Lead based materials

These lead-based materials (PZT, PLZT, PMN) form a class of ceramics with either important dielectric, relaxor, pie2oelectric, or electrooptic properties, and are thus used for appHcations ia actuator and sensor devices. Resistive properties of these materials ia film form mirror the conduction processes ia the bulk material. Common problems associated with their use are low dielectric breakdown, iacreased aging, and electrode iajection, decreasiag the resistivity and degrading the properties. 

PLZT and PNM are, with LiNb03 and LiTa03, the systems related to elec-trooptical ceramics that have been the most studied. Chemical low-temperature routes are particularly attractive for lead-containing materials, since lead oxide is quite volatile in comparison with other metal oxides thus control of the stoichiometry of lead-based materials is tedious. 

Lead stabilizers hold about M)% of the European PVC stabilizer market and organotins 10-15%, while the remainder is liquid or paste combinations of calcium and barium salts with zinc (according to estimates by Akcros). Stabilizers for UPVC window profile are lead-based materials at 68%, barium, cadmium and lead, and barium cadmium at 29%, and calcium- and zinc-based materials at 3%. 

You have just read about how the EPA Lead Renovation, Repair, and Painting Program came to be. That is the tip of the iceberg. This ruling from EPA is very comprehensive and has generated a lot of talk in the construction trades. Like it or not, the rules must be followed when working with lead-based materials. Here we examine some of the more specific requirements of the rule. 

The laws, regulations, and rules governing working with lead-based materials are set forth by both federal and state agencies. Any failure to comply with the requirements detailed by governing authorities can result in stiff fines and potential lawsuits. These requirements are extensive and can be complex. 

Because of the risk of lead poisoning, the exposure of children to lead-based paint is a significant public health concern. The first step in the quantitative analysis of lead in dried paint chips is to dissolve the sample. Corl evaluated several dissolution techniques. " In this study, samples of paint were collected and pulverized with a Pyrex mortar and pestle. Replicate portions of the powdered paint were then taken for analysis. Results for an unknown paint sample and for a standard reference material, in which dissolution was accomplished by a 4-6-h digestion with HNO3 on a hot plate, are shown in the following table. 

The %w/w lead in a lead-based paint Standard Reference Material and in unknown paint chips is determined by atomic absorption using external standards. 

Cellulosics. CeUulosic adhesives are obtained by modification of cellulose [9004-34-6] (qv) which comes from cotton linters and wood pulp. Cellulose can be nitrated to provide cellulose nitrate [9004-70-0] which is soluble in organic solvents. When cellulose nitrate is dissolved in amyl acetate [628-63-7] for example, a general purpose solvent-based adhesive which is both waterproof and flexible is formed. Cellulose esterification leads to materials such as cellulose acetate [9004-35-7], which has been used as a pressure-sensitive adhesive tape backing. Cellulose can also be ethoxylated, providing hydroxyethylceUulose which is useful as a thickening agent for poly(vinyl acetate) emulsion adhesives. Etherification leads to materials such as methylceUulose [9004-67-5] which are soluble in water and can be modified with glyceral [56-81-5] to produce adhesives used as wallpaper paste (see Cellulose esters Cellulose ethers). 

Other Metals. Tellurium has been added to copper-base, lead-base, and tin-base bearing aUoys. In babbit-type aUoys, teUurium controls the stmcture and improves uniformity and fatigue resistance by restraining the tendency to segregation (see Bearing Materials). 

Because of the stringent U.S. requirements on handling lead-based powders, these stabilizers are only found in flexible electrical wire insulation in the United States because no other stabilizers have been developed which have the low conductivity afforded by these materials. 

Arsenic added ia amounts of 0.1—3% improves the properties of lead-base babbitt alloys used for beatings (see Bearing materials). Arsenic (up to 0.75%), has been added to type metal to increase hardness and castabiUty (21). Addition of arsenic (0.1%) produces a desirable fine-grain effect in electrotype metal without appreciably affecting the hardness or ductihty. Arsenic (0.5—2%) improves the sphericity of lead ammunition. Automotive body solder of the composition 92% Pb, 5.0% Sb, and 2.5% Sn, contains 0.50% arsenic (see Solders and brazing alloys). 

Paste Mixing. The active materials for both positive and negative plates are made from the identical base materials. Lead oxide, fibers, water, and a dilute solution of sulfuric acid are combined in an agitated batch mixer or reactor to form a pastelike mixture of lead sulfates, the normal, tribasic, and tetrabasic sulfates, plus PbO, water, and free lead. The positive and negative pastes differ only in additives to the base mixture. Organic expanders, barium sulfate [7727-43-7] BaSO carbon, and occasionally mineral oil are added to the negative paste. Red lead [1314-41 -6] or minium, Pb O, is sometimes added to the positive mix. The paste for both electrodes is characterized by cube weight or density, penetration, and raw plate density. 

Because of very high dielectric constants k > 20, 000), lead-based relaxor ferroelectrics, Pb(B, B2)02, where B is typically a low valence cation and B2 is a high valence cation, have been iavestigated for multilayer capacitor appHcations. Relaxor ferroelectrics are dielectric materials that display frequency dependent dielectric constant versus temperature behavior near the Curie transition. Dielectric properties result from the compositional disorder ia the B and B2 cation distribution and the associated dipolar and ferroelectric polarization mechanisms. Close control of the processiag conditions is requited for property optimization. Capacitor compositions are often based on lead magnesium niobate (PMN), Pb(Mg2 3Nb2 3)02, and lead ziac niobate (PZN), Pb(Zn 3Nb2 3)03. 

Selection. The widely used cathode materials iaclude Hg, Pb, Al, Zn, Ni, Fe, Cu, Sn, Cd, and C. Because of mechanical iaconvenience, mercury is not an attractive electrode material for large cells. The preferred material is lead or an amalgam. Because Pb is soft and has a tendency to deform, however, it presents some mechanical problems. The problems can be overcome by hot dip or electroplating on steel, copper, or other rigid base material. 

There are obviously situations which demand considerable over-design of a cathodic protection system, in particular where regular and efficient maintenance of anodes is not practical, or where temporary failure of the system could cause costly damage to plant or product. Furthermore, contamination of potable waters by chromium-containing or lead-based alloy anodes must lead to the choice of the more expensive, but more inert, precious metal-coated anodes. The choice of material is then not unusual in being one of economics coupled with practicability. 

It should be noted that lead dioxide will discharge if electronically connected to a more base material, when in an unenergised state. The reverse current leakage of a rectifier will allow this to happen to a small extent if the rectifier is faulty, with the consequent formation of lead chloride and corrosion of the anode. 

These have been developed for special uses. For example, since petroleum-based materials harm natural rubber, a grease based on castor oil and lead stearate is available for use on the steel parts of rubber bushes, engine mountings, hydraulic equipment components, etc. (but not on copper or cadmium alloys). Some soft-film solvent-deposited materials have water-displacing properties and are designed for use on surfaces which cannot be dried properly, e.g. water-spaces of internal combustion engines and the cylinders or valve chests of steam engines. 

Most of over six million dentures produced annually in the USA are made of acrylics (PMMAs) that includes full dentures, partial dentures, teeth, denture reliners, fillings and miscellaneous uses. Plastics have been edging into the dental market for over a half century. Even before the introduction of acrylics to the dental profession in 1937, nitrocellulose, phenol-formaldehyde and vinyl plastics were used as denture base materials. Results, however, were not wholly satisfactory because these plastics did not have the proper requisites of dental plastics. Since then, PMMAs have kept their lead as the most useful dental plastics, although many new plastics have appeared and are still being tested. Predominance of PMMAs is not surprising, for they are reasonably strong, have exceptional optical properties, low water absorption and solubility, and excellent dimensional stability. Most denture base materials, therefore, contain PMMA as the main ingredient. 

These are exciting times for peptide based materials. The number of investigators in this field and consequently the number of publications in this area have increased tremendously in recent years. Not since the middle of the past century has there been so much activity focused on the physical properties of peptidic materials. Then, efforts were focused on determination of the fundamental elements that make up protein structures, leading to the discoveries of the a—helix and the (3-sheet. Many years of study followed where the propensities of individual and combinations of amino acids to adopt and stabilize these structures were investigated. Now, this knowledge is being applied to the preparation, assembly, and use of peptide based materials with designed sequences. This volume summarizes recent developments in all these areas. 

The activity and stability of catalysts for methane-carbon dioxide reforming depend subtly upon the support and the active metal. Methane decomposes to carbon and hydrogen, forming carbon on the oxide support and the metal. Carbon on the metal is reactive and can be oxidized to CO by oxygen from dissociatively adsorbed COj. For noble metals this reaction is fast, leading to low coke accumulation on the metal particles The rate of carbon formation on the support is proportional to the concentration of Lewis acid sites. This carbon is non reactive and may cover the Pt particles causing catalyst deactivation. Hence, the combination of Pt with a support low in acid sites, such as ZrO, is well suited for long term stable operation. For non-noble metals such as Ni, the rate of CH4 dissociation exceeds the rate of oxidation drastically and carbon forms rapidly on the metal in the form of filaments. The rate of carbon filament formation is proportional to the particle size of Ni Below a critical Ni particle size (d<2 nm), formation of carbon slowed down dramatically Well dispersed Ni supported on ZrO is thus a viable alternative to the noble metal based materials. 

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