927 resultados para Polymers and Plastics (091209)


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Copoly(2-oxazoline)s, prepared by cationic ring-opening polymerization of 2-(dec-9-enyl)-2-oxazoline with either 2-methyl-2-oxazoline or 2-ethyl-2-oxazoline, have been crosslinked with small dithiol molecules under UV-irradiation to form homogeneous networks. In-situ monitoring of the crosslinking reaction by photo-rheology revealed network formation within minutes. The degree of swelling in water was found to be tunable by the hydrophilicity of the starting macromers and the proportion of alkene side arms. Furthermore, degradable hydrogels have been prepared based on a hydrolytically cleavable dithiol crosslinker.

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Molecular dynamics simulations were carried out on single chain models of linear low-density polyethylene in vacuum to study the effects of branch length, branch content, and branch distribution on the polymer’s crystalline structure at 300 K. The trans/gauche (t/g) ratios of the backbones of the modeled molecules were calculated and utilized to characterize their degree of crystallinity. The results show that the t/g ratio decreases with increasing branch content regardless of branch length and branch distribution, indicating that branch content is the key molecular parameter that controls the degree of crystallinity. Although t/g ratios of the models with the same branch content vary, they are of secondary importance. However, our data suggests that branch distribution (regular or random) has a significant effect on the degree of crystallinity for models containing 10 hexyl branches/1,000 backbone carbons. The fractions of branches that resided in the equilibrium crystalline structures of the models were also calculated. On average, 9.8% and 2.5% of the branches were found in the crystallites of the molecules with ethyl and hexyl branches while C13 NMR experiments showed that the respective probabilities of branch inclusion for ethyl and hexyl branches are 10% and 6% [Hosoda et al., Polymer 1990, 31, 1999–2005]. However, the degree of branch inclusion seems to be insensitive to the branch content and branch distribution.

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We sought to determine the impact of electrospinning parameters on a trustworthy criterion that could evidently improve the maximum applicability of fibrous scaffolds for tissue regeneration. We used an image analysis technique to elucidate the web permeability index (WPI) by modeling the formation of electrospun scaffolds. Poly(3-hydroxybutyrate) (P3HB) scaffolds were fabricated according to predetermined conditions of levels in a Taguchi orthogonal design. The material parameters were the polymer concentration, conductivity, and volatility of the solution. The processing parameters were the applied voltage and nozzle-to-collector distance. With a law to monitor the WPI values when the polymer concentration or the applied voltage was increased, the pore interconnectivity was decreased. The quality of the jet instability altered the pore numbers, areas, and other structural characteristics, all of which determined the scaffold porosity and aperture interconnectivity. An initial drastic increase was observed in the WPI values because of the chain entanglement phenomenon above a 6 wt % P3HB content. Although the solution mixture significantly (p < 0.05) changed the scaffold architectural characteristics as a function of the solution viscosity and surface tension, it had a minor impact on the WPI values. The solution mixture gained the third place of significance, and the distance was approved as the least important factor.

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Production of nanofibrous polyacrylonitrile/calcium carbonate (PAN/CaCO3) nanocomposite web was carried out through solution electrospinning process. Pore generating nanoparticles were leached from the PAN matrices in hydrochloric acid bath with the purpose of producing an ultimate nanoporous structure. The possible interaction between CaCO3 nanoparticles and PAN functional groups was investigated. Atomic absorption method was used to measure the amount of extracted CaCO3 nanoparticles. Morphological observation showed nanofibers of 270–720 nm in diameter containing nanopores of 50–130 nm. Monitoring the governing parameters statistically, it was found that the amount of extraction (ε) of CaCO3was increased when the web surface area (a) was broadened according to a simple scaling law (ε = 3.18 a0.4). The leaching process was maximized in the presence of 5% v/v of acid in the extraction bath and 5 wt % of CaCO3 in the polymer solution. Collateral effects of the extraction time and temperature showed exponential growth within a favorable extremum at 50°C for 72 h. Concentration of dimethylformamide as the solvent had no significant impact on the extraction level.

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Nanocomposites are recently known to be among the most successful materials in biomedical applications. In this work we sought to fabricate fibrous scaffolds which can mimic the extra cellular matrix of cartilaginous connective tissue not only to a structural extent but with a mechanical and biological analogy. Poly(3-hydroxybutyrate) (P3HB) matrices were reinforced with 5, 10 and 15 %wt hydroxyapatite (HA) nanoparticles and electrospun into nanocomposite fibrous scaffolds. Mechanical properties of each case were compared with that of a P3HB scaffold produced in the same processing condition. Spectroscopic and morphological observations were used for detecting the interaction quality between the constituents. Nanoparticles rested deep within the fibers of 1 μm in diameter. Chemical interactions of hydrogen bonds linked the constituents through the interface. Maximum elastic modulus and mechanical strength was obtained with the presence of 5%wt hydroxyapatite nanoparticles. Above 10%wt, nanoparticles tended to agglomerate and caused the entity to lose its mechanical performance; however, viscoelasticity interfered at this concentration and lead to a delayed failure. In other words, higher elongation at break and a massive work of rupture was observed at 10%wt.

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Fibrous scaffolds of engineered structures can be chosen as promising porous environments when an approved criterion validates their applicability for a specific medical purpose. For such biomaterials, this paper sought to investigate various structural characteristics in order to determine whether they are appropriate descriptors. A number of poly(3-hydroxybutyrate) scaffolds were electrospun; each of which possessed a distinguished architecture when their material and processing conditions were altered. Subsequent culture of mouse fibroblast cells (L929) was carried out to evaluate the cells viability on each scaffold after their attachment for 24 h and proliferation for 48 and 72 h. The scaffolds’ porosity, pores number, pores size and distribution were quantified and none could establish a relationship with the viability results. Virtual reconstruction of the mats introduced an authentic criterion, “Scaffold Percolative Efficiency” (SPE), with which the above descriptors were addressed collectively. It was hypothesized to be able to quantify the efficacy of fibrous scaffolds by considering the integration of porosity and interconnectivity of the pores. There was a correlation of 80% as a good agreement between the SPE values and the spectrophotometer absorbance of viable cells; a viability of more than 350% in comparison to that of the controls.

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This work is motivated by the need to efficiently machine the edges of ophthalmic polymer lenses for mounting in spectacle or instrument frames. The polymer materials used are required to have suitable optical characteristics such high refractive index and Abbe number, combined with low density and high scratch and impact resistance. Edge surface finish is an important aesthetic consideration; its quality is governed by the material removal operation and the physical properties of the material being processed. The wear behaviour of polymer materials is not as straightforward as for other materials due to their molecular and structural complexity, not to mention their time-dependent properties. Four commercial ophthalmic polymers have been studied in this work using nanoindentation techniques which are evaluated as tools for probing surface mechanical properties in order to better understand the grinding response of polymer materials.

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The role of polymer chemistry (pure and applied sciences) is very prominent in the world of science today, but it is heading away from polymers and polymer blends towards composites and nanocomposites. This allows for the creation of new materials with unique properties and new possibilities which is the subject of this new book.

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The purpose of this review is to showcase the present capabilities of ambient sampling and ionisation technologies for the analysis of polymers and polymer additives by mass spectrometry (MS) while simultaneously highlighting their advantages and limitations in a critical fashion. To qualify as an ambient ionisation technique, the method must be able to probe the surface of solid or liquid samples while operating in an open environment, allowing a variety of sample sizes, shapes, and substrate materials to be analysed. The main sections of this review will be guided by the underlying principle governing the desorption/extraction step of the analysis; liquid extraction, laser ablation, or thermal desorption, and the major component investigated, either the polymer itself or exogenous compounds (additives and contaminants) present within or on the polymer substrate. The review will conclude by summarising some of the challenges these technologies still face and possible directions that would further enhance the utility of ambient ionisation mass spectrometry as a tool for polymer analysis. (C) 2013 Elsevier B. V. All rights reserved.

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In our effort to explore the use of the sulfite ion to design hybrid and open-framework materials, we have been able to prepare, under hydrothermal conditions, zero-dimensional [Zn(C12H8N2)(SO3)]center dot 2H(2)O, I (a = 7.5737(5) angstrom, b = 10.3969(6) angstrom, c = 10.3986(6) angstrom, alpha = 64.172(1)degrees, beta = 69.395(1)degrees, gamma = 79.333(1)degrees, Z = 2, and space group P (1) over bar), one-dimensional [Zn-2(C12H8N2)(SO3)(2)(H2O)], II (a = 8.0247(3) angstrom, b = 9.4962(3) angstrom, c = 10.2740(2) A, alpha = 81.070(1)degrees, beta = 80.438(1)degrees, gamma = 75.66(5)degrees, Z = 2, and space group P (1) over bar), two-dimensional [Zn-2(C10H8N2)(SO3)(2)]center dot H2O, III (a = 16.6062(1) angstrom, b = 4.7935(1) angstrom, c = 19.2721(5) angstrom, beta = 100.674(2)degrees, Z = 4, and space group C2/c), and three-dimensional [Zn-4(C6H12N2)(SO3)(4)(H2O)(4)], IV (a = 11.0793(3) angstrom, c = 8.8246(3) angstrom, Z = 2, and space group P42nm), of which the last three are coordination polymers. A hybrid open-framework sulfite-sulfate of the composition [C2H10N2][Nd(SO3)(SO4)(H2O)](2), V (a = 9.0880(3) angstrom, b = 6.9429(2) angstrom, c = 13.0805(5) A, beta = 91.551(2)degrees, Z = 2, and space group P2(1)/c), with a layered structure containing metal-oxygen-metal bonds has also been described.

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Binary mixtures have strong influence on activities of polymers and biopolymers even at low cosolvent concentration. Among the several aqueous binary mixtures studied, water-DMSO especially stands out for its unusual behavior at certain specific concentrations of DMSO. In the present work, we study the effect of water-DMSO binary mixture on polymers and biopolymers by taking a simple linear hydrocarbon chain of intermediate length (n = 30) and the protein lysozyme, respectively. We find that at a mole fraction of 0.05 of DMSO (x(DMSO) = 0.05) in aqueous solution, the hydrocarbon chain adopts the collapsed conformation as the most stable and rigid state. In this case of 0.05 mole fraction of DMSO in bulk, the DMSO concentration in the first hydration layer around the polymer is found to be as large as 17%. Formation of such hydrophobic environment around the polymer is the reason for the collapsed state gaining so much stability. Interestingly, similar quench of conformational fluctuation is also observed for the protein investigated. It is observed that in the case of alkane polymer chains, long wavelength fluctuation gets easily quenched, the polymer being purely hydrophobic. However, in case of the protein, quench of fluctuation is prominent only at the hydrophobic surface, and quench of long wavelength fluctuation becomes insignificant for the full protein. As protein contains both hydrophobic and hydrophilic moieties, the extent of quench of conformational fluctuation with respect to that in pure water is almost half for the biopolymer complex (16.83%) than the same for pure hydrophobic polymer chain (32.43%).

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The spectral photocurrent characteristics of two donor-acceptor diketopyrrolopyrrole (DPP)-based copolymers (PDPP-BBT and TDPP-BBT) blended with a fullerene derivative [6,6]-phenyl C-61-butyric acid methyl ester (PCBM) were studied using Fourier-transform photocurrent spectroscopy (FTPS) and monochromatic photocurrent (PC) method. PDPP-BBT: PCBM shows the onset of the lowest charge transfer complex (CTC) state at 1.42 eV, whereas TDPP-BBT: PCBM shows no evidence of the formation of a midgap CTC state. The FTPS and PC spectra of P3HT:PCBM are also compared. The larger singlet state energy difference of TDPP-BBT and PCBM compared to PDPP-BBT/P3HT and PCBM obliterates the formation of a midgap CTC state resulting in an enhanced photovoltaic efficiency over PDPP-BBT: PCBM. (C) 2011 American Institute of Physics. [doi:10.1063/1.3670043]