Ultrasonic degradation of poly(methyl methacrylate-co-alkyl acrylate) copolymers

The copolymers, poly(methyl methacrylate-co-methyl acrylate) (PMMAMA), poly(methyl methacrylate-co-ethyl acrylate) (PMMAEA) and poly(methyl methacrylate-co-butyl acrylate) (PMMABA), of different compositions were synthesized and characterized. The effect of alkyl acrylate content, alkyl group substituents and solvents on the ultrasonic degradation of these copolymers was studied. A model based on continuous distribution kinetics was used to study the kinetics of degradation. The rate coefficients were obtained by fitting the experimental data with the model. The linear dependence of the rate coefficients on the logarithm of the vapor pressure of the solvent indicated that vapor pressure is the crucial parameter that controls the degradation process. The rate of degradation increases with an increase in the alkyl acrylate content. At any particular copolymer composition, the rate of degradation follows the order: PMMAMA > PMMAEA > PMMABA. It was observed that the degradation rate coefficient varies linearly with the mole percentage of the alkyl acrylate in the copolymer.

Applications of coralline hydroxyapatite with bioabsorbable containment and reinforcement as bone graft substitute : An experimental study

The aim of the present experimental study was to find out if the applications of coralline hydroxyapatite (HA) can be improved by using bioabsorbable containment or binding substance with particulate HA in mandibular contour augmentation and by using bioabsorbable fibre-reinforced HA blocks in filling bone defects and in anterior lumbar interbody fusion. The use of a separate curved polyglycolide (PGA) containment alone or together with a fast resorbing polyglycolide/polylactide (PGA/PLA) binding substance were compared to the conventional non-contained method in ridge augmentation in sheep. The contained methods decreased HA migration, but the augmentations did not differ significantly. The use of the containment caused a risk for wound dehiscence and infection. Histologically there was a rapid connective tissue ingrowth into the HA graft and it was more abundant with the PGA containment compared to the non-contained augmentation and even additionally rich when the HA particles were bound with PGA/PLA copolymer. However, the bone ingrowth was best in the non-contained augmentation exceeding 10-12 % of the total graft area at 24 weeks. Negligible or no bone ingrowth was seen in the cases where the polymer composite was added to the HA particles and, related to that, foreign-body type cells were seen at the interface between the HA and host bone. The PGA and poly-dl/l-lactide (PDLLA) fibre-reinforced coralline HA blocks were studied in the metaphyseal and in the diaphyseal defects in rabbits. A rapid bone ingrowth was seen inside the both types of implants. Both PGA and PDLLA fibres induced an inflammatory fibrous reaction around themselves but it did not hinder the bone ingrowth. The bone ingrowth pattern was directed according to the loading conditions so that the load-carrying cortical ends of the implants as well as the implants sited in the diaphyseal defects were the most ossified. The fibre-reinforced coralline HA implants were further studied as stand-alone grafts in the lumbar anterior interbody implantation in pigs. The strength of the HA implants proved not to be adequate, the implants fractured in six weeks and the disc space was gradually lost similarly to that of the discectomized spaces. Histologically, small quantities of bone ingrowth was seen in some of the PGA and PDLLA reinforced coralline implants while no bone formation was identified in any of the PDLLA reinforced synthetic porous HA implants. While fragmented, the inner structure of the implants was lost, the bone ingrowth was minimal, and the disc was replaced by the fibrous connective tissue. When evaluated radiologically the grade of ossification was assessed as better than histologically, and, when related to the histologic findings, CT was more dependable than the plain films to show ossification of the implanted disc space. Local kyphosis was a frequent finding along with anterior bone bridging and ligament ossification as a consequence of instability of the implanted segment.

Synthesis of mesoporous TiO2/SiO2 hybrid films as an efficient photocatalyst by polymeric micelle assembly

Thermally stable mesoporous TiO2/SiO2 hybrid films with pore size of 50 nm have been synthesized by adopting the polymeric micelle-assembly method. A triblock copolymer, poly(styrene-b-2-vinyl pyridine-b-ethylene oxide), which serves as a template for the mesopores, was utilized to form polymeric micelles. The effective interaction of titanium tetraisopropoxide (TTIP) and tetraethyl orthosilicate (TEOS) with the polymeric micelles enabled us to fabricate stable mesoporous films. By changing the molar ratio of TEOS and TTIP, several mesoporous TiO2/SiO2 hybrid films with different compositions can be synthesized. The presence of amorphous SiO2 phase effectively retards the growth of anatase TiO2 crystal in the pore walls and retains the original mesoporous structure, even at higher temperature (650 °C). These TiO2/SiO2 hybrid films are of very high quality, without any cracks or voids. The addition of SiO2 phase to mesoporous TiO2 films not only adsorbs more organic dyes, but also significantly enhances the photocatalytic activity compared to mesoporous pure TiO2 film without SiO2 phase.

Direct probe of end-segment distribution in tethered polymer chains

End-tethered chains made of an adsorbed diblock copolymer of polystyrene (PS)-polyisoprene (PI) bearing an end-segment including a Ge atom are built by the Langmuir-Schaeffer technique. They are studied both in the dry state and in a good solvent for the PI chain using grazing incidence X-ray standing waves. The analysis of the signal provides a direct measurement of the end-segment distribution which is found to be singular and mostly localized to a plane in the dry case. In the good solvent case, end-segments are found to span the entire assembly and compare very well with results obtained by Kreer et al.

Synthesis of Diketopyrrolopyrrole Containing Copolymers: A Study of Their Optical and Photovoltaic Properties

The diketopyrrolopyrrole-based copolymers PDPP-BBT and TDPP-BBT were synthesized and used as donor for bulk heterojunction photovoltaic devices. The photophysical properties of these polymers showed absorption in the range 500-600 nm with a maximum peak around 563 nm, while TDPP-BBT showed broadband absorption in the range 620 - 800 nm with a peak around 656 nm. The power conversion efficiencies (PCE) of the polymer solar cells based on these copolymers and [6,6]-phenyl C61 butyric acid methyl ester (PCBM) were 0.68% (as cast PDPP-BBT:PCBM), 1.51% (annealed PDPP-BBT:PCBM), 1.57% (as cast TDPPBBT: PCBM), and 2.78% (annealed TDPP-BBT:PCBM), under illumination of AM 1.5 (100 mW/cm2). The higher PCE for TDPP-BBT-based polymer solar cells has been attributed to the low band gap of this copolymer as compared to PDPP-BBT, which increases the numbers of photogenerated excitons and corresponding photocurrent of the device. These results indicate that PDPP-BBT and TDPP-BBT act as excellent electron donors for bulk heterojunction devices.

Enzymatic Degradation of Poly(soybean oil-g-methyl methacrylate)

This study discusses grafting of methyl methacrylate units from thepolymeric soybean oil peroxide to produce poly(soybean oil-graft-methyl methacrylate) (PSO-g-PMMA). The degradation of this copolymer in solution was evaluated in the presence of different lipases, viz Candida rugosa (CR), Lipolase 100T (LP), Novozym 435 (N435) and Porcine pancreas (PP), at different temperatures The copolymer degraded by specific chain end scission and the mass fraction of the specific product evolved was determined The degradation was modeled using continuous distribution kinetics to determine the rate coefficients ofmenzymatic chain end scission and deactivation of the enzyme The enzymes, CR. LP and N435 exhibited maximum activity for the degradation of PSO-g-PMMA at 60 degrees C, while PP was most active at 50 degrees C. The thermal degradability of the copolymer, assessed by thermo-gravimetry, indicated that the activation energy of degradation of the copolymer was 154 kJ mol(-1), which was lesser than that of the PMMA homopolymer.

Ultrasonic degradation of poly (styrene-co-alkyl methacrylate) copolymers

The ultrasonic degradation of poly (styrene-co-methyl methacrylate) (SMMA), poly (styrene-co-ethyl methacrylate) (SEMA) and poly (styrene-co-butyl methacrylate) (SBMA) copolymers of different compositions was studied. The copolymers were synthesized and NMR spectroscopy was used to determine the composition, and the glass transition temperatures were determined by DSC. The reactivity ratios were determined by the Kelen-Tudos method and it indicated that the copolymers were random. The effect of solvent, temperature and copolymer composition on the ultrasonic degradation rate of these copolymers was investigated. A model based on continuous distribution kinetics was employed to study the degradation kinetics. The degradation rate coefficients of the copolymers decreased with an increase in the styrene content in the copolymer. At any particular copolymer composition the rate of degradation follows the order: SBMA >SEMA > SMMA. Thermogravimetric analysis (TGA) of the copolymers was carried in order to assess their thermal stability. The same order of degradation was observed for the thermal degradation of the copolymers as that observed for ultrasonic degradation. (C) 2010 Elsevier B.V. All rights reserved.

High Rate Capability of Porous LiNi1/3Co1/3Mn1/3O2 Synthesized by Polymer Template Route

Layered LiNi1/3Co1/3Mn1/3O2, which is isostructural with LiCoO2, is considered as a potential cathode material for Li-ion batteries. Submicrometer sized porous particles are useful for high discharge rates. The present work involves a synthesis of submicrometer sized porous particles of LiNi1/3Co1/3Mn1/3O2 using a triblock copolymer as a soft template. The precursor obtained from the reaction is heated at different temperatures between 600 and 900 degrees C for 6 h to get the final product samples. The compound attains increased crystallinity with an increase in the temperature of preparation. However, there is a decrease in the surface area and also in the porosity of the sample. Nevertheless, the LiNi1/3Co1/3Mn1/3O2 sample prepared at 900 degrees C exhibits a high rate capability and stable capacity retention on cycling. The electrochemical performance of LiNi1/3Co1/3Mn1/3O2 prepared in the absence of the polymer template is inferior to that of the sample prepared in the presence of the polymer template. (C) 2010 The Electrochemical Society. [DOI: 10.1149/1.3364944] All rights reserved.

Mechanical and Thermal Properties of Eva Blended with Biodegradable Ethyl Cellulose

In this study, biodegradable blend of Poly (Ethylene-co-Vinyl Acetate) (EVA) and Ethyl Cellulose (EC) were prepared. Ethylene vinyl alcohol (EVOH) copolymer was used as an interfacial compatibilizer to enhance adhesion between EVA and EC. The melt blended compatibilized biocomposites were examined for mechanical and thermal properties as per the ASTM standards. It has been found that the EC has a reinforcing effect on EVA leading to enhanced tensile strength and also impart biodegradability. Thus, a high loading of 50% EC could be added without compromising Much on the mechanical properties. Analysis of the tensile data using predictive theories showed an enhanced interaction of the dispersed phase (EC) and the matrix (EVA). The compatibilizing effects of EVOH on these blends were confirmed by the significant improvement in the mechanical properties comparable with neat EVA as also observed by SEM microscopy. The TGA thermograms exhibits two-stage degradation and as EC content increases, the onset temperature for thermal degradation reduces. (C) 2009 Wiley Periodicals, Inc. J Appl Polym Sci 116: 1044-1056, 2010

Degradation Kinetics of Poly(HDDA-co-MMA)

1,6-hexanediol diacrylate (HDDA) and methyl methacrylate (MMA) were copolymerized in different weight ratios using UV light induced photo-polymerization to give poly(HDDA-co-MMA). Differential scanning calorimetry shows that copolymer was formed. The thermogravimetric and differential scanning calorimetric studies with different heating rates were carried out on these copolymers to understand the nature of degradation and to determine its kinetics. Different kinetic models were adopted to evaluate various parameters like the activation energy, the order, and the frequency factor. These analyses are important to study the binder removal from 3D-shaped ceramic objects made by techniques like Solid free form fabrication. (C) 2010 Wiley Periodicals, Inc. J Appl Polym Sci 117: 2444-2453, 2010.

Hexagonally ordered arrays of metallic nanodots from thin films of functional block copolymers

We demonstrate a new and simple route to fabricate highly dense arrays of hexagonally close packed inorganic nanodots using functional diblock copolymer (PS-b-P4VP) thin films. The deposition of pre-synthesized inorganic nanoparticles selectively into the P4VP domains of PS-b-P4VP thin films, followed by removal of the polymer, led to highly ordered metallic patterns identical to the order of the starting thin film. Examples of Au, Pt and Pd nanodot arrays are presented. The affinity of the different metal nanoparticles towards P4VP chains is also understood by extending this approach to PS-b-P4VP micellar thin films. The procedure used here is simple, eco-friendly, and compatible with the existing silicon-based technology. Also the method could be applied to various other block copolymer morphologies for generating 1-dimensional (1D) and 2-dimensional (2D) structures. (c) 2010 Elsevier Ltd. All rights reserved.

A low-cost lead-acid battery with high specific-energy

Lightweight grids for lead-acid battery grids have been prepared from acrylonitrile. butadiene styrene (ABS) copolymer followed by coating with lead. Subsequently, the grids have been electrochemically coated with a conductive and corrosion-resistant layer of polyaniline. These grids are about 75% lighter than those employed in conventional lead-acid batteries. Commercial-grade 6V/3.5 Ah (C-20-rate) lead-acid batteries have been assembled and characterized employing positive and negative plates constituting these grids. The specific energy of such a lead-acid battery is about 50 Wh/kg. The batteries can withstand fast charge-discharge duty cycles.

Photoluminescence spectroscopy and lifetime measurements from self-assembled semiconductor-metal nanoparticle hybrid arrays

We present results of photoluminescence spectroscopy and lifetime measurements on thin film hybrid arrays of semiconductor quantum dots and metal nanoparticles embedded in a block copolymer template. The intensity of emission as well as the measured lifetime would be controlled by varying the volume fraction and location of gold nanoparticles in the matrix. We demonstrate the ability to both enhance and quench the luminescence in the hybrids as compared to the quantum dot array films while simultaneously engineering large reduction in luminescence lifetime with incorporation of gold nanoparticles. (C) 2010 American Institute of Physics. [doi:10.1063/1.3483162].

Controlled photoluminescence from self-assembled semiconductor-metal quantum dot hybrid array films

Thin films of hybrid arrays of cadmium selenide quantum dots and polymer grafted gold nanoparticles have been prepared using a BCP template. Controlling the dispersion and location of the respective nanoparticles allows us to tune the exciton-plasmon interaction in such hybrid arrays and hence control their optical properties. The observed photoluminescence of the hybrid array films is interpreted in terms of the dispersion and location of the gold nanoparticles and quantum dots in the block copolymer matrix.

Miscibility of poly(phenyl acrylate) with acrylonitrile/styrene copolymers

The Blase transition and phase behavior of blends of poly(pheny1 acrylate) with poly(acrylonitri1eco-styrene) was studied by differential scanning calorimetry. It was found that poly(pheny1 acrylate) is miscible with poly(acrylonitri1e-co-styrenes) within a specific range of copolymer composition. The segmental interaction parameters were estimated and found to be positive for all three pairs. The miscibility in thissystem appears to be the consequence of the intramolecular repulsion between styrene and acrylonitrile units.