Poly(Styrene‐Divinylbenzene) Based Media for Liquid Chromatography

The latest developments and in particular important synthetic aspects for the preparation of modern poly(styrene‐divinylbenzene) (PS‐DVB) based liquid chromatography (LC) supports are reviewed. In this context, the chemistry of particular porous and nonporous, functionalized, monolithic, coated silica and more specialized mixed organic PS‐DVB media is covered. Special consideration is given to modern approaches such as micro‐(μ)‐HPLC and coating techniques and their most important applications. Synthetic particularities relevant to the corresponding applications are outlined.     

Novel one-step route for synthesizing sub-micrometer PSt hollow spheres via redox interfacial-initiated method in inversed emulsion

Interfacial-initiated polymerization of styrene (St) was carried out in inversed emulsion with cumene hydroperoxide (CHPO) and ferrous sulfate (FeSO₄)/disodium ethylenediaminetetraacetate (NaEDTA)/sodium formaldehyde sulfoxylate (SFS) as the redox initiation system. The water-soluble Fe²⁺-NaEDTA-SFS acted as the reducing component and the oil-soluble CHPO as the oxidant component of the redox initiation system. Therefore, the primary radicals were produced mainly at the oil/water interface to initiate the polymerization of St. Thus, sub-micrometer hollow polystyrene (PSt) spheres were obtained by one-stage polymerization, which was supported by the techniques of transmission electron microscopy (TEM) and field emission scanning electron microscopy (FESEM).     

Material removal and surface damage in EDM of Ti3SiC2 ceramic

Material removal and surface damage of Ti₃SiC₂ ceramic during electrical discharge machining (EDM) were investigated. Melting and decomposition were found to be the main material removal mechanisms during the machining process. Material removal rate was enhanced acceleratively with increasing discharge current, i_e, working voltage, u_i, but increased deceleratively with pulse duration, t_e. Microcracks in the surface and loose grains in the subsurface resulted from thermal shock were confirmed, and the surface damage in Ti₃SiC₂ ceramic led to a degradation of both strength and reliability.     

Surface Preparation of Aluminum Nitride for Metallization: Effect of Temperature on Surface Reactivity

The current aqueous cleaning step in the surface preparation of aluminum nitride (AlN) prior to metallization causes performance and reliability issues for the substrates used for microelectronic packaging due to surface reactions. These issues limit the use of AlN and its replacing of BeO, an environmentally hazardous material currently used. The aim of this investigation was to determine the effects of different solutions on the surface of AlN substrates under varying conditions at times up to 2419.2 ks (28 days). Concentration of the solutions, temperature, and immersion time were varied for the AlN samples in the solutions. Both elevated temperatures (50°C and 90°C) and low temperatures (5°C) were investigated.

Four general types of behavior were observed: minor changes in average surface roughness and microstructure, linear change in average surface roughness and pitted grains, nonlinear change in average surface roughness and product formation on AlN surface, and miscellaneous change in average surface roughness with surface product formation.

The surface roughening kinetics were very complex due to changes in both the reaction product morphology and reaction mechanism with temperature, solvent, and pH for a specific solvent. Minor changes in average surface roughness and microstructure were observed for HCl pH = 5, H₂ SO₄ pH = 5, NaOH pH = 8, NaOH pH = 10, NaOH pH = 12, deionized water and Alfred tap water at 5°C, HCl pH = 3 and oleic acid at 50°C and citric acid and oleic acid at 90°C. Linear changes in average surface roughness and pitted grains were observed for HCl pH = 2 and H₂SO₄ pH = 3 at 50°C and HCl pH = 2, H₂SO₄ pH = 3, and deionized water at 90°C. Non-linear change in average surface roughness and product formation on AlN surface was observed for HCl pH = 5, NaOH pH = 8 and Alfred tap water at 50°C and HCl pH = 5 and H₂SO₄ pH = 2 at 90°C. Miscellaneous changes in average surface roughness with surface product formation were observed for H₂SO₄ pH = 2, H₂SO₄ pH = 5, NaOH pH = 10, NaOH pH = 12, citric acid, Micro-90 and deionized water at 50°C and HCl pH = 3, H₂SO₄ pH = 5, NaOH pH = 8, NaOH pH = 10, NaOH pH = 12, Micro-90 and Alfred tap water at 90°C.     

Preparation of a crack-free rough titania coating on stainless steel mesh by electrophoretic deposition

TiO₂ (anatase) coating was prepared on stainless mesh by electrophoretic (EPD) process utilizing an isopropyl alcohol (IPA)-based suspension with submicron TiO₂ powder. When the deposition time was 30 s, a smooth thin coating was obtained. It remained crack-free even after sintering. Coating surface morphology was roughened by UV pre-illumination of the suspension. Photocatalytic decomposition of IPA to acetone and resultant electrochemical reaction at cathode during EPD provides heterogeneous deposition.     

Interfacial electron density profile in Nb/Si bilayer films: an X-ray reflectivity study

This article describes a systematic study of the nature of interfaces involved in a Nb layer deposited on Si (Nb-on-Si) and Si layer deposited on Nb (Si-on-Nb) bilayer films by using a UHV electron beam evaporation technique, having individual layer thickness of 35 and 100 Å each. By using Grazing angle X-ray reflectivity and adopting a proper modelling technique the electron density profile (EDP) as a function of depth has been determined in the samples. EDP determined in as-deposited 35 Å Nb and 35 Å Si bilayer films show that the width of Si-on-Nb and Nb-on-Si interfaces are 20 Å and 40 Å, respectively. The difference observed in the width of two interfaces is attributed to the different growth morphology of 35 Å Nb and 35 Å Si single-layer films as revealed by atomic force microscopy (AFM) investigations. EDP determined from measured XRR data for 100 Å Nb and 100 Å Si deposited bilayer film shows that the width of Si-on-Nb interface is 10 Å. This observed width is smaller than the similar interface in the case of samples having an individual layer thickness of 35 Å. The corresponding interface width of Nb-on-Si is found to be 45 Å and marginally more than the similar interface in the case of the 35 Å Nb/35 Å Si bilayer samples. AFM studies carried out on 100 Å Nb and Si layers deposited separately on float glass substrate indicate similar gross as well as subtle morphological features and cannot be attributed to the observed asymmetry in this case. The observed asymmetry in EDP of two interfaces in this case is due to the enhanced diffusion of Si into the formed metal layer relative to the diffusion into the already deposited metal layer.     

The effect of noble gas bombarding on nitrogen diffusion in steel

The low energy (∼50–350 eV) noble gases ion bombardment of the steel surface shows that the pre-treatments increase nitrogen diffusion by modifying the outermost structure of the material. The surface microstructure and morphology of the studied samples were characterized by Scanning Electron Microscopy (SEM) and Atomic Force Microscopy (AFM). The crystalline and chemical structures in the outermost layers of the surface were analyzed by grazing angle X-ray diffraction (GAXRD) and photoemission electron spectroscopy (XPS). Temperature effusion studies of the implanted ions are used to elucidate the noble gases site localization in the network. The local compressive stress induced by the nearby iron atoms on the core level electron wave functions of the trapped noble gases are studied by photoemission electron spectroscopy (XPS) and interpreted considering a simple mechanical model. Nano-hardness measurements show the dependence of the material elastic constant on the energy of the implanted noble gases. Although the ion implantation range is about few nanometers, the atomic attrition effect is larger enough to modify the material structure in the range of micrometers. Two material stress zones were detected where the outermost layers shows compressive stress and the underneath layers shows tensile stress. The implanted noble gases can be easily removed by heating. A diffusion model for polycrystalline-phase systems is used in order to discuss the influence of the atomic attrition on the N diffusion coefficient. The concomitant effect of grain refining, stress, and surface texture on the enhancing nitrogen diffusion effect is discussed.     

Distinct dispersion stability of various TiO2 nanopowders using ammonium polyacrylate as dispersant

The dispersion stabilities of three titania (TiO₂) nanopowders with different particle sizes and surface chemistries in aqueous suspensions containing a common water-based dispersant, ammonium polyacrylate (PAA-NH₄), have been investigated and compared. According to adsorption isotherm and Fourier transform infrared spectroscopy analyses, the adsorption conformations of PAA-NH₄ are distinct for the different TiO₂ nanopowders. In addition, PAA-NH₄ exhibited the greatest adsorption affinity to the larger, hydrophilic TiO₂ nanopowder and the least affinity to smaller, hydrophobic nanopowder. From sedimentation and rheological results, the dispersion stability of the larger, hydrophilic TiO₂ nanopowder was demonstrated to be the greatest. Based on thermodynamic and kinetic calculations for the stabilization energies, the larger, hydrophilic TiO₂ nanopowder was also shown to be the best-stabilized powder, although it settles faster than the smaller, hydrophilic TiO₂ nanopowder; this is due to the greater affection of sedimentation flux on the larger nanopowder. In contrast, the hydrophobic TiO₂ nanopowder formed a gel-like structure in the aqueous suspension when the solid content was greater than 10 wt%, which is attributed to polymer bridging between PAA-NH₄-adsorbed TiO₂ nanoparticles.     

Pure and Ni2O3-decorated CeO2 nanoparticles applied as CO gas sensor: Experimental and theoretical insights

In the present work, the structural, morphological and electrical properties of CeO₂ nanoparticles with spherical and rod-like morphologies and rods decorated with Ni₂O₃ were investigated. Morphological, structural and electronic analyses showed a relationship between the shape/size of particles and the respective surface types, number of carriers, density of vacancies and local structural atomic order, in addition to an influence on the electrical properties of the materials. Electrical analyses revealed that the rod-like morphology has a better CO sensor response than the spherical one. In order to complement and rationalize the experimental findings, simulations at the density functional theory (DFT) were carried out to investigate the two possible mechanisms (Langmuir?Hinshelwood and Mars-Van Krevelen) acting on the CO adsorption process and elucidate the behavior of the sensor in heterojunction-type samples.     

Porous ceramics with tailored pore size and morphology as substrates for coral larval settlement

The growing demand for stony corals as ornamental aquarium animals requires defined aquacultural breeding strategies. For the sexual propagation of corals, material substrates are needed, that attract larvae and support their settlement and development. In this study, five types of highly porous ceramic materials were developed following the example of coral skeleton. The applicability of these settlement substrates was tested using larvae of the stony coral Pocillopora damicornis. Partial sintering of pressed clay pellets, freeze casting of clay and alumina-mullite based slurries and direct foaming of high alkane phase emulsified suspensions (HAPES) using alumina were employed. By the addition of mm-sized spherical polystyrene beads as sacrificial templates during freeze casting (alumina-mullite), superficial pores in the size of the larvae were created. The inorganic substrates featured open porosities between 35% (pressed clay) and 83% (foamed alumina), pore sizes ranging from nm to mm-scale and pore morphologies dominated by interparticle porosity (pressed), lamellar pores (freeze casting) and cellular pore types (direct foaming). The ceramic substrates were incubated in artificial sea water for 3 months to induce necessary biofilm formation and algae growth. Afterwards, individual substrates were exposed to 5 coral larvae, and their settlement behavior was monitored over 14 days. At the end of this period, all ceramic materials were successfully accepted as settlement substrates, with a mean settlement rate of 46.2%, and no significant differences between the substrate types. On samples with large surface superficial pores, a significantly reduced survival of settled larvae (79%) compared to the other porous materials (93–98%) was determined, suggesting a non-ideal surface topography. While alumina foam samples (HAPES) exhibit the most promising results in terms of settlement and survival of larvae, clay-based substrates provide a more economic solution for the sexual propagation of corals in aquaculture.