Synthesis of copolymers of tert‐butyl vinyl ether with maleic and citraconic anhydrides

In the present study, the effects of charge‐transfer complex formation and intramolecular fragmentation (side‐chain lactonization) in radical copolymerization of tert‐butyl vinyl ether (t‐BVE) with anhydrides of maleic (MA) and citraconic (CA) acids and the structure–thermal behavior relationships of the resulting copolymers were examined using the ¹H‐NMR, FTIR, DSC, and TGA analysis methods. It was shown that copolymerization under the chosen conditions proceeded through intramolecular fragmentation with the formation of γ‐lactone units. Side‐chain fragmentation of t‐BVE–MA and t‐BVE–CA copolymers also was confirmed by TGA and DSC analysis. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 2455–2463, 2006 2006     

Optimizing BRDF orientations for the manipulation of anisotropic highlights

This paper introduces a system for the direct editing of highlights produced by anisotropic BRDFs, which we call anisotropic highlights. We first provide a comprehensive analysis of the link between the direction of anisotropy and the shape of highlight curves for arbitrary object surfaces. The gained insights provide the required ingredients to infer BRDF orientations from a prescribed highlight tangent field. This amounts to a non‐linear optimization problem, which is solved at interactive framerates during manipulation. Taking inspiration from sculpting software, we provide tools that give the impression of manipulating highlight curves while actually modifying their tangents. Our solver produces desired highlight shapes for a host of lighting environments and anisotropic BRDFs.     

Catalyst’s Sulfur Displacement by Thiophene, as Monitored by Exchange of 35S Radiotracer

The isotopic exchange has been studied between catalyst radiosulfur and H₂S, formed in thiophene hydrodesulfurization (HDS) (named S-displace) on alumina supported molybdena, on CoMoO_x, PdMoO_x, PtMoO_x and on silica–alumina supported NiWO_x. S-displace was compared with radiosulfur exchange data between catalyst radiosulfur and gas phase H₂S (S^exc) determined previously. The extent of S^exc was higher than that of the S-displace for Mo, CoMo in and NiW, whereas the extent of S-displace from PdMoO and PtMoO was significantly higher, than that of S^exc. Thiophene HDS product distribution data are discussed in terms of increased C=C hydrogenation and C–C hydrogenolysis activity, explained by increasing H₂S production with longer circulation time of the thiophene/H₂ mixture, The C₁/C₃<1 ratios among C₄-hydrogenolysis products indicate some coke formation. The decrease of thiophene HDS activity is presumably a consequence of increasing site-blocking with the formation of more H₂S and coke with longer duration of thiophene treatment.     

Constitutive modeling of HDPE polymer/clay nanocomposite foams

A constitutive model for tensile behavior of high density polyethylene (HDPE)/clay nanocomposite foams was proposed. The elastic modulus of HDPE/clay nanocomposite was developed using micromechanics theory, and the modulus for foams was obtained by using representative volume element (RVE) concept. In order to describe the tensile behavior of the foams, a constitutive equation obtained from a viscoelastic model was proposed. The constitutive model was expressed in terms of microstructural properties of polymer, and physical properties of the foams. The effects of the material parameters and processing conditions on the foam morphologies and mechanical properties of HDPE/clay nanocomposite foams were investigated. Microcellular closed-cell nanocomposite foams were manufactured with HDPE, where the nanoclay loadings of 0.5, 1.0, and 2.0 wt% were used. The effect of clay loading and foaming conditions on the volume expansion ratio, elastic modulus, tensile strength, and elongation at break was investigated. Except for the elongation at break, the mechanical properties were improved with nanoclay loading. The tensile experimental data of the foams were compared with the prediction by the theoretical model. It was demonstrated that the tensile behaviors of HDPE/clay nanocomposite foams were well described by the constitutive model.     

A genetic algorithm for job-shop scheduling with operators enhanced by weak Lamarckian evolution and search space narrowing

The job-shop scheduling problem with operators is a very interesting problem that generalizes the classic job-shop problem in such a way that an operation must be algorithm to solve this problem considering makespan minimization. The genetic algorithm uses permutations with repetition to encode chromosomes and a schedule generation scheme, termed OG&T, as decoding algorithm. This combination guaranties that at least one of the chromosomes represents and optimal schedule and, at the samhat machines and operators are idle while an operation is available to be processed. To improve the quality of the schedules for large instances, we use Lamarckian evolution and modify the OG&T algorithm to further reduce the idle time of the machines and operators, in this case at the risk of leaving all optimal schedules out of the search space. We conducted a large experimental study showing that these improvements allow the genetic algorithm to reach high quality solutions in very short time, and so it is quite competitive with the current state-of-the-art methods.     

Physical agglomeration behavior in preparation of cellulose‐N‐methyl morpholine N‐oxide hydrate solutions by simple mixing

The different melting temperatures of N‐methyl morpholine N‐oxide (NMMO) hydrates in the cellulose–NMMO hydrate solution may be explained by the rather different crystal structures of NMMO hydrates, which are determined by the amount of the hydrates. The preparative process of cellulose–NMMO hydrate solution may result in cellulose structural change from cellulose I to cellulose II, depending on the amount of the hydrate. Mixtures of cellulose and NMMO hydrate in a blender was changed from the granules to slurry with increasing mixing time at 60–70°C, which is below the melting point of the NMMO hydrate. In the case of 15 wt % cellulose–NMMO hydrate granules, which were made by mixing for 20 min, the melting points of various NMMO hydrates were obtained as 77.8°C (n = 0.83), 70.2°C (n = 0.97), and 69.7°C (n = 1.23), respectively, depending on the hydrate number. However, the melting points of cellulose–NMMO hydrate slurry and solution were shifted lower than those of cellulose granules, while the mixing time of slurry and solution are 25 and 35 min, respectively. These melting behaviors indicate instantaneous liquefaction of the NMMO hydrate and the diffusion of the NMMO hydrate into cellulose during mixing in a blender. When cellulose was completely dissolved in NMMO hydrate, the crystal structure of cellulose showed only cellulose II structure. In the cellulose–NMMO products of granules or slurry obtained by high‐speed mixing, which is a new preparation method, they still retained the original cellulose I structure. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 1687–1697, 2004     

Crystallization behavior of poly(N‐methyldodecano‐12‐lactam). IV. Nonisothermal crystallization

Nonisothermal crystallization of poly(N‐methyldodecano‐12‐lactam) (MPA) was investigated using DSC method at cooling rates of 2–40 K/min. With increasing cooling rate, crystallization exotherms decreased in magnitude and shifted toward lower temperatures. Subsequent heating runs (10 K/min) showed an exotherm just above T_g, which increased in magnitude with the rate of preceding cooling run, corresponding to the continuation of primary crystallization interrupted as the system crossed T_g on cooling. Kinetic evaluation by the Avrami method gave values of exponent n close to 2.0, suggesting two‐dimensional crystal growth combined with heterogeneous nucleation. The Tobin method, covering the intermediate range of relative crystallinities, provided n ? 2.20, suggesting possible partial involvement of homogeneous nucleation at later stages of nonisothermal crystallization. The crystallization rate parameter k^1/n showed a linear dependency on cooling rate for both methods, the Tobin values being slightly higher. The Ozawa approach failed to provide reasonable values of the kinetic exponent m of MPA. The Augis–Bennet method was used to determine the effective activation energy of the entire nonisothermal crystallization process of MPA. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 95: 564–572, 2005     

Population balances for particulate processes—a volume approach

Population balance models have been used in chemical engineering since the 1960s and have evolved to become the most important tools for design and control of particulate processes. In this paper we show that the intrinsic particle parameter that determines changes in the process and should thus be included in the population balance is the particle volume. The basic population that is modeled should be the mass distribution, or the volume distribution if the density is constant. The population balance thus describes the change of the volume distribution of volume with time. Furthermore, we suggest that the “birth” and “death” terms that are often used to describe discrete events in particulate processes can almost always be replaced by a rate of change term.To design and control existing and future processes, a multi-dimensional population balance model is required. We propose a volume-based model in which the particle properties that are modeled are the volumes of solid, liquid, and air, respectively. In the most general case the model will consist of a properties vector and a distribution tensor. Depending on the complexity of the process, one or more of the properties may be omitted from the model. This is shown in three examples of increasing complexity: comminution, sintering, and granulation.     

Synthesis,characterization, and antitumor activity of poly(maleic anhydride‐co‐vinyl acetate‐co‐acrylic acid)

The ternary copolymerization of maleic anhydride (MA), vinyl acetate (VA), and acrylic acid (AA) [P(MA‐co‐VA‐co‐AA)], which is considered to be an acceptor–donor–acceptor system, was carried out in 1,4‐dioxane with benzoyl peroxide as an initiator at 70°C under a nitrogen atmosphere. Constants of complex formation for the monomer systems in the study were determined by UV–visible (hydrogen‐bonding complex) and ¹H‐NMR (charge transfer complex) methods, respectively. The results show that polymerization of the P(MA‐co‐VA‐co‐AA) system proceeds by an alternating terpolymerization mechanism. It is shown that the synthesized copolymers have typical polyelectrolyte behavior, ability for reversible hydrolysis–anhydrization reactions, and semicrystalline structures. In these cases, including radical polymerization, and formation of semicrystalline structures, the hydrogen‐bonding effect plays a significant role. The in vitro cytotoxicities of the synthesized terpolymer and alternating copolymer were evaluated using Raji cells (human Burkitt lymphoma cell line). The antitumor activities of prepared anion‐active copolymers were studied using methyl–thiazol–tetrazolium colorimetric assay and 50% of the cytotoxic dose of each copolymer and terpolymer were calculated. Hydrolyzed P(MA‐co‐VA‐co‐AA) and P(MA‐alt‐AA) copolymers have sufficiently high antitumor activity, which depends on the amount of hydrogen‐bonding carboxylic groups and their regular distribution in the side chain of functional macromolecules. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 3425–3432, 2006     

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.