Adsorption of block copolymers at latex surface and their utilization in emulsion polymerization

Amphiphilic block copolymers have been investigated for their utilization in emulsion polymerization of butyl methacrylate. Special attention has been paid to the adsorption mechanism of the block copolymers from systematic measurements of equilibrium adsorption isotherms. A series of well-defined water-soluble amphiphilic block copolymers, composed of poly(butyl methacrylate) and poly(sodium methacrylate) blocks, were synthesized by anionic polymerization of butyl methacrylate and tert-butyl methacrylate followed by the thermal deprotection of the tert-butyl ester groups and final hydrolysis. The number density of emulsion polymer particles N_P varied as [copolymer]^α, α lying between 0.44 and 0.73 according to the hydrophilic content of the copolymers. In contrast with SDS taken as a reference emulsifier, the adsorption of the copolymers was very strong and this provided quite an efficient stabilization of the polymer particles during emulsion polymerization, even at low concentrations (<10⁻⁴ mol L⁻¹) and low coverages (<10% of the interfacial area).     

Synthesis and characterization of long-chain fatty acid cellulose ester (FACE)

Long-chain fatty acid cellulose esters (FACE) were synthesized by the acid chloride-pyridine reaction with different degrees of substitution (DS). The hydrolyzed soybean oil was used as unsaturated fatty acids, its unsaturation degree, and composition were analyzed by ¹H and ¹³C NMR methods. The chemical structures of FACE were confirmed by solid-state ¹³C NMR, and substitution reaction of fatty acid chloride on cellulose were analyzed by IR spectroscopy. FACE(s) are insoluble in common organic solvents, such as benzene, toluene, THF, etc., at refluxing temperature. As the DS increased, the tensile strength of extruded FACE films decreased, but elongation increased. © 1994 John Wiley & Sons, Inc.     

Biochemical,functional, and histochemical effects of essential fatty acid deficiency in rat kidney

The present study was designed to examine the effects of EFA deficiency (EFAD) on biochemical, functional, and structural aspects of the kidney in growing and adult rats fed a normal or EFAD diet for 9 wk after weaning. Food and fluid intake (FI), urine volume, and Na⁺ and K⁺ excretions were measured weekly from weeks 4 to 8 by placing the rats in individual metabolic cages for 24 h. At week 9, Li⁺ and a 5% water load, respectively, were administered at 14 and 1.5 h prior to glomerular and proximal tubular function studies, as assessed by 3-h creatinine (C_Cr) and Li⁺ (C_Li+) clearances. Hematocrit and urine volume; serum and urine [Cr], [Li⁺], [Na⁺], and [K⁺]; and renal FA distribution were also measured. Data [corrected to 100 g/body weight (bw) and presented as means ±SEM] were significant, at P<-0.05. Despite a similar ingestion of solids from weeks 4 to 7 (weeks 7 to 10 of life), the rats on the EFAD diet showed a decreased body weight from week 5. From weeks 4 to 8, Fl and urine volume were similar for both groups, but the Fl increased at week 6 in the EFAD group; 24-h Na⁺ and K⁺ excretions were similar at all weeks, except for an increase in the EFAD group for both ions at week 7. In the EFAD group, C_Cr and C_Li+ decreased by 27 and 56.3%, respectively (385.7±33.4 vs. 280±21.1, and 21.0±2.1 vs. 9.2±1.1 μL/min/100 g; n=9 vs. 10), the latter result suggesting increased proximal reabsorption. The 3-h Na⁺ and K⁺ excretions were similar, but the Li⁺ decreased (0.78±0.06×10⁻² vs. 0.32±0.03×10⁻² μeq/min/100 g) in the EFAD group, giving additional support to the suggestion. Renal structure was normal and similar for both groups, but the EFAD group showed a more prominent proximal tubule brush border, together with heavier periodic acid-Schiff staining in all specimens from weeks 5 to 9. In the EFAD group, FA of the n−9 and n−7 series were higher, but most of the n−6 series were lower as a percentage of total lipids in the medulla and cortex. Medullary levels of 20∶4n−6 were maintained, 22∶4n−6 declined twice, arachidonic acid was maintained, and 20∶5n−3 was lower. The EFAD diet affected glomerular function, proximal tubular structure and function, and FA distribution in the rat kidney.     

Zinc-rich powder coatings corrosion in sea water: influence of conductive pigments

The effect of addition of conductive pigments like carbon blacks on the corrosion behavior of zinc-rich powder paints coated steel in artificial sea water was investigated. Open circuit potential measurements were used to characterize the cathodic protection ability and duration. Micro-Raman spectroscopy analysis was performed in order to identify the corrosion products and to follow the penetration of the solution inside the coatings.

Two different effects were pointed out: an increase of the porosity induced by carbon addition and a galvanic action between zinc and carbon pigments. The performance of the powder coatings, strongly improved if the carbon amount is sufficient, was compared to the one reported for solvent-based zinc-rich paints.     

Kinetics of the selective catalytic reduction of NO by NH3 on a Cu-faujasite catalyst

The kinetics of the selective catalytic reduction (SCR) of NO by NH₃ in the presence of O₂ has been studied on a 5.5% Cu-faujasite (Cu-FAU) catalyst. Cu-FAU was composed of cationic and oxocationic Cu species. The SCR was studied in a gas phase-flowing reactor operating at atmospheric pressure. The reaction conditions explored were: 458<T_R<513 K, 2503 (ppm) < 4000, 12 (%) < 4. The kinetic orders were 0.8–1 with respect to NO, 0.5–1 with respect to O₂, and essentially 0 with respect to NH₃. Based on these kinetic partial orders of reactions and elementary chemistry, a wide variety of mechanisms were explored, and different rate laws were derived. The best fit between the measured and calculated rates for the SCR of NO by NH₃ was obtained with a rate law derived from a redox Mars and van Krevelen mechanism. The catalytic cycle is described by a sequence of three reactions: (i) Cu^I is oxidized by O₂ to “Cu^II-oxo”, (ii) “Cu^II-oxo” reacts with NO to yield “Cu^II-N_xO_y”, and (iii) finally “Cu^II-N_xO_y” is reduced by NH₃ to give N₂, H₂O, and the regeneration of Cu^I (closing of the catalytic cycle). The rate constants of the three steps have been determined at 458, 483, and 513 K. It is shown that Cu^I or “Cu^II-oxo” species constitute the rate-determining active center.     

Motional heterogeneity of polystyrene-block-polybutadiene: a spin probe study

Polystyrene-block-polybutadiene copolymers (SB) with 0.5 mass fraction of styrene were studied by electron spin resonance (ESR) of nitroxide spin probes. The influence of the block length ( and ) and the solvation power of casting solvents on the motional dynamics of spin probe were measured over a wide temperature range. Two nitroxide radicals as spin probes were selected: 2,2,6,6-tetramethyl-4-hydroxypiperidine-1-oxyl benzoate (BzONO) and 2,2,6,6-tetramethyl-4-hydroxypiperidine-1-oxyl (Tempol). Irrespective of the spin probe used two ESR spectral components differing in their motional properties above the phase transition of polybutadiene blocks (PB) were observed. The fast component was assigned to spin probes located in polybutadiene-rich domains and the slow component to spin probes in polystyrene-rich domains. The range of two spectral components and the phase transition of the slow ESR component, T_5mT, depend on the block length. The influence of the interphase and accumulation of free volume in the interphase on the Tempol probe motion was investigated by changing copolymer morphology in the films casted from selective and nonselective solvents. The analysis of the motional heterogeneity from the ratio of the fast and slow motional component presents evidence that in the selective solvent for polystyrene (PS) blocks (2-butanone) the most irregular structure with a large interphase is formed. The difference in fast motion of spin probes indicates that the motional dynamic is related to the change of domain structure.     

Electrochemical behaviour of copper in neutral aerated chloride solution. I. Steady-state investigation

The electrochemical behaviour of a Cu rotating disc electrode in neutral aerated NaCl solution was investigated in the cathodic and anodic ranges and at the corrosion potential. In the cathodic range, where the reduction of oxygen takes place, reduction peaks allow the identification and quantitative evaluation of insoluble corrosion products (CuCl and Cu₂O). In the anodic range Cu is dissolved, most likely as CuCl ₂ ^– . A new mechanism for the anodic dissolution is proposed after comparing our data with previously published mechanisms. Corrosion currents were found to decrease with time and to be a function of the rotation rate of the electrode. Both the mixed kinetics of the anodic partial reaction and diffusion through a porous layer seem to be relevant in controllingl _corr.     

Interaction between dietary protein and fat in triglyceride metabolism in the rat: Effects of soy protein and menhaden oil

The objective of the present study was to determine the mechanisms by which dietary proteins interact with dietary lipids in the regulation of triglyceridemia in rats. Male Sprague-Dawley rats (n=56) were subjected to 28-d experimental diets containing different combinations of proteins (20% w/w) and lipid sources (14% w/w): (i) casein-menhaden oil, (ii) casein-beef tallow, (iii) soy protein-menhaden oil, and (iv) soy protein-beef tallow. Significant protein-lipid interactions were observed on triglyceridemia and hepatic cholesterol in fasted rats. The combination of casein and beef tallow was associated with high plasma TG and hepatic cholesterol concentrations, which were reduced by substitution either of soy for casein or of menhaden oil for beef tallow. Therefore, triglyceridemia and liver cholesterol remained low with soy protein feeding, independently of the lipid source, as well as with menhaden oil feeding, regardless of the protein source. The menhaden oil diets reduced plasma cholesterol, hepatic TG, and TG secretion compared with beef tallow diets independently of the dietary protein source. Modifying the source of dietary proteins and lipids had no effect on post-heparin plasma lipoprotein lipase activity. These results demonstrate that soy protein can lower rat triglyceridemia relative to casein when associated with beef tallow consumption, whereas menhaden oil can attenuate hypertriglyceridemia when rats are fed casein. The data further suggest that part of the hypotriglyceridemic effect of soy protein in the rat may be mediated by reduced hepatic lipid synthesis, as is the case for menhaden oil.     

Air impingement and intermittent drying: Application to apple and to mango

An original drying process combining air impingement and intermittent drying was studied on apple slices and mango cubes. The influence of four operating parameters (air velocity, drying/tempering periods, upper height, and air temperature) on the drying time and on the drying rate was evaluated. Continuous and intermittent drying were compared. The intermittency α = 1/7 (τ_on = 10 seconds and τ_off = 60 seconds) gave the best results. A time savings of 54% for apple and 67% for mango was reached. In continuous drying, a time savings of 4620 seconds was observed by increasing the air velocity from 6 to 40 m s^?1 for apple. Air temperatures of 328 K for apple and of 328 K or 338 K for mango were determined as optimum to prevent case‐hardening. Experimental results were fitted with the analytical solution of Fick's second law and the modified Page equation (average values R² = 0.985 and 0.961, for apple and mango, respectively). For both products, the apparent moisture diffusivity D_app, the drying constant k, the drying coefficient n, and the activation energy E_a, were identified. Activation energies calculated from the analytical solution were 30.3 and 36.8 kJ mol^?1 and were 25.4 and 30.0 kJ mol^?1 using the modified Page equation for apple and mango, respectively. Mango has an increased temperature sensitivity and thus will need less energy for drying than apple.     

Copper diffusion into silicon substrates through TaN and Ta/TaN multilayer barriers

A study of copper (Cu) diffusion into silicon substrates through Ta nitride (TaN) and tantalum (Ta/TaN) layers was investigated based on an experimental approach. TaN _x and Ta/TaN _x thin films were deposited by radiofrequency sputtering under argon (Ar) and Ar-nitrogen (N) plasma. The influence of the N₂ partial pressure on the microstructure and the electrical properties is reported. X-ray diffraction patterns showed that the increase of the N₂ partial pressure, from 2 to 10.7%, induces a change in the composition of the δTaN phase, from TaN to TaN_1.13, as well as an evolution of the dominant crystallographic orientation. This composition change is related to a drastic increase of the electrical resistivity over a N₂ partial pressure of 7.3%. The efficiency of TaN layers and Ta/TaN multilayer diffusion barriers was investigated after annealing at temperatures between 600 and 900 °C in vacuum. Secondary ion mass spectrometry profiles showed that Cu diffuses from the surface layer through the TaN barrier from 600 °C. Cu diffusion mechanisms are modified in the presence of a Ta sublayer. 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 the 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.