Potassium sorbate solutions as copper chemical mechanical planarization (CMP) based slurries

Copper depassivation and repassivation characteristics in potassium sorbate solutions, subsequent to mechanical abrading are reported. The identification of copper repassivation kinetics obtained subsequent to mechanical damage of copper protective films formed in sorbate based solutions is discussed. The repassivation rate of copper in sorbate based solutions was measured by means of a slurryjet system capable of measuring single particle impingments on microelectrodes. Copper repassivation rates measured by this slurryjet system in sulfate solutions containing 10 g L⁻¹ potassium sorbate were found to be in the range of 0.5-1.5 ms. An increase in the potassium sorbate concentration leads to a decrease in copper repassivation time at potentials ranging from 200 to 600 mV_Ag/AgCl. The impingement angle between the copper surface and a single abrasive particle has no impact on copper repassivation time nor peak current (I_max) values. XPS studies revealed that copper passivation in potassium based solution was due to the formation of a thin film which is constituted of: Cu₂O, Cu(OH)₂ and Cu(II)-sorbate, while copper(II)-sorbate is mainly present at the top levels of the passive film. It is therefore recommended that the use of potassium sorbate as a passivating component in conjunction with the addition of strong oxidizing agents in chemical mechanical planarization (CMP) slurry design should be considered.     

Microstructure and Microchemistry of Polymer-Derived Crystalline SiC Fibers

Stoichiometric and near-stoichiometric silicon carbide fibers, derived from the polymer polycarbosilane, have been characterized by scanning Auger and transmission electron microscope techniques. Excess carbon usually appeared in the fibers, but it could be eliminated by controlling processing conditions. The fibers consisted mainly of submicrometer-sized SiC microcrystals, with a considerably twinned and stacking-faulted β-SiC structure. Free carbon, which appeared in the form of graphite, was the only detectable intergranular phase in the nonstoichioinetric SiC fibers, while the stoichiometric SiC fibers contained no detectable second phase whatsoever.     

Structure/property relationships in flexible alkoxysilane automotive coatings

Flexible automotive coatings are susceptible to scratch and mar damage, especially during finishing and assembly operations. One-component (1K) flexible clearcoats exhibit very good scratch and mar resistance, but unfortunately suffer from poor durability and environmental etch resistance. Two-component clearcoats offer improvements in both etch and durability, but at the expense of scratch and mar. In this paper, the concept and properties of 1K flexibilized silane clearcoats for use on automotive plastics will be introduced and their structure/property relationships examined as they apply to scratch and mar. The role of coating crosslink density, toughness, glass transition temperature (T_g), and surface profile on the scratch damage of coated plastic substrates will be described. In addition, a new scratch methodology, termed Scratcho, is utilized to determine relative scratch performance and is compared to conventional scratch resistance testing. Results to date indicate that hardness, as affected by the glass transition temperature, and crosslink density, as it contributes to higher essential work values, both affect resultant scratch propensity of the flexible coatings. The relative ranking of different coating systems employing alternate crosslinkers (e.g., isocyanate and melamine) is also presented and compared to the newly developed silane crosslinked coatings. Presented at the 28th International Waterborne, High-Soids, and Powder Coatings Symposium, Feb. 21–23, 2001, in New Orleans. LA. 377 Fairall St., Ajax, Ont., L1S 1R7, Canada. 401 Southfield Rd., P.O. Box 6231, Dearborn, MI 48121-6231.     

Photocatalytic mineralisation of organic compounds: a comparison of flame-made TiO2 catalysts

A comparative photocatalytic analysis was carried out on TiO₂ made in a Flame Spray Pyrolysis (FSP) process and flame-made Degussa P25. Both have similar crystallinity, phase composition, phase segregation and a non-porous surface. Hence comparison was made based on their difference in specific surface area, organic adsorption and the amount of OH• generated upon illumination. The photocatalytic activity tests were carried out using the following series of organic compounds: sucrose, glucose, fructose, maleic acid, glyoxylic acid, oxalic acid, isobutyric acid, phenol and methanol. FSP-made TiO₂ outperformed P25 for saccharides mineralisation, while for phenol and methanol mineralisation P25 was better than FSP-made TiO₂. Similar mineralisation rates were observed for both FSP-made and P25 TiO₂ for the mineralisation of carboxylic acids. This shows that the relative performance of the photocatalysts depends on the type of organic compounds to be degraded. The high surface area and possibly a more efficient interfacial charge transfer of FSP-made TiO₂ provided an efficient pathway for saccharides mineralisation. As for phenol and methanol, the mineralisation rates were higher when using P25 due to the greater amount of OH• radicals generated by this photocatalyst. The fast mineralisation rates of carboxylic acids made degradation of these organic compounds to be less affected by the TiO₂ photocatalyst properties and conditions tested in this work.     

Modeling the large‐strain constitutive behavior of polycarbonate under isothermal and anisothermal conditions

The tensile behavior of polycarbonate was studied at large strains below the glass‐transition temperature. Experiments were carried out at a series of constant temperatures and also under conditions of falling temperatures. The specimens necked with a natural draw ratio of approximately 2, and the study was mainly focused on the necked material. Isothermal experiments revealed an elastic mechanism that initiated beyond the natural draw ratio. A model consisting of an Eyring process and two Gaussian elastic mechanisms was found to be applicable to both the isothermal and anisothermal stress‐relaxation and stress–strain results. The same model also produced reasonable estimates of the stresses generated during the necking process. In addition, a simple relationship between the isothermal and anisothermal stress relaxation was demonstrated. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 2105–2116, 2005     

Ammoxidation of toluene over Y-Ba-Cu-Co-O perovskites

Ammoxidation of toluene over the perovskites YBa₂Cu₃O_6.1, YBa₂Cu₂CoO_6.7 and YBaCuCoO_4.9 was investigated at 400 °C. At low partial pressures of O₂ benzonitrile was selectively formed, while CO₂ was the main product at high pressures of O₂. Systematic differences in activity were observed for the three phases and are related to the crystal contents of Cu and Co. At low O₂ pressures, Cu-sites are active for nitrile formation, while Co-sites give CO₂. At high O₂ pressures, the activity for CO₂ of Cu-sites increases more than that of Co-sites due to filling of near-surface oxygen vacancies.     

Relationship between chemical degradation and thickness loss of an amine-cured epoxy coating exposed to different UV environments

The relationship between chemical degradation and thickness loss of an unpigmented, non UV-stabilized, crosslinked amine-cured epoxy coating exposed to three UV conditions was investigated. Spin-coated samples having a thickness of approximately 7 μm on an Si substrate were prepared from a stochiometric mixture of a bisphenol A epoxy resin and a tetra-functional amine curing agent. Samples were exposed outdoors and to two accelerated laboratory UV environments. Chemical degradation and thickness loss were measured by transmission Fourier transform infrared spectroscopy (FTIRS) and laser scanning confocal microscopy (LSCM), respectively. In addition, surface roughness and morphological changes were measured by atomic forcemicrosocopy (AFM) and LSCM. Substantial chemical degradation, thickness loss, and morpholocal changes occurred in the exposed films, and the rate of chemical degradation was greater than that due to the thickness loss. This additional chemical loss was attributed to an inhomogeneous degradation process in which nanoscale localized depressions initiate at certain sites on the surface, which then enlarge and deepen with exposure time. The results of this study provide a better understanding of the degradation mechanism and should lead to the development of scientific-based models for predicting the service life of crosslinked amine-cured epoxy coatings. Presented at the 82nd Annual Meeting of the Federation of Societies for Coatings Technology, October 27–29, 2004, in Chicago, IL     

Pt-V2O5-WO3/TiO2 catalysts supported on SiC filter for NO reduction at low temperature

The catalytic filter, V₂O₅-WO₃-TiO₂ supported on a ceramic filter, is known as a promising material for treating particulates and NO _x simultaneously at optimum temperatures around 320°C. In order to improve its catalytic activity at low temperatures, the effect of Pt addition on the catalytic filter has been investigated. Catalytic filters, Pt-V₂O₅-WO₃-TiO₂/SiC, were prepared by co-impregnation of Pt, V, and W precursors on TiO₂ coated-SiC filter by vacuum aided-dip coating. The Pt-added catalytic filter shifted the optimum working temperature from 280–330°C (for the non Pt-impregnated filter) to 180–230°C, providing N _x slip concentration less than 20 ppm for the treatment of 700 ppm NO at a face velocity of 2 cm/s with the same value over the non Pt-added catalytic filters. The promotional effect following the addition of Pt is believed to result from electrical modification of the catalyst maintaining a high electron transfer state. Ammonia oxidation was also observed to be dominant above the optimal temperature for SCR.     

Interactions between immunoglobulin-like and catalytic modules in Clostridium thermocellum cellulosomal cellobiohydrolase CbhA

Cellobiohydrolase CbhA from Clostridium thermocellum cellulosome is a multi-modular protein composed starting from the N-terminus of a carbohydrate-binding module (CBM) of family 4, an immunoglobulin(Ig)-like module, a catalytic module of family 9 glycoside hydrolases (GH9), X1(1) and X1(2) modules, a CBM of family 3 and a dockerin module. Deletion of the Ig-like module from the Ig-GH9 construct results in complete inactivation of the GH9 module. The crystal structure of the Ig-GH9 module pair reveals the existence of an extensive module interface composed of over 40 amino acid residues of both modules and maintained through a large number of hydrophilic and hydrophobic interactions. To investigate the importance of these interactions between the two modules, we compared the secondary and tertiary structures and thermostabilities of the individual Ig-like and GH9 modules and the Ig-GH9 module pair using both circular dichroism (CD) spectroscopy and differential scanning calorimetry (DSC). Thr230, Asp262 and Asp264 of the Ig-like module are located in the module interface of the Ig-GH9 module pair and are suggested to be important in 'communication' between the modules. These residues were mutated to alanyl residues. The structure, stability and catalytic properties of the native Ig-GH9 and its D264A and T230A/D262A mutants were compared. The results indicate that despite being able to fold relatively independently, the Ig-like and GH9 modules interact and these interactions affect the final fold and stability of each module. Mutations of one or two amino acid residues lead to destabilization and change of the mechanism of thermal unfolding of the polypeptides. The enzymatic properties of native Ig-GH9, D264A and T230A/D262A mutants are similar. The results indicate that inactivation of the GH9 module occurs as a result of multiple structural disturbances finally affecting the topology of the catalytic center.     

Explicit reference modeling methodology in parametric CAD system

Today parametric associative CAD systems must help companies to create more efficient virtual development processes. While dealing with complex parts (e.g. the number of surfaces of the solid) no CAD modeling methodology is existing. Based on the analysis of industrial designers' practices as well as student practices on CAD, we identified key factors that lead to better performance. Our objective in this article is to propose a practical method for complex parts modeling in parametric CAD system. An illustration of the performances and the results obtained by this method are presented comparing the traditional method with the proposed one while using an academic case and then an industrial case.