Thermal treatment on composite γ-zirconium phosphate-silica

The prepared amorphous γ-ZrP\SiO₂ composite had a complicated composition, since a part of γ-ZrP is converted to α-form during the exfoliation of it. The γ-ZrP\SiO₂ composite have specific surface area of 421 m²g^–1. The acidic P–OH groups of the lamellae species placed on the surface (it is ≈1.0 meq g^–1), do not destroy until the temperature of 1030 K. During the thermal treatment the total mass loss of 7.79% was found. This value corresponds to 0.42 mole of H₂O per molecule unit. The water loss process was found very slow, because of the placing of bilamellar species in the composite.     

Effects of Polymer Bridging and Electrostatics on the Rheological Behavior of Aqueous Colloidal Dispersions†

Effects of a low molecular weight physically adsorbed polyethylene oxide (PEO) and the range of the electrostatic repulsion on the rheological behavior of silica dispersions (as a model system) has been investigated. Particular attention is given to the evolution of the rheological behavior with increasing the polymer concentration in the system and also effectiveness of the polymer as a dispersant under extreme conditions (high ionic strength). Results indicate that at small separation distances and low polymer coverage, the polymer chains are long enough to adsorb on the surface of two particles simultaneously causing bridging flocculation in the system and hence increasing the viscosity and linear viscoelastic functions of the dispersion. A significant increase was observed in the viscosity of the dispersion at salt concentrations high enough to eliminate electrostatics between the particles. Under these conditions,the viscosity of the system increased significantly when PEO was added to the dispersion showing that at high electrolyte concentrations, a neutral polymer such as PEO is not able to stabilize the system.     

Evaluation of Polycation-Stabilized Lactate Oxidase in a Silica Sol–Gel as a Biosensor Platform

 Whereas glucose oxidase and related proteins are encapsulated readily in silica sol–gels, α-hydroxy enzymes such as lactate oxidase (LOx), are reported to be damaged by electrostatic interaction with these matrices. Based on a previous report, poly(ethyleneimine), PEI, was evaluated as a protecting compound under conditions suited to analytical measurements. With LOx and PEI co-encapsulated in a silica sol–gel, the enzyme retained 62% of its initial activity after 20 days. In the absence of PEI, activity was lost during the processing. Batch analytical measurements with enzyme-doped sol–gel yielded a linear response over the range 0.5–2.0 mM lactate and a detection limit of 0.03 mM lactate. Both simple incorporation of LOx in a silica sol–gel and an alternative protection method, blocking the ion-exchange sites on silica with La(III), failed. These negative results supported the hypothesis that the efficacy of PEI was related to its formation of a protective sheath around the enzyme. Author for correspondence. E-mail: coxja@muohio.edu Received July 29, 2002; accepted December 15, 2002 Published online May 19, 2003     

Gelation of poly(n-butylisocyanate) in benzene

Poly (n-butylisocyanate)-benzene solutions prepared by solubilization at 45°C, followed by aging at room temperature were found to be metastable for months, although, eventually, they separated into a birefringent polymer-rich phase and an isotropic solution. These metastable solutions, as well as isothermally phase-separated biphasic samples, flowed and exhibited dynamic moduli indicative of low polymer connectivity. By contrast samples prepared by a freeze-thaw cycle were uniformly and highly birefringent and showed network (gel) behavior at room temperature. The mechanism of gel formation is most likely the exclusion of the polymer from the benzene crystal during crystallization, forcing the polymer to align and exist at grain boundaries. Films formed from solutions have different moduli than those formed from gels, and are consistent with the proposed mechanism.     

Modeling of environmentally significant interfaces: Two case studies

When some parameters cannot be easily measured experimentally, mathematical models can often be used to deconvolute or interpret data collected on complex systems, such as those characteristic of many environmental problems. These models can help quantify the contributions of various physical or chemical phenomena that contribute to the overall behavior, thereby enabling the scientist to control and manipulate these phenomena, and thus to optimize the performance of the material or device. In the first case study presented here, a model is used to test the hypothesis that oxygen interactions with hydrogen on the catalyst particles of solid oxide fuel cell anodes can sometimes occur a finite distance away from the triple phase boundary (TPB), so that such reactions are not restricted to the TPB as normally assumed. The model may help explain a discrepancy between the observed structure of SOFCs and their performance. The second case study develops a simple physical model that allows engineers to design and control the sizes and shapes of mesopores in silica thin films. Such pore design can be useful for enhancing the selectivity and reactivity of environmental sensors and catalysts. This paper demonstrates the mutually beneficial interactions between experiment and modeling in the solution of a wide range of problems.     

Influence of Particle Morphology and Flow Conditions on the Dispersion Behavior of Fumed Silica in Silicone Polymers

The dispersion behavior of agglomerates of several grades of fumed silica in poly(dimethyl siloxane) liquids has been studied as a function of particle morphology and applied flow conditions. The effects of primary particle size and aggregate density and structure on cohesivity were probed through tensile and shear strength tests on particle compacts. These cohesivity tests indicated that the shear strength of particle compacts was two orders of magnitude higher than the tensile strength at the same overall packing density. Experiments carried out in both steady and time‐varying simple‐shear flows indicate that dispersion occurs through tensile failure. In the steady‐shear experiments,enhanced dispersion was obtained at higher levels of applied stress and, at comparable levels of applied stress, dispersion was found to proceed faster at higher shear rates. Experiments conducted in time‐varying flows further corroborated the results obtained in tensile cohesivity tests. Experiments in which the mean and maximum stresses in the time‐varying flows were matched to the stresses produced in steady shear flows highlight the influence of flow dynamics on dispersion behavior.     

Separation of Monovinyl and Divinyl Protochlorophyllides Using C30 Reverse Phase High Performance Liquid Chromatography Column: Analytical and Preparative Applications

A new, high performance liquid chromatography method has been developed for the separation of monovinyl- and divinyl-protochlorophyllides, using commercially available, C₃₀ reverse phase column and isocratic elution. This method can be used both for analytical applications and preparative scale purification of monovinyl- and divinyl-protochlorophyllides using the same column where submilimolar concentrations of the crude protochlorophyllide extract can be separated in one run. The purity of the obtained protochlorophyllides was demonstrated by spectroscopic methods, as well by the formation of aggregates in toluene.     

Preparation of silane-grafted pellets: silica bound reagents in a very convenient form

High surface area silica pellets are excellent supports for the preparation of silica supported reagents and solid-phase basal linkers through reaction with (RO)₃Si(CH₂)₃FG (FG=NH₂, NHMe, Cl, NHC(O)NH₂, OC(O)CMe(CH₂), NCO, NEt₂). High loadings (0.66-2.15 mmol g⁻¹) of grafted silane materials are realised at synthetically useful loadings per pellet (ca. 0.06 mmol). Preliminary trials show that trial linker chemistry and ligand synthesis can be carried out on these materials and that these reactions can be monitored by solid state ¹³C NMR studies on individual pellets.     

Nonlinear rheological behavior of silica filled solution‐polymerized styrene butadiene rubber

The reinforcement and nonlinear viscoelastic behavior have been investigated for silica (SiO₂) filled solution‐polymerized styrene butadiene rubber (SSBR). Experimental results reveal that the nonlinear viscoelastic behavior of the filled rubber is similar to that of unfilled SSBR, which is inconsistent with the general concept that this characteristic comes from the breakdown and reformation of the filler network. It is interesting that the curves of either dynamic storage modulus (G′) or loss tangent (tan δ) versus strain amplitude (γ) for the filled rubber can be superposed, respectively, on those for the unfilled one, suggesting that the primary mechanism for the Payne effect is mainly involved in the nature of the entanglement network in rubbery matrix. It is believed there exists a cooperation between the breakdown and reformation of the filler network and the molecular disentanglement, resulting in enhancing the Payne effect and improving the mechanical hysteresis at high strain amplitudes. Moreover, the vertical and the horizontal shift factors for constructing the master curves could be well understood on the basis of the reinforcement factor f(φ) and the strain amplification factor A(φ), respectively. The surface modification of SiO₂ causes a decrease in f(φ), which is ascribed to weakeness of the filler–filler interaction and improvement of the filler dispersion. However, the surface nature of SiO₂ hardly affects A(φ). © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 2594‐2602, 2007     

Thickness of a silica-tethered poly(ethylene oxide) layer measured by spin labeling

EPR spectroscopy of labeled poly(ethylene oxide) (PEO) grafted on silica has been used to characterize the conformation and local dynamics of the chains. Grafted molecules of MW 2000 with grafting ratios of 0.045, 0.057, 0.126, and 0.42 molecules/nm² were in contact with benzene. The mobility of the label was compared with that observed for solution of PEO from very diluted to highly concentrated and even bulk PEO. Thus, the concentration inside the grafted layer could be evaluated and also the thickness, which evolves rather linearly with the grafting ratio. © 1995 John Wiley & Sons, Inc.