Studies of water-soluble oligomers formed in emulsion copolymerization

A polymer chain transfer agent was synthesized by the reaction between poly(vinylbenzyl chloride) latex particles and 2-aminoethanethiol in a basic environment. In subsequent emulsion polymerization reactions, low molecular weight species were formed when waterborn oligomeric radicals diffused to the surface of these seed particles. These low molecular weight oligomers were separated by membrane filtration and their composition and molecular weight weight were analyzed by FTIR and mass spectroscopy. The measured composition results were compared with those that were calculated from the copolymerization equation. The molecular weights were compared with earlier experimental results that were obtained by isolation of oligomers formed when a water-soluble inhibitor was added to a reacting emulsion. Three seeded emulsion copolymerization systems, that is, styrene–acrylic acid, styrenemethacrylic acid, and styrene–methyl methacrylate, were investigated. The distribution of monomer in the water phase and in the copolymer particles was analyzed. The results show that the oligomer compositions for different copolymerization systems can be approximated reasonable well by the copolymerization equation, using the reactivity ratios obtained from bulk copolymerization. The length of the oligomer radicals formed depends on their composition and the properties of the polymer particles, such as surface charge, composition, size, and concentration. © 1994 John Wiley & Sons, Inc.     

Densification and Sintering Kinetics in Sintered Silicon Nitride

The sintering sequence of Y₂O₃-Al₂O₃-doped Si₃N₄ was investigated with respect to the relationship between densification, α→β transformation, and microstructural development. Quenching studies were performed to reveal these interactions during a complete sintering cycle. Isothermal studies were conducted to examine the sintering kinetics and compared to Kingery's liquid-phase sintering model. The bulk density increased to ≥90% of theoretical density with only minor transformation taking place. Major transformation occurred in a late sintering stage and was accompanied by the development of elongated grains. The kinetic order of the densification process, taking into account an appropriate correction, was larger than any of the rate exponents predicted by the Kingery model, indicating that other single or mixed mechanisms were active.     

HOW LIQUIDS SPREAD ON SOLIDS

A theory of the wetting of solids by liquids is put forward. The theory accounts for capillary pressure gradient, gravitational potential gradient, surface tension gradient, disjoining pressure gradient driving forces of flow in thick thin-films and of surface diffusion in thin thin-films. Disjoining pressure stems from the way intermolecular forces aggregate in submicroscopically thin films. For thick thin-films of slowly varying thickness the lubrication approximation to velocity distributions is appropriate. With this approximation the spontaneous, unsteady, two-dimensional spreading of liquid is shown to be governed by a nonlinear convective-diffusion equation for the evolution of the film thickness profile. The predictions of the theory agree with Marmur and Lelah's (1980, 1981) observations of water drops spreading on glass and with Bascom, Cottington and Singleterry's (1964) and Ludviksson and Lightfoot's (1971) observations of oils spreading on high energy surfaces. The theory is used to analyze Derjaguin and co-workers' (1944, 1957, 1970) blowing-off experiments designed to measure thin-film rheology. The theory is also used to buttress the proposition that much contact angle hysteresis is due simply to slow attainment of equilibrium.     

Modeling of the dynamics of transient liquid films in ternary systems

The presence of a concentration gradient across a thin liquid film leads to the phenomenon of isothermal liquid film migration (LFM). In most cases, the concentration gradient is due to coherency stresses, and the migration of the liquid film results in the relaxation of these stresses. It is also possible to envisage cases in which LFM occurs as a result of chemical solubility differences between stable and metastable phases. Both situations are examined in this contribution with special emphasis on the effect of adding a second solute element to the liquid phase. The kinetics of LFM is examined as a function of the initial liquid concentration and the ratio of the solute diffusion coefficients in a model coherency-driven ternary system. The growth of the Γ₂ inside δ particles in the Zn-Fe-Al system is presented as a possible example of chemically driven LFM. This article was presented at the Multicomponent-Multiphase Diffusion Symposium in Honor of Mysore A. Dayananda, which was held during TMS 2006, the 135th Annual Meeting and Exhibition, March 12–16, 2006, in San Antonio, TX. The symposium was organized by Yongho Sohn of University of Central Florida, Carelyn E. Campbell of National Institute of Standards and Technology, Richard D. Sisson, Jr., of Worcester Polytechnic Institute, and John E. Morral of Ohio State University.     

In situ, noninvasive characterization of superhydrophobic coatings

Light scattering was used to measure the time-dependent loss of air entrapped within a submerged microporous hydrophobic surface subjected to different environmental conditions. The loss of trapped air resulted in a measurable decrease in surface reflectivity and the kinetics of the process was determined in real time and compared to surface properties, such as porosity and morphology. The light-scattering results were compared with measurements of skin-friction drag, static contact angle, and contact-angle hysteresis. The in situ, noninvasive optical technique was shown to correlate well with the more conventional methods for quantifying surface hydrophobicity, such as flow slip and contact angle.     

Optimisation of four-sensor probes for measuring bubble velocity components in bubbly air-water and oil-water flows

In a previous paper Lucas and Mishra (2005) [3] a local four-sensor conductance probe was introduced to measure the velocity vectors of dispersed bubbles in bubbly two-phase flow in which the continuous phase is water. There are a very limited number of alternative methods available for bubble velocity vector measurement with which results from, for example, computational fluid dynamic models can be compared and so the four-sensor probe technique is of interest to the multiphase flow community. In the previous paper [3] a mathematical model was presented to calculate the velocity vector of each gas bubble from seven time intervals which were measured using the output signals from each of four ‘needle’ conductance sensors located within the probe. In the present paper, a new technique for making the local four-sensor probe is introduced to minimise interference with the measured bubbles. A new signal processing method is presented using criteria to ensure that (i) the group of sensor signals from which the bubble velocity vector is to be determined are all produced by the same bubble and (ii) bubbles which contact the local four-sensor probe in an ambiguous manner are ignored. The accuracy with which the locations of each of the rear sensors in the probe relative to the lead sensor can be measured influences the accuracy with which the bubble velocity vector can be measured. However, the degree to which the accuracy of the measured velocity vector is affected by errors in the measured probe dimensions is dependent upon the geometrical arrangement of the four sensors within the probe. Experimental results and an error analysis are presented which show that the susceptibility of the velocity vector measurement technique to errors in the measured probe dimensions is reduced if the geometrical arrangement of the four sensors is optimised. As a result of this initial work, an optimised probe, known as the P30 probe, was designed and built and results obtained from the P30 probe in swirling oil-in-water bubbly flow are presented. A probe calibration factor is defined in this paper which can be interpreted as a measure of the interference of a probe with the motion of the bubbles with which it interacts. For the probes described in this paper the calibration factor was found to be much closer to unity than for previous four-sensor probes described in the literature (e.g. [3]) suggesting that these new probes have a much smaller effect on the bubbles’ motion than previous probes.     

Development of a new indicator of pollutant loads and its application to the Chesapeake Bay watershed

Pollutant load reductions are often required to restore aquatic ecosystems experiencing eutrophication. Loads can be estimated using watershed models or data from monitoring stations, however data availability can limit the timeliness or comprehensiveness of the load estimates. We developed an approach to address this challenge that used watershed model results to estimate the proportion of annual nonpoint source nitrogen (N), phosphorus (P) and sediment (Sed) loads derived from unmonitored catchments. This proportion was multiplied by the nonpoint portion of United States Geological Survey (USGS) estimated annual river loads to account for annual variation in hydrologic conditions. Total loads were calculated as the sum of measured river loads, reported point sources from unmonitored areas and the estimated nonpoint source loads from unmonitored catchments. We applied this approach to the Chesapeake Bay because of its socio‐economic and ecological importance. Median watershed loads for N, P and Sed were 140, 6.4 and 3030 Mg year^?1, respectively (1990–2004). Nonpoint source loads from the monitored areas constituted the greatest source of N, P and Sed (55, 47 and 74% respectively) to the Bay. The high N, P and Sed yield rates (7.3, 0.38 and 99 kg ha^?1 year^?1, respectively) from nonpoint loads originating from unmonitored areas near the Bay resulted in 25, 32 and 26% (N, P and Sed, respectively) of the Bay's total loads (excluding direct atmospheric deposition, shoreline erosion and oceanic inputs). Disproportionately high loads of P and Seds were associated with years that experienced elevated discharge whereas N loads were directly related to discharge. Error estimates indicated that our methods were most reliable for N (±6%) but reasonable for P (±22%) and provide an effective technique for the timely estimation of pollutant loads from watersheds with unmonitored catchments. Management strategies that decrease N deposition and reduce runoff to control P and Sed transport will effectively reduce pollutant loads. Published in 2010 by John Wiley & Sons, Ltd.     

A neural network job-shop scheduler

This paper focuses on the development of a neural network (NN) scheduler for scheduling job-shops. In this hybrid intelligent system, genetic algorithms (GA) are used to generate optimal schedules to a known benchmark problem. In each optimal solution, every individually scheduled operation of a job is treated as a decision which contains knowledge. Each decision is modeled as a function of a set of job characteristics (e.g., processing time), which are divided into classes using domain knowledge from common dispatching rules (e.g., shortest processing time). A NN is used to capture the predictive knowledge regarding the assignment of operation’s position in a sequence. The trained NN could successfully replicate the performance of the GA on the benchmark problem. The developed NN scheduler was then tested against the GA, Attribute-Oriented Induction data mining methodology and common dispatching rules on a test set of randomly generated problems. The better performance of the NN scheduler on the test problem set compared to other methods proves the feasibility of NN-based scheduling. The scalability of the NN scheduler on larger problem sizes was also found to be satisfactory in replicating the performance of the GA.     

Silver Bullet Talks with Jeremiah Grossman

Silver Bullet Security Podcast host Gary McGraw interviews Jeremiah Grossman, founder and CTO of WhiteHat Security, who is well known for his work in Web application security.     

Magnetic quadrupole doublet focusing system for high energy ions

A high energy focused ion beam microprobe using a doublet arrangement of short magnetic quadrupole lenses was used to focus 1-3 MeV protons to spot sizes of 1x1 microm2 and 1-4.5 MeV carbon and silicon ion beams to spot sizes of 1.5x1.5 microm2. The results presented clearly demonstrate that this simple doublet configuration can provide high energy microbeams for microanalysis and microfabrication applications.