A kind of carbon whiskers in new structure and morphology

Carbon whiskers with new structure and morphology were observed when heating the milled graphite. Transmission electron microscopy (TEM) and high resolution electron microscopy (HREM) show that carbon layers are almost perpendicular to the growth axes of carbon whiskers. Field emission scanning electron microscopy (FESEM) indicates that there are spirals appearing on the surface of the whiskers. The structure analysis shows that the growth mechanism of carbon whiskers is related to the trace amount of ZrC in the heated samples.     

聚乙烯载体催化剂的制备与表征

不同目数的聚乙烯粉末通过辐射方法接枝了4-乙烯基吡啶官能团.经甲基铝氧烷(MAO)预处理后负载了茂金属催化剂Cp₂ZrCl₂.光电子能谱和红外光谱结果表明催化剂通过MAO的作用负载在聚乙烯接枝4-乙烯基吡啶聚合物上.4-乙烯基吡啶的接枝含量、催化剂的负载率以及载体催化剂对乙烯单体的活性均随着聚乙烯粉末的颗粒减小而增大.     

Characterizing the ZrC(111)/c-ZrO2(111) Hetero-Ceramic Interface: First Principles DFT and Atomistic Thermodynamic Modeling

The mechanical and physical properties of zirconium carbide (ZrC) are limited to its ability to deteriorate in oxidizing environments. Low refractory oxides are typically formed as layers on ZrC surfaces when exposed to the slightest concentrations of oxygen. However, this carbide has a wide range of applications in nuclear reactor lines and nozzle flaps in the aerospace industry, just to name a few. To develop mechanically strong and oxygen-resistant ZrC materials, the need for studying and characterizing the oxidized layers, with emphasis on the interfacial structure between ZrC and the oxidized phases, cannot be understated. In this paper, the ZrC(111)//c-ZrO₂ (111) interface was studied by both finite temperature molecular dynamic simulation and DFT. The interfacial mechanical properties were characterized by the work of adhesion which revealed a Zr|OO|Zr|OO//ZrC(111) interface model as the most stable with an oxygen layer from ZrO₂ being deposited on the ZrC(111) surface. Further structural analysis at the interface showed a crack in the first ZrO₂ layer at the interfacial region. Investigations of the electronic structure using the density of state calculations and Bader charge analysis revealed the interfacial properties as local effects with no significant impacts in the bulk regions of the interface slab.     

Preparation of ZrC nano-particles reinforced amorphous carbon composite coating by atmospheric pressure chemical vapor deposition

To eliminate cracks caused by thermal expansion mismatch between ZrC coating and carbon-carbon composites, a kind of ZrC/C composite coating was designed as an interlayer. The atmospheric pressure chemical vapor deposition was used as a method to achieve co-deposition of ZrC and C from ZrCl₄-C₃H₆-H₂-Ar source. Zirconium tetrachloride (ZrCl₄) powder carrier was especially made to control accurately the flow rate. The microstructure of ZrC/C composite coating was studied using analytical techniques. ZrC/C coating shows same morphology as pyrolytic carbon. Transmission electron microscopy (TEM) shows ZrC grains with size of 10-50 nm embed in turbostratic carbon. The formation mechanism is that the growth of ZrC crystals was inhibited by surrounding pyrolytic carbon and kept as nano-particles. Fracture morphologies imply good combination between coating and substrate. The ZrC crystals have stoichiometric proportion near 1, with good crystalline but no clear preferred orientation while pyrolytic carbon is amorphous. The heating-up oxidation of ZrC/C coating shows 11.58 wt.% loss. It can be calculated that the coating consists of 74.04 wt.% ZrC and 25.96 wt.% pyrolytic carbon. The average density of the composite coating is 5.892 g/cm³ by Archimedes’ principle.     

Synthesis and characterization of a novel precursor‐derived ZrC/ZrB2 ultra‐high‐temperature ceramic composite

ZrC and ZrB₂, two valuable members of ultra‐high‐temperature ceramics (UHTCs), are potentially useful as structural materials in aerospace engineering and hypersonic flight vehicles. This work focused on the preparation of ZrC/ZrB₂ UHTC composite by employing a precursor‐derived method. The precursor polymer PZCB was synthesized by the reaction between Cp₂Zr(CH═CH₂)₂ and borane. The composition, structure, element distribution and pyrolysis process of PZCB were investigated by NMR, IR, X‐ray photoelectron spectroscopy, scanning electron microscopy and TGA. The ceramic yield was 50% and the obtained well‐distributed ZrC/ZrB₂ ceramic composites had very good high‐temperature resistance. Copyright © 2012 John Wiley & Sons, Ltd.     

Chemical composition of ZrC thin films grown by pulsed laser deposition

ZrC films were grown on (1 0 0) Si substrates by the pulsed laser deposition (PLD) technique using a KrF excimer laser working at 40 Hz. The nominal substrate temperature during depositions was set at 300 °C and the cooling rate was 5 °C/min. X-ray diffraction investigations showed that films deposited under residual vacuum or under 2 × 10⁻³ Pa of CH₄ atmosphere were crystalline, exhibiting a (2 0 0)-axis texture, while those deposited under 2 × 10⁻² Pa of CH₄ atmosphere were found to be equiaxed and with smaller grain size. The surface elemental composition of as-deposited films, analyzed by Auger electron spectroscopy (AES) and X-ray photoelectron spectroscopy (XPS), showed the usual high oxygen contamination of carbides. Once the topmost 2-4 nm region was removed, the oxygen concentration rapidly decreased, down to around 3-8% only in bulk. Simulations of the X-ray reflectivity (XRR) curves indicated a smooth surface morphology, with roughness values below 1 nm (rms) and films density values of around 6.30-6.45 g/cm³, very close to the bulk density. The growth rate, estimated from thickness measurements by XRR was around 8.25 nm/min. Nanoindentation results showed for the best quality ZrC films a hardness of 27.6 GPa and a reduced modulus of 228 GPa.     

Epitaxial ZrC thin films grown by pulsed laser deposition

ZrC thin films were grown on (0 0 1)Si, (1 1 1)Si and (0 0 0 1)sapphire substrates by the pulsed laser deposition (PLD) technique. X-ray diffraction, X-ray reflectivity and Auger electron spectroscopy investigations were used to characterize the structure and composition of the deposited films. It has been found that films grown at temperatures higher than 700 °C under very low water vapor pressures were highly textured. Films deposited on (0 0 1)Si grew with the (0 0 1) axis perpendicular to the substrate, while those deposited on (1 1 1)Si and (0 0 0 1)sapphire grew with the (1 1 1) axis perpendicular to the substrate. Pole figures investigations showed that films were epitaxial, with in-plane axis aligned to those of the substrate.     

Synthesis and pyrolysis of a novel preceramic polymer PZMS from PMS to fabricate high‐temperature‐resistant ZrC/SiC ceramic composite

As a valuable ultra‐high‐temperature ceramic (UHTC), ZrC was introduced to SiC ceramic for the preparation of high‐temperature‐resistant ZrC/SiC composite by a polymer‐derived method through the reaction between Cp₂Zr(CH=CH₂)₂ and polymethylsilane (PMS). The composition, structure, element distribution and pyrolysis process of the preceramic polymer polyzirconomethylsilane (PZMS) were investigated by nuclear magnetic resonance, infrared, gel permeation chromatography, X‐ray photoelectron spectroscopy, energy‐dispersive X‐ray spectroscopy, scanning electron microscopy and thermogravimetric analysis. The obtained ZrC/SiC ceramic composites had very good high‐temperature resistance with a weight loss of 7.1% after being subjected to temperatures ranging from 1200 to 2200°C, as the introduction of ZrC prevented the fast growth of crystalline β‐SiC. The ceramic composites prepared by this method were homogeneous with well‐distributed element components, and the ceramic yield reached as high as 78.4%. Copyright © 2013 John Wiley & Sons, Ltd.     

Thermodynamic properties of cubic ZrC under high pressure from first-principles calculations

The elastic and thermodynamic properties of Zirconium carbide (ZrC) are investigated by ab initio plane-wave pseudopotential density function theory method. The obtained lattice constant, elastic constant and bulk modulus B are consistent with the experimental and theoretical data. Through the quasi-harmonic Debye model, the dependences of the normalized volume V/V ₀ and the bulk modulus B on pressure P, as well as the specific heat C _V on the temperature T are obtained successfully. The relationships of the thermal expansion α with temperature and pressure are also investigated, which indicate the temperature hardly has any effect on the thermal expansion α at high pressure. Supported by the National Natural Science Foundation of China (Grant No. 10776022)     

Characteristics of ZrC/ZrN and ZrC/TiN multilayers grown by pulsed laser deposition

ZrC/ZrN and ZrC/TiN multilayers were grown on (1 0 0) Si substrates at 300 °C by the pulsed laser deposition (PLD) technique using a KrF excimer laser. X-ray diffraction investigations showed that films were crystalline, the strain and grain size depending on the nature and pressure of the gas used during deposition. The elemental composition, analyzed by Auger electron spectroscopy (AES) and X-ray photoelectron spectroscopy (XPS), showed that films contained a low level of oxygen contamination. Simulations of the X-ray reflectivity (XRR) curves acquired from films indicated a smooth surface morphology, with roughness below 1 nm (rms) and densities very close to bulk values.Nanoindentation results showed that the ZrC/ZrN and ZrC/TiN multilayer samples exhibited hardness values between 30 and 33 GPa, slightly higher than the values of 28-30 GPa measured for pure ZrC, TiN and ZrN films.