Adaptive Linear Dynamic Matrix Control applied to an integrating process

Dynamic Matrix Control (DMC) has proven to be a powerful tool for optimal regulation of chemical processes under constrained conditions. It is based on a linear convolution model derived from step-response measurements. A model predictive control algorithm optimises closed-loop performance for a nominal operating point. However, as the process moves away from this point, control usually becomes sub-optimal due to process non-linearity. As seen in this work, the DMC algorithm can be made adaptive, to establish a new local model, by recursive estimation of the local step response parameters from normal plant variations. However, when used for control of plants containing integrating process units, steady-state offsets occur for sustained changes. Thus, a novel Adaptive Linear Dynamic Matrix Control (ALDMC) algorithm has been developed and used to control a 2-input/2-output system with an integrating behaviour. Comparisons of model control and plant control with and without these features demonstrated the importance of integral compensation for integrating processes, and model adaptation in the case of plant/model mismatch. Some cross-compensation of integration by the adaptive feature was also noted. An holistic technique is demonstrated which simultaneously recognises residual integration disturbances and matrix parameter variations, whereas previous techniques which recognise only one of these will fail in the presence of the other.     

Mechanical Activation of Tetracalcium Phosphate

It was found that prolonged high-energy ball-milling of Hilgenstokite (tetracalcium phosphate, TTCP) resulted in a decrease in both particle and crystallite size, leading to a mechanical activation of the compound. This mechanically activated material demonstrated a high reactivity such that, in contrast to highly crystalline TTCP, a setting reaction with water to nanocrystalline hydroxyapatite (HA) and Ca(OH)₂ could be achieved at 37°C. However, crystalline TTCP is practically unreactive at physiologic temperatures because of the formation of a thin HA layer on the particle surface preventing further reaction.     

New inhibitors of the Tat-TAR RNA interaction found with a "fuzzy" pharmacophore model

TAR RNA is a potential target for AIDS therapy. Ligand-based virtual screening was performed to retrieve novel scaffolds for RNA-binding molecules capable of inhibiting the Tat-TAR interaction, which is essential for HIV replication. We used a "fuzzy" pharmacophore approach (SQUID) and an alignment-free pharmacophore method (CATS3D) to carry out virtual screening of a vendor database of small molecules and to perform "scaffold-hopping". A small subset of 19 candidate molecules were experimentally tested for TAR RNA binding in a fluorescence resonance energy transfer (FRET) assay. Both methods retrieved molecules that exhibited activities comparable to those of the reference molecules acetylpromazine and chlorpromazine, with the best molecule showing ten times better binding behavior (IC50 = 46 microM). The hits had molecular scaffolds different from those of the reference molecules.     

Transfer efficiency for airless painting systems

Spray transfer efficiency (TE) is defined as the mass fraction of sprayed paint which is deposited on the intended target, the remainder of the sprayed paint becomes undesirable overspray. The relationship between TE and gun supply pressure (or paint mass flow rate), gun-to-target distance, gun traverse speed, the angle of the spray gun relative to the target (gun-to-target angle), plus spray cone angle is reported herein for a typical fan spray system. Experimental results indicate that spray momentum rate (SMR) and droplet size dictate the TE for the various combinations of parameters considered here. The key finding is that TE correlates with SMR and spray mean drop size (Sauter mean diameter, or D₃₂) via an expression of the form TE=a+b SMR − c (SMR)²+d D₃₂, where a, b, c, and d are coefficients, determined by fitting the experimental data, and SMR is estimated via SMR=m²/ρA, where the paint mass flow rate m, the paint density is ρ, and the gun exit orifice effective tip cross sectional area is A. This expression accounts for physical phenomena that govern sprayed droplet deposition characteristics, such as entrainment, bounce-back, and drop size. Experimental results also show that, for the range of parameters studied, gun traverse speed has no effect on TE, but increasing the angle of the spray gun relative to the target (gun-to-target angle), increasing the spray cone angle, or increasing the gun-to-target distance will decrease TE.     

Catalytic conversion of methane to benzene over Mo/ZSM-5

Dehydroaromatization of methane to benzene occurs over a 2 wt% Mo/ZSM-5 catalyst at 700C under non-oxidizing conditions. Following an initial induction period, during which CH₄ reactant reduces the original Mo⁶⁺ ions in the zeolite to Mo₂C and deposition of coke occurs, a benzene selectivity of 70% at a CH₄ conversion of 8–10% could be sustained for more than 16 h. X-ray photoelectron spectroscopy and X-ray powder diffraction measurements indicate that the reduced Mo is highly dispersed in the channels of the zeolite. Initial activation of CH₄ reactant occurs on Mo₂C sites, leading to the formation of C₂H₄ as the primary product. The latter then undergoes subsequent oligomerization reactions on acidic sites of the zeolite to form aromatic products.     

Electrochemical cell current requirements for toxic organic waste destruction in Ce(IV)-mediated electrochemical oxidation process

The electrochemical cell for cerium oxidation and reactor for organic destruction are the most important operation units for the successful working mediated electrochemical oxidation (MEO) process. In this study, electrochemical cells with DSA electrodes of two types, single stack and double stack connected in series, were used. The performances towards the electrochemical generation of Ce(IV) in nitric acid media at 80 °C were studied. The current-voltage curves and cerium electrolysis kinetics showed the dependence on number of cell stacks needed to be connected in series for the destruction of a given quantity of organic pollutant. The presence of an optimum region for Ce(III) oxidation with a contribution of oxygen evolution, especially at low Ce(III) concentration (high conversion ratios), was found. The cells were applied for the Ce(IV) regeneration during the organic destruction. The cell and reactor processes were fitted in a simple model proposed and used to calculate the current needed in terms of Ce(III) oxidation rate and the number of cell stacks required for maintaining Ce(IV)/Ce(III) ratio at the same level during the organic destruction. This consideration was based on the kinetic model previously developed by us for the organic destruction in the MEO process.     

Controlled coagulation of emulsion polymers

Coagulation of latex particles is most often carried out in the diffusion limited aggregation (DLA) regime where the time for coagulation to take place is on the millisecond timescale. This process produces aggregates of low density, irregular shape, and a broad particle size distributions. When the coagulation is carried out in the reaction limited aggregation (RLA) regime, a coagulation time of about 1–120 sec, the system can be controlled by mixing to yield dense, spheroidal aggregates with a very narrow particle size distribution. The important variables in the RLA process for butyl acrylate/methyl methacrylate (BA/MMA) latexes were found to be mixing intensity, latex copolymer composition, and coagulation temperature. Dried aggregates formed in the RLA process were found to have excellent powder flow properties and low dustiness.     

Fabrication and characterization of planar and channel polymer waveguides. III. Compositional distribution and solute loss in polymer thin films

For many microelectronic and optoelectronic applications, polymer thin films require the addition of small molecules. However, the thin‐film geometry and associated processing techniques will influence the final morphology and compositional distribution of the constituents. It is therefore important that these be examined directly rather than inferred from bulk measurements. As an example system, the concentration and distribution of Disperse Red 1 (DR1) molecules in poly(methyl methacrylate) thin films were examined. Ultraviolet visibility spectroscopy and dynamic secondary ion mass spectrometry indicate that the composition of the molecules decreased dramatically with thermal treatment of the film. The sublimation of the chromophore was observed to occur at temperatures well below the melting point of the small molecule and the glass transition of the pure polymer; this solute loss manifested itself in changes in the glass transition temperature of the film. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 2021–2024, 2002     

Effects of Particle Size on the Fusion of Soda–Lime–Silicate Glass Containing NaCl

The coupled effects of particle size and 1 wt% NaCl additions on the sequence of melting reactions in a multicomponent system (sand–soda ash–calcite–dolomite–feldspar) were studied using data from DTA, DTGA, and XRD interactively. Glass batches varied in average particle size from 250 μm to finer than 45 μm. Milestone events in the fusion process of the coarse particle base glass were elucidated. The termination temperature of the last significant reaction associated with CO₂ release was 35°C lower in the fine particle size batch than with the coarsest batch. Liquid-phase formation at ∼523°C in the batch with 1 wt% NaCl occurred to an increasingly sizable extent with decreasing particle size. This contrasts with a similar effect at ∼630°C for a comparable batch without NaCl via eutectic melting between soda ash and dolomite. Sodium chloride additions significantly enhanced dissolution of CaO relic.     

Two-Dimensional Whisker Percolation in Ceramic Matrix–Ceramic Whisker Composites

A computer model that treats ceramic-powder matrix–ceramic whisker composites as a percolative network of whiskers has been developed. The model calculates the critical fraction of whiskers at the percolation threshold for a two-dimensional random network of whiskers. The computed critical fraction was found to display an inverse dependence on whisker aspect ratio. In addition, the computed critical fraction (27 vol% for a whisker aspect ratio of 7) agreed well with the zero-shrinkage whisker fraction of 30 vol% in the densification of a colloid-pressed alumina–silicon carbide composite that exhibited a two-dimensional orientation of such whiskers.