Micro‐contact reconstruction of adjacent carbon nanotubes in polymer matrix through annealing‐Induced relaxation of interfacial residual stress and strain

Thermoplastic polyurethane (TPU)/multi‐walled carbon nanotubes (CNT) nanocomposites were prepared by twin‐screw extrusion and micro injection molding. The electrical conductivity of micro injection molded polymer nanocomposites exhibits a low value and uneven distribution in the micromolded samples. Real‐time tracing of electrical conductivity was conducted to investigate the post thermal treatment on the electrical conductivity of microinjection molded composites. The results show that postmolding thermal treatment leads to a significant increase in the electrical conductivity by over three orders of magnitude for 5 wt % CNT‐filled TPU composites. In‐situ Transmission electron microscopy confirms the conductive CNT network does not change at the micron/sub‐micron scale during thermal treatment. TEM image analysis by a statistical method was used to determine the spatial distribution of CNT in the sample and showed that the average distance between adjacent CNT reduced slightly at the nanometer scale after postmolding thermal treatment. A new conductive mechanism is proposed to explain the enhancement of electrical conductivity after thermal treatment, i.e. micro‐contact reconstruction of adjacent CNT in the polymer matrix through annealing‐induced relaxation of interfacial residual stress and strain. Raman spectra and small angle X‐ray scattering curve of annealed samples provide supporting evidence for the proposed new conductive mechanism. The electron tunneling model was used to understand the effect of inter‐particle distance on the conductivity of polymer composites. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42416.     

Measurement and numerical prediction of fiber‐reinforced thermoplastics' thermal conductivity in injection molded parts

Recent improvements in injection molding numerical simulation software have led to the possibility of computing fiber orientation in fiber reinforced materials during and at the end of the injection molding process. However, mechanical, thermal, and electrical properties of fiber reinforced materials are still largely measured experimentally. While theoretical models that consider fiber orientation for the prediction of those properties exist, estimating them numerically has not yet been practical. In the present study, two different models are used to estimate the thermal conductivity of fiber reinforced thermoplastics (FRT) using fiber orientation obtained by injection molding numerical simulation software. Experimental data were obtained by measuring fiber orientation in injection molded samples' micrographs by image processing methods. The results were then compared with the numerically obtained prediction and good agreement between numerical and experimental fiber orientation was found. Thermal conductivity for the same samples was computed by applying two different FRT thermal conductivity models using numerically obtained fiber orientation. In the case of thermal conductivity, predicted results were consistent with experimental data measurements, showing the validity of the models. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39811.     

Improved through‐plane electrical conductivity in a carbon‐filled thermoplastic via foaming

Flow‐induced orientation of the conductive fillers in injection molding creates parts with anisotropic electrical conductivity where through‐plane conductivity is several orders of magnitude lower than in‐plane conductivity. This article provides insight into a novel processing method using a chemical blowing agent to manipulate carbon fiber (CF) orientation within a polymer matrix during injection molding. The study used a fractional factorial experimental design to identify the important processing factors for improving the through‐plane electrical conductivity of plates molded from a carbon‐filled cyclic olefin copolymer (COC) containing 10 vol% CF and 2 vol% carbon black. The molded COC plates were analyzed for fiber orientation, morphology, and electrical conductivity. With increasing porosity in the molded foam part, it was found that greater out‐of‐plane fiber orientation and higher electrical conductivity could be achieved. Maximum conductivity and fiber reorientation in the through‐plane direction occurred at lower injection flow rate and higher melt temperature. These process conditions correspond with foam flow during filling of the mold cavity, indicating the importance of shear stress on the effectiveness of a fiber being rotated out‐of‐plane during injection molding. POLYM. ENG. SCI., 2008. © 2008 Society of Plastics Engineers     

Effect of Al2O3 fibers on the thermal conductivity and mechanical properties of high density polyethylene with the absence and presence of compatibilizer

Alumina (Al₂O₃) fiber/high density polyethylene (HDPE) composites were prepared by molding injection with or without compatibilizer, in which, maleic anhydride‐grafted polyethylene (PE‐g‐MA) and acrylic acid‐grafted polyethylene (PE‐g‐AA) were used as the compatibilizers. The thermal conductivities of the composites were anisotropic and the conductivities in the injection direction of the samples were higher than those in perpendicular direction of the injection. The anisotropic thermal conductivity for Al₂O₃/PE‐g‐AA/HDPE was the most obvious and this composite also gave the best mechanical performance. The SEM and DMA test revealed that PE‐g‐AA was more effective than PE‐g‐MA in improving the matrix–filler interaction. The high interfacial interaction was more favorable for the viscous flow‐induced fiber orientation, which resulted in the largest anisotropic degree of thermal conductivity of the Al₂O₃/PE‐g‐AA/HDPE among the studied composite. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Modeling of anisotropic thermal conductivity of polymer composites containing aligned boron nitride platelets: Effect of processing methods

Hexagonal boron nitride (h‐BN) can remarkably enhance the thermal conductivity (TC) of polymer composites, while maintaining high electrical insulation. In this article, the previously developed analytical model, which can simultaneously solve the anisotropic TC of polymer composites containing aligned h‐BN platelets, was improved by introducing a power function to define the polymer thickness ratio in the unit cell. The modified model was validated by an excellent agreement with the experimental results from three independent literatures, in which the samples were prepared by either casting (including tape casting and spin casting) or injection molding. The influence of key parameters on the composite TCs was analyzed. It was found that the power n closely relates to the possessing methods for the polymer composites, which are also well correlated with the behavior of anisotropic TC. POLYM. COMPOS., 38:2670–2678, 2017. © 2015 Society of Plastics Engineers     

The property of polycarbonate/acrylonitrile butadiene styrene‐based conductive composites filled by nickel‐coated carbon fiber and nickel–graphite powder

The filled conductive composites were prepared with a polycarbonate/acrylonitrile butadiene styrene matrix and both nickel‐coated carbon fiber (NiCF) and nickel–graphite powder (NCG) as fillers by using injection molding and injection‐compression molding. The effect of the NiCF content, NCG content, coupling agent, and molding methods on the properties of composites was studied. The results showed that the conductivity of the composites increased with raising the NiCF content and NCG content. NiCF treated with silane coupling agent could further improve the conductivity of the composites without any significant change in mechanical properties. Furthermore, compared with injection molding, the composites prepared by injection‐compression molding possessed better conductivity. POLYM. COMPOS., 38:157–163, 2017. © 2015 Society of Plastics Engineers     

Multiple percolation in a carbon‐filled polymer composites via foaming

This article describes an investigation into the effects of foaming on the electrical conductivity for a carbon‐filled cyclic olefin copolymer (COC) composite incorporating both chopped carbon fibers (cCF) and carbon black (CB). Foamed and solid samples were injection molded and then analyzed for cell size, fiber length, fiber orientation, and electrical conductivity. Foamed samples exhibited higher electrical conductivity in the through‐plane direction for materials containing only CB or composites containing both filler types, and reduced electrical conductivity in the cCF‐filled composites. The increased electrical property gained by foaming was attributed to multiple percolation with CB aggregates forming more effective conductive clusters and networks in the continuous polymer phase during growth of the gas domains. A mechanism for the phenomenon was proposed based on these experimental observations. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Mechanical performance of starch based bioactive composite biomaterials molded with preferred orientation

Composites of blends of starch with ethylene vinyl alcohol copolymer (SEVA‐C) filled with 10, 30 and 50% by weight (wt.) of hydroxyapatite (HA–the major inorganic constituent of human bone) were produced by twin‐screw extrusion (TSE) compounding. These composites were molded into tensile test bars using two molding techniques: (i) conventional injection molding and (ii) shear controlled orientation in injection molding (SCORIM). The bars produced were mechanically characterized by means of tensile testing and dynamical mechanical analysis (DMA). The structure of the moldings was assessed by wide‐angle X‐ray diffraction (WAXD) and the failure surfaces of the moldings analyzed by scanning electron microscopy (SEM). The enhancement of stiffness observed with HA reinforcement results partially from the stiffening effect of the blend associated with the decrease in plasticizer content during the compounding stage. SCORIM was able to further increase the stiffness of SEVA‐C/HA composites, allowing a maximum improvement of 12% for 30% wt. HA as compared to conventional molding. DMA results showed that the reinforcement of SEVA‐C causes the broadening of the relaxation peak of the polymer, suggesting a structural change within the starch fraction that may be related with thermal degradation of the polymer. The addition of HA particles reduces the preferred orientation exhibited by the SEVA‐C matrix, which is believed to limit the maximum mechanical performance that can be attained. Nevertheless, composites based on a biodegradable matrix with modulus above 7 GPa (in the bounds of the lower limit for human cortical bone) could be successfully produced.     

Temperature dependence of effective thermal conductivity and thermal diffusivity of treated and untreated polymer composites

Thermal properties, such as thermal conductivity, thermal diffusivity, and specific heat, of treated and untreated oil palm fiber–reinforced PF composites were measured simultaneously at room temperature and normal pressure using the transient plane source (TPS) technique. An increase in thermal conductivity was observed in the fiber‐treated and resin‐treated composites. Surface modifications of fibers by prealkali, potassium permanganate, and peroxide treatments increased the fiber–matrix adhesion by increasing porosity and pore size of the fiber surfaces. The increase in crosslinking enhanced the thermal conductivity of a composite of resin treated with peroxide compared to other composites. Also an attempt was made to explain the temperature dependence of thermal conductivity and thermal diffusivity of amorphous polymer samples using the same technique. It was observed that at the glass‐transition peak of the polymer, thermal conductivity and diffusivity were maximum. Below and above this temperature their values decreased. This has been explained on the basis of predominant scattering processes. An empirical relationship was established for the theoretical prediction of thermal conductivity and diffusivity. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 1708–1714, 2003     

Recyclability of a glass fiber poly(butylene terephthalate) composite

The recyclability of a fiber-reinforced poly(butylene terephthalate) (PET) composite has been studied. After treatment with a suitable silane, processed regrind composites are successfully recycled, with mechanical properties as good as a comparable, commercial composite. The three processing techniques investigated are injection molding, extrusion compression molding and compression molding. As expected, processing technique and processing parameters are important in determining the mechanical properties of the molded regrind. Our results show that injection- and extrusion-compression-molded regrind composites have good fiber bundle dispersion and fiber alignment, resulting in tensile properties better than the compression-molded samples. On the other hand, compression-molded samples, which show random fiber orientation and low fiber bundle dispersion, have lower tensile properties, but better impact strength than injection- and extrusioncompression-molded composites.     

Interface and mechanical properties of poly(methyl methacrylate)–fiber composites

Long‐fiber pellets were made by an in situ pultrusion process. Fiber‐reinforced composites were prepared by an injection‐molding process and an extrusion/injection‐molding method with pellets, respectively. SEM observations showed that the strong interface was maintained during the injection process for low shearing forces, although polymer adhesion to the fiber surface was completely delaminated in the process of extrusion/injection molding for very high shearing forces. Enhanced adhesion of composites promoted substantial improvement of mechanical properties compared to those with poor adhesion. However, the enhanced adhesion between the fiber and the matrix also sacrificed the impact resistance properties. Longer fibers substantially enhanced the properties of composites. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 2478–2483, 2004     

Measurement and prediction of thermal conductivity for hemp fiber reinforced composites

The thermal conductivity of hemp fiber reinforced polymer composites were studied from the steady state temperature drop across samples exposed to a known heat flux. The transverse and in-plane thermal conductivities for oriented and randomly oriented composites for different volume fractions of fiber were investigated. Experimental results showed that the orientation of fibers has a significant effect on the thermal conductivity of composites. To validate the experimental results, the heating tests for the thermal conductivity measurements were simulated by a finite element model using the thermal conductivity values obtained from the experiments. Predicted temperatures show close agreement with measured temperatures. Moreover, the experimental results of thermal conductivities of composites at different directions were compared with two theoretical models and illustrated good agreement between the obtained results and models. POLYM. ENG. SCI. 47:977–983, 2007. © 2007 Society of Plastics Engineers     

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.     

Multifunctional polypropylene composites produced by incorporation of exfoliated graphite nanoplatelets

The potential of using exfoliated graphite nanoplatelets, xGnP^TM, as a reinforcement that can produce multifunctional polymer composites was explored. xGnP-polypropylene (PP) composites fabricated by melt mixing using a twin-screw extruder followed by injection molding were investigated for their thermal, viscoelastic and barrier properties as a function of xGnP concentration and aspect ratio. These properties of the xGnP-PP composites were compared to the properties of composites made with PAN-based carbon fibers, VGCF, carbon black and nanoclay. Results indicate that when oriented properly, the xGnP will not only stiffen the composite but also reduce the coefficient of thermal expansion in two directions rather than in one as in the case of aligned fiber composites. Furthermore, the large aspect ratio of xGnP, even at low loadings, increases the oxygen barrier of PP at least as effectively as the commonly used nanoclays and finally, addition of xGnP significantly enhances the thermal conductivity of the polymer matrix.     

Measurement,modeling, and variability of thermal conductivity for structural polymer composites

The through‐thickness thermal conductivity of polymer composite molds has a strong effect on out‐of‐autoclave manufacturing operations. Limited thermal conductivity and variability data is available for composites made from carbon fibers that are widely used in mold and aircraft construction. This article presents in‐plane and through‐thickness thermal conductivity data for structural carbon fiber polymer composites made from three types of reinforcements. Variability is quantified in all cases. Techniques for the predictive modeling of through‐thickness transverse thermal conductivity are assessed. Effects of variations in model geometry on conductivity are quantified. Conclusive observations on variability and recommendations on modeling techniques appropriate for the different reinforcements are made. POLYM. COMPOS., 2010. © 2009 Society of Plastics Engineers     

High Thermal Conductivity Polymer Composites Fabrication through Conventional and 3D Printing Processes: State-of-the-Art and Future Trends

The lifespan and the performance of flexible electronic devices and components are affected by the large accumulation of heat, and this problem must be addressed by thermally conductive polymer composite films. Therefore, the need for the development of high thermal conductivity nanocomposites has a strong role in various applications. In this article, the effect of different particle reinforcements such as single and hybrid form, coated and uncoated particles, and chemically treated particles on the thermal conductivity of various polymers are reviewed and the mechanism behind the improvement of the required properties are discussed. Furthermore, the role of manufacturing processes such as injection molding, compression molding, and 3D printing techniques in the production of high thermal conductivity polymer composites is detailed. Finally, the potential for future research is discussed, which can help researchers to work on the thermal properties enhancement for polymeric materials.     

Estimating the residual fatigue lifetimes of impact‐damaged composites using thermoelastic stress analysis

A new experimental method is presented for quantifying impact damage and estimating the remaining fatigue lifetime of impact damaged polymer matrix composite materials. The procedure is demonstrated using composites of glass fiber reinforced polyurethane produced by injection molding and structural reaction injection molding. Thermoelastic stress analysis (TSA) was used to quantify the stress concentration associated with impact‐damage in test samples of each composite. Following impact and TSA imaging, the samples were fatigued to failure over a range of stress amplitudes. The TSA‐derived stress concentration factors were used to determine a modified stress amplitude that collapsed the impact‐fatigue data onto a master stress‐life curve. This approach provides a quantitative measure of impact damage and a practical methodology for estimating the residual fatigue lifetime of impact; damaged composites.     

Effects of flow induced orientation of ferromagnetic particles on relative magnetic permeability of injection molded composites

Composite samples consisting of ferromagnetic asymmetric particles incorporated into a polyolefin binder were injection molded using custom designed molds which produced preferential fiber orientations. The relative magnetic permeability values of the composites were measured as a function of the filler volume fraction, injection rate, gate diameter, temperature, aspect ratio of the fibers, and fiber orientation. Fiber orientation was affected by the molding conditions and controlled the relative magnetic permeability of the composites. The degree of fiber orientation was significantly affected by the size of the opening (gate) to the mold, or by the mold geometry going from an edge-gated cylindrical to a center-gated disk cavity. Relative permeability values of the composites were observed to increase when the fiber orientation and the applied field were parallel to one another. For instance, highly aligned composite samples exhibited up to 30% greater relative permeability values compared to those samples which exhibit fiber orientation distributions approaching a random distribution. To our knowledge this is the first study that provides data linking the fiber orientation distribution functions of ferromagnetic asymmetric particles to the relative magnetic permeability values of injection molded composites.     

Shear Enhanced Fiber Orientation and Adhesion in PP/Glass Fiber Composites

Summary: In order to achieve better mechanical properties, most work on polymer/fiber composites has been focused on the importance of the chemistry used to modify the surface of the fibers and improving the adhesion between the fiber and the matrix using coupling agents. Our purpose in this study was to determine the effect of shear on the fiber orientation and interfacial adhesion in poly(propylene)/glass fiber composites via dynamic packing injection molding (DPIM), in which the melt is first injected into the mold and then forced to move repeatedly in a chamber by two pistons that move reversibly with the same frequency as the solidification progressively occurs from the mold wall to the molding core part. SEM, TGA, FT‐IR, AFM and mechanical testing were used to characterize the samples obtained. The majority of fibers are aligned parallel to the flow direction along the sample thickness, even at the core, in contrast to the products obtained via conventional injection molding where the orientation of fibers is observed only at the skin. More importantly, we found that shear could enhance not only the fiber orientation, but also the interfacial adhesion between the fibers and the matrix, particularly for samples with higher fiber contents, resulting in an obvious increase in tensile strength and the onset degradation temperature. A possible transcrystallization was evidenced by AFM investigations of the dynamic packing injection molded samples, which is worth further study.

SEM micrographs representing the glass fiber after PP in the composites was extracted (GF30, dynamic sample).     

Thermally conductive nylon 6,6 and polycarbonate based resins. I. Synergistic effects of carbon fillers

Increasing the thermal conductivity of typically insulating polymers, such as nylon 6,6, opens new markets. A thermally conductive resin can be used for heat‐sink applications. This research focused on performing compounding runs followed by injection molding and thermal conductivity testing of carbon filled nylon 6,6 and polycarbonate based resins. The three carbon fillers investigated included an electrically conductive carbon black, synthetic graphite particles, and a milled pitch‐based carbon fiber. For each polymer, conductive resins were produced and tested that contained varying amounts of these single carbon fillers. In addition, combinations of fillers were investigated by conducting a full 2³ factorial design and a complete replicate in each polymer. The objective of this article was to determine the effects and interactions of each filler on the thermal conductivity properties of the conductive resins. From the through‐plane thermal conductivity results, it was determined that for both nylon 6,6 and polycarbonate based resins, synthetic graphite particles caused the largest increase in composite thermal conductivity, followed by carbon fibers. The combination of synthetic graphite particles and carbon fiber had the third most important effect on composite thermal conductivity. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 112–122, 2003