Oxidized carbon nanofiber/polymer composites prepared by chaotic mixing

Composites of oxidized carbon nanofibers (ox-CNFs) and polymethyl methacrylate and thermoplastic polyurethane (TPU) were prepared in a chaotic mixer and their electrical and mechanical properties were compared with those prepared using untreated carbon nanofibers (CNFs). X-ray photoelectron spectroscopy data of ox-CNFs showed higher oxygen to carbon ratio than CNFs indicating the presence of polar functional groups on the surfaces of ox-CNFs. Consequently, dispersion of ox-CNFs improved in both polymers and the resultant composites showed improved thermal-oxidative stability, higher storage modulus, and higher glass transition temperature. The electrical conductivity, however, decreased with improved nanofiber dispersion. In the case of TPU/ox-CNF composites, maximum values of tensile strength and Young’s modulus were obtained with 1 wt.% fiber content; higher amounts of ox-CNFs promoted phase mixing of soft and hard segment domains and consequently caused a reduction in tensile properties.     

Carbonaceous fillers for shape memory actuation of polyurethane composites by resistive heating

The effectiveness of carbonaceous, electrically conductive fillers in shape memory actuation of polyurethane composites by resistive heating was evaluated. Specifically, the dependence of electrical resistivity on specimen temperature and imposed tensile strains encountered in shape memory test cycles was determined for shape memory polyurethane (SMPU) composites of carbon nanofiber (CNF), oxidized carbon nanofiber (ox-CNF), and carbon black (CB). The SMPU composites with crystalline soft segments were synthesized from diphenylmethane di-isocyanate, 1,4-butanediol, and poly(caprolactone)diol in a low-shear chaotic mixer and in an internal mixer. The materials synthesized in the chaotic mixer showed higher soft segment crystallinity and lower electrical percolation threshold. A reduction in soft segment crystallinity was observed in the presence of CNF and ox-CNF; the reduction was smaller in the case of ox-CNF. Only the composites of CB showed pronounced positive temperature coefficient (PTC) effects. The observed PTC effects bore a close relationship with non-linear thermal expansion during heating. The composites of CNF and ox-CNF did not show PTC effects due to low levels of soft segment crystallinity. The resistivity of composites of CB increased by several orders of magnitude with imposed tensile strain while composites of CNF and ox-CNF showed weak dependence on strain.     

Evaluation of nanoparticulate fillers for development of shape memory polyurethane nanocomposites

The effects of nano-size fillers on shape memory (SM) properties of polyurethane (PU) nanocomposites were evaluated. Organoclay, carbon nanofiber (CNF), silicon carbide (SiC), and carbon black (CB) were selected as the fillers in an attempt to reinforce the PU and to obtain significantly increased shape recovery stress. The shape memory PU was synthesized from diphenylmethane diisocyanate, 1,4-butanediol, and poly(caprolactone)diol, the latter with a molecular weight of 4000 g/mol. The composites were prepared by melt mixing of extended chain PU with the fillers. The shape memory behavior was triggered by heating the specimen above the melting point of the crystalline soft segment. Our results indicate that exfoliated organoclay significantly augments SM performance, while CNF and SiC diminish it by interfering with crystallization of the soft segment. CB destroys the shape memory properties beyond a certain loading. Better SM performance with organoclay can be attributed to mechanical reinforcement without much interference with the soft segment crystallinity. The reduction of soft segment crystallinity in the presence of CNF and SiC was analyzed. It was found that the extent of crystallinity, as well as the crystallization temperature, was significantly reduced in the presence of these fillers.     

Influence of carbon nanofiber structure on properties of linear low density polyethylene composites

Three types of carbon nanofibers (MJ, Pyrograf®III PR‐19 and PR‐24) were incorporated into linear low density polyethylene (LLDPE) using intensive mixing. The electrical volume resistivity of composites decreased with the addition of CNFs from over 10¹² Ω cm for pure LLDPE to less than 10⁴ Ω cm for carbon nanofibers (CNF) contents of 15 wt% or more. Tensile modulus increased from 110 MPa for pure LLDPE to 200 MPa and 300 MPa for 15 wt% MJ and 15 wt% PR composites, respectively. However, the tensile strength remained fairly unchanged at about 20 MPa. Strain‐to‐failure decreased from 690% for pure LLDPE to 460% and 120% for 15 wt% MJ and 15 wt% PR composites, respectively. It was inferred that the interfacial interactions of LLDPE matrix with MJ fibers is better than that with PR fibers, resulting from the rougher surface of MJ fibers. POLYM. ENG. SCI., 2010. © 2009 Society of Plastics Engineers     

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     

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.     

Study of nanoreinforced shape memory polymers processed by casting and extrusion

Multi‐walled carbon nanotubes (CNTs) and cellulose nanofibers (CNFs) reinforced shape memory polyurethane (PU) composite fibers and films have been fabricated via extrusion and casting methods. Cellulose nanofibers were obtained through acid hydrolysis of microcrystalline cellulose. This treatment aided in achieving stable suspensions of cellulose crystals in dimethylformamide (DMF), for subsequent incorporation into the shape memory matrix. CNTs were covalent functionalized with carboxyl groups (CNT‐COOH) and 4,4′‐methylenebis (phenylisocyanate) (MDI) (CNT‐MDI) to improve the dispersion efficiency between the CNT and the polyurethane. Significant improvement in tensile modulus and strength were achieved by incorporating both fillers up to 1 wt% without sacrificing the elongation at break. Electron microscopy was used to investigate the degree of dispersion and fracture surfaces of the composite fibers and films. The effects of the filler (type and concentration) on the degree of crystallinity and thermal properties of the hard and soft segments that form the PU sample were studied by calorimetry. Overall, results indicated that the homogeneous dispersion of nanotubes and cellulose throughout the PU matrix and the strong interfacial adhesion between nanotubes and/or cellulose and the matrix are responsible for the enhancement of mechanical and shape memory properties of the composites. POLYM. COMPOS., 2011. © 2011 Society of Plastics Engineers     

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.     

碳纳米纤维增强聚甲醛复合材料制备及性能

通过纳米碳纤维(CNFs)在聚甲醛(POM)基体中的均匀分散以及取向,制备了具有优异力学性能和热性能的POM/CNFs复合材料。利用扫描电子显微镜、透射电子显微镜、拉伸性能测试、热重分析、动态热机械分析测试表征了POM/CNFs复合材料的结构和力学、热学性能。结果表明,CNFs与POM分子链形成氢键相互作用,促进了CNFs在POM基体内分散,同时使POM/CNFs复合材料的结晶度显著提高。随着CNFs含量增加,POM/CNFs复合材料的拉伸强度、储能模量和损耗模量均得到提高。当添加0.5%的CNFs时,拉伸强度、储能模量及损耗模量分别提高了20.5%,127%和58%。进一步研究了高温拉伸对POM/CNFs复合材料性能的影响。结果表明,CNFs沿拉伸方向定向排列,同时复合材料拉伸后结晶度提高,拉伸强度显著增加。     

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.     

Preparation and characterization of carbon nanofiber reinforced thermoplastic polyurethane nanocomposites

The effect of CNFs on hard and soft segments of TPU matrix was evaluated using Fourier transform infrared (FTIR) spectroscope. The dispersion and distribution of the CNFs in the TPU matrix were investigated through wide angle X‐ray diffraction (WAXD), field emission scanning electron microscope (FESEM), high resolution transmission electron microscope (HRTEM), polarizing optical microscope (POM), and atomic force microscope (AFM). The thermogravimetric analysis (TGA) showed that the inclusion of CNF improved the thermal stability of virgin TPU. The glass transition temperature (T_g), crystallization, and melting behaviors of the TPU matrix in the presence of dispersed CNF were observed by differential scanning calorimetry (DSC). The dynamic viscoelastic behavior of the nanocomposites was studied by dynamical mechanical thermal analysis (DMTA) and substantial improvement in storage modulus (E') was achieved with the addition of CNF to TPU matrix. The rheological behavior of TPU nanocomposites were tested by rubber processing analyzer (RPA) in dynamic frequency sweep and the storage modulus (G') of the nanocomposites was enhanced with increase in CNF loading. The dielectric properties of the nanocomposites exhibited significant improvement with incorporation of CNF. The TPU matrix exhibits remarkable improvement of mechanical properties with addition of CNF. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Significantly improving electro‐activated shape recovery performance of shape memory nanocomposite by self‐assembled carbon nanofiber and hexagonal boron nitride

This study presents two effective approaches to significantly improve the electro‐thermal properties and electro‐activated shape recovery performance of shape memory polymer (SMP) nanocomposites that are incorporated with carbon nanofibers (CNFs) and hexagonal boron nitrides (h‐BNs), and show Joule heating triggered shape recovery. CNFs were self‐assembled and deposited into buckypaper form to significantly improve the electrical properties of SMP and achieve the shape memory effect induced by electricity. The h‐BNs were either blended into or self‐assembled onto CNF buckypaper to significantly improve the thermally conductive properties and electro‐thermal performance of SMPs. Furthermore, the shape recovery behavior and temperature profile during the electrical actuation of the SMP nanocomposites were monitored and characterized. It was found that a unique synergistic effect of CNFs and h‐BNs was presented to facilitate the heat transfer and accelerate the electro‐activated shape recovery behavior of the SMP nanocomposites. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40506.     

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.     

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     

Thermal characterization of carbon‐nanofiber‐reinforced tetraglycidyl‐4,4′‐diaminodiphenylmethane/4,4′‐diaminodiphenylsulfone epoxy composites

The thermal properties of carbon nanofibers (CNF)/epoxy composites, composed of tetraglycidyl‐4,4′‐diaminodiphenylmethane (TGDDM) resin and 4,4′‐diaminodiphenylsulfone (DDS) as a curing agent, were investigated with differential scanning calorimetry (DSC), thermogravimetric analysis, and dynamic mechanical thermal analysis. DSC results showed that the presence of CNF had no pronounced influence on the heat of the cure reaction. However, the incorporation of CNF slightly improved the thermal stability of the epoxy. Furthermore, the storage modulus of the TGDDM/DDS epoxy was significantly enhanced, whereas the glass‐transition temperature was not significantly affected, upon the incorporation of CNFs. The storage modulus of 5 wt % CNF/epoxy composites at 25°C was increased by 35% in comparison with that of the pure epoxy. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 295–298, 2006     

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.     

Microstructure of carbon nanofiber/thermotropic liquid crystalline polymer composites

The properties and microstructure of a thermotropic liquid crystalline polymer (TLCP, Vectran V400P) were investigated in the presence of carbon nanofibers (CNF). The electrical conductivity of TLCP increased with an addition of CNFs. The thermal analysis of pure TLCP and its composites revealed that a glass transition at ～ 110°C did not change significantly. However, a decrease of tensile modulus and strength was observed with the addition of CNFs. WAXD studies showed a decrease of Herman's orientation parameter, indicating reduction of anisotropy of TLCP. Further, the disruption of molecular orientation of TLCPs was inferred by SEM and TEM analysis. SEM micrographs revealed a fibrillar structure for pure TLCPs at a macro‐scale (2–5 μm). However, this structure was not observed in composites at the same scale even though micro‐size fibrils (0.05 μm) were found with the addition of CNFs. TEM micrographs displayed banded structures of pure TLCPs, but these structures were not significant in the vicinity of CNFs. These observations confirmed that a decrease of molecular alignment and disruption of fibrillar structure of TLCP, in the presence of nanofibers, are attributed to a significant decrease in tensile modulus and strength. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Thermoplastic composites of polyamide‐12 reinforced by cellulose nanofibers with cationic surface modification

Cellulose nanofibers (CNFs) have many useful properties, including high strength and low thermal expansion, and are also environmentally friendly, readily renewable, safe, and biodegradable. The focus of this study was the development of lightweight thermoplastic polymer composites with good mechanical properties based on the incorporation of CNFs that have undergone surface pretreatment with a cationic reagent. The polyamide (PA12) was mixed with surface‐treated CNFs using a twin screw extruder and the resulting pellets were injection molded. The Izod impact strength without notch of CNF‐based composites exceeded that of composites incorporating organophilic montmorillonite (OMMT), a representative nanocomposite material. When the Izod impact test without notch, the impact hammer was stopped by the specimen with incorporation of surface treated CNF. Furthermore, the bending modulus and strength were equal to or greater than that of OMMT composites. The heat distortion temperature was improved as 33°C from neat PA12, and moreover improved as 29°C from OMMT composites. Cationic pretreatment of the CNF surfaces was found to increase the dispersion of the fibers and also to greatly improve the mechanical and thermal properties of the composites. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40920.     

Preparation and characterization of low‐density polyethylene/thermoplastic starch composites reinforced by cellulose nanofibers

In the current study, the effect of extracted cellulose nanofibers (CNFs) on rheological and mechanical properties and biodegradability of polyethylene/starch blend was investigated. The CNFs were extracted from wheat straws using a chemo‐mechanical method. Polyethylene/starch blend was reinforced by different amounts of CNF (6–14 wt%) using an internal mixer followed by a single screw extruder. The flow properties of nanocomposites were investigated by determining Melt Flow Index (MFI) and viscosity. Due to the weak interaction of cellulosic nanofibers and polymers, the flow behavior of nanocomposites was undesirable. Tensile tests were performed to evaluate the mechanical performance of nanocomposites. By increasing the CNF content, the tensile strength and elongation at break declined; whereas, the Young's modulus was improved. The biodegradation of cellulose nanocomposites was investigated by water absorption and degradability tests. Both experiments confirmed the progressive effect of cellulose nanofibers on the degradation of the composites. POLYM. COMPOS., 36:2309–2316, 2015. © 2014 Society of Plastics Engineers     

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.