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.

Direct Synthesis of Terminally ``Clickable'' Linear and Hyperbranched Polyesters

1,3-Dipolar cycloaddition of an organic azide and an acetylenic unit,often referred to as the ``click reaction'', has become an important ligation tool both in the context of materials chemistry and biology. Thus, development of simple approaches to directly generate polymers that bear either an azide or an alkyne unit has gained considerable importance. We describe here a straightforward approach to directly prepare linear and hyperbranched polyesters that carry terminal propargyl groups. To achieve the former, we designed an AB-type monomer that carries a hydroxyl group and a propargyl ester, which upon self-condensation under standard transesterification conditions yielded a polyester that carries a single propargyl group at one of its chain-ends. Similarly, an AB(2) type monomer that carries one hydroxyl group and two propargyl ester groups, when polymerized under the same conditions yielded a hyperbranched polymer with numerous clickable'' propargyl groups at its molecular periphery. These propargyl groups can be readily clicked with different organic azides, such as benzyl azide, omega-azido heptaethyleneglycol monomethylether or 9-azidomethyl anthracene. When an anthracene chromophore is clicked, the molecular weight of the linear polyester could be readily estimated using both UV-visible and fluorescence spectroscopic measurements. Furthermore, the reactive propargyl end group could also provide an opportunity to prepare block copolymers in the case of linear polyesters and to generate nanodimensional scaffolds to anchor variety of functional units, in the case of the hyperbranched polymer. (C) 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 3200-3208, 2010.

Periodically Clickable Polyesters: Study of Intrachain Self-Segregation Induced Folding, Crystallization, and Mesophase Formation

A series of polyesters based on 2-propargyl-1,3-propanediol or 2,2-dipropargyl-1,3-propanediol or 2-allyl-2-propargyl-1,3-propanediol and 1,20-eicosanedioic acid were prepared by solution polycondensation using the corresponding diacid chloride; these polyesters were quantitatively ``clicked'' with a fluoroalkyl, azide, namely CF3(CF2)(7)CH2CH2N3, to yield polyesters carrying long-chain alkylene segments in the backbone and either one or two perfluoroalkyl segments located at periodic intervals along the polymer chain. The immiscibility of the alkylene and fluoroalkyl segments causes the polymer chains to fold in a zigzag fashion to facilitate the segregation of these segments; the folded chains further organize in the solid state to form a lamellar structure with alternating domains of alkyl (HC) and fluoroalkyl (FC) segments. Evidence for the self-segregation is provided by DSC, SAXS, WAXS, and TEM studies; in two of the samples, the DSC thermograms showed two distinct endotherms associated with the melting of the individual domains, while the WAXS patterns confirm the existence of two separate peaks corresponding to the interchain distances within the crystalline lattices of the HC and FC domains. SAXS data, on the other hand, reveal the formation of an extended lamellar morphology with an interlamellar spacing that matches reasonably well with those estimated from TEM studies. Interestingly, a smectic-type liquid crystalline phase is observed at temperatures between the two melting transitions. These systems present a unique opportunity to develop interesting nanostructured polymeric materials with precise control over both the domain size and morphology; importantly, the domain sizes are far smaller than those typically observed in traditional block copolymers.

Thermal degradation processes in polysulfide copolymers investigated by direct pyrolysis mass spectrometry and flash pyrolysis-gas chromatography/mass spectrometry

This is the first report on the analysis of random block polysulfide copolymers containing different amounts of repeating units in the copolymer backbone, which has been studied by direct pyrolysis mass spectrometry (DPMS) and by pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS). The homopolymers such as poly(ethylene sulfide) (PES), poly(styrene sulfide) (PSS), and two random copolymers, viz., poly(ethylene sulfide(x)-co-styrene sulfide(y)) [copolymer I (x = y = 0.5) and copolymer II (x = 0.74, y = 0.26)] were investigated by both DPMS and Py-GC/MS (except copolymer II) techniques. In the case of copolymer I, the thermal degradation products of SE1, SE2, S-2, and S2E (S = styrene sulfide, E = ethylene sulfide) were detected in DPMS, whereas the formation of SE1 and SE2 were observed by Py-GC/MS technique. However, for copolymer II, SE3 was also found along with SE1, SE2, S-2, and S2E in DPMS. The formation of additional product (SE3) observed in copolymer II could be due to an increase in the block length formed during copolymerization. Further, a comparative study on thermal degradation of PES, poly(ethylene disulfide) (PEDS), and poly(ethylene tetrasulfide) (PETS) were investigated by Py-GC/MS. The pyrolysis products detected by both DPMS and Py-GC/MS indicates that the thermal decomposition of these polymers yield cyclic sulfides through an intramolecular exchange or by backbiting processes. The linear products with thiol and vinyl groups were also observed by Py-GC/MS along with the cyclic products via carbon hydrogen transfer reaction.

Photocatalytic and Thermal Degradation of Poly(methyl methacrylate), Poly(butyl acrylate), and Their Copolymers

The photocatalytic and thermal degradations of poly(methyl methacrylate), poly(butyl acrylate), and their copolymers of different compositions were studied. The photocatalytic degradation was investigated in o-dichlorobenzene in the presence of two different catalysts, namely, Degussa P-25 and combustion synthesized nanotitania (CSN-TiO2). The samples were analyzed by using gel permeation chromatography (GPC) to obtain the molecular weight distributions (MWDs) as a function of reaction time. Experimental data indicated that the photodegradation of these polymers occurs by both random and chain end scission. A continuous distribution kinetic model was used to determine the degradation rate coefficients by fitting the experimental data with the model. Both the random and specific rate coefficients of the copolymers decreased with increasing percentage of butyl acrylate (BA). Thermal degradation of the copolymers was investigated by thermo-gravimetry. The normalized weight loss profiles for the copolymers showed that the thermal stability of the copolymers increased with mole percentage of BA in the copolymer (PMMABA). The Czawa method was used to determine the activation energies at different conversions. At low acrylate content in the copolymer, the activation energy depends on conversion, indicating multiple degradation mechanisms. At high acrylate content in the copolymer, the activation energy is independent of conversion, indicating degradation by a one-step mechanism.

Solid fuel block as an alternate fuel for cooking and barbecuing: Preliminary result

A large part of the rural people of developing countries use traditional biomass stoves to meet their cooking and heating energy demands. These stoves possess very low thermal efficiency; besides, most of them cannot handle agricultural wastes. Thus, there is a need to develop an alternate cooking contrivance which is simple, efficient and can handle a range of biomass including agricultural wastes. In this reported work, a highly densified solid fuel block using a range of low cost agro residues has been developed to meet the cooking and heating needs. A strategy was adopted to determine the best suitable raw materials, which was optimized in terms of cost and performance. Several experiments were conducted using solid fuel block which was manufactured using various raw materials in different proportions; it was found that fuel block composed of 40% biomass, 40% charcoal powder, 15% binder and 5% oxidizer fulfilled the requirement. Based on this finding, fuel blocks of two different configurations viz. cylindrical shape with single and multi-holes (3, 6, 9 and 13) were constructed and its performance was evaluated. For instance, the 13 hole solid fuel block met the requirement of domestic cooking; the mean thermal power was 1.6 kWth with a burn time of 1.5 h. Furthermore, the maximum thermal efficiency recorded for this particular design was 58%. Whereas, the power level of single hole solid fuel block was found to be lower but adequate for barbecue cooking application.

On a Two-Dimensional Problem in the End-Block Design of Post-Tensioned Prestressed Concrete Beams

Abstract is not available.

Behaviour of methylmethacrylate-acrylonitrile random copolymers in dilute solution

Studies on the dilute solution properties of methylmethacrylate-acrylonitrile random copolymers of three different compositions, 0.236, 0.5 and 0.74 mole fraction (m.f.) of acrylonitrile (AN) designated as MAa, MAb and MAc, respectively, have been made in good solvents and theta solvents. MAa has been studied in benzene (Bz) and ethylacetate (EAc). MAb in acetonitrile (MeCN), dimethyl sulphoxide (DMSO) and a binary solvent mixture of Bz and dimentyl formamide (DMF) in the volume ratio 6.5:1 designated as BM1 and MAc in MeCN, DMSO and Bz + DMF in the volume ratio 1.667:1 designated as BM2. The Mark-Houwink exponent ‘a’ reveals that Bz is a theta solvent for MAa at 20°C. For MAb and MAc, BM1 and BM2, respectively have ‘a’ values of 0.5 at all three temperatures studied (30°, 40° and 50°C). It is not clear whether they represent theta states or preferential adsorption plays a role complicating the behaviour in solution. The values of A2 are very low in MeCN considering that it is a very good solvent for the copolymer, ‘a’ values for MAb and MAc being 0.75 and 0.7, respectively.

Biodegradation of gelatin graft copolymers. IV

Gelatin graft copolymers of different compositions were tested for microbial susceptibility in a synthetic medium with pure cultures of Pseudomonas aeruginosa, Bacillus subtilis, and Serratia marcescens. The percent weight losses were recorded over 6 weeks of incubation period in nitrogen-free and nitrogen-rich media. The relationship between [log(rate)] during the first week of the test period and composition of the grafted samples showed a linear behavior. There was no difference in the aggressivity of these bacterial strains. Nitrogen analysis data and pH measurements of the media seem to reinforce our earlier observations. Soil burial tests also indicate degradation of polymer samples under natural weathering conditions. This article also summarizes the salient features of our series of investigations.

Biodegradation of gelatin graft copolymers. III

Gelatin-g-poly(methyl acrylate) and gelatin-g-poly(acrylonitrile) copolymers were prepared in an aqueous medium using K2S2O8 initiator. A plausible mechanism has been put forward for the observed grafting behavior of monomers. Gelatin-g-PAN showed a greater resistance to mixed bacterial inolucum compared to gelatin-g-PMA samples. The rate of degradation decreased with the increase in grafting efficiency. A parallel set of experiments carried out by employing the samples as the only source of both carbon and nitrogen showed a marginal but definite increase in the utilization of the polymer. The nitrogen analysis also showed the utilization of the polymer. Scanning electron micographs of the polymer films do show extensive pitting after microbiological testing.

Photooxidative and pyrolytic degradation of methyl methacrylate-alkyl acrylate copolymers

Different compositions of poly(methyl methacrylate-co-methyl acrylate) (PMMAMA), poly(methyl methacrylate-co-ethyl acrylate) (PMMAEA) and poly(methyl methacrylate-co-butyl acrylate) (PMMABA) copolymers were synthesized and characterized. The photocatalytic oxidative degradation of all these copolymers were studied in presence of two different catalysts namely Degussa P-25 and combustion synthesized titania using azobis-iso-butyronitrile and benzoyl peroxide as oxidizers. Gel permeation hromatography (GPC) was used to determine the molecular weight distribution of the samples as a function of time. The GPC chromatogram indicated that the photocatalytic oxidative degradation of all these copolymers proceeds by both random and chain end scission.Continuous distribution kinetics was used to develop a model for photocatalytic oxidative degradation considering both random and specific end scission. The degradation rate coefficients were determined by fitting the experimental data with the model. The degradation rate coefficients of the copolymers decreased with increase in the percentage of alkyl acrylate in the copolymer. This indicates that the photocatalytic oxidative stability of the copolymers increased with increasing percentage of alkyl acrylate. From the degradation rate coefficients, it was observed that the photocatalytic oxidative stability follows the order PMMABA > PMMAEA > PMMAMA. The thermal degradation of the copolymers was studied by using thermogravimetric analysis (TGA). The normalized weight loss and differential fractional weight loss profiles indicated that the thermal stability of the copolymer increases with an increase in the percentage of alkyl acrylate and the thermal stability of poly(methyl methacrylate-co-alkyl acrylate)s follows the order PMMAMA > PMMAEA > PMMABA. The observed contrast in the order of photostability and thermal stability of the copolymers was attributed to different mechanisms involved for the scission of polymer chain and formation of different products in both the processes.

Dilute Solution Properties of Methyl Methacrylate/Acrylonitrile Random Copolymers, 2a)

The Stockmayer-Fixman relation was used to evaluate the short range and long range interaction parameters for methyl methacrylate/acrylonitrile copolymers of 0,566 and 0,657 mole fraction of monomeric units of acrylonitrile in the solvents acetonitrile, 2-butanone, dimethyl formamide, and y-butyrolactone, at different temperatures (30, 45, and 60 “C). The values of KO were found to be lower than those of the parent homopolymers, and their values depend on both solvent and temperature. Even negative Ko-values were obtained, in cases in which the Mark Houwink exponent a is nearly unity. The values of the polymer-solvent interaction parameter, x, , are high and close to 0,5, indicating that these solvents are not good. The values of the excess interaction parameter, xAB, are negative and are not affected by temperature. The large extension of these copolymer chains, as exhibited by a and a;-values, can be understood in terms of unusual short range interactions only. Similar results were obtained for some cellulose derivatives.

Influence of Joint Thickness and Mortar-Block Elastic Properties on the Strength and Stresses Developed in Soil-Cement Block Masonry

Soil-cement blocks are employed for load bearing masonry buildings. This paper deals with the study on the influence of bed joint thickness and elastic properties of the soil-cement blocks, and the mortar on the strength and behavior of soil-cement block masonry prisms. Influence of joint thickness on compressive strength has been examined through an experimental program. The nature of stresses developed and their distribution, in the block and the mortar of the soil-cement block masonry prism under compression, has been analyzed by an elastic analysis using FEM. Influence of various parameters like joint thickness, ratio of block to mortar modulus, and Poisson's ratio of the block and the mortar are considered in FEM analysis. Some of the major conclusions of the study are: (1) masonry compressive strength is sensitive to the ratio of modulus of block to that of the mortar (Eb/Em) and masonry compressive strength decreases as the mortar joint thickness is increased for the case where the ratio of block to mortar modulus is more than 1; (2) the lateral tensile stresses developed in the masonry unit are sensitive to the Eb/Em ratio and the Poisson's ratio of mortar and the masonry unit; and (3) lateral stresses developed in the masonry unit are more sensitive to the Poisson's ratio of the mortar than the Poisson's ratio of the masonry unit.

Block- and strand-multiplexing for fast computation of a class of transforms

The transforms dealt with in this paper are defined in terms of the transform kernels which are Kroneeker products of the two or more component kernels. The signal flow-graph for the computation of such a transform is obtained with the flow-graphs for the component transforms as building blocks.

Sequence distribution in Acrylonitrile-methylacrylate random copolymers by N.M.R spectroscopy

The sequence distribution studies on the acrylonitrile-methylmethacrylate copolymer of high methylmethacrylate (M) content (30%