Process for forming alumino-silicate derivatives

A process for the preparation of an amorphous alumino-silicate derivative which involves reacting a solid corresponding starting material with MOH where M is alkali metal or ammonium cation. The solid corresponding starting material may be selected from montmorillonite, kaolin, natural zeolite (e.g., clinoliptolite/heulandite) as well as illite, palygorskite and saponite and additional reactant MX wherein X is halide may be utilized in conjunction with MOH. The invention also includes alumino-silicate derivatives of the general formula M.sub.p Al.sub.q Si.sub.2 O.sub.r (OH).sub.s X.sub.t.uH.sub.2 O as well as alumino-silicate derivatives of the general formula M.sub.p Al.sub.q Si.sub.2 O.sub.r (OH).sub.s.uH.sub.2 O.

Kaolin derivatives

Amorphous derivatives of kaolin group minerals characterized by high specific surfaces and/or high cation exchange capacities and a .sup.27 AL MAS NMR spectrum having a dominant peak at about 55 ppm relative to Al(H.sub.2 O).sub.6.sup.3+. Such derivatives are prepared by reacting a kaolin group mineral with a reagent, such as, an alkali metal halide or an ammonium halide which converts the majority of the octahedrally coordinated aluminum in the kaolin group mineral to tetrahedrally coordinated aluminum. Such derivatives show high selectivity in its cation exchange towards the metals: Pb.sup.2+, Cu.sup.2+, Cd.sup.2+, Ni.sup.2+, CO.sup.2+, Cr.sup.3+, Sr.sup.2-, Zn.sup.2+, Nd.sup.3+ and UO.sub.2.sup.+.

A preconditioned Lanczos method for space-fractional reaction-diffusion equations on two-dimensional unstructured meshes

We consider a two-dimensional space-fractional reaction diffusion equation with a fractional Laplacian operator and homogeneous Neumann boundary conditions. The finite volume method is used with the matrix transfer technique of Ilić et al. (2006) to discretise in space, yielding a system of equations that requires the action of a matrix function to solve at each timestep. Rather than form this matrix function explicitly, we use Krylov subspace techniques to approximate the action of this matrix function. Specifically, we apply the Lanczos method, after a suitable transformation of the problem to recover symmetry. To improve the convergence of this method, we utilise a preconditioner that deflates the smallest eigenvalues from the spectrum. We demonstrate the efficiency of our approach for a fractional Fisher’s equation on the unit disk.

Layered silicates in Chondritic Porous Aggregate W7029*A : a case of primary growth

An important subset of extraterrestrial particles that reach the Earth's stratosphere include the so-called Chondritic Porous Aggregates (CPA's) [1-3]. In general, CPA's have a fluffy morphology and consist of numerous (>104)subparticles that are often <100A in size [4]. Mineral species in CPA's include Mg-rich pyroxene and olivine, Fe- and (Fe,Ni)-sulphides, taenite, Fe,Ni-carbides, magnetite, Ti-metal, a Bi-phase (metal or oxide), and variable amounts of carbonaceous material [1, 5-7]. Hydrated silicates are rare in CPA's and are limited to aggregates that have not been severely altered (thermo-metamorphosed) during atmospheric entry [8]. The presence of hydrated silicates in one cosmic dust particle was established by X-ray diffraction [2] and has been inferred in others by infra-red spectroscopy [8]. If CPA's are cometary, their mineralogy and morphology suggest that at least two episodes of aggregation occurred and that variations in porosity may be related to local differences in ice-to-dust ratio [3].

Water absorption, permeability, and resistance to chloride-ion penetration of lightweight aggregate concrete

This paper presents an experimental study to evaluate effect of cumulative lightweight aggregate (LWA) content (including lightweight sand) in concrete [water/cement ratio (w/c) = 0.38] on its water absorption, water permeability, and resistance to chloride-ion penetration. Rapid chloride penetrability test (ASTM C 1202), rapid migration test (NT Build 492), and salt ponding test (AASHTO T 259) were conducted to evaluate the concrete resistance to chloride-ion penetration. The results were compared with those of a cement paste and a control normal weight aggregate concrete (NWAC) with the same w/c and a NWAC (w/c = 0.54) with 28-day compressive strength similar to some of the lightweight aggregate concrete (LWAC). Results indicate that although the total charge passed, migration coefficient, and diffusion coefficient of the LWAC were not significantly different from those of NWAC with the same w/c of 0.38, resistance of the LWAC to chloride penetration decreased with increase in the cumulative LWA content in the concretes. The water penetration depth under pressure and water sorptivity showed, in general, similar trends. The LWAC with only coarse LWA had similar water sorptivity, water permeability coefficient, and resistance to chloride-ion penetration compared to NWAC with similar w/c. The LWAC had lower water sorptivity, water permeability and higher resistance to chloride-ion penetration than the NWAC with similar 28-day strength but higher w/c. Both the NWAC and LWAC had lower sorptivity and higher resistance to chloride-ion penetration than the cement paste with similar w/c.

Effect of cumulative lightweight aggregate volume in concrete on its resistance to chloride-ion penetration

This paper presents an experimental study on the resistance of lightweight aggregate concretes to chloride-ion penetration in comparison to that of normal weight concrete of similar w/c. Salt ponding test (based on AASHTO T 259), rapid chloride permeability test (ASTM C 1202) and rapid migration test (NT Build 492) were carried out to evaluate the concrete resistance to the chloride-ion penetration. Results indicate that in general the resistance of the LWAC to the chloride-ion penetration was in the same order as that of NWAC of similar w/c. However, the increase in cumulative LWA volume and the incorporation of finer LWA particles led to higher charge passed, migration coefficient, and diffusion coefficient. Since the LWACs had lower 28-day compressive strength compared with that of the NWAC of similar w/c, the LWACs may have equal or better resistance to the chloride-ion penetration compared with the NWAC of equivalent strength. The trend of the resistance of concretes to chloride-ion penetration determined by the three test methods was reasonably consistent although there were some discrepancies due to different test methods.

Development of lightweight aggregate concrete with high resistance to water and chloride-ion penetration

This paper presents an experimental study to evaluate the effect of coarse and fine LWA in concrete on its water absorption and permeability, and resistance to chloride-ion penetration. In additions, LWC with lower unit weight of about 1300 kg/m3 but high resistance to water and chloride-ion penetration was developed and evaluated. The results indicate that the incorporation of coarse LWA in concrete increases water sorptivity and permeability slightly compared to NWC of similar w/c. The resistance of the sand-LWC to chloride-ion penetration depends on porosity of the coarse LWA. Fine LWA has more influence on the transport proper-ties of concrete than coarse LWA. Use of lightweight crushed sand <1.18 mm reduced the resistance of the LWC to water and chloride-ion penetration to some extent. With low w/cm and silica fume, low unit weight LWC (~1300 kg/m3) was produced with higher resistance to water and chloride ion penetration compared with concretes of higher unit weights.

Addition of diazomethane to armchair single-walled carbon nanotubes and their reaction sequences : A computational study

The sidewall additions of diazomethane to (n, n), n = 3–10 armchair single-walled carbon nanotubes (SWCNTs) on two different orientations of C–C bonds have been studied using the ONIOM(B3LYP/6-31G(d):PM3) approach. The binding energies of SWCNTs complexes with CH2N2, CH2 and their transition-state structures were computed at the B3LYP/6-31G(d) level. The effects of diameters of armchair SWCNTs on their binding energies were studied. Relative reactivities of all the SWCNTs and their complexes based on their frontier orbital energies gaps are reported.

Insights into the mechanism of the reaction between ttrachloro-p-bnzoquinone and hydrogen peroxide and their implications in the catalytic role of water molecules in producing the hydroxyl radial

Detailed mechanisms for the formation of hydroxyl or alkoxyl radicals in the reactions between tetrachloro-p-benzoquinone (TCBQ) and organic hydroperoxides are crucial for better understanding the potential carcinogenicity of polyhalogenated quinones. Herein, the mechanism of the reaction between TCBQ and H2O2 has been systematically investigated at the B3LYP/6-311++G** level of theory in the presence of different numbers of water molecules. We report that the whole reaction can easily take place with the assistance of explicit water molecules. Namely, an initial intermediate is formed first. After that, a nucleophilic attack of H2O2 onto TCBQ occurs, which results in the formation of a second intermediate that contains an OOH group. Subsequently, this second intermediate decomposes homolytically through cleavage of the O-O bond to produce a hydroxyl radical. Energy analyses suggest that the nucleophilic attack is the rate-determining step in the whole reaction. The participation of explicit water molecules promotes the reaction significantly, which can be used to explain the experimental phenomena. In addition, the effects of F, Br, and CH3 substituents on this reaction have also been studied.

A combined temperature-programmed reaction spectroscopy and Fourier-transform infrared spectroscopy study of CO2/H2 and CO/CO2/H2 interactions with model ZnO/SiO2, Cu/SiO2 and Cu/ZnO/SiO2 methanol-synthesis catalysts

The reaction of CO2 and H2 with ZnO/SiO2 catalyst at 295 K gave predominantly hydrogencarbonate on zinc oxide and a small quantity of formate was evolved after heating at 393 K. Elevation of the reaction temperature to 503 K enhanced the rate of formation of zinc formate species. Significantly these formate species decomposed at 573 K almost entirely to CO2 and H2. Even after exposure of CO2-H2 or CO-CO2-H2 mixtures to highly defected ZnO/SiO2 catalyst, the formate species produced still decomposed to give CO2 and H2. It was concluded that carboxylate species which were formed at oxygen anion vacancies on polar Zn planes were not significantly hydrogenated to formate. Consequently it was proposed that the non-polar planes on zinc oxide contained sites which were specific for the synthesis of methanol. The interaction of CO2 and H2 with reduced Cu/ZnO/SiO2 catalyst at 393 K gave copper formate species in addition to substantial quantities of formate created at interfacial sites between copper and zinc oxide. It was deduced that interfacial formate species were produced from the hydrogenation of interfacial bidentate carbonate structures. The relevance of interfacial formate species in the methanol synthesis reaction is discussed. Experiments concerning the reaction of CO2-H2 with physical mixtures of Cu/SiO2 and ZnO/SiO2 gave results which were simply characteristic of the individual components. By careful consideration of previous data a detailed proposal regarding the role of spillover hydrogen is outlined. Admission of CO to a gaseous CO2-H2 feedstock resulted in a considerably diminished amount of formate species on copper. This was ascribed to a combination of over-reduction of the surface and site-blockage.

A simplified approach for calculating the moments of action for linear reaction-diffusion equations

The mean action time is the mean of a probability density function that can be interpreted as a critical time, which is a finite estimate of the time taken for the transient solution of a reaction-diffusion equation to effectively reach steady state. For high-variance distributions, the mean action time under-approximates the critical time since it neglects to account for the spread about the mean. We can improve our estimate of the critical time by calculating the higher moments of the probability density function, called the moments of action, which provide additional information regarding the spread about the mean. Existing methods for calculating the nth moment of action require the solution of n nonhomogeneous boundary value problems which can be difficult and tedious to solve exactly. Here we present a simplified approach using Laplace transforms which allows us to calculate the nth moment of action without solving this family of boundary value problems and also without solving for the transient solution of the underlying reaction-diffusion problem. We demonstrate the generality of our method by calculating exact expressions for the moments of action for three problems from the biophysics literature. While the first problem we consider can be solved using existing methods, the second problem, which is readily solved using our approach, is intractable using previous techniques. The third problem illustrates how the Laplace transform approach can be used to study coupled linear reaction-diffusion equations.

Effects of mobile phone distraction on drivers’ reaction times

Distraction resulting from mobile phone use whilst driving has been shown to increase the reaction times of drivers, thereby increasing the likelihood of a crash. This study compares the effects of mobile phone conversations on reaction times of drivers responding to traffic events that occur at different points in a driver’s field of view. The CARRS-Q Advanced Driving Simulator was used to test a group of young drivers on various simulated driving tasks including a traffic event that occurred within the driver’s central vision—a lead vehicle braking suddenly—and an event that occurred within the driver’s peripheral—a pedestrian entering a zebra crossing from a footpath. Thirty-two licensed drivers drove the simulator in three phone conditions: baseline (no phone conversation), and while engaged in hands-free and handheld phone conversations. The drivers were aged between 21 to 26 years and split evenly by gender. Differences in reaction times for an event in a driver’s central vision were not statistically significant across phone conditions, probably due to a lower speed selection by the distracted drivers. In contrast, the reaction times to detect an event that originated in a distracted driver’s peripheral vision were more than 50% longer compared to the baseline condition. A further statistical analysis revealed that deterioration of reaction times to an event in the peripheral vision was greatest for distracted drivers holding a provisional licence. Many critical events originate in a driver’s periphery, including vehicles, bicyclists, and pedestrians emerging from side streets. A reduction in the ability to detect these events while distracted presents a significant safety concern that must be addressed.

A parametric duration model of the reaction times of drivers distracted by mobile phone conversations

The use of mobile phones while driving is more prevalent among young drivers—a less experienced cohort with elevated crash risk. The objective of this study was to examine and better understand the reaction times of young drivers to a traffic event originating in their peripheral vision whilst engaged in a mobile phone conversation. The CARRS-Q Advanced Driving Simulator was used to test a sample of young drivers on various simulated driving tasks, including an event that originated within the driver’s peripheral vision, whereby a pedestrian enters a zebra crossing from a sidewalk. Thirty-two licensed drivers drove the simulator in three phone conditions: baseline (no phone conversation), hands-free and handheld. In addition to driving the simulator each participant completed questionnaires related to driver demographics, driving history, usage of mobile phones while driving, and general mobile phone usage history. The participants were 21 to 26 years old and split evenly by gender. Drivers’ reaction times to a pedestrian in the zebra crossing were modelled using a parametric accelerated failure time (AFT) duration model with a Weibull distribution. Also tested where two different model specifications to account for the structured heterogeneity arising from the repeated measures experimental design. The Weibull AFT model with gamma heterogeneity was found to be the best fitting model and identified four significant variables influencing the reaction times, including phone condition, driver’s age, license type (Provisional license holder or not), and self-reported frequency of usage of handheld phones while driving. The reaction times of drivers were more than 40% longer in the distracted condition compared to baseline (not distracted). Moreover, the impairment of reaction times due to mobile phone conversations was almost double for provisional compared to open license holders. A reduction in the ability to detect traffic events in the periphery whilst distracted presents a significant and measurable safety concern that will undoubtedly persist unless mitigated.

Galvanic replacement mediated synthesis of hollow Pt nanocatalysts : significance of residual Ag for the H2 evolution reaction

With the increasing popularity of the galvanic replacement approach towards the development of bimetallic nanocatalysts, special emphasis has been focused on minimizing the use of expensive metal (e.g. Pt), in the finally formed nanomaterials (e.g. Ag/Pt system as a possible catalyst for fuel cells). However, the complete removal of the less active sacrificial template is generally not achieved during galvanic replacement, and its residual presence may significantly impact on the electrocatalytic properties of the final material. Here, we investigate the hydrogen evolution reaction (HER) activity of Ag nanocubes replaced with different amounts of Pt, and demonstrate how the bimetallic composition significantly affects the activity of the alloyed nanomaterial.

A study of the galvanic replacement reaction at surfaces and the role of lateral charge propagation

The galvanic replacement of isolated nanostructures of copper and silver on conducting supports as well as continuous films of copper with gold is reported. The surface morphology was characterized by scanning electron microscopy and the replacement with gold was confirmed by EDX analysis. It was found that lateral charge propagation during the replacement reaction had a significant effect in all cases. For the isolated nanostructures the deposition of gold was observed not only at the sacrificial template but also at the surrounding unmodified areas of the conducting substrate. In the case of copper films the role of lateral charge propagation was also confirmed by connecting it to an ITO electrode through an external circuit upon which gold deposition was also observed to occur. Interestingly, by inhibiting the rate of charge propagation, through the introduction of a series resistor, the morphology of gold on the copper substrate could be changed from discrete surface decoration with cube like nanoparticles to a more porous rough surface.