The Use of Lewis Acids During Rapid Steam Hydrolysis

Mixed hardwood chips were treated with various concentrations of aluminum chloride hexahydrate, aluminum sulfate hydrate, and ferric chloride and were subjected to rapid steam hydrolysis pretreatment (RASH). The three levels included 0.01, 0.03, and 0.05 moles of catalyst per 1000 grams of wood. Rapid steam hydrolysis (RASH) was done from 180° to 260°C at 20°C intervals for one minute. The Lewis acid catalyst affected the overall recovery yield of solids, the recovery values of the individual components, the enzymatic rates, and the methanol and water solubility. Overall recovery of pretreated solids generally decreased with the increase in levels of the catalyst. The one exception was AlCl₃ ·6H₂O where the minimum recovery levels were reached at 0.03 moles per 1000 grams of wood and increased at the higher level of catalyst. Cellulose degradation occurred in the temperature range of 250° to 260°C for the control and at the two lower concentrations of the catalyst. At the higher levels of catalyst, appreciable amounts of cellulose degradation occurred at lower temperatures. Hemicellulose solubilization and degradation were extremely sensitive to the RASH temperature and to the levels of catalyst. Almost all hemicellulose was lost at high temperatures or at high levels of catalyst. Losses of lignin appeared to be affected mainly by the RASH temperature and not by the changes in the levels of catalyst.

In contrast, both the temperature and the level of catalyst strongly affected the rates of enzymatic hydrolysis. Generally, the intermediate level of catalyst seemed to give the highest rates of enzymatic hydrolysis at the lowest temperature. Methanol and water solubles increased in the presence of the catalyst and reached a maximum at levels of 0.03 moles between 230° to 250°C.     

Combined Model Calibration and Spatial Aggregation

A methodology is proposed for estimating a combined transportation model that accommodates spatial aggregation. It employs maximum likelihood estimation using a joint probability function that includes destination and mode choice simultaneously. The main contribution of the paper is the incorporation of a spatial aggregation strategy to validate the method when the survey data are insufficient. By aggregating small zones into larger districts, estimation of the trip distribution parameters can be achieved with limited data, while mode choice continues to be estimated using disaggregated data. Our results demonstrate that including trip distribution in the travel decision induces variations in the utility function parameter estimators obtained for the different travel modes when only mode choice is estimated. The methodology thus corrects omission bias.     

Manipulating microstructure and mechanical properties of CuO doped 3Y-TZP nano-ceramics using spark-plasma sintering

Nano-powder composites of 3Y-TZP doped with 8 mol% CuO were processed by spark-plasma sintering (SPS). A 96% dense composite ceramic with an average grain size of 70 nm was obtained by applying the SPS process at 1100 °C and 100 MPa for 1 min. In contrast to normal, pressureless, sintering during SPS reactions between CuO and 3Y-TZP were suppressed, the CuO phase was reduced to metallic Cu, while the 3Y-TZP phase remained almost purely tetragonal. Annealing after SPS results in grain growth and tetragonal to monoclinic zirconia phase transformation. The grain size and monoclinic zirconia phase content are strongly dependent on the annealing temperature. By combining the processing techniques studied in this work, including traditional pressureless sintering, properties of the composite ceramic can be tuned via manipulation of microstructure. Tuning the mechanical properties of dense 8 mol% CuO doped 3Y-TZP composite ceramic by utilising different processing techniques is given as an example.     

Digitally Controlled Potentiostat for Electrochemical Studies

ABSTRACT

A potentiostat employing digital selection of sweep range, sweep rate, and cell current measurement time has been built for use in staircase voltammetry, square wave polarography and voltammetry, and tast polarography. The use of these techniques enables background current reduction and therefore provides high sensitivity. The method of cell potential generation and control allows very high measurement precision. The instrument can be operated either manually or under complete computer control.     

Autoranging in High Speed Data Acquisition Systems

ABSTRAC

This paper is a presentation of various types of autoranging amplifiers and methods of incorporating them into fast digital data acquisition systems. The advantages and drawbacks of each type of autoranging method are examined. An example of fast autoranging using rapid scan square wave polarography is presented in which trace amounts of materials are detected in the presence of large amounts of other electroactive species.     

A THERMOMECHANICAL MODEL OF SOLIDIFICATION ON A MOLD MOVING WITH CONSTANT VELOCITY

A thermomechanical model of pure metal solidification on a moving mold plate is considered. The goal of the model is to obtain a formula for the contact pressure at the shell/mold interface as the mold moves into the molten liquid. From the contact pressure it is possible to infer the effects of the mold velocity and the mold microgeometry on the time and location of gap nucleation which results from irregular distortion of the shell as it grows from the melt. The mold, which moves at a constant velocity into the molten liquid, has a sinusoidal surface with a low aspect ratio: this means that its wavelength greatly exceeds its amplitude. The mold is of infinite area and is assumed to be perfectly conducting and thermomechanically rigid. We therefore neglect the complexities associated with the physics of edge constraints and/or free boundaries of the solidifying shell and the interacting distortions between deformable mold and shell materials along their interface. The ratio of the velocity of the solid/liquid interface to the mold velocity is identified as another dimensionless parameter in the analysis. In order to arrive at an analytical solution for the contact pressure along the shell/mold interface, we assume that this parameter is small. This makes the velocity ratio a convenient perturbation parameter for the analysis of thermomechanical distortion of the thin shell material as it grows from the melt. This necessarily limits the analysis to situations where the mold moves at faster rather than slower speeds. It is assumed that there is zero tangential shear stress between the fluid and the solidifying shell. As the molten liquid flows over the mold, it perfectly wets the surface. This precludes wetting effects due to surface tension. A hypoelastic constitutive law, which is a rate formulation of thermoelasticity, is assumed to govern deformation of the shell as it grows from the molten liquid. Latent heat liberated at the freezing front is extracted across a constant contact resistance at the shell/mold interface. Peculiar fluid motion at the tip is neglected. A solution for the contact pressure that is valid near the liquid surface (i.e., the meniscus) is derived from the main theoretical developments. Beyond the time of gap nucleation at the shell/mold interface, the model is no longer valid since it cannot account for gross distortion of the shell (i.e., distortions that greatly exceed the spatial perturbations considered in the model).     

Analytical Method for Forming Limit Diagram Prediction with Application to a Magnesium ZEK100-O Alloy

A significant barrier to broader implementation of magnesium alloys is their poor room temperature formability, a consequence of the anisotropic response of the Mg hexagonal closed-packed (hcp) crystal structure. Additions of rare earth (RE) elements, such as in the ZEK100 alloys, weaken the texture and improve formability. Room temperature forming limit analyses of RE-containing Mg alloys, particularly Mg ZEK100, have not been explored to any significant extent in the literature. In this paper, strain-based forming limit diagrams (FLDs) are derived for an Mg ZEK100-O alloy (Zn1.34Zr0.23Nd0.182, wt.%) using an analytical method that combines the vertex theory of Storen and Rice (J Mech Phys Solids, 23:421-441, 1979), the anisotropic yield criterion of Barlat and Lian (Int J Plast, 5:51-66, 1989), and a hardening law. The method does not rely on assumptions about pre-existing defects, is broadly applicable to sheet alloys exhibiting in-plane anisotropy requiring a higher-order yield criterion, and requires only minimal experimental inputs. Results from the analytical method are compared with experimentally derived FLDs based upon the well-known Nakajima test and tensile deformation, and with predictions from an existing analytical method for FLDs. Close agreement between the experimentally derived FLDs and the present theoretical method was obtained. Sheet materials where the theoretical method does not apply are also discussed.