Correction for particle-wall interactions in the separation of colloids by flow field-flow fractionation

In the characterization of materials by field-flow fractionation (FFF), the experienced analyst understands the importance of incorporating additives in the carrier liquid that minimize or eliminate interactions between the analyte and accumulation wall, particularly in aqueous systems. However, as FFF is applied to more difficult samples, such as those with high surface energies, it is increasingly difficult to find additives that completely eliminate particle-wall interactions. Furthermore, the analyst may wish to use specific conditions that preserve the high surface energy of particles, to study their interaction with other materials through their behavior in the FFF channel. With this in mind, Williams and co-workers developed a model that quantifies the effect of particle-wall interactions in FFF using an empirically determined interaction parameter. In this work, the model is evaluated for the application of flow FFF in carrier liquids of low ionic strength, where particle-wall interactions are magnified. The retention of particles ranging in size from 64 to 1000 nm is measured using a wide range of field strengths and retention levels. The model is found to be generally valid over the entire range, except for minor discrepancies at lower levels of retention. Although retention levels are dramatically affected by particle-wall interactions, the point of steric inversion (500 nm), where the size-based elution order reverses, is not affected. When particle-wall interactions are not accounted for, they lead to a bias in particle sizes calculated from standard retention theory of up to 70%. The model can also be used to refine the measurement of channel thickness, which is important for the accurate conversion of retention parameters to particle sizes. In this work, for example, errors in channel thickness led to systematic errors on the order of 10% in particle diameter.     

Magnetocaloric effect of Pr2Fe17−x Mn x alloys

Polycrystalline Pr2Fe17-xMnx（x = 0, 1, and 2）alloys were studied by X-ray diffraction（XRD）, heat capacity, ac susceptibility, and isothermal magnetization measurements. All the alloys adopt the rhombohedral Th2Zn17-type structure. The Curie temperature increases from 283 K at x = 0 to 294 K at x = 1, and then decreases to 285 K at x = 2. The magnetic phase transition at the Curie temperature is a typical second-order paramagnetic–ferromagnetic transition. For an applied field change from0 to 5 T, the maximum-△SM for Pr2Fe17-xMnxalloys with x = 0, 1, and 2 are 5.66, 5.07, and 4.31 J·kg^-1·K^-1,respectively. The refrigerant capacity（RC） values range from 458 to 364 J·kg^-1, which is about 70 %–89 % that of Gd. The large, near room temperature △SM and RC values,chemical stability, and a high performance-to-cost ratio make Pr2Fe17-xMnxalloys be selectable materials for room temperature magnetic refrigeration applications.     

Comparison of laser-wavelength operation for drilling of via holes in AlGaN/GaN HEMTs on SiC substrates

By using a frequency-tripled Nd:YVO₄ laser source (355 nm) for drilling through-wafer via holes in SiC substrates, we can reduce the surface contamination and achieve better smoothness inside the via holes compared to use of the more common 1064-nm Nd:YVO₄ laser. The sheet and contact resistance of AlGaN/GaN HEMT layers grown on SiC substrates were similar after formation of vias by 355-nm laser drilling to those of the undrilled reference sample. By sharp contrast, 1064-nm laser drilling produces significant redeposition of ablated material around the via and degrades the electrical properties of the HEMT layers.     

Accurate molecular weight distribution of polymers using thermal field-flow fractionation with deconvolution to remove system dispersion

Thermal field-flow fractionation (ThFFF) is an elution process that separates polymeric materials by molecular weight. Elution profiles thus provide approximations to the molecular weight distributions of polymers. The accuracy of such approximate distributions is expected to be improved by accounting for the effect on the elution profile of band-broadening processes in the FFF system. Fortunately this intrinsic band broadening, referred to as system dispersion, is theoretically well-defined in ThFFF. In this article we present an algorithm that corrects ThFFF elution profiles by removing system dispersion. The program is applied to ThFFF fractograms of standard polymers having both narrow and broad molecular weight distributions. The increased accuracy obtained by accounting for system dispersion is demonstrated. For the narrow standard, deconvolution shows that the polydispersity (weight/number-average mol. wt.) is only 1.004. For the broad standard, NBS 706, the molecular weight distribution and parameters obtained agree well with previously published results. Application to a simulated fractogram resulting from mixing five narrow standards helps define the conditions under which accurate molecular weight information can be recovered.     

Cocoa polyphenols accelerate vitamin B12 degradation in heated chocolate milk

The rate of vitamin B₁₂ loss was 3X greater in heated, chocolate‐flavoured milk than in unflavoured milk. Studies of B₁₂ stability in the presence of cocoa powder components were performed to identify the reactive agents. Cocoa polyphenols with a strong capacity both for reduction and for peroxide generation accelerated B₁₂ destruction as much as 20‐fold vs. polyphenols without both capacities. Polyphenols with both capacities include the cocoa polyphenol (+)‐catechin and oligomers thereof, but also the structurally related polyphenols gallic acid, caffeic acid and (?)‐epigallocatechin gallate. The demonstrated physical affinity of cocoa powder for B₁₂ was a significant factor in the destructive process. B₁₂ may exhibit decreased stability in heated, neutral pH, polyphenol‐fortified foods.     

Compositional effects in the retention of colloids by thermal field-flow fractionation

The retention of polystyrene and silica colloids that have been chemically modified is measured in several aqueous carrier liquids. Retention levels are governed by particle size and composition but are also sensitive to subtle changes in the carrier. Size-based selectivities are higher in aqueous carriers compared to acetonitrile. In aqueous carriers, retention varies dramatically with the nature of the additive, and for a given additive, retention increases with ionic strength, regardless of modifications to the particle surface. The role played by electrostatic effects in retention is studied by varying the ionic strength of the carrier, estimating electrical double layers, determining particle-wall interaction parameters, and calculating the coefficients of mass diffusion and thermal diffusion. Although electrostatic phenomena can affect mass diffusion and particle-wall interactions in carriers of low ionic strength (<10(-3) M), such effects are not great enough to explain the dependence of retention on ionic strength. Therefore, thermal diffusion must be affected directly. Thermal diffusion is found to increase with pH, and at a given pH with the surface tension of the suspended particle. Finally, while the addition of the surfactant FL-70 generally decreases retention, greater retention levels can ultimately be achieved with FL-70 because larger temperature gradients can be used without particle adsorption to the accumulation wall.     

Wavefront sensor based on the Talbot effect with the precorrected holographic grating

A holographic wavefront sensor based on the Talbot effect is proposed. Optical wavefronts are measured by sampling the light amplitude distribution with a two-dimensional (2D) precorrected holographic grating. The factors that allow changing an angular measurement range and a spatial resolution of the sensor are discussed. A comparative analysis with the Shack-Hartmann sensor is illustrated with some experimental results.     

Investigation of the thermochemical transformations in the LiAlH4-LiNH2 system

The thermal transformations in the lithium alanate-amide system consisting of lithium aluminum hydride (LiAlH₄) and lithium amide (LiNH₂), mixed in a 1:1 M ratio, were investigated using the pressure-composition-temperature analysis, solid-state nuclear magnetic resonance, X-ray powder diffraction, and residual gas analysis. Below 250 °C, the alanate decomposes into Al, LiH and H₂, through the formation of Li₃AlH₆, whereas the amide remains largely intact. The release of gaseous hydrogen corresponds to approximately 5 wt%. Above 250 °C, additional ∼4 wt% of hydrogen is produced through solid-state reactions among LiNH₂, LiH and metallic Al, through the formation of intermetallic Li-Al binary alloy and an unidentified intermediate. The overall reaction of the thermochemical transformation of the LiAlH₄-LiNH₂ mixture results in the production of Li₃AlN₂, metallic Al, LiH and the release of 9 wt% of gaseous hydrogen. The reaction mechanism of the thermal decomposition is different from one identified earlier during mechanical treatment of the same system. Rehydrogenation of the thermally-decomposed products of LiAlH₄-LiNH₂ mixture using high hydrogen pressure (180 bar) and heating (275 °C) yields LiNH₂ and amorphous aluminum nitride (AlN).