Control of free-radical emulsion polymerization of methyl methacrylate by oxygen injection. II. Experimental study

Oxygen injection has been proposed and experimentally demonstrated as an effective control measure for limiting the rate of heat release and altering the rate of polymerization in emulsion processes. A detailed mathematical model has been previously developed to describe the system behavior with and without oxygen injection. A simple lab scale apparatus was constructed and run extensively. Only trace quantities of oxygen are needed to inhibit the reaction completely. The facile response makes this method attractive for fast temperature control. However, because of the rapid penetration of dissolved oxygen into the polymer particles, growing radical chains are terminated prematurely, lowering product molecular weights. To minimize this detrimental effect, pulsed oxygen control is used and extensive experimental work was performed to determine the effects of controller set points on molecular weight. Moderate oxygen flows and moderate set point temperatures are found to give the optimal response without significant lowering of the final molecular weight. Injected quantities agree well with the order-of-magnitude sparging calculations needed to completely stop initiation. However, complete agreement between model simulations and experimental results was not reached due to an unmeasured loss of monomer from the reactor. Chain transfer to monomer is found to be important in modeling the polymer molecular weight. It has, however, a negligible effect on the reaction rate.     

A process model for active brazing of ceramics: Part II Optimization of brazing conditions and joint properties

In the present investigation, the process model developed in Part I has been applied to evaluate the microstructure and strength evolution during active brazing of ceramics. As a starting point, reaction-layer growth is assumed to occur isothermally with no restrictions in the supply of reactive element. Different kinds of diagrams are then constructed to show how specific process variables (e.g. the heating and cooling period, the limiting layer thickness, and the diffusion mechanism) affect the growth kinetics. It is concluded that the key to improved joint properties lies in control of the reaction-layer thickness through optimization of the brazing conditions, and an illustration of this is given. This revised version was published online in November 2006 with corrections to the Cover Date.     

An 8-bit, 200 MSPS Folding and Interpolating ADC

An 8-bit, 200 MSPS folding and interpolating analog-to-digitalconverter, ADC, has been implemented in a 1.2 µmBiCMOS-process. It achieves 7.5 effective bits with a power dissipationof 575mW. The active area is 4mm². The implementationand measured results are presented. A simple analytical modelfor the interpolation-induced nonlinearity in a folding and interpolatingADC using sinusoidal folding is presented. The bowing of thereference ladder due to interaction with the input stages isanalyzed, and analytical models are derived.     

Treatment of Humic Waters By Ozone

Two different generators for ozone were tested, a traditional electrical discharge generator and a generator based upon UV–irradiation of air at 150–180 nm. It was demonstrated that the traditional generator gave slightly higher reductions in levels of color for equivalent ozone dosages. Both gases affected the molecular weight distribution in the way that the bigger molecules were broken down to smaller ones. No significant difference between the molecular weight reduction efficiency of the gases was found.     

Activated dissociative chemisorption of methane on Ni(100): a direct mechanism under thermal conditions?

The dissociative chemisorption of methane on a Ni(100) single crystal has been studied under thermal conditions as a function of pressure and temperature. The initial sticking coefficient was measured in the pressure range of 0.010–7.0 mbar at temperatures ranging from 375 to 500 K. A strong pressure dependence was observed, consistent with a direct dissociation mechanism under these thermal conditions. This was further confirmed by experiments where the gas at a low pressure was heated by a thermal finger facing the crystal surface. With the thermal finger at the same temperature as the surface, it was possible to ensure that the methane was fully equilibrated to the crystal and an activation energy of 59±1.5 kJ/mol was determined under isothermal conditions.     

On the solubility of aluminum in cryolitic melts

The solubility of aluminum in NaF-AlF₃-Al₂O₃ melts with various additives was found to increase with increasing NaF/AlF₃ molar ratio (CR) and increasing temperature and to decrease with additions of A1₂O₃, CaF₂, MgF₂, and LiF to the melts. With the use of literature data for the activities of NaF and A1F₃ in cryolitic melts, three dissolution reaction models were found to give a good fit to the experimental solubility data. According to the most probable of these models the total concentration of dissolved aluminum (aluminum and sodium species) is given by c_Al = c_Na(diss) + c_AlF2- + c_Al2F3- + c_Al3F4- + c_Al4F5- In NaF rich melts, aluminum will dominantly dissolve as sodium, while at cryolite ratios commonly used in aluminum electrowinning (CR = 2.25 to 2.7) the AlF _-2 ^- -ion is the predominant dissolved metal species. Other species (A1₂F₃ ^-, A1₃F₄-, A1₄F₅-) were found to be of some significance only in melts with high excess A1F₃ (CR < 2).     

Passivation of the aluminium cathode during deposition of aluminium from aluminium chloride-sodium chloride melts

The kinetics of aluminium deposition from NaCl-AlCl₃ melts (c_AlCl3 < 10 mol%) contained in alumina crucibles was studied by linear sweep voltammetry and potential step amperometry at temperatures around 820°C. At low concentrations (c_AlCl3 < 0.4 mol%) the reduction of AlCl₃ on liquid aluminium has been found to be diffusion controlled. At higher concentrations a passivation of the aluminium electrode was observed during the deposition reaction. The passivation appears to be caused by precipitation of alumina from supersaturated melt in the diffusion layer at the aluminium cathode.     

Engineering Analysis and Design with ALE-VMS and Space–Time Methods

Flow problems with moving boundaries and interfaces include fluid–structure interaction (FSI) and a number of other classes of problems, have an important place in engineering analysis and design, and offer some formidable computational challenges. Bringing solution and analysis to them motivated the Deforming-Spatial-Domain/Stabilized Space–Time (DSD/SST) method and also the variational multiscale version of the Arbitrary Lagrangian–Eulerian method (ALE-VMS). Since their inception, these two methods and their improved versions have been applied to a diverse set of challenging problems with a common core computational technology need. The classes of problems solved include free-surface and two-fluid flows, fluid–object and fluid–particle interaction, FSI, and flows with solid surfaces in fast, linear or rotational relative motion. Some of the most challenging FSI problems, including parachute FSI, wind-turbine FSI and arterial FSI, are being solved and analyzed with the DSD/SST and ALE-VMS methods as core technologies. Better accuracy and improved turbulence modeling were brought with the recently-introduced VMS version of the DSD/SST method, which is called DSD/SST-VMST (also ST-VMS). In specific classes of problems, such as parachute FSI, arterial FSI, ship hydrodynamics, fluid–object interaction, aerodynamics of flapping wings, and wind-turbine aerodynamics and FSI, the scope and accuracy of the FSI modeling were increased with the special ALE-VMS and ST FSI techniques targeting each of those classes of problems. This article provides an overview of the core ALE-VMS and ST FSI techniques, their recent versions, and the special ALE-VMS and ST FSI techniques. It also provides examples of challenging problems solved and analyzed in parachute FSI, arterial FSI, ship hydrodynamics, aerodynamics of flapping wings, wind-turbine aerodynamics, and bridge-deck aerodynamics and vortex-induced vibrations.     

Improvement of cyclodextrin glucanotransferase as an antistaling enzyme by error-prone PCR

In an effort to improve the properties of cyclodextrin glucanotransferase (CGTase) as an antistaling enzyme, error-prone PCR was used to introduce random mutations into a CGTase cloned from alkalophilic Bacillus sp. I-5 (CGTase I-5). A mutant CGTase[3-18] with the three mutations M234T, F259I and V591A was selected by agar plate assay. Sequence alignment of various CGTases indicated that M234 and F259 are located in the vicinity of the catalytic sites of the enzyme and V591 in the starch binding domain E. The cyclization activity of CGTase[3-18] was dramatically decreased by 10-fold, while the hydrolyzing activity was increased by up to 15-fold. These mutations near subsite +1 (M234T) and at subsite +2 (F259I) are likely to alter the enzyme activity in a concerted manner, promoting hydrolysis of substrate while retarding cyclization. The addition of CGTase[3-18] reduced the retrogradation rate of bread by as much as did the commercial antistaling enzyme Novamyl during 7-day storage at 4 degrees C. No cyclodextrin (CD) was detected in bread treated with CGTase[3-18], whereas 21 mg of CD per 10 g of bread was produced in bread treated with wild-type CGTase.     

Torrefied agro-industrial residue as filler in natural rubber compounds

This study explored the feasibility of using torrefied biomass as a reinforcing filler in natural rubber compounds. Carbon black was then replaced with the torrefied biomass in elastomer formulations for concentrations varying from 0% to 100% (60 parts per hundred rubber or phr total). Their influence on the curing process, dynamic properties, and mechanical properties was investigated. Results were compared with the properties of vulcanizates containing solely carbon black fillers. Time to cure (t₉₀) for compounds with torrefied biomass fillers increased, while filler-filler interactions (ΔG') decreased, compared to carbon black controls. At low strains, the tan δ values of the torrefied fillers vulcanizates were similar to the controls. Incorporation of torrefied biomass into natural rubber decreased compound tensile strength and modulus but increased elongation. Replacement with torrefied fillers resulted in a weaker filler network in the matrix. Still, results showed that moderate substitution concentrations (~20 phr) could be feasible for some natural rubber applications.