Enhanced thermal conductivity for PVDF composites with a hybrid functionalized graphene sheet-nanodiamond filler

A new thermal conductive poly(vinylidene fluoride) (PVDF) composite has been developed via a hybrid functionalized graphene sheets (FGS)-nanodiamonds (NDs) filler by a simple solution method. The PVDF composite showed different thermal conductivities at different proportion of hybrid filler. The thermal conductivity of the composite was up to 0.66 W/m·K for a mixture containing 45 wt% hybrid filler, which is about 2-fold increment in comparison to the PVDF martrix. The PVDF composites consisting of 20 wt% hybrid FGS/ND filler at the weight ratio of 1:3 shows the best thermal stability. The electrical conductivity of composites was increased from 5.1×10^?15 S cm^?1 (neat PVDF) to 7.1×10^?7 S cm^?1 of the PVDF composite with 10 wt% hybrid filler.     

Facile In-situ Polymerization of Thermotropic Liquid Crystalline Polymers as Thermally Conductive Matrix Materials

Although thermally conductive composites that can efficiently dissipate the heat generated from electronic devices are in high demand, most neat polymers used as matrix materials are problematic because they have poor thermal conductivities. The low thermal conductivity of polymeric materials is caused by structural defects; therefore, it can be improved by increasing the orientational regularity of the polymer chains. Here, main-chain liquid crystalline polymers (LCPs) were designed and synthesized to investigate the effects of liquid crystallinity-induced structural regularity on the thermal conductivity of the polymers. In addition, an in-situ polymerization method was devised for commercial applicability, and the thermal conductivity of the obtained polymer was compared to that of a conventionally polymerized polymer having the same structure. The designed polymers exhibited thermotropic liquid crystalline characteristics, and the polymer with longer spacers between the rigid segments showed relatively higher thermal conductivity exceeding 0.5 W·m^-1· K^-1 after sample preparation by injection molding. In addition, X-ray diffraction analysis revealed that the differences in the thermal conductivity, depending on the molding temperature during specimen preparation, were caused by variations in chain orientation within the same polymer. Based on the obtained results, it was concluded that LCPs are strong candidate matrix materials for thermally conductive composites; the suggested in-situ polymerization method could be applied practically to the polymerization of polyester-type LCPs.     

Enhanced thermal properties for epoxy composites with a three-dimensional graphene oxide filler

In this study, we report a simple and efficient method to prepare three-dimensional graphene oxide (3DGO) network by freeze drying and investigate the effect of 3DGO network on thermal properties of epoxy composites. It was found that the 3DGO network not only improved thermal conductivity, thermal stability, glass transition temperature and storage modulus of epoxy composites, but also reduced the thermal expansion properties of epoxy composites. For instance, the thermal conductivity value of epoxy composite with only 1.3 wt% 3DGO is 0.62 Wm^-1K^-1, increased by 148 % in comparison with that of the neat epoxy (0.25 Wm^-1K^-1).     

Crystallization of poly(vinylidene fluoride)-SiO2 hybrid composites prepared by a Sol-gel process

Organic-inorganic hybrid composites consisting of poly(vinylidene fluoride) (PVDF) and SiO₂ were prepared through a sol-gel process and the crystallization behavior of PVDF in the presence of SiO₂ networks was investigated by spectroscopic, thermal and x-ray diffraction measurements. The hybrid composites obtained were relatively transparent, and brittleness increased with increasing content of tetraethoxysilane (TEOS). It was regarded from FT-IR and DSC thermal analyses that at least a certain interaction existed between PVDF molecules and the SiO₂ networks. X-ray diffraction measurements showed that all of the hybrid samples had a crystal structure of PVDFγ-phase. Fresh gel prepared from the sol-gel reaction showed a very weak x-ray diffraction peak near 2θ=21° due to PVDF crystallization, and intensity increased gradually with time after gelation. The crystallization behavior of PVDF was strongly affected by the amount of SiO₂ networks. That is, SiO₂ content directly influenced preference and disturbance for crystallization. In polymer-rich hybrids, SiO₂ networks had a favorable effect on the extent of PVDF crystallization. In particular, the maximum percent crystallinity of PVDF occurred at the content of 3.7 wt% SiO₂ and was higher than that of pure PVDF. However, beyond about 10 wt% SiO₂, the crystallization of PVDF was strongly confined.     

Conductive 3D structure nanofibrous scaffolds for spinal cord regeneration

The complex nature of spinal cord injuries has provided much inspiration for the design of novel biomaterials and scaffolds which are capable of stimulating neural tissue repair strategies. Recently, conductive polymers have gained much attention for improving the nerve regeneration. In our previous study, a three-dimensional (3D) structure with reliable performance was achieved for electrospun scaffolds. The main purpose in the current study is formation of electrical excitable 3D scaffolds by appending polyaniline (PANI) to biocompatible polymers. In this paper, an attempt was made to develop conductive nanofibrous scaffolds, which can simultaneously present both electrical and topographical cues to cells. By using a proper 3D structure, two kinds of conductive scaffolds are compared with a non-conductive scaffold. The 3D nanofibrous core-sheath scaffolds, which are conductive, were prepared with nanorough sheath and aligned core. Two different sheath polymers, including poly(lactic-co-glycolic acid) PLGA and PLGA/PANI, with identical PCL/PANI cores were fabricated. Nanofibers of PCL and PLGA blends with PANI have fiber diameters of 234±60.8 nm and 770±166.6 nm, and conductivity of 3.17×10^-5 S/cm and 4.29×10^-5 S/cm, respectively. The cell proliferation evaluation of nerve cells on these two conductive scaffolds and previous non-conductive scaffolds (PLGA) indicate that the first conductive scaffold (PCL/ PANI-PLGA) could be more effective for nerve tissue regeneration. Locomotor scores of grafted animals by developed scaffolds showed significant performance of non-conductive 3D scaffolds. Moreover, the animal studies indicated the ability of two new types of conductive scaffolds as spinal cord regeneration candidates.     

Effects of date palm leaf fiber on the thermal and tensile properties of recycled ternary polyolefin blend composites

This work investigated the effects of date palm leaf fiber (DPLF) content on the thermal and tensile properties; and morphology of compatibilized polyolefin ternary blend. Recycled polyolefin ternary blend consisting of low density polyethylene (RLDPE), high density polyethylene (RHDPE) and polypropylene (RPP) were fabricated at different parts per hundred resin (phr) of DPLF. Maleic anhydride grafted polyethylene (MAPE) was used as compatibilizer to enhance the adhesion between filler and polymer matrix. The composites were prepared using melt extrusion and tests samples were produced via injection molding process. Thermal conductivity results showed that as much as 11 % reduction in thermal conductivity was achieved with the incorporation of 30 phr DPLF. Highest tensile strength was observed with the incorporation of 10 phr DPLF. The elongation at break was reduced with the addition of DPLF due to impediment of chain mobility by the fillers. Initial degradation temperature increased with the addition of DPLF. Hence, it is concluded that DPLF can be used to develop green and thermally insulating composites. It is hoped that the present results will stimulate further studies on the thermally insulative materials based on natural fibers reinforced polymer composites for applications in the building industries.     

Polypropylene/high-density polyethylene/carbon fiber composites: Manufacturing techniques,mechanical properties,and electromagnetic interference shielding effectiveness

This study uses polypropylene (PP)/high-density polyethylene (HDPE) polyblends (80/20 wt.%) as matrices, which are then melt-blended with inorganic carbon fibers (CF) as reinforcement to form electrically conductive PP/HDPE composites. Tensile test, flexural test, Izod impact test, scanning electron microscopy (SEM), differential scanning calorimetry (DSC), and X-ray diffraction (XRD) are performed to evaluate different physical properties of samples. A surface resistance and electromagnetic interference shielding effectiveness (EMI SE) measurements are used to evaluate the electrical properties of the PP/HDPE/CF composites. Test results show that an increasing content of carbon fibers results in an 18 %, 23 %, and 60 % higher tensile strength, flexural strength, and impact strength, respectively. SEM results show that carbon fibers break as a result of applied force, thereby bearing the force and increasing the mechanical properties of composites. DSC and XRD results show that the addition of carbon fibers causes heterogeneous nucleation in PP/HDPE polyblends, thereby increasing crystallization temperature. However, the crystalline structure of PP/HDPE composites is not affected. Surface resistivity results show that 5 wt.% of carbon fibers can form a conductive network in PP/HDPE polyblends and reduce the surface resistivity from 12×10¹² ohm/sq to 4×10³ ohm/sq. EMI SE results show that, with a 20 wt.% CF and a frequency of 2-3 GHz, the average EMI SE of PP/HDPE/CF composites is between -48 and -52 dB, qualifying their use for EMI SE, which is required for standard electronic devices.     

Composites of polyvinyl alcohol and carbon nanotubes decorated with silver nanoparticles

A simple method to decorate carbon nanotubes (CNTs) with silver nanoparticles was developed to enhance the electrical conductivity of CNTs. The acid-treated CNTs were suspended in the silver acetate solution, ammonia solution was then added, and the CNTs decorated with silver nanoparticles (Ag@CNTs) were produced. The Ag@CNTs were dispersed in polyvinyl alcohol (PVA) to fabricate electrically conducting polymer composites. The electrical, thermal and mechanical properties of the composites were measured. The electrical conductivity of the composites containing 0.8 % (o.w.f.) Ag@CNTs was more than four orders of magnitude higher than those of pristine and functionalized CNTs respectively, which confirmed the effectiveness of the Ag@CNTs as conducting filler. However, the improved electrical conductivity led to somewhat decrease of mechanical properties of PVA/Ag@CNTs composites.     

Synthesis and characterization of electrically conductive composite films of polypyrrole/poly(acrylonitrile-co-styrene)

Homogeneus Polypyrrole (PPy)/poly(acrylonitrile-co-styrene) (SAN) composite thin films were prepared by chemical polymerization of pyrrole on poly(acrylonitrile-co-styrene) matrix. Ce (IV) is used as an oxidant for in-situ polymerizion of pyrrole on SAN matrix, having an advantageous over the impregnation method. The formation and incorporation of PPy in the copolymer matrix were confirmed by FTIR-ATR and UV-Visible spectrophotometric measurements. Thermal analyses showed that after polymerization of Py in copolymer matrix, thermal behavior of SAN was changed and derivative of weight loss at this temperature was increased by increasing of PPy content. XPS and FTIR-ATR analysis of composite films indicated cerium salt with nitrate ion acted as a dopant. The increase in the AC electrical conductivity of the PPy/SAN composites over pure SAN was observed. At lower frequency up to 10⁵ Hz, conductivity was shown an independent behavior from frequency; but at high frequencies (10⁵–10⁷ Hz), dependence on frequency was explained by polaron and bipolaron formations of PPy. The dispersion of PPy particles in copolymer matrix was proven by SEM, AFM and digital camera. By the increase of PPy content in the composite films, increase in AC conductivities, and decrease in dielectric constants and loss were observed.     

Nano-SiO2 filled rice husk/polypropylene composites: Physico-mechanical properties

In this research, reinforcing effect of hybrid filler including rice husk (RH), beech bark (BB) and nano-SiO₂, in polypropylene has been investigated. In the sample preparation, four levels of filler loading were used for waste lignocellulosic materials (55-58 wt.%) and nano-SiO₂ (0-4 wt.%). In order to increase the interphase adhesion, polypropylene grafted with maleic anhydride was added as a coupling agent to all the composites studied. The physical properties, viz. the thickness swelling and water absorption, and mechanical properties, namely, the tensile, flexural and notched Izod impact strengths, of the composites were determined. Generally, high amount of filler content in composites can lead to the reduction of interfacial adhesion between matrix polymer and filler, and it limits their applications. The results showed that while flexural properties and elongation at break were moderately improved by the increase in the amount of filler in the matrix, tensile and Izod impact strengths decreased dramatically. However, the composites had acceptable mechanical strength levels. The mechanical properties of composites filled with RH are generally greater than BB composites. The thickness swelling and water absorption of the composites increased with the increase in the filler loading, but to a negligible extent as compared with the wood-based composites and the solid woods. Nano-SiO₂ addition showed little positive effect on the mechanical properties. It can be concluded from this study that the used waste lignocellulosic materials are attractive reinforcements from the standpoint of their physico-mechanical properties.     

Facile fabrication of carbon nanotubes/polystyrene composite nanofibers for high-performance electromagnetic interference shielding

Polystyrene (PS) composites with nanofibrous structure consisting of multi-walled carbon nanotubes (MWCNTs) with 0-10 wt.% of nanofiller have been fabricated via electrospinning technique. The surface morphology and thermal properties of the composites were evaluated by scanning electron microscopy (SEM) and thermo-gravimetric analysis (TGA). The SEM analysis of the composite nanofibers samples revealed that the average diameter of the nanofibers increases with increasing MWCNTs content. The resultant MWCNTs/PS composite nanofibers diameters were in the range of 391±63 to 586±132 nm. The thermal stability of composites was increased after addition of MWCNTs to PS matrix. The electrical conductivity of the composites with different weight percentage of MWCNTs was investigated at room temperature. Electrical conductivity of MWCNTs/PS composite nanofiber followed percolation theory having a percolation threshold V _c= 0.45 vol% (~0.75 wt. %) and critical exponent q=1.21. The electrical conductivity and thermal properties confirmed the presence of good dispersion and alignment MWCNTs encapsulated within the electrospun nanofibers. The electromagnetic interference (EMI) shielding effectiveness of the MWCNTs/PS composites was examined in the measurement frequency range of 8.2-12.4 GHz (X-band). The total EMI shielding efficiency of MWCNTs/PS composite nanofibers increased up to 32 dB. The EMI shielding results for MWCNTs/PS composite nanofibers showed that absorption loss was the major shielding mechanism and reflection was the secondary mechanism. The present study has shown the possibility of utilizing MWCNTs/PS composite nanofibers as EMI shielding/absorption materials.     

Electrospinning and microwave absorption of polyaniline/polyacrylonitrile/multiwalled carbon nanotubes nanocomposite fibers

Electrical conductive nanocomposite fibers were prepared with polyaniline (PANI), polyacrylonitrile (PAN) and multi-walled carbon nanotubes (MWCNTs) via electrospinning. The morphology and electrical conductivity of the PANI/PAN/MWCNTs nanocomposite fibers were characterized by scanning electron microscope (SEM) and Van De Pauw method. Electrical conductivity of nanocomposite fibers increased from 1.79 S·m^?1 to 7.97 S·m^?1 with increasing the MWCNTs content from 3.0 wt% to 7.0 wt%. Compared with PANI/PAN membranes, the mechanical property of PANI/PAN/MWCNTs nanocomposites fiber membranes decreased. The microwave absorption performance of composite films was analyzed using waveguide tube, which indicated that with the thickness increasing the value of R_L reduced from ?4.6 to ?5.9 dB.     

Controlling the Properties of OPEFB/PLA Polymer Composite by Using Fe<Subscript>2</Subscript>O<Subscript>3</Subscript> for Microwave Applications

Microwave-absorptive polymer composite materials provide protection against interference to communication systems caused by microwave-inducing devices. Microwave-absorptive polymer composites were prepared from polylactic acid (PLA) biocomposite blended with oil palm empty fruit bunch (OPEFB) fiber and commercial Iron oxide (Fe₂O₃) as filler using the melt-blending method. The composites characterization was carried out using the scanning electron microscopy (SEM) and X-ray diffraction (XRD) analyses. The coefficient of reflection S₁₁ and coefficient of transmission S₂₁ of the composites for various Fe₂O₃ filler percentages were determined using a rectangular waveguide in connection with microwave vector network analyser (HP/Agilent model PNA N5227). These coefficients were then used to calculate microwave-absorption properties (in decibels). XRD analysis showed that increasing amounts of reinforced material (Fe₂O₃) reduces the crystallinity of the composites. SEM data indicated that Fe₂O₃ filler ratio increased in the composites, and adhesion to the cellulose fiber grew gradually until the highest percentage of filler was added. The complex relative permittivity and relative permeability were obtained within the broad frequency range of 8–12 GHz at room temperature for various percentages of filler and were measured by the transmission/reflection method using a vector network analyser. Fe₂O₃ embedment in OPEFB/PLA was observed to have resulted in enhancing the dielectric and magnetic properties. The values of permittivity and permeability increased with increasing Fe₂O₃ filler content. Theoretical simulation studied the relation between ε′ and ε″ of the relative complex permittivity in terms of Cole-Cole dispersion law. The result indicated that the processes of Debye relaxation in Fe₂O₃/OPEFB/PLA, the unique dielectric characteristics of Fe₂O₃ cannot be accounted for by both the Debye dipolar relaxation and natural resonance. Results further showed that the material transmission, reflection, and absorption properties could be controlled by changing the percentage of Fe₂O₃ filler in the composites.     

Enhanced physico-mechanical properties of polyester resin film using CaCO<Subscript>3</Subscript> filler

Bio-based CaCO₃ powder was synthesized via size reduction method from waste eggshells. The XRD analysis revealed that eggshell powder consists of CaCO₃ in calcite form. The inclusion level of CaCO₃ contents were varied of 5, 10, 15, 20 and 25 wt.% of prepared CaCO₃-polyester film. Effects of different proportions of prepared chicken eggshell and commercial CaCO₃ filler on the polyester resin composites films were compared by means of mechanical and physical test. It was found that the addition of CaCO₃ filler to the polyester films leads to improve the mechanical properties. The findings revealed that the best and optimum CaCO₃ filler content was 10 wt.% and among the prepared polyester films, eggshell CaCO₃-polyester films showed the best performance. The mechanical properties of CaCO₃-polyester films were measured in terms of tensile strength, elongation-at-break, tensile modulus, flexural strength and impact strength. For eggshell CaCO₃- polyester films, the maximum values of the aforementioned mechanical properties were 52.70 MPa, 4.63 %, 1868.70 MPa, 101.20 MPa and 8.40 kJ/m², respectively, whereas for commercial CaCO₃-polyester films those values were 48.12 MPa, 4.50 %, 1790.30 MPa, 97.50 MPa and 8.21 kJ/m², respectively. Further, water absorption of the composite films as a function of time had also been investigated at 10 wt.% filler content.     

Fabrication and characterization of nano Al<Subscript>2</Subscript>O<Subscript>3</Subscript> filled PVA:NH<Subscript>4</Subscript>SCN electrolyte nanofibers by electrospinning

Present paper reports a method of preparing polymer composite electrolyte nanofiber mat using polyvinyl alcohol (PVA), ammonium thiocynate (NH₄SCN) salt, and aluminium oxide (Al₂O₃) nano particles based on electrospinning technique. Two-stage process of preparation of nanofibers, namely, preparation of nano particles filled PVA electrolyte gel solution followed by its electrospinning has been used. The so obtained nanofibers have been characterized by XRD, DSC, SEM, and Conductivity measurements. XRD patterns affirm the formation of nanocomposite while SEM pictures reveal formation of fibers on a nano scale format (300–800 nm). Fibers of the electrolytes are seen to be thermally stable. Ionic conductivity of electrolyte fiber is seen to improve in the presence of nano filler at room temperature with a maximum at 5.31×10⁻³ Scm⁻¹ for 4 wt% filler concentration, which is comparable to that for corresponding dried gel electrolyte films.     

Chitosan-filled polypropylene composites: The effect of filler loading and organosolv lignin on mechanical,morphological and thermal properties

In this work, the effect of organosolv lignin on properties of polypropylene (PP)/chitosan composites was investigated. Mechanical and thermal properties of the composites were analyzed by means of ASTM D 638-91, ASTM D 256, thermogravimetry analysis (TGA) and differential scanning calorimetry (DSC). Tensile strength and elongation at break of the PP composites decreased upon the presence of chitosan filler, but Young’s modulus improved. Impact strength was found to increase with the maximum value at 30 php of filler loading. At a similar loading, treated PP/chitosan composites were found to have higher tensile strength, elongation at break, Young’s modulus as well as impact strength than untreated composites. Furthermore, the presence of organosolv lignin imparted a plasticizing effect. Thermal properties of the treated PP/chitosan composites were better as compared with the untreated PP/chitosan composites; although the chemical treatment did not alter the thermal degradation mechanism. In addition, the obtained results were comparable to results from previous studies. This finding implied that the organosolv lignin could be a potential reagent to replace its synthetic counterpart.     

Structures and physical properties of graphene/PVDF nanocomposite films prepared by solution-mixing and melt-compression

We have manufactured poly(vinylidene fluoride) (PVDF)-based nanocomposite films with different graphene contents of 0.1～10.0 wt% by ultrasonicated solution-mixing and melt-compression. As a reinforcing nanofiller, graphene sheets are prepared by rapid thermal expansion of graphite oxide, which are from the oxidation of natural graphite flakes. Graphene sheets are characterized to be well exfoliated and dispersed in the nanocomposite films. X-ray diffraction data confirm that the α-phase crystals of PVDF are dominantly developed in the nanocomposite films during the meltcrystallization. DSC cooling thermograms show that the graphene sheets serve as nucleating agents for the PVDF α-form crystals. Thermal stability of the nanocomposite films under oxygen gas atmosphere is noticeably improved, specifically for the nanocomposite with 1.0 wt% graphene. Electrical volume resistivity of the nanocomposite films is substantially decreased from ～10¹⁴ to ～10⁶ W cm, especially at a critical graphene content between 1.0 and 3.0 wt%. In addition, mechanical storage modulus is highly improved with increasing the graphene content in the nanocomposite films. The increment of the storage modulus for the nanocomposite film at 30 °C with increasing the graphene content is analyzed by adopting the theoretical model proposed by Halpin and Tsai.     

Viscoelastic behaviour of untreated and chemically treated banana Fiber/PF composites

The dynamic mechanical properties such as storage modulus, loss modulus, and tan δ of banana fiber reinforced PF composites fabricated by RTM and CM techniques were investigated as a function of fiber content, fiber treatment, temperature and frequency. Storage modulus (E′) increases with increase in fiber content and records maximum for the composites having a fiber loading of 40 wt % at all temperature ranges. The loss modulus and damping increases to great extent by the addition of filler, a maximum was observed for filler with 10–20 wt % fiber content followed by a slight decrease in loss modulus and damping with increasing filler content. Alkali treatment of the fiber shows a great enhancement in E′ and T _g of the composites. Comparison is made between the composites fabricated by RTM and CM. RTM composites exhibited higher storage modulus and lower damping compared to CM composites.     

Decay of electrical conductivity in p-toluene sulfonate doped polypyrrole films

Long term performance of conductivity of p-toluene sulfonic acid (pTSA) doped electrochemically synthesized polypyrrole (PPy) films was estimated from accelerated aging studies between 80 °C and 120 °C. Conductivity decay experiments indicated that overall aging behavior of PPy films deviated from first order kinetics at prolonged aging times at elevated temperatures. However, an approximate value for the activation energy of the conductivity decay of PPy was calculated as E=47.4 kJ/mol, enabling an estimate of a rate constant of k=8.35×10⁻⁶/min at 20 °C. The rate of decrease of conductivity was not only temperature dependent but also influenced by the dopant concentration. A concentration of 0.005 M pTSA in the electrolyte resulted in a conductive film and when this film was exposed to 120 °C for a period of 40 h, the conductivity decayed to about 1/20 of its original value. The concentration of pTSA was increased to 0.05 mol/l and when the resulting film was aged in the same way, it showed a decrease in the conductivity to about 1/3 of its original value. Both microwave transmission and dc conductivity data revealed that highly doped films were considerably more electrically stable than lightly doped films. The dopant had a preserving effect on the electrical properties of PPy.     

Structure and properties of silk fibroin modified cotton

In this research, a novel cotton fiber with a silk fibroin (SF) coating was prepared by the oxidation of a cotton thread with sodium periodate and subsequent treatment in a solution of silk fibroin. The structures of both the oxidized cotton samples and the SF modified cotton samples were investigated by Fourier transform infrared (FT-IR) in combination with X-ray photoelectron spectroscopy (XPS) analysis. Other performances such as surface morphology and breaking strength were also studied. The results indicated that the weight of the oxidized cotton samples increased during SF treatment, while that of the un-oxidized cotton (pure cotton) samples reduced after SF treatment. Compared with the pure cotton samples, the oxidized cotton clearly showed a characteristic absorption band at 1730 cm⁻¹ due to the stretching vibration of the C=O double bond of the aldehyde group. After being treated with the SF solution, the oxidized cotton fiber showed a weakened characteristic absorption band at 1730 cm⁻¹ and a new absorption band at round 1540 cm⁻¹, suggesting the formation of C-N bond between aldehyde groups in the oxidized cotton and primary amines in the silk fibroin. The results were also confirmed by XPS analysis. Compared with the oxidized cotton samples, the SF treated cottons had relatively smooth surfaces, similar breaking strength, and the improved wrinkle recovery angles. The results in this research suggest that cotton based materials with protein coating can be achieved without using any other crosslinking agents by the method introduced.