Preparation and properties of ABA block polymers of styrene and butadiene or isoprene made with sec-C4H9Li·2(C2H5)2O

ABA-type “tapered” block polymers were prepared from styrene (monomer A) and butadiene or isoprene, using an initiator of sec-butyllithium complexed with two molecules of ethyl ether. The stress–strain curves of polymers containing about 20–50% styrene show the usual resemblance to curves of crosslinked elastomers. The SBS polymers had higher tensile strengths than the SIS polymers. They also had slightly higher tensile strengths than comparable SBS polymers made with sec-butyllithium. The SIS polymers, however, had generally lower tensile strengths than those made with sec-butyllithium. This is probably caused by higher styrene content of the isoprene block, brought about by increased randomization of the styrene–isoprene copolymerization due to the presence of the ether. The A and B blocks become more compatible, producing loss of strength in the polymer. Infrared analyses of polydienes made with the sec-C₄H₉Li·2(C₂H₅)₂O initiator showed a 6% to 8% increase in 1,2-content (for polybutadiene) or 3,4-content (for polyisoprene), compared to polymers made with sec-butyllithium. The polymer microstructures still have high (>80%) total 1,4-content, however. Thus, this amount of ether can be tolerated in the polymerization system without great loss of rubbery properties or block structure in the resultant polymers.     

Reactive Laser Ablation Synthesis of Nanosize Alumina Powder

An aluminum (Al) target was laser ablated in an oxygen (O₂) atmosphere, producing nanosize alumina (Al₂O₃) powder. The powder surface area decreased (and the particle size increased) with both increasing oxygen pressure and laser fluence. All powders produced had surface areas between 135 and 250 m²/g, corresponding to primary particle sizes ranging from 7 to 3 nm in radius. Phase evolution with temperature was studied via X-ray diffraction. These powders showed a direct transformation from γ- to α-alumina at approximately 1200°C, bypassing other transition alumina phases, while still maintaining small particle size ( 30 nm). Despite the nanosize particles, green densities equal to 54% of the skeletal density (i.e., true density of the solid phase) were obtained by uniaxial pressing at 40 MPa.     

Micropore characterization using the Dubinin-Astakhov equation to analyze high pressure CO2 (273 K) adsorption data

The characterization of the pore structure of microporous materials is of interest because of the usefulness of these materials in many applications. Of these, the characterization of carbon adsorbents is particularly problematic because of the presence of small pores with size on the order of small molecules (micropores) along with a wide distribution of pore sizes, and their non-crystalline structure. In this paper, we present results obtained using the Dubinin-Astakhov equation to analyze data from high pressure CO₂ adsorption at 273 K to characterize two sets of microporous carbons. Our results support the conclusions of previous workers that the Dubinin-Astakhov (DA) equation is able to linearize adsorption data that gives rise to curved Dubinin-Radushkevich plots. However, when applied over different ranges of relative pressure on the adsorption isotherm, the Dubinin-Astakhov plots result in different values of micropore volume and characteristic adsorption potential. Furthermore, DA analysis of CO₂ (273 K) adsorption data over a wide range of pressures (10^–3–22000 Tort), gives results different from DA analysis of CO₂ (273 K) isotherms measured at low pressures only (10^–3–830 Tort). It would appear desirable to apply the DA equation to data that reflects the entire range of micropore filling on the adsorption isotherm, as opposed to data over a limited relative pressure range. For CO₂ adsorption at 273 K, this would necessitate adsorption studies at high pressures, to about 28 atm. Micropore volumes obtained in this manner, agreed with the total pore volumes determined by nitrogen (77 K) adsorption for all the activated carbons studied.     

Influence of dry operating conditions: observation of oscillations and low temperature CO oxidation over Co3O4 and Au/Co3O4 catalysts

A Sm(III) exchanged NaY zeolite prepared from aqueous SmCl₃ was modified with various amounts of fluorine using NH₄F. These fluorinated zeolites exhibit enhanced catalytic activity for the dealkylation of cumene. The evaluation of acid sites by infrared spectroscopy and pyridine adsorption was correlated with fluorine content.     

Comparison of various modeling methods for analysis of powder compaction in roller press

Recently used models relating basic properties of the feed material, roller press design and its operating parameters are reviewed. In particular, we discuss the rolling theory for granular solids proposed by J.R. Johanson in the 1960s, later trials utilizing slab method and newly developed final element models. These methods are compared in terms of efficiency and accuracy of predicting the course of basic process variables like nip angle, pressure distribution in roll nip region, neutral angle, roll torque and roll force.

The finite element method offers the most versatile approach because it incorporates adequate information about powder behavior, geometry and frictional conditions. This enables to perform realistic computer experiments minimizing costs, time and resources needed for process and equipment optimization.     

Reactive Laser Ablation Synthesis of Nanosize Aluminum Nitride

An aluminum (Al) target was laser ablated in a nitrogen (N₂) atmosphere, producing aluminum nitride (AlN) powder. These powders were calcined at 900°C for 2 h. Powders were produced at various nitrogen pressures, and the calcined powders were tested for unreacted aluminum content, using differential thermal analysis (DTA). The AlN powder, produced at a laser fluence of 12 J/cm² and a nitrogen pressure of 10.0 kPa (75 torr), showed no evidence of unreacted aluminum by DTA and was phase-pure AlN by X-ray diffraction (XRD). The surface area of this powder is 82 m²/g, corresponding to a particle size of ∼11 nm, which is in good agreement with TEM observations.     

Lipase-catalyzed synthesis and properties of estolides and their esters

Eight lipases were screened for their ability to synthesize estolides from a mixture that contained lesquerolic (14-hydroxy-11-eicosenoic) acid and octadecenoic acid. With the exception ofAspergillus niger lipase, all 1,3-specific enzymes (fromRhizopus arrhizus andRhizomucor miehei lipases) were unable to synthesize estolides.Candida rugosa andGeotrichum lipases catalyzed estolide formation at >40% yield, with >80% of the estolide formed being monoestolide from one lesquerolic and one octadecenoic acyl group:Pseudomonas sp. lipase synthesized estolides at 62% yield, but the product mixture contained significant amounts of monoestolide with two lesquerolic acyl groups as well as diestolide. ImmobilizedR. miehei lipase was chosen to catalyze the esterification of mono-and polyestolide, derived synthetically from oleic acid, with fatty alcohols or α,ω-diols. Yields were >95% for fatty alcohol reactions and >60% for diol reactions. In addition, the estolide linkage remained intact through the course of the esterification process. Esterification of estolides improved the estolide’s properties—for example, lower viscosity and higher viscosity index—but slightly raised the melting point. Estolides and, particularly, estolide esters may be suitable as lubricants or lubricant additives.     

A method for the design of flexible distillation sequence

A simple method has been developed to optimally design a distillation sequence with a fixed degree of flexibility in feed composition and flowrate, and accounts for uncertainty in stage efficiency, K-value and beat transfer coefficient calculations. The method minimizes a weighted cost function and ensures both optimal and feasible operation in the range of flexibility/uncertainty by using an approach termed “practical feasibility”. The method was tested on a 4 column distillation sequence separating a 5 component light alkane feed mixture. Results are presented to illustrate the effect of uncertainty on sequence cost and column overdesign.     

Exploring the effect of dry premixing of sand and cement on the mechanical properties of mortar

A spout-fluid bed device was developed for dry premixing sand and cement to produce mortar. The goal of the work was to explore the efficacy of a new method for dispersing cement in sand to produce a mortar with better mechanical and physical properties. This strategy was found to work best at high sand/cement ratios, indicating that the dry premixing is more effective as the cement content is reduced and that it may be possible to produce commercially acceptable mortars with a lower cement content. Other properties of the mortar are also positively affected, including a decrease in the shrinkage and an increase in the workability.     

Non-Isothermal crystallization of isotactic polypropylene in dotriacontane. II: Effects of dilution,cooling rate,and nucleating agent addition on growth rate

Non-isothermal crystallization growth rates of nucleated and non-nucleated isotactic polypropylene (iPP) in dotriacontane were determined experimentally by thermal optical microscopy. Adipic acid was used as the nucleating agent. The non-isothermal growth rates of the nucleated and non-nucleated systems were compared with experimentally determined isothermal growth rates. The Lauritzen and Hoffman growth rate equation, originally developed for isothermal crystallization, was modified to describe the non-isothermal growth. The modified Lauritzen-Hoffman equation was used to predict isothermal growth rates from non-isothermal crystallization for the nucleated and non-nucleated polymer-diluent mixtures. This study is the first to deal with polymer-diluent-nucleating agent systems vital to membrane production.