Hydroformylation of 1-octene using rhodium–phosphite catalyst in a thermomorphic solvent system

The use of a liquid–liquid biphasic thermomorphic or temperature-dependent multicomponent solvent (TMS) system, in which the catalyst accumulates in one of the liquid phases and the product goes preferably to the other liquid phase, can be an enabling strategy of commercial hydroformylation processes with high selectivity, efficiency and ease of product separation and catalyst recovery. This paper describes the synthesis of n-nonanal, a commercially important fine chemical, by the hydroformylation reaction of 1-octene using a homogeneous catalyst consisting of HRh(PPh₃)₃(CO) and P(OPh)₃ in a TMS-system consisting of propylene carbonate (PC), dodecane and 1,4-dioxane. At a reaction temperature of 363 K, syngas pressure of 1.5 MPa and 0.68 mM concentration of the catalyst, HRh(CO)(PPh₃)₃, the conversion of 1-octene and the yield of total aldehyde were 97% and 95%, respectively. With a reaction time of 2 h and a selectivity of 89.3%, this catalytic system can be considered as highly reactive and selective compared to conventional ones. The resulting total turnover number was 600, while the turnover frequency was 400 h^?1. The effects of increasing the concentration of 1-octene, catalyst loading, partial pressure of CO and H₂ and temperature on the rate of reaction have been studied at 353, 363 and 373 K. The rate was found to be first order with respect to concentrations of the catalyst and 1-octene, and the partial pressure of H₂. The dependence of the reaction rate on the partial pressure of CO showed typical substrate inhibited kinetics. The kinetic behavior differs significantly from the kinetics of conventional systems employing HRh(CO)(PPh₃)₃ in organic solvents. Most notable are the lack of olefin inhibition and the absence of a critical catalyst concentration. A mechanistic rate equation has been proposed and the kinetic parameters evaluated with an average error of 5.5%. The activation energy was found to be 69.8 kJ/mol.     

Experimental investigation of a multi‐stage air‐steam gasification process for hydrogen enriched gas production

To achieve hydrogen‐rich and low‐tar producer gas, multi‐stage air‐blown and air‐steam gasification processes were studied in this research. Results showed that the tar content from multi‐stage air‐blown and air‐steam gasification were lower, compared to the average value of that from downdraft gasification. In the cases of air supplies of 80, 100 l min^?1 and 100, 100 l min^?1 with steam, hydrogen yields were increased by 40.71 and 41.62%, respectively, compared to that without steam. These were about 1.6 times of hydrogen flow rate of the base case (S/B = 0). However, it was found that too much steam added to the process was disadvantageous. The equilibrium model was also applied to predict the hydrogen production and the composition of producer gas obtained from the multi‐stage air‐blown and air‐steam gasification processes. The predicted result showed a better match for the case of multi‐stage air‐blown gasification process. Copyright © 2010 John Wiley & Sons, Ltd.     

Experimental study on sawdust gasification in a spout–fluid bed reactor

This paper summarizes the experimental results of sawdust gasification in a spout–fluid bed reactor. Three scenarios were investigated in this study. In the base case scenario, a total of 15 experiments consisting of three different flow rates (55, 65 and 75 m³ h^{? 1}) of primary air of each of having five equivalence ratios (ER) (0.35, 0.3, 0.25, 0.2 and 0.15) were conducted. The influence of secondary air in the freeboard and the effect of the recirculation of carryover captured by the cyclone to the reactor's freeboard at an ER of 0.25 were investigated in two other scenarios. Higher heating values of 3.02 and 5.15 MJ Nm^{? 3} were obtained with the ER values of 0.35 and 0.15, respectively, in the base case. However, opposite trend was observed for the tar content in the producer gas. At ER of 0.35, a value of 2.35 g Nm^{? 3} was found compared with 8.4 g Nm^{? 3} at ER of 0.15. The tar content in the producer gas was reduced from 5.63 to 1.53 g Nm^{? 3} when secondary air was supplied in the freeboard due to an increase in temperature. The gasification efficiency was increased from 24.96% at the base case to 36.22% with the recirculation of carryover. Higher heating value of producer gas was found to be 4.2–4.4 MJ Nm^{? 3} in this case. The second law analysis of this process estimated the average exergy efficiency as 35.92% at ER of 0.35 and it increased with increasing ER. The recirculation of carryover not only increased the carbon conversion efficiency but also the exergy efficiency. Copyright © 2010 John Wiley & Sons, Ltd.     

Social‐based reputation‐aware data forwarding for improved multicast delivery in the presence of selfish nodes in DTNs

Delay/disruption tolerant networks (DTNs) are potentially applicable in the challenged scenarios like post‐disaster environments. In such networks, data forwarding generally relies on the mutual cooperation of the nodes. However, in reality, despite the availability of necessary resources for data forwarding, a node could misbehave by dropping messages received from other nodes with whom it has no strong social ties. Such a node is called a socially selfish node, which would cause a poor delivery ratio in the network. In this paper, we aim to address the problem of multicast data forwarding in the presence of such selfish nodes, by means of efficient relay selection in DTNs. First, we define a realistic reputation model, in contrast to existing models, to define the socially selfish/misbehaving nodes in the network. Further, a game‐theoretic analysis is carried out that implies data forwarding cost is also an influential parameter in handling selfishness/misbehavior. Subsequently, the problem is formulated as a constrained optimization problem, which is NP hard. Therefore, a heuristic is proposed by combining the reputation of a node and the cost of message forwarding to appropriately identify relay nodes, thus improve the performance of the multicast message delivery in the network. We utilize a social metric, centrality to minimize the message forwarding cost in terms of the number of relay nodes. Finally, the comparative performance evaluation in ONE simulator with practical scenarios shows the superiority of the proposed scheme over the other prominent schemes.     

Process optimization for high electron mobility in nMOSFETs with aggressively scaled HfO/sub 2//metal stacks

The performance of aggressively scaled (1.4nm相似文献   

Almost Boolean Functions: The Design of Boolean Functions by Spectral Inversion

The design of Boolean functions with properties of cryptographic significance is a hard task. In this paper, we adopt an unorthodox approach to the design of such functions. Our search space is the set of functions that possess the required properties. It is "Boolean-ness" that is evolved.     

Synthesis of Nanocrystalline FeS2 with Increased Band Gap for Solar Energy Harvesting

In this paper,we have reported the synthesis of FeS2 of higher band gap energy（2.75 eV） by using capping reagent and its successive application in organic-inorganic based hybrid solar cells.Hydrothermal route was adopted for preparing iron pyrite（FeS2） nanoparticles with capping reagent PEG-400.The quality of synthesized FeS2 material was confirmed by X-ray diffraction,field emission scanning electron microscopy,transmission electron microscopy,Fourier transform infrared,thermogravimetric analyzer,and Raman study.The optical band gap energy and electro-chemical band gap energy of the synthesized FeS2 were investigated by UV-vis spectrophotometry and cyclic voltammetry.Finally band gap engineered FeS2 has been successfully used in conjunction with conjugated polymer MEHPPV for harvesting solar energy.The energy conversion efficiency was obtained as 0.064%with a fill-factor of 0.52.     

Numerical investigation of fatigue characteristics of concrete pavement

In concrete pavements, fatigue is one of the major causes of distress. Repeated loads result in the formation of cracks. The propagation of these cracks cause internal progressive damage within the structure, which ultimately leads to failure of the pavement due to fatigue. This paper presents a theoretical investigation of crack propagation within concrete pavement and its fatigue characteristics under cyclic loading. A numerical fatigue performance model has been developed for this purpose. The model is based on fictitious crack approach for the propagation of cracks and stress degradation approach for estimating the bridging stress under cyclic loading. Using the numerical model, a parametric study has been performed for a typical concrete pavement to evaluate its fatigue characteristics for different foundation strengths. The method can be used for prediction of crack propagation in concrete pavement under cyclic loading and gives an estimate of the incremental damage or the entire crack history of the pavement.     

Restoration of pedicle screw fixation with an in situ setting calcium phosphate cement

STUDY DESIGN: Pedicle screws were pulled out of human cadaveric vertebrae before and after augmentation with polymethylmethacrylate or in situ-setting calcium phosphate cement. The fixation strength of screws augmented with calcium phosphate cement was compared with that of screws augmented with polymethylmethacrylate. OBJECTIVES: To determine whether a new in situ-setting calcium phosphate cement might be suitable for augmenting the fixation of pedicle screws. The principle objective was to compare the pull-out resistance of screws augmented with calcium phosphate cement with the pull-out behavior of screws augmented with polymethylmethacrylate. Polymethylmethacrylate augmentation was chosen as the standard because of its current clinical use. Five types of screws were tested to determine whether screw design had an effect on the efficacy of augmentation. SUMMARY OF BACKGROUND DATA: Although many factors affect the pull-out resistance of pedicle screws, a key determinant of their performance is the strength of their attachment to the spine. In elderly, osteopenic patients, the screw-bone interface is especially at risk for stripping during insertion or pull-out after surgery. In these patients, polymethylmethacrylate has been used to augment pedicle screw fixation, although its use is not without risk. In situ-setting calcium phosphate cements may provide an alternative to polymethylmethacrylate in this application. Like polymethylmethacrylate, calcium phosphate cements can be injected into the prepared screw hole. They have the added advantage of being resorbed and replaced during healing and normal bone remodeling. METHODS: Thirty human lower lumbar vertebrae (L3-L5) were implanted bilaterally with one of five types of pedicle screws (n = 6 for each screw type). The screws were pulled out 3.0 mm at 0.25 mm/sec with a servohydraulic materials testing machine. The 3.0-mm pull-out distance, which was slightly longer than one thread pitch, was designed to strip the screw-bone interface but to leave the pedicle otherwise intact. After the initial testing, the screws in each vertebrae were removed, and the screw tracks were filled with 2.0 cc of polymethylmethacrylate (one side) or calcium phosphate cement (contralateral side). After augmentation, the screws were reinserted, and the cements were allowed to harden for 24 hours. Postaugmentation testing followed the protocols for preaugmentation testing, and the pull-out resistance of screws augmented with calcium phosphate cement was compared with the pull-out resistance of screws augmented with polymethylmethacrylate. RESULTS: Mechanically, calcium phosphate cement compared favorably with polymethylmethacrylate for augmenting pedicle screws. Both restored the strength of the screw-bone interface: across all screw types, the average increase in pull-out strength was 147% with polymethylmethacrylate augmentation and 102% with calcium phosphate cement. There were no significant differences because of screw type with either type of augmentation. CONCLUSIONS: The in situ-setting calcium phosphate cement investigated in this study compared favorably with polymethylmethacrylate in a single-cycle, pull-out test of augmented pedicle screws in senile trabecular bone. With further evaluation, this cement may offer an alternative to polymethylmethacrylate for the enhancement of pedicle screw fixation clinically.