Preferentially oriented vanadium nitride films deposited by magnetron sputtering

Because of solid state lubricious properties of vanadium oxides, wear resistant coatings based on nitrides and carbides of that metal are still of interest for research teams. The aim of this report is to show phase composition evolution from metallic vanadium through intermediate phases up to δ-VN phase supersaturated with nitrogen in thin films deposited by reactive, pulsed magnetron sputtering from vanadium target. This analysis is completed by remarks on preferential orientation, lattice constant and crystallite size. Presented work is a part of research on composite hard coatings for woodworking tools where vanadium nitrides and carbides are considered as a component reducing friction.     

Electronic properties of ruthenium sulfide–carbon cluster composite material obtained by calcination of an alternating ruthenium–S–phenylene hybrid copolymer

Calcination of an alternating ruthenium–S–phenylene hybrid copolymer under an argon atmosphere was found to give nano-sized ruthenium sulfide/carbon cluster composite material. ESR spectral examinations of the material revealed that an electron transfer from ruthenium sulfide particles to carbon clusters took place to raise a visible-light responsive oxidation–reduction function with an oxidation site at ruthenium sulfide particles and a reduction site at carbon clusters. The surface of the calcined material was modified with Pt particles, and the reduction ability of the resulting modified material was examined.     

Superhardenability behavior of vanadium in 40CrNiMoV steel

The effects of vanadium on the hardenability, microstructures and mechanical properties of 40CrNiMoV steel were investigated after stabilizing nitrogen with aluminum by using an electron microprobe, a scanning electron microscope, a transmission electron microscope, and a hardness tester, etc. The existence state of vanadium in steel was also analyzed. Results showed that aluminum can effectively stabilize nitrogen by producing aluminum nitride. This phenomenon promoted the segregation of solid solution vanadium in grain boundaries, delayed the transformation of ferrite and improved the stability of austenite. Thus, vanadium can potentially improve the hardenability of steels. Excellent mechanical properties of 40CrNiMoV steel were obtained during slow cooling with the addition of vanadium, and this process can be used to produce heavy section steel components.     

High visible light photocatalytic activities obtained by integrating g-C3N4 with ferroelectric PbTiO3

Graphitic carbon nitride (g-C3 N4) with the merits of high visible light absorption,proper electronic band structure with high conduction band edge and variable modulation,is viewed as a promising photocatalyst for practical use.To alleviate its high recombination rate of photo-excited charge carriers and maximize the photocatalytic performances,it is paramount to design highly effective transfer channels for photo-excited charge carriers.Ferroelectric materials can have the charge carriers transport in opposite directions owing to the internal spontaneous polarization,which may be suitable for constructing the heterostructure with g-C3N4 for efficient charge separation.Inspired by this concept,herein ferroelec tric PbTiO3,which can be the visible-light absorber,is coupled with g-C3N4 to construct PbTiO3/g-C3N4 heterostructure with close contact via Pb-N bond by the facile post thermal treatment.The optimized PbTiO3/g-C3N4 heterostructure exhibited excellent photocatalytic and photoelectrochemical activities under visible light irradiation.Moreover,the simultaneous application of ultrasound-induced mechanical waves can further improve its photocatalytic activities through reinforcing the built-in piezoelectric field.This work proposes a widely applicable strategy for the fabrication of high-performance ferroelectric based photocatalysts and also provides some new ideas for developing the understanding of ferroelectric photocatalysis.     

空气氧化法提纯碳纳米管的研究

以乙炔为原料气，采用铁-镍复合催化剂，在700℃下，由化学气相沉积法(CVD)制得了直径为10nm～30nm的多壁碳纳米管(MWNT)。然后通过空气氧化法对所获碳纳米管进行提纯，去除了碳纳米管中的无定形炭、炭纳米颗粒及炭纤维等非晶碳成分，提高了碳纳米管的纯度；并研究了提纯温度和时间的关系。结果表明：碳纳米管在空气中440℃加热3h后，烧损率趋于平稳，基本上稳定在2％左右。使用透射电镜(TEM)考察提纯前后碳纳米管的形貌，发现碳纳米管在空气中440℃加热3h后，非晶碳成分基本去除，纯度得到提高。     

Synthesis of Vanadium Nitride by a One Step Method

Vanadium nitrides were prepared via one step method of carbothermal reduction and nitridation of vanadium trioxide. Thermalgravimetric analysis （TGA） and X-ray diffraction were used to determine the reaction paths of vanadium carbide, namely the following sequential reaction： V2O3→V8C7 in higher temperature stage, the rule of vanadium nitride synthesized was established, and defined conditions of temperature for the production of the carbides and nitrides were determined. Vanadium oxycarbide may consist in the front process of carbothermal reduction of vanadium trioxide. In one step method for vanadium nitride by carbothermal reduction and nitridation of vanadium trioxide, the nitridation process is simultaneous with the carbothermal reduction. A one-step mechanism of the carbothermal reduction with simultaneous nitridation leaded to a lower terminal temperature in nitridation process for vanadium nitride produced, compared with that of carbothermal reduction process without nitridation. The grain size and shape of vanadium nitride were uniform, and had the shape of a cube. The one step method combined vacuum carborization and nitridation （namely two step method） into one process. It simplified the technological process and decreased the costs.     

Molybdenum-doped vanadium dioxide coatings on glass produced by the aqueous sol-gel method

Thin films of vanadium dioxide (VO₂) on glass substrates were produced by the aqueous sol-gel method. Various levels of doping were achieved by adding small quantities of a water-soluble molybdenum compound to the sol. After dip coating, the substrates were reduced by heat treatment in a low-pressure carbon monoxide/carbon dioxide (CO/CO₂) atmosphere. The change in electrical conductivity with temperature, and optical reflectance in the semiconductor and metallic phases were measured and compared to undoped VO₂ films. Doping the VO₂ films with molybdenum lowered the transition temperature of the semiconductor-to-metal phase change; at a doping level of 7 at.% the transition temperature was measured at 24 °C, as indicated by the electrical conductivity. All the films showed a substantial change in reflectance upon heating through the transition. The optical reflectance in the semiconductor state increased slightly with additional dopant, while the reflectance in the metallic state remained constant.     

Effect of the nature the carbon precursor on the physico-chemical characteristics of the resulting activated carbon materials

Carbon materials, including amorphous carbon, graphite, carbon nanospheres (CNSs) and different types of carbon nanofibers (CNFs) [platelet, herringbone and ribbon], were chemically activated using KOH. The pore structure of carbon materials was analyzed using N₂/77 K adsorption isotherms. The presence of oxygen groups was analyzed by temperature programmed desorption in He and acid–base titration. The structural order of the materials was studied by X-ray diffraction and temperature programmed oxidation. The morphology and diameter distribution of CNFs and CNSs were characterized by transmission electron microscopy. The materials were also characterized by temperature-desorption programmed of H₂ and elemental composition. The ways in which the different structures were activated are described, showing the type of pores generated. Relationships between carbon yield, removed carbon, activation degree and graphitic character were also examined. The oxygen content in the form of oxygen-containing surface groups increased after the activation giving qualitative information about them. The average diameter of both CNFs and CNSs was decreased after the activation process as consequence of the changes produced on the material surface.     

Removal of vanadium from wastewater by multi-walled carbon nanotubes

Nitric acid heating reflux modified multi-walled carbon nanotubes (HMWCNTs) were used for the removal of vanadium(V) in aqueous solution. The removal rate of vanadium(V) decreased with the increase of the initial vanadium(V) concentration and the solution pH, and increased with the increase of reaction time, HMWCNTs amount and solution temperature. The adsorption equilibrium and dynamic kinetics fitted the Langmuir adsorption isotherm and pseudo-second order models. The results obtained by scanning electron micrography and Fourier transform infrared spectroscopy analysis revealed that the hydroxyl and carboxyl functional groups are mainly responsible for the vanadium adsorption. This study showed that the HMWCNTs proved to be a considerable adsorbent for the removal of vanadium from wastewater.     

Determination of the oxidation state and coordination of a vanadium doped chalcogenide glass

Vanadium doped chalcogenide glass has potential as an active gain medium, particularly at telecommunications wavelengths. This dopant has three spin allowed absorption transitions at 1100, 737 and 578 nm, and a spin forbidden absorption transition at 1000 nm. X-ray photoelectron spectroscopy indicated the presence of vanadium in a range of oxidation states from V⁺ to V⁵⁺. Excitation of each absorption band resulted in the same characteristic emission spectrum and lifetime, indicating that only one oxidation state is optically active. Arguments based on Tanabe-Sugano analysis indicated that the configuration of the optically active vanadium ion was octahedral V²⁺. The calculated crystal field parameters (Dq/B, B and C/B) were 1.85, 485.1 and 4.55, respectively.     

Formation of metallic vanadium nanoparticles in SiO2 by ion implantation and of vanadium oxide nanoparticles by additional thermal oxidation

Metallic V nanoparticles (NPs) were formed in silica glass by implantation with V⁺ ions of 60 keV to a fluence of 1.0 × 10¹⁷ ions/cm². Annealing in oxygen gas at 800 °C transformed the metallic NPs to oxide NPs. While the mean diameter of the metal V NPs was 8.4 nm in the as-implanted state, the diameters steeply increased during oxidation, with some exceeding 100 nm. Since at least 15 different composition phases, such as V₂O₃, V₃O₇, V₆O₁₃, V₉O₁₇, etc., are known for vanadium oxides, identification of the oxide phase of the NPs was not easy. X-ray diffraction (XRD) was not a powerful tool for phase identification of the NPs, because the diffraction peaks were broad due to the nanometric sizes of the particles and readily shift due to stress effects. The temperature dependence of the optical absorption spectrum was measured. The observed spectra were almost unchanged between 3.3 and 370 K. Combining the spectral result and the XRD results, the candidates were narrowed down to three phases, V₂O₅, V₄O₉, and V₇O₁₃, from the 15 candidates. Among the three, the V₂O₅ phase is the most probable because the absorption spectrum and the oxygen partial pressure for its formation were both consistent.     

Modifying the morphology and structure of graphene oxide provides high-performance LiFePO4/C/rGO composite cathode materials

In this study we synthesized LiFePO₄/carbon/reduced graphene oxide (LFP/C/rGO) composite cathode materials using a method involving sol–gel processing, spray-drying, and calcination. To improve the electrochemical performance of LFP/C, we tested graphene oxides (GOs) of various morphologies as conductive additives, including pristine GO, three-dimensional GO, and hydrothermal porous GO (HTGO). Among our samples, the cathode material prepared through spray-drying with the addition of 1 wt% of HTGO (denoted SP-LFP/C/1%rHTGO) displayed the best electrochemical performance; its discharge capacities at 0.1C, 1C, 5C, and 10C were 160.5, 151.8, 138.8, and 130.3 mA h g⁻¹, respectively. From measurements of its long-term cycling performance, the discharge capacity in the first cycle and the capacity retention after 30 cycles at 0.1C were 160.2 mA h g⁻¹ and 99.6%, respectively; at 10C, these values were 132.2 mA h g⁻¹ and 91.8%, respectively. The electronic conductivity of SP-LFP/C/1%rHTGO (6.58 × 10⁻⁵ S cm⁻¹) was higher than that of the pristine LFP/C (9.24 × 10⁻⁶ S cm⁻¹). The Li⁺ ion diffusivities (D_Li⁺) of the SP-LFP/C/1%HTGO cathode, measured using AC impedance (3.91 × 10⁻¹³ cm² s⁻¹) and cyclic voltammetry (6.66 × 10⁻¹⁰ cm² s⁻¹ for discharge), were superior to those of the LFP/C cathode (9.31 × 10⁻¹⁵ cm² s⁻¹ and 1.79 × 10⁻¹⁰ cm² s⁻¹ for discharge, respectively). Galvanostatic intermittent titration revealed that the value of D_Li⁺ was located in a reasonable range from 1 × 10⁻¹⁰ to 1 × 10⁻¹⁷ cm² s⁻¹; its value dropped to its lowest point when the state of charge was close to 50%. Thus, the use of spray-drying and the addition of conductive HTGO (having a 3D wrinkled morphology and interconnected pore structure) can enhance the electronic conductivity and Li⁺ ion diffusivity of LFP/C cathode materials, thereby improving the electrochemical performance significantly.     

Recent advances in the incorporation and identification of vanadium species in microporous materials

Major advances have recently been made concerning the determination of the local environment of vanadium ions incorporated in microporous materials. Different spectroscopic techniques used in combination allow us to provide detailed information about the environment of V ions introduced in these materials. In particular, photoluminescence spectroscopy indicates the presence of different kinds of distorted tetrahedral V species in V-containing silica-based microporous materials.     

Characterization of composite materials made from discontinuous carbon fibres within the framework of composite recycling

Recycling carbon fibres from waste composite materials would only be efficient if it were possible to separate the fibres and the matrix and to re-use the recycled fibres as new reinforcements. The challenge is to use non-continuous fibres to produce high-strength materials. The formation of defects in “semi-long” fibre composites has not yet been taken into account. In this paper the influence of fibre length and fibre alignment on the strength and the modulus of composite materials is illustrated. It is shown that the presence of defects may be modelled in order to understand what the quality of a second generation composite material would be.     

Predicting the thermal conductivity of composite materials with imperfect interfaces

This paper compares the predicted values of the thermal conductivity of a composite made using the equivalent inclusion method (EIM) and the finite element method (FEM) using representative volume elements. The effects of inclusion anisotropy, inclusion orientation distribution, thermal interface conductance, h, and inclusion dimensions have been considered. Both methods predict similar overall behaviour, whereby at high h values, the effective thermal conductivity of the composite is limited by the inclusion anisotropy, while at lower h values, the effect of anisotropy is greatly diminished due to the more dominant effect of limited heat flow across the inclusion/matrix interface. The simulation results are then used to understand why in those cases where it has been possible to produce CNF reinforced Cu matrix composites with a large volume fraction of well dispersed CNFs, the measured thermal properties of the composite have failed to meet the expectations in terms of thermal conductivity, with measured conductivities in the range 200–300 W/m K. The simulation results show that, although degradation of the thermal properties of the CNFs and a poor interfacial thermal conductance are very likely the reasons behind the low conductivities reported, great care should be taken when measuring the thermal conductivity of this new class of materials, to avoid misleading results due to anisotropic effects.     

Thermochromic properties of vanadium oxide films prepared by dc reactive magnetron sputtering

A transparent vanadium oxide film has been one of the most studied electrochromic (EC) and Thermochromic (TC) materials. Vanadium oxide films were deposited at different substrate temperatures up to 400 °C and different ratios of the oxygen partial pressure (P_O2). SEM, AFM and X-ray diffraction's results show detail structure data of the films. IR mode assignments of the films measured by IR reflection-absorbance in NGIA (near grazing incidence angle) are given. It is found that the film has V₂O₅ and VO₂ combined structures. The films exhibit clear changes in transmittance when the environment temperature (T_e) is varied, especially in the 3600-4000 cm^− 1 range. Applying a T_e that is higher than a critical temperature (T_c) to the samples, the as-RT (room temperature) deposited film with 9% P_O2 has a transmittance variation of 30%, but the films that were deposited on a heated substrate of 400 °C have little variation. There is tendency of bigger variation in transmittance for the sample deposited at a larger P_O2, when it is applied by 200 °C T_e.     

Characterization of date palm lignocellulosic by-products and self-bonded composite materials obtained thereof

In the present work, we investigated the possibility of valorizing four date palm tree by-products: leaflets, rachis, leaf sheath and fibrillum as self-bonded materials. First, their chemical composition and morphological properties were studied and showed high neutral detergent fiber values for all samples (65–91%) as normally required for self-bonding adhesion. Particleboard composites were then manufactured by thermopressing without any pretreatment or addition of synthetic binders. The properties of the resulting composites were assessed using bending test, internal bonding measurement, thickness swelling, water absorption and dynamical mechanical analysis. The fibrillum, leaflets and rachis based- composites have sufficient modulus of rupture to meet the Japanese Industrial Standard. However, only the fibrillum panels meet the French Standards. Furthermore, the results of dynamic mechanical analysis of leaflets composites reveal a relaxation peak which could be attributed to higher molecular weight carbohydrates. These preliminary results will allow to discriminate the various sources of fibrous particles on the same tree and to choose adequate preprocessing for further research.     

Design of composite materials with improved impact properties

Composites have been widely used in applications where there is a risk of impact, due to the excellent properties these materials display for absorbing impact energy. However, composites during impact situations typically generate an enormous number of small pieces, due to the energy absorption mechanism of these materials, a mechanism which does not include plastic deformation. This can prove dangerous in sports competitions, where the small fragments of the original structure may harm competitors.This study was designed to explore the possibility of incorporating a material which, whilst maintaining a high level of energy absorption without any plastic deformation mechanism, was able to maintain its original form, or at least significantly reduce the number of pieces generated after impact.The addition of a polyamide layer, NOMEX^®, to a monolithic fabric laminate was investigated in this paper. The process of fabrication is described and the different properties of the material under consideration: interlaminar fracture toughness energy (G_IC), indentation (id) and delamination after impact (A_i) and compression after impact (σ_CAI), were measured and compared with those of the original monolithic fabric.     

An assessment of methods to determine the directional moisture diffusion coefficients of composite materials

An assessment was made of methods of determining the directional moisture diffusivities in a unidirectional carbon–fibre/epoxy composite with a distinctly anisotropic microstructure. Experimental data were collected for samples cut from 25 mm thick panels in three orthogonal directions during conditioning in water and humid environments. Using the full 3D Fickian solution and an optimisation process on the full data set was the best method of determining the diffusivities. Diffusivity across the fibres was 40% and through thickness diffusivity was 13% of that along fibres, which was found to be close to that of the unreinforced resin. A critical analysis was made of methods of approximating the 3D Fickian solution.