Iridium, deposition

Iridium, deposited by MOC VD, which has shown remarkable resistance to corrosion in small rocket nozzles at temperatures up to 2000°C. 

A careful analysis of the novel depression structures can be performed best, by first studying these features for just a few Ir atoms at the Cu surface. An STM image with atomic resolution is presented in Fig. 13a as measured after 0.05 ML iridium deposition at 200 K followed by post-annealing at 650 K. Two basic features can be emphasized, the appearance of an ordered array of white dots and additional star-like depressions which are irregularly spread over the displayed surface area. The array of dots in Fig. 13a has been identified as the location of first layer Cu atoms. Further on, it was verified by corresponding ab initio calculations by Heinze at al. [102] that no bias voltage dependent corrugation reversal as e.g. predicted for W( 110) [103] occurs on the Cu(lOO)... 

Iridium on barium sulfate or calcium carbonate [1, 519, before Iron], The most stereoselective reduction of the methylene compound (1) to the 16/3-methyl compound (2) was accomplished by use of iridium deposited on barium sulfate or calcium carbonate less than 2% of the 16a-methyl isomer was formed. Platinum catalysts were less stereoselective.1... 

Direct ammonia oxidation is well understood for platinum and some other noble metals [17]. The actual reactant is free ammonia (NH3) therefore more ammonia is oxidized at higher pH values. At low overpotentials, nearly all anrnuuiia is oxidized to N2 as the potential increases, some nitrate and nitrite are produced, and at even higher potentials, the electrodes are poisoned by nitrogen adsorption. Of all tested noble metal electrodes, those with platinum and iridium deposits exhibit a particularly high performance (see, e.g., [18]). Direct anunonia oxidation has also been reported for electrodes without noble metals. Two examples are BDD [12] or... 

Platinum occurs native, accompanied by small quantities of iridium, osmium, palladium, ruthenium, and rhodium, all belonging to the same group of metals. These are found in the alluvial deposits of the Ural mountains, of Columbia, and of certain western American states. Sperrylite, occurring with the nickel-bearing deposits of Sudbury, Ontario, is the source of a considerable amount of metal. 

Iridium occurs uncombined in nature with platinum and other metals of this family in alluvial deposits. It is recovered as a by-product from the nickel mining industry. 

The second form consists of Pt metal but the iridium is present as iridium dioxide. Iridium metal may or may not be present, depending on the baking temperature (14). Titanium dioxide is present in amounts of only a few weight percent. The analysis of these coatings suggests that the platinum metal acts as a binder for the iridium oxide, which in turn acts as the electrocatalyst for chlorine discharge (14). In the case of thermally deposited platinum—iridium metal coatings, these may actually form an intermetallic. Both the electrocatalytic properties and wear rates are expected to differ for these two forms of platinum—iridium-coated anodes. 

Other Metals. Ruthenium, the least expensive of the platinum group, is the second best electrical conductor, has the hardest deposit, and has a high melting point. A general purpose bath uses 5.3 g/L of mthenium as the sulfamate salt with 8 g/L sulfamic acid, and is operated at 25—60°C with a pH of 1—2. Osmium has been plated from acid chloride solutions (130) and iridium from bromide solutions, but there are no known appHcations for these baths. 

Iridium has been deposited from chloride-sulphamate and from bromide electrolytes , but coating characteristics have not been fully evaluated. The bromide electrolytes were further developed by Tyrrell for the deposition of a range of binary and some ternary alloys of the platinum metals, but, other than the platinum-iridium system, no commercial exploitation of these processes has yet been made. 

Platinum Platinum-coated titanium is the most important anode material for impressed-current cathodic protection in seawater. In electrolysis cells, platinum is attacked if the current waveform varies, if oxygen and chlorine are evolved simultaneously, or if some organic substances are present Nevertheless, platinised titanium is employed in tinplate production in Japan s. Although ruthenium dioxide is the most usual coating for dimensionally stable anodes, platinum/iridium, also deposited by thermal decomposition of a metallo-organic paint, is used in sodium chlorate manufacture. Platinum/ruthenium, applied by an immersion process, is recommended for the cathodes of membrane electrolysis cells. ... 

Ruthenium, iridium and osmium Baths based on the complex anion (NRu2Clg(H20)2) are best for ruthenium electrodeposition. Being strongly acid, however, they attack the Ni-Fe or Co-Fe-V alloys used in reed switches. Reacting the complex with oxalic acid gives a solution from which ruthenium can be deposited at neutral pH. To maintain stability, it is necessary to operate the bath with an ion-selective membrane between the electrodes . 

Iridium and osmium are rarely deposited. A new osmium bath is based on the hexachloroosmate ion . Procedures were outlined for depositing osmium on targets for nuclear reactions . 

For scientific work the fundamental standard of mass is the international prototype kilogram, which is a mass of platinum-iridium alloy made in 1887 and deposited in the International Bureau of Weights and Measures near Paris. Authentic copies of the standard are kept by the appropriate responsible authorities in the various countries of the world these copies are employed for the comparison of secondary standards, which are used in the calibration of weights for scientific work. The unit of mass that is almost universally employed in laboratory work, however, is the gram, which may be defined as the one-thousandth part of the mass of the international prototype kilogram. 

A particularly interesting case is that of the platinum metal group which, in addition to platinum (Pt), comprises ruthenium (Ru), osmium (Os), rhodium (Rh), iridium (Ir), and palladium (Pd). These carbonyl halides are usually the most practical precursors for metal deposition because of their high volatility at low temperature. Indeed two of them, palladium and platinum, do not form carbonyls but only carbonyl halides. So does gold. 

The acetylacetonates are stable in air and readily soluble in organic solvents. From this standpoint, they have the advantage over the alkyls and other alkoxides, which, with the exception of the iron alkoxides, are not as easily soluble. They can be readily synthesized in the laboratory. Many are used extensively as catalysts and are readily available. They are also used in CVD in the deposition of metals such as iridium, scandium and rhenium and of compounds, such as the yttrium-barium-copper oxide complexes, used as superconductors. 1 1 PI Commercially available acetyl-acetonates are shown in Table 4.2. 

Iridium i s the most corrosion and oxidation resi stant metal and the densest element after osmium. It i s hard and brittle and as such it i s difficult to machine or form. Thi s limitati on has spurred the devel opment of vapor deposition. 

The nozzle of original design was fabricated from a niobium alloy coated with niobium silicide and could not operate above 1320°C. This was replaced by a thin shell of rhenium protected on the inside by a thin layer of iridium. The iridium was deposited first on a disposable mandrel, from iridium acetylacetonate (pentadionate) (see Ch. 6). The rhenium was then deposited over the iridium by hydrogen reduction of the chloride. The mandrel was then chemically removed. Iridium has a high melting point (2410°C) and provides good corrosion protection for the rhenium. The nozzle was tested at 2000°C and survived 400 cycles in a high oxidizer to fuel ratio with no measurable corrosion.O l... 

Rufus IB, Viswanathan B, Ramakrishnan V, Kuriacose JC (1995) Cadmium sulfide with iridium sulfide and platinum sulfide deposits as a photocatalyst for the decomposition of aqueous sulfide. J Photochem Photobiol A 91 63-66... 

Vapor deposition allows the production of sunglass lenses with an extremely thin protective coating of iridium. 

Depending on the fabrication techniques and deposition parameters, the pH sensitive slope of IrOx electrodes varies from near-Nemstian (about 59 mV/pH) to super-Nemstian (about 70mV/pH or higher). Since the compounds in the oxide layers are possibly mixed in stoichiometry and oxidation states, most reported iridium oxide reactions use x, y in the chemical formulas, such as lr203 xH20 and IrOx(OH)y. Such mixed oxidation states in IrOx compounds may induce more H+ ion transfer per electron, which has been attributed to causing super-Nerstian pH responses [41],... 

In Gubbio, Italy, a 1 cm layer of clay between extensive limestone formations marks the boundary between the Cretaceous and Tertiary Periods. This clay layer was known to have been deposited about 65 million years ago when many life forms became extinct, but the length of time associated with the deposition was not known. In an attempt to measure this time with normally deposited meteoritic material as a clock, extensive measurements of iridium abundances (and those of many other elements) were made on the Gubbio rocks. Neutron activation analysis was the principal tool used in these studies. About 50 elements were searched for in materials like the earth s crust, about 40 were detected and about 30 were measured with useful precision [26-28]2. 

The unique chemical composition of cosmogenous debris has provided some insight into why approximately 70% of the species of organisms on Earth were driven extinct over a relatively short time interval approximately 66 million years ago. Evidence for this mass extinction has been observed in marine sediments throughout all the ocean basins. In a contemporaneous layer deposited at the end of the Cretaceous period, the hard parts of many species of marine plankton abruptly vanished from the sedimentary record. This sedimentary layer is also characterized by a large enrichment in the rare element iridium. 

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