Overview of Hydroxyapatite–Graphene Nanoplatelets Composite as Bone Graft Substitute: Mechanical Behavior and In-vitro Biofunctionality

Hydroxyapatite (HA) and related materials have been frequently studied as ceramic-based bone graft materials due to their outstanding biocompatibility and osteoconduction. Since the bones are the load supporting parts of a vertebrate, they must have good fracture toughness (K_IC) to avoid fracture at high loading during limb movements. However, the main shortcomings of HA are the poor fracture toughness and brittleness. The mechanical properties of HA need to be improved for orthopedic applications, therefore it is often fabricated with other materials into a composite. This article focuses on the effect of carbon nanostructures (CNSs) especially graphene nanoplatelets (GNPs) on the mechanical, physicochemical properties and in-vitro bio-functional performances of HA. We provide an overview on the preparation and characterization of the HA–GNPs composites. To conclude, the challenges in the fabrication of multi-substituted HA–GNPs composites and future outlooks in the biomedical domain are discussed.     

Charge‐transfer behavior of polyaniline single wall carbon nanotubes nanocomposites monitored by resonance Raman spectroscopy

Highly dispersed nanocomposites of polyaniline(PANI) and oxidized single wall carbon nanotubes(SWNTs) have been prepared using dodecylbenzenesulfonic acid as dispersant. The materials were characterized via resonance Raman and electronic absorption spectroscopies. The behavior of the composites as a function of the applied potential was also investigated using in situ Raman electrochemical measurements. The results obtained at E_laser = 1.17 eV suggest that a charge‐transfer process occur between PANI and semiconducting nanotubes for samples where the metallic tubes are previously oxidized. The spectroelectrochemical data show that the presence of SWNTs prevents the oxidation of PANI rings. Copyright © 2010 John Wiley & Sons, Ltd.     

Thermal transport enhancement of multi-walled carbon nanotubes/ high-density polyethylene composites

Multi-walled carbon nanotubes (MWCNTs) enhanced high-density polyethylene (HDPE) composites were prepared and their thermophysical properties were measured. The thermal diffusivity of the composites increases with the increase in the amount of MWCNTs. A thermal diffusivity of more than three times that of pure HDPE was obtained for 38 vol. % MWCNTs/HDPE composites. An equation based on an effective medium approach model was used to discuss the thermal diffusivity enhancement of MWCNTs/HDPE composites as a function of the volume fraction of MWCNTs. The results from this analysis can be a predictive guideline for further improvements in the thermal transport properties of MWCNTs/HDPE composites. Moreover, the intrinsic longitudinal thermal conductivity k_z of an individual MWCNT was deduced from the measured results on the MWCNTs/HDPE composites. PACS 67.55.Hc; 61.46.Fg; 66.30.Xj     

Evaluation on the interfacial fracture toughness of fiber-reinforced titanium matrix composites by push out test

The models for single-fiber push out test are developed to evaluate the fracture toughness G_IIc of the fiber/matrix interface in titanium alloys reinforced by SiC monofilaments. The models are based on fracture mechanics, taking into consideration of the free-end surface and Poisson expansion. Theoretical solutions to G_IIc are obtained, and the effects of several key factors such as the initial crack length, crack length, friction coefficient, and interfacial frictional shear stress are discussed. The predictions by the models are compared with the previous finite element analysis results for the interfacial toughness of the composites including Sigma1240/Ti-6-4, SCS/Ti-6-4, SCS/Timetal 834, and SCS/Timetal 21s. The results show that the models can reliably predict the interfacial toughness of the titanium matrix composites, in which interfacial debonding usually occurs at the bottom of the samples.     

The influence of interface reaction zone on interfacial fracture toughness of SiC fiber reinforced titanium matrix composites

A fiber-reaction zone-matrix three-phase model is developed to evaluate the interfacial fracture toughness of titanium alloys reinforced by SiC monofilaments. Based on fracture mechanics, theoretical equations of G_IIc are presented, and the effects of several key factors such as crack length and the interface reaction zone thickness on the critical applied stress necessary for crack growth and interfacial fracture toughness are discussed. Finally, the interfacial fracture toughness of typical composites including Sigma1240/Ti-6Al-4V, SCS-6/Ti-6Al-4V, SCS-6/Timetal 834, SCS-6/Timetal 21s, SCS-6/Ti-24Al-11Nb and SCS-6/Ti-15V-3Cr are predicted by the model. The results show that the model can reliably predict the interfacial fracture toughness of the titanium matrix composites.     

Physical properties,thermal stability,and glass transition temperature of multi-walled carbon nanotube/polypyrrole nanocomposites

Polypyrrole (PPy) was synthesized and doped with 1, 2, 4, and 8?wt.% of functionalized multi-wall carbon nanotubes (MWCNTs) by in situ polymerization. TGA/DTA analysis of nanocomposites revealed an increase in thermal stability by increasing the CNTs wt.%. Measurement of electrical resistivity showed a reduction in the resistivity of the composites at all temperatures. The glass transition temperature (T_g) of the samples was measured using electrical resistivity measurements and showed that by increasing the amount of functionalized MWCNTs in PPy, its T_g was increased. Temperature dependence of resistivity of pressed pure PPy showed that by increasing the pelletization pressure, the T_g increased. Also the hardness of nanocomposites was increased by increasing the MWCNTs wt.%.     

Influence of air-oxidation on electric double layer capacitances of multi-walled carbon nanotube electrodes

In this work, air-oxidized multi-walled carbon nanotube (MWCNT) electrodes have been prepared from catalytically grown MWCNTs of high purity and narrow diameter distribution. The experimental results show that air-oxidation modifies the intrinsic structure of individual MWCNTs and a little improves the dispersity of the MWCNTs. The specific capacitances of the electrodes in electric double layer capacitors (EDLCs) based on oxidized MWCNTs are obviously improved through air-oxidation. The specific capacitance of 50 F/g is obtained in the air-oxidized MWCNTs at 600 °C on a single cell device with 35 wt% H₂SO₄ as an electrolyte. This is probably increased BET specific surface area and mesopore volume of the oxidized MWCNT electrode materials of EDLCs. These properties are, therefore highly desirable for the development of electrochemical capacitors with high power and long cycle life.     

Preparation, magnetic and electromagnetic properties of polyaniline/strontium ferrite/multiwalled carbon nanotubes composite

Strontium ferrite particles were firstly prepared by sol-gel method and self-propagating synthesis, and then the polyaniline/strontium ferrite/multiwalled carbon nanotubes composites were synthesized through in situ polymerization approach. Structure, morphology and properties of the composite were characterized by various instruments. XRD analysis shows that the output of PANI increases with the increase of the content of MWCNTs, due to the large surface area of MWCNTs. Because of the coating of PANI, the outer diameter of MWCNTs increases from 10 nm to 20-40 nm. The electrical conductivity of the composites increases with the amount increase of MWCNTs and reaches 7.2196 S/cm in the presence of 2 g MWCNTs. The coercive force of the composites prepared with 2 g MWCNTs is 7457.17 Oe, which is much bigger than that of SrFe₁₂O₁₉ particles 6145.6 Oe, however, both the saturation magnetization and the remanent magnetization of the composite become much smaller than those of SrFe₁₂O₁₉ particles. The electromagnetic properties of the composite are excellent in the frequency range of 2-18 GHz, which mainly depend on the dielectric loss in the range of 2-9 GHz, and mainly on the magnetic loss in the range of 9-18 GHz.     

Thermal and electrical conductivity of poly(l-lactide)/multiwalled carbon nanotube nanocomposites

Multiwalled carbon nanotubes (MWCNTs) are considered to be the ideal reinforcing agent for high-strength polymer composites, because of their fantastic mechanical strength, high electrical and thermal conductivity and high aspect ratio. Polymer/MWCNTs composites are easily molded, and the resulting shaped plastic articles have a perfect surface appearance compared with polymer composites made using usual carbon or glass fibers. Good interfacial adhesion between the MWCNTs and the polymer matrix is essential for efficient load transfer in the composite. The ultrahigh strength polymer composites demand the uniform dispersion of the MWCNTs in the polymer matrix without their aggregation and the good miscibility between MWCNT and polymer matrix. This approach can also be applied to biodegradable synthetic aliphatic polyesters such as poly(l-lactide) (PLLA), which has received a great deal of attention due to environmental concerns. In this study, PLLA was melt-compounded with MWCNTs. A high degree of dispersion of the MWCNTs in the composites was obtained by grafting PLLA onto the MWCNTs (PLLA-g-MWCNTs). After oxidizing the MWCNTs by treating them with strong acids, they were reacted with l-lactide to produce the PLLA-g-MWCNTs. The mechanical properties of the PLLA/PLLA-g-MWCNT composite were higher than those of the PLLA/MWCNT composite. The electrical conductivity of the composites was determined by measuring the volume resistivity, which is a value of the resistance expressed in a unit volume by two-probe method. The thermal diffusivity and heat capacity of composites was measured by laser flash method, and the effects of modification of the MWCNT in PLLA matrix are discussed.     

Electrostatic Layer-by-Layer Assembly of Hierarchical Structure of Multi-Walled Carbon Nanotubes With Glass Fiber Cloth Reinforced Epoxy Composites

A hierarchical structure of glass fiber cloth (GFC) deposited with multiwalled carbon nanotubes (MWCNTs) and cationic polyelectrolyte poly (diallyldimethylammonium chloride) (PDDA) was fabricated by the layer-by-layer (LBL) assembly method. We demonstrated that negatively charged MWCNTs, by acid functionnalization, and positively charged PDDA were sequentially adsorbed onto the GFC to form a uniform and porous interconnected network structure of MWCNTs. Multiscale composites with GFC-[PDDA-MWCNTs] _n were prepared by compression molding. The presence of the MWCNTs with their porous nanostructure helped in the formation of an interpenetrating network with the matrix at the interface layer. The resulting interlaminar strength increased by 18～37% and the surface electrical resistance (～10⁵ Ω) dropped greatly compared to those of epoxy/GFC composites (10¹⁴ Ω), showing them to be promising structural composites with GFC-[PDDA-MWCNTs] _n reinforcement with an improvement in properties over epoxy/GFC composites.     

Effects of different carbon precursors on synthesis of multiwall carbon nanotubes: Purification and Functionalization

Cyclohexanol and xylene were used as carbon precursors, for synthesis of multiwall carbon nanotubes (MWCNTs) arrays in a CVD system at temperature of 750 °C, using nitrogen as carrier gas and ferrocene as catalyst. Different characterization methods were employed to compare the MWCNTs structure synthesized by these two precursors. All scanning electron microscopy (SEM), transmission electron microscopy (TEM), thermal gravimetric analysis (TGA) and Raman spectroscopy results illustrated that using cyclohexanol could significantly reduce formation of amorphous carbon and catalyst particles in the as-grown CNTs. The less amorphous carbon can be attributed to in situ oxidation in presence of oxygen atom of cyclohexanol. Characterizations showed that MWCNTs with high purity could be obtained using cyclohexanol as carbon precursor. The as-grown MWCNTs were purified by oxidation and acid treatment. Characterization of the purified MWCNTs using HNO₃/H₂SO₄ (1/3 or 1/1), 8 M HCl or 8 M HNO₃ was carried out. The results showed that 8 M HNO₃ could be considered as the best chemical to obtain more pure MWCNTs, less amorphous and metal particles and less damaged MWCNTs. The Raman spectroscopy results demonstrated that HNO₃/H₂SO₄ (1/3) treatment could more disorder the MWCNTs structure and this was attributed to the bigger destroying effect of this acid treatment. Furthermore, the TEM analysis of MWCNTs before and after acid treatment revealed that acid treatment could remove encapsulated catalyst particles. The FTIR analysis illustrated that purification of the MWCNTs with nitric acid could connect the functional groups onto the outer surface of MWCNTs and this resulted in more dispersion of the MWCNTs in water.     

A facile method to modify carbon nanotubes with nitro/amino groups

Nitro groups (-NO₂) have been introduced on the surface of multi-walled carbon nanotubes (MWCNTs) by treatment with a mixture of concentrated H₂SO₄/HNO₃ solution at low temperature (60 °C). Such a low-temperature treatment simultaneously can well prevent MWCNTs from the structural damage. From the nitro-modified MWCNTs, MWCNTs can be readily modified with amino groups by reduction of nitro groups. The prepared amino-modified MWCNTs are highly soluble in polar solvents such as dimethylformamide (DMF), alcohol and acetone. Further, as a demonstration, MWCNTs can be functionalized with guest objects, provided by the strong bonding ability of amino groups.     

Modification of multi-walled carbon nanotubes for electric double-layer capacitors: Tube opening and surface functionalization

Multi-walled carbon nanotubes (MWCNTs) obtained opening the closed ends and using surface functionalization by means of a combination of partial oxidation in air and chemical modifications are characterized systematically in 0.3 M H₂SO₄ between 0 and 1.0 V, and these nanotubes were planned to be used as electrode materials in electric double-layer capacitors (EDLCs). Opening of MWCNTs, clearly observed by means of transmission electron microscopy (TEM), can be easily achieved by the partial oxidation in air through a seven-step temperature program identified by thermogravimetric/differential thermal analyses (TG/DTA). An increase in 175% specific capacitance is obtained for the MWCNTs, partially oxidized in air and chemically modified in H₂SO₄+HNO₃. The temperature-programmed desorption (TPD) data showed that evolutions of CO and CO₂ are, respectively, promoted by the application of partial oxidation in air and chemical modification in H₂SO₄+HNO₃. The above increase in specific capacitance for modified MWCNTs is attributed to an obvious increase in the BET surface area (double-layer capacitance) and the density of oxygen-containing surface functional groups (pseudocapacitance).     

Excitation energy dependence of Raman bands in multiwalled carbon nanotubes

Vertically aligned multiwalled carbon nanotubes (MWCNTs) were grown on 1‐ and 3‐nm cobalt (Co) films, at various growth times by microwave plasma enhanced chemical vapor deposition technique and their microstructural properties were analyzed with the help of Raman spectra that were obtained from different sources of laser excitation energies (E_L: 2.41, 1.96 and 1.58 eV). The variation of D and G band positions in MWCNTs grown on 1‐ and 3‐nm Co films follows a similar behavior, and an anomalous behavior was observed in the E_L dependence of the D′‐band wavenumber. In the second‐order spectra, the G′ band varied strongly according to structure with the laser excitation energy (E_L). The I_D/I_G ratio decreased with the increase of E_L for all MWCNTs; however, for a fixed E_L, the I_D/I_G dispersion is higher at lower E_L. The crystallite sizes were estimated using I_DI_G and E_L. We have shown that, for all MWCNTs, I_D/I_G ratio is inversely proportional to . Copyright © 2010 John Wiley & Sons, Ltd.     

Synthesis and gas sensing characteristic based on metal oxide modification multi wall carbon nanotube composites

A new type of gas sensing material based on metal oxide modification multi wall carbon nanotube (MO/MWCNT) composites is presented since the interface between the composites enhance the carrier density so as to improve the gas sensitivity. Three kinds of MO/MWCNT composite materials, such as ZnO/MWCNT, SnO₂/MWCNT and TiO₂/MWCNT, have been acquired in situ growth using catalytic pyrolysis method. The MO nano particles have decorated on side of MWCNTs, whereas the introduction of SnO₂ nano particles makes part of MWCNT showing two-dimensional form of carbon nano-wall structure. Among four kinds of cathode of ZnO/MWCNTs, SnO₂/MWCNTs, TiO₂/MWCNTs and pure MWCNT composite film, TiO₂/MWCNTs composite has the lowest threshold electric field required to draw current of 12 μA has been found to be ∼1.2 V/μm, and also TiO₂/MWCNTs composite has the highest sensitivity of 16% to ethanol. The TiO₂/MWCNTs composite is superior to the others both in vacuum electron transportation and gas sensitivity.     

High temperature Raman spectroscopy studies of carbon nanowalls

High temperature Raman experiments were carried out on carbon nanowalls (CNWs). The intensity of the defect‐induced D mode decreased significantly after the sample was heated in air ambient. The Raman intensity ratio of D mode and G mode, I_D/I_G, changed from 2.3 at room temperature to 1.95 after the sample was heated to 600 °C. This change was attributed to the removal of surface amorphous carbon by oxidation. In contrast to I_D/I_G, the intensity ratio of the D′ mode and the G mode, I_D′/I_G, did not change much after heating, indicating that the surface amorphous carbon and surface impurity do not contribute as much to the intensity of the D′ mode. The dominant contributor to the D′ mode could be the intrinsic defects. Copyright © 2007 John Wiley & Sons, Ltd.     

Effect of dispersion state of carbon nanotube on the thermal conductivity of poly(dimethyl siloxane) composites

Herein, the effect of dispersion uniformity of multi-walled carbon nanotube (MWCNT) on the thermal conductivity of poly(dimethyl siloxane) (PDMS) composites was investigated by comparing experimentally obtained and calculated results based on simple models. Two different MWCNTs, i.e., raw and oxidized/masterbatched MWCNTs, were used and compared. For raw MWCNT, the dispersion in PDMS was poor, resulting in the significant reduction in the aspect ratio of MWCNT. However, for composites using masterbatched MWCNT, the thermal conductivity was always about 10% greater than those prepared with raw MWCNT and the aspect ratio calculated by the model equation was also 1.7 times greater. Above 1.5 phr masterbatched MWCNT concentrations, the aspect ratio of 430 was maintained. Finally, the results suggest that the thermal conductivity can be correlated with the degree of dispersion and aspect ratio obtained from the model equation used.     

Ablation properties of carbon/carbon composites with tungsten carbide

The ablation properties and morphologies of carbon/carbon (C/C) composites with tungsten carbide (WC) filaments were investigated by ablation test on an arc heater and scanning electron microscopy. And the results were compared with those without tungsten carbide (WC) filaments tested under the same conditions. It shows that there is a big difference between C/C composites with and without WC filaments on both macroscopic and microscopic ablation morphologies and the ablation rates of the former are higher than the latter. It is found that the ablation process of C/C composites with WC filaments includes oxidation of carbon fibers, carbon matrices and WC, melting of WC and WO₃, and denudation of WC, WO₃ and C/C composites. Oxidation and melting of WC leads to the formation of holes in z directional carbon fiber bundles, which increases the coarseness of the ablation surfaces of the composites, speeds up ablation and leads to the higher ablation rate. Moreover, it is further found that the molten WC and WO₃ cannot form a continuous film on the ablation surface to prevent further ablation of C/C composites.     

Effect of Thermal Treatment on the Structure of Multi-walled Carbon Nanotubes

The effects of vacuum annealing and oxidation in air on the structure of multi-walled carbon nanotubes (MWCNTs) produced by a large-scale catalytic chemical vapor deposition (CCVD) process are studied using Raman spectroscopy and transmission electron microscopy (TEM). A detailed Raman spectroscopic study of as-produced nanotubes has also been conducted. While oxidation in air up to 400°C removes disordered carbon, defects in tube walls are produced at higher temperatures. TEM reveals that MWCNTs annealed at 1,800°C and above become more ordered than as-received tubes, while the tubes annealed at 2,000°C exhibit polygonalization, mass transfer and over growth. The change in structure is observable by the separation of the Raman G and D′ peaks, a lower R-value (I _D/I _G ratio), and an increase in the intensity of the second order peaks. Using wavelengths from the deep ultraviolet (UV) range (5.08 eV) extending into the visible near infrared (IR) (1.59 eV), the Raman spectra of MWCNTs reveal a dependence of the D-band position proportional to the excitation energy of the incident laser energies.     

INVESTIGATION OF STATIC AND DYNAMIC FRACTURE TOUGHNESS OF SHORT CERAMIC FIBER REINFORCED POLYPROPYLENE COMPOSITES

Short ceramic fiber reinforced polypropylene composites have been investigated to determine their static and dynamic fracture toughness for different reinforcing fiber contents. The composites were reinforced with fibers produced by a carding technique combined with needle-punching. Static fracture toughness (K _c) was measured on single-edge notched tensile (SEN-T) specimens, while dynamic fracture toughness (K _d) was tested by impact strength Charpy specimens. Specimens in both cases were cut transverse (T) and in longitudinal (L) directions. Test results show that dynamic fracture toughness is larger than the static one. During loading of SEN-T specimens the burst-type acoustic emission (AE) signals were monitored. From AE signals it can be concluded that the main damage form is the pull-out in the T specimens, and debonding in L ones. These results were supported by scanning electron microscopy micrographs taken from fracture surfaces.