Ring-chain interconversion in high-performance polymer systems. 3. Cyclodepolymerization of poly(m-phenylene isophthalamide) (Nomex) and entropically driven ring-opening polymerization of the macrocyclic oligomers so produced

A homologous series of macrocyclic oligoamides has been prepared in high yield by reaction of isophthaloyl chloride with m-phenylenediamine under pseudo-high-dilution conditions. The products were characterized by infrared and H-1 NMR spectroscopies, matrix assisted laser desorption-ionization time-of-flight mass spectrometry, and gel permeation chromatography (GPC). A series of linear oligomers was prepared for comparison. The macrocycles ranged in size from the cyclic trimer up to at least the cyclic nonamer (90 ring atoms). The same homologous series of macrocyclic oligomers was prepared in high yield by the cyclodepolymerization of poly(m-phenylene isophthalamide) (Nomex). Cyclodepolymerization was best achieved by treating a 1% w/v solution of the polymer in dimethyl sulfoxide containing calcium chloride or lithium chloride with 3-4 mol % of sodium hydride or the sodium salt of benzanilide at 150 degreesC for 70 h. Treatment of a concentrated solution of the macrocyclic oligomers (25% w/v) with 4 mol % of sodium hydride or the sodium salt of benzanilide in a solution of lithium chloride in dimethyl sulfoxide at 170 degreesC for 6 h resulted in efficient entropically driven ring-opening polymerizations to give poly(m-phenylene isophthalamide), characterized by infrared and H-1 NMR spectroscopies and by GPC. The molecular weights obtained were comparable with those of the commercial polymer.

Self-nucleation and crystallization kinetics of double crystalline poly(p-dioxanone)-b-poly(epsilon-caprolactone) diblock copolymers

The crystallization kinetics of each constituent of poly(p-dioxanone)-b-poly(epsilon-caprolactone) diblock copolymers (PPDX-b-PCL) has been determined in a wide composition range by differential scanning calorimetry and compared to that of the equivalent homopolymers. Spherulitic growth rates were also measured by polarized optical microscopy while atomic force microscopy was employed to reveal the morphology of one selected diblock copolymer. It was found that crystallization drives structure formation and both components form lamellae within mixed spherulitic superstructures. The overall isothermal crystallization kinetics of the PPDX block at high temperatures, where the PCL is molten, was determined by accelerating the kinetics through a previous self-nucleation procedure. The application of the Lauritzen and Ho. man theory to overall growth rate data yielded successful results for PPDX and the diblock copolymers. The theory was applied to isothermal overall crystallization of previously self-nucleated PPDX ( where growth should be the dominant factor if self-nucleation was effective) and the energetic parameters obtained were perfectly matched with those obtained from spherulitic growth rate data of neat PPDX. A quantitative estimate of the increase in the energy barrier for crystallization of the PPDX block, caused by the covalently bonded molten PCL as compared to homo-PPDX, was thus determined. This energy increase can dramatically reduce the crystallization rate of the PPDX block as compared to homo-PPDX. In the case of the PCL block, both the crystallization kinetics and the self-nucleation results indicate that the PPDX is able to nucleate the PCL within the copolymers and heterogeneous nucleation is always present regardless of composition. Finally, preliminary results on hydrolytic degradation showed that the presence of relatively small amounts of PCL within PPDX-bPCL copolymers substantially retards hydrolytic degradation of the material in comparison to homo-PPDX. This increased resistance to hydrolysis is a complex function of composition and its knowledge may allow future prediction of the lifetime of the material for biomedical applications.

Exploring the spatial relations between soil physical properties and apparent electrical conductivity

Relations between the apparent electrical conductivity of the soil (ECa) and top- and sub-soil physical properties were examined for two arable fields in southern England (Crowmarsh Battle Farms and the Yattendon Estate). The spatial variation of ECa and the soil properties was explored geostatistically. The variogram ranges showed that ECa varied on a similar spatial scale to many of the soil physical properties in both fields. Several features in the map of kriged predictions of ECa were also evident in maps of the soil properties. In addition, the correlation coefficients showed a strong relation between ECa and several soil properties. A moving correlation analysis enabled differences in the relations between ECa and the soil properties to be examined within the fields. The results indicated that relations were inconsistent; they were stronger in some areas than others. A regression of ECa on the principal component scores of the leading components for both fields showed that the first two components accounted for a large proportion of the variance in ECa, whereas the others accounted for little or none. For Crowmarsh topsoil sand and clay, loss on ignition and volumetric water measured in the autumn had large correlations on the first component, and for Yattendon they were large for topsoil sand and clay, and autumn and spring volumetric water. The cross-variograms suggested strong coregionalization between ECa and several soil physical properties; in particular subsoil sand and silt at Crowmarsh, and subsoil sand and clay at Yattendon. The structural correlations from the linear model of coregionalization confirmed the strength of the relations between ECa and the subsoil properties. Nevertheless, no one property was consistently important for both fields. Although a map of ECa can indicate the general patterns of spatial variation in the soil, it is not a substitute for information on soil properties obtained by sampling and analysing the soil. Nevertheless, it could be used to guide further sampling. (c) 2005 Elsevier B.V. All rights reserved.

A comparison of the relative toxicity of bone meal and other P sources used as remedial treatments to the earthworm Eisenia fetida

It has been suggested that sources of P could be used to remediate metal-contaminated soil. The toxicity of four potential P sources, potassium hydrogen phosphate (PHP), triple superphosphate (TSP), rock phosphate (RP) and raw bone meal (RBM) to Eisenia fetida was determined. The concentration of P that is statistically likely to kill 50% of the population (LC50) for PHP, TSP and RBM was determined in OECD acute toxicity tests. 14 day LC50s expressed as bulk P concentration lay in the range 3319–4272 mg kg−1 for PHP, 3107–3590 mg kg−1 for TSP and 1782–2196 mg kg−1 for RBM (ranges present the 95% confidence intervals). For PHP and TSP mortality was significantly impacted by the electrical conductivity of the treated soils. No consistent relationship existed between mortality and electrical conductivity, soil pH and available (Olsen) P across the PHP, TSP and RBM amendment types. In RP toxicity tests mortality was low and it was not possible to determine a LC50 value. Incineration of bone meal at temperatures between 200 and 300 ◦C, pre-washing the bone meal, co-amendment with 5% green waste compost and delaying introduction of earthworms after bone meal amendments by 21 days or more led to significant reductions in the bone meal toxicity. These results are consistent with the toxicity being associated with the release and/or degradation of a soluble organic component present in raw bone meal. Bone meal can be used as an earthworm-friendly remedial amendment in metal-contaminated soils but initial additions may have a negative effect on any earthworms surviving in the contaminated soil before the organic component in the bone meal degrades in the soil.

The effect of thermal conductivity of RIM moulds in kinetics cure

Reaction Injection Moulding (RIM) is a moulding technology used for the production of large size and complex plastic parts. The RIM process is characterized essentially by the injection of a highly reactive chemical system (usually polyurethane) and fast cure, in a mould properly closed and thermally controlled. Several studies show that rapid manufacturing moulds obtained in epoxy resins for Thermoplastic Injection Moulding (TIM) affect the moulding process and the final properties of parts. The cycle time and mechanical properties of final parts are reduced, due to a low thermal conductivity of epoxy materials. In contrast, the low conductivity of materials usually applied for the rapid manufacturing of RIM moulds, increase the mechanical properties of final injected parts and reduce the cycle time. This study shows the effect of the rapid manufacturing moulds material during the RIM process. Several materials have been tested for rapid manufacturing of RIM moulds and the analysis of both, temperature profile of moulded parts during injection and the cure data experimentally obtained in a mixing and reaction cell, allow to determine and model the real effect of the mould material on the RIM process.

Solvent Effects on the Formation of Nanoparticles and Multilayered Coatings Based on Hydrogen-Bonded Interpolymer Complexes of Poly(acrylic acid) with Homo- and Copolymers of N-Vinyl Pyrrolidone

The formation of hydrogen-bonded interpolymer complexes between poly(acrylic acid) and poly(N-vinyl pyrrolidone) as well as amphiphilic copolymers of N-vinyl pyrrolidone with vinyl propyl ether has been studied in aqueous and organic solutions. It was demonstrated that introduction of vinyl propyl ether units into the macromolecules of the nonionic polymer enhances their ability to form complexes in aqueous solutions due to more significant contribution of hydrophobic effects. The complexation was found to be a multistage process that involves the formation of primary polycomplex particles, which further aggregate to form spherical nanoparticles. Depending on the environmental factors (pH, solvent nature), these nanoparticles may either form stable colloidal solutions or undergo further aggregation, resulting in precipitation of interpolymer complexes. In organic solvents, the intensity of complex formation increases in the following order: methanol < ethanol < isopropanol < dioxane. The multilayered coatings were developed using layer-by-layer deposition of interpolymer complexes on glass surfaces. It was demonstrated that the solvent nature affects the efficiency of coating deposition.

Effect of sequence distribution on the morphology, crystallization, melting, and biodegradation of poly(epsilon-caprolactone-co-epsilon-caprolactam) copolymers

Two types of poly(epsilon-caprolactone (CLo)-co-poly(epsilon-caprolactam (CLa)) copolymers were prepared by catalyzed hydrolytic ring-opening polymerization. Both cyclic comonomers were added simultaneously in the reaction medium for the First type or materials where copolymers have a random distribution of counits, as evidenced by H-1 and C-13 NMR. For the second type of copolymers, the cyclic comonomers were added sequentially, yielding diblock poly(ester-amides). The materials were characterized by differential scanning calorimetry (DSC), wide- and small-angle X-ray scattering (WAXS and SAXS), and transmission and scanning electron microscopies (TEM and SEM). Their biodegradation in compost was also studied. All copolymers were found to be miscible by the absence of structure in the melt. TEM revealed that all samples exhibited a crystalline lamellar morphology. DSC and WAXS showed that in a wide composition range (CLo contents from 6 to 55%) only the CLa units were capable of crystallization in the random copolymers. The block copolymer samples only experience a small reduction of crystallization and melting temperature with composition, and this was attributed to a dilution effect caused by the miscible noncrystalline CLo units. The comparison between block and random copolymers provided a unique opportunity to distinguish the dilution effect of the CLo units on the crystallization and melting of the polyamide phase from the chemical composition effect in the random copolymers case, where the CLa sequences are interrupted statistically by the CLo units, making the crystallization of the polyamide strongly composition dependent. Finally, the enzymatic degradation of the copolymers in composted soil indicate a synergistic behavior where much faster degradation was obtained for random copolymers witha CLo content larger than 30% than for neat PCL.

Formation of crystalline macrocyclic phases during electrophilic precipitation-polycondensation syntheses of poly(arylene ether ketone)s

Elongated crystalline particles formed as by-products during poly(arylene ether ketone) synthesis by electrophilic precipitation-polycondensation of 4,4'-diphenoxybenzophenone with terephthaloyl chloride or isophthaloyl chloride, thought previously to be polymer-whiskers, have now been identified as macrocyclic phases. Single crystal X-ray analysis of the needle-like particles formed in the reaction with terephthaloyl chloride, using the microdiffraction technique with synchrotron radiation, revealed that they consist of a macrocylic compound containing ten phenylene units, i.e. the [2 + 2] cyclic dimer. An analogous structure has also been demonstrated for the corresponding macrocycle derived from the reaction of 4,4-diphenoxybenzophenone with isophthaloyl chloride. Chloroform extraction of the products of the two polycondensations dissolved the macrocyclic material (but not the linear polymer), and analysis of the extracts by MALDI-TOF mass spectrometry demonstrated the presence in both cases of homologous families of macrocyclic products. Higher yields of macrocycles were obtained under pseudo-high dilution conditions, enabling the [2 + 2] cyclodimers from reactions of 4,4'-diphenoxybenzophenone with both terephthaloyl and isophthaloyl chloride to be isolated as pure compounds and fully characterised. (C) 2003 Published by Elsevier Ltd.

On the electrical properties of insulation oils

Insulating oils are a major component of high voltage plant, including transformers, switchgear and cables. Consequentially, in terms of plant failure, changes in the electrical characteristics of the oil during ageing are of crucial importance. To address this issue, commercial insulating oil was subjected to controlled ageing under laboratory conditions. The electrical properties of the aged oils were then characterized using dielectric spectroscopy. The data suggest that a degree of electrical conductivity occurs in the aged oils, which reduces the insulating properties of the oil as ageing proceeds. The role of atmosphere and additives on the electrical properties of the oils were also explored. Results are compared with model samples, which contain known amounts of materials that may occur as by-products of the ageing process.

Mechanisms of femtosecond laser-induced refractive index modification of poly(methyl methacrylate)

The mechanisms of refractive index change in poly(methyl methacrylate) by frequency doubled femtosecond laser pulses are investigated. It is demonstrated that positive refractive index modificaton can be caused by a combination of depolymerization and crosslinking.

Crystallization and stereocomplexation behavior of poly(D- and L-lactide)-b-poly(N,N-dimethylamino-2-ethyl methacrylate) block copolymers

The thermal properties, crystallization, and morphology of amphiphilic poly(D-lactide)-b-poly(N,N-dimethylamino- 2-ethyl methacrylate) (PDLA-b-PDMAEMA) and poly (L-lactide)-b-poly(N,N-dimethylamino-2-ethyl methacrylate) (PLLA-b-PDMAEMA) copolymers were studied and compared to those of the corresponding poly(lactide) homopolymers. Additionally, stereocomplexation of these copolymers was studied. The crystallization kinetics of the PLA blocks was retarded by the presence of the PDMAEMA block. The studied copolymers were found to be miscible in the melt and the glassy state. The Avrami theory was able to predict the entire crystallization range of the PLA isothermal overall crystallization. The melting points of PLDA/PLLA and PLA/PLA-b-PDMAEMA stereocomplexes were higher than those formed by copolymer mixtures. This indicates that the PDMAEMA block is influencing the stability of the stereocomplex structures. For the low molecular weight samples, the stereocomplexes particles exhibited a conventional disk-shape structure and, for high molecular weight samples, the particles displayed unusual star-like shape morphology.

Rheological and thermal behaviour of poly(N-isopropylacrylamide)/alginate smart polymeric networks

Interpenetrating polymeric networks based on sodium alginate and poly(N-isopropylacrylamide) (PNIPAAm) covalently crosslinked with N,N′-methylenebisacrylamide have been investigated using rheology, thermogravimetry, differential scanning calorimetry, X-ray diffraction measurements and scanning electron microscopy (SEM). An improved elastic response of the samples with a higher PNIPAAm content and increased amount of crosslinking agent was found. The temperature-responsive behaviour of the hydrogel samples was evidenced by viscoelastic measurements performed at various temperatures. It is shown that the properties of these gels can be tuned according to composition, amount of crosslinking agent and temperature changes. X-ray scattering analysis revealed that the hydrophobic groups are locally segregated even in the swollen state whilst cryo-SEM showed the highly heterogeneous nature of the gels.

Bacillus subtilis natto: a non-toxic source of poly-γ-glutamic acid that could be used as a cryoprotectant for probiotic bacteria

It is common practice to freeze dry probiotic bacteria to improve their shelf life. However, the freeze drying process itself can be detrimental to their viability. The viability of probiotics could be maintained if they are administered within a microbially produced biodegradable polymer - poly-γ-glutamic acid (γ-PGA) - matrix. Although the antifreeze activity of γ-PGA is well known, it has not been used for maintaining the viability of probiotic bacteria during freeze drying. The aim of this study was to test the effect of γ-PGA (produced by B. subtilis natto ATCC 15245) on the viability of probiotic bacteria during freeze drying and to test the toxigenic potential of B. subtilis natto. 10% γ-PGA was found to protect Lactobacillus paracasei significantly better than 10% sucrose, whereas it showed comparable cryoprotectant activity to sucrose when it was used to protect Bifidobacterium breve and Bifidobacterium longum. Although γ-PGA is known to be non-toxic, it is crucial to ascertain the toxigenic potential of its source, B. subtilis natto. Presence of six genes that are known to encode for toxins were investigated: three component hemolysin (hbl D/A), three component non-haemolytic enterotoxin (nheB), B. cereus enterotoxin T (bceT), enterotoxin FM (entFM), sphingomyelinase (sph) and phosphatidylcholine-specific phospholipase (piplc). From our investigations, none of these six genes were present in B. subtilis natto. Moreover, haemolytic and lecithinase activities were found to be absent. Our work contributes a biodegradable polymer from a non-toxic source for the cryoprotection of probiotic bacteria, thus improving their survival during the manufacturing process.

Hydrogen-bonded complexes and blends of poly(acrylic acid) and methylcellulose: nanoparticles and mucoadhesive films for Ocular Delivery of Riboflavin

Poly(acrylic acid) (PAA) and methylcellulose (MC) are able to form hydrogen-bonded interpolymer complexes (IPCs) in aqueous solutions. In this study, the complexation between PAA andMC is explored in dilute aqueous solutions under acidic conditions. The formation of stable nanoparticles is established,whose size and colloidal stability are greatly dependent on solution pH and polymers ratio in the mixture. Poly(acrylic acid) and methylcellulose are also used to prepare polymeric films by casting from aqueous solutions. It is established that uniform films can be prepared by casting from polymer mixture solutions at pH 3.4–4.5. At lower pHs (pH<3.0) the films have inhomogeneous morphology resulting from strong interpolymer complexation and precipitation of polycomplexes, whereas at higher pHs (pH 8.3) the polymers form fully immiscible blends because of the lack of interpolymer hydrogen-bonding. The PAA/MC films cast at pH 4 are shown to be non-irritant to mucosal surfaces. These films provide a platform for ocular formulation of riboflavin, a drug used for corneal crosslinking in the treatment of keratoconus. An in vitro release of riboflavin as well as an in vivo retention of the films on corneal surfaces can be controlled by adjusting PAA/MC ratio in the formulations.