Sheet extrusion of microcomposites based on thermotropic liquid crystalline polymers and polypropylene

This work is concerned with the extrusion of sheets from pellets of polypropylene (PP) containing pregenerated microfibrils of thermotropic liquid crystal polymers (TLCPs), referred to as microcomposites. The TLCPs used were HX6000 and Vectra A950. The microcomposites are produced by drawing strands of PP and TLCPs generated by means of a novel mixing technique and pelletizing the strands. The work was undertaken in an effort to improve on the properties for in situ composites in which the TLCP fibrils are generated in contractions in the die and the subsequent drawing step. In situ composites usually exhibit highly anisotropic mechanical properties and the properties do not reflect the full reinforcing potential of the TLCP fibers. Factors affecting the mechanical properties of the composite sheets considered include the effect of in situ composite strand properties and TLCP concentration. In addition, the properties of the extruded sheets are compared to those of microcomposites processed by means of injection molding. It is shown that the sheets produced using microcomposites have a good balance between the machine and transverse direction properties (ratios of these properties ranging from 0.8 to 1.2) and those properties compare well to those obtained by processing microcomposites in injection molding. The tensile modulus of the composite sheets increases with increasing in situ composite strand modulus. The moduli of the 20 wt% Vectra A950 and HX6000 composites are about equal to the modulus of 20 wt% glass reinforced PP (about 2.1 GPa), while the tensile strength of the TLCP reinforced composites is 28% lower than that of the glass reinforced PP. Furthermore, it is shown that the tensile modulus of the 10 wt% TLCP composites approach the predictions of composite theory, while at 20 and 30 wt% TLCP negative deviations from the predictions of composite theory are seen. Finally, it is concluded that the properties of the sheets produced through the extrusion of microcomposites may be further improved by improving the modulus of in situ composite strands and reducing the TLCP fiber diameter.     

The effects of reclamation on a thermotropic liquid crystalline polymer

In previous work, a process was developed to reclaim a thermotropic liquid crystalline polymer (DuPont HX8000) from composites comprised of polypropylene (PP) reinforced with HX8000. The reclamation was accomplished by chemically degrading the PP and then dissolving the PP away in heated mineral oil. From this work, it was found that there were significant drops in dynamic and steady shear viscosity for the reclaimed HX8000, but that there were no losses in mechanical properties when the recovered HX8000 was used to generate PP–HX8000 injection-molded composites. In the present work, the reclaimed HX8000 was analyzed to understand the contradiction between rheological and mechanical properties. The effects of the reclamation process on the recovered HX8000 were investigated by using pycnometry (density), thermogravimetric analysis (TGA), parallel plate rheometry, mechanical testing, scanning electron microscopy (SEM), and differential scanning calorimetry (DSC). © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 2517–2524, 1999     

Composites based on drawn strands of thermotropic liquid crystalline polymer reinforced polypropylene

This paper is concerned with the use of two thermotropic liquid crystalline polymers (TLCPs), HX1000 and Vectra B950, to reinforce a thermoplastic matrix of polypropylene (PP). The goal was to pregenerate the optimal TLCP reinforcement in PP and then process the material at a lower temperature than the melting point of the TLCP to form a composite structure. Specifically, strands of the blend were produced using a dual extrusion process, which resulted in the formation of axially continuous TLCP fibrils within the PP matrix. It was found that the mechanical properties of the strands were greatly improved by increased draw ratio and that optimal reinforcement, as predicted by the rule of mixtures, could be achieved. Initial studies indicated that injection molding and sheet extrusion of the pelletized strands caused the TLCP phase to agglomerate and deform, which resulted in a reduction of the mechanical property enhancement. However, the TLCP fibrillar morphology in the pregenerated strands was maintained during compression molding, which resulted in uniaxial composites with properties equal to or greater than properties of the strands. In addition, composites were made using compression molding in which strands were randomly oriented prior to consolidation to show the limits of properties possible in composites produced from the pregenerated strands. It was found that this process could be used to produce composites in which the mechanical properties were isotropic in the plane of the sample and approached the properly limits predicted by composite theory. Additionally, it was found that many of the mechanical properties of the VB/PP materials were greatly enhanced by the addition of a maleated PP throughout the composite forming process.     

In situ composites based on blends of a polyetherimide and thermotropic liquid crystalline polymers subjected to shearfree deformations

The effects of shearfree elongational flows on the morphology and mechanical properties of blends of a polyetherimide (PEI) with thermotropic liquid crystalline polymers (TLCP) have been investigated. Extruded sheets and injection molded plaques of PEI/Vectra A and PEI/HX1000 blends, with a TLCP concentration of ≤30 wt%, were subjected to uniaxial elongation, planar and biaxial deformations at 240°C, above the glass transition temperature of the PEI, and at 265°C, which is below the melting point of the TLCPs. Experimental results revealed that each particular mode of shearfree deformation had a distinct effect on the morphology and properties of the blends. For instance, TLCP droplets were deformed into elongated fibrils by application of uniaxial elongation, deformed into elongated ribbon-like structures after planar deformation, and deformed into a disc-like shape by application of equibiaxial flow. Regarding mechanical properties, it was observed that the tensile modulus and strength of molded plaques of PEI/HX1000 80/20 wt% increased to about twice their initial values (from 5.13 to 10.40 GPa and from 105 to 198 MPa, respectively) after a strain of 0.75 was applied in a direction parallel to the initial direction of the TLCP fibers. In addition, samples exhibiting equal values of flow and transverse direction tensile modulus of ∼5.0 GPa were obtained when molded plaques of PEI/HX1000 80/20 wt% were subjected to planar stretching in a direction transverse to the initial direction of the fibers. Thus, by subjecting injection molded plaques to planar stretching, it was possible to obtain a sample exhibiting balanced flow and transverse direction mechanical properties and, consequently, reduced anisotropy.     

Modification of the processing window of a thermotropic liquid crystalline polymer by blending with another thermotropic liquid crystalline polymer

This paper is concerned with properties and processing performance of two thermotropic liquid crystalline polymers (TLCPs) produced by DuPont (HX6000 and HX8000) with widely varying melting points and blends of these two TLCPs. This work was carried out in an effort to develop a TLCP suitable for generating poly(ethylene terephthalate) (PET) composites in which the melting point of the TLCP was higher than the processing temperature of PET. Strands of the neat TLCPs and a 50/50 wt % TLCP–TLCP blend were spun and tested for their tensile properties. It was determined that the moduli of the HX8000, HX6000, and HX6000–HX8000 blend strands were 47.1, 70, and 38.5 GPa, respectfully. Monofilaments of PET–HX6000–HX8000 (50/25/25 wt %) were spun with the use of a novel dual extruder process. The strands had moduli as high as 28 GPa, exceeding predictions made using the rule of mixtures and tensile strengths around 275 MPa. The strands were then uniaxially compression molded at 270°C. It was found that after compression molding, the modulus dropped from 28 GPa to roughly 12 GPa due to the loss of molecular orientation in the TLCP phase. However, this represents an improvement over the use of HX8000. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 2209–2218, 1999     

Extrusion blow molding of microcomposites based on thermotropic liquid crystalline polymers and polypropylene

This work is concerned with the extrusion blow molding of bottles from pellets of polypropylene (PP) containing pregenerated microfibrils of thermotropic liquid crystal polymers (TLCPs), referred to as microcomposites. The TLCPs used are HX6000 and Vectra A950. The microcomposites are produced by drawing strands of PP and TLCPs generated by means of a novel mixing technique and pelletizing the strands. The work was undertaken in an effort to improve on the properties observed for in situ composites in which the TLCP fibrils are generated in elongational flow fields that occur in polymer processing operations and to determine if TLCP reinforced bottles could be produced by extrusion blow molding of microcomposites. In situ composites usually exhibit highly anisotropic mechanical properties and the properties do not reflect the full reinforcing potential of the TLCP fibers. Factors considered include the effect of TLCP concentration and in situ composite strand properties on the mechanical properties and anisotropy of bottles made from microcomposites. Specifically, strands having three different draw ratios are used to produce bottles at 10 and 20 wt% TLCP. Increasing the in situ composite strand modulus is shown to cause an increase in both the machine and transverse direction moduli of the composite bottles. The mechanical properties of the bottles increase with increasing TLCP composition. Finally, the machine and transverse direction properties are not balanced in the composite bottles produced in this study (degrees of anisotropy ranging from 1.5 to 1.8). The mechanical anisotropy is probably the result of a low blow up ratio (2) in the bottles and the TLCP fibers being oriented primarily in the machine direction due to the shear flow in the die.     

Injection molding of poly(ethylene terephthalate) reinforced with pregenerated thermotropic liquid crystalline polymer microfibrils

This work was concerned with the injection molding of poly(ethylene terephthalate) (PET) reinforced with pregenerated thermotropic liquid crystalline polymer (TLCP) fibrils, where the TLCP had a higher melt processing temperature than PET. These composites, referred to as pregenerated microcomposites, were produced using a two step processing scheme. First, a novel dual extrusion process was used to spin strands of PET reinforced with nearly continuous TLCP fibrils. Second, these strands were subsequently chopped into pellets and injection molded below the melt processing temperature of the TLCP but above that of PET. This allowed the high modulus TLCP fibrils generated in the spinning step to be retained in the injection molded samples. TLCP concentration and strand draw ratio were varied in the composite strands to determine how they affected mechanical properties. It was shown that the best properties were obtained using strands containing 50 weight percent TLCP with draw ratios greater than 50, which were diluted to the desired loading level with a low viscosity injection molding grade of PET. Specifically, these composites had tensile moduli as high as 5.7 GPa when reinforced with 30 weight percent HX1000. Also, it was determined that pregenerated microcomposites had smoother surfaces than glass-filled PET.     

Morphology and mechanical properties of thermoplastic composites containing a thermotropic liquid crystalline polymer

Blends of two thermotropic liquid crystalline polymers (TLCPs), with brittle and ductile matrix materials were both injection molded and spun into fibers, in order to investigate the mechanism of in-situ mechanical reinforcement. In the injection molded samples, the TLCP was only moderately elongated into fibrils, and the mechanical properties were below predictions of the rule of mixtures. Fibers spun out of the blends contained numerous fine fibrils with nearly infinite aspect ratio, and as expected, the modulus increased linearly with the TLCP volume fraction, obeying the Tsai-Halpin equation for transversely isotropic composites. Wide angle X-ray diffraction measurements, as well as determination of the fiber-moduli, revealed that during spinning not only a macroscopic elongation of the fibrils was achieved, but also a considerable molecular orientation within the TLCP domains.     

Wholly thermoplastic composites from woven preforms based on nylon-11 fibers reinforced in situ with a hydroquinone-based liquid crystalline polyester

This work concerns a novel means to generate wholly thermoplastic composites based on low-melting thermoplastics reinforced with high-melting thermotropic liquid crystalline polymers (TLCPs). A novel dual extrusion process was employed to generate nylon-11 fibers that are reinforced with continuous fibrils of a hydroquinone-based liquid crystalline polyester (DuPont TLCP, HX8000). These composite fibers display tensile properties significantly higher than those predicted by composite theory. These fibers were subsequently woven into a fabric, which in turn serves as a composite preform. Several layers of the fabric preform were stacked and consolidated to yield a composite plaque. The consolidation was carried out at temperatures just high enough for nylon-11 to melt, but well below the melting temperature of HX8000. Fabric preform composites based on the composite fibers with ∼35 wt% HX8000 gave modulus values close to five and one half times that of nylon-11, and strength values approximately two and one half times that of nylon-11. The tensile and flexural properties of these composites are superior to continuous glass-fiber reinforced composites at comparable loadings on a volume basis. Moreover, as the reinforcing fibrils are already encapsulated by the matrix, fiber wetting and fabric impregnation issues that are critical in the fabrication of continuous glass and carbon fiber composites are eliminated.     

Dynamic rheology,mechanical performance,shrinkage, and morphology of chemically coupled talc‐filled polypropylene

The oscillatory shear rheological properties, mechanical performance, shrinkage, and morphology of polypropylene (PP)‐talc composites chemically coupled by maleic‐anhydride‐grafted polypropylene (MAPP) were studied. The samples were prepared in a co‐rotating L/D = 40, 25 mm twin‐screw extruder. Tensile tests carried out on injection‐molded samples showed a reinforcing effect of talc up to 20 wt% on PP. Upon using MAPP, the mechanical performance of PP‐30% talc showed a maximum of about 10% increase in tensile strength at 1.5 wt% of MAPP. A Newtonian plateau (η₀) at the terminal zone was observed for the complex viscosity curve of pure PP and PP‐talc composites plotted against frequency up to 30 wt%. Upon increasing the talc content to 40 and 50 wt%, the complex viscosity at very low shear rates sharply increased and showed yield behavior that might be due to the formation of a network of filler agglomerates in the melt. Analysis of viscosity behavior in the power‐law region revealed that the flow behavior index‐n‐decreased from 0.45 for 10 wt% of talc down to about 0.4 for 40 wt% of talc. Upon increasing the talc content to 50 wt%, n decreased to a value even lower than that of the neat PP resin. The frequency of the crossover point represents molecular mobility and relaxation‐time behavior. The crossover frequency of the composites was nearly constant up to 30 wt% of talc and decreased at higher filler loadings. The optimum amount of coupling agent could be correlated with the minimum point in crossover frequency and crossover modulus. The shrinkage behavior of the composites with and without MAPP resin was studied and correlated with the rheological properties. J. VINYL ADDIT. TECHNOL., 2010. © 2010 Society of Plastics Engineers     

Effects of processing conditions on the mechanical performance of maleic anhydride compatibilized in-situ composites of polypropylene with liquid crystalline polymer

Maleic anhydride compatibilized blends of isotactic polypropylene (PP) and thermotropic liquid crystaline polymer (LCP) were prepared either by the direct injection molding (one-step process), or by twin-screw extrusion blending, after which specimens were injection molded (two-step process). The morphology and mechanical properties of these injection molded in situ LCP composites were studied by means of scanning electron microscopy (SEM), Izod impact testing, static tensile, and dynamic mechanical measurements. SEM observations showed that fine and elongated LCP fibrils are formed in the maleic anhydride compatibilized in situ composites fabricated by means of the one-step process. The tensile strength and modulus of these composites were considerably close to those predicted from the rule of mixtures. Furthermore, the impact behavior of LCP fibril reinforced composites was similar to that of the glass fiber reinforced polymer composites. On the other hand, the maleic anhydride compatibilized blends prepared from the two-step process showed lower mechanical performance, which was attributed to the poorer processing behavior leading to the degradation of PP. The effects of the processing steps, temperatures, and compatibilizer addition on the mechanical properties of the PP/LCP blends are discussed.     

Shrinkage behavior and mechanical performances of injection molded polypropylene/talc composites

In this research, the influences of adding talc mineral particles of 10 μm particle size on the shrinkage and the mechanical properties of injection molded polypropylene (PP)/talc composites were investigated. PP has a crystalline molecular structure and hence it possesses nonisotropic shrinkage along and across the flow directions. Addition of the talc mineral filler to PP induced an isotropic shrinkage in the molded part because of the nonisotropic shape of talc particles. The results of experiments indicated that the maximum flexural strength, maximum impact strength, and isotropic shrinkage were achieved by adding 10, 20, and 30 by weight percent of talc respectively. By incorporating of 10 wt% of talc particles into the PP matrix, the tensile strength was hardly affected but the occurrence of cold drawing phenomena in the tensile test was hindered considerably. The flake‐shape structure of talc filler played an important role in determining the molded part shrinkage and mechanical properties. POLYM. ENG. SCI., 47:2124–2128, 2007. © 2007 Society of Plastics Engineers     

Effect of the compatibilizer on the physical properties of biaxially deformed in situ composites

The effect of a compatibilizer (poly(ester imide), PE^sI) on the biaxial deformation of a thermotropic liquid crystalline polymer (TLCP, poly(ester amide)) in a poly(ether imide) and the properties of biaxially deformed in situ composites were studied. The compatibilizer improved dispersion of the TLCP and the adhesion between TLCP and the matrix. The properties of blown films were affected by the amount of the compatibilizer used. The morphology evidently shows that ca. 0.6 wt% PEsI provides the best morphology when 10 wt% VB phase is included. The mechanical properties, especially in the hoop direction, were significantly improved for the compatibilized films compared to uncompatibilized one. The impact strength of a compatibilized blend film with 0.6 wt% PEsI was almost twice that of an uncompatibilized blend film.     

Water absorption and mechanical properties of PP/HIPS hybrid composites filled with wood flour

Water absorption and mechanical performance of the injection‐molded hybrid composites prepared from different ratios of two polymer blends (57 wt%), two compatibilizers (3 wt%), and two wood species (40 wt%) were investigated. The ratio of polypropylene and high‐impact polystyrene (HIPS) gradually increased in the blend (from 10 to 30 wt%). Styrene–ethylene–butylene–styreneblock copolymer and maleic anhydride‐grafted PP (MAPP) were used as compatibilizer (3 wt%). The shore D hardness of the PP/wood composites was improved by the incorporation of the HIPS. The HIPS/wood flour composites showed higher tensile modulus but lower tensile strength than the PP/wood composites. The water resistance of the PP/wood composites decreased with increasing HIPS content. POLYM. COMPOS., 38:863–869, 2017. © 2015 Society of Plastics Engineers     

粉末浸渍长玻璃纤维增强聚丙烯的注塑

采用粉末浸渍的方法制备连续玻璃纤维增强聚丙烯预浸料,经切割获得长纤维增强聚丙烯粒子,探索了材料的注塑工艺,研究了注塑后材料的力学性能及其影响因素。结果表明,粉末浸渍的长纤维增强聚丙烯经注塑后可获得力学性能的制品;随着预浸料切割长度的增长、纤维含量的增加,材料的力学性能提高;在基体聚丙烯中添加接枝极性基团的功能化聚丙烯,可改善体系的界面结合,提高材料的力学性能,但功能化聚丙烯的含量超过一定值后,材料的冲击强度有所下降;控制注塑时的模具温度,可以改变材料的一些力学性能。     

Influence of compatibilizers and processing temperature on microcellular injection‐molded polypropylene/(waste tire powder) composites

Nowadays the economic recycling of waste tires has become a global challenge. The use of waste tire powder as a dispersed elastomeric phase in a polypropylene (PP) matrix offers an interesting opportunity for recycling of waste tire rubber. Compatibilized PP/(waste tire powder) composites are microcellularly processed to create a new class of materials with unique properties. Recent studies have demonstrated the feasibility of developing microcellular structures in PP/waste ground rubber tire (WGRT) composites. Microcellular PP/WGRT composites are prepared by an injection‐molding process using a chemical blowing agent. In this study, cell sizes, cell density, void fraction, and mechanical properties of the composite foams were measured, as well as the shear viscosity of the unfoamed composites. The influence of various compatibilizers and processing temperatures on cell morphology and the mechanical properties of injection‐molded PP/WGRT composites were investigated. It was seen that the addition of maleic anhydride‐grafted styrene‐ethylene‐butylene‐styrene (SEBS‐g‐MA) increased the shear viscosity of the composites. The void fraction and cell density of the PP/WGRT composites increased with addition of compatibilizers, whereas the average cell sizes decreased. A processing temperature range of 180–195°C gave finer microcellular structure and regular cell distribution. The SEBS‐g‐MA enhanced the elongation properties and acted as an effective compatibilizer in this particular system. J. VINYL ADDIT. TECHNOL., 2011. © 2011 Society of Plastics Engineers     

Mechanical properties and morphology of polypropylene‐calcium carbonate nanocomposites prepared by dynamic packing injection molding

In this article, dynamic packing injection molding (DPIM) technology was used to prepare injection samples of Polypropylene‐Calcium Carbonate (PP/CaCO₃) nanocomposites. Through DPIM, the mechanical properties of PP/nano‐CaCO₃ samples were improved significantly. Compared with conventional injection molding (CIM), the enhancement of the tensile strength and impact strength of the samples molded by DPIM was 39 and 144%, respectively. In addition, the tensile strength and impact strength of the PP/nano‐CaCO₃ composites molded by DPIM increase by 21 and 514%, respectively compared with those of pure PP through CIM. According to the SEM, WAXD, DSC measurement, it could be found that a much better dispersion of nano‐CaCO₃ in samples was achieved by DPIM. Moreover, γcrystal is found in the shear layer of the DPIM samples. The crystallinity of PP matrix in DPIM sample increases by 22.76% compared with that of conventional sample. The improvement of mechanical properties of PP/nano‐CaCO₃ composites prepared by DPIM attributes to the even distribution of nano‐CaCO₃ particles and the morphology change of PP matrix under the influence of dynamic shear stress. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Mechanical properties of injection molded long fiber polypropylene composites,Part 2: Impact and fracture toughness

This study describes the effect of fiber length and compatibilizer content on notched izod impact and fracture toughness properties. Long fiber polypropylene (LFPP) pellets of different sizes were prepared by extrusion process using a new radial impregnation die, and subsequently, pellets were injection molded as described in previous publication 1 . The content of glass fiber reinforcement was maintained same for all compositions. Maleic‐anhydride grafted polypropylene (MA‐g‐PP) was chosen as a compatibilizer to increase the adhesion between glass fiber and PP matrix and its content was maintained at 2 wt%. Notched izod impact property was studied for LFPP composites prepared with and without compatibilizer for different pellet sizes. Failure mechanism due to sudden impact was analyzed with scanning electron micrographs and was correlated with impact property of LFPP composites. Fracture and failure behavior of injection molded LFPP composite were studied and relationship between fracture toughness and microstructure of LFPP composite was analyzed. The microstructure of the composites was characterized by the dimensionless reinforcing effectiveness parameter, which accounts for the influence of fiber layer structure, fiber alignment, fiber volume fraction, fiber length distribution, and aspect ratio. Matrix stress condition factor and energy absorption ratio were determined for LFPP composites prepared with and without compatibilizer. Failure mechanism of both the matrix and fiber, revealed with SEM images, were discussed. POLYM. COMPOS., 2008. © 2008 Society of Plastics Engineers     

Utilization of polyethylene terephthalate waste as a carbon filler in polypropylene matrix: Investigation of mechanical,rheological, and thermal properties

Polyethylene terephthalate (PET) waste was converted into carbon and the feasibility of utilizing it as a reinforcing filler material in a polypropylene (PP) matrix was investigated. The carbon produced by the pyrolysis of waste PET at 900°C in nitrogen atmosphere contains high carbon content (>70 wt%). PP/carbon composites were produced by melt blending process at varying loading concentrations. Scanning electron microscopy images at the fractured surface revealed that the carbon filler has better compatibility with the PP matrix. The mechanical, thermal, and rheological properties and surface morphology of the prepared composites were studied. The thermogravimetric analysis studies showed that the thermal stability of the PP/carbon composites was enhanced from 300 to 370°C with 20 wt% of carbon. At lower angular frequency (0.01 rad/s), the storage modulus (G′) of PP was 0.27 Pa and those of PP with 10 and 20 wt% carbon was 4.06 and 7.25 Pa, respectively. Among the PP/carbon composite prepared, PP with 5 wt% carbon showed the highest tensile strength of 38 MPa, greater than that of neat PP (35 MPa). The tensile modulus was enhanced from 0.9 to 1.2 GPa when the carbon content was increased from 0 to 20 wt%.     

Compatibilizing effect of ethylene–propylene–diene grafted maleic anhydride terpolymer on the blend of polyamide 66 and thermal liquid crystalline polymer

Polyamide 66–thermal liquid crystalline polymer (PA66/TLCP) composites containing 10 wt% TLCP was compatibilized by ethylene–propylene–diene‐grafted maleic anhydride terpolymer (MAH‐g‐EPDM). The blending was performed on a twin‐screw extrusion, followed by an injection molding. The rheological, dynamic mechanical analysis (DMA), thermal, mechanical properties, as well as the morphology and FTIR spectra, of the blends were investigated and discussed. Rheological, DMA, and FTIR spectra results showed that MAH‐g‐EPDM is an effective compatibilizer for PA66/TLCP blends. The mechanical test indicated that the tensile strength, tensile elongation, and the bending strength of the blends were improved with the increase of the content of MAH‐g‐EPDM, which implied that the blends probably have a great frictional shear force, resulting from strong adhesion at the interface between the matrix and the dispersion phase; while the bending modulus was weakened with the increase of MAH‐g‐EPDM content, which is attributed to the development of the crystalline phase of PA66 hampered by adding MAH‐g‐EPDM. POLYM. COMPOS., 27:608–613, 2006. © 2006 Society of Plastics Engineers