Spin probe study of semi‐interpenetrating polymer networks based on polyurethane and polymethacrylate functional prepolymers

The motional transition and heterogeneity of semi‐interpenetrating networks (SIPNs) based on polyurethane (PU) with carboxylic groups and methacrylic copolymer (PM) with tertiary amine groups were studied by the electron spin resonance (ESR) spin probe method. The concentration of functional groups in both prepolymers varied from 0 to 0.45 mmol g^?1. Spin‐probed SIPNs show that the temperature‐dependent spectra are sensitive to polymer interactions imposed by functional groups. These interactions determine the free volume distribution in the matrix and temperature at which motional transition takes place. The fraction of free volume increases with functional group concentration and reaches its maximum at 0.25 mmol g^?1. Further increases in the functional group concentration reduce the free volume. The results of the networks with strong interactions are discussed in terms of the interference of the plasticizing effect of the PU component and the formation of possible cluster cross‐links, which restricts segmental motions. Copyright © 2003 Society of Chemical Industry     

Batch cultures of Penicillium camembertii on glucose and amino acids—model for growth and ammonium production

BACKGROUND: Three groups of amino acids were previously characterized based on their ability to be assimilated as carbon source by Penicillium camembertii. To describe the diauxic growth recorded on glucose and amino acids from the second group, such as arginine, an unstructured model was previously developed, based on the sequential consumption of both carbon substrates, glucose, followed after its exhaustion, by arginine. The model was modified to describe also the behaviour recorded during growth on other amino acids. RESULTS: The growth model involved the carbon substrate consumption (Verlhust model) and the biomass on carbon substrate yield. Glucose was therefore considered during P. camembertii growth on nitrogen source amino acids (lysine—first group); and amino acid consumption was considered during growth on carbon source amino acids (glutamate—third group), with glucose being dissimilated only for energy supply. The excess nitrogen from amino acids was released as ammonium; the linking of this production to growth was found to increase with the ability of the amino acid to be assimilated as carbon source by P. camembertii. CONCLUSION: The various metabolic behaviours recorded during P. camembertii growth on amino acids, in the presence of a primary carbon source such as glucose, were proved to be satisfactorily described by the model, showing the robustness of the model. Copyright © 2007 Society of Chemical Industry     

Synthesis and characterization of phenolic and amino resins based on α, β-unsaturated aldehydes

Phenolic and amino resins on the basis of α,β-unsaturated aldehydes were synthesized in bulk or solution. Catalysts were HCl, H₃PO₄, or formic acid, and in some cases NaOH. The course of the reactions was followed by GPC and NMR while the structure of the reaction products was determined by one- and two-dimensional NMR. The course of the reactions is influenced by experimental conditions: the type of monomers, their molar ratio, the type and quantity of the catalyst, the reaction time and temperature, and the reaction medium. At the beginning of the reaction the addition of a nucleophile to an aldehyde takes place through parallel 1,2-addition to and 1,4-addition to group. Oligomers with ? OH, , and ? CHO functional groups are able to add new monomer units or to react mutually to form higher molecular weight addition and condensation products. The overall rate constants for the beginning of the reactions were between 10^?3 L/mol s for the high reactive mixtures and 10^?7 L/mol s for the less reactive mixtures. The resins were cured by heating at temperatures above 135°C with the addition of hexamethylenetetramine.     

Ionic polymers with tunable liquid‐crystalline properties

Side‐chain polyesters were synthesized from N‐octyl‐, N‐dodecyl‐ or N‐hexadecyl‐diethanolamine and succinic acid anhydride. These polyesters were then transformed into polyester hydrochlorides by protonation of the amino groups using different amounts of HCl (20–100 mol%). Above 60 mol% the reaction is not quantitative and a degree of protonation of up to 88% is obtained. The structures of the synthesized polyesters and their hydrochlorides were determined by ¹H nuclear magnetic resonance spectroscopy. The thermal properties of the synthesized polyesters and their hydrochlorides were also studied using differential scanning calorimetry in relation to the side‐chain length and the degree of polyester protonation. The polyester with octyl side chains and its hydrochlorides were amorphous liquids at room temperature, while the polyester and polyester hydrochlorides with hexadecyl side chains formed a smectic crystalline phase, S_mB, or its tilted analogues. The polyester with a dodecyl side chain was also an amorphous liquid at room temperature, while its hydrochlorides with various degrees of protonation were smectic liquid crystals, as determined by X‐ray diffraction. By simply varying the degree of protonation the liquid crystal isotropization temperature was increased from 32 °C to 82 °C. Copyright © 2011 Society of Chemical Industry     

A simple procedure to eliminate known poles from a time series

An extremely simple procedure is presented for eliminating known or previously computed poles from a time series and for obtaining a `deflated' time series which contains only the remaining poles. Time-series deflation can be used in combination with any numerical algorithm used to compute poles. As an important example, it is demonstrated how the time-series deflation technique combined with Prony's method can produce more accurate results than the use of Prony's method alone     

Effect of cobalt doping on the dielectric response of Ba0.95Pb0.05TiO3 ceramics

Dielectric response of Ba_0.95Pb_0.05TiO₃ ceramics doped with 0.1 and 1 wt.% of Co₂O₃, synthesized by conventional high-temperature method, was studied in wide temperature and frequency range. The temperature dependences of the real and the imaginary parts of dielectric permittivity of the ceramics were compared with those of BaTiO₃ and Ba_0.95Pb_0.05TiO_3. The addition of Co³⁺ ions results in a broadening of dielectric anomalies related to the transition to paraelectric cubic phase, and the structural transition between the tetragonal and the orthorhombic phases. At low temperatures (125–200 K) the dielectric absorption of Co-doped Ba_0.95Pb_0.05TiO₃ ceramics was found to exhibit relaxor-like properties. The dielectric response has been found to contain the contributions characteristic of fluctuations of the polar nanoregion boundaries and reorientations of the dipole moments between allowed directions in the nanoregions in the rhombohedral and the orthorhombic phases. The behavior speaks in favor of ordering of polar defects in the host lattice of Ba_0.95Pb_0.05TiO₃ in a form polar nanoregions_.     

A modified creep model of epoxy adhesive at ambient temperature

The paper presents the results of experimental investigations of the creep behavior of epoxy adhesive-hardened samples. The determined creep characteristics for an assumed range of tensile stresses show that the rheological effects in the examined adhesive have already occurred very distinctly at room temperature, for a relatively short time; moreover, the examined adhesive is a nonlinear viscoelastic medium and does not obey the Boltzmann's superposition principle. The obtained results of experimental investigations were subjected to detailed analysis and mathematical treatments. As a result of these actions, the so-called modified Burgers model has been finally developed for the studied adhesive with a constant modulus of elasticity for the non-relaxing part (describing the instant elastic strain) and variables, dependent on the tensile stress, the parameter values for its relaxing part (describing non-linearly viscoelastic properties of this adhesive). The creep deformations calculated for this model have demonstrated a very good consistency with the results of experimental investigations over the assumed range of stresses and the duration time of measurements.     

Energy substrate efficiency during batch cultures of Geotrichum candidum

BACKGROUND: Metabolisation of carbon and nitrogen substrates is a key factor during the ripening process of white soft cheeses but has not previously been examined in terms of energy substrate efficiency. Such work could be useful to improve physiological knowledge concerning Geotrichum candidum, a yeast involved in the neutralisation of curd during ripening. Its behaviour was therefore examined during batch cultures on simple (glutamate) or complex (peptones) substrates as nitrogen and carbon sources and lactate as a second carbon source. RESULTS: In addition to their assimilation as carbon and nitrogen sources, G. candidum used peptides and amino acids as energy sources during growth in preference to lactate. Contrarily, during stationary state, lactate was preferred over peptides and amino acids for carbon dissimilation for energy supply, allowing the avoidance of ammonium production. Indeed, lactate dissimilation theoretically yields 15 adenosine triphosphates (ATPs), while only nine ATPs are theoretically yielded during the dissimilation of an amino acid such as glutamate. CONCLUSION: This behaviour can be considered as an energy‐saving response. Indeed, the use of peptides and amino acids as energy sources in addition to being used as carbon and nitrogen sources during G. candidum growth can be related to its deaminating activity and was in agreement with the better energy efficiency expected from utilisation of the same substrate as both carbon and energy source. Contrarily, the better efficiency of lactate dissimilation led to its use during stationary state instead of peptides and amino acids. Copyright © 2008 Society of Chemical Industry