Metals Deposition

Local deposition is interesting in technology, and several studies show that this can be performed with in-situ scanning probe microscopes. On graphite Li et al. 

---

At potentials positive to the bulk metal deposition, a metal monolayer-or in some cases a bilayer-of one metal can be electrodeposited on another metal surface this phenomenon is referred to as underiDotential deposition (upd) in the literature. Many investigations of several different metal adsorbate/substrate systems have been published to date. In general, two different classes of surface stmetures can be classified (a) simple superstmetures with small packing densities and (b) close-packed (bulklike) or even compressed stmetures, which are observed for deposition of the heavy metal ions Tl, Hg and Pb on Ag, Au, Cu or Pt (see, e.g., [63, 64, 65, 66, 62, 68, 69 and 70]). In case (a), the metal adsorbate is very often stabilized by coadsorbed anions typical representatives of this type are Cu/Au (111) (e.g. [44, 45, 21, 22 and 25]) or Cu/Pt(l 11) (e.g. [46, 74, 75, and 26 ]) It has to be mentioned that the two dimensional ordering of the Cu adatoms is significantly affected by the presence of coadsorbed anions, for example, for the upd of Cu on Au(l 11), the onset of underiDotential deposition shifts to more positive potentials from 80"to Br and CE [72]. 

The aqueous solution has a low conductivity, indicating that mercury(II) chloride dissolves essentially as molecules Cl—Hg—Cl and these linear molecules are found in the solid and vapour. A solution of mercury(II) chloride is readily reduced, for example by tin(ll) chloride, to give first white insoluble mercury(I) chloride and then a black metallic deposit of mercury, The complexes formed from mercury(II) chloride are considered below. 

The catalyst is also employed in the form of the finely-divided metal deposited upon activated carbon (usually containing 5 or 10 per cent. Pd) two methods of preparation are described, in one reduction is effected with alkaline formaldehyde solution and in the other with hydrogen ... 

Europium is now prepared by mixing EU2O3 with a 10%-excess of lanthanum metal and heating the mixture in a tantalum crucible under high vacuum. The element is collected as a silvery-white metallic deposit on the walls of the crucible. 

Indium chemicals and electroplated metal deposits ate replacing mercury (qv) in the manufacture of alkaline batteries (qv). Indium, like mercury, functions to reduce outgassing within the battery and promotes the uniform corrosion of the anode and cathode while the battery is under electrical load. Indium inorganic chemicals also find use as catalysts in various chemical processes. 

Fused Salt Electrolysis. Only light RE metals (La to Nd) can be produced by molten salt electrolysis because these have a relatively low melting point compared to those of medium and heavy RE metals. Deposition of an alloy with another metal, Zn for example, is an alternative. The feed is a mixture of anhydrous RE chlorides and fluorides. The materials from which the electrolysis cell is constmcted are of great importance because of the high reactivity of the rare-earth metals. Molybdenum, tungsten, tantalum, or alternatively iron with ceramic or graphite linings are used as cmcible materials. Carbon is frequently used as an anode material. 

A typical example might involve use of a krypton fluoride excimer laser operating at 249 nm with a pulse duration around 100 nanoseconds and a pulse repetition rate which can be varied up to 200 Hz. For metal deposition, energy densities in the range from 0.1 to 1 J/cm per pulse are typical. 

The concentration of most metals in the earth s cmst is very low, and even for abundant elements such as aluminum and iron, extraction from common rock is not economically feasible. An ore is a metallic deposit from which the metal can be economically extracted. The amount of valuable metal in the ore is the tenor, or ore grade, usually given as the wt % of metal or oxide. Eor precious metals, the tenor is given in grams per metric ton or troy ounces per avoirdupois short ton (2000 pounds). The tenor and the type of metallic compounds are the main characteristics of an ore. The economic feasibihty of ore processing, however, depends also on the nature, location, and size of the deposit the availabihty and cost of a suitable extraction process and the market price of the metal. 

The most common Schottky contacts for compound semiconductors are gold-based metallizations deposited by thermal or electron beam evaporation. The metal may include a thin titanium layer in direct contact with the semiconductor which acts as an adhesion layer. AdditionaHy, a thin layer... 

Sulfamic acid and its salts retard the precipitation of barium sulfate and prevent precipitation of silver and mercury salts by alkah. It has been suggested that salts of the type AgNHSO K [15293-60 ] form with elemental metals or salts of mercury, gold, and silver (19). Upon heating such solutions, the metal deposits slowly ia mirror form on the wall of a glass container. Studies of chemical and electrochemical behavior of various metals ia sulfamic acid solutions are described ia Reference 20. 

Production and Economic Aspects. Thallium is obtained commercially as a by-product in the roasting of zinc, copper, and lead ores. The thallium is collected in the flue dust in the form of oxide or sulfate with other by-product metals, eg, cadmium, indium, germanium, selenium, and tellurium. The thallium content of the flue dust is low and further enrichment steps are required. If the thallium compounds present are soluble, ie, as oxides or sulfates, direct leaching with water or dilute acid separates them from the other insoluble metals. Otherwise, the thallium compound is solubilized with oxidizing roasts, by sulfatization, or by treatment with alkaU. The thallium precipitates from these solutions as thaUium(I) chloride [7791 -12-0]. Electrolysis of the thaUium(I) sulfate [7446-18-6] solution affords thallium metal in high purity (5,6). The sulfate solution must be acidified with sulfuric acid to avoid cathodic separation of zinc and anodic deposition of thaUium(III) oxide [1314-32-5]. The metal deposited on the cathode is removed, kneaded into lumps, and dried. It is then compressed into blocks, melted under hydrogen, and cast into sticks. 

Easily decomposed, volatile metal carbonyls have been used in metal deposition reactions where heating forms the metal and carbon monoxide. Other products such as metal carbides and carbon may also form, depending on the conditions. The commercially important Mond process depends on the thermal decomposition of Ni(CO)4 to form high purity nickel. In a typical vapor deposition process, a purified inert carrier gas is passed over a metal carbonyl containing the metal to be deposited. The carbonyl is volatilized, with or without heat, and carried over a heated substrate. The carbonyl is decomposed and the metal deposited on the substrate. A number of papers have appeared concerning vapor deposition techniques and uses (170—179). 

In the presence of metallic copper, metallic silver, or a copper-silver alloy used in the form of gauze or as metal deposited on a low surface area inert support, methanol can be dehydrogenated to formaldehyde at 400—500°C. 

Plating T anks. An electroless plating line consists of a series of lead-lined (for plastics etching) or plastic-lined tanks equipped with filters and heaters, separated by rinse tanks (24). Most metal tanks, except for passivated stainless steel used for electroless nickel, cannot be used to hold electroless plating baths because the metal initiates electroless plating onto itself. Tank linings must be stripped of metal deposits using acid at periodic intervals. 

Cathode Efficiency. Faraday s law relates the passage of current to the amount of a particular metal being deposited ie, 96,485 coulombs, equal to one Faraday, deposits one gram-equivalent weight of a metal at 100% efficiency. The cathode efficiency, an important factor in commercial electroplating, is the ratio of the actual amount of metal deposited to that theoretically calculated multipHed by 100%. 

Reference 38 is a good guide to the selection of plate thickness test methods. Test methods may vary with the purity and electrochemical activity of the deposit. Metals deposited from commercial plating solutions are seldom pure. For example, zinc deposits from the three commonly used baths, ie, cyanide, chloride, and zincate, vary significantly in purity and activity (39). Standard ASTM test methods for determining plate thickness are... 

Ductility Tests. The ductihty of plated metals differs considerably from the corresponding thermally cast metals. Additionally, ductihty which is an important property if parts are to be deformed after plating, varies with the chemical composition of the plating solution, as well as the operating conditions of a given plating process. Ductihty can also be important when plated parts are stressed in use. Some metal deposits have coefficients of... 

AU other carbon steel, low-intermediate, and high-aUoy steels, ferritic steels Base metal Deposited weld metal and heat-affected zone (See Note 1) 2. Except when conchtions conform to Note 2, the material shall be heat-treated to control its microstructure by a method appropriate to the material as outlined in the specification applicable to the product form and then impact-tested. (See Note 1.) Deposited weld metal and heat-affected zone shall be impact-tested. 

Eitch indented into the tube. Tube 48 was a clean copper tube that ad 50 longitudinal flutes pressed into the wall (Gener Electric double-flute profile, Diedrich, U.S. Patent 3,244,601, Apr. 5, 1966). Tubes 47 and 39 had a specially patterned porous sintered-metal deposit on the boihng side to promote nucleate boiling (Minton, U.S. 

Metal depositors. Metal-depositing bacteria oxidize ferrous iron (Fe ) to ferric iron (Fe ). Ferric hydroxide is the result. Some bacteria oxidize manganese and other metals. Gallionella bacteria, in particular, have been associated with the accumulation of iron oxides in tubercles. In fact, up to 90% of the dry weight of the cell mass can be iron hydroxide. These bacteria appear filamentous. The oxide accumulates along very fine tails or excretion stalks generated by these organisms. 

Some metal carbonyls, such as nickel, cobalt and manganese compounds have been used to produce metallic deposition. The decomposition occurs in a stepwise manner, producing one CO(g) molecule at each step. 

A number of attempts to produce tire refractory metals, such as titanium and zirconium, by molten chloride electrolysis have not met widr success with two exceptions. The electrolysis of caesium salts such as Cs2ZrCl6 and CsTaCle, and of the fluorides Na2ZrF6 and NaTaFg have produced satisfactoty products on the laboratory scale (Flengas and Pint, 1969) but other systems have produced merely metallic dusts aird dendritic deposits. These observations suggest tlrat, as in tire case of metal deposition from aqueous electrolytes, e.g. Ag from Ag(CN)/ instead of from AgNOj, tire formation of stable metal complexes in tire liquid electrolyte is the key to success. 

Metal deposition onto polymers microfibrous metal surfaces... 

An alternate form of catalyst is pellets. The pellets are available in various diameters or extruded forms. The pellets can have an aluminum oxide coating with a noble metal deposited as the catalyst. The beads are placed in a tray or bed and have a depth of anywhere from 6 to 10 inches. The larger the bead (1/4 inch versus 1/8 inch) the less the pressure drop through the catalyst bed. However, the larger the bead, the less surface area is present in the same volume which translates to less destruction efficiency. Higher pressure drop translates into higher horsepower required for the oxidation system. The noble metal monoliths have a relatively low pressure drop and are typically more expensive than the pellets for the same application. 

Composite Plate—an electrodeposit that consists of two or more layers of metals deposited separately. 

The isolation of zinc, over 90% of which is from sulfide ores, depends on conventional physical concentration of the ore by sedimentation or flotation techniques. This is followed by roasting to produce the oxides the SO2 which is generated is used to produce sulfuric acid. The ZnO is then either treated electrolytically or smelted with coke. In the former case the zinc is leached from the crude ZnO with dil H2SO4, at which point cadmium is precipitated by the addition of zinc dust. The ZnS04 solution is then electrolysed and the metal deposited — in a state of 99.95% purity — on to aluminium cathodes. 

---