline polymer consisting of 80/20 of parahydroxybenzoic acid and poly(ethylene terephthalate) (PHB/PET). The viscosity ratio (viscosity of LCP: viscosity of matrix) was varied by using two processing temperatures. Due to the different sensitivity of materials to temperature, variation in the processing temperature will lead to varying viscosity of the components in the blends. Based on this principle, the processing temperature could be manipulated to provide a favourable viscosity ratio of below unity for fibre formation. To study the effect of shear rate, the flow rate of the blend and the mould thickness were varied. The shear rate has a significant effect on the fibrillation of the LCP phase. The effect was more prominent when the viscosity ratio was low and the matrix viscosity was high. At 5 wt% LCP, fibrillation did not occur even at low viscosity ratios and high shear rates. It was also observed that the LCP content must be sufficiently high to allow coalescence of the dispersed phase for subsequent fibrillation to occur. © 2002 Society of Chemical Industry     

Mechanical properties of recycled kenaf/polyethylene terephthalate (PET) fiber reinforced polyoxymethylene (POM) hybrid composite

Environmental concerns have attracted researchers to study the recycling of composite materials and thermoplastics due to the desire not to waste materials and reduce disposal of scraps that may eventually pollute the environment. The main objective of this article is to study the effect of recycling on the mechanical properties of kenaf fiber/PET reinforced POM hybrid composite. The virgin hybrid composite was produced by compression molding and later subjected to mechanical testing. The scraps obtained after the mechanical testing were shredded, granulated and subjected to compression molding to produce samples for mechanical testing. Tensile strength of 27 MPa was obtained and (after second recycling process) which is lower compared to 73.8 MPa obtained for the virgin hybrid composite. There was a significant increase in flexural modulus (4.7 GPa) compared to the virgin hybrid composite. The impact strength dropped to 4.3 J cm^?1 as against 10.5 J cm^?1 for the virgin hybrid composite. The results of thermal degradation showed about 80% weight loss for kenaf fiber between 300 and 350°C. The weight loss may be due to the degradation of cellulose and hemicellulose content of the fiber. The percentage water absorption of the recycled composite dropped by about 80% compared to the virgin hybrid composite. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39831.     

Fiber orientation and its effect upon thermoelastic properties of short carbon fiber reinforced poly(etheretherketone) (PEEK)

Experimental and analytical techniques are employed in the present study to investigate the influence of microstructure on thermoelastic properties of short carbon fiber reinforced poly(etheretherketone). The test specimen geometry is an edge gated, injection molded dogbone tensile bar. Typical of injection molded structures, three distinct layers of fiber orientation were discernable through the sample thickness. The thermoelastic properties of the surface layer (machined from the specimen) are measured for direct correlation with a micromechanics model. In addition to measuring the volume fractions and constituent properties, microstructural features such as fiber aspect ratio and the process-induced fiber orientation distribution are quantified. Correlation of experimental data with micromechanics model predictions is found to be quite good.     

Effects of fiber orientation on strain concentrations in glass reinforced polyamides

Orientation of reinforcement fibers in injection molded parts is a key factor in determining their strength and stiffness: therefore stress-strain analyses based on isotropic material models produce only rough results. We present a flow/strain analysis methodology that accounts for the actual anisotropic material properties and fiber orientation. Material properties are determined by experiment, fiber orientation is inferred from flow simulation results (velocity vectors). Stress/strain fields are calculated by means of finite element analysis. Results show that for notched parts molded from short glass reinforced polyamide resin, there is a significant dependence of the strain concentration on the local fiber orientation resulting from different injection molding conditions.     

Morphology and properties of blends of polyethylene with a semiflexible liquid crystalline polymer

Blends of three polyethylene (PE) samples (two HDPE grades and LLDPE) with an experimental sample of a semiflexible liquid crystalline polymer (SBH 1:1:2 by Eniricerche) have been prepared in a Brabender compounder. The processing-aid effect of the LCP has been demonstrated by the decreased energy required for extruding the blends, as compared to that needed for neat PE. The thermal properties, as studied by differential scanning calorimetry (DSC), have shown that the two components of the blends are immiscible. However, the dispersed SBH phase has been found to act as a nucleating agent for the crystallization of LLDPE, whereas no such effect was observed for HDPE. This has been taken as an indication that the phase interactions of SBH with LLDPE are more pronounced than with HDPE. The morphological study of the blends, done by scanning electron microscopy (SEM), has confirmed this conclusion. In fact, the SBH particles show a much better dispersion and a narrower size distribution in the LLDPE/SBH blends. The mechanical properties of the blends have been studied on compression-molded specimens. The results indicate that the reinforcing effect of SBH is practically none for both HDPE grades. In fact, the elongation at break decreases to very low values, and the tensile strength is also reduced, when the LCP concentration increases beyond 5–10%, whereas the tensile modulus does not vary appreciably, over the whole (0–20%) LCP range investigated. On the contrary, the tensile modulus of the LLDPE/SBH blends increases up to ca. 50%, and the elongation at break decreases more smoothly, on increasing the SBH content up to 20%. © 1995 John Wiley & Sons, Inc.     

Effects of fiber length and orientation distribution on the elastic modulus of short fiber reinforced thermoplastics

A method including the effects of fiber length and orientation distribution to predict elastic moduli of short fiber reinforced thermplastics (FRTP) is presented. The fiber length distribution in FRTP has an asymmetric character with a tail at the long fiber end. Statistical distribution functions such as Weibull or log-normal can be used to represent this kind of distribution. Orientation distribution of fibers in FRTP can be characterized by a single parameter exponential function, $F(\theta) = \frac{{1 - \lambda \theta }}{{1 - e^{ - \frac{\P}{2}\lambda } }}$. A large λ indicates a highly oriented material whereas small λ represents a quasi-isotropic material. As fiber length and orientation distribution functions have been characterized, the elastic moduli of FRTP can be predicted. First, the mean elastic moduli of unidirectional plies are predicted through the fiber length distribution. Then the stacking sequence of laminate is assumed to be as the fiber orientation distribution of FRTP, and the overall elastic moduli of FRTP are estimated based on the laminate-plate method.     

Effect of ethylene/propylene ratio on reinforcing characteristics of liquid crystalline polymer (LCP) in EPDM-LCP composites

Abstract

Two ethylene/propylene diene monomer (EPDM) polymers were blended with a liquid crystalline polymer (LCP) at concentrations of 10, 20, 30 and 40 wt-%. The effects of ethylene/propylene (EP) ratio on the in situ fibrillation, and hence the reinforcing characteristics, of the LCP in EPDM-LCP blends were studied. The fibre forming capacity of the LCP depended on the viscosity of the EPDM rubber. Under high temperature processing conditions (at 300°C), the high EP ratio EPDM, which had the higher viscosity, facilitated the fibrillation of the LCP. Further melt processing at 100°C, followed by curing at 150°C, decreased the reinforcing effects of the LCP owing to breakage of the fibrils under the high shear stresses developed in the high viscosity matrix. However, this degradation of fibre lengths depended on the LCP concentration. After curing, the more viscous EPDM formed blends with higher stiffnesses and strengths than those obtained from the low viscosity EPDM. Both the nucleation and growth of crystal domains in the EPDM matrix were promoted by small amounts of LCP. Again the effects were more pronounced in the EPDM with the higher EP ratio.     

Influence of fiber length,fiber orientation,and interfacial adhesion on poly (butylene terephthalate)/polyethylene alloys reinforced with short glass fibers

Blends of poly(butylene terephthalate) and high density polyethylene at a ratio of 80:20 wt% were reinforced with short glass fibers varying from 10 to 30 wt% to enhance mechanical properties. Considerable fiber damage occurred during injection molding, reducing the number average fiber length from the starting value of 4.5 mm to < 1 mm. This value decreased with increasing fiber content, which is also responsible for lowering the reinforcement efficiency. The variation in mechanical properties has been explained on the basis of fiber concertration. The effect of an ionomer, which was used to compatibilize the blends, on properties of corresponding composites has also been studied.