Hemilabile phosphine ligands in molybdenum and tungsten octahedral environments

The synthesis of three bidentate, hemilabile phosphine ligands, newly synthesized in the research group (TPOdiphos, DPPrPOdiphos and SODPdiphos), has been up-scaled and optimized. The ligand substitution reaction on Mo(CO)6 and W(CO)6 has been studied and the corresponding complexes fac-[MTPOdiphos(CO)3], fac-[MDPPrPOdiphos(CO)3], and fac-[MSODPdiphos(CO)3], (M= Mo, W) have been isolated in good yields and characterized by NMR, IR and HR MS. In the case of fac- [MoTPOdiphos(CO)3] the XRD crystal structure was resolved. The complexes were found to be octahedral, neutral molecules, with the metal in the zero oxidation state and the ligand adopting a facial P,P,O-coordination. The hard ligand atom (oxygen) is expected to exhibit special features the future applications of these novel ligands.

Evaluation of Carbide Waste Lime for Soil Stabilization, Progress Report, HR-111

A lime by-product from the manufacture of acetylene from calcium carbide will be commercially available in Iowa. Since the cost of carbide waste lime f.o.b. source is only about half that of ordinary commercial lime, this material was investigated for potential uses in soil stabilization. The by-product lime is calcium hydroxide in a water slurry with approximately 40% solid concentration. Its effectiveness at stabilizing soils was checked by comparing with commercial high-calcium and dolomitic monohydrate varieties of lime. This was done by soil strength and plasticity tests in addition to studies of the reaction products by X-ray diffraction and chemical methods.

Real-time monitoring of the silicidation process of tungsten filaments at high temperature used as catalysers for silane decomposition

The scope of this work is the systematic study of the silicidation process affecting tungsten filaments at high temperature (1900ºC) used for silane decomposition in the hot-wire chemical vapour deposition technique (HWCVD). The correlation between the electrical resistance evolution of the filaments, Rfil(t), and the different stages of the their silicidation process is exposed. Said stages correspond to: the rapid formation of two WSi2 fronts at the cold ends of the filaments and their further propagation towards the middle of the filaments; and, regarding the hot central portion of the filaments: a initial stage of silicon dissolution into the tungsten bulk, with a random duration for as-manufactured filaments, followed by the inhomogeneous nucleation of W5Si3 (which is later replaced by WSi2) and its further growth towards the filaments core. An electrical model is used to obtain real-time information about the current status of the filaments silicidation process by simply monitoring their Rfil(t) evolution during the HWCVD process. It is shown that implementing an annealing pre-treatment to the filaments leads to a clearly repetitive trend in the monitored Rfil(t) signatures. The influence of hydrogen dilution of silane on the filaments silicidation process is also discussed.

Monte Carlo derivation of filtered tungsten anode X-ray spectra for dose computation in digital mammography

Abstract Objective: Derive filtered tungsten X-ray spectra used in digital mammography systems by means of Monte Carlo simulations. Materials and Methods: Filtered spectra for rhodium filter were obtained for tube potentials between 26 and 32 kV. The half-value layer (HVL) of simulated filtered spectra were compared with those obtained experimentally with a solid state detector Unfors model 8202031-H Xi R/F & MAM Detector Platinum and 8201023-C Xi Base unit Platinum Plus w mAs in a Hologic Selenia Dimensions system using a direct radiography mode. Results: Calculated HVL values showed good agreement as compared with those obtained experimentally. The greatest relative difference between the Monte Carlo calculated HVL values and experimental HVL values was 4%. Conclusion: The results show that the filtered tungsten anode X-ray spectra and the EGSnrc Monte Carlo code can be used for mean glandular dose determination in mammography.

Degradation of thin tungsten filaments at high temperature in HWCVD

The degradation of the filaments is usually studied by checking the silicidation or carbonization status of the refractory metal used as catalysts, and their effects on the structural stability of the filaments. In this paper, it will be shown that the catalytic stability of a filament heated at high temperature is much shorter than its structural lifetime. The electrical resistance of a thin tungsten filament and the deposition rate of the deposited thin film have been monitored during the filament aging. It has been found that the deposition rate drops drastically once the quantity of dissolved silicon in the tungsten reaches the solubility limit and the silicides start precipitating. This manuscript concludes that the catalytic stability is only guaranteed for a short time and that for sufficiently thick filaments it does not depend on the filament radius.

Flow analysis by using solenoid valves for As(III) determination in natural waters by an on-line separation and pre-concentration system coupled to a tungsten coil atomizer

A flow system coupled to a tungsten coil atomizer in an atomic absorption spectrometer (TCA-AAS) was developed for As(III) determination in waters, by extraction with sodium diethyldithiocarbamate (NaDDTC) as complexing agent, and by sorption of the As(III)-DDTC complex in a micro-column filled with 5 mg C18 reversed phase (10 µL dry sorbent), followed by elution with ethanol. A complete pre-concentration/elution cycle took 208 s, with 30 s sample load time (1.7 mL) and 4 s elution time (71 µL). The interface and software for the synchronous control of two peristaltic pumps (RUN/ STOP), an autosampler arm, seven solenoid valves, one injection valve, the electrothermal atomizer and the spectrometer Read function were constructed. The system was characterized and validated by analytical recovery studies performed both in synthetic solutions and in natural waters. Using a 30 s pre-concentration period, the working curve was linear between 0.25 and 6.0 µg L-1 (r = 0.9976), the retention efficiency was 94±1% (6.0 µg L-1), and the pre-concentration coefficient was 28.9. The characteristic mass was 58 pg, the mean repeatability (expressed as the variation coefficient) was 3.4% (n=5), the detection limit was 0.058 µg L-1 (4.1 pg in 71 µL of eluate injected into the coil), and the mean analytical recovery in natural waters was 92.6 ± 9.5 % (n=15). The procedure is simple, economic, less prone to sample loss and contamination and the useful lifetime of the micro-column was between 200-300 pre-concentration cycles.

NANOPARTICLES OF TUNGSTEN AS LOW-COST MONOMETALLIC CATALYST FOR SELECTIVE HYDROGENATION OF 3-HEXYNE

Low-cost tungsten monometallic catalysts containing variable amounts of metal (4.5, 7.1 and 8.5%W) were prepared by impregnating alumina with ammonium metatungstate as an inexpensive precursor. The catalysts were characterized using ICP, XPS, XRD, TPR and hydrogen chemisorption. These techniques revealed mainly WO3-Al2O3 (W6+) species on the surface. The effects of the content of W nanoparticles and reaction temperature on activity and selectivity for the partial hydrogenation of 3-hexyne, a non-terminal alkyne, were assessed under moderate conditions of temperature and pressure. The monometallic catalysts prepared were found to be active and stereoselective for the production of (Z )-3-hexene, had the following order: 7.1WN/A > 8.5 WN/A ≥ 4.5 WN/A. Additionally, the performance of the synthesized xWN/A catalysts exhibited high sensitivity to temperature variation. In all cases, the maximum 3-hexyne total conversion and selectivity was achieved at 323 K. The performance of the catalysts was considered to be a consequence of two phenomena: a) the electronic effects, related to the high charge of W (+6), causing an intensive dipole moment in the hydrogen molecule (van der Waals forces) and leading to heterolytic bond rupture; the H+ and H- species generated approach a 3-hexyne adsorbate molecule and cause heterolytic rupture of the C≡C bond into C- = C+; and b) steric effects related to the high concentration of WO3 on 8.5WN/A that block the Al2O3 support. Catalyst deactivation was detected, starting at about 50 min of reaction time. Electrodeficient W6+ species are responsible for the formation of green oil at the surface level, blocking pores and active sites of the catalyst, particularly at low reaction temperatures (293 and 303 K). The resulting best catalyst, 7.1WN/A, has low fabrication cost and high selectivity for (Z )-3-hexene (94%) at 323 K. This selectivity is comparable to that of the classical and more expensive industrial Lindlar catalyst (5 wt% Pd). The alumina supported tungsten catalysts are low-cost potential replacements for the Lindlar industrial catalyst. These catalysts could also be used for preparing bimetallic W-Pd catalysts for selective hydrogenation of terminal and non-terminal alkynes.

Weld joint characteristics by nano-materials addition

The need for industries to remain competitive in the welding business, has created necessity to develop innovative processes that can exceed customer’s demand. Significant development in improving weld efficiency, during the past decades, still have their drawbacks, specifically in the weld strength properties. The recent innovative technologies have created smallest possible solid material known as nanomaterial and their introduction in welding production has improved the weld strength properties and to overcome unstable microstructures in the weld. This study utilizes a qualitative research method, to elaborate the methods of introducing nanomaterial to the weldments and the characteristic of the welds produced by different welding processes. The study mainly focuses on changes in the microstructural formation and strength properties on the welded joint and also discusses those factors influencing such improvements, due to the addition of nanomaterials. The effect of nanomaterial addition in welding process modifies the physics of joining region, thereby, resulting in significant improvement in the strength properties, with stable microstructure in the weld. The addition of nanomaterials in the welding processes are, through coating on base metal, addition in filler metal and utilizing nanostructured base metal. However, due to its insignificant size, the addition of nanomaterials directly to the weld, would poses complications. The factors having major influence on the joint integrity are dispersion of nanomaterials, characteristics of the nanomaterials, quantity of nanomaterials and selection of nanomaterials. The addition of nanomaterials does not affect the fundamental properties and characteristics of base metals and the filler metal. However, in some cases, the addition of nanomaterials lead to the deterioration of the joint properties by unstable microstructural formations. Still research are ongoing to achieve high joint integrity, in various materials through different welding processes and also on other factors that influence the joint strength.

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.

On the preparation of clean tungsten single crystals

The cleaning procedure consists of two-step-flashing: (i) cycles of low power flashes T similar to 1200 K) at an oxygen partial pressure of P(o2) = 6 x 10(-8) mbar, to remove the carbon from the surface, and (ii) a single high power flash (T similar to 2200 K), to remove the oxide layer. The removal of carbon from the surface through the chemical reaction with oxygen during low power flash cycles is monitored by thermal desorption spectroscopy. The exposure to O(2) leads to the oxidation of the W surface. Using a high power flash, the volatile W-oxides and the atomic oxygen are desorbed, leaving a clean crystal surface at the end of procedure. The method may also be used for cleaning other refractory metals like Mo, Re and It. (C) 2009 Elsevier B.V. All rights reserved.

Design/Evaluation of A Methodology For Performance Optimization Of Indexable Carbide Inserts

In this project, two broad facets in the design of a methodology for performance optimization of indexable carbide inserts were examined. They were physical destructive testing and software simulation.For the physical testing, statistical research techniques were used for the design of the methodology. A five step method which began with Problem definition, through System identification, Statistical model formation, Data collection and Statistical analyses and results was indepthly elaborated upon. Set-up and execution of an experiment with a compression machine together with roadblocks and possible solution to curb road blocks to quality data collection were examined. 2k factorial design was illustrated and recommended for process improvement. Instances of first-order and second-order response surface analyses were encountered. In the case of curvature, test for curvature significance with center point analysis was recommended. Process optimization with method of steepest ascent and central composite design or process robustness studies of response surface analyses were also recommended.For the simulation test, AdvantEdge program was identified as the most used software for tool development. Challenges to the efficient application of this software were identified and possible solutions proposed. In conclusion, software simulation and physical testing were recommended to meet the objective of the project.