A review of vapor grown carbon nanofiber/polymer conductive composites

Vapor grown carbon nanofiber (VGCNF)/polymer conductive composites are elegant materials that exhibit superior electrical, electromagnetic interference (EMI) shielding effectiveness (SE) and thermal properties compared to conventional conductive polymer composites. This article reviews recent developments in VGCNF/polymer conductive composites. The article starts with a concise and general background about VGCNF production, applications, structure, dimension, and electrical, thermal and mechanical properties. Next composites of VGCNF/polymer are discussed. Composite electrical, EMI SE and thermal properties are elaborated in terms of nanofibers dispersion, distribution and aspect ratio. Special emphasis is paid to dispersion of nanofibers by melt mixing. Influence of other processing methods such as in-situ polymerization, spinning, and solution processing on final properties of VGCNF/polymer composite is also reviewed. We present properties of CNTs and CFs, which are competitive fillers to VGCNFs, and the most significant properties of their composites compared to those of VGCNF/polymer composites. At the conclusion of the article, we summarize the most significant achievements and address the future challenges and tasks in the area related to characterizing VGCNF aspect ratio and dispersion, determining the influence of processing methods and conditions on VGCNF/polymer composites and understanding the structure/property relationship in VGCNF/polymer composites.     

Morphological,electrical and electromagnetic interference shielding characterization of vapor grown carbon nanofiber/polystyrene nanocomposites

The influence of melt mixing conditions on the level of dispersion and the aspect ratio of vapor grown carbon nanofibers (VGCNFs) in a polystyrene (PS) matrix was studied. Final electrical and electromagnetic shielding capabilities in the 0.05–1.5 GHz frequency range are reported and discussed in the light of the composites' microstructure. The morphological study was based on analyzing scanning electron microscopy and optical microscopy micrographs and measuring the VGCNF length as a function of shear mixing conditions. The influence of mixing conditions on the microstructure was also indirectly studied by analyzing the dynamic mechanical behavior of the composites via rheology. Degradation of the VGCNF aspect ratio was found to be a function of the mixing energy. VGCNFs lost one‐third of their aspect ratio under gentle (low shear stress and mixing energy) mixing conditions. After VGCNFs had lost 40% of their aspect ratio, they had more resistance to breakage with increase in mixing energy. The dispersion of the VGCNFs was remarkably enhanced with increase in mixing energy. The percentage of area taken up by big agglomerates in the micrographs decreased from 14.1% to 5.5% when the mixing energy was increased from 100 J mL^?1 to 453 J mL^?1. The electrical and electromagnetic shielding properties of the 7.5 vol% VGCNF/PS composites were not affected by changing the processing energy because the enhancement of VGCNF dispersion with increasing mixing energy was accompanied by a loss in nanofiber aspect ratio. © 2012 Society of Chemical Industry     

Electromagnetic interference shielding effectiveness of hybrid multifunctional Fe3O4/carbon nanofiber composite

Electromagnetic interference shielding effectiveness (EMI SE) of multifunctional Fe₃O₄/carbon nanofiber composites in the X-band region (8.2–12.4 GHz) is studied. Here, we examine the contributing effects of various parameters such as Fe₃O₄ content, carbonization temperature and thickness on total shielding efficiency (SE_total) of different samples. The maximum EMI SE of 67.9 dB is obtained for composite of 5 wt.% Fe₃O₄ (0.7 mm thick) with the dominant shielding by absorption (SE_A) of electromagnetic radiation. The enhanced electromagnetic shielding performance of Fe₃O₄/carbon nanofiber composites is attributed to the increment of both magnetic and dielectric losses due to the incorporation of magnetite nanofiller (Fe₃O₄) in electrically conducting carbon nanofiber matrix as well as the specific nanofibrous structure of carbon nanofiber mats, which forms a higher aspect ratio structure with randomly aligned nanofibers. Furthermore, we prove that the addition of elastomeric polydimethylsiloxane (PDMS) as a coating for carbon nanofiber composite strengthens the composite structure without interfering with its electromagnetic shielding efficiency.     

EMI shielding effectiveness of carbon based nanostructured polymeric materials: A comparative study

The microstructure, electromagnetic interference (EMI) shielding effectiveness (SE), DC electrical conductivity, AC electrical conductivity and complex permittivity of nanostructured polymeric materials filled with three different carbon nanofillers of different structures and intrinsic electrical properties were investigated. The nanofillers were multiwall carbon nanotubes (MWCNT), carbon nanofibers (CNF) and high structure carbon black (HS-CB) nanoparticles and the polymer was acrylonitrile-butadiene-styrene (ABS). In addition, the EMI SE mechanisms and the relation between the AC electrical conductivity in the X-band frequency range and the DC electrical conductivity were studied. The nanocomposites were fabricated by solution mixing and characterized by uniform dispersion of the nanofillers within the polymer matrix. It was found that, at the same nanofiller loading, the EMI SE, permittivity and electrical conductivity of the nanocomposites decreased in the following order: MWCNT > CNF > CB. MWCNT based nanocomposites exhibited the lowest electrical percolation threshold and the highest EMI SE owning to the higher aspect ratio and electrical conductivity of MWCNT compared to CNF and HS-CB. The AC conductivity in the X-band frequency range was found to be independent of frequency.     

The influence of the dispersion method on the electrical properties of vapor-grown carbon nanofiber/epoxy composites

The influence of the dispersion of vapor-grown carbon nanofibers (VGCNF) on the electrical properties of VGCNF/Epoxy composites has been studied. A homogenous dispersion of the VGCNF does not imply better electrical properties. In fact, it is demonstrated that the most simple of the tested dispersion methods results in higher conductivity, since the presence of well-distributed nanofiber clusters appears to be a key factor for increasing composite conductivity.PACS: 72.80.Tm; 73.63.Fg; 81.05.Qk.     

Graphene nanoplate and multiwall carbon nanotube–embedded polycarbonate hybrid composites: High electromagnetic interference shielding with low percolation threshold

This study has reported the preparation of polycarbonate (PC)/graphene nanoplate (GNP)/multiwall carbon nanotube (MWCNT) hybrid composite by simple melt mixing method of PC with GNP and MWCNT at 330°C above the processing temperature of the PC (processing temperature is 280°C) followed by compression molding. Through optimizing the ratio of (GNP/MWCNT) in the composites, high electromagnetic interference shielding effectiveness (EMI SE) value (∼21.6 dB) was achieved at low (4 wt%) loading of (GNP/MWCNT) and electrical conductivity of ≈6.84 × 10⁻⁵ S.cm⁻¹ was achieved at 0.3 wt% (GNP/MWCNT) loading with low percolation threshold (≈0.072 wt%). The high temperature melt mixing of PC with nanofillers lowers the melt viscosity of the PC that has helped for better dispersion of the GNPs and MWCNTs in the PC matrix and plays a key factor for achieving high EMI shielding value and high electrical conductivity with low percolation threshold than ever reported in PC/MWCNT or PC/graphene composites. With this method, the formation of continuous conducting interconnected GNP‐CNT‐GNP or CNT‐GNP‐CNT network structure in the matrix polymer and strong π–π interaction between the electron rich phenyl rings and oxygen atom of PC chain, GNP, and MWCNT could be possible throughout the composites. POLYM. COMPOS., 37:2058–2069, 2016. © 2015 Society of Plastics Engineers     

Effect of processing technique on the transport and mechanical properties of vapour grown carbon nanofibre/rubbery epoxy composites for electronic packaging applications

Vapour grown carbon nanofibre (VGCNF)/rubbery epoxy (RE) composites were produced, by either mechanical mixing, three-roll milling (RM) or combined ultrasonication/mechanical mixing. Incorporation of VGCNFs resulted in significant enhancements in the thermal and electrical conductivities of the material. Appropriate selection of processing technique and parameters can help to maximise the potential of VGCNF additions by improving their dispersion in the matrix. The composites produced by RM have superior transport properties compared with those produced by other techniques. The thermal conductivity of such composites at 40 wt.% VGCNFs reached 1.845 W/m K, a 10-fold increase compared to RE alone. The thermal conductivity data of VGCNF/RE composites best fits to the Hatta–Taya model. The lowest electrical percolation threshold is at 2 wt.%, obtained for composites produced by RM. The thermal conductivity of VGCNF/glassy epoxy (GE) composites at 12 wt.% is 10% lower than the corresponding RE composite but its electrical conductivity is 2 orders of magnitude higher than the corresponding RE composite. VGCNFs at 40 wt.% increase the compressive strength of rubbery epoxy by ～5× but the compressive modulus of 40 wt.% VGCNF/RE composite is 12 times lower than that of 12 wt.% VGCNF/GE composite, demonstrating highly compliant nature of RE composites.     

Characterization,prediction, and optimization of flexural properties of vapor‐grown carbon nanofiber/vinyl ester nanocomposites by response surface modeling

A design of experiments and response surface modeling were performed to investigate the effects of formulation and processing factors on the flexural moduli and strengths of vapor‐grown carbon nanofiber (VGCNF)/vinyl ester (VE) nanocomposites. VGCNF type (pristine, surface‐oxidized), use of a dispersing agent (no, yes), mixing method (ultrasonication, high‐shear mixing, and a combination of both), and VGCNF weight fraction (0.00, 0.25, 0.50, 0.75, and 1.00 parts per hundred parts resin (phr)) were selected as independent factors. Response surface models were developed to predict flexural moduli and strengths as a continuous function of VGCNF weight fraction. The use of surface‐oxidized nanofibers, a dispersing agent, and high‐shear mixing at 0.48 phr of VGCNF led to an average increase of 19% in the predicted flexural modulus over that of the neat VE. High‐shear mixing with 0.60 phr of VGCNF resulted in a remarkable 49% increase in nanocomposite flexural strength relative to that of the neat VE. This article underscores the advantages of statistical design of experiments and response surface modeling in characterizing and optimizing polymer nanocomposites for automotive structural applications. Moreover, response surface models may be used to tailor the mechanical properties of nanocomposites over a range of anticipated operating environments. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 2087–2099, 2013     

In situ TPU/graphene nanocomposites: Correlation between filler aspect ratio and phase morphology

An in situ polymerization method to prepare thermoplastic polyurethanes (TPU)/graphene and TPU/graphite composites have been studied to clarify the influence of intrinsic filler properties and dispersion level on the morphology and properties of the TPU. Two types of graphene, one high-aspect ratio and one low, and graphite flake at various loadings were studied. Rotational rheology experiments on the suspensions of filler in polyol were used to characterize the agglomeration level of the filler after the dispersive mixing step and an effective aspect ratio reflective of the dispersion level was obtained. Variations in the glass transition temperature and thermal transitions of the TPU composites were related to the agglomeration level and intrinsic filler properties.     

Synthesis and characterization of fibrous nanosilica/polydimethylsiloxane composites

This article reports the synthesis of silica nanofiber/polydimethylsiloxane composites. Hollow silica nanofibers were synthesized through soft‐template mediated synthesis using nitric acid catalyst and extensively characterized. Amorphous nanofibers were obtained by this method with mean diameter of 80 nm and length extending over several micrometers. Nanofibers were also prepared by varying the surfactant concentration and its effect on aspect ratio was investigated. Incorporation of these nanofibers into PDMS matrix was accomplished through in situ and ex situ preparative techniques. The composites prepared exhibited a significant enhancement of various properties. In situ prepared composites yielded maximum improvement in properties with 120% improvement in tensile strength, 175% improvement in room temperature storage modulus and 190°C increase in temperature of maximum degradation (T_max) even at low filler loading. Extent of nanofiller dispersion solely determined the property improvement of the composites. Nanofiller aspect ratio was also found to play an important role on the property improvement of the composites. Composite formation and hence property improvement were explained in depth in the light of free energy change and interaction parameter of the components of the hybrid material. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 1005‐1019, 2013     

Electrical,rheological and electromagnetic interference shielding properties of thermoplastic polyurethane/carbon nanotube composites

Electrically conducting rubbery composites based on thermoplastic polyurethane (TPU) and carbon nanotubes (CNTs) were prepared through melt blending using a torque rheometer equipped with a mixing chamber. The electrical conductivity, morphology, rheological properties and electromagnetic interference shielding effectiveness (EMI SE) of the TPU/CNT composites were evaluated and also compared with those of carbon black (CB)‐filled TPU composites prepared under the same processing conditions. For both polymer systems, the insulator–conductor transition was very sharp and the electrical percolation threshold at room temperature was at CNT and CB contents of about 1.0 and 1.7 wt%, respectively. The EMI SE over the X‐band frequency range (8–12 GHz) for TPU/CNT and TPU/CB composites was investigated as a function of filler content. EMI SE and electrical conductivity increased with increasing amount of conductive filler, due to the formation of conductive pathways in the TPU matrix. TPU/CNT composites displayed higher electrical conductivity and EMI SE than TPU/CB composites with similar conductive filler content. EMI SE values found for TPU/CNT and TPU/CB composites containing 10 and 15 wt% conductive fillers, respectively, were in the range ?22 to ?20 dB, indicating that these composites are promising candidates for shielding applications. © 2013 Society of Chemical Industry     

Functionalized Graphene–PVDF Foam Composites for EMI Shielding

Novel foam composites comprising functionalized graphene (f‐G) and polyvinylidene fluoride (PVDF) were prepared and electrical conductivity and electromagnetic interference (EMI) shielding efficiency of the composites with different mass fractions of f‐G have been investigated. The electrical conductivity increases with the increase in concentration of f‐G in insulating PVDF matrix. A dramatic change in the conductivity is observed from 10^?16 S · m^?1 for insulating PVDF to 10^?4 S · m^?1 for 0.5 wt.% f‐G reinforced PVDF composite, which can be attributed to high‐aspect‐ratio and highly conducting nature of f‐G nanofiller, which forms a conductive network in the polymer. An EMI shielding effectiveness of ≈20 dB is obtained in X‐band (8–12 GHz) region and 18 dB in broadband (1–8 GHz) region for 5 wt.% of f‐G in foam composite. The application of conductive graphene foam composites as lightweight EMI shielding materials for X‐band and broadband shielding has been demonstrated and the mechanism of EMI shielding in f‐G/PVDF foam composites has been discussed.

     

The effect of surface chemistry of graphene on rheological and electrical properties of polymethylmethacrylate composites

Graphene sheets with different oxygen contents were prepared to functionalize the electrically insulating polymethylmethacrylate (PMMA). The influences of surface chemistry of graphene on rheological, electrical and electromagnetic interference (EMI) shielding properties of its PMMA composites were investigated. The appearance of frequency-independent storage modulus at low frequency suggests a solid-like viscoelastic behavior and the formation of an interconnected network of graphene in the matrix. Due to the favorable interfacial interactions arising from polarity matching, the graphene with a C/O ratio of 13.2 (graphene-13.2) shows a better dispersion in PMMA than those with lower C/O ratios, and thus its PMMA composites exhibit lower rheological and electrical percolation thresholds. The EMI shielding properties of the graphene/PMMA composites exhibit similar dependence on the oxygen content of graphene. A high EMI shielding effectiveness of ～30 dB was obtained for the PMMA composite with 4.2 vol.% of graphene-13.2 with microwave absorption as the dominant EMI shielding mechanism.     

Influence of Graphite Filler on Physicochemical Characteristics of Polymer/Graphite Composites: A Review

In this article, carbon nanofiller, in particular graphite, has been reviewed for the preparation of polymer-based composites. The dispersion of graphite relies on fabrication methods employed such as solution mixing, melt blending, and in situ polymerization. The consequences of surface modification on thermal, mechanical, and electrical characteristics were explored. Moreover, the properties and parameters involved in feature enhancement of graphite-based materials have been highlighted. Topical development in field of thermal, mechanical, and other physical properties of polymer/graphite composites was investigated. Furthermore, worth of materials regarding electrodes, resistors, dye-sensitized solar cells, electromagnetic interference shielding, packaging, and flame retardant applications has been discussed.     

Electrical, morphological and rheological properties of carbon nanotube composites with polyethylene and poly(phenylene sulfide) by melt mixing

Electrical, morphological and rheological properties of polyethylene (PE)/multi-walled carbon nanotube (MWCNT) and poly(phenylene sulfide) (PPS)/MWCNT composites were studied with the MWCNT content using vector network analyzer, scanning electron microscopy and rotational rheometry. From the results of electrical conductivity and electromagnetic interference shielding efficiency (EMI SE) of the PE/MWCNT and PPS/MWCNT composites, the electrical percolation threshold of the composites has found to be 5 and 3 wt% MWCNT, respectively. From the results of the EMI SE of the composites, it was suggested that the increase in homogeneous dispersion of the MWCNT in the PPS matrix has been attributed to the increase in connectivity of the MWCNT-MWCNT network structure of the composite. Therefore, the higher values of the EMI SE with the MWCNT content were observed in the PPS/MWCNT than the PE/MWCNT composites. From the results of the rheological properties of the PE/MWCNT and PPS/MWCNT composites, the increase in the complex viscosity was observed for the PPS/MWCNT than the PE/MWCNT composites. The increase in complex viscosity maybe due to the increase in homogeneous dispersion of the MWCNT in the PPS matrix than that in the PE matrix. From the results of the rheological properties of the PE/MWCNT and PPS/MWCNT composites, it was suggested that the homogeneous dispersion of the MWCNT in the polymer matrix has affected the increase in complex viscosity of the PPS/MWCNT composite. This result of rheological behavior is consistent with the results of the EMI SE of the PE/MWCNT and PPS/MWCNT composites.     

Facile preparation of light-weight biodegradable and electrically conductive polymer based nanocomposites for superior electromagnetic interference shielding effectiveness

Harmful electromagnetic radiations that are generated from different electronic devices could be absorbed by a light weight and mechanically flexible good electromagnetic interference (EMI) shielding polymer nanocomposite. On the other hand, different electronic wastes (“e-wastes”) which are generally polymer building materials generated from wastes of dysfunctional electronic devices are not naturally biodegradable. Our recent effort has been employed to produce bio-degradable EMI shielding polymer nanocomposite. For that purpose, we had prepared a 50:50 ratio polylactic acid/thermoplastic polyurethane polymer nanocomposite by mixing the conducting carbon black with the blend following the facile and industrially feasible solution mixing method. Morphological characterizations by scanning electron microscopy and transmission electron microscopy analysis revealed the co-continuous morphology of the neat blend as well as polymer nanocomposites with the preferential distribution of conductive filler on a particular polymer phase. The polymer nanocomposites gave good mechanically with improved thermal properties. We got EMI shielding effectiveness around −27 dB with a low percolation threshold at around 30 wt% filler loading in the polymer nanocomposite at the X-band frequency domain (8.2–12.4 GHz). Later we had studied the biodegradability of the PLA/TPU along with their composites (T_XP_XC_X) by employing the respirometry method and got a satisfactory result to ensure their biodegradability.     

Response surface predictions of the viscoelastic properties of vapor‐grown carbon nanofiber/vinyl ester nanocomposites

A full factorial design of experiments and response surface methodology were used to investigate the effects of formulation, processing, and operating temperature on the viscoelastic properties of vapor‐grown carbon nanofiber (VGCNF)/vinyl ester (VE) nanocomposites. Factors included VGCNF type (pristine, oxidized), use of a dispersing agent (DA) (no, yes), mixing method (ultrasonication, high‐shear mixing, and a combination of both), VGCNF weight fraction (0.00, 0.25, 0.50, 0.75, and 1.00 parts per hundred parts resin (phr)), and temperature (30, 60, 90, and 120°C). Response surface models (RSMs) for predicting storage and loss moduli were developed, which explicitly account for the effect of complex interactions between nanocomposite design factors and operating temperature on resultant composite properties; such influences would be impossible to assess using traditional single‐factor experiments. Nanocomposite storage moduli were maximized over the entire temperature range (～20% increase over neat VE) by using high‐shear mixing and oxidized VGCNFs with DA or equivalently by employing pristine VGCNFs without DA at ～0.40 phr of VGCNFs. Ultrasonication yielded the highest loss modulus at ～0.25 phr of VGCNFs. The RSMs developed in this investigation may be used to design VGCNF‐enhanced VE matrices with optimal storage and loss moduli for automotive structural applications. Moreover, a similar approach may be used to tailor the mechanical, thermal, and electrical properties of nanomaterials over a range of anticipated operating environments. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

The effects of MWCNT length on the mechanical,crystallization and electromagnetic interference shielding effectiveness of PP/MWCNT composites

The length of multi-walled carbon nanotubes (MWCNT) has an important influence on the properties of polymer/MWCNT composites. This study aims to examine the influence of the length of MWCNT on the mechanical properties, distribution, melting and crystallization behavior, and electromagnetic interference shielding effectiveness (EMI SE) of PP/MWCNT composites. The test results show that MWCNT of a short length contribute to better mechanical properties and have a better dispersion in the matrix. MWCNT also serve as a nucleating agent for PP, thereby increasing the crystallization temperature (T_c). In particular, short MWCNT provide PP/MWCNT composites with a greater degree of cyrstallinity. The conjunction of 8 wt% long MWCNT in PP/MWCNT composites results in an optimal electrical resistivity of 65.02 Ω-cm, and an average EMI SE of ?29.47 dB. The polymer/MWCNT composites have properties that can be adjusted by using different lengths of MWCNT, which is advantageous for application in diverse products.     

碳纳米管填充聚合物基电磁屏蔽复合材料的研究进展

对碳纳米管填充聚合物基电磁屏蔽复合材料的研究进展进行了综述。在阐述研究电磁屏蔽材料必要性的基础上,介绍了复合材料的电磁屏蔽机理,重点论述了碳纳米管填充量、长径比及管径、屏蔽体的厚度、复合材料的加工方式等对复合材料电磁屏蔽性能的影响。最后对碳纳米管填充聚合物基复合电磁屏蔽材料的研究进行了展望,指出低成本填料与碳纳米管协同作用、可提高碳纳米管分散性的制备工艺的研究以及复合材料电磁屏蔽机理的研究等为未来的研究方向。     

Morphology,thermal, and electrical properties of polypropylene hybrid composites co‐filled with multi‐walled carbon nanotubes and graphene nanoplatelets

In this study, nanocomposites of polypropylene (PP) with various loadings of multi‐wall carbon nanotubes (MWCNT) and graphene nanoplatelets (GnP) were formed by masterbatch dilution/mixing approach from individual masterbatches PP‐MWCNT and PP‐GnP. Melt mixing on a twin‐screw extruder at two different processing temperatures was followed by characterization of morphology by transmitted‐light microscopy including the statistical analysis of agglomeration behavior. The influence of processing temperature and weight fractions of both nanofillers on the dispersion quality is reported. Thermal properties of the nanocomposites investigated by DSC and TGA show sensitivity to the nanofillers weight fraction ratio and to processing conditions. Electrical conductivity is observed to increase up to an order of magnitude with the concentration of each nanofiller increasing from 0.5 wt % to 1.0 wt %. This is related with a decrease of electrical conductivity observed for unequal concentration of both nanofillers. This particular behavior shows the increase of electrical properties for higher MWCNT loadings and the increase of thermo‐mechanical properties for higher GnP loadings. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42793.