Composites of poly(ε-caprolactone) and Mo6S3I6 Nanowires

Composites of poly(e-caprolactone) (PCL) and molybdenum sulfur iodine (MoSI) nanowires were prepared using twin-screw extrusion. Extensive microscopic examination of the composites revealed the nanowires were well dispersed in the PCL matrix, although bundles of Mo6S3I6 ropes were evident at higher loadings. Secondary electron imaging (SEI) showed the nanowires had formed an extensive network throughout the PCL matrix, resulting in increased electrical conductivity of PCL, by eight orders of magnitude, and an electrical percolation threshold of 6.5T10S3vol%. Thermal analysis (DSC), WAXD, and hot stage polarized optical microscopy (HSPOM) experiments revealed Mo6S3I6 addition altered PCL crystallization kinetics, nucleation density, and crystalline content. A greater number of smaller spherulites were formed via heterogeneous nucleation. The onset of thermal decomposition (TGA) of PCL decreased by 70-C, a consequence of the thermal degradation of Mo6S3I6 to MoO3, which in turn accelerates the formation of volatile gases during the first stage of PCL decomposition.

Rheological Evaluation of the Isothermal Cure Characteristics of Medical Grade Silicone Elastomers

Silicone elastomer systems have been shown to offer potential for the fabrication of medical devices and sustained release drug delivery devices comprising low molecular weight drugs and protein therapeutics. For drug delivery systems in particular, there is often no clear rationale for selection of the silicone elastomer grade, particularly in respect of optimizing the manufacturing conditions to ensure thermal stability of the active agent and short cycle times. In this study, the cure characteristics of a range of addition-cure and condensation-cure, low-consistency, implant-grade silicone elastomers, either as supplied or loaded with the model protein bovine serum albumin (BSA) and the model hydrophilic excipient glycine, were investigated using oscillatory rheology with a view to better understanding the isothermal cure characteristics. The results demonstrate the influence of elastomer type, cure temperature, protein loading, and glycine loading on isothermal cure properties. By measuring the cure time required to achieve tan delta values representative of early and late-stage cure conditions, a ratio t(1)/t(2) was defined that allowed the cure characteristics of the various systems to be compared. Sustained in vitro release of BSA from glycine-loaded silicone elastomer covered rod devices was also demonstrated over 14 days. (C) 2010 Wiley Periodicals, Inc. J Appl Polym Sci 116: 2320-2327, 2010

Accelerated degradation behaviour of poly(epsilon-caprolactone) via melt blending with poly(aspartic acid-co-lactide) (PAL)

Poly(epsilon-caprolactone) (PCL) has many favourable attributes for tissue engineering scaffold applications. A major drawback, however, is its slow degradation rate, typically greater than 3 years. In this study PCL was melt blended with a small percentage of poly(aspartic acid-co-lactide) (PAL) and the degradation behaviour was evaluated in phosphate buffer solution (PBS) at 37 degrees C. The addition of PAL was found to significantly enhance the degradation profile of PCL. Subsequent degradation behaviour was investigated in terms of the polymer's mechanical properties, Molecular weight (M-w), mass changes and thermal characteristics. The results indicate that the addition of PAL accelerates the degradation of PCL, with 20% mass loss recorded after just 7 months in vitro for samples containing 8 wt% PAL. The corresponding pure PCL samples exhibited no mass loss over the same time period. In vitro assessment of PCL and PCL/PAL composites in tissue Culture medium in the absence of cells revealed stable pH readings with time. SEM studies of cell/biomaterial interactions demonstrated biocompatibility of C3H10T1/2 cells with PCL and PCL/PAL composites at all concentrations of PAL additive. (C) 2008 Elsevier Ltd. All rights reserved.

Reversibly collapsible macroporous poly(styrene-divinylbenzene) resins

A series of poly(styrene-divinylbenzene) (poly(PS-DVB)) resins have been prepared by suspension polymerisation of styrene-DVB mixtures with DVB contents of 1-12 mol%. In each case 2-ethyl-hexan-1-ol was used as a porogen. Those resins prepared with

Investigation of swelling and network parameters of poly (ethylene glycol)-crosslinked poly (methyl vinyl ether-co-maleic acid) hydrogels

he influence of poly(ethylene glycol) (PEG) plasticiser content and molecular weight on the physicochemical properties of films cast from aqueous blends of poly(methyl vinyl ether-co-maleic acid) was investigated using thermal analysis, swelling studies, scanning electron microscopy (SEM) and attenuated total reflectance (ATR)-Fourier transform infrared (FTIR) spectroscopy. FTIR spectroscopy revealed a shift of the CO peak from 1708 to 1731 cm-1, indicating that an esterification reaction had occurred upon heating, thus producing crosslinked films. Higher molecular weight PEGs (10,000 and 1000 Da, respectively), having greater chain length, producing hydrogel networks with lower crosslink densities and higher average molecular weight between two consecutive crosslinks. Accordingly, such materials exhibited higher swelling rates. Hydrogels crosslinked with a low molecular weight PEG (PEG 200) showed rigid networks with high crosslink densities and, therefore, lower swelling rates. Polymer:plasticizer ratio alteration did not yield any discernable patterns, regardless of the method of analysis. The polymer–water interaction parameter (?) increased with increases in the crosslink density. SEM studies showed that porosity of the crosslinked films increased with increasing PEG MW, confirming what had been observed with swelling studies and thermal analysis, that the crosslink density must be decreased as the Mw of the crosslinker is increased. Hydrogels containing PMVE/MA/PEG 10,000 could be used for rapid delivery of drug, due to their low crosslink density. Moderately crosslinked PMVE/MA/PEG 1000 hydrogels or highly crosslinked PMVE/MA/PEG 200 systems could then be used in controlling the drug delivery rates. We are currently evaluating these systems, both alone and in combination, for use in sustained release drug delivery devices.

Measurement of Polymer-to-Polymer Contact Friction in Thermoforming

Contact friction plays a critical role in all the major thermoforming processes for polymers. However, these effects are very difficult to measure in practice and, as a result, have received little scientific investigation. In this work, two independently developed test methods for the measurement of elevated temperature polymer-to-polymer contact friction are presented, and their results are compared in detail for the first time. One is based on a modified moving sled friction test, whereas the other uses a rotational rheometer. In each case, friction tests were conducted between two plug and two sheet materials. The results show that broadly similar coefficients of friction were obtained from the two test methods. The measured values were quite low (<0.3) at lower temperatures and typically were higher for polypropylene (PP) sheet than for polystyrene (PS). On approaching the glass transition temperature for PS (95°C) and the crystalline melting point for PP (165°C), the friction coefficients rose very sharply, and both test techniques became increasingly unreliable. It was concluded that despite their physical differences, both test techniques were able to capture the highly temperature sensitive nature of friction between polymer materials used in thermoforming.

Melt-compounded nanocomposites of titanium dioxide atomic-layer-deposition-coated polyamide and polystyrene powders

Polyamide and polystyrene particles were coated with titanium dioxide films by atomic layer deposition (ALD) and then melt-compounded to form polymer nanocomposites. The rheological properties of the ALD-created nanocomposite materials were characterized with a melt flow indexer, a melt flow spiral mould, and a rotational rheometer. The results suggest that the melt flow properties of polyamide nanocomposites were markedly better than those of pure polyamide and polystyrene nanocomposites. Such behavior was shown to originate in an uncontrollable decrease in the polyamide molecular weight, likely affected by a high thin-film impurity content, as shown in gel permeation chromatography (GPC) and scanning electron microscope (SEM) equipped with an energy-dispersive spectrometer. Transmission electron microscope image showed that a thin film grew on both studied polymer particles, and that subsequent melt-compounding was successful, producing well dispersed ribbon-like titanium dioxide with the titanium dioxide filler content ranging from 0.06 to 1.12wt%. Even though we used nanofillers with a high aspect ratio, they had only a minor effect on the tensile and flexural properties of the polystyrene nanocomposites. The mechanical behavior of polyamide nanocomposites was more complex because of the molecular weight degradation. Our approach here to form polymeric nanocomposites is one way to tailor ceramic nanofillers and form homogenous polymer nanocomposites with minimal work-related risks in handling powder form nanofillers. However, further research is needed to gauge the commercial potential of ALD-created nanocomposite materials. Copyright (C) 2011 John Wiley & Sons, Ltd.

Is the pinning of ordinary dislocations in γ-TiAl intrinsic or extrinsic in nature? A combined atomistic and kinetic Monte Carlo approach

We address the question of the observed pinning of 1/2

Electron-beam treatment of poly(lactic acid) to control degradation profiles

Bioresorbable polymers such as polylactide (PIA) and polylactide-co-glycolide (PLGA) have been used successfully as biomaterials in a wide range of medical applications. However, their slow degradation rates and propensity to lose strength before mass have caused problems. A central challenge for the development of these materials is the assurance of consistent and predictable in vivo degradation. Previous work has illustrated the potential to influence polymer degradation using electron beam (e-beam) radiation. The work addressed in this paper investigates further the utilisation of e-beam radiation in order to achieve a more surface specific effect. Variation of e-beam energy was studied as a means to control the effective penetrative depth in poly-L-lactide (PLEA). PLEA samples were exposed to e-beam radiation at individual energies of 0.5 MeV, 0.75 MeV and 1.5 MeV. The near-surface region of the PLEA samples was shown to be affected by e-beam irradiation with induced changes in molecular weight, morphology, flexural strength and degradation profile. Moreover, the depth to which the physical properties of the polymer were affected is dependent on the beam energy used. Computer modelling of the transmission of each e-beam energy level used corresponded well with these findings. (C) 2010 Elsevier Ltd. All rights reserved.

Effect of the incorporation of hydroxy-terminated liquid silicones on the cure characteristics, morphology, and release of a model protein from silicone elastomer-covered rods

Silicone elastomer systems have previously been shown to offer potential for the sustained release of protein therapeutics. However, the general requirement for the incorporation of large amounts of release enhancing solid excipients to achieve therapeutically effective release rates from these otherwise hydrophobic polymer systems can detrimentally affect the viscosity of the precure silicone elastomer mixture and its curing characteristics. The increase in viscosity necessitates the use of higher operating pressures in manufacture, resulting in higher shear stresses that are often detrimental to the structural integrity of the incorporated protein. The addition of liquid silicones increases the initial tan delta value and the tan delta values in the early stages of curing by increasing the liquid character (G '') of the silicone elastomer system and reducing its elastic character (G'), thereby reducing the shear stress placed on the formulation during manufacture and minimizing the potential for protein degradation. However, SEM analysis has demonstrated that if the liquid character of the silicone elastomer is too high, the formulation will be unable to fill the mold during manufacture. This study demonstrates that incorporation of liquid hydroxy-terminated polydimethylsiloxanes into addition-cure silicone elastomer-covered rod formulations can both effectively lower the viscosity of the precured silicone elastomer and enhance the release rate of the model therapeutic protein bovine serum albumin. (C) 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011

Microstructure evolution of a 10Cr heat-resistant steel during high temperature creep

The microstructure evolution of a 10Cr ferritic/martensitic heat-resistant steel during creep at 600°C was investigated in this work. Creep tests demonstrated that the 10Cr steel had higher creep strength than conventional ASME-P92 steel at 600°C. The microstructure after creep was studied by transmission electron microscopy, scanning electron microscopy and electron probe microanalysis. It was revealed that the martensitic laths were coarsened with time and eventually developed into subgrains after 8354 h. Laves phase was observed to grow and cluster along the prior austenite grain boundaries during creep and caused the fluctuation of solution and precipitation strengthening effects, which was responsible for the two slope changes on the creep rupture strength vs rupture time curve. It was also revealed that the microstructure evolution could be accelerated by stress, which resulted in the lower hardness in the deformed part of the creep specimen, compared with the aging part.