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.     

Osteocompatibility characterization of polyacrylonitrile carbon nanofibers containing bioactive glass nanoparticles

A kind of composite carbon nanofibers (CNF) containing bioactive glass (BG) nanoparticles was produced for bone regeneration by a combination of electrospinning and sol–gel techniques. To produce the BG, compounds such as calcium nitrate, triethyl phosphate and tetraethyl orthosilicate were used as precursors and hydrolyzed to form a sol–gel solution, which was then added to a polyacrylonitrile (PAN) solution in N,N-dimethylformamide. The resulting mixture was electrospun to form PAN nanofibers containing the BG precursors. Upon oxidation and carbonization, the PAN nanofibers and BG precursors transformed into continuous CNF embedded with BG nanoparticles (CNF/BG). Through this fabrication technique, several CNF/BG composites were obtained by controlling the feeding ratios of the different precursors giving rise to BG nanoparticles with various compositions (i.e. containing 70–90 mol% of SiO₂ component). In vitro biomineralization in a simulated body fluid and co-culture with MC3T3-E1 osteoblasts studies were performed to evaluate the osteocompatibility of the CNF/BG nanoparticle composites. When compared to pure CNF, the CNF/BG composites showed an improved ability to promote the in vitro formation of apatite and MC3T3-E1 proliferation, which was found to be dependent upon the composition of BG nanoparticles.     

Multifunctional carbon nanofiber-reinforced Ge25Sb10S65 chalcogenide glassy composites

Carbon nanomaterials have wide applications in sensors, batteries, electromagnetic shielding, and mechanical reinforcement. Here, carbon nanofiber (CNF)-reinforced Ge₂₅Sb₁₀S₆₅ chalcogenide glassy composites with excellent mechanical and electrical properties were obtained. These glassy composites maintained the amorphous properties of glass. Thermodynamic parameters, microscopic morphology, and structural characteristics were further studied. Benefiting from the remarkable high strength and conductivity of CNFs, as well as the great interface connection between CNFs and glass, the electrical and mechanical properties of glassy composites were greatly enhanced. The Vickers hardness improved by 36% (from 200 kg/mm² to 272 kg/mm²), the tensile modulus increased from 45.9 GPa to 57 GPa, and the shear modulus increased from 22.2 GPa to 23.7 GPa when the CNF concentration increased from 0 wt% to 3.0 wt%. Furthermore, DC conductivity was raised by several orders of magnitude compared with bulk glass at 293 K (from 4.55 × 10⁻¹⁰ S/cm to 3.15 × 10⁻⁴ S/cm) owing to the formation of a continuous conductive network. Thus, these CNF-reinforced glassy composites provide a new way for realizing multifunctional composites.     

The effect of tricalcium silicate incorporation on bioactivity,injectability, and mechanical properties of calcium sulfate/bioactive glass bone cement

The conventional Polymethyl methacrylate (PMMA) bone cement is not biodegradable and not bioactive to bond with the native bone and causes tissue necrosis resulting from its high exothermic polymerization. Hence, biodegradable bioactive bone cements with suitable setting time and mechanical properties should be introduced. In this study, novel bioactive bone cements containing Calcium Sulfate Hemihydrate (CSH), Bioactive Glass (BG), and Tricalcium Silicate (TSC) were developed. Firstly, CSH and BG binary system was optimized based on preliminary setting and mechanical tests. Secondly, the composite bioactive bone cements were obtained by adding different quantities of TCS to the optimized CS-BG (1.3:1 wt % ratio) system. All groups exhibited desirable handling properties, an initial setting time of lower than 15 min, injectability of greater than 85%, and controlled degradability. Moreover, they demonstrated initial compressive strength values of higher than 12 MPa, superior to trabecular bone. After 28 days of hydration, the compressive strength of the cement containing 30% TCS reached 51.04 MPa. Furthermore, the present bone cements showed favorable bioactivity and bone-bonding ability as a result of calcium carbonate and hydroxyapatite (HA) formation. Furthermore, this novel bone cement exhibited appropriate biocompatibility and mesenchymal stem cell attachment, suggesting its potential for clinical applications.     

Synthesis of composite materials of carbon nanofibres and ceramic monoliths with uniform and tuneable nanofibre layer thickness

Composite materials consisting of ceramic monoliths and carbon nanofibres (CNFs) have been synthesized by catalytic growth of CNFs on the γ-alumina washcoating layer covering the walls of a ceramic monolith. The composites possess a relatively uniform mesoporous layer of CNFs of relatively small diameter. The thin alumina washcoating (ca. 0.1 μm) prevents the CNFs from being trapped inside the alumina pores and hence the CNFs grow freely throughout the washcoating layer to form a uniform layer of CNFs that completely covers the surface of the monolith walls. The growth temperature is found to control the thickness of the CNF layer (2-4 μm), the growth rate of the nanofibres, and the mechanical strength of the resulting CNF-monolith composite. At ideal conditions, a complete adhesion of the CNF layer and higher mechanical strength than the original cordierite monolith can be obtained. The CNF layer has an average pore size of 17 nm with absence of microporosity which renders these monoliths promising candidates for the use as catalyst supports, especially for liquid phase reactions. The CNFs have small diameters (5-30 nm) due to the high dispersion of Ni particles in the growth catalyst and the CNFs exhibit an unusual branched structure.     

How Carbon-Nano-Fibers attach to Ni foam

A stable Carbon-Nano-Fiber (CNF) layer was catalytically grown on Ni foam by decomposing ethylene. Scanning electron microscopy of the cross-section of the deposited layer on Ni foam revealed the presence of two distinct carbon layers; an apparently dense layer (‘C-layer’) at the carbon-Ni interface and a CNF layer on top of that. Variation of the growth time demonstrated that both layers develop in parallel. Characterization using temperature programmed gasification in H₂, Raman spectroscopy and transmission electron microscopy confirmed that both layers consists of graphene planes, which are better ordered in CNFs as compared to C-layer. The nickel surface and the attached carbon layer have similar morphological features. This may be the reason for strong adhesion of the C-layer to Ni. CNFs are strongly attached to the C-layer via roots that penetrate into the C-layer. The interconnections of the Ni surface, C-layer and CNFs induce mechanical stability. The C-layer grows continuously with time, whereas CNF growth needs typically 20 min initiation because of the need to form small Ni particles that allow CNF formation. The continuing formation of the C-layer, also after initiation of CNF growth, is thought to be responsible for the formation of CNF roots in the C-layer.     

Flame synthesis of carbon nanofibers on carbon paper: Physicochemical characterization and application as catalyst support for methanol oxidation

We developed a simple, rapid and highly efficient flame synthesis method for direct growing carbon nanofibers (CNFs) on carbon paper (CP) using a common laboratory ethanol flame as both heat and carbon sources. High density CNFs with tangled solid-cored structure were uniformly formed over the Ni-plated CP surface in ∼20 s. The morphologies of the CNFs were characterized by scanning electron microscopy and transmission electron microscopy. X-ray diffraction study revealed the graphitic nature of the CNFs. Raman spectroscopy analysis confirmed that the CNFs are disordered graphitic nanocrystallites with high degree of exposed edges. Electrochemical impedance spectroscopy and cyclic voltammetry were used to show that growing CNFs directly on CP facilitates electron transfer with concomitant increase in double-layer capacitance. The CNF/CP was used as support for Pt nanoparticles to study their supporting effect on the catalyst performance. The as prepared Pt/CNF electrocatalyst exhibited much improved electrocatalytic activity for methanol oxidation compared to Pt/CP and commercial Pt/C on CP. High electronic conductivity and improved electrochemical behavior of the CNF/CPs, resulted from direct contact of the nanofibers with CP, combined with unique properties of CNFs, make the synthesized CNF/CPs promising for fuel cell applications.     

Characterization of carbon nanofiber composites synthesized by shaping process

Catalytically grown carbon nanofibers (CNFs) are shaped into pellets in desired size and configuration by a conventional molding process so as to extend the potential applications of CNFs in industrial heterogeneous catalysis. After shaping, a novel carbon nanofiber composite with sufficient mechanical strength is produced, in which isolated CNFs are connected by a carbon network formed through polymer binder carbonization. Characterization of the synthesized CNF composite is performed by using HRTEM, XRD, Raman, N₂ physisorption, TPD and TGA. A comparison of the textural and structural properties, as well as the surface chemistry is made amongst the CNFs, the CNF composite, and a commercial coal-based activated carbon, in order to attain a comprehensive understanding of the CNF composite. The results show that the CNF composite preserves the mesoporous texture of the CNFs which will be beneficial to those reactions of mass transfer control. The modification effect of oxidative treatments on physico-chemical properties of the CNF composite is also investigated. More surface oxygen-containing groups are introduced to the composite by treating the material either in boiling HNO₃ solution or in static air at 400 °C.     

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.     

Strain dependent energy dissipation in multi-scale carbon fiber composites containing carbon nanofibers

This study investigates strain dependent energy dissipation characteristics in carbon nanofiber (CNF) reinforced carbon fiber epoxy composites (multi-scale composites) by characterizing their viscoelastic properties and vibrational damping response. The air damping effect on the energy dissipation characteristics is also examined. The viscoelastic properties of epoxy containing two weight fractions (3 and 5 wt%) of added CNFs were characterized using dynamic mechanical analysis. Carbon fiber layers were then infiltrated with the two epoxy resins containing the CNFs to form multi-scale composites. A strain dependent loss factor behavior of the multi-scale composites was observed in the dynamic cyclic testing due to CNF’s stick–slip friction, showing a 53% increase in loss factor for the composites containing 5 wt% CNFs. The beam vibration test results also indicated an improvement in loss factor for the multi-scale composite beams relative to those without the CNF addition in the first two resonant frequencies. The multi-scale composite beams exhibit an increase in loss factor, up to 43%, at high amplitude excitation, while a reduction in loss factor was seen at low amplitude. These observed strain dependent damping characteristics seem to result from both the stick–slip friction and the air damping effect.     

Fabrication of Uniform Au–Carbon Nanofiber by Two-Step Low Temperature Decomposition

This paper presents a facile and efficient way to prepare carbon nanofibers ornamented with Au nanoparticles (Au/CNFs). Gold nanoparticles were first deposited in the channels of an anodized aluminum oxide (AAO) membrane by thermal decomposition of HAuCl₄ and then carbon nanofibers were produced in the same channels loaded with the Au nanoparticles by decomposition of sucrose at 230 °C. An electron microscopy study revealed that the carbon nanofibers, ~10 nm thick and 6 μm long, were decorated with Au nanoparticles with a diameter of 10 nm. This synthetic route can produce uniform Au nanoparticles on CNF surfaces without using any additional chemicals to modify the AAO channels or the CNF surfaces.     

Facile Fabrication of PEDOT:PSS-Based Free-Standing Conducting Film for Highly Efficient Electromagnetic Interference Shielding

With the growing popularity of portable and wearable smart electronics, the electromagnetic shielding materials with high shielding effectiveness (SE) as well as light weight and excellent mechanical strength are in high. In this work, the PEDOT:PSS-based free-standing conducting film with superior conductivity and mechanical strength is prepared through a facile fabrication. The cellulose nanofibers (CNFs) are first introduced to induce an orderly grow and stack of the PEDOT grains. A phosphoric acid immersion process is then employed to remove the insulating CNF and PSS in the film. The obtained free-standing conducting film shows a record conductivity of 3508 S cm⁻¹ and its elongation at break reaches 3.75%. Encouragingly, the film delivers an excellent electromagnetic interference (EMI) shielding behavior with a SE of 49 dB in the X-band (8.2–12.4 GHz) at a thickness of 4 µm. The superior conductivity, mechanical strength, and high SE as well as its facile solution processability make this free-standing conducting film to be an attractive EMI material for portable and wearable smart electronics.     

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.     

Chemical vapor-deposited carbon nanofibers on carbon fabric for supercapacitor electrode applications

Entangled carbon nanofibers (CNFs) were synthesized on a flexible carbon fabric (CF) via water-assisted chemical vapor deposition at 800°C at atmospheric pressure utilizing iron (Fe) nanoparticles as catalysts, ethylene (C₂H₄) as the precursor gas, and argon (Ar) and hydrogen (H₂) as the carrier gases. Scanning electron microscopy, transmission electron microscopy, and electron dispersive spectroscopy were employed to characterize the morphology and structure of the CNFs. It has been found that the catalyst (Fe) thickness affected the morphology of the CNFs on the CF, resulting in different capacitive behaviors of the CNF/CF electrodes. Two different Fe thicknesses (5 and 10 nm) were studied. The capacitance behaviors of the CNF/CF electrodes were evaluated by cyclic voltammetry measurements. The highest specific capacitance, approximately 140 F g⁻¹, has been obtained in the electrode grown with the 5-nm thickness of Fe. Samples with both Fe thicknesses showed good cycling performance over 2,000 cycles.     

Transmission electron microscopy study of the microstructure of carbon/carbon composites reinforced with in situ grown carbon nanofibers

Introduction of carbon nanofibers (CNFs) into carbon/carbon (C/C) composites is an effective method to improve the mechanical properties of C/C composites. In situ grown CNFs reinforced C/C composites as well as conventional C/C composites without CNFs were fabricated by chemical vapor infiltration. Transmission electron microscopy investigations indicate that the entangled CNFs (30–120 nm) formed interlocking networks on the surface of carbon fibers (CFs). Moreover, a thin high-textured (HT) pyrocarbon (PyC) layer (～20 nm) was deposited on the surface of CFs during the growth of CNFs. We find the microstructure of C/C composites depends strongly on the local distribution density (LDD) of CNFs. In regions of low CNF LDD, a triple-layer structure was formed. The inner layer (attached to CF) is HT PyC (～20 nm), the middle layer (150–200 nm) is composed of HT PyC coated CNFs (HT/CNFs) and medium-textured PyC, and the outmost layer (several microns) is composed of HT/CNFs and micropores. In regions of high CNF LDD, a double-layer structure was formed. The inner layer is HT PyC (～20 nm), and the outer layer is composed of HT/CNFs, isotropic PyC and nanopores. However, only medium-textured PyC and micropores were found in the matrix of the conventional C/C composites.     

Carbon nanoflake growth from carbon nanotubes by hot filament chemical vapor deposition

We report the growth of carbon nanoflakes (CNFs) on Si substrate by the hot filament chemical vapor deposition without the substrate bias or the catalyst. CNFs were grown using the single wall carbon nanotubes and the multiwall carbon nanotubes as the nucleation center, in the Ar-rich CH₄–H₂–Ar precursor gas mixture with 1% CH₄, at the chamber pressure and the substrate temperature of 7.5 Torr and 840 °C, respectively. In the H₂-rich condition, CNF synthesis failed due to severe etch-removal of carbon nanotubes (CNTs) while it was successful at the optimized Ar-rich condition. Other forms of carbon such as nano-diamond or mesoporous carbon failed to serve as the nucleation centers for the CNF growth. We proposed a mechanism of the CNF synthesis from the CNTs, which involved the initial unzipping of CNTs by atomic hydrogen and subsequent nucleation and growth of CNFs from the unzipped portion of the graphene layers.     

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.     

Activated porous carbon nanofibers using Sn segregation for high-performance electrochemical capacitors

Activated porous carbon nanofibers (CNFs) with three different types of porous structures, which were controlled to contain 1, 4, and 8 wt% of Sn–poly(vinylpyrrolidone) (PVP) precursors in the core region and 7 wt% polyaniline (PAN)–PVP precursors in the shell region during electrospinning, were synthesized using a co-electrospinning technique with H₂-reduction. The formation mechanisms of activated porous CNF electrodes with the three different types of samples were demonstrated. The activated porous CNFs, for use as electrodes in high-performance electrochemical capacitors, have excellent capacitances (289.0 F/g at 10 mV/s), superior cycling stability, and high energy densities; these values are much better than those of the conventional CNFs. The improved capacitances of the activated porous CNFs are explained by the synergistic effect of the improved porous structures in the CNF electrodes and the formation of activated states on the CNF surfaces.     

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.     

Effectual dispersion of carbon nanofibers in polyetherimide composites and their mechanical and tribological properties

The use of proliferation of nanotechnology in commercial applications is driving requirements for minimal chemical processing and simple processes in industry. Carbon nanofiber (CNF) products possess very high purity levels without the need of purification processing before use and are in growing demand for this quality. Polyetherimide (PEI) has excellent mechanical and thermal performance, but its high viscosity makes its nanocomposites processing very challenging. In this study, a facile melt‐mixing method was used to fabricate PEI nanocomposites with as received and physically treated CNFs. The dispersion of CNFs was characterized by scanning electron microscopy, transmitted optical microscopy, and electrometer with large‐area electrodes. The results showed that the facile and powerful melt‐mixing method is effective in homogeneously dispersing CNFs in the PEI matrix. The flexural and tribological characteristics were investigated and the formation of spatial networks of CNFs and weak interfacial bonding were considered as competitive factors to enhanced flexural properties. The composites with 1.0 wt% CNFs showed flexural strength and toughness increased by more than 50 and 550%, respectively, but showed very high wear rate comparable with that of pure PEI. The length of the CNFs also exerted great influences on both mechanical and tribological behaviors. POLYM. ENG. SCI., 50:1914–1922, 2010. © 2010 Society of Plastics Engineers