A theoretical assessment of surface defect machining and hot machining of nanocrystalline silicon carbide

In this paper, a newly proposed machining method named “surface defect machining” (SDM) [Wear, 302, 2013 (1124-1135)] was explored for machining of nanocrystalline beta silicon carbide (3C-SiC) at 300K using MD simulation. The results were compared with isothermal high temperature machining at 1200K under the same machining parameters, emulating ductile mode micro laser assisted machining (µ-LAM) and with conventional cutting at 300 K. In the MD simulation, surface defects were generated on the top of the (010) surface of the 3C-SiC work piece prior to cutting, and the workpiece was then cut along the <100> direction using a single point diamond tool at a cutting speed of 10 m/sec. Cutting forces, sub-surface deformation layer depth, temperature in the shear zone, shear plane angle and friction coefficient were used to characterize the response of the workpiece. Simulation results showed that SDM provides a unique advantage of decreased shear plane angle which eases the shearing action. This in turn causes an increased value of average coefficient of friction in contrast to the isothermal cutting (carried at 1200 K) and normal cutting (carried at 300K). The increase of friction coefficient however was found to aid the cutting action of the tool due to an intermittent dropping in the cutting forces, lowering stresses on the cutting tool and reducing operational temperature. Analysis shows that the introduction of surface defects prior to conventional machining can be a viable choice for machining a wide range of ceramics, hard steels and composites compared to hot machining.

Topical Review: The current understanding on the diamond machining of silicon carbide

The Glenn Research Centre of NASA, USA (www.grc.nasa.gov/WWW/SiC/, silicon carbide electronics) is in pursuit of realizing bulk manufacturing of silicon carbide (SiC), specifically by mechanical means. Single point diamond turning (SPDT) technology which employs diamond (the hardest naturally-occurring material realized to date) as a cutting tool to cut a workpiece is a highly productive manufacturing process. However, machining SiC using SPDT is a complex process and, while several experimental and analytical studies presented to date aid in the understanding of several critical processes of machining SiC, the current knowledge on the ductile behaviour of SiC is still sparse. This is due to a number of simultaneously occurring physical phenomena that may take place on multiple length and time scales. For example, nucleation of dislocation can take place at small inclusions that are of a few atoms in size and once nucleated, the interaction of these nucleations can manifest stresses on the micrometre length scales. The understanding of how stresses manifest during fracture in the brittle range, or dislocations/phase transformations in the ductile range, is crucial in understanding the brittle–ductile transition in SiC. Furthermore, there is a need to incorporate an appropriate simulation-based approach in the manufacturing research on SiC, owing primarily to the number of uncertainties in the experimental research that includes wear of the cutting tool, poor controllability of the nano-regime machining scale (effective thickness of cut), and coolant effects (interfacial phenomena between the tool, workpiece/chip and coolant), etc. In this review, these two problems are combined together to posit an improved understanding on the current theoretical knowledge on the SPDT of SiC obtained from molecular dynamics simulation.

Long-Range Lateral Dopant Diffusion in Tungsten Silicide Layers

Novel diode test structures have been manufactured to characterize long-range dopant diffusion in tungsten silicide layers. A tungsten silicide to p-type silicon contact has been characterized as a Schottky barrier rectifying contact with a silicide work function of 4.8 eV. Long-range diffusion of boron for an anneal at 900 °C for 30 min has been shown to alter this contact to become ohmic. Long-range diffusion of phosphorus with a similar anneal alters the contact to become a bipolar n-p diode. Bipolar diode action is demonstrated experimentally for anneal schedules of 30 min at 900 °C, indicating long-range diffusion of phosphorus (~38 µm), SIMS analysis shows dopant redistribution is adversely affected by segregation to the silicide/oxide interface. The concept of conduit diffusion has been demonstrated experimentally for application in advanced bipolar transistor technology. © 2009 IEEE.

Performance and wear of coated carbide drill in machining of carbon fibre reinforced composite/titanium stack

In this research we investigate the performance of drilling process in carbon fibre reinforced composite (CFC) material, titanium alloy and the hybrid stack of these two materials, using coated carbide drill bit. We study the effect of the process parameters such as the feed rate and speed on the induced forces and torques, also on the wear of drill and surface roughness of the holes. In the composite material the percentage of surface damage in both drilling CFC on its own and drilling in stack form is estimated. Also, the effect of worn drill on the surface damage is identified. In the titanium, the burr formation in stack and non-stack form is investigated. The wear of the drill results in increased forces and torques required for drilling. This increases the surface delaminations substantially at the entrance in drilling of CFC. However, the surface roughness of the holes reduces with the wear of the drill in CFC drilling. Also, the surface delamination and surface roughness of the holes in the CFC whilst drilled in hybrid form reduces significantly. This is despite the increase of the forces and torques required in drilling CFC in stack form. Copyright © 2012 Inderscience Enterprises Ltd.

ELM-induced transient tungsten melting in the JET divertor

The original goals of the JET ITER-like wall included the study of the impact of an all W divertor on plasma operation (Coenen et al 2013 Nucl. Fusion 53 073043) and fuel retention (Brezinsek et al 2013 Nucl. Fusion 53 083023). ITER has recently decided to install a full-tungsten (W) divertor from the start of operations. One of the key inputs required in support of this decision was the study of the possibility of W melting and melt splashing during transients. Damage of this type can lead to modifications of surface topology which could lead to higher disruption frequency or compromise subsequent plasma operation. Although every effort will be made to avoid leading edges, ITER plasma stored energies are sufficient that transients can drive shallow melting on the top surfaces of components. JET is able to produce ELMs large enough to allow access to transient melting in a regime of relevance to ITER.

Transient W melt experiments were performed in JET using a dedicated divertor module and a sequence of I-P = 3.0 MA/B-T = 2.9 T H-mode pulses with an input power of P-IN = 23 MW, a stored energy of similar to 6 MJ and regular type I ELMs at Delta W-ELM = 0.3 MJ and f(ELM) similar to 30 Hz. By moving the outer strike point onto a dedicated leading edge in the W divertor the base temperature was raised within similar to 1 s to a level allowing transient, ELM-driven melting during the subsequent 0.5 s. Such ELMs (delta W similar to 300 kJ per ELM) are comparable to mitigated ELMs expected in ITER (Pitts et al 2011 J. Nucl. Mater. 415 (Suppl.) S957-64).

Although significant material losses in terms of ejections into the plasma were not observed, there is indirect evidence that some small droplets (similar to 80 mu m) were released. Almost 1 mm (similar to 6 mm(3)) of W was moved by similar to 150 ELMs within 7 subsequent discharges. The impact on the main plasma parameters was minor and no disruptions occurred. The W-melt gradually moved along the leading edge towards the high-field side, driven by j x B forces. The evaporation rate determined from spectroscopy is 100 times less than expected from steady state melting and is thus consistent only with transient melting during the individual ELMs. Analysis of IR data and spectroscopy together with modelling using the MEMOS code Bazylev et al 2009 J. Nucl. Mater. 390-391 810-13 point to transient melting as the main process. 3D MEMOS simulations on the consequences of multiple ELMs on damage of tungsten castellated armour have been performed.

These experiments provide the first experimental evidence for the absence of significant melt splashing at transient events resembling mitigated ELMs on ITER and establish a key experimental benchmark for the MEMOS code.

Activity and coke formation of nickel and nickel carbide in dry reforming: A deactivation scheme from density functional theory

Dry reforming is a promising reaction to utilise the greenhouse gases CO2 and CH4. Nickel-based catalysts are the most popular catalysts for the reaction, and the coke formation on the catalysts is the main obstacle to the commercialisation of dry reforming. In this study, the whole reaction network of dry reformation on both flat and stepped nickel catalysts (Ni(111) and Ni(211)) as well as nickel carbide (flat: Ni3C(001); stepped: Ni3C(111)) is investigated using density functional theory calculations. The overall reaction energy profiles in the free energy landscape are obtained, and kinetic analyses are utilised to evaluate the activity of the four surfaces. By careful examination of our results, we find the following regarding the activity: (i) flat surfaces are more active than stepped surfaces for the dry reforming and (ii) metallic nickel catalysts are more active than those of nickel carbide, and therefore, the phase transformation from nickel to nickel carbide will reduce the activity. With respect to the coke formation, the following is found: (i) the coke formation probability can be measured by the rate ratio of CH oxidation pathway to C oxidation pathway (r(CH)/r(C)) and the barrier of CO dissociation, (ii) on Ni(111), the coke is unlikely to form, and (iii) the coke formations on the stepped surfaces of both nickel and nickel carbide can readily occur. A deactivation scheme, using which experimental results can be rationalised, is proposed. 

Comment on "multiconfiguration Dirac-Fock energy levels and radiative rates for Br-like tungsten" by S. Aggarwal, A.K.S. Jha, and M. Mohan [Can. J. Phys. 91, 394 (2013)]

We report calculations of energy levels and oscillator strengths for transitions in W XL, undertaken with the general-purpose relativistic atomic structure package (GRASP) and flexible atomic code (FAC). Comparisons are made with existing results and the accuracy of the data is assessed. Discrepancies with the most recent results of S. Aggarwal et al. (Can. J. Phys. 91, 394 (2013)) are up to 0.4 Ryd and up to two orders of magnitude for energy levels and oscillator strengths, respectively. Discrepancies for lifetimes are even larger, up to four orders of magnitude for some levels. Our energy levels are estimated to be accurate to better than 0.5% (i.e., 0.2 Ryd), whereas results for oscillator strengths and lifetimes should be accurate to better than 20%.

Microstructural evolution and mechanical properties of short-term thermally exposed 9/12Cr heat-resistant steels

The microstructural evolution during short-term (up to 3000 hours) thermal exposure of three 9/12Cr heat-resistant steels was studied, as well as the mechanical properties after exposure. The tempered martensitic lath structure, as well as the precipitation of carbide and MX type carbonitrides in the steel matrix, was stable after 3000 hours of exposure at 873 K (600 °C). A microstructure observation showed that during the short-term thermal exposure process, the change of mechanical properties was caused mainly by the formation and growth of Laves-phase precipitates in the steels. On thermal exposure, with an increase of cobalt and tungsten contents, cobalt could promote the segregation of tungsten along the martensite lath to form Laves phase, and a large size and high density of Laves-phase precipitates along the grain boundaries could lead to the brittle intergranular fracture of the steels.

Importance of surface carbide formation on the activity and selectivity of Pd surfaces in the selective hydrogenation of acetylene

A recent experimental investigation (Kim et al. J. Catal. 306 (2013) 146-154) on the selective hydrogenation of acetylene over Pd nanoparticles with different shapes concluded that Pd(100) showed higher activity and selectivity than Pd(111) for acetylene hydrogenation. However, our recent density functional calculations (Yang et al. J. Catal. 305 (2013) 264-276) observed that the clean Pd(111) surface should result in higher activity and ethylene selectivity compared with the clean Pd(100) surface for acetylene hydrogenation. In the current work, using density functional theory calculations, we find that Pd(100) in the carbide form gives rise to higher activity and selectivity than Pd(111) carbide. These results indicate that the catalyst surface is most likely in the carbide form under the experimental reaction conditions. Furthermore, the adsorption energies of hydrogen atoms as a function of the hydrogen coverage at the surface and subsurface sites over Pd(100) are compared with those over Pd(111), and it is found that the adsorption of hydrogen atoms is always less favoured on Pd(100) over the whole coverage range. This suggests that the Pd(100) hydride surface will be less stable than the Pd(111) hydride surface, which is also in accordance with the experimental results reported.

Electron-impact excitation and ionization of W 3+ for the determination of tungsten influx in a fusion plasma

Tungsten will be employed as a plasma facing material in the ITER fusion reactor under construction in Cadarache, France; therefore, there is a significant need for accurate electron-impact excitation and ionization data for the ions of tungsten. We report on the results of extensive calculations of ionization and excitation for W 3+ that are intended to provide the atomic data needed for the determination of impurity influx diagnostics of tungsten in several existing tokamak reactors. The electron-impact excitation rate coefficients for this study were determined using the relativistic R -matrix method. The contribution to direct electron-impact ionization was determined using the distorted-wave approximation, the accuracy of which was verified by an R -matrix with pseudo states calculation. Contributions to total ionization from excitation autoionization were also generated from the relativistic R -matrix method. These results were then employed to calculate values of ionization per emitted photon, or SXB ratios, for four carefully selected spectral lines; these data will allow the determination of impurity influx from tungsten facing surfaces. For the range of densities of importance in the edge region of a tokamak reactor, these SXB ratios are found to be nearly independent of electron density but vary significantly with electron temperature.

Polytypism and Silicon carbide : a solid state nuclear magnetic resonance study

A survey of predominantly industrial silicon carbide has been carried out using Magic Angle Spinning nuclear magnetic resonance (MAS nmr); a solid state technique. Three silicon carbide polytypes were studied; 3C, 6H, and 15R. The 13C and 29 Si MAS nmr spectra of the bulk SiC sample was identified on the basis of silicon (carbon) site type in the d iff ere n t pol Y t Y pes • Out to 5.00 A fro mac en t r a lsi 1 i con (0 r carbon) atom four types of sites were characterized using symmetry based calculations. This method of polytype analysis was also considered, in the prelminary stages, for applications with other polytypic material; CdBr 2 , CdI 2 , and PbI 2 " In an attempt to understand the minor components of silicon carbide, such as its surface, some samples were hydrofluoric acid washed and heated to extreme temperatures. Basically, an HF removable species which absorbs at -110 ppm (Si0 2 ) in the 29 Si MAS nmr spectrum is found in silicon carbide after heating. Other unidentified peaks observed at short recycle delays in some 29 Si MAS nmr spectra are considered to be impurities that may be within the lattice. These components comprise less than 5% of the observable silicon. A Tl study was carried out for 29 Si nuclei in a 3C ii polytype sample, using the Driven Equilibrium Single-Pulse Observation of T1 (DESPOT) technique. It appears as though there are a number of nuclei that have the same chemical shift but different T1 relaxation times. The T1 values range from 30 seconds to 11 minutes. Caution has to be kept when interpreting these results because this is the first time that DESPOT has been used for solid samples and it is not likely in full working order. MAS nmr indicates that the 13C and 29 Si ~sotropic chemical shifts of silicon carbide appear to have a reciprocal type of relationship_ Single crystal nmr analysis of a 6H sample is accordance with this finding when only the resultant isotropic shift is considered. However, single crystal nmr also shows that the actual response of the silicon and carbon nuclear environment to the applied magnetic field at various angles is not at all reciprocal. Such results show that much more single crystal nmr work is required to determine the actual behavior of the local magnetic environment of the SiC nuclei.

Transformation of maize using silicon carbide whiskers

As the most commercially valuable cereal grown worldwide and the best-characterized in genetic terms, maize was predictably the first target for transformation among the important crops. Indeed, the first attempt at transformation of any plant was conducted on maize (1). These early efforts, however, were inevitably unsuccessful, since at that time, there were no reliable methods to permit the introduction of DNA into a cell, the expression of that DNA, and the identification of progeny derived from such a “transgenic” cell (2). Almost 20 years later, these technologies were finally combined, and the first transgenic cereals were produced. In the last few years, methods have become increasingly efficient, and transgenic maize has now been produced from protoplasts as well as from Agrobacterium-medieited or “Biolistic” delivery to embryogenic tissue (for a general comparison of methods used for maize, the reader is referred to a recent review—ref. 3). The present chapter will describe probably the simplest of the available procedures, namely the delivery of DNA to the recipient cells by vortexing them in the presence of silicon carbide (SiC) whiskers (this name will be used in preference to the term “fiber,” since it more correctly describes the single crystal nature of the material).

A tungsten complex containing a highly delocalized metal-ligand system

Nucleophilic attack of (triphenylphosphonio) cyclopentadienide on the dichlorodiazomethane-tungsten complex trans[ BrW(dppe)(2)(N2CCl2)]PF6 [dppe is 1,2-bis(diphenylphosphino) ethane] results in C-C bond formation and affords the title compound, trans-[W(C24H18ClN2P)Br(C26H24P2)(2)]PF6 center dot 0.6CH(2)Cl(2). This complex, bis[1,2- bis(diphenylphosphino)ethane] bromido{chloro[3-(triphenylphosphonio) cyclopentadienylidene] diazomethanediido} tungsten hexafluorophosphate dichloromethane 0.6-solvate, contains the previously unknown ligand chloro[3-(triphenylphosphonio) cyclopentadienylidene] diazomethane. Evidence from bond lengths and torsion angles indicates significant through-ligand delocalization of electron density from tungsten to the nominally cationic phosphorus(V) centre. This structural analysis clearly demonstrates that the tungsten-dinitrogen unit is a powerful pi-electron donor with the ability to transfer electron density from the metal to a distant acceptor centre through an extended conjugated ligand system. As a consequence, complexes of this type could have potential applications as nonlinear optical materials and molecular semiconductors.

Isomeric olefin tetracarbonyl complexes of tungsten(I): an infrared spectroelectrochemical study at low temperatures

In situ electrolysis within an optically transparent thin-layer electrochemical (OTTLE) cell was applied at 293-243 K in combination with FTIR spectroscopy to monitor spectral changes in the carbonyl stretching region accompanying oxidation of four tetracarbonyl olefin complexes of tungsten(0), viz., trans-[W(CO)(4)(eta(2)-ethene)(2)], trans-[W(CO)(4)(eta(2)-norbornene)(2)], [W(CO)(4)(eta(4)-cycloocta-1,5-diene)], and [W(CO)(4)(eta(4)-norbornadiene)]. In all cases, the one-electron-oxidized radical cations (17-electron complexes) have been identified by their characteristic nu(CO) patterns. For the bidentate diene ligands, the cis stereochemistry is essentially fixed in both the 18- and 17-electron complexes. The radical cation of the trans-bis(ethene) complex was observed only at 243 K, while at room temperature it isomerized rapidly to the corresponding cis-isomer. The thermal stability of the three studied radical cations in the cis configuration correlates with the relative strength of the W-CO bonds in the positions trans to the olefin ligand, which are more affected by the oxidation than the axial W-CO bonds. For the bulky norbornene ligands, their trans configuration in the bis(norbornene) complex remains preserved after the oxidation in the whole temperature range studied. The limited thermal stability of the radical cations of the trans-bis(alkene) complexes is ascribed to dissociation of the alkene ligands. The spectroelectrochemical results are in very good agreement with data obtained earlier by DFT (B3LYP) calculations.