The role of microstructure on high-temperature oxidation behavior of hafnium carbide

Microstructure development of the products formed upon oxidation of hafnium carbide (HfC_x, x = 0.65, 0.81, or 0.94) at 1300°C and 0.8 mbar oxygen pressure was investigated using Raman spectroscopy, X-ray diffraction, electron microscopy, and electron energy-loss spectroscopy. For all specimens a multilayered oxide scale was observed featuring an outermost porous hafnia layer and an interlayer adjacent to the parent carbide containing hafnia interspersed with carbon. The outermost hafnia features coarse pores presumably formed during initial stages of oxidation to allow rapidly evolving gaseous products to escape from the oxidation front. As the oxidation scale thickens, diffusional resistance results in slower oxidation rates and smaller quantities of gaseous products that are removed via networks of increasingly fine pores until the local oxygen partial pressure is sufficiently low to selectively oxidize the parent carbide. Electron microscopy studies suggest that the oxidation sequence at this stage begins with the transformation of parent carbide to an amorphous material having empirical formula HfO₂C_x that subsequently phase separates into hafnia and carbon domains. Hafnia polymorphs in the phase-separated region vary from cubic to monoclinic as grains coarsen from ca. 2–20 nm, respectively. Immediately adjacent to the phase-separated region is carbon-free mesoporous hafnia whose pore morphology is inherited from that of prior carbon domains. The average pore size and pore volume fraction observed in mesoporous hafnia are consistent with predictions from kinetic models that ascribe gaseous diffusion through a pore network as the rate determining step in oxidation behavior of hafnium carbide. These observations imply that high-temperature oxidation behavior of hafnium carbide under the employed test conditions is linked to microstructure development via phase separation and coarsening behaviors of an initially formed amorphous HfO₂C_x product.     

Competing Effects of Radio Frequency Fields on Carbon Nanotube/Resin Systems: Alignment versus Heating

This work shows that radio-frequency (RF) fields can simultaneously align carbon nanotubes (CNTs) dispersed in a resin and induce Joule heating to cure the resin. The timescales of alignment and curing using RF heating are numerically computed and compared at different field strengths in order to determine a temperature where alignment happens before the matrix crosslinks. Composites are experimentally fabricated at the desired target temperature and are optically analyzed and quantified; the CNT network is successfully aligned in the direction of the applied electric field. This methodology can be used to create composites where the local alignment can be varied across the sample. Composites fabricated using RF fields have higher electrical conductivity in the direction of the aligned CNTs than an oven-cured, randomly aligned sample. Also, RF-cured nanocomposites exhibit higher tensile strength and modulus in the direction of alignment compared to an oven-cured sample. Finally, it is further demonstrated how this methodology can be coupled with a direct ink writing additive manufacturing process to induce alignment in any desired direction, even orthogonal to the shear forces in the extrusion direction.     

Mesoporous Natural Fiber Welded Cellulose Containing Silver Nanoparticles as a Recyclable Heterogeneous Catalyst

Silver nanoparticles (AgNPs) are presented within mesoporous natural fiber welded (NFW) cellulose and demonstrated as robust catalysts to reduce 4-nitrophenol using sodium borohydride. Growing AgNPs this way enables their retention within a nonderivatized, mesoporous, all-cellulose NFW composite. At an AgNP loading of 1.0 wt%, no leaching is observed during rinsing with polar and nonpolar solvents or any of 12 catalyst cycles and the cloth is easily retrievable and reusable. Comparatively, a 1.0 wt% AgNP loading on non-NFW cotton thread loses ≈95% of the starting Ag under similar conditions. Only at higher loadings is a very slow leaching observed in the NFW composite (<10% Ag loss). With a turnover frequency of 0.9 h^–1 (as compared to 2.2 h^–1 for the non-NFW cotton thread), the catalytic activity suffers only minor impedance from the NFW structure while affording significant promise in future applications for leach-resistant nonderivatized cotton (e.g., TiO₂ or photonic nanomaterials). Finally, it is shown that combustion of AgNPs-NFW composites creates Ag residues distinct from materials produced via combustion of AgNPs on non-NFW cotton. While the residues produced comprise Ag and residual carbon, this method is viable for producing metal “sponges” from monometallic and bimetallic NPs on mesoporous cellulose.     

Use of surfactants and blends to remove DDT from contaminated soils

Removal of dichloro‐diphenyl‐trichloroethane (DDT) from soils using surfactant‐enhanced solubilisation was studied both in batch and continuous flow arrangements to determine if there were advantages to using a combination of non‐ionic (Tween and Brij) and anionic surfactants. It was observed that the presence of the anionic surfactant sodium dodecyl benzene sulphonate improved the DDT removal efficiency, but had a potentially negative effect on flow rates in column leaching experiments at concentrations over 0.1%. The potential for re‐use of the surfactant mixture was studied and demonstrated by removing DDT and its metabolites from the surfactant solution using activated carbon. © 2011 Canadian Society for Chemical Engineering     

The effect of scale and interfacial tension on liquid–liquid dispersion in in-line Silverson rotor–stator mixers

The effect of scale, processing conditions, interfacial tension and viscosity of the dispersed phase on power draw and drop size distributions in three in-line Silverson rotor–stator mixers was investigated with the aim to determine the most appropriate scaling up parameter. The largest mixer was a factory scale device, whilst the smallest was a laboratory scale mixer. All the mixers were geometrically similar and were fitted with double rotors and standard double emulsor stators. 1 wt.% silicone oils with viscosities of 9.4 mPa s and 339 mPa s in aqueous solutions of surfactant or ethanol were emulsified in single and multiple pass modes. The effect of rotor speed, flow rate, dispersed phase viscosity, interfacial tension and scale on drop size distributions was investigated.     

Transport properties of sulfonated poly (styrene‐isobutylene‐styrene) membranes with counter‐ion substitution

In this study, the transport properties of poly(styrene‐isobutylene‐styrene) (SIBS) were determined as a function of sulfonation level (0–94.9%) and counter‐ion substitution (Ba⁺², Ca⁺², Mg⁺², Mn⁺², Cu⁺², K⁺¹) for fuel cell applications. Increasing the sulfonation level improved the ion exchange capacity (IEC) of the membranes up a maximum (1.71 mequiv/g), suggesting a complex three‐dimensional network at high sulfonation levels. Results show that proton conductivity increases with IEC and is very sensitive to hydration levels. Methanol permeability, although also sensitive to IEC, shows a different behavior than proton conductivity, suggesting fundamental differences in their transport mechanism. The incorporation of counter‐ion substitution decreases both methanol and proton transport. Methanol permeability seems to be related to the size of the counter‐ion studied, while proton conductivity is more sensitive to water content, which is also reduced upon the incorporation of counter‐ions. To complement the studies, selectivity (i.e., proton conductivity/methanol permeability) of the studied membranes was determined and compared to Nafion® 117. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

The Synthesis of Ba‐ and Fe‐ Substituted CsAlSi2O6 Pollucites

Barium‐substituted CsAlSi₂O₆ pollucites, Cs_xBa_(1?x)/2AlSi₂O₆, and barium‐ and iron‐substituted pollucites, Cs_xBa_(1?x)/2Al_xFe_1?xSi₂O₆ and Cs_xBa_1?xAl_xFe_1?xSi₂O₆ were synthesized with 1 ≥ x≥ 0.7 using a hydrothermal synthesis procedure. Rietveld analysis of X‐ray diffraction data confirmed the substitution of Ba for Cs and Fe for Al, respectively. The crystallographic analysis also describes the effects of three different types of pollucite substitutions on the pollucite unit cell: Ba²⁺ for Cs¹⁺ cation results in little effect on cell dimensions, intermediate concentrations of Ba²⁺ and Fe³⁺ substitution result in net minor expansion due to Fe³⁺ addition, and large Ba and Fe substitutions result in overall framework contraction. Elemental analysis combined with microscopy further supports the phase purity of these new phases. These materials can be used to study the stability of CsAlSi₂O₆ as a durable ceramic waste form, which could accommodate with time Cs and its decay product, Ba. Furthermore, success in iron substitution for aluminum into the pollucite lattice predicts that redox charge compensation for Cs cation decay is possible.     

Chemical Analysis with High Spatial Resolution by Rutherford Backscattering and Raman Confocal Spectroscopies: Surface Hierarchically Structured Glasses

Copper and iron in glasses constitute classical aims of study because of the optical effects that they produce. Structured materials are also interesting due to the incorporated functionalities derived from their spatial organization. Here, CuO and Fe₂O₃ were incorporated into a standard glass, from which glass coatings with different thicknesses were studied. Whereas iron cations dissolved in the glassy matrix, copper cations saturated it and crystallized at the surface, forming a hierarchical microstructure. The surface microstructure consisted of crystallizations of Tenorite (CuO) forming interconnected walls. The walls surrounding areas of glassy matrix gave rise to a cells microstructure. Rutherford Backscattering Spectrometry provided the composition of the samples with high depth resolution, and Raman Confocal Microscopy determined the phases location and their distribution forming the microstructure. The joint information from both techniques allowed high chemical and spatial resolution of the main cations location for the hierarchical surface microstructure.