Methanol synthesis over Cu/SiO2 catalysts

The rates of CO and CO/CO₂ hydrogenation at 4.2 MPa and 523 K are reported for a series of Cu/SiO₂ catalysts containing 2 to 88 wt.% Cu. These catalysts were prepared on a variety of silica sources using several different Cu deposition techniques. In CO/CO₂ hydrogenation, the rate of methanol formation is proportional to the exposed Cu surface area of the reduced catalyst precursor, as determined by N₂O frontal chromatography. The observed rate, 4.2×10^–3 mole CH₃OH/Cu site-sec, is within a factor of three of the rates reported by others over Cu/ZnO and Cu/ZnO/Al₂O₃ catalysts under comparable conditions. These results suggest that the ZnO component is only a moderate promoter in methanol synthesis. Hydrogenation of CO over these catalysts also gives methanol with high selectivity, but the synthesis rate is not proportional to the Cu surface area. This implies that another type of site, either alone or in cooperation with Cu, is involved in the synthesis of methanol from CO.     

Effect of non‐isothermal processing and moisture content on the anthocyanin degradation and colour kinetics of cherry pomace

Anthocyanins (ACY) and colour changes in cherry pomace under non‐isothermal processing were investigated. Pomace at moisture levels of 70% (MC‐70), 41% (MC‐41) and 25% (MC‐25) was heated at 126.7 °C in a retort for 25, 40 and 60 min. Total ACY, Hunter colour values, total colour difference (ΔE), chroma, hue angle (h°) and browning index (BI) were analysed. Thermal degradation kinetics for colour parameters were determined using zero‐ and first‐order models. ACY degradation increased with heating time and ranged from 34 to 68% for 25 and 60 min heating, respectively. The half‐life of ACY was 38, 33 and 27 min for MC‐70, MC‐41 and MC‐25 pomace, respectively. The ΔE increased with increasing heating time, whereas BI exhibited an inverse trend. Except for ?E for MC‐70, the zero‐order kinetic model showed better fit (R² = 0.85–0.97) to experimental data than the first‐order kinetic model for Hunter colour b values and ?E.     

Kinetics of hydroformylation of 1-octene in ionic liquid-organic biphasic media using rhodium sulfoxantphos catalyst

Biphasic hydroformylation of 1-octene was performed using rhodium sulfoxantphos catalyst dissolved in [BuPy][BF₄] ionic liquid. Preliminary experiments proved this system to retain the catalytic complex within the ionic liquid phase and to maintain a high selectivity towards the linear aldehyde (n:iso ratio of 30) over several cycles. Process parameter investigation showed a first order dependence of the initial rate with respect to the catalyst and 1-octene concentrations, but a more complex behavior with respect to hydrogen (fractional order) and carbon monoxide partial pressures (inhibition at high pressures). Different mathematical models were selected based on the trends observed and evaluated for data fitting. Also, rate models were derived from a proposed mechanism, using Christiansen matrix approach. To calculate concentrations of substrates in the catalytic phase as required by this kinetic modeling, solubility measurements were preformed for the gases (pressure drop technique), as well as for 1-octene and n-nonanal (thermogravimetry analysis).     

Structural,morphological, and dynamic mechanical properties of Zn‐filled Nylon 11

Nylon 11 samples were filled with metal (Zn) fillers of two different concentrations (1 and 5% w/w) each. The samples in the form of disc were obtained by using hot press molder. The structural properties have been investigated using density measurement and wide angle X‐ray diffraction (WAXD) technique. The morphology of pure and Zn‐filled samples has been studied using scanning electron microscopy. Glass transition (T_g) temperature was determined using dynamic mechanical thermal analyzer (DMTA). The result shows that there is slight crystal modification due to the addition of metal fillers (Zn), and the crystallinity has improved. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 3094–3098, 2007     

在双镶嵌铜互联中O.13微米器件生成用的基于PVD和ALD阻挡层的先进技术

1. Introduction The requirement of minimal bottom coverageand thick sidewall coverage for PVD-based films forlow via resistance and improved stress migration isnot easy to achieve with traditional depositionmethods. Modern I-PVD techniques give high bot-tom coverage, due to the ionized component of thedeposition flux. Sidewall coverage tends to be low,which is mainly due to off-normal deposition fluxand a less than unity sticking coefficient.     

Numerical and experimental analysis of large passivation opening for solder joint reliability improvement of micro SMD packages

In this paper, using a recently developed solder fatigue model for wafer level-chip scale package (WL-CSP), we investigated the improvement on solder joint reliability for a 8-bump micro SMD package by enlarging the passivation layer opening at the solder–die interface. The motivation to enlarge the passivation opening is to reduce the severity of the stress concentration caused by the original design, and also to increase the contact area between the solder bump and aluminum bump pad. It was confirmed in the thermal shock test that with the new design, package fatigue life improved by more than 70%. To numerically predict this improvement represents a unique challenge to the modeling. This is because in order to capture the slightest geometrical difference on the order of a few microns between the two designs, the multiple-layer solder-die interface needs to be modeled using extremely fine mesh, while the overall dimensions of the package and the test board are on the order of millimeters. To bridge this tremendous gap in geometry, a single finite element model that incorporates all necessary geometrical details is deemed computationally prohibitive and impractical. In this paper, we applied a global–local modeling scheme that was also suggested by others [1, 2 and 3]. The global model contains the complete package with much simplified solder–die interface whereas the local model includes only one solder joint, but with detailed solder–die interface. Unlike most global–local models proposed by others, we included time-independent plasticity and temperature-dependent materials in the global model. This greatly improved model correlation accuracy with only moderate increase in run time. Energy-based solder fatigue model was used to correlate the inelastic strain energy with the package fatigue life. In an earlier study [4], we have found that Darveaux’s equations tended to be conservative when applied to the micro SMD, and hence new correlations based on curve-fitting the test data were derived. In this paper, we used the newly derived equation and achieved less than 20% error in N₅₀ life for both designs, which is on par with Darveaux’s equations when used for BGAs. The analysis also revealed two factors that may account for the life improvement. First, a slight decrease in inelastic energy dissipation after enlarging the passivation opening. Second, the shift of the crack initiation location which leads to longer crack growth length for the new design. The second factor was also independently confirmed by the failure analysis.     

Evaluation of the Crack Face Bridging Mechanism in a MgAl2O4 Spinel

The effectiveness of a grain bridging mechanism in the following wake zone of two MgAl₂O₄ spinel microstructures has been demonstrated through renotching experiments with double-cantilevered-beam (DCB) specimens. Measurements of d K_R /dδ a agree with previous crack growth resistance curves of similar materials, obtained from single-edgenotch-beam specimens. However, even the extended test ligaments available from the present DCB specimens did not permit the full development of the following wake zone of these coarse microstructures.     

Phase Equilibria in the Ti-AI-O System at 945°C and Analysis of Ti/Al2O3 Reactions

Phase relations in the Ti-Al-O system were evaluated experimentally at 945°C. The tie lines were established using equilibrated samples with phase compositions determined by electron probe microanalysis. The phase relations were in agreement with previous estimates but the phase fields of α-Ti[O,Al] and Ti₃Al[O] were significantly different. The Ti₃Al[O] phase has a maximum solubility of 22 at. % O, corresponding to a nominal stoichiometry of Ti₃AlO, whereas the α-Ti[O,Al] phase, at a maximum O solubility of 33.33 at. %, has a negligible amount of Al in solution. The disagreement between these results and previous studies was attributed to the differences in experimental techniques for sample preparation and analysis. The reported layer sequences at the Ti/Al₂O₃ interface were evaluated based on the ternary section and the corresponding O activity diagram. The layered interfaces were found to be stable, with the evolution of the reaction products governed by the thickness of the initial Ti layer and the O partial pressure in the ambient.