Heterogeneous reactions of polymers: 4. Melting behaviour of heterogeneously chlorinated and sulphonated polyethylenes

The melting behaviour of heterogeneously chlorinated and sulphonated high-density polyethylene was studied by differential scanning calorimetry. It was found that an increase in T_m takes place at high degrees of substitution in the amorphous phase. For sulphonated polyethylenes the increase in T_m was also dependent on the type of the counterion. The effect is interpreted as a decrease in configurational entropy upon fusion due to the restraints that the highly chlorinated and sulphonated amorphous regions impose on the adjacent crystallites.     

Solvent-Polymeric Membranes for Separation of Li+ From Other Alkali Metal and Alkaline Earth Ions

Lithium may be recovered from the Dead Sea brines by a process which combines membrane separation with ion-exchange. Solvent-polymeric membranes based on alkyl-arylphosphates cause selective permeation of lithium ions with Br⁻₃ as counter ions. Addition of the derivatives of neutral “crown” ethers did not improve their performance and an adverse effect, due to the decrease in the fluidity of the membrane system, was observed. Incorporation of ionizable “crown” ethers compatible with the system may, however, be advantageous; pH gradients could act as a driving force for transport of lithium in such systems. Membranes prepared with (2-ethylhexyl)-diphenyl phosphate (Santicizer 141) gave the best results from the point of view of selectivity of Li⁺ transport vs. Mg²⁺ and Ca²⁺. Maintenance of ca. 10⁻³ M concentrations of Br₂ in the end-brine solutions gives optimal membrane performance. No significant change in membrane permeability and selectivity occurred during six months of their operation. Lithium ions in the product solution of the membrane separation process may be further separated from the residual Mg²⁺ and Ca²⁺ ions and concentrated up to 1 M by ion exchange processes. Lithium may be precipitated from such solutions, free from alkaline earth ions, as Li₂CO₃.     

Dissolution of perfluoroalkyl oligomers in lubricating oil for enhancing wear resistance and fuel economy

Perfluorobutyl-1,1,2-tri-H-1-hexene and perfluoroalkyl methacrylate have been solubilized in lubricating oil by single-step free radically grafting onto poly(ethylene-co-propylene). Perfluoroalkyl-1,1,2,2-tetra-H-ethanol and perfluoropolyether carboxylic acid were solubilized by condensing with poly[(ethylene-co-propylene)-g-glycidyl methacrylate], generating the corresponding perfluoroalkyl ether or ester, respectively. Solubilization of 1,1,2,2-tetra-H-ethanol was also achieved by condensing with poly[(ethylene-co-propylene)-g-2-isocyanoethyl methacrylate] to the corresponding perfluoroalkyl urethane. Scar diameter reductions ranged from 9.4 to 58% using perfluoro-modified graft copolymers as determined using the Four Ball Wear Test, although optimum reductions were obtained using perfluoroalkyl urethane-modified graft copolymers. Moreover, a semiquantitative correlation of scar reductions and thermal instability was determined. Sequence VI engine testing of perfluoroalkyl urethane graft copolymers containing pendant perfluoroalkyl chain lengths of 8.2 and 7.2 had an Equivalent Fuel Economy Index of 4.33 and 4.27, respectively. © 1994 John Wiley & Sons, Inc.     

Lipids ofCrassostrea virginica. I. Preliminary investigations of aldehyde and phosphorous containing lipids in oyster tissue

Oyster tissue contained 2.4% lipid, 0.14 μmole aldehyde per milligram lipid and at least 10 μg phosphorous per milligram lipid. The neutral lipid represented 58%, the glycolipid 6%, and the polar lipid 36% of the total lipid recovered after silicic acid column chromatography. Aldehydes were found in all fractions, but the presence of plasmalogen was verified in only the neutral and polar lipid fractions. At least 68% of the plasmalogen in oyster lipid was found in the polar lipid fraction. At least 13% of the phosphorous in oyster lipids was present as phosphonolipid. The distribution of phosphate and phosphonate lipids was: diacyl phospholipid 38.1%, plasmalogen phospholipid 21.8%, sphingophosphonolipid 13.5%, glyceryl ether phospholipid 8.3%, sphingophospholipid 6.9%, plasmalogen phosphonolipid 6.4%, diacyl phosphonolipid 2.6%, and glyceryl ether phosphonolipid 2.4%. When the per cent of phosphorous as phosphonolipid within the plasmalogen and glyceryl ether classes was calculated, similar values were obtained. These results support the hypothesis that there is a product precursor relationship between these two classes of lipids. Some of the data taken from a thesis to be submitted to the Graduate School, University of Maryland, by Leslye Johnson in partial fulfillment of the requirements for the M.S. degree in biochemistry.     

Hydrogenation of 3,4-epoxy-1-butene over Cu–Pd/SiO2 catalysts prepared by electroless deposition

Electroless deposition has been used to prepare Cu–Pd/SiO₂ bimetallic catalysts wherein initial Cu coverages are limited only to the pre-existing Pd surface. Cu loading on the Pd surface can be systematically varied by modification of deposition kinetic parameters. In this case deposition time was used as the kinetic variable for the preparation of a series of Cu–Pd catalysts. These materials have been characterized using atomic absorption, CO chemisorption, and FT-IR (adsorption of CO), and then evaluated for the hydrogenation of 3,4-epoxy-1-butene, a functionalized olefin having many potential reaction pathways. Catalyst performance and characterization results suggest that Cu is not distributed in a monodisperse manner on the Pd surface, indicating the existence of autocatalytic deposition of Cu on Cu sites. The FT-IR results suggest that although CO adsorption on all sites is suppressed by Cu addition, initial Cu deposition occurs more readily on certain sites. The bimetallic Cu–Pd sites that are formed exhibit unusually high activity for EpB conversion and formation of unsaturated alcohols and aldehydes. This bimetallic effect on catalyst activity and selectivity is best explained, not by the existence of either ligand or ensemble effects, but rather by the bifunctional nature of the Cu–Pd sites present on the surface of these catalysts.     

SOME ASPECTS OF THEORETICAL COMPARISON OF FISCHER-TROPSCH REACTORS

The reactor systems used for the Fischer-Tropsch synthesis, fixed bed, fluidized bed and slurry bed, are compared on the basis of space time yield (STY) and level of conversion obtainable under the same set of feed and operating conditions. The slurry bed and fluidized bed reactor were compared on the basis of a first order reaction model. The performance of these two reactors was found to be comparable at low values of WHSV, but at higher values of WHSV, the fluidized bed reactor gave higher conversions and STY. A power law kinetic expression was used to compare the performance of the slurry bed and fixed bed reactors. Higher conversions and STY were obtained from the fixed bed with varying WHSV. This may be due to the omission of the intra and inter phase mass transfer resistances in the modelling of the fixed bed reactor.     

Effect of layering pattern on dynamic mechanical properties of randomly oriented short banana/sisal hybrid fiber–reinforced polyester composites

Dynamic mechanical test methods have been widely employed for investigating the structures and viscoelastic behavior of polymeric materials to determine their relevant stiffness and damping characteristics for various applications. Randomly oriented short banana/sisal hybrid fiber–reinforced polyester composites were prepared by keeping the volume ratio of banana and sisal 1 : 1 and the total fiber loading 0.40 volume fraction. Bilayer (banana/sisal), trilayer (banana/sisal/banana and sisal/banana/sisal), and intimate mix composites were prepared. The effect of layering pattern on storage modulus (E′), damping behavior (tan δ), and loss modulus (E″) was studied as a function of temperature and frequency. Bilayer composite showed high damping property while intimately mixed and banana/sisal/banana composites showed increased stiffness compared to the other pattern. The Arrhenius relationship has been used to calculate the activation energy of the glass transition of the composites. The activation energy of the intimately mixed composite was found to be the highest. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 2168–2174, 2005     

Chemical Defense in the Plant Bug Lopidea robiniae (Uhler)

Secretions from the metathoracic glands (MTG) of the black locust bug, Lopidea robiniae (Uhler) (Heteroptera: Miridae) contained six major compounds, including (E)-2-hexenal, (E)-2-hexen-1-ol, (E)-2-octenal, (E)-2-octen-1-ol (E)-2-heptenal, and (Z)-3-octen-1-ol. Males and females did not differ significantly in the relative compositions of identified compounds. In feeding trials, six bird species [robin (Turdus migratorious), blue jay (Cyanocitta cristata), brown thrasher (Toxostoma rufum), killdeer (Charadrius vociferus), starling (Sturnus vulgaris), and house wren (Troglodytes aedon)] demonstrated feeding aversions towards L. robiniae, implying that black locust bugs are chemically defended. Bugs discharged the liquid contents of their MTG when attacked, thereby producing a strong and distinct odor. Some birds immediately ejected bugs out of their mouth after biting them, suggesting that the MTG secretion was a deterrent.     

Hydrodynamics and mass transfer in a bubble column with an organic liquid

Hydrodynamic and mass transfer data in Soltrol-130 (a mixture of C₉+ iso-paraffins) were measured in a 0.305 m diameter bubble column. The gas holdup structure (i.e., the contributions to holdup from the small and large bubble fractions of the dispersion) for this hydrocarbon liquid in the churn turbulent flow regime was analyzed using the dynamic gas disengagement technique. The validity of the assumption of axially uniform gas holdup structure was checked. Literature correlations were found inadequate to explain the observed gas holdup and the volumetric mass transfer coefficients for Soltrol-130. The volumetric mass transfer coefficient per unit volume of large bubbles is shown to be independent of superficial gas velocity for the fully developed churn turbulent regime. The present hydrodynamic and mass transfer data in the churn turbulent regime should be useful in the design and scale-up of bubble columns used in organic process industries.     

Catalytic Combustion of Model Carbon Particles (CPs) over Pt/β-SiC Catalyst

Platinum catalyst supported on a medium surface area -SiC was successfully used for the catalytic combustion of model carbon particles and compared to a catalyst supported on a low surface area -SiC. The -SiC-based catalyst showed no deactivation as a function of cycling tests while a strong deactivation was observed on the -SiC-based catalyst. This deactivation was attributed to the progressive encapsulation of the platinum particles by a layer of silica which built up during the combustion cycle. These results render possible the use of Pt/-SiC catalyst as a diesel carbon particle catalytic filter with continuous regeneration.