Control of free-radical emulsion polymerization of methyl methacrylate by oxygen injection. II. Experimental study

Oxygen injection has been proposed and experimentally demonstrated as an effective control measure for limiting the rate of heat release and altering the rate of polymerization in emulsion processes. A detailed mathematical model has been previously developed to describe the system behavior with and without oxygen injection. A simple lab scale apparatus was constructed and run extensively. Only trace quantities of oxygen are needed to inhibit the reaction completely. The facile response makes this method attractive for fast temperature control. However, because of the rapid penetration of dissolved oxygen into the polymer particles, growing radical chains are terminated prematurely, lowering product molecular weights. To minimize this detrimental effect, pulsed oxygen control is used and extensive experimental work was performed to determine the effects of controller set points on molecular weight. Moderate oxygen flows and moderate set point temperatures are found to give the optimal response without significant lowering of the final molecular weight. Injected quantities agree well with the order-of-magnitude sparging calculations needed to completely stop initiation. However, complete agreement between model simulations and experimental results was not reached due to an unmeasured loss of monomer from the reactor. Chain transfer to monomer is found to be important in modeling the polymer molecular weight. It has, however, a negligible effect on the reaction rate.     

“Metallisation” of oxide surfaces observed by in situ high-resolution electron microscopy

Intense irradiation (25–40 A/cm²) at intermediate energy (400 keV) has been found to cause “metallisation” of tungsten oxide and titanium niobate crystal surfaces. The possible mechanisms and the likely consequences for high-resolution imaging of clean oxide surfaces are briefly discussed.     

Synthesis of N,N-diethyl-N-{4-[(E)-(4-nitrophenyl)diazenyl]phenyl}amine via in situ diazotisation and coupling in supercritical carbon dioxide

The synthesis of azo dyes via a conventional aqueous-based diazotisation and coupling reaction requires the use of relatively high concentrations of mineral acids, which leads to high electrolyte concentrations in wastewater. Reported in this paper is an environmentally benign one-pot method for the synthesis of a nonionic azo dye, N,N -diethyl- N -{4-[( E )-(4-nitrophenyl)diazenyl]phenyl}amine, in supercritical carbon dioxide without using a mineral acid. The product yield increased significantly with temperature, with 91% theoretical yield afforded at 80 °C. The pressure of the system had little influence on product yield.     

Summary of discussion on ‘Sciences related to pitch and coke usage in carbon manufacture’

This article is a brief summary of the Discussion session held after the presentation of the preceding papers at the conference organized by the Industrial Carbon and Graphite Group of the Society of Chemical Industry, London, March 1984.     

Introduction of a nonlinearity measure for principal component models

Although principal component analysis (PCA) is an important tool in standard multivariate data analysis, little interest has been devoted to assessing whether the underlying relationship within a given variable set can be described by a linear PCA model or whether nonlinear PCA must be utilized. This paper addresses this deficiency by introducing a nonlinearity measure for principal component models. The measure is based on the following two principles: (i) the range of recorded process operation is divided into smaller regions; and (ii) accuracy bounds are determined for the sum of the discarded eigenvalues. If this sum is within the accuracy bounds for each region, the process is assumed to be linear and vice versa. This procedure is automated through the use of cross-validation. Finally, the paper shows the utility of the new nonlinearity measure using two simulation studies and with data from an industrial melter process.     

Linear demosaicing inspired by the human visual system.

There is an analogy between single-chip color cameras and the human visual system in that these two systems acquire only one limited wavelength sensitivity band per spatial location. We have exploited this analogy, defining a model that characterizes a one-color per spatial position image as a coding into luminance and chrominance of the corresponding three colors per spatial position image. Luminance is defined with full spatial resolution while chrominance contains subsampled opponent colors. Moreover, luminance and chrominance follow a particular arrangement in the Fourier domain, allowing for demosaicing by spatial frequency filtering. This model shows that visual artifacts after demosaicing are due to aliasing between luminance and chrominance and could be solved using a preprocessing filter. This approach also gives new insights for the representation of single-color per spatial location images and enables formal and controllable procedures to design demosaicing algorithms that perform well compared to concurrent approaches, as demonstrated by experiments.