The effect of transcrystallinity on the transverse mechanical properties of single-polymer polyethylene composites

The microstructure of polyethylene (PE)/PE composites, consisting of the high-density PE (HDPE) matrix and ultrahigh molecular-weight PE (UHMWPE) fibers, was investigated. Single-fiber composites were prepared and analyzed in a hot-stage crystallization unit attached to a polarizing microscope, aiming to find out how the conditions of crystallization affected the transcrystallinity (tc) growth at the fiber-matrix interface. Thermal treatments leading to two extreme microstructures, of either maximum or minimum thickness of the transcrystalline zone, were sought. It was found that a uniform transcrystalline layer was developed on the UHMWPE fiber from the HDPE melt under isothermal conditions, whereas rapid cooling from the melt prevented the generation of tc. The mechanical properties of unidirectional composite laminae either with or without the transcrystalline zone were measured. A comparison of the transverse strength predicted by theoretical models with the experimental values revealed good interfacial adhesion in the PE/PE system. It was shown that the tc growth had a negligible effect on the composite mechanical properties in the longitudinal direction, whereas it resulted in a 50% decrease of the transverse tensile strength and strain to failure. Scanning electron microscopy attributed that observation to premature brittle failure at tc/tc contact regions. © 1995 John Wiley & Sons, Inc.     

Polyethylene fibers-polyethylene matrix composites: Preparation and physical properties

Drawing on the difference in melting points of UHMPE fiber (150°C) and HDPE matrix (130°C), single-polymer composites were fabricated under various processing conditions. Because of the chemical similarity of the composite components, good bonding at the fiber-matrix interface could be expected. The matrix, the fiber, and unidirectional composite laminae were studied using TMA and DSC analyses, a hot-stage crystallization unit attached to a polarizing microscope, and an universal tensile testing machine. The TMA showed negative thermal expansion of the fiber over the complete temperature range of the experiment. Three regimes of contraction according to the values of the thermal expansion coefficient were detected. DSC analyses of either the fiber or the composite specimens did not show any appreciable changes after various thermal treatments. They also showed no evidence of fiber relaxation during manufacture, probably because of the pressure-related transverse constraint. The tensile strength and modulus values of the composite appeared to be fairly high and close to those reported for other composites reinforced with polyethylene (PE) fibers. An apparent maximum on the temperature dependencies of tensile properties was observed. A study of the matrix microstructure did not give any proof of transcrystalline growth at the fiber-matrix interface even for chemical or plasma surface-treated fibers. © 1993 John Wiley & Sons, Inc.     

The effects of transcrystalline interphase in advanced polymer composites

Surface-induced transcrystallization in fibers has been reported in some advanced polymer composites. It is believed that transcrystalline interphase may affect stress transfer efficiency between the reinforcing fiber and the matrix. In this study, attempts were made to examine the effects of transcrystallinity on composite performance, particularly on fiber-matrix interfacial bond strength, and to investigate possible attributes of transcrystallization. Three polymer resins, poly(etherketoneketone) (PEKK), poly(etheretherketone) (PEEK), and poly(phenylenesulfide) (PPS), and four types of fiber, polyacrylonitrile (PAN)-based AU-4 (untreated AS-4) carbon, pitch-based carbon, poly (p-phenylene terephthalamide) (PPDT) aramid, and E-glass were used. It was found that PPDT aramid and pitch-based carbon fibers induce a transcrystalline interphase in all three polymers because of an epitaxial effect. Under certain conditions, transcrystallization was also observed in PAN-based carbon and E-glass fibers, which may be partially attributed to the thermal conductivity mismatch between the fiber and the matrix. Plasma treatment on fiber surface showed a negligible effect on inducing transcrystallization, whereas solution-coating of PPDT on the fiber surface showed a positive effect. The Microdebonding test, which measures the interfacial bond strength between the fiber and the matrix, consistently showed more than 40% increments for various single filament systems with transcrystalline interphase versus without. However, the effects of transcrystallinity on the interfacial bond strength appeared to decrease as the fiber content increased in composites.     

Transcrystallization in syndiotactic polypropylene induced by high-modulus carbon fibers

SUMMARY It was first shown that transcrystallization can be induced in syndiotactic polypropylene (sPP) when a carbon fiber (CF) of high-modulus (HM) is embedded in the melt of sPP crystallizing under quiescent conditions. High-tenacity carbon fiber (HTCF), on the other hand, did not cause transcrystalline growth. Coating of HMCF by silicon carbide (SiC) stopped the transcrystallization of sPP. The difference in the morphology of the transcrystalline layer between isotactic PP (iPP) and sPP was revealed by phase contrast light (PCLM), scanning electron (SEM) and atomic force microscopy (AFM) taken from the etched surface of single fiber microcomposite specimens. Received: 31 March 1998/Revised version: 29 May 1998/Accepted: 10 June 1998     

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.     

Facilitating transcrystallization of polypropylene/glass fiber composites by imposed shear during injection molding

The transcrystal plays an important role in the enhancement of mechanical and thermal performances for polymer/glass fiber composites. Shear has been found to be a very effective way for the formation of transcrystal. Our purpose of this study was to explore the possibility to obtain the transcrystal in real processing such as injection molding. We will report our recent efforts on exploring the development of microstructure of polypropylene (PP)/glass fiber composite from skin to core in the injection-molded bars obtained by so-called dynamic packing injection molding which imposed oscillatory shear on the melt during solidification stage. A clear-cut shear-facilitated transcrystallization of PP on glass fibers was observed in the injection-molding bar for the first time. We suggested that shear could facilitate the transcrystalline growth through significantly improving the fiber orientation and the interfacial adhesion between fiber and matrix.     

Influence of carbon fiber surface treatments on the structure and properties of conductive carbon fiber/polyethylene films

Effects of carbon fiber (CF) surface modification on the crystalline structure and both electrical and mechanical properties of conductive CF/high‐density polyethylene (HDPE) films were studied. Three different types of surface‐treated CF, epoxy‐sized, unsized, and sized but thermally treated, were considered. It was found that the uniformity of the transcrystalline zone around CF and the overall crystallinity of the polyethylene matrix decreased when epoxy‐sized CF was used. Epoxy‐sized CF caused a significant reduction not only in electrical resistivity and temperature coefficient of resistivity (TCR) but also tensile strength and coefficient of linear thermal expansion (CLTE) of composite films compared with that of unsized or sized CF that was thermally treated. We observed the systematic changes of TCR and CLTE values in accordance with CF surface modification and CF content in composite films. It was concluded that thermal expansion of the polymer matrix is the main reason for the positive TCR of CF/HDPE films. As the most probable reasons for decreased resistivity and strength of the CF/HDPE films with epoxy‐sized CF, the diffusion of epoxy sizing agent into the polyethylene matrix and the formation of loosened semiconductive interphase structure in the film are considered. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 2040–2048, 2002; DOI 10.1002/app.10500     

Transcrystalline morphology of nylon 6 on the surface of aramid fibers

In this paper, the isothermal crystallization of nylon 6 in the presence of Kevlar 129 fiber was investigated by polarized optical microscopy (POM). The formation of a transcrystalline domain was found to be mainly controlled by crystallization conditions, such as the temperature of the isothermal crystallization, residual time at melting temperature and the cooling rate of the melt. The nucleation rate of nylon 6 on the fibers was mainly affected by the crystallization temperature. The interfacial transcrystallinity of nylon 6 occurred on the surface of Kevlar 129 fiber in the temperature range 130–190 °C. The reason for the formation of interfacial transcrystalline morphology is discussed from the molecular level, based on the understanding of the packing mode of nylon 6 chains around fibers and the interaction between matrix and fibers. It was found that the lattice matching and hydrogen‐bonding between nylon 6 and poly(p‐phenylene terephthalamide) (PPTA) crystals play an important role in the epitaxial crystallization. Copyright © 2004 Society of Chemical Industry     

The preparation and tensile properties of polyethylene composites

Single polymer composites have been prepared using different morphologies of polyethylene as matrix and as the reinforcement. Depending on annealing conditions, the ultraoriented fibers used as reinforcement can have higher melting points (ca. 139°C) than the matrix made from the same conventionally crystallized high-density polyethylene (ca. 132°C) or from low-density polyethylene (ca. 110°C). The optimum temperature has been assessed for bonding to occur by growth of transcrystalline regions from the melt matrix without considerable modulus reduction of the annealed ultraoriented and reinforcement fiber or film. Pullout tests have been used for determining the interfacial shear strength of these single polymer composites. The interfacial shear strength for the high-density polyethylene films embedded in a low-density polyethylene matrix is 7.5 MPa and for high-density polyethylene self-composites is 17 MPa. These values are greater than the strength for glass-reinforced resins. The strength is mainly due to the unique epitaxial bonding which gives greater adhesion than the compressive and radial stresses arising from the differential shrinkage of matrix and reinforcement. The tensile modulus of composites prepared from uniaxial and continuous high-density polyethylene films embedded in low-density polyethylene obeys the simple law of mixtures and the reinforced low-density polyethylene modulus is increased by a factor of 10. High strength cross-ply high-density-polyethylene—low-density-polyethylene laminates have also been prepared and the mechanical properties have been studied as the film orientation is varied with respect to the tensile axis.     

Co‐crystallization in ternary polyethylene blends: tie crystal formation and mechanical properties improvement

Understanding the co‐crystallization behavior of ternary polyethylene (PE) blends is a challenging task. Herein, in addition to co‐crystallization behavior, the rheological and mechanical properties of melt compounded high density polyethylene (HDPE)/low density polyethylene (LDPE)/Zeigler ? Natta linear low density polyethylene (ZN‐LLDPE) blends have been studied in detail. The HDPE content of the blends was kept constant at 40 wt% and the LDPE/ZN‐LLDPE ratio was varied from 0.5 to 2. Rheological measurements confirmed the melt miscibility of the entire blends. Study of the crystalline structure of the blends using DSC, wide angle X‐ray scattering, small angle X‐ray scattering and field emission SEM techniques revealed the formation of two distinct co‐crystals in the blends. Fine LDPE/ZN‐LLDPE co‐crystals, named tie crystals, dispersed within the amorphous gallery between the coarse HDPE/ZN‐LLDPE co‐crystals were characterized for the first time in this study. It is shown that the tie crystals strengthen the amorphous gallery and play a major role in the mechanical performance of the blend.© 2016 Society of Chemical Industry     

Studies on thermal,mechanical, morphological,and viscoelastic properties of polybenzimidazole fiber reinforced high density polyethylene composites

High density polyethylene (HDPE) and polybenzimidazole fiber (PBI) composites were prepared by melt blending in a twin screw extruder. The thermomechanical properties of PBI fiber reinforced HDPE composite samples (1%, 4%, and 8%) of fiber lengths 3 mm and 6 mm were investigated using differential scanning calorimeter (DSC), universal testing machine, rheometer, and scanning electron microscopy (SEM). The effects of fiber content and fiber lengths on the thermomechanical properties of the HDPE‐PBI composites were studied. The DSC analysis showed a decrease in crystallinity of HDPE‐PBI composites with an increase of fiber loading. SEM images revealed homogeneous distribution of the fibers in the polymer matrix. The thermal behavior of the composites was evaluated from thermogravimetric analysis and the thermal stability was found to increase with the addition of fibers. The evidence of homogeneous distribution was verified by the considerably high values of tensile strength and flexural strength. In the rheology study, the complex viscosities of HDPE‐PBI composites were higher than the HDPE matrix and increased with the increasing of PBI fiber loading. POLYM. COMPOS., 5–13, 2016. © 2014 Society of Plastics Engineers     

Transcrystallinity and relevant interfacial strength induced by carbon nanotube fibers in a polypropylene matrix

For polymer composites, interfacial crystalline structures retain an important role in the macroscopic properties and are significantly affected by the processing conditions, such as the temperature, time, and external field. In this study, the transcrystallization behavior of the carbon nanotube fiber and isotactic polypropylene composite was investigated by polarizing light microscopy. The influence of the formation of the transcrystalline layer on the interfacial adhesion was evaluated by a single‐fiber fragmentation test. The results show that the growth rate of the transcrystalline layer was strongly influenced by the isothermal crystallization temperature, and the interfacial shear strength was markedly enhanced by the formation of the layer. The interfacial adhesion was further increased with the gradual perfection and growth of transcrystallinity. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42119.     

Crystallization of poly(etheretherketone) (PEEK) in carbon fiber composites

The tendency of carbon fiber to nucleate the zation of poly(etherettterlcetone) (PEEK) has been evaluated by DSC and other techniques. As the carbon fiber content was increased, the supercooling necessary for PEEK crystallization decreased. The repeated melting (at 396°C) of the same PEEK sample results in a decrease of the number of nuclei for crystallization. At equivalent thermal histories, PEEK with carbon fiber was found to have a higher nucleation density than PEEK itself. The surface of carbon fibers and nuclei in the PEEK matrix compete for crystallization growth. As the holding time in melt was increased, the number of matrix spherulites formed on cooling decreased, hence a more pronounced transcrystalline region was developed. Correspondingly, the composites preheated in the melt for 100 min showed about two times the transverse tensile strength and strain-to-failure of those preheated for only 30 min. Corresponding fracture surface produced in tension showed that the former samples had a greater matrix adhesion to the carbon fiber than the latter. A strong interfacial bond is thus developed by crystallization on carbon fiber surface. Destroying nuclei in the PEEK matrix by long preheating enhances crystallization on the carbon fiber.     

Transcrystallization in fiber-reinforced isotactic polypropylene composites in a temperature gradient

Transcrystallization of isotactic polypropylene (iPP) on different fibers (carbon fiber, glass fiber, and aramid fiber) was conducted in a temperature gradient. The Ultra-High-Module carbon fiber (UHMCF), the High-Module carbon fiber, and the aramid fiber (Twaron) showed sufficient nucleation ability to form transcrystallization of iPP in certain temperature ranges. Among them, the UHMCF showed the best nucleation ability. On the contrary, the Intermediate-Module carbon fiber, the High-Tenacity carbon fiber, and the E-glass fiber showed too low nucleation ability to form transcrystallization of iPP. One efficient way to induce transcrystallization on these fibers was proved by pulling the fibers in supercooled iPP melts. The interface shear between fiber and supercooled matrix melt on crystallization and the interface temperature gradient between fiber and supercooled matrix melt on crystallization are considered to be two very important factors for the formation of transcrystallization. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 65: 67–75, 1997     

Influence of surface morphology of the kraft pulp fibers on the growth of the transcrystalline layer of polypropylene

The objective of this study was to evaluate the influence of the wood fiber surface on the crystallization behavior of thermoplastic polymers. Unbleached and bleached kraft pulp fibers were used for this study with 100% polypropylene (PP), 95% PP/5% maleic anhydride polypropylene (MAPP), and 100% MAPP at 150°C. Nuclei were induced at the ends of the fibers and on damaged surfaces while poor crystallization behavior was observed on the fiber surfaces using 100% PP. Enhanced MAPP induced transcrystallization on the wood fiber surfaces; the nucleation density also increased with the addition of MAPP. Oxygen/carbon (O/C) ratios of smooth surfaces, damaged surfaces, and the ends of wood fibers also indicated that the oxidation process of both wood fiber and thermoplastic polymer affected the crystallization process without MAPP addition. It was observed that the MAPP played a role in increasing numbers of nuclei on the linear fiber surface to induce transcrystallization. Dynamic mechanical properties increased 52% with 100% MAPP compared to the use of 100% PP. Therefore, the increased thickness of transcrystalline layer and nucleation density on the surface of wood fiber positively correlated with the dynamic mechanical properties of wood fiber‐plastic composites. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

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.     

Insert injection molding of high‐density polyethylene single‐polymer composites

A process for making high‐density polyethylene (HDPE) single‐polymer composites (SPCs) by insert injection molding was investigated. HDPE SPCs with relatively good tensile and interfacial properties were prepared within a short cycle time within a temperature range of 40°C. Melt‐spun HDPE fibers were made from the same resin as the matrix. The fibers were heat treated in silicone oil, with and without tension, to study the changes of fiber properties upon exposure to high temperature. HDPE SPCs containing about 30 wt% lab‐made HDPE fabric achieved a tensile strength of 50 MPa, 2.8 times that of neat HDPE. The peel strength of HDPE SPCs increased with increasing injection temperature and achieved a maximum value of 16.7 N/cm. Optical micrographs of polished transverse cross‐sections of the SPC samples showed that higher injection temperature is beneficial to the wetting and permeation properties of the matrix. Scanning electronic microscope photographs suggested good bonding and compatibility between the fibers and the matrix. POLYM. ENG. SCI., 55:2448–2456, 2015. © 2015 Society of Plastics Engineers     

Fabrication of polyethylene/graphite nanocomposite from modified expanded graphite

A novel process was employed to fabricate a polymer/expanded graphite nanocomposite by modifying the conducting filler expanded graphite (EG) with unsaturated polyester resin (UPR). The modified expanded graphite (MEG) was prepared from EG in which the graphite nanosheets, already present in EG, were wrapped and isolated by the UPR during processing. The as‐prepared MEG was reduced to powder form to improve its dispersion in the matrix. MEG powders were embedded into a high‐density polyethylene (HDPE) matrix via melt‐extrusion in a single‐screw extruder to prepare the conducting composite. The as‐prepared HDPE/EG conducting composite exhibited a low percolation threshold of ～5.7 wt% due to the high aspect ratio of graphite nanosheets. Mechanical properties such as the tensile and impact strength were also studied. Scanning electron microscopy was used to characterize the microstructure of EG, MEG powder and the resulting nanocomposites. Copyright © 2006 Society of Chemical Industry     

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.     

Functionalization of high density polyethylene in melt state through ultrasonic initiation and its effect on mechanical properties of glass fiber reinforced composites

Summary Functionalization reaction of high density polyethylene (HDPE) with γ-methacryloxy-propyltrimethoxysilane (MAS) or with MAS and MAH performed in melt state through ultrasonic initiation by a laboratory-scale ultrasonic extruding reactor was studied in this paper. The effect of ultrasonic intensity on the percentage of grafting and melt flow rate of the functionalized products was investigated. The results show that by imposing ultrasonic vibration during melt-extruding process, the scission of HDPE chain bonds can be caused to form macroradicals, the functionalization reaction of HDPE with MAS or with MAS and MAH can be realized. The percentage of grafting and the melt flow rate of the functionalized products depend upon the ultrasonic intensity and reaction temperature. The fuctionalization reaction of HDPE with MAS can be promoted by adding a second grafting monomer MAH. The ultrasonic-induced products have a higher reactivity with the coupling agents coated on the surface of glass fibers, the mechanical properties of the composite improved by the ultrasonic induced product are higher than that of by peroxide initiated product and the mechanical properties of HDPE/GF composite modified by HDPE-g-MAH-MAS are higher than that of by HDPE-g-MAH. The SEM experimental results indicate that an oriented crystal layer exists between the interface of glass fiber and the HDPE matrix, the interfacial bonding strength is the determining factor of the formation of the oriented crystal layer.