True stabilization: the behaviour of lead compounds against the thermal decomposition of polyvinyl chloride

Investigations which have been conducted within the last two decades into the behaviour of basic lead compounds as stabilizers against the thermal dehydrochlorination of polyvinyl chloride are summarized. It is shown that the results can be explained satisfactorily in terms of a free radical dehydrochlorination mechanism and a regenerative exchange process which interferes with the dehydrochlorination. This may be regarded as true stabilization in contrast to hydrogen chloride scavenging. In true stabilization it is proposed that aliphatic carboxylate groups (such as the stearate ion) react with reservoirs of basic lead compounds (such as white lead) to form relatively mobile salts (such as stearates of lead). Also, it is proposed that these salts take part in exchange reactions with chlorine atoms released by the PVC during free radical decomposition, to give innocuous chlorides of lead and the corresponding aliphatic carboxylate free radicals. Hence the chlorine atoms are trapped and no longer able to propagate dehydrochlorination of the polymer. Further, it is proposed that the aliphatic carboxylate free radicals can esterify PVC chains at sites where prior attack by chlorine atoms has abstracted methylenic hydrogen atoms leaving unpaired electrons. This step eliminates the stimulus for loss of chlorine atoms from the PVC, thereby also interfering with the free radical propagation mechanism. Subsequently, the pendant aliphatic carboxylate groups dissociate from the polymer chains with neighbouring chloromethylenic hydrogen atoms to form the corresponding acids, and leaving the chlorine atoms adjacent to carbon-carbon double bonds in relatively stable vinyl-type positions. The aliphatic carboxylic acids so formed can react with the basic lead compounds reservoir to regenerate mobile salts so that the stabilizing process is therefore continuous and cyclic. It is demonstrated that ionic and unimolecular mechanisms which normally are put forward to explain the behaviour of primary stabilizers in PVC are not satisfactory because they do not account for all observations made with basic lead stabilizing regimes. Other evidence which favours the free radical decomposition and stabilization mechanisms is cited, and a suggestion is made for further work.     

A boundary element method for two dimensional linear elastic fracture analysis

A boundary element method is developed for the analysis of fractures in two-dimensional solids. The solids are assumed to be linearly elastic and isotropic, and both bounded and unbounded domains are treated. The development of the boundary integral equations exploits (as usual) Somigliana's identity, but a special manipulation is carried out to regularize certain integrals associated with the crack line. The resulting integral equations consist of the conventional ordinary boundary terms and two additional terms which can be identified as a distribution of concentrated forces and a distribution of dislocations along each crack line. The strategy for establishing the integral equations is first outlined in terms of real variables, after which complex variable techniques are adopted for the detailed development. In the numerical implementation of the formulation, the ordinary boundary integrals are treated with standard boundary element techniques, while a novel numerical procedure is developed to treat the crack line integrals. The resulting numerical procedure is used to solve several sample problems for both embedded and surface-breaking cracks, and it is shown that the technique is both accurate and efficient. The utility of the method for simulating curvilinear crack propagation is also demonstrated.     

A survey of anesthesia support personnel in teaching programs

Although the amount and complexity of equipment and supplies used in the practice of anesthesia have sharply increased in the past decade, the role of technical support personnel dealing with this technology has not been assessed. In an effort to determine that role, a questionnaire survey was conducted of the apportionment, direction, duties, and training of anesthesia technicians in teaching departments. Two-thirds of the inquiries were returned, disclosing a typical allocation of three anesthetizing locations (or 2000 annual anesthetics) per technician. A large majority of these departments have direct control of their technicians. Virtually all of these personnel are responsible for the routine upkeep and setup of anesthesia machines and monitors, although about one-third perform more specialized clinical functions. The preparation of these technicians for their duties varies widely, with almost 60% high school graduates and virtually all reporting training as on-the-job. The authors conclude that the term "anesthesia technician" remains poorly defined and unstandardized, and that current diverse efforts to address this issue deserve attention.     

Feature detection in 3-d medical images using shape information

Three methods for identifying the left ventricular apex in 3-D medical images of the heart called gated blood pool tomograms were investigated. The first method assumed a known orientation and positioning of the entire blood pool. The second and third methods used shapes described by quadratic surfaces, which are invariant to position and orientation. The first method performed best when the blood pool was accurately oriented, but as expected, could not handle blood pools in the wrong orientations. The quadratic surface methods performed well whether or not the blood pool was accurately oriented. The best quadratic surface method predicted the x, y, z value of the apex with correlations of 0.97, 0.98, 0.99.     

Feature-based registration of retinal images

Registration of retinal images taken at different times frequently is required to measure changes caused by disease or to document retinal location of visual stimuli. Cross-correlation has been used previously for such registration, but it is computationally intensive. We have modified a faster algorithm, sequential similarity detection (SSD), to use only the portion of the template that contains retinal vessels. When compared to standard SSD and cross-correlation, this modification improves the reliability of detection for a variety of retinal imaging modalities. The improved reliability enables implementation of a two-stage registration strategy that further decreases the amount of computation and increases the speed of registration.     

Determination of erythroid variants of human leukemias using monoclonal antibodies

Expression of erythroid antigens identifying with the use of monoclonal antibodies (mab) HAE3 and HAE9 was studied in 333 patients with different types of hemoblastoses. Frequency of erythroid variants based on the reaction with mab was 5.7%. In 2.4% of cases erythroid markers were the only indication on the nature of leukemia. In 2.7% of cases the types of leukemia were accounted for as "mixed" ones, i.e. erythrolymphoid and erythromyeloid variants. Only in 0.6% of cases erythroid variant was detected by the morphological criteria.     

Sondermetalle und ihre Anwendung im Chemieapparatebau

Refractory Metals and their Application in the Chemical Process Industry Special metals, such as titanium, zirconium and tantalum, are being used increasingly for chemical plant. The exceptional resistance of special metals to many corrosive chemicals - they show it even at high temperatures and pressures - arises not from natural immunity but from the formation of a protective oxide passive layer on the metal surface. Special metals are well suited for welding. Their reactions with gases of the atmosphere must be taken into account though. Welding is therefore possible only under inert gas or a high vacuum. Similarly, alloying with iron-based materials during welding must be avoided under all circumstances. It should be taken into consideration that the melting point of tantalum, for example, is about twice as high as that of steel. Tantalum and niobium are machined with high-speed cutting steels; the cutting speed and cutting angle are similar to those used for stainless steels. In detail, the outstanding properties of special metals in chemical plant are as follows:

• — the stability of titanium under oxidizing conditions
• — the stability of zirconium under reducing and alkaline conditions
• — the resistance of molybdenum to hydrofluoric acid and fluoride
• — the stability of tantalum under oxidizing and reducing conditions.

In pure mineral acids the passive behaviour generally improves in the order titanium - zirconium - tantalum. Except where molybdenum is concerned, the medium should not contain fluoride. The material with the widest range of applications is tantalum. The addition of niobium as an alloying element leads to favourably priced but similarly resistant materials whose prospects of becoming established in the chemical industry and playing a part similar in importance to that of tantalum itself are good.