Photolysis of arene chromium tricarbonyl complexes in presence of amine-boranes: Observation of sigma-borane complexes in solution

Activation of the B-H sigma-bond of amine-boranes on the chromium(0) center of arene chromium tricarbonyl complexes (eta(6)-arene) Cr(CO)(3) (arene = fluorobenzene, 1a; benzene, 1b and mesitylene, 1c) has been studied. Photolysis of 1b in presence of ammonia-borane (H3N center dot BH3, AB) and tert-butylamine-borane ((BuH2N)-Bu-t center dot BH3, TBAB) resulted in H-2 evolution and precipitation of a BNHx polymer. On the other hand, photolysis in the presence of trimethylamine-borane (Me3N center dot BH3, TMAB) resulted in the formation of a sigma-borane complex (2) along with Cr(CO)(5)(eta(1)-HBH2 center dot NMe3) (3). The sigma-borane complexes (eta(6)-arene) Cr-( CO)(2)(eta(1)-HBH2 center dot NMe3) (arene = fluorobenzene, 2a; benzene, 2b and mesitylene, 2c) were characterized in solution by H-1, B-11, and C-13 NMR spectroscopy. Electron withdrawing substituents on the arene ring provide the more stable sigma-borane moiety in this series of complexes. (C) 2011 Elsevier B.V. All rights reserved.

Instability map for cold and warm working of as-cast 304 stainless steel

The deformation characteristics of as-cast 304 stainless steel under compression in the temperature range 20-600 degrees C and strain rate range 0.001-100 s(-1) have been studied with a view to characterizing the flow instabilities occurring in the microstructure. Ar strain rates of less than 0.05 s(-1), as-cast 304 stainless steel exhibits flow localization in the temperature range 20-600 degrees C, whereas dynamic strain ageing occurs at intermediate temperatures and below 5 s(-1). At room temperatures and strain rates of less than 0.05 s(-1), martensite formation is observed. To avoid the above microstructural instabilities warm working should be carried out at strain rates greater than 10 s(-1) in the temperature range 400-600 degrees C and cold working could be done in the range of about 0.05-0.8 s(-1). The continuum criterion developed on the basis of the principles of maximum rate of entropy production and separability of the dissipation function, predicts accurately all of the above instability features. (C) 1997 Elsevier Science S.A.

Sliding wear of Al2O3-SiC-(Al,Si) composites against a steel counterface

The sliding-wear behavior of Al2O3-SiC-Al composites prepared by melt oxidation against a steel counterface has been recorded in a pin-on-disk machine. At high speeds and pressures (10 m/s, 20 MPa), friction and wear appear to be principally controlled by the in-situ formation of an interfacial film that consists of a layer of Fe3O4. The formation of this him is examined as a function of sliding speed, lubrication, and composite microstructure. A model is proposed in which high surface temperatures cause the preferential extrusion of aluminum from the composite onto the pin/disk interface. This promotes the adhesive pickup of iron and its oxidation to form a stable tribologically beneficial layer of Fe3O4.

The role of the interface in foam-bearing glass-epoxy composites subjected to impact loading

foam, either stacked together as three layers (MC) or inserted at three different positions (3L) while arranging the stacking sequence during the fabrication of glass fiber-epoxy composites, form the subject of investigation. This stacking variation resulted in a different interfacial area between these foam materials and the glass-epoxy regions in the laminates. This area in designed to be maximum for the 3L variety. The energy of impact being high enough to cause development of the crack in the samples, how the change in interfacial area affects the traverse of the crack front and the failure feature of the laminated composite are reported in the form of photomacrographs in this work. The results point to significant changes for the impact data, like for instance the peak load attained by the different samples, through thickness crack propagation and tensile fracture features on the non-impacted end for the plain variety, separation about the mid-zone for the MC laminates and two or more layer separations for the 3L variety. The separation for the foam-bearing systems occur invariably at the interface and here again one of the (two identical) interfaces only is chosen for the separation.

Studies on the variations in compression strengths of graphite powders bearing glass-epoxy composites exposed to humid conditions

The moisture absorption and changes in compression strengths in glass-epoxy (G-E composites without and with discrete quantities of graphite powders introduced into the resin mix prior to its spreading on specific glass fabric (layers) during the lay-up (stacking) sequence forms the subject matter of this report. The results point to higher moisture absorption for graphite bearing specimens. The strengths of graphite-free coupons show a continuous decrease, while the filler bearing ones show an initial rise followed by a drop for larger exposure times. Scanning Fractographic features were examined for an understanding of the process. The observations were explained invoking the effect of matrix plasticizing and the role of interfacial regions.

Tensile flow behaviour of 2.25Cr-1Mo ferritic steel base metal and simulated heat affected zone structures of 2.25Cr-1Mo weld joint

Tensile tests in the temperature range 298 to 873 K have been performed on 2.25Cr-1Mo base metal and simulated heat affected zone (HAZ) structures of its weld joint, namely coarse grain bainite, fine grain bainite and intercritical structure. Tensile flow behaviour of all the microstructural conditions could be adequately described by the Hollomon equation (sigma = K-1 epsilon(n1)) at higher (> 623 K) temperatures. Deviation from the Hollomon equation was observed at low strains and lower (< 623 K) temperatures. The Ludwigson modification of Hollomon's equation, sigma = K-1 epsilon(n1) + exp (K-2 + n(2) epsilon), was found to describe the flow curve. In general, the flow parameters n(1), K-1, n(2) and K-2 were found to decrease with increase in temperature except in the intermediate temperature range (423 to 623 K). Peaks/plateaus were observed in their variation with temperature in the intermediate temperature range coinciding with the occurrence of serrated flow in the load-elongation curve. The n(1) Value increased and the K-1 value decreased with the type of microstructure in the order: coarse grain bainite, fine grain bainite, base metal and intercritical structure. The variation of nl with microstructure has been rationalized on the basis of mean free path (MFP) of dislocations which is directly related to the inter-particle spacing. Larger MFP of dislocations lead to higher strain hardening exponents n(1).

California bearing ratio behavior of cement-stabilized fly ash-soil mixes

Thermal power stations using pulverized coal as fuel generate large quantities of fly ash as a byproduct, which has created environmental and disposal problems. Using fly ash for gainful applications will solve these problems. Among the various possible uses for fly ash, the most massive and effective utilization is in geotechnical engineering applications like backfill material, construction of embankments, as a subbase material, etc. A proper understanding of fly ash-soil mixes is likely to provide viable solutions for its large-scale utilization. Earlier studies initiated in the laboratory have resulted in a good understanding of the California Bearing Ratio (CBR) behavior of fly ash-soil mixes. Subsequently, in order to increase the CBR value, cement has been tried as an additive to fly ash-soil mixes. This paper reports the results.

Effect of molecular association and reactivity on substitution in chromium(III)-salprn complexes

A new chromium(III)-Schiff base complex, [Cr(5-chlorosalprn)(H2O)(2)]ClO4, where salprn=N,N'-propylenebis(salicylideneimine) has been prepared and characterized by electrospray ionization mass spectrometric (ESIMS) analysis and other spectroscopic techniques. Single crystal X-ray data reveal that the complex assumes a trans-diaquo structure, [Cr(C17H18Cl2N2O4)]ClO4.H2O. The effect of phenyl ring substituents on the rate of formation of [O=Cr-V Schiff base](+) has been investigated. The bimolecular rate constant for the formation of O=Cr-V species by the [Cr(Schiff base)(H2O)(2)]ClO4, where the Schiff base=salprn, (1) and 5-chlorosalprn, (2) with PhOI was compared. In the case of (2) the rate was found to be faster by an order of magnitude at pH=4 compared to (1). The introduction of a chloro-substituent on the phenyl ring not only influences the rate of redox reactivity but also the pKa values of aquo ligands of the complexes, indicating the difference in the electronic environment around the metal ion in both (1) and (2).

Fabrication and evaluation of 450 F electrochemical redox supercapacitors using inexpensive and high-performance, polyaniline coated, stainless-steel electrodes

Redox supercapacitors using polyaniline (PANI) coated. stainless-steel (SS) electrodes have been assembled and characterized. PANI has been deposited on SS substrate by a potentiodynamic method from an acidic electrolyte which contains aniline monomer. By employing stacks of electrodes, each with a geometrical area of 24 cm(2), in acidic perchlorate electrolyte, a capacitance value of about 450 F has been obtained over a long cycle-life. Characterization studies have been carried out by galvanostatic charge-discharge cycling of the capacitors singly, as well as in series and parallel configurations. Various electrical parameters have been evaluated. Use of the capacitors in parallel with a battery for pulse-power loads. and also working of a toy fan connected to the charged capacitors have been demonstrated. A specific capacitance value of about 1300 F g(-1) of PANI has been obtained at a discharge power of about 0.5 kW kg(-1). This value is several times higher than those reported in the literature for PANI and is, perhaps, the highest value known for a capacitor material. The inexpensive SS substrate and the high-capacitance PANI are favorable factors for commercial exploitation. (C) 2002 Elsevier Science B.V. All rights reserved.

Performance of monolithic and TiB2 reinforced MoSi2 in dry sliding contact with steel

MoSi2 and its composite with TiB2 (10 and 20 wt.%) particulates were synthesized by the hot pressing technique. Dry sliding wear experiments were done on these samples by pin-on-disc method on an EN-24 steel disc. It was observed that the densification and the reinforcement of the matrix are beneficial in reducing the friction and wear Of MoSi2. The tribofilm that was formed during sliding contained both the disc and the pin material. (C) 2002 Elsevier Science B.V. All rights reserved.

Potentiodynamically deposited polyaniline on stainless steel - Inexpensive, high-performance electrodes for electrochemical supercapacitors

Polyaniline (PANI) has been studied as an active material for electrochemical capacitors. Polymerization of aniline to PANI has been carried out potentiodynamically on a stainless steel (SS) substrate, instead of Pt-based substrates generally employed for this application. The PANI/SS electrodes have been evaluated by assembling symmetrical capacitors in NaClO(4) + HClO(4) mixed electrolyte and subjecting them to galvanostatic charge/discharge cycles between 0 and 0.75 V. The effect of substrate has been assessed by comparing the capacitance of PANI/SS and PANI/Pt electrodes. The capacitance of PANI/SS electrode is higher than that of PANI/Pt electrode by several times. The effect of sweep rate of potentiodynamic deposition of PANI/SS on capacitance has been investigated. At a power density of 0.5 kW kg(-1), a capacitance value of 815 F g(-1) of PANI is obtained for the deposition sweep rate of 200 mV s(-1). Increase in thickness of PANI on the SS substrate results in an increase in capacitance of PANI. This value of capacitance is the highest ever reported for any electrochemical capacitor material. Thus, in addition to a favorable economic aspect involved in using SS instead of Pt or Pt-based substrate, the advantage of higher capacitance of PANI has also been achieved. (C) 2002 The Electrochemical Society.

Seismic bearing capacity factors for spread foundations

The effect of horizontal earthquake body forces on the bearing capacity of foundations has been examined computationally in a rigorous manner by employing the method of stress characteristics. The bearing capacity factors N-c, N-q and N-y, due to the components of soil cohesion, ground surcharge pressure and soil unit weight respectively, have been plotted as a function of earthquake acceleration coefficient (a(h)) for different values of soil friction angle (phi). The inclusion of earthquake body forces causes a considerable reduction in the bearing capacity factors. The bearing capacity factors N-c and N-q are seen to be approximately of the same magnitude as those reported in the literature on the basis of different solution methods. However, the obtained values of N-y are found to be significantly smaller than the available results. The nature of the pressure distribution along the footing base and the geometry of the observed failure patterns vary with the consideration of earthquake body forces.