Electrochemical surface oxidation of carbon nanofibers

Carbon nanofiber (CNF) surfaces were functionalized with oxygen-bearing groups through electrochemical oxidation. The electrode was prepared without a binder, allowing easy separation of the functionalized CNFs for subsequent applications. The relationships between the applied potential and the CNF structure with the resulting O/C atomic ratio and the distribution of oxygen functional groups were investigated. Surface groups were identified and characterized by elemental analyses, X-ray photoelectron spectroscopy, micro-attenuated total reflectance FTIR, and cyclic voltammetry. The oxidation of herringbone CNFs was initiated at a relatively low potential at both the anodic and cathodic electrodes, while the O/C atomic ratio remained relatively constant within the range of potentials investigated. The relative concentration of carbonyl and hydroxyl groups increased with increasing potential while the amount of carboxylic groups decreased. The structure of the CNF was important in determining the O/C atomic ratio, which was especially dependent on the spatial arrangement of graphene layers. Tubular CNFs exhibited low O/C atomic ratios while herringbone CNFs, which have a higher surface area, exhibited the largest ratios. The dispersion of the CNFs in water was much more homogeneous following electrochemical oxidation.     

Impact of processing method and surface functionality on carbon nanofiber dispersion in polyimide matrix and resulting mechanical properties

Composites were produced with functionalized carbon nanofibers (CNF) and polyimide (PI) matrix using either in situ polymerization or blending processes. The impact of the composite processing method, CNF surface chemistry, and fiber loadings on the dispersion of fibers and mechanical properties of composites were investigated. Specifically, functionalization of oxidized CNF with a diamine and polyimide oligomer that mimicked the structure of the base polyimide led to improved dispersion of CNF in the matrix polymer. Samples produced using precipitation blending from hot solvent and in situ polymerization exhibited improved dispersion and reduced agglomeration of CNF relative to samples made using direct blending. While SEM images showed poorly dispersed pristine CNF in PI in the form of agglomerations and thick deposition layer on the bottom of composite film, there was clearly better dispersion for functionalized CNFs. Composites produced with functionalized CNF exhibited improvements in modulus, glass transition temperature and tensile strength relative to the base polyimide. POLYM. COMPOS. 35:1473–1485, 2014. © 2013 Society of Plastics Engineers     

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.     

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     

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.     

Cellulose NANOFIBER‐polyethylene nanocomposites modified by polyvinyl alcohol

The uniform dispersion of cellulose nanofibers (CNFs) in non‐polar polymer matrices is a primary problem to overcome in creating novel nanocomposites from these materials. The aim of this study was to produce CNF‐polyethylene (PE) nanocomposites by melt compounding followed by injection molding to investigate the possibility of using polyvinyl alcohol (PVA) to improve the dispersion of CNF in the PE matrix. The tensile strength of CNF‐ filled composites was 17.4 MPa with the addition of 5 wt % CNF–PVA, which was 25% higher than the strength of neat PE. The tensile modulus of elasticity increased by 40% with 5% CNF–PVA addition. Flexural properties also significantly increased with increased CNF loading. Shear viscosity increased with increasing CNF content. The elastic moduli of the PE/CNF composites from rheological measurements were greater than those of the neat PE matrix because of the intrinsic rigidity of CNF. Melt creep compliance decreased by about 13% and 45% for the composites with 5 wt % CNF and 10 wt % CNF, respectively. It is expected that the PVA carrier system can contribute to the development of a process methodology to effectively disperse CNFs containing water in a polymer matrix. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 42933.     

Effects of surface modification,carbon nanofiber concentration,and dispersion time on the mechanical properties of carbon‐nanofiber–polycarbonate composites

The time effect of ultrasonication was investigated for dispersing carbon nanofibers (CNFs) into a polycarbonate (PC) matrix on the mechanical properties of thus‐produced composites. The effects of CNF surface modification by plasma treatment and the CNF concentration in composites on their mechanical properties were also explored. The plasma coating was characterized by HRTEM and FT‐IR. Furthermore, the plasma polymerization (10 w) treatment on the CNF enhanced the CNF dispersion in the polymer matrix. The mechanical properties of the CNF–PC composites varied with the dispersion time, at first increasing to a maximum value and then dropping down. After a long ultrasonic treatment (24 h), the properties increased again. At a high concentration, the CNF‐PC suspension became difficult to disperse. Additionally, the possible mechanisms for these behaviors are simply proposed. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 3792–3797, 2007     

Completely biodegradable composites reinforced by the cellulose nanofibers of pineapple leaves modified by eco-friendly methods

In this study, cellulose nanofibers (CNF) derived from waste pineapple leaves (PALF) were incorporated into poly (lactic acid) (PLA) with the aim of developing completely biodegradable and sustainable composites. CNF was first prepared by the 2,2,6,6-tetramethylpiperidine-1-oxyl radical (TEMPO) method, and then, different surface modifications of the eco-friendly method were carried out for better dispersion in the PLA matrix. Then, a series of eco-friendly modified CNF/PLA composites were prepared by melt-blending. According to the contact angle experiment, the values of eco-friendly modified CNFs increased from 12.02° to 61.49 and 57.45°, respectively. DSC thermograms show that eco-friendly modified CNFs have a significant nucleating effect for the crystallization of PLA compared to the original CNF. Mechanical testing reveals that the tensile and impact strengths of eco-friendly modified CNF containing composites are improved by 5.4~22.7% and 17.5~56.1%, respectively, through the addition of only 1~3 wt% of modified CNF, and are all higher than that of the original CNF containing composite. Moreover, eco-friendly modified CNF containing composites can allow good light transmittance due to better dispersity of the modified CNF. Consequently, the addition of modified CNFs to the PLA matrix results in increased mechanical and thermal properties of the composites, as well as transparency. Moreover, the addition of CNFs extracted from pineapple leaves by eco-friendly methods can not only reduce the amount of agriculture waste but also avoid the usage of an organic solvent and meet the requirements of environmental protection.     

Biomimetic synthesis and characterization of carbon nanofiber/hydroxyapatite composite scaffolds

Three dimensional electrospun carbon nanofiber (CNF)/hydroxyapatite (HAp) composites were biomimetically synthesized in simulated body fluid (SBF). The CNFs with diameter of ∼250 nm were first fabricated from electrospun polyacrylonitrile precursor nanofibers by stabilization at 280 °C for 2 h, followed by carbonization at 1200 °C. The morphology, structure and water contact angle (WCA) of the CNFs and CNF/HAp composites were characterized. The pristine CNFs were hydrophobic with a WCA of 139.6°, resulting in the HAp growth only on the very outer layer fibers of the CNF mat. Treatment in NaOH aq. solutions introduced carboxylic groups onto the CNFs surfaces, and hence making the CNFs hydrophilic. In the SBF, the surface activated CNFs bonded with Ca²⁺ to form nuclei, which then easily induced the growth of HAp crystals on the CNFs throughout the CNF mat. The fracture strength of the CNF/HAp composite with a CNF content of 41.3% reached 67.3 MPa. Such CNF/HAp composites with strong interfacial bondings and high mechanical strength can be potentially useful in the field of bone tissue engineering.     

Polyester composite water uptake and organic contaminant release affected by carbon nanofiber reinforcements

The incorporation of carbon nanofiber (CNF) into glass fiber (GF) composites is a potential route to extend polymer composite service‐life and enhance mechanical properties. Under nonstatic conditions, only limited information concerning water uptake and contaminant release properties of nanocomposite materials is currently available. Polyester composites containing GF and oxidized CNF were immersed in water for 30 days under nominal pressure at 23 °C, below the polymer's glass‐transition temperature. Water was analyzed and changed every three days to simulate water chemistry regeneration similar to exposures in flowing systems. Composites with oxidized CNF had greater water sorption capacity and leaching rates than CNF‐free composites. The total mass of organic contaminant released correlated with the amount of water sorbed by each composite (r² = 0.91), although CNF dispersion was found to vary greatly within composites. The greatest and least contaminant release rates were found for the polyester‐CNF and the polyester‐GF composites, respectively. While volatile aromatic resin solvents and stabilizer compounds were detected, their concentrations declined over the 30 day exposure period. We hypothesize that the hydrophilic nature of the oxidized CNF increased the water sorption capacity of the polyester composites. Additional studies are warranted that examine the impact of this phenomenon on composite mechanical and long‐term durability properties. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43724.     

Mechanical and thermal transmission properties of carbon nanofiber‐dispersed carbon/phenolic multiscale composites

The present article reports the development and characterization of carbon nanofiber (CNF)‐incorporated carbon/phenolic multiscale composites. Vapor‐grown CNFs were dispersed homogeneously in to phenolic resin using an effective dispersion route, and carbon fabrics were subsequently impregnated with the CNF‐dispersed resin to develop carbon fiber/CNF/phenolic resin multiscale composites. Mechanical and thermal transmission properties of multiscale composites were characterized. Elastic modulus and thermal conductivity of neat carbon/phenolic and multiscale composites were predicted and compared with the experimental results. It was observed that incorporation of only 1.5 wt % CNF resulted in 10% improvement in Young's modulus, 12% increase in tensile strength, and 36% increase in thermal conductivity of carbon/phenolic composites. Fracture surface of composite samples revealed the formation of stronger fiber/matrix interface in case of multiscale composites than neat carbon/phenolic composites. Enhancement of above properties through CNF addition has been explained, and the difference between the predicted values and experimental results has been discussed. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

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.     

Highly dispersed and electrically conductive polycarbonate/oxidized carbon nanofiber composites for electrostatic dissipation applications

The influence of low cost, commercially oxidized carbon nanofibers (ox-CNFs) on the morphological, thermal, mechanical and electrical properties of polycarbonate (PC) composites was examined. Using a simple solution mixing process leads to good dispersion and high packing density of CNFs in the resultant composites. The composite materials exhibit a dramatic improvement in the DC conductivity; for example, increasing from 2.36 × 10⁻¹⁴ S/m for PC to ca. 10⁻² S/m for the composite at only 3.0 wt.% of CNFs, and exhibits a very fast static charge dissipation rate. Dynamic mechanical analysis showed a remarkable increase in storage modulus (282%) at 165 °C, compared to pure PC. Thermogravimetric analysis showed that thermal stability of the composites increased by 54 °C compared to the pure PC. To our knowledge, the measured electrical conductivity and thermal properties for PC/CNF are the highest values yet reported for PC/CNF composites at comparable loadings. The AC/DC conductivity is shown to play an important role to predict the state of dispersion.     

Poly(ϵ‐caprolactone)‐functionalized carbon nanofibers by surface‐initiated ring‐opening polymerization

Carbon nanofibers (CNFs) were covalently functionalized with biodegradable poly(?‐caprolactone) (PCL) by in situ ring‐opening polymerization (ROP) of ?‐caprolactone in the presence of stannous octoate. Surface oxidation treatment of the pristine CNFs afforded carboxylic CNFs (CNF‐COOH). Reaction of CNF‐COOH with excess thionyl chloride (SOCl₂) and glycol produced hydroxyl‐functionalized CNFs (CNF‐OH). Using CNF‐OH as macroinitiator, PCL was covalently grafted from the surfaces of CNFs by ROP, in either the presence or absence of sacrificial initiator, butanol. The grafted PCL content was achieved as high as 64.2 wt %, and can be controlled to some extent by adjusting the feed ratio of monomer to CNF‐OH. The resulting products were characterized by FTIR, NMR, Raman spectroscopy, TGA, DSC, SEM, TEM, HRTEM, and XRD. Core–shell nanostructures were observed under HRTEM for the PCL‐functionalized CNFs because of the thorough grafting. The PCL‐grafted CNFs showed different melting and crystallization behaviors from the mechanical mixture of PCL and CNF‐OH. This approach to PCL‐functionalized CNFs opens an avenue for the synthesis, modification, and application of CNF‐based nanomaterials and biomaterials. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Poly dimethylsiloxane/carbon nanofiber nanocomposites: fabrication and characterization of electrical and thermal properties

This article presents the fabrication and characterization of poly dimethylsiloxane/carbon nanofiber (CNF)-based nanocomposites. Although silica and carbon nanoparticles have been traditionally used to reinforce mechanical properties in PDMS matrix nanocomposites, this article focuses on understanding their impacts on electrical and thermal properties. By adjusting both the silica and CNF concentrations, 12 different nanocomposite formulations were studied, and the thermal and electrical properties of these materials were experimentally characterized. The developed nanocomposites were prepared using a solvent-assisted method providing uniform dispersion of the CNFs in the polymer matrix. Scanning electron microscopy was employed to determine the dispersion of the CNFs at different length scales. The thermal properties, such as thermal stability and thermal diffusivity, of the developed nanocomposites were studied using thermogravimetirc and laser flash techniques. Furthermore, the electrical volume conductivity of each type of nanocomposite was tested using the four-probe method to eliminate the effects of contact electrical resistance during measurement. Experimental results showed that both CNFs and silica were able to impact on the overall properties of the synthesized PDMS/CNF nanocomposites. The developed nanocomposites have the potential to be applied to the development of new load sensors in the future.     

Effect of carbon nanofiber (CNF) silanization on the properties of CNF/epoxy nanocomposites

Carbon nanofibers (CNFs) were functionalized by a multistage process including oxidation, reduction and silanization. The chemical modifications were examined by Fourier transform infrared spectroscopy, X‐ray photoelectron spectrometry, Raman spectroscopy and thermogravimetric analysis. The silanized CNFs were then added into an epoxy resin (EPON 828) to study the effect of the surface modification of CNFs on the properties of nanocomposites. For comparison, nanocomposites containing original unmodified CNFs were also investigated. Scanning electron microscopy indicates better dispersion of modified fibers in the epoxy polymer matrix; the mechanical and thermal properties of composites are also improved; the electrical conductivity of the composites is reduced. Copyright © 2011 Society of Chemical Industry     

Effects of crystallization on dispersion of carbon nanofibers and electrical properties of polymer nanocomposites

Polymer nanocomposites filled with low volume fractions of carbon nanofibers (CNFs) were prepared by melt‐compounding. Three types of polymers with different crystallization behavior, i.e., weakly‐crystallized low density polyethylene (LDPE), strongly crystallized high density polyethylene (HDPE) and amorphous polystyrene (PS), were selected as matrices for the nanocomposites. The effects of polymer crystallization on the dispersion of CNFs were examined. Optical and electron microscopic examinations revealed that the dispersion of CNFs in the nanocomposite matrices was strongly depended on the crystallization behavior of polymer matrices. The CNFs were found to disperse uniformly in weakly crystallized LDPE and amorphous PS matrices, but agglomerated in HDPE due to its strong crystallization tendency. Such a distinct dispersion behavior of CNFs in polymers had a profound effect on the electrical properties of the nanocomposites investigated. The PS/CNF nanocomposites exhibited the lowest percolation threshold. The HDPE/CNF nanocomposites showed the largest percolation threshold due to the CNF agglomeration within the amorphous phase of HDPE. POLYM. ENG. SCI., 48:177–183, 2008. © 2007 Society of Plastics Engineers     

Surface modification of cellulose nanofibrils for poly(lactic acid) composite application

3-Methacryloxypropyltrimethoxysilane (MEMO) was used to modify the surface of cellulose nanofibrils (CNF) to improve the interfacial adhesion between the hydrophilic CNF and the hydrophobic poly(lactic acid) (PLA). MEMO modified CNF (M-CNF) were characterized by means of Fourier transform infrared spectroscopy (FTIR), thermo gravimetric analysis (TGA), and atomic force microscope (AFM). Testing thin films with good transparency were obtained by casting the DMAC solutions of the composites onto glass plates and evaporating the solvent at 80°C. PLA/M-CNF composites were tested by tensile testing, scanning electron microscope (SEM), and AFM. The effect of MEMO and CNF on performance of PLA was investigated. The FTIR analysis successfully showed that coupling reaction has been successfully occurred and the hydroxyl groups of MEMO are strongly hydrogen bonded to that of CNF. The thermal stability of M-CNF was little decreased. The M-CNF kept their morphological integrity. The highest tensile strength of composites was obtained for PLA with 1.0% v/v MEMO and 1.0 wt % CNF. M-CNF disperse well and cross with each other in the PLA matrix. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Comparative study of interphase evolution in polysiloxane resin-derived matrix containing carbon micro and nanofibers during thermal treatment

The work presents the results of research on composite materials made of silicon-containing polymer-derived ceramic matrix composites (PDC-Cs) and nanocomposites (PDC-NCs). Carbon micro and nanofibers (CFs and CNFs) were used as reinforcements. The interactions between carbon micro and nanofibers and polysiloxane matrix, as well as interphase evolution mechanism in composite samples during their heating to 1000 °C were studied. CF/resin and CNF/resin composites were prepared via liquid precursor infiltration process of unidirectionally aligned fibers. After heating to 700 °C–800 °C, decomposition of the resin in the presence of CNFs led to the formation of fiber/organic-inorganic composites with pseudo-plastic properties and improved oxidation resistance compared to as-prepared fiber/resin composites. The most favourable mechanical properties and oxidation resistance were obtained for composites and nanocomposites containing the maximum amount of carbon nanoparticles precipitated in the SiOC matrix during the heat treatment at 800 °C. The precipitated carbon phase improves fiber/matrix adhesion of composites.