Catalyst fragmentation during propylene polymerization: Part I. The effects of grain size and structure

Fragmentation of support/catalyst particles during propylene polymerization in the gas phase is analyzed via a mathematical model including energy and mass transfer with chemical reaction processes. The rupture phenomenon is considered specifically by the model, and evaluated as it proceeds in time, Two different regions are recognized in the polymerizing particle at fragmentation time: an inner core resembling the original solid support/catalyst structure, and an external set of layers where most of the polymerization occurs. Model predictions concerning the effects of fragmentation on polymerization are discussed. The influence of different degrees of fragmentation on thermal runaways and monomer availability at active sites located inside the support/catalyst/polymer complex is shown. Monomer concentration profiles inside the growing particles are explained in terms of the combined fragmentation-polymerization interaction. Results show a strong influence of catalyst structure on critical phenomena during early polymerization stages, and suggest the possibility of controlling critical parameters via the definition of fragment structure at catalyst preparation time.     

A quantitative feedback solution to the multivariable tracking error problem

This paper introduces a novel solution for the multi‐input multi‐output (MIMO) quantitative feedback theory control design problem with tracking error specifications. Looking for a minimum controller overdesign, the technique finds new controller quantitative feedback theory bounds based on necessary and sufficient conditions for the existence of suitable associated prefilter matrix elements. It improves previous approaches to the subject and includes (i) the possibility of a free selection of the nominal plant, (ii) a less conservative application of the Schwartz inequality to decisively reduce the potential controller overdesign, (iii) a methodology to design independently the elements of the prefilter matrix, and (iv) a scope of application to both sequential and nonsequential MIMO controller design methods. The benefits of the new control design technique are illustrated by means of two examples. The first one, a standard 2 × 2 MIMO problem, is provided for comparison purposes with previous approaches. The second example, included as a major control challenge, deals with a well‐known demanding distillation column benchmark problem. Copyright © 2013 John Wiley & Sons, Ltd.     

Metabolic behavior in rats of a nonprotein microemulsion resembling low-density lipoprotein

A protein-free microemulsion (LDE) with a lipid composition resembling that of low-density lipoprotein (LDL) was used in metabolic studies in rats to compare LDE with the native lipoprotein. LDE labeled with radioactive lipids was injected into the bloodstream of male Wistar rats, and plasma kinetics of the labeled lipids were followed on plasma samples collected at regular intervals for 12 h after injection. The 24-h LDE uptake by different tissues was also measured in tissue samples excised after the animals had been sacrificed. We found that LDE plasma kinetics were similar to those described for native LDL [fractional clearance rate (FCR) of cholesteryl ester, 0.42±0.11 h⁻¹]. The major site for LDE uptake was the liver, and the tissue distribution of the LDE injected radioactivity was as one would expect for LDL. To test whether LDE was taken up by the specific LDL receptors, the LDE emulsion was injected into rats treated with 17α-ethinylestradiol, which is known to increase the activity of these receptors; as expected, removal of LDE from the bloodstream increased (FCR=0.90±0.35 h⁻¹). On the other hand, saturation of the receptors that remove remnants by prior infusion of massive amounts of lymph chylomicrons did not change LDE plasma kinetics. These results indicate that LDE is cleared from plasma by B,E receptors and not by the E receptors that remove remnants. Incorporation of free cholesterol into LDE increased LDE plasma clearance. Incubation studies also showed that LDE incorporates a variety of apolipoproteins, including apo E, a ligand for recognition of lipoproteins by specific receptors. Our data suggest that LDE can be a useful tool to test LDL metabolism and B,E receptor function.     

1H nuclear magnetic resonance study of polyurethane prepolymers from toluene diisocyanate and polypropylene glycol

Polyurethane prepolymers prepared from toluene 2,4‐diisocyanate, toluene 2,6‐diisocyanate, and polypropylene glycol with a ratio between the isocyanate and hydroxyl groups equal to 2 were analyzed by ¹H nuclear magnetic resonance (NMR) spectroscopy in acetone‐d₆. Different temperatures and concentrations were used. Toluene 2,4‐dimethylurethane and toluene 2,6‐dimethylurethane were synthesized and used as model compounds to assign prepolymers signals. Measurements of spin–lattice relaxation time T₁ by “inversion recovery” experiments were carried out on toluene 2,4‐diisocyanate, toluene 2,6‐diisocyanate, toluene 2,4‐dimethylurethane, toluene 2,6‐dimethylurethane, and polyurethane prepolymers. Differences in T₁ times were used to interpret prepolymers spectra, by means of the strong observed effect on protons due to the presence of adjacent isocyanate groups. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 347–357, 2003     

X-ray crystal structure of the dye 2-cyano-4-bromo-4′-N,N-diethylaminoazobenzene

The crystal structure and molecular conformation of 2-cyano-4-bromo-4′-N,N-diethylaminoazobenzene (C₁₇H₁₇N₄Br, mol. wt. = 357·2 a.m.u) has been determined from X-ray diffraction data; triclinic, P$\text{1}$ (No. 2), a = 10·132(11) Å, b = 12·216(16) Å, c = 6·966(11) Å, α = 104·21(9)°, β = 92·67(12)°, γ = 97·22(7)°, V = 826·5(9) ų, Z = 2, D_c = 1·436 g cm^?3, F(000) = 378, λ(MoKα) = 0·71069 Å, μ(MoKα) = 26·0 cm^?1. The structure was solved by the multiple solution direct method and refined by full-matrix least-squares to R = 0·059 for 1538 independent observed reflections. The azobenzene skeleton is planar to within 0·06 Å. Most significant bonding data are: NN, 1·290(8) Å; BrC, 1·866(6) Å; mean CN (azo) 1·380(8) Å; NNC, 113·6(4) and 115·3(4)°; NCC (cis relative to NN) 125·9(4)° and 126·7(4)°; NCC (trans) 116·8°(5)° and 116·1(4)°.     

The Torque Transmission Capabilities of the Adhesively-Bonded Tubular Single Lap Joint and the Double Lap Joint

With the wide application of fiber-reinforced composite materials in aircraft, space structures and robot arms, the design and manufacture of composite joints have become a very important research area because they are often the weakest areas in composite structures.

In this paper, the stress and torque transmission capabilities of the adhesively-bonded tubular single lap joint and the double lap joint were experimentally tested. In order to compare the experimental results with the calculated results, the stress and torque transmission capabilities were analyzed by the 3-dimensional finite element method taking into consideration the nonlinear properties of the adhesive.

From the experiments it was found that the torque transmission capabilities of the adhesively-bonded double lap joint was 2.7 times as large as that of the single lap joint. Also, it was found that the fatigue limit of the double lap joint was 16 times as large as that of the single lap joint.     

Breaking Bad in Cyberspace: Understanding why and how Black Hat Hackers Manage their Nerves to Commit their Virtual Crimes

Information Systems Frontiers - What is happening in hacker’s minds when they are committing criminal activities? How black hat hackers manage nerves, which is about managing fear and...     

A scalable solution to the nearest neighbor search problem through local-search methods on neighbor graphs

Pattern Analysis and Applications - Nearest neighbor search is a powerful abstraction for data access; however, data indexing is troublesome even for approximate indexes. For intrinsically...     

The Resource-Energy Nexus as a Key Factor for Circular Economy

The extraction of raw materials is associated with energy input and CO₂ emissions. What is obvious for extraction from mining, however, also applies to recycling. Mostly, recycling is preferred for reasons of climate protection or because of the geological scarcity of raw materials, which is controversially discussed. While in mining, the declining ore grade is a driver for the energy demand, in case of recycling it is the dissipation of materials into products or waste. As concentration decreases, the effort required also increases disproportionately. The “closing the loop” metaphor of Circular Economy is therefore inappropriate in its stricter meaning. It is rather about optimizing the overall system and finding the optimal recycling rate. However, first, it must be clarified what the political goals for Circular Economy are.     

Compatibilization of an immiscible blend of EPDM and POM with an Ionomer

Immiscible blends of ethylene-propylene-diene-monomer (EPDM) and polyoxymethylene (POM), when EPDM is the major phase were compatibilized on the addition of an ionomer, poly(ethylene-co-methacrylic acid). The inclusion of the ionomer reduced the interfacial tension between the two phases, such that the diameter of the POM domains were significantly reduced to between 0.5 and 2 μm, typical of that required to toughen ductile polymers. The mechanical properties of the resultant compatibilized blends were significantly enhanced with increases in Young's modulus (↑54%), tensile strength (σ, ↑139%), elongation at break (ε, ↑97%), and tensile toughness (↑500%) with increasing ionomer content, relative to EPDM rubber alone. The ShoreA hardness of the compatibilized blend was 70.1 compared with 56.8 for the immiscible binary blend and, 50.2 for neat EPDM rubber.