The surface chemistry of silicon nitride powder in the presence of dissolved ions

Colloidal processing of silicon nitride (Si₃N₄) powders depends largely on the control of reactions at the solid-solution interface. The role of dissolved ions in the surface chemistry of Si₃N₄ powders has been investigated, and the implications of these results for the effects of impurities, contaminants and additives in processing are discussed. The interaction of ions at the solid-solution interface was characterized by particle electrokinetic behaviour determined from electroacoustic measurements in moderately concentrated suspensions. Ions were classified according to chemical similarity and surface specificity. Specific adsorption was inferred from the movement of the isoelectric point relative to the endemic native value. Most simple univalent electrolytes behaved indifferently towards the Si₃N₄ surface, with the exception of fluoride which specifically adsorbed and may have formed a strong complex with surface silicon sites. The alkaline-earth cations exhibited a similar weak specificity. In the presence of hydrolysable transition metal cations, powder surface chemistry was controlled by the adsorption of hydroxy metal complexes and by the solubility of a surface-precipitated metal hydroxide phase. Oxo anions, such as sulphate and carbonate, adsorbed specifically on the Si₃N₄ surface, but the interactions were weaker than previously observed on metal oxide surfaces.     

Automatic alerting does not speed late motoric processes in a reaction-time task

When an irrelevant 'accessory' stimulus is presented at about the same time as the imperative signal in a choice reaction time-task, the latency of the voluntary response is markedly reduced. The most prominent cognitive theories agree that this effect is attributable to a brief surge in arousal ('automatic alerting'), but they disagree over whether the facilitation is localized to a late, low-level motoric process or to an earlier stage, the process of orienting to and then perceptually categorizing the reaction stimulus. To test these alternative hypotheses, we used the onset of the lateralized readiness potential (a movement-related brain potential) as a temporal landmark to partition mean reaction time into two time segments. The first segment included the time required to perceive the visual stimulus and decide which hand to react with; the second included only motoric processes. Presentation of an irrelevant acoustic stimulus shortened the first interval but had no effect on the second. We therefore rejected the motoric hypothesis.     

Influence of Barium Dissolution on the Electrokinetic Properties of Colloidal BaTiO3 in an Aqueous Medium

Hysteresis in the electrokinetic behavior of colloidal hydrothermal BaTiO₃ occurs during sequential acid and base titrations. Ba dissolution during acid titration results in an oxide-rich surface. When the acid-treated BaTiO₃ is titrated back to pH 10, dissolved Ba is specifically adsorbed and/or precipitated onto the particle surface. The combined effects of dissolution and subsequent adsorption–precipitation results in titration hysteresis. Most of the labile Ba can be removed by multiple acid treatments, which result in a TiO₂-like surface layer composition. Barium dissolution increases with decreasing pH but levels off below pH 4 due to diffusion through the surface oxide layer as predicted previously. A phenomenological model is offered to explain the electrokinetic behavior as a function of pH. It is suggested that inherent BaCO₃ contamination is not the primary source of dissolved Ba from hydrothermal BaTiO₃ in acidic solution.     

Aqueous Processing of Sintered Reaction-Bonded Silicon Nitride: I, Dispersion Properties of Silicon Powder

An aqueous-based system (Si-Al₂O₃-Y₂O₃-Fe₂O₃) for processing sintered reaction-bonded silicon nitride (SRBSN) was investigated with an emphasis on chemical control of suspension component interactions. Chemical stability and dispersion properties of a commercial silicon powder were characterized using electroacoustic, adsorption isotherm, and rheological measurements. The interactions of silicon with nitriding agent, sintering aids, dispersants, and binder were considered. The effects of pH, electrolyte, aging, particle size, and solids loading were examined. The suspension properties of the silicon powder were influenced by the native oxide film and powder treatment history. The silicon-oxide composite particles exhibit dispersion behavior similar to silica, characterized by a negative surface potential above pH 2. A method to improve the dispersion and homogeneity of suspension components based on the use of quaternary amine dispersants is proposed.     

Influence of Solids Concentration on the Isoelectric Point of Aqueous Barium Titanate

We report on findings that the particle surface charge is influenced by solids concentration in aqueous suspensions of BaTiO₃. Three decades in solids concentration were analyzed by combining results from two different electrokinetic methods. Combined results demonstrate a systematic acidic shift in the isoelectric pH with decreasing solids concentration. The shift is attributed to the development of a Ba-depleted, TiO₂-rich surface layer. Using kinetic arguments, it is shown that the thickness of this layer will be proportional to the surface-to-volume ratio.     

Measurement of 100 nm and 60 nm Particle Standards by Differential Mobility Analysis

The peak particle size and expanded uncertainties (95 % confidence interval) for two new particle calibration standards are measured as 101.8 nm ± 1.1 nm and 60.39 nm ± 0.63 nm. The particle samples are polystyrene spheres suspended in filtered, deionized water at a mass fraction of about 0.5 %. The size distribution measurements of aerosolized particles are made using a differential mobility analyzer (DMA) system calibrated using SRM^® 1963 (100.7 nm polystyrene spheres). An electrospray aerosol generator was used for generating the 60 nm aerosol to almost eliminate the generation of multiply charged dimers and trimers and to minimize the effect of non-volatile contaminants increasing the particle size. The testing for the homogeneity of the samples and for the presence of multimers using dynamic light scattering is described. The use of the transfer function integral in the calibration of the DMA is shown to reduce the uncertainty in the measurement of the peak particle size compared to the approach based on the peak in the concentration vs. voltage distribution. A modified aerosol/sheath inlet, recirculating sheath flow, a high ratio of sheath flow to the aerosol flow, and accurate pressure, temperature, and voltage measurements have increased the resolution and accuracy of the measurements. A significant consideration in the uncertainty analysis was the correlation between the slip correction of the calibration particle and the measured particle. Including the correlation reduced the expanded uncertainty from approximately 1.8 % of the particle size to about 1.0 %. The effect of non-volatile contaminants in the polystyrene suspensions on the peak particle size and the uncertainty in the size is determined. The full size distributions for both the 60 nm and 100 nm spheres are tabulated and selected mean sizes including the number mean diameter and the dynamic light scattering mean diameter are computed. The use of these particles for calibrating DMAs and for making deposition standards to be used with surface scanning inspection systems is discussed.     

Colloidal Processing of Silicon Nitride with Poly(acrylic acid): I, Adsorption and Electrostatic Interactions

The role of poly(acrylic acid) (PAA) in the dispersion of silicon nitride suspensions was investigated experimentally. The effects of concentration, relative molecular mass, and suspension pH were evaluated. The ionization of PAA was characterized by potentiometric titration and indicated a pH-dependent conformational transition. The isoelectric point for silicon nitride decreased from pH 6.3 to pH 3 as the PAA concentration increased, roughly independent of relative molecular mass. A broadening of the stability region for silicon nitride was attributed to this effect. Redispersion in alkaline media, subsequent to destabilization by surface-charge neutralization, improved following preadsorption of PAA in acidic media. This effect was attributed to formation of a protective polymer adlayer on the surface, which prevented primary minimum aggregation; an electrosteric contribution also may be present. The influence of free polymer on the suspension properties also is discussed.     

CO2 laser debridement of sulphur mustard (bis-2-chloroethyl sulphide) induced cutaneous lesions accelerates production of a normal epidermis with elimination of cytological atypia

Sulphur mustard (bis-2-chloroethyl sulphide; HD) exposure acutely produces lesions that vary from mild erythema, to blister formation, to necrosis. When blisters occur, with or without necrosis, healing of the lesions is delayed. Weanling pigs exposed to a mild erythema-producing dose of HD and to a moderate erythema-producing dose that consistently gave microblister formation were treated with CO2 laser (Tru-Pulse) debridement at 6, 24 or 48 h after exposure. The histopathological features observed at 14 days after exposure in control skin and skin exposed to both HD doses were compared with the features observed in CO2 laser-debrided skin in non-exposed and HD-exposed skin sites. The overlying epidermis in the non-laser treated lesions was thin, with cytological atypia and squamoid changes within the basal cell layer, as well as scattered apoptotic/necrotic keratinocytes. An increased inflammatory infiltrate and necrobiotic changes in the dermis were seen at the higher HD dose. All laser-treated lesions appeared identical, with a thick, differentiated epidermis and a well-formed basal cell layer. There was minimal inflammatory infiltrate. In the papillary dermis there were increased stromal cells. Laser debridement of mild clinical lesions induced by HD produced a more functional epidermis by 14 days as well as clearing the epidermis of damaged keratinocytes.     

Tumor necrosis factor interaction with gold nanoparticles

We report on a systematic investigation of molecular conjugation of tumor necrosis factor-α (TNF) protein onto gold nanoparticles (AuNPs) and the subsequent binding behavior to its antibody (anti-TNF). We employ a combination of physical and spectroscopic characterization methods, including electrospray-differential mobility analysis, dynamic light scattering, polyacrylamide gel electrophoresis, attenuated total reflectance-Fourier transform infrared spectroscopy, fluorescence assay, and enzyme-linked immunosorbent assay. The native TNF used in this study exists in the active homotrimer configuration prior to conjugation. After binding to AuNPs, the maximum surface density of TNF is (0.09 ± 0.02) nm(-2) with a binding constant of 3 × 10(6) (mol L(-1))(-1). Dodecyl sulfate ions induce desorption of monomeric TNF from the AuNP surface, indicating a relatively weak intermolecular binding within the AuNP-bound TNF trimers. Anti-TNF binds to both TNF-conjugated and citrate-stabilized AuNPs, showing that non-specific binding is significant. Based on the number of anti-TNF molecules adsorbed, a substantially higher binding affinity was observed for the TNF-conjugated surface. The inclusion of thiolated polyethylene glycol (SH-PEG) on the AuNPs inhibits the binding of anti-TNF, and the amount of inhibition is related to the number ratio of surface bound SH-PEG to TNF and the way in which the ligands are introduced. This study highlights the challenges in quantitatively characterizing complex hybrid nanoscale conjugates, and provides insight on TNF-AuNP formation and activity.     

Electrophysiological evidence for temporal overlap among contingent mental processes.

A series of studies assessed perceptual-motor transmission of stimulus information by measuring lateralization of movement-related brain potentials in a choice reaction task with no-go trials. When stimuli varied in shape and size, lateralized potentials on no-go trials suggested that easily recognized shape information was used to initiate motor preparation and that this preparation was aborted when size analysis signified that the response should be withheld. This indicates that movement preparation can begin once partial perceptual information about a stimulus becomes available, contrary to an assumption of fully discrete models of information processing. By contrast, when stimuli varied only in size, no evidence for preliminary response preparation was obtained, contrary to an assumption of fully continuous models but consistent with asynchronous discrete coding models (J. Miller, 1982, 1988). (PsycINFO Database Record (c) 2010 APA, all rights reserved)