The Effect of Tacticity on the Conformational Properties of Poly(1-olefin sulfone)s

The effect of tacticity on the conformational properties of poly(olefin sulfone)s was studied. Tactic polymers, prepared from racemic thiirane monomers using chiral inititators were compared with atactic polymers prepared by free radical co-polymerisation of the 1-olefin with sulfur dioxide. Analysis of the XRD patterns showed that the tactic polymers formed more ordered structures in the bulk with longer layer spacings, consistent with a model in which their side chains meet at the tips in contrast with the atactic polymers whose side chains interdigitate. 13C MAS nmr experiments suggest that as tacticity increases so too does the proportion of C-S bonds in the gauche conformation, however the proportion of S-C bonds in the trans conformation falls, in contrast to a reported molecular mechanics study. Finally, DSC measurements on the polymers with longer side chains showed the presence of two endotherms on heating, illustrating definite liquid crystalline behaviour.

The rotational molding characteristics of metallocene polyethylene skin/foam structures

This article reports on the results of ongoing work in which the foaming characteristics of metallocene-catalyzed linear low density polyethylenes for rotational molding are investigated. Earlier publications related rheological and thermal parameters to the polymer structure and mechanical properties and found that metallocene polyethylene can be used in rotational foam molding to produce a foam that will perform as well as a Ziegler-Natta catalyzed foam. Through adjustments to molding conditions, the significant processing and physical material parameters, which optimize metallocene catalyzed linear low-density polyethylene foam structure, have been identified. This article details the optimum processing route for the production of two layer skin/foam parts using the drop box method. © SAGE Publications 2007.

Process monitoring approach using fast moving window PCA

This paper introduces a fast algorithm for moving window principal component analysis (MWPCA) which will adapt a principal component model. This incorporates the concept of recursive adaptation within a moving window to (i) adapt the mean and variance of the process variables, (ii) adapt the correlation matrix, and (iii) adjust the PCA model by recomputing the decomposition. This paper shows that the new algorithm is computationally faster than conventional moving window techniques, if the window size exceeds 3 times the number of variables, and is not affected by the window size. A further contribution is the introduction of an N-step-ahead horizon into the process monitoring. This implies that the PCA model, identified N-steps earlier, is used to analyze the current observation. For monitoring complex chemical systems, this work shows that the use of the horizon improves the ability to detect slowly developing drifts.

Atomistic studies of interactions between the dominant lattice dislocations and γ/γ-lamellar boundaries in lamellar γ-TiAl

This paper reports on atomistic simulations of the interactions between the dominant lattice dislocations in ?-TiAl (<1 0 1] superdislocations) with all three kinds of ?/?-lamellar boundaries in polysynthetically twinned (PST) TiAl. The purpose of this study is to clarify the early stage of lamellar boundary controlled plastic deformation in PST TiAl. The interatomic interactions in our simulations are described by a bond order potential for L10-TiAl which provides a proper quantum mechanical description of the bonding. We are interested in the dislocation core geometries that the lattice produces in proximity to lamellar boundaries and the way in which these cores are affected by the elastic and atomistic effects of dislocation-lamellar boundary interaction. We study the way in which the interfaces affect the activation of ordinary dislocation and superdislocation slip inside the ?-lamellae and transfer of plastic deformation across lamellar boundaries. We find three new phenomena in the atomic-scale plasticity of PST TiAl, particularly due to elastic and atomic mismatch associated with the 60° and 120° ?/?-interfaces: (i) two new roles of the ?/?-interfaces, i.e. decomposition of superdislocations within 120° and 60° interfaces and subsequent detachment of a single ordinary dislocation and (ii) blocking of ordinary dislocations by 60° and 120° interfaces resulting in the emission of a twinning dislocation.

Characterization of the Rheological, Mucoadhesive, and Drug Release Properties of Highly Structured Gel Platforms for Intravaginal Drug Delivery

This investigation describes the formulation and characterization of theologically structured vehicles (RSVs) designed for improved drug delivery to the vagina. Interactive, multicomponent, polymeric platforms were manufactured containing hydroxyethylcellulose (HEC, 5% w/w) polyvinylpyrrolidone (PVP, 4% w/w), Pluronic (PL, 0 or 10% w/w), and either polycarbophil (PC, 3% w/w) or poly(methylvinylether-co-maleic anhydride) (Gantrez S97, 3% w/w) as a mucoadhesive agent. The rheological (torsional and dynamic), mechanical (compressional), and mucoadhesive properties were characterized and shown to be dependent upon the mucoadhesive agent used and the inclusion/exclusion of PL. The dynamic theological properties of the gel platforms were also assessed following dilution with simulated vaginal fluid (to mimic in vivo dilution). RSVs containing PC were more rheologically structured than comparator formulations containing GAN. This trend was also reflected in formulation hardness, compressibility, consistency, and syringeability. Moreover, formulations containing PL (10% w/w) were more theologically structured than formulations devoid of PL. Dilution with simulated vaginal fluids significantly decreased rheological structure, although RSVs still retained a highly elastic stnicture (G' > G '' and tan delta <1). Furthermore, RSVs exhibited sustained drug release properties that were shown to be dependent upon their rheological structure. It is considered that these semisolid drug delivery systems may be useful as site-retentive platforms for the sustained delivery of therapeutic agents to the vagina.

Physicochemical Characterization of Poly(ethylene glycol) Plasticized Poly(methyl vinyl ether-co-maleic acid) Films

The influence of the poly(ethylene glycol) (PEG) plasticizer content and molecular weight on the physicochemical properties of films cast from aqueous blends of poly(methyl vinyl ether-co-maleic acid) (PMVE/MA) was investigated with tensile mechanical testing, thermal analysis, and attenuated total reflectance/Fourier transform infrared spectroscopy. Unplasticized films and those containing high copolymer contents were very difficult to handle and proved difficult to test. PEG with a molecular weight of 200 Da was the most efficient plasticizer. However, films cast from aqueous blends containing 10% (w/w) PMVE/MA and either PEG 1000 or PEG 10,000 when the copolymer/plasticizer ratio was 4 : 3 and those cast from aqueous blends containing 15% (w/w) PMVE/MA and either PEG 1000 or PEG 10,000 when the copolymer/plasticizer ratio was 2 : 1 possessed mechanical properties most closely mimicking those of a formulation we have used clinically in photodynamic therapy. Importantly, we found previously that films cast from aqueous blends containing 10% (w/w) PMVE/MA performed rather poorly in the clinical setting, where uptake of moisture from patients' skin led to reversion of the formulation to a thick gel. Consequently, we are now investigating films cast from aqueous blends containing 15% (w/w) PMVE/MA and either PEG 1000 or PEG 10,000, where the copolymer/plasticizer ratio is 2 : 1, as possible Food and Drug Administration approved replacements for our current formulation, which must currently be used only on a named patient basis as its plasticizer, tripropylene glycol methyl ether, is not currently available in pharmaceutical grade

Effect of acetonitrile on the solubility of carbon dioxide in 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl) amide

The effect of the addition of acetonitrile on the solubility of carbon dioxide in an ionic liquid, the 1-ethyl-3- methylimidazolium bis(trifluoromethanesulfonyl)amide, [C(2)mim][NTf2], was studied experimentally at pressures close to atmospheric and as a function of temperature between 290 and 335 K. It was observed that the solubility of carbon dioxide decreases linearly with the mole fraction of acetonitrile from a value of 2.6 x 10(-2) in the pure ionic liquid at 303 K to a mole fraction of 1.3 x 10(-2) in the mixture [C(2)mim][NTf2] + CH3CN with x(CH3CN) = 0.77 at the same temperature. The gas solubility decreases with temperature, and the thermodynamic properties of solvation could be calculated. The vapor pressures of the [ C2mim][ NTf2] + CH3CN mixtures were measured in the same temperature range, and strong negative deviations from Raoult's law were obtained: up to 36% for a mixture with x(CH3CN) = 0.46 at 334 K. Negative excess molar volumes of approximately -1 cm(3) mol(-1) at equimolar composition could also be calculated from density measurements of the pure components and of the mixtures. These observations are confirmed by neutron diffraction studies and are compatible with the existence of strong ion-dipole interactions in the mixed liquid solvent.

Development of operator independent bone cement vacuum mixing system for joint replacement surgery,

(2006) Vol. 35 No. 8 317

Effect of temperature and mixing conditions on quality and consistency of poly(methyl methacrylate) bone cement

The mixing of poly(methyl methacrylate) (PMMA) bone cement has been studied to develop methods for preparing a consistently high quality cement. A novel droplet test experimental procedure was developed that characterised the wetting characteristics involved in bone cement mixing. Using this technique it was established that increased wetting occurred by mixing bone cement at a lower temperature (-28 degreesC) than normal mixing at room temperature.

Ionic liquid-reconstituted cellulose composites as solid support matrices for biocatalyst immobilization

Preparation of cellulose-polyamine composite films and beads, which provide high loading of primary amines on the surface allowing direct one-step bioconjugation of active species, is reported using an ionic liquid (IL) dissolution and regeneration process. Films and bead architectures were prepared and used as immobilization supports for laccase as a model system demonstrating the applicability of this approach. Performance of these materials, compared to commercially available products, has been assessed using millimeter-sized beads of the composites and the lipase-catalyzed transesterification of ethyl butyrate.

Application of poly(ethylene glycol)-based aqueous biphasic systems as reaction and reactive extraction media

Poly(ethylene glycol)-based aqueous biphasic systems (PEG-ABSs) have been investigated as tunable reaction media, in the example presented here, to control the oxidation of cyclohexene to adipic acid with hydrogen peroxide. The production of adipic acid was found to increase from the monophasic to the biphasic regimes, was greatest at short tie-line lengths (close to the system's critical point), and demonstrates how control of the ABS media, through changes in system composition, PEG, salt, and tie-line length, can be used to readily tune and control reactivity and product isolation in these aqueous biphasic reactive extraction systems. Challenges in using this system, including possible oxidation reactions of the PEG-OH end groups, are also discussed.