In Situ X-Ray Radiography and Tomography Observations of the Solidification of Aqueous Alumina Particle Suspensions—Part I: Initial Instants

This paper investigates by in situ high-resolution X-ray radiography and tomography the behavior of colloidal suspensions of alumina partic les during directional solidification by freezing. The combination of these techniques provided both qualitative and quantitative information about the propagation kinetic of the solid/liquid interface, the particle redistribution between the crystals and a particle-enriched phase, and the three-dimensional organization of the ice crystals. In this first part of two companion papers, the precursor phenomena leading to directional crystallization during the first instants of solidification are studied. Mullins–Sekerka instabilities are not necessary to explain the dynamic evolution of the interface pattern. Particle redistribution during these first instants is dependent on the type of crystals growing into the suspension. The insights gained into the mechanisms of solidification of colloidal suspensions may be valuable for the materials processing routes derived for this type of directional solidification (freeze-casting), and of general interest for those interested in the interactions between solidification fronts and inert particles.     

Architectural Control of Freeze-Cast Ceramics Through Additives and Templating

The freezing of concentrated colloidal suspensions is a complex physical process involving a large number of parameters. These parameters provide unique tools to manipulate the architecture of freeze-cast materials at multiple length scales in a single processing step. However, we are still far from developing predictive models to describe the growth of ice crystals in concentrated particle slurries. In order to exert reliable control over the microstructural formation of freeze-cast materials, it is necessary to reach a deeper understanding of the basic relationships between the experimental conditions and the microstructure of the growing solid. In this work, we explore the role of several processing variables (e.g., composition of the suspension, freezing rate, and patterning of the freezing surface) that could affect the formulation strategies for the architectural manipulation of freeze-cast materials. We also demonstrate, using freeze-cast lamellar structures, that reducing the lamellar thickness by less than half increases the compressive strength by more than one order of magnitude.     

A critical approach to viscosity index

The viscosity index (VI) is a useful tool for lubricant users and refiners, since it is a measure of the effect of temperature changes on the viscosity of the oil. However, it was found that the viscosity index does not correlate with the flow activation energy E_a, which is the theoretically defined dependence of the viscosity on temperature. In this way, two oils may have the same flow activation energy but a viscosity index varying by up to 120. We therefore believe that the VI does not always give a proper representation of the effect of temperature on the kinematic viscosity.¹³C NMR spectroscopy was used to identify the molecules with a high VI. Twenty different oil samples produced from eight different vacuum gas oils with viscosity indices ranging from −104 to 146 were analyzed and key parameters identified for high VI molecules: long alkyl chains, methyl branching in the centre of the molecule, low content of aromatic compounds, no ethyl branching and no tertiary carbons.A correlation based on four selected peaks was developed, giving a very good prediction of the viscosity index.     

Influence of surface tension, osmotic pressure and pores morphology on the densification of ice-templated ceramics

We attempt here to clarify the influence of the nature of the solvent on the ice-templating process, based on literature experimental results of porosity and suspension concentration. In particular, we compare the relative influence of surface tension, osmotic pressure and the pore size and radius of curvature on the densification of the green bodies. Variations of the osmotic pressure when changing the solvent can yield significantly different behaviour during the freezing stage and therefore significantly affect the densification behaviour, an effect not apparent when using the Shanti model. In addition, and equally important, a modification of the macropores morphology is induced by the evolution of the solvent crystals morphology, and resulting in smaller and more intricate crystals and macropores which facilitates the densification. The radius of curvature is probably also an essential parameter controlling the densification of ice-templated ceramics.     

Concomitant use of liquid–liquid batch and continuous plug flow reactors for kinetic model discrimination. Application to the Rh/TPPTS catalysed reduction of the C–C double bond in dimethylitaconate

The biphasic catalytic reduction of the C–C double bond of dimethylitaconate with a water soluble rhodium/triphenylphosphinetrisulphonated sodium salt (TPPTS) complex is investigated. Kinetic studies in a well-mixed batch reactor provide kinetics parameters and an activation energy of 71 kJ mol⁻¹ but cannot discriminate between a first order or a complex kinetic model within the range of substrate concentration where the approximation of linear liquid/liquid partition is respected. Catalytic tests in the centrifugal partition chromatograph (CPC) reactor under steady-state operations in chemical regime and plug flow mode allow discriminating the kinetic models, the complex kinetic rate law being preferred.     

Synthesis and Microstructural Characterization of Substoichiometric Ti2Al(CxNy) Solid Solutions and Related Ti2AlCx and Ti2AlN End‐Members

Ti, TiC, Al and AlN powders were mixed to synthesize Ti₂Al(C_xN_y) (x + y < 1) solid solutions, Ti₂AlC_x (x < 1) and Ti₂AlN‐related end‐members by hot isostatic pressing at 1400°C/80 MPa for 4 h. For the pure carbides, it is demonstrated that single‐phased samples can only be obtained when about 15% of substoichiometry on the carbon site is applied. Such a result likely implies that Ti₂AlC_x can only exist in a narrow range of carbon composition. Ti₂AlN nitride can be synthesized with y = 1. Assuming that vacancy content varies linearly from 0 to 0.15 going from Ti₂AlN to Ti₂AlC_0.85 in the solid solutions, element concentrations have been calculated to synthesize different solid solutions. Thus, it is demonstrated that single‐phased and fully dense Ti₂Al(C_0.23N_0.71), Ti₂Al(C_0.45N_0.45), and Ti₂Al(C_0.66N_0.22) carbonitrides can be synthesized.