Electrical behavior and positive temperature coefficient effect of graphene/polyvinylidene fluoride composites containing silver nanowires

Polyvinylidene fluoride (PVDF) composites filled with in situ thermally reduced graphene oxide (TRG) and silver nanowire (AgNW) were prepared using solution mixing followed by coagulation and thermal hot pressing. Binary TRG/PVDF nanocomposites exhibited small percolation threshold of 0.12 vol % and low electrical conductivity of approximately 10^-7 S/cm. Hybridization of TRGs with AgNWs led to a significant improvement in electrical conductivity due to their synergistic effect in conductivity. The bulk conductivity of hybrids was higher than a combined total conductivity of TRG/PVDF and AgNW/PVDF composites at the same filler loading. Furthermore, the resistivity of hybrid composites increased with increasing temperature, giving rise to a positive temperature coefficient (PTC) effect at the melting temperature of PVDF. The 0.04 vol % TRG/1 vol % AgNW/PVDF hybrid exhibited pronounced PTC behavior, rendering this composite an attractive material for making current limiting devices and temperature sensors.     

Suppression of AC conductivity by crystalline transformation in poly(vinylidene fluoride)/carbon nanofiber composites

Poly(vinylidene fluoride) (PVDF) is an important ferroelectric semi-crystalline polymer with multiple-phase behavior. In this study, remarkable effects of the various crystalline structures of PVDF nanocomposites on alternating current (AC) conductivity were discovered using carbon nanofibers (CNF). It was found that the transformation from α-phase to β-phase in PVDF, induced by the addition of CNFs, had a surprisingly suppressive effect on the AC conductivity of the nanocomposites. These unexpected results indicate that the decline in conductivity occurs after re-crystallization treatment (annealing) of the nanocomposites, and the reduction levels increase with increasing amounts of CNFs. Interestingly, the AC conductivity of annealed 5 wt% CNF/PVDF composites becomes even lower than that of re-crystallized nanocomposites with 3 wt% CNFs. These findings are believed to be very significant for fabrication and long-term service of PVDF composites in industry, which often involves exposure to repeated thermal cycling.     

Effect of amine functionalization of CNF on electrical, thermal, and mechanical properties of epoxy/CNF composites

This paper presents experimental results of the effect of amine functionalization of carbon nanofibers (CNF) on the electrical, thermal, and mechanical properties of CNF/epoxy composites. The functionalized and non-functionalized CNFs (up to 3 wt%) were dispersed into epoxy using twin screw extruder. The specimens were characterized for electrical resistivities, thermal conductivity (K), UTS, and Vicker’s microhardness. The properties of the nanocomposites were compared with that of neat epoxy. The volume conductivity of the specimens increased by E12 S/cm and E09 S/cm in f-CNF/epoxy and CNF/epoxy, respectively, at 3 wt% filler loading. The increase in K for former was 106% at 150 °C, while for the latter it was only 64%. Similarly, UTS increased by 61% vs. 45% and hardness 65% vs. 43%. T _g increased with increase in filler content. SEM examinations showed that functionalization resulted in better dispersion of the nanofibers and hence greater improvement in the studied properties of the nanocomposites.     

Hot pressed and spark plasma sintered zirconia/carbon nanofiber composites

Zirconia/carbon nanofiber composites were prepared by hot pressing and spark plasma sintering with 2.0 and 3.3 vol.% of carbon nanofibers (CNFs). The effects of the sintering route and the carbon nanofiber additions on the microstructure, fracture/mechanical and electrical properties of the CNF/3Y-TZP composites were investigated. The microstructure of the ZrO₂ and ZrO₂–CNF composites consisted of a small grain sized matrix (approximately 120 nm), with relatively well dispersed carbon nanofibers in the composite. All of the composites showed significantly higher electrical conductivity (from 391 to 985 S/m) compared to the monolithic zirconia (approximately 1 × 10⁻¹⁰ S/m). The spark plasma sintered composites exhibited higher densities, hardness and indentation toughness but lower electrical conductivity compared to the hot pressed composites. The improved electrical conductivity of the composites is caused by CNFs network and by thin disordered graphite layers at the ZrO₂/ZrO₂ boundaries.     

Desirable electrical and mechanical properties of continuous hybrid nano-scale carbon fibers containing highly aligned multi-walled carbon nanotubes

The continuous highly aligned hybrid carbon nanofibers (CNFs) with different content of acid-oxidized multi-walled carbon nanotubes (MWCNTs) were fabricated through electrospinning of polyacrylonitrile (PAN) followed by a series of heat treatments under tensile force. The effects of MWCNTs on the micro-morphology, the degree of orientation and ordered crystalline structure of the resulting nanofibers were analyzed quantitatively by diversified structural characterization techniques. The orientation of PAN molecule chains and the graphitization degree in carbonized nanofibers were distinctly improved through the addition of MWCNTs. The electrical conductivity of the hybrid CNFs with 3 wt% MWCNTs reached 26 S/cm along the fiber direction due to the ordered alignment of MWCNTs and nanofibers. The reinforcing effect of hybrid CNFs in epoxy composites was also revealed. An enhancement of 46.3% in Young’s modulus of epoxy composites was manifested by adding 5 wt% hybrid CNFs mentioned above. At the same time, the storage modulus of hybrid CNF/epoxy composites was significantly higher than that of pristine epoxy and CNF/epoxy composites not containing MWCNTs, and the performance gap became greater under the high temperature regions. It is believed that such a continuous hybrid CNF can be used as effective multifunctional reinforcement in polymer matrix composites.     

挤出牵引速度对聚乙烯/金属锡导电复合材料性能的影响

采用高温挤出热拉伸-低温注射成型的加工工艺,制备了聚乙烯/金属锡（PE/Sn）导电复合材料,研究了挤出造粒时不同切粒机转速（即热牵引速度）和Sn用量对其微观结构、导电性能及力学性能的影响。结果表明,当切粒机的转速由常规的35 r/min提高到50 r/min时,Sn在PE基体中成纤更细更长,PE/Sn复合材料导电所需的Sn的最低含量由常规时的9.2 %（质量分数,下同）降低到6.2 %,即导电逾渗值降低,且复合材料的力学性能略有上升。     

Processing and properties of polymer composites containing aligned functionalized carbon nanofibers

AC electric field was used to align functionalized carbon nanofibers (CNFs), carboxylic acid-functionalized CNFs (O-CNFs) and amine-functionalized CNFs (A-CNFs), in an epoxy resin. The resulting composites were characterized for dispersion and alignment structure as well as for their mechanical and electrical properties in the CNF alignment direction. Optical images of the composites revealed uniform distribution and alignment of the CNFs in the direction of the electric field. Due to the similarity in the alignment structure, it was observed that alignment of the functionalized CNFs was independent of the functional groups attached to the CNFs. Compression tests (parallel to the direction of the aligned A-CNFs) of A-CNF/epoxy composites showed an increase of 19% in compressive modulus and 9% in compressive strength at a CNF concentration of 4.5 wt.%, with respect to the neat composite. Electrical resistivity of composites measured parallel to the direction of aligned CNFs (containing up to 4.5 wt.% O-CNFs and A-CNFs) were found to be approximately three orders of magnitude lower than composites with non-aligned CNFs. The electrical resistivity percolation threshold for composites with aligned O-CNFs and A-CNFs occurred at approximately 0.75 wt.%. Discussion regarding the contribution of CNF type towards the mechanical and electrical properties is also presented.     

Low percolation threshold of graphene/polymer composites prepared by solvothermal reduction of graphene oxide in the polymer solution

Graphene/polyvinylidene fluoride (PVDF) composites were prepared using in-situ solvothermal reduction of graphene oxide in the PVDF solution. The electrical conductivity of the composites was greatly improved by doping with graphene sheets. The percolation threshold of such composite was determined to be 0.31 vol.%, being much smaller than that of the composites prepared via blending reduced graphene sheets with polymer matrix. This is attributed to the large aspect ratio of the SRG sheets and their uniform dispersion in the polymer matrix. The dielectric constant of PVDF showed a marked increase from 7 to about 105 with only 0.5 vol.% loading of SRG content. Like the other conductor-insulator systems, the AC conductivity of the system also obeyed the universal dynamic response. In addition, the SRG/PVDF composite shows a much stronger nonlinear conduction behavior than carbon nanotube/nanofiber based polymer composite, owing to intense Zener tunneling between the SRG sheets. The strong electrical nonlinearity provides further support for a homogeneous dispersion of SRG sheets in the polymer matrix.     

Poly(vinylidene fluoride)/thermoplastic polyurethane flexible and 3D printable conductive composites

This work focus on the development of polymeric blends to produce multifunctional materials for 3D printing with enhanced electrical and mechanical properties. In this context, flexible and highly conductive materials comprising poly(vinylidene fluoride)/thermoplastic polyurethane (PVDF/TPU) filled with carbon black-polypyrrole (CB-PPy) were prepared by compression molding, filament extrusion and fused filament fabrication. In order to achieve an optimal compromise between electrical conductivity, mechanical properties and printability, blends composition was optimized and different CB-PPy content were added. Overall, the electrical conductivities of PVDF/TPU 50/50 vol% co-continuous blend were higher than those found for PVDF/TPU 50/50 wt% (i.e., 38/62 vol%) composites at same filler content. PVDF/TPU/CB-PPy 3D printed samples with 6.77 vol% filler fraction presented electrical conductivity of 4.14 S m⁻¹ and elastic modulus, elongation at break and maximum tensile stress of 0.43 GPa, 10.3% and 10.0 MPa, respectively. These results highlight that PVDF/TPU/CB-PPy composites are promising materials for technological applications.     

VGCF填充PVDF/PMMA复合材料导电性能的研究

以气相生长碳纤维（VGCF）为导电填料,聚偏氟乙烯（PVDF）、聚甲基丙烯酸甲酯（PMMA）为基体制备复合型导电高分子材料。考察了填料用量、基体种类、配比以及PVDF结晶行为对复合材料导电性能的影响。结果表明,VGCF填充PMMA、PVDF、PVDF／PMMA（50／50）体系的渗滤阔值分别为5、4、3phr的填料用量。VGCF的加入会导致PVDF／PMMA体系发生微观相分离,而且VGCF会选择性富集在PVDF的非晶相中,所以PVDF／PMMA／VGCF体系的导电性呈现双重渗滤现象,该体系的体积电阻率不仅取决于富集相中VGCF的含量,而且还与PVDF相的连续性及其结晶行为密切相关。     

Electromagnetic interference properties of carbon nanofiber–reinforced acrylonitrile–styrene–acrylate/natural graphite composites

Acrylonitrile–styrene–acrylate/natural graphite/carbon nanofiber composites (ASA/NG/CNF) were prepared using a melting blending method. The effects of CNFs on the morphology, rheological properties, dynamical mechanical properties, electrical resistivity, and electromagnetic interference shielding effectiveness (EMI SE) were studied using a scanning electron microscope, a rotational rheometer, and dynamic mechanical analysis (DMA). The addition of CNFs changed the oriented and laminated structure of the ASA/NG composite. The flexural strength of the ASA composite reached a maximum at 6% CNF, and then it began to decrease. The addition of CNFs did not alter the glass‐transition temperature of ASA, but it largely increased the storage modulus of the composite in DMA tests. In the rheological measurements, the complex viscosity and storage modulus of the composite increased as CNF content increased, and the resistance to creep of the composites was significantly increased by the addition of CNFs. The electrical resistivity of the ASA composites decreased from 49.8 Ω cm to 2.3 Ω cm as the CNF content was increased from 0 to 12%. At the same time, the EMI properties of the composites rose from 15 dB to 30 dB in the frequency range 30–1500 MHz. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45455.     

Mechanical and electrical properties of carbon nanofibers reinforced aluminum nitride composites prepared by plasma activated sintering

High density carbon nanofibers (CNFs) reinforced aluminum nitride (AlN) composites were successfully fabricated by plasma activated sintering (PAS) method. The effects of CNFs on the microstructure, mechanical and electrical properties of the AlN composites were investigated. The experimental results showed that the grain growth of AlN was significantly inhibited by the CNFs. With 2 wt.% CNFs added into the composites, the fracture toughness and flexural strength were increased, respectively to 5.03 MPa m^1/2 and 354 MPa, which were 20.9% and 13.4% higher than those of monolithic AlN. The main toughening mechanisms were CNFs pullout and bridging, and the main reason for the improvements in strength should be the fine-grain-size effect caused by the CNFs. The DC conductivity of the composites was effectively enhanced through the addition of CNFs, and showed a typical percolation behavior with a very low percolation threshold at the CNFs content of about 0.93 wt.% (1.51 vol.%).     

Effects of hybrid fillers on the electrical conductivity,EMI shielding effectiveness,and flame retardancy of PBT and PolyASA composites with carbon fiber and MWCNT

The effects of hybrid fillers of carbon fiber (CF) and multiwall carbon nanotube (MWCNT) on the electrical conductivity, electromagnetic interference shielding effectiveness (EMI SE), flame retardancy, and mechanical properties of poly(butylene terephthalate) (PBT)/poly(acrylonitrile-co-styrene-co-acrylate) (PolyASA) (70/30, wt %) with conductive filler composites were investigated. The CF was used as the main filler, and MWCNT was used as the secondary filler to investigate the hybrid filler effect. For the PBT/PolyASA/CF (8 vol %)/MWCNT (2 vol %) composite, a higher electrical conductivity (1.4 × 10⁰ S cm⁻¹) and EMI SE (33.7 dB) were observed than that of the composite prepared with the single filler of CF (10 vol %), which were 9.0 × 10⁻² S cm⁻¹ and 23.7 dB, respectively. This increase in the electrical properties might be due to the longer CF length and hybrid filler effect in the composites. From the results of aging test at 85 °C, 120 h, the electrical conductivity and EMI SE of the composites decreased slightly compared to that of the composite without aging. The results of electrical conductivity, EMI SE, and flame retardancy suggested that the composite with the hybrid fillers of CF and MWCNT showed a synergetic effect in the PBT/PolyASA/CF (8 vol %)/MWCNT (2 vol %) composite. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 48162.     

Mechanical enhancement of C/C composites via the formation of a machinable carbon nanofiber interphase

C/C composites with improved mechanical strength were synthesized using a filler constituted by a carbon felt covered with catalytically grown carbon nanofibers (CNFs) and a carbonaceous matrix generated by the pyrolysis of a phenolic resin. First, the synthesis method of the filler allows the homogeneous deposition and anchorage of CNFs on the host microfilaments at a rapid densification rate. Carbon nanofibers grown this way lead to the formation of numerous micro- and nanobridges between the microfilaments, conferring a significant improvement of the mechanical resistance of the CNF/C system allowing one to tailor its dimensions and shape. Thus, further fabrication of C/C composites can be achieved: the CNF/microfilament structure was infiltrated with a phenolic resin and carbonized at 650 °C to generate a carbonaceous matrix by thermal decomposition. Similar experiments on the microfilaments carried out at the same synthesis time, without catalyst and at higher reaction temperatures led to the deposition of a pyrolytic carbon sheath and to poor mechanical enhancements. This clearly indicates the advantage of using CNF growth as an efficient densification process before infiltration. Such C/C composites exhibit high-quality bonding between the two carbon phases, the matrix and the CNF/microfilament filler, via the formation of a considerable amount of CNF interphase.     

Surface modification of CNFs via plasma polymerization of styrene monomer and its effect on the properties of PS/CNF nanocomposites

Carbon nanofibers (CNF) were modified via plasma assisted polymerization in a specially designed reactor. The effect of the plasma reactor conditions, such as power and time, on the extent of the CNFs modification was examined. Polystyrene (PS) coated nanofibers plus PS polymer were then processed in a Brabender torque rheometer mixing chamber to obtain PS/CNF nanocomposites, with 0.5, 1.0, 3.0, and 5.0 wt % of CNF. The effect of the plasma treatment on the dispersion of the nanofibers and on the compatibility between the nanofibers and the polymer matrix was also examined. Modification of the CNFs was assessed by measuring the contact angle of water in a “bed” of nanofibers and by examining its dispersion in several solvents. The morphology of PS/CNF nanocomposites was studied through scanning electron microscopy (SEM). Contact angles decreased in all cases, indicating a change in hydrophobicity of the modified CNFs. This change was confirmed in the CNF dispersion tests in several solvents. SEM micrographs show the difference between the original and the PS coated CNF. In addition, fractured samples show the effect of this treatment, in the sense that the CNF seem to be completely embedded in the polymer matrix, which clearly indicates the high compatibility between the PS and the modified (PS coated) CNF. As a consequence, a much better dispersion of the treated CNF was observed. Finally, the tensile modulus of PS/CNF composites increased slightly with respect to PS when using untreated CNFs, but more than doubled when using plasma treated CNFs. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Electrical conductivity of carbon‐filled polypropylene‐based resins

Adding conductive carbon fillers to insulating thermoplastic resins increases composite electrical conductivity. Often, as much of a single type of carbon filler is added to achieve the desired conductivity and still allow the material to be molded into a bipolar plate for a fuel cell. In this study, various amounts of three different carbons (carbon black, synthetic graphite particles, and carbon nanotubes) were added to polypropylene resin. The resulting single‐filler composites were tested for electrical resistivity (1/electrical conductivity). The effects of single fillers and combinations of the different carbon fillers were studied via a factorial design. The percolation threshold was 1.4 vol % for the composites containing only carbon black, 2.1 vol % for those containing only carbon nanotubes, and 13 vol % for those containing only synthetic graphite particles. The factorial results indicate that the composites containing only single fillers (synthetic graphite followed closely by carbon nanotubes and then carbon black) caused a statistically significant decrease in composite electrical resistivity. All of the composites containing combinations of different fillers had a statistically significant effect that increased the electrical resistivity. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Effects of surface modification of carbon nanofibers on the mechanical properties of polyamide 1212 composites

In this study, the effects of carbon nanofiber (CNF) surface modification on mechanical properties of polyamide 1212 (PA1212)/CNFs composites were investigated. CNFs grafted with ethylenediamine (CNF‐g‐EDA), and CNFs grafted with polyethyleneimine (CNF‐g‐PEI) were prepared and characterized. The mechanical properties of the PA1212/CNFs composites were reinforced efficiently with addition of 0.3 wt % modified CNFs after drawing. The reinforcing effect of the drawn composites was investigated in terms of interfacial interaction, crystal orientation, crystallization properties and so on. After the surface modification of CNFs, the interfacial adhesion and dispersion of CNFs in PA1212 matrix were improved, especially for CNF‐g‐PEI. The improved interfacial adhesion and dispersion of CNFs in PA1212 matrix was beneficial to reinforcement of the composites. Compared with pure PA1212, improved degree of crystal orientation in the PA1212/CNF‐g‐PEI (CNF‐g‐EDA) composites was responsible for reinforcement of mechanical properties after drawing. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41424.     

Hyperbranched polyol/carbon nanofiber composites

Carbon nanofiber (CNF) and carbon nanotube (CNT) composites have enhanced mechanical and electrical properties that make these composites desirable for antistatic and electronic dissipation technology. These applications require a homogenous dispersion of CNFs within a polymer matrix. To improve the compatibility/dispersability of CNFs within a polymer matrix, a hyperbranched polyol CNF composite was synthesized by the chemical modification of oxidized CNFs with glycidol and boron trifluoride diethyl etherate. The resulting polyol CNFs were characterized by TGA, FTIR, TEM/SEM and XPS. The hydroxyl groups were reacted with heptafluorobutyryl chloride to determine the amount of oxidized groups in the sample. The resulting composite was characterized by FTIR and elemental analysis. The amount of hydroxyl groups increased by 550% for the polyol CNFs as compared to the oxidized CNFs and an improvement in dispersion ability was observed.     

Carbon nanofiber type and content dependence of the physical properties of carbon nanofiber reinforced polypropylene composites

The variation of the physical properties of four different carbon nanofibers (CNFs), based‐polymer nanocomposites incorporated in the same polypropylene (PP) matrix by twin‐screw extrusion process was investigated. Nanocomposites fabricated with CNFs with highly graphitic outer layer revealed electrical isolation‐to‐conducting behaviors as function of CNF's content. Nanocomposites fabricated with CNFs with an outer layer consisting on a disordered pyrolitically stripped layer, in contrast, revealed better mechanical performance and enhanced thermal stability. Further, CNF's incorporation into the polymer increased the thermal stability and the degree of crystallinity of the polymer, independently on the filler content and type. In addition, dispersion of the CNFs' clusters in PP was analyzed by transmitted light optical microscopy, and grayscale analysis (GSA). The results showed a correlation between the filler concentration and the variance, a parameter which measures quantitatively the dispersion, for all composites. This method indicated a value of 1.4 vol% above which large clusters of CNFs cannot be dispersed effectively and as a consequence only slight changes in mechanical performance are observed. Finally, this study establishes that for tailoring the physical properties of CNF based‐polymer nanocomposites, both adequate CNFs structure and content have to be chosen. POLYM. ENG. SCI., 54:117–128, 2014. © 2013 Society of Plastics Engineers