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111.
Polymer‐supported phase transfer catalysts with active sites mostly on the surface were prepared by suspension copolymerization of styrene (St), divinylbenzene (DVB), and vinylbenzyl chloride (VBC) with AIBN, followed by the quaternization of the resulting copolymer beads with triethylamine. Active sites on the surface were achieved by the delayed addition of functional monomer (VBC) to the partially copolymerized St/DVB. Polymer beads enriched with active sites were characterized by SEM, EDAX, FTIR, and ESCA. The electron micrographs showed that the exterior surface of delayed‐addition functional monomer catalysts (type 1) has a large number of nodules attached to the surface compared to the smooth surface exhibited by the conventional type 2 catalyst upon the simultaneous addition of all three monomers. In the EDAX analysis up to a depth of 100 Å, the surface chloride of type 1 peak intensity is greater (compared with type 2), indicating the CH2Cl enrichment on the surface. In FTIR, the peak intensities of the C N stretching (quaternary onium group) in type 1 are greater than those of type 2, confirming the evidence of more quaternization on the surface than in the bulk. From ESCA analysis to a depth of about 30 Å, it was found that type 1 (beads) contains 26% and type 2 contains 14% of covalent chloride on the surface, which strongly supports the grafting of VBC on St/DVB. In the estimation found by the Volhard method, type 1 has 4.73 m eq g−1 and type 2 has 2.29 m eq g−1 of ionic chloride, thus supporting the surface grafting of VBC. The catalytic activity of these two different catalysts was tested by studying the reaction, that is, the C‐alkylation of phenylacetone. The rate constants of this reaction for type 1 are almost twofold greater than those of type 2, a finding that could uphold the preceding experimental observations. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 408–418, 2000 相似文献
112.
This article presents the systematic study of kinetics and mechanism of phase‐transfer‐catalyzed free‐radical polymerization of acrylonitrile (AN) and water‐soluble initiator potassium peroxomonosulphate (PMS) coupled with tetrabutyl phosphonium chloride (TBPC) in ethyl acetate/water biphase system in the temperature range 45–55°C at fixed pH and ionic strength. The rate of polymerization increases with an increase in concentrations of AN, PMS, and phase transfer catalyst, PTC. It was observed that Rp is proportional to [AN]1.5, [KHSO55−]0.5, and [TBPC]0.5. A suitable kinetic scheme has been proposed to account for the experimental observations and its significance was discussed. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 1564–1571, 2000 相似文献
113.
ABS was melt grafted with maleic anhydride at three different levels of 1, 2, and 3 wt %. These three different modified ABSs were melt blended with polycarbonate using a single‐screw extruder to choose a suitable maleic anhydride grafting level on ABS for better performance. For the compatibility study, binary blends of polycarbonate with ABS and maleic anhydride‐grafted ABS were prepared over the entire range of compositions. Compatibility of these blends was studied using a Dynamic Mechanical Analyzer and by Differential Scanning Calorimetry. Both techniques suggest more partial compatibility for modified blend systems. In addition to this, DSC thermograms show multiple peaks between the transition points of ABS fractions and polycarbonate fractions for the polycarbonate/maleic anhydride‐grafted ABS blends. These multiple peaks are characteristic of better partial compatibility with fine microstructure. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 2102–2110, 1999 相似文献
114.
The operating characteristics of a pulsed (10 ns) tunable near-infrared (NIR) laser source are described for temperature-jump (T-jump) applications. A Q-switched Nd:YLF laser (approximately 10 ns pulses) with a 1 kHz repetition rate is used to pump a potassium titanyl arsenate (KTA) crystal-based optical parametric oscillator (OPO), producing approximately 1 mJ NIR pulses that are tunable (1.80-2.05 microm) across the 1.9 microm vibrational overtone band of water. This T-jump source has been coupled to a deep ultraviolet (UV) probe laser for Raman studies of protein dynamics. T-jumps of up to 30 degrees C, as measured via the O-H stretching Raman band of water, are readily achieved. Application to cytochrome c unfolding is demonstrated. 相似文献
115.
An attempt has been made to discuss the various phenomena taking place at a nickel electrode during the deposition of bright nickel from a Watts bath containing different concentrations of thiourea. The potential, polarization and capacity measurements indicate that the decomposition products rather than thiourea itself are responsible for the increased polarization arid the decrease in capacity and so for the consequent inhibition. Spectrophotometric measurements in the ultra violet region indicate the presence of another absorption range, in addition to that corresponding to thiourea, for the solution of thiourea in a Watts bath. It remains to be confirmed, however, whether it corresponds to the nickel-thiourea complex or to the decomposition products of thiourea. Spectrophotometric measurements have also indicated that the consumption of thiourea at the cathode is greater than at the anode and the difference is still greater in the presence of oxygen. 相似文献
116.
117.
A gasdynamic model of two-phase combustion fields is proposed. The model is based on an extension of our dilute heterogeneous-continuum formulation, where now the particle phase is modeled thermodynamically as a particle gas (with a pressure p 2, temperature T 2, and internal energy u 2, given by the kinetic theory for hard spheres with γ 2 = 5/3), thereby, resulting in particle gas conservation laws for mass, momentum, and total energy. The particles also possess a thermal storage capacity, expressed in terms of an internal energy of the solid e s = c s T s with its own temperature T s , and the corresponding energy conservation law. The consequence of this formulation is that both phases are hyperbolic, but decoupled; so each phase has it own complete set of eigenvalues and eigenvectors. The conservation laws for each phase can be integrated with a high-order Godunov scheme. Phases are coupled only through drag, heat, and mass transfer. The model is used to simulate aluminum particle combustion in a shock-dispersed-fuel explosion. Taking advantage of the point symmetry inherent in this problem, the flow field is azimuthally averaged in θ and φ directions to extract the mean and root-mean-square radial profiles of the thermodynamic fields, velocity fields, and reaction zone profiles. We find that the particle gas pressure influences the flow only during the initial phase of particle acceleration: as the compaction wave moves through the powder, followed by the rarefaction wave from the free surface. Thereafter, the particle pressure decays rapidly and particle accelerations are dominated by drag. Nevertheless, this seems to affect the dispersion process because the combustion cloud shape is somewhat different from previous results. 相似文献
118.
Rodrigues J Cancho VG de Castro M Balakrishnan N 《Statistical methods in medical research》2012,21(6):585-597
In this article, we propose a new Bayesian flexible cure rate survival model, which generalises the stochastic model of Klebanov et al. [Klebanov LB, Rachev ST and Yakovlev AY. A stochastic-model of radiation carcinogenesis - latent time distributions and their properties. Math Biosci 1993; 113: 51-75], and has much in common with the destructive model formulated by Rodrigues et al. [Rodrigues J, de Castro M, Balakrishnan N and Cancho VG. Destructive weighted Poisson cure rate models. Technical Report, Universidade Federal de S?o Carlos, S?o Carlos-SP. Brazil, 2009 (accepted in Lifetime Data Analysis)]. In our approach, the accumulated number of lesions or altered cells follows a compound weighted Poisson distribution. This model is more flexible than the promotion time cure model in terms of dispersion. Moreover, it possesses an interesting and realistic interpretation of the biological mechanism of the occurrence of the event of interest as it includes a destructive process of tumour cells after an initial treatment or the capacity of an individual exposed to irradiation to repair altered cells that results in cancer induction. In other words, what is recorded is only the damaged portion of the original number of altered cells not eliminated by the treatment or repaired by the repair system of an individual. Markov Chain Monte Carlo (MCMC) methods are then used to develop Bayesian inference for the proposed model. Also, some discussions on the model selection and an illustration with a cutaneous melanoma data set analysed by Rodrigues et al. [Rodrigues J, de Castro M, Balakrishnan N and Cancho VG. Destructive weighted Poisson cure rate models. Technical Report, Universidade Federal de S?o Carlos, S?o Carlos-SP. Brazil, 2009 (accepted in Lifetime Data Analysis)] are presented. 相似文献
119.
Aggressive scaling of silicon technology over the years has pushed CMOS devices to their fundamental limits. Pioneering works on carbon nanotube during the last decade possessing exceptional electrical properties have provided an intriguing solution for high performance integrated circuits. So far, at best, carbon nanotubes have been considered only for the channel, with metal electrodes being used for source/drain. Here, alternative schemes of 'All-Nanotube' transistor are presented where even the transistor components are derived from carbon nanotubes which hold the promise for smaller, faster, denser and more power efficient electronics. 相似文献
120.
Both AF Balakrishnan A Joseph B Marshall JD 《Environmental science & technology》2011,45(13):5629-5636
We measured outdoor fine particulate matter (PM(2.5)) concentrations in a low- and a nearby middle-income neighborhood in Bangalore, India. Each neighborhood included sampling locations near and not near a major road. One-minute average concentrations were recorded for 168 days during September 2008 to May 2009 using a gravimetric-corrected nephelometer. We also measured wind speed and direction, and PM(2.5) concentration as a function of distance from road. Average concentrations are 21-46% higher in the low- than in the middle-income neighborhood, and exhibit differing spatiotemporal patterns. For example, in the middle-income neighborhood, median concentrations are higher near-road than not near-road (56 versus 50 μg m(-3)); in the low-income neighborhood, the reverse holds (68 μg m(-3) near-road, 74 μg m(-3) not near-road), likely because of within-neighborhood residential emissions (e.g., cooking; trash combustion). A moving-average subtraction method used to infer local- versus urban-scale emissions confirms that local emissions are greater in the low-income neighborhood than in the middle-income neighborhood; however, relative contributions from local sources vary by time-of-day. Real-time relative humidity correction factors are important for accurately interpreting real-time nephelometer data. 相似文献