Substrate-mediated interactions and intermolecular forces between molecules adsorbed on surfaces

Adsorbate interactions and reactions on metal surfaces have been investigated using scanning tunneling microscopy. The manners in which adsorbates perturb the surface electronic structure in their vicinity are discussed. The effects these perturbations have on other molecules are shown to be important in overlayer growth. Interactions of molecules with surface steps are addressed, and each molecule's electron affinity is shown to dictate its adsorption sites at step edges. Standing waves emanating from steps are demonstrated to effect transient molecular adsorption up to 40 A away from the step edge. Halobenzene derivatives are used to demonstrate how the surface is important in aligning reactive intermediates.     

TGA analysis of γ‐irradiated linear low‐density polyethylene

Linear low‐density polyethylene (LLDPE), based on butene‐1 or hexene‐1, was irradiated with γ‐rays under vacuum or in the presence of air. The study focused on the influence of the dose rate and the γ‐dose on the thermal properties of LLDPE. Differential scanning calorimetry, thermogravimetric analysis (TGA), and TGA/FTIR techniques were used to address the thermal behavior as a result of γ‐irradiation. During this irradiation, competition between crosslinking and scission reactions, subsequent to oxidation reactions, occurred in the polymeric material, which strongly depends on the experimental conditions. A decrease of the crystallinity for γ‐irradiated samples was observed in particular for samples irradiated under vacuum. This observation may be explained by increased hindrance of segment mobility due to crosslinking reactions that prevent crystal growth. TGA investigations revealed an enhancement of the thermal stability for samples irradiated under vacuum but not for those irradiated in air. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 2790–2795, 2006     

Estimating the processed value of soybeans

Interest in marketing soybeans on the basis of protein and oil content is increasing. Producers, breeders, handlers and buyers of soybeans need a method of evaluating soybean lots of different composition. A model is presented that predicts, given soybean composition and processing conditions, the yield of crude soybean oil and soybean meal from the processing of soybeans in a solvent extraction plant. From these yields, an estimated processed value (EPV) was calculated. For one set of price conditions, the EPV of typical soybeans had a range of $0.93 per bushel if premiums were paid for meal protein in excess of specifications and a range of $0.53 per bushel if meal protein premiums were not paid. Trading rules established by the National Oilseed Processors Association for domestic meal markets have a significant effect on the value and composition of soybean meal.     

Spatio‐temporal geometry fusion for multiple hybrid cameras using moving least squares surfaces

Multi‐view reconstruction aims at computing the geometry of a scene observed by a set of cameras. Accurate 3D reconstruction of dynamic scenes is a key component for a large variety of applications, ranging from special effects to telepresence and medical imaging. In this paper we propose a method based on Moving Least Squares surfaces which robustly and efficiently reconstructs dynamic scenes captured by a calibrated set of hybrid color+depth cameras. Our reconstruction provides spatio‐temporal consistency and seamlessly fuses color and geometric information. We illustrate our approach on a variety of real sequences and demonstrate that it favorably compares to state‐of‐the‐art methods.     

The role of clay network on macromolecular chain mobility and relaxation in isotactic polypropylene/organoclay nanocomposites

It is well known that a so-called “three-dimensional filler network structure” will be constructed in the polymer/layered silicate nanocomposites when the content of layered clay reaches a threshold value, at which the silicate sheets are incapable of freely rotating, due to physical jamming and connecting of the nanodispersed layered silicate. In this article, the effect of such clay network on the mobility and relaxation of macromolecular chains in isotactic polypropylene(iPP)/organoclay nanocomposites was investigated in detail with a combination of DMTA, DSC, TGA, TEM, rheometry and melt flow index measurements. The main aim is to establish a relationship between the mesoscopic filler network structure and the macroscopic properties of the polymer nanocomposites, particularly to explore the role of the clay network on the mobility and relaxation of macromolecular chains. It was found that the nanodispersed clay tactoids and layers play less important or dominant roles on the mobility of iPP chains depending on the formation of percolating filler network. The turning point of macroscopic properties appeared at 1 wt% organoclay content. Before this point, the effect of organoclay can be negligible, and the increase of chain mobility was ascribed to the decrease of molecular weight of polymer chains, as commonly occurs during dynamic melt processing; after this point, however, a reduced mobility of chains and a retarded chain relaxation were observed and attributed to the formation of a mesoscopic filler network. The essential features of such a mesoscopic organoclay network were estimated and discussed on the basis of stress relaxation and structural reversion measurements. A schematic model was proposed to describe the different relaxation and motion behaviors of macromolecular chains in the unfilled polymer and the filled hybrids with partial and percolated organoclay networks, respectively.     

Rheology of poly(n‐butyl methacrylate) and its composites with calcium carbonate

Poly(n‐butyl methacrylate) (PBMA) composites with calcium carbonate (CaCO₃) were prepared by in situ radical copolymerization of butyl methacrylate (BMA) and methacrylic acid (MA) with precipitated calcium carbonate. To compare the different rheological behaviors of the monomer mixtures with CaCO₃ and the composites, the steady and dynamic viscosities of BMA/MA/CaCO₃ and poly(BMA/MA/CaCO₃) were measured by means of steady and oscillatory shear flows. The viscosity of the mixture BMA/MA/CaCO₃ was found to increase evidently with the increasing of CaCO₃%. The influence of MA% on viscosity of BMA/MA/CaCO₃ was slight. During the in situ polymerization, the viscosity of the reacting system was measured to be enhanced by a factor of about 10⁴ from the monomer/CaCO₃ mixture to composites. The dependency of zero‐shear viscosity on molar mass of PBMA was also investigated. The relation between the zero‐shear viscosity and molar mass is η₀ = 10^?15 M_w^3.5. The evolution of the viscosity with the temperature for both PBMA and its composites was obtained and time–temperature superposition was used to build master curves for the dynamic moduli. The flow activation energies were found to be 115.0, 148.6, and 178.7 kJ/mol for PBMA, composite PBMA/CaCO₃ (90/10), and PBMA/MA/CaCO₃ (89/1/10), respectively. The viscosity of the composites containing less than 10% CaCO₃ was lower than that of pure PBMA with the same molar mass. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 1376–1383, 2003     

Glutarimide acrylic copolymer: A new route to high heat PVC

PVC is the second largest polymer produced and used in the U.S. It is a self-extinguishing material with excellent chemical resistance and good dimensional stability. It's greatest asset, however, is it's versatility. By specifically formulating PVC with the numerous types of additives available, a balance of properties can be tailored for a wide range of applications. The most serious disadvantage of PVC is it's low heat resistance which limits the service temperature of finished articles to about 70°C. Now an additive is available that can be formulated with PVC to form miscible, transparent blends with increased service temperature. With proper formulating, the higher HDT can be achieved without sacrificing other properties. It is especially important in clear PVC applications where no increase in haze was noted with the addition of the acrylic imide copolymer. Indications are that substantial market opportunities exist for a high heat PVC. Major market segments include clear packaging with it's need for hot-fill containers, building products where the desire to use darker colors provides the driving force, and in custom injection molding applications where improved heat resistance would allow vinyl to compete more effectively with FR-styrenics.     

Fischer-tropsch synthesis on a precipitated iron catalyst: Influence of silica support on product selectivities

The influence of silica support on the α-olefins, internal olefins and branched hydrocarbon selectivities of the gasoline range products of a precipitated iron catalyst in the Fischer-Tropsch synthesis was investigated. Three catalysts with varying silica content and constant promoter content were studied. It was found that there is a linear relationship between the silica content of the catalysts and the internal olefin and branched hydrocarbon product selectivities. The selectivities of the aromatic and alcohol products remain relatively constant, indicating that the production of these two groups of compounds is not affected by the presence of silica support in the catalysts.     

Electrophoretic Deposition of YSZ Particles on Non-Conducting Porous NiO–YSZ Substrates for Solid Oxide Fuel Cell Applications

This paper reports a method of performing electrophoretic deposition (EPD) on non-conducting substrates overcoming the requirement of a conducting substrate through the use of porous substrates. The conductivity of the substrate is therefore no longer a limiting factor in the application of EPD. This method is applicable to the fabrication of thick or thin layers of ceramic or metal for various applications. As an example, thin and dense yttria-stabilized zirconia (YSZ) layers have been deposited on a non-conducting NiO–YSZ substrate by EPD from a non-aqueous suspension. A solid oxide fuel cell constructed on these sintered bilayers exhibited power densities of 384 and 611 mW/cm² at 750° and 850°C, respectively.