The effects of silica fillers on the gelation and vitrification of highly filled epoxy-amine thermosets

Highly filled thermosets are used in applications such as integrated circuit (IC) packaging. However, a detailed understanding of the effects of the fillers on the macroscopic cure properties is limited by the complex cure of such systems. This work systematically quantifies the effects of filler content on the kinetics, gelation and vitrification of a model silica-filled epoxy/amine system in order to begin to understand the role of the filler in IC packaging cure. At high cure temperatures (100 degreesC and above) there appears to be no effect of fillers on cure kinetics and gelation and vitrification times. However, a decrease in the gelation and vitrification times and increase the reaction rate is seen with increasing filler content at low cure temperatures (60-90 degreesC). An explanation for these results is given in terms of catalysation of the epoxy amine reaction by hydrogen donor species present on the silica surface and interfacial effects.

Activation energy distribution of thermal annealing of a bituminous coal

A bituminous coal was pyrolyzed in a nitrogen stream in an entrained flow reactor at various temperatures from 700 to 1475 degreesC. Char samples were collected at different positions along the reactor. Each collected sample was oxidized nonisothermally in a TGA for reactivity determination. The reactivity of the coal char was found to decrease rapidly with residence time until 0.5 s, after which it decreased only slightly. On the bases of the reactivity data at various temperatures, a new approach was utilized to obtaining the true activation energy distribution function for thermal annealing without the assumption of any distribution function form or a constant preexponential factor. It appears that the true activation energy distribution function consists of two separate parts corresponding to different temperature ranges, suggesting different mechanisms in different temperature ranges. Partially burnt coal chars were also collected along the reactor when the coal was oxidized in air at various temperatures from 700 to 1475 degreesC. The collected samples were analyzed for the residual carbon content and the specific reaction rate was estimated. The characteristic time of thermal deactivation was compared with that of oxidation under realistic conditions. The characteristic times were found to be close to each other, indicating the importance of thermal deactivation during combustion of the coal studied.

Comparison of taurine- and glycine-induced conformational changes in the M2-M3 domain of the glycine receptor

In the ionotropic glutamate receptor, the global conformational changes induced by partial agonists are smaller than those induced by full agonists. However, in the pentameric ligand-gated ion channel receptor family, the structural basis of partial agonism is not understood. This study investigated whether full and partial agonists induce different conformation changes in the glycine receptor chloride channel ( GlyR). A substituted cysteine accessibility analysis demonstrated previously that glycine binding induced an increase in surface accessibility of all residues from Arg(271) to Lys(276) in the M2-M3 domain of the homomeric alpha1 GlyR. Here we compare the surface accessibility changes induced by the full agonist, glycine, and the partial agonist, taurine. In GlyRs incorporating the A272C, S273C, L274C, or P275C mutation, the reaction rate of the cysteine-specific compound, methanethiosulfonate ethyltrimethylammonium, depended on how strongly the receptors were activated but was agonist-independent. Reaction rates could not be compared in the R271C and K276C mutant GlyRs because methanethiosulfonate ethyltrimethylammonium did not modify the extremely small currents induced by saturating taurine or equivalent low glycine concentrations. The results indicate that bound taurine and glycine molecules impose identical conformational changes to the M2-M3 domain. We therefore conclude that the higher efficacy of glycine is due to an increased ability to stabilize a common activated configuration.

A picrotoxin-specific conformational change in the glycine receptor M2-M3 loop.

The external loop linking the M2 and M3 transmembrane domains is crucial for coupling agonist binding to channel gating in the glycine receptor chloride channel (GlyR). A substituted cysteine accessibility scan previously showed that glycine activation increased the surface accessibility of 6 contiguous residues (Arg(271) Lys(276)) toward the N-terminal end of the homomeric alpha 1 GlyR M2 - M3 loop. In the present study we used a similar approach to determine whether the allosteric antagonist, picrotoxin, could impose conformational changes to this domain that cannot be induced by varying agonist concentrations alone. Picrotoxin slowed the reaction rate of a sulfhydryl-containing compound ( MTSET) with A272C, S273C, and L274C. Before interpreting this as a picrotoxin-specific conformational change, it was necessary to eliminate the possibility of steric competition between picrotoxin and MTSET. Accordingly, we showed that picrotoxin and the structurally unrelated blocker, bilobalide, were both trapped in the R271C GlyR in the closed state and that a point mutation to the pore-lining Thr(6') residue abolished inhibition by both compounds. We also demonstrated that the picrotoxin dissociation rate was linearly related to the channel open probability. These observations constitute a strong case for picrotoxin binding in the pore. We thus conclude that the picrotoxin-specific effects on the M2 - M3 loop are mediated allosterically. This suggests that the M2 - M3 loop responds differently to the occupation of different binding sites.

Stochastic delay differential equations for genetic regulatory networks

Time delay is an important aspect in the modelling of genetic regulation due to slow biochemical reactions such as gene transcription and translation, and protein diffusion between the cytosol and nucleus. In this paper we introduce a general mathematical formalism via stochastic delay differential equations for describing time delays in genetic regulatory networks. Based on recent developments with the delay stochastic simulation algorithm, the delay chemical masterequation and the delay reaction rate equation are developed for describing biological reactions with time delay, which leads to stochastic delay differential equations derived from the Langevin approach. Two simple genetic regulatory networks are used to study the impact of' intrinsic noise on the system dynamics where there are delays. (c) 2006 Elsevier B.V. All rights reserved.

Copolymerization of methyl methacrylate and allyl acetate Part I. Rate of reaction

Free radical bulk copolymerization of methyl methacrylate (MMA) and allyl acetate (AAc) has been investigated using electron spin resonance (ESR) and FT-near infrared (FTNIR) spectroscopy. Data are used to evaluate the rate constants. The mole fraction of AAc plays an important role in the copolymerization of these two monomers. AAc not only delays the Trommsdorff effect but also increases the onset of percentage total conversion at which the Trommsdorff region begins. With AAc fraction 0.5 and higher, no Trommsdorff effect was observed. Inclusion of AAc into copolymer structure mainly occurs in the Trommsdorf region or when the AAc fraction in the comonomer feed is dominant. This is associated with a drop in the concentration of propagating radicals. However, ESR spectra indicate that the MMA propagating radical is predominant during the reaction. In the comonomer mixtures where a Trommsdorff region can be observed, the addition of AAc does not produce any significant change in k(p) and k(t) in the steady state region. Major changes in k(p) and k(t) are observed after the gel point and glassy state, respectively. (C) 2001 Society of Chemical Industry.

Prediction of absolute rate coefficients and product branching ratios for the C(P-3) plus allene reaction system

Complex chemical reactions in the gas phase can be decomposed into a network of elementary (e.g., unimolecular and bimolecular) steps which may involve multiple reactant channels, multiple intermediates, and multiple products. The modeling of such reactions involves describing the molecular species and their transformation by reaction at a detailed level. Here we focus on a detailed modeling of the C(P-3)+allene (C3H4) reaction, for which molecular beam experiments and theoretical calculations have previously been performed. In our previous calculations, product branching ratios for a nonrotating isomerizing unimolecular system were predicted. We extend the previous calculations to predict absolute unimolecular rate coefficients and branching ratios using microcanonical variational transition state theory (mu-VTST) with full energy and angular momentum resolution. Our calculation of the initial capture rate is facilitated by systematic ab initio potential energy surface calculations that describe the interaction potential between carbon and allene as a function of the angle of attack. Furthermore, the chemical kinetic scheme is enhanced to explicitly treat the entrance channels in terms of a predicted overall input flux and also to allow for the possibility of redissociation via the entrance channels. Thus, the computation of total bimolecular reaction rates and partial capture rates is now possible. (C) 2002 American Institute of Physics.

Role of oxygen in the nitrous oxide/carbon reaction

An investigation of the role of oxygen in the nitrous oxide/carbon reaction was carried out on various carbon samples (both graphitic and nongraphitic) over a range of temperatures and partial pressures. Previous work reported that oxygen strongly inhibited the nitrous oxide/carbon reaction. Large ratios of O-2/N2O were used in all previous work. In this work, the O-2/N2O ratio was kept below 1, and we found that oxygen did not inhibit the rate of the C + N2O reaction. Instead, the rate of the reaction in the presence of oxygen was essentially that predicted by the two independent reactions, nitrous oxide/carbon and oxygen/carbon, occurring simultaneously. A simple theoretical explanation is given for the observations, both past and present, on the basis of competitive chemisorption of nitrous oxide and oxygen on active sites.

On the validity of thermogravimetric determination of carbon gasification kinetics

Thermogravimetric analysis has been widely applied in kinetic studies of carbon gasification, with the associated temporal weight change profiles being used to extract kinetic information and to validate gasification models. However the weight change profiles are not always governed by the intrinsic gasification activity because of the effect of chemisorption and its dynamics. In the present work we theoretically determine the criteria under which weight change profiles can be used to determine intrinsic kinetics for CO2 and O2 gasification by examining the region in which the chemisorption dynamics can be assumed pseudo-steady. It is found that the validity of the pseudo-steady assumption depends on the experimental conditions as well as on the initial surface area of carbon. Based on known mechanisms and rate constants an active surface area region is identified within which the steady state assumption is valid and the effect of chemisorption dynamics is negligible. The size of the permissible region is sensitive to the reaction temperature and gas pressure. The results indicate that in some cases the thermogravimetric data should be used with caution in kinetic studies. A large amount of literature on thermogravimetric analyzer determined char gasification kinetics is examined and the importance of chemisorption dynamics for the data assessed.

A master equation model for bimolecular reaction via multi-well isomerization intermediates

A reversible linear master equation model is presented for pressure- and temperature-dependent bimolecular reactions proceeding via multiple long-lived intermediates. This kinetic treatment, which applies when the reactions are measured under pseudo-first-order conditions, facilitates accurate and efficient simulation of the time dependence of the populations of reactants, intermediate species and products. Detailed exploratory calculations have been carried out to demonstrate the capabilities of the approach, with applications to the bimolecular association reaction C3H6 + H reversible arrow C3H7 and the bimolecular chemical activation reaction C2H2 +(CH2)-C-1--> C3H3+H. The efficiency of the method can be dramatically enhanced through use of a diffusion approximation to the master equation, and a methodology for exploiting the sparse structure of the resulting rate matrix is established.

Percolative fragmentation of char particles during gasification

Percolative fragmentation was confirmed to occur during gasification of three microporous coal chars. Indirect evidence obtained by the variation of electrical resistivity (ER) with conversion was supported by direct observation of numerous fragments during gasification. The resistivity increases slowly at low conversions and then sharply after a certain conversion value, which is a typical percolation phenomenon suggesting the occurrence of internal fragmentation at high conversion. Two percolation models are applied to interpret the experimental data and determine the percolation threshold. A percolation threshold of 0.02-0.07 was found, corresponding to a critical conversion of 92-96% for fragmentation. The electrical resistivity variation at high conversions is found to be very sensitive to diffusional effects during gasification. Partially burnt samples with a narrow initial particle size range were also observed microscopically, and found to yield a large number of small fragments even when the particles showed no disintegration and chemical control prevailed. It is proposed that this is due to the separation of isolated clusters from the particle surface. The particle size distribution of the fragments was essentially independent of the reaction conditions and the char type, and supported the prediction by percolation theory that the number fraction distribution varies linearly with mass in a log-log plot. The results imply that perimeter fragmentation would occur in practical combustion systems in which the reactions are strongly diffusion affected.

Identifying rate-limiting nodes in large-scale cortical networks for visuospatial processing: an illustration using fMRI

With the advent of functional neuroimaging techniques, in particular functional magnetic resonance imaging (fMRI), we have gained greater insight into the neural correlates of visuospatial function. However, it may not always be easy to identify the cerebral regions most specifically associated with performance on a given task. One approach is to examine the quantitative relationships between regional activation and behavioral performance measures. In the present study, we investigated the functional neuroanatomy of two different visuospatial processing tasks, judgement of line orientation and mental rotation. Twenty-four normal participants were scanned with fMRI using blocked periodic designs for experimental task presentation. Accuracy and reaction time (RT) to each trial of both activation and baseline conditions in each experiment was recorded. Both experiments activated dorsal and ventral visual cortical areas as well as dorsolateral prefrontal cortex. More regionally specific associations with task performance were identified by estimating the association between (sinusoidal) power of functional response and mean RT to the activation condition; a permutation test based on spatial statistics was used for inference. There was significant behavioral-physiological association in right ventral extrastriate cortex for the line orientation task and in bilateral (predominantly right) superior parietal lobule for the mental rotation task. Comparable associations were not found between power of response and RT to the baseline conditions of the tasks. These data suggest that one region in a neurocognitive network may be most strongly associated with behavioral performance and this may be regarded as the computationally least efficient or rate-limiting node of the network.

Time-dependent master equation simulation of complex elementary reactions in combustion: Application to the reaction of (CH2)-C-1 with C2H2 from 300-2000 K

Computational simulations of the title reaction are presented, covering a temperature range from 300 to 2000 K. At lower temperatures we find that initial formation of the cyclopropene complex by addition of methylene to acetylene is irreversible, as is the stabilisation process via collisional energy transfer. Product branching between propargyl and the stable isomers is predicted at 300 K as a function of pressure for the first time. At intermediate temperatures (1200 K), complex temporal evolution involving multiple steady states begins to emerge. At high temperatures (2000 K) the timescale for subsequent unimolecular decay of thermalized intermediates begins to impinge on the timescale for reaction of methylene, such that the rate of formation of propargyl product does not admit a simple analysis in terms of a single time-independent rate constant until the methylene supply becomes depleted. Likewise, at the elevated temperatures the thermalized intermediates cannot be regarded as irreversible product channels. Our solution algorithm involves spectral propagation of a symmetrised version of the discretized master equation matrix, and is implemented in a high precision environment which makes hitherto unachievable low-temperature modelling a reality.