Graft copolymerization studies. III. Methyl methacrylate onto polypropylene and polyethylene terephthalate

The tert‐butoxy radical‐facilitated grafting of methyl methacrylate (MMA) onto commercial polypropylene (PP) pellets and fiber was investigated in heterogeneous conditions similar to practical systems. Free‐radical grafting of several other monomers onto PP fiber was also investigated. Also, preliminary data from the grafting of MMA onto poly(ethylene terephthalate) pellets is presented. The PP‐graft‐PMMA residues were detected by solid‐state ¹³C‐NMR and photoacoustic IR spectroscopy. There was a good correlation between the degree of grafting (DG) determined from these spectroscopic techniques and the results from gravimetric methods. A maximum grafting efficiency of over 50% was found, whereas DG (20%) remained constant at various PP pellet, initiator, and monomer concentrations. However, at relatively low PP fiber concentrations, the DG was 27%; the increase was most likely due to the greater surface area of the fiber. There was also a reduction in DG (14%) at relatively low initiator concentrations. The reaction conditions were altered to favor grafting by the addition of more polymer substrate. When the ratio of tert‐butoxy radicals to PP was decreased, more of the substrate remained unmodified, and empirical calculations showed the formation of grafts with up to 40 monomer units. At high initiator concentrations, calculations showed that the graft residues were 1–2 units long. Therefore, variation of the polymer, initiator, and monomer concentrations was shown to have a significant effect on grafting. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 898–915, 2002     

Epoxidation of soybean oil by the methyltrioxorhenium-CH2Cl2/H2O2 catalytic biphasic system

We studied the methyltrioxorhenium (MTO)-CH₂Cl₂/H₂O₂ biphasic system for epoxidizing soybean oil. The reactions were optimized (reactant ratio, time, and temperature), which resulted in a better performance (higher conversion and selectivity) than those described in the literature. Total doublebond conversion and 95% selectivity were obtained in 2 h at room temperature. Furthermore, it was possible to reach desired epoxidation degrees by changing the oxidant and MTO amounts. The rhenium-epoxidized soybean oil remained stable in the absence of stabilizers for up to 30 d when stored at mild conditions.     

Formaldehyde-free durable-press finishes

Durable-press finishing agents that neither contain nor release formaldehyde when applied to cotton fabrics are reviewed and compared with conventional N-methylolamides in regard to fabric wrinkle resistance, smooth drying properties, strength retention and yellowing imparted. The need for agents that are not derived from formaldehyde results from international recognition that formaldehyde is a probable human carcinogen. When formaldehyde-free cellulose crosslinking agents are screened to eliminate those having toxicity, odour and environmental problems of their own, the most likely candidates are seen to be polycarboxylic acids and 1,3-dimethyl-4, 5-dihydroxy-ethyleneurea (also known as DHDMI). These differ in cost and effectiveness, and will require further research and development to become fully practical.     

Ahiflower oil: A novel non‐GM plant‐based omega‐3+6 source

Ahiflower oil, a novel and proprietary dietary oil with the richest effective combined essential fatty acids from a single non‐GM plant, has been developed agronomically in a unique vertically integrated “soil to oil” model at commercial scale by Nature's Crops International. Ahiflower oil helps resolve a persistent dilemma in sustainable global omega‐3 nutrition from marine sources while dramatically improving dietary omega‐3 EPA conversion from plant sources and while supplying beneficial anti‐inflammatory GLA not found in fish or algal oils. Having achieved key regulatory clearances in the US and EU, Ahiflower oil is launching in the latter half of 2015 in supplements and foods.     

The influence of gas velocity, salt type and concentration on transition concentration for bubble coalescence inhibition and gas holdup

The influence of gas velocity (3.5, 10, and 18 mm/s), salt type (NaCl, NaF, NaBr, NaI and CsCl) and salt concentration (0.001-3 M) on bubble coalescence in a small bubble column were studied. The bubble coalescence was determined by the relative change in the measured light intensities passing through the salt solutions and clean deionised water. It was shown that the transition salt concentration for bubble coalescence inhibition (determined at 50% of bubble coalescence) of all investigated salts decreases with increasing superficial gas velocity. The difference in the transition concentration between NaCl, NaF, NaBr and CsCl does not significantly change with the gas velocity. However that difference between NaI and the other salts significantly decreases with increasing the gas velocity. The gas holdup significantly increases with NaCl, NaF, NaBr and CsCl concentrations but does not significantly change with NaI concentration. These new results imply that the transition salt concentration for bubble coalescence and gas holdup depend not only on the salt properties (i.e. the ion type and their combination) as previously reported, but also on the hydrodynamic conditions.     

Influence of Phenological Stage on Swainsonine and Endophyte Concentrations in Oxytropis sericea

Locoweeds are defined as Astragalus and Oxytropis species that cause intoxication due to the alkaloid swainsonine. Swainsonine concentrations in Oxytropis sericea were influenced by location, plant part, and the developmental stage of the plant. Concentrations followed similar trends at each location, generally increasing over the growing season in above-ground parts until the plant reaches maturity with no change in concentration in the crowns. At the onset of senescence, swainsonine decreased in floral parts to less than half of the peak concentration. Similar to swainsonine concentrations, endophyte amounts were influenced by location, plant part, and the developmental stage of the plant. Likewise, endophyte amounts generally increased over the growing season in above ground parts and remained static in the crowns at all four locations. Swainsonine in Oxytropis sericea was positively associated with the endophyte Undifilum, which is responsible for swainsonine biosynthesis.     

Thermal and nonthermal physiochemical processes in nanoscale films of amorphous solid water

Amorphous solid water (ASW) is a disordered version of ice created by vapor deposition onto a cold substrate (typically less than 130 K). It has a higher free energy than the crystalline phase of ice, and when heated above its glass transition temperature, it transforms into a metastable supercooled liquid. This unusual form of water exists on earth only in laboratories, after preparation with highly specialized equipment. It is thus fair to ask why there is any interest in studying such an esoteric material. Much of the scientific interest results from the ability to use ASW as a model system for exploring the physical and reactive properties of liquid water and aqueous solutions. ASW is also thought to be the predominant form of water in the extremely cold temperatures of many interstellar and planetary environments. In addition, ASW is a convenient model system for studying the stability of amorphous and glassy materials as well as the properties of highly porous materials. A fundamental understanding of such properties is invaluable in a diverse range of applications, including cryobiology, food science, pharmaceuticals, astrophysics, and nuclear waste storage, among others. Over the past 15 years, we have used molecular beams and surface science techniques to probe the thermal and nonthermal properties of nanoscale films of ASW. In this Account, we present a survey of our research on the properties of ASW using this approach. We use molecular beams to precisely control the deposition conditions (flux, incident energy, and incident angle) and create compositionally tailored, nanoscale films of ASW at low temperatures. To study the transport properties (viscosity and diffusivity), we heat the amorphous films above their glass transition temperature, T(g), at which they transform into deeply supercooled liquids prior to crystallization. The advantage of this approach is that at temperatures near T(g), the viscosity is approximately 15 orders of magnitude larger than that of a normal liquid. As a result, the crystallization kinetics are dramatically slowed, increasing the time available for experiments. For example, near T(g), a water molecule moves less than the distance of a single molecule on a typical laboratory time scale (～1000 s). For this reason, nanoscale films help to probe the behavior and reactions of supercooled liquids at these low temperatures. ASW films can also be used for investigating the nonthermal reactions relevant to radiolysis.     

On the physical interpretation of the Kawakita and Adams parameters derived from confined compression of granular solids

The objective of this paper was to investigate the physical significance of the Kawakita and Adams parameters derived from the compression of some granular solids. Four model granules of different expected deformation behaviour were prepared by varying the composition and porosity of the granules. The granules were nearly spherical and of similar size and showed a variation in mechanical properties in terms of their elasticity, plasticity, fracture strength and brittleness. Due to the size and shape of the granules, compression due to granule rearrangement was generally limited. The Kawakita a parameter approximated the maximal engineering strain of the granular solids and both the Kawakita a and b^− 1 parameter reflected the plasticity of the granules. The Adams parameter τ₀ seemed to reflect the initial cracking of granules. Thus, the combined use of the Kawakita parameters a and b^− 1 and the Adams parameter τ₀ may give a comprehensive representation of the compression behaviour of granular solids.     

Contraction of Investment Cast H13 Tool Steel Real Time Measurement

This paper presents the results of an investigation into the dimensional changes and variability of investment cast H13 tool steel. An experimental apparatus has been developed to measure the dimensional changes during the casting process. Investigating the dynamics of mould expansion and alloy contraction during investment casting, it has been possible to determine in greater detail the contributions of the cast alloy and the mould to the final contraction of unconstrained castings. Contraction and dimensional variability of the final cast product is defined and experimental estimations of the contributions of each stage of investment casting are made. A technique for combining the variability of sequential stages is discussed. The measured contraction appears to be non-uniform and dependent on the position along the casting.