Efficiency of 4,4′‐bis(N,N‐diethylamino) benzophenone for the polymerization of dimethacrylate resins in thick sections

The efficiency of 4,4′‐bis(N,N‐diethylamino)benzophenone (DEABP) for the polymerization of dimethacrylate monomers in thick sections ( 1 – 2 mm) was studied. DEABP (λ_max = 365 nm) represents a complete initiating system as it contains both ketone and amine functional groups. During irradiation, DEABP photobleaches at a fast rate causing deeper penetration of light through the underlying layers, but the photoinitiation efficiency (rate of polymerization per photon absorption rate) is relatively poor. As a result, irradiation of methacrylate monomers at 365 nm results in a slow average polymerization rate and a reduced monomer conversion for thick sections due to the light attenuation caused by the high absorptivity of DEABP and photolysis products. These results highlight the inherent interlinking of light attenuation and photobleaching rate in polymerization of thick sections. Copyright © 2011 Society of Chemical Industry     

An improved kinetic model for the peroxide initiated modification of polyethylene

We propose a generalized kinetic model for the peroxide initiated modification of polyethylene. It takes into account not only combination reactions but also transfer to polymer and scission. The model describes the length of the polymer chain and the concentration of vinyl groups simultaneously. Any number of vinyl groups per molecule is allowed. The resulting infinite system of mass balance equations is solved using a double moment technique. The model calculates number, weight and z-average molecular weights and the average concentration of vinyl groups as functions of time. The kinetic constants and the initiation efficiency were estimated through a nonlinear regression using experimental data. The relevance of each one of the reactions included in the mechanism was assessed. By means of the model we studied the influence of temperature and initial peroxide concentration on the modified polymer properties. It follows well the observed experimental trends and gives good estimates of both average molecular weights and average vinyl content, within experimental error.     

Dense silicon carbonitride ceramics by pyrolysis of cross-linked and warm pressed polysilazane powders

This study reports on the pyrolysis and densifaction behavior of cross-linked poly(hydridomethylsilazane) powders. The influence of the cross-linking procedure such as temperature and annealing time of the polymer powders on the compaction behavior under cold and warm pressing conditions is discussed. The degree of cross-linking is determined by thermal mechanical analysis (TMA). In addition to particle sliding which is assumed to be the compaction mechanism obtained by cold-pressing, the polymer powder consolidates by plastic deformation applying warm-pressing. A continuous 3-dimensional polysilazane network is formed after a dwelling time under these conditions. Pyrolysis of the cross-linked and compacted polysilazane powder in argon at 1100°C gives crack-free amorphous silicon carbonitride Si_3+xC_x+yN₄ with compositions ranging from x=1·47 and y=0·88 for cold pressed samples to x=1·47 and y=1·86 for warm pressed materials. The residual open porosity is significantly reduced from 10–15 vol% in the cold pressed specimens to 1·3–5 vol% by the warm pressing procedure. The weight loss during pyrolysis between room temperature and 1300°C is about 5 wt% lower than that for cold pressed specimens. This result is explained by a reduced methane evolution during the polymer-to-ceramic conversion and is in accordance with the enhanced carbon content of the warm pressed material.     

Liquid-crystallization induced reactions. Microstructure and morphology of copolyesters synthesized by transesterification of PET with some LCP monomers

The transesterification of poly(ethylene terephthalate) (PET) with a mixture of sebacic acid (S), 4,4′-diacetoxybiphenyl (B) and 4-acetoxybenzoic acid (H), carried out under conditions expectedly favoring the formation of a p(ET-SBH) random copolyester, produces biphasic materials with an isotropic matrix and a highly fibrous, liquid-crystalline dispersed phase. Spectroscopic, calorimetric, microscopic and diffractometric characterization of the fractions separated by solvent extraction has shown that the two phases consist of practically random copolyesters having different average composition. Interestingly, the degree of aromaticity of the matrix is even lower than that of PET, whereas that of the minor phase is appreciably higher than that calculated for the SBH copolyester that would be produced from the monomer mixture in the absence of PET. This unexpected result is interpreted on the basis of an enthalpy-driven progressive diffusion of aromatic-rich material toward the mesophase which segregates at an early stage of the polycondensation within the isotropic mixture of low molar mass oligomers initially produced by the PET acidolysis. Thus, an increasing differentiation, rather than an equilibration, of the composition of the two phases takes place. It is noteworthy that, despite the strong compositional difference, the two phases of these products show fairly good compatibility and interfacial adhesion.     

Characterisation of Phenolic Compounds in Oils Produced from Frosted Olives

Frost is one of the most important weather related hazards for the Australian olive industry and it has caused significant economic losses during the last decade. Its impact on oil quality was significant in 2006 with more than 20% of Australian oil of that year being affected to some degree. Early frosts will normally affect the fruit leading to significant changes in the chemical and organoleptic characteristics of the oils. The aim of this work was to study the effect of freeze damage on the phenolic composition and quality parameters of oils from three different varieties: Frantoio, Barnea and Picual. Quality chemical parameters showed significant differences in oils produced from fruit that was frozen for 2 and 4 weeks. Those chemical parameters were not significantly different in the oil produced from fruit immediately after being frosted. Nonetheless, the sensorial profile and the polyphenols showed significant changes even with oils produced within a short time after the freezing event. Those changes became more evident with the oils produced at increasing time from the moment of fruit freezing.     

Luminescent Eu(III) hybrid sensors for in situ copper detection

In this work we used the sol-gel technique to develop luminescent Eu(III) transparent films deposited on glass slides to build for sensor devices capable of monitoring transition metal ions in aqueous solutions. The films were obtained from a bis(trialkoxysilyl) organic precursor synthesized from the amide of the 2,6-pyridinedicarboxylic acid (DPA) with aminopropyltriethoxysilane (APTES) in the presence or absence of cetyl trimethyl ammonium bromide (CTAB) surfactant as templating agent and triethylethoxysilane (TEOS) as crosslinker. These sensor devices were used to perform in situ quenching experiments by Cu(II), Fe(III), Co(II) and Ni(II) ions. The results indicate that the templated films allow the detection and quantification of these metals down to ppb levels by means of the values of the Stern-Volmer constants. In particular, it was shown that Cu(II) acts as an extremely efficient quencher (K_SV = 3.5 × 10⁵ M⁻¹) when compared with the results obtained for the other metals, opening the possibility to use these devices as potential Cu(II) sensors for actual applications in aqueous media.     

Depleted parental psychological resources as mediators of the association of income with adherence and metabolic control.

For adolescents with Type 1 diabetes, lower family income may be associated with poorer diabetes management through depleted parental psychological resources (i.e., higher parental depressive symptoms, lower parental acceptance). Adolescents (N = 252; 46% male) aged 10–14 years with Type 1 diabetes assessed the acceptance of their mother and father (e.g., “gives me the feeling that she likes me as I am”; “she doesn't feel she has to make me over into someone else”). Mothers provided information on family income and demographics. Both mothers and fathers reported their depressive symptoms. HbA1c scores were indexed via medical records. Lower family income was associated with higher (i.e., worse) HbA1c, more mother and father depressive symptoms, and less acceptance from both parents. Mediation analyses revealed that the relationship of lower family income with metabolic control occurred indirectly through lower maternal and paternal acceptance and lower adherence. Lower family income may impair the quality of parent—adolescent relationships that are beneficial for good diabetes management. (PsycINFO Database Record (c) 2011 APA, all rights reserved)