Copper-metal passivation

These additive features include protection against wear, resistance to thickening by the use of antioxidants, rust protection, copper-metal passivation, demulsification, air release and foam control, among others. Industrial gear oUs have to achieve the following requirements excellent resistance to aging and oxidation, low foam-... 

Some electrodes are made of substances that participate in the redox reactions that transfer electrons. These are active electrodes. Other electrodes serve only to supply or accept electrons but are not part of the redox chemistry these are passive electrodes. In Figure 19-7. both metal strips are active electrodes. During the redox reaction, zinc metal dissolves from the anode while copper metal precipitates at the cathode. The reactions that take place at these active electrodes are conversions between the metals contained in the electrodes and their aqueous cations. 

Metals develop a natural corrosion-resistant film when exposed to the environment. Examples include the rusting of iron, tarnishing of silver, and the formation of the patina on copper. These passive films help prevent further corrosion. However, films do not provide complete resistance to chemical attack and are destroyed by various corrosive agents. 

Another process of physical protection is the formation of an oxide layer that makes the metal passive. This procedure is used for aluminium. Aluminium is normally anodized in 10 per cent sulphuric acid with steel or copper cathodes until an oxide thickness of 10-100 pm is obtained. As the more superficial part of the oxide layer has a fairly open structure it is possible to deposit metals (cobalt, nickel, etc.) or organic pigments in the pores and seal with boiling water or with an alkaline solution. The colours after metallic deposition are due to interference effects. Chromic and oxalic acids are also used significantly as electrolyte. 

The 64k, 80 pm x 80pm sized tilting mirrors are built on the top of a CMOS-based control ASIC. In order to reduce the topography of the underlying metallization/passivation structures, a 2.5pm-thick PECVD oxide film is first deposited on the ASIC. An ILD oxide CMP step based on Klebosol 30N50 colloidal silica slurry is used for planarization. In order to connect the ASIC with the deflection electrodes above (see Fig. 14.10), vias have to be etched into the planarized dielectric film. Then, a copper metal stack including a TaN barrier has to be deposited and a two-step Cu damascene CMP process has to be performed. As this process is equivalent to Cu damascene in microelectronics fabrication, standard Cu CMP slurries can be used. 

Benzotriazole is a useful corrosion inhibitor, especially for copper. It renders the metal passive by forming a layer of insoluble copper(I) benzotriazole. Benzotriazole stabilizes photographic emulsions and delays fogging. 

The early work on passive iron by Priestley, Bergman, Wenzel, and Keir (see Vol. Ill, index, p. 846), had been forgotten until the phenomenon was rediscovered by N. W. Fischer, G. Wetzlar and G. T. Fechner. The latter published a complete German translation of Keir s paper. Experiments of 1825 (before Wetzlar s) by J. F. W. Herschel were first published in 1833 attributed the passivity to a certain permanent electric state of the surface of the metal. Passivity was once more rediscovered by Schonbein. The passivity of copper and bismuth in nitric acid was discovered by T. Andrews." ... 

The injection charge polarity relationships we have shown for various metal electrodes are consistent with the ordering of the Galvanic series of alloys, proceeding from most negative to positive as zinc, aluminum, active steel, brass, copper, and passivated steel. To verify this ordering for highly purified water (resistivity 26 MQ-cm at 20 C,... 

Often interfacial corrosion initiates from pinholes in the film. Interfacial corrosion may also be due to reactive species trapped at the interface migration down through-porosity, permeation, or diffusion through the substrate or permeation or diffusion through the film material. Surface corrosion of films can sometimes be reduced by formation of a passive layer or deposition of an inert film. For example, a thin film of gold ( flash ) is often deposited on the surface of a copper metallization to prevent surface corrosion. 

For example,copper has relatively good corrosion resistance under non-oxidizing conditions. It can be alloyed with zinc to yield a stronger material (brass), but with lowered corrosion resistance. Flowever, by alloying copper with a passivating metal such as nickel, both mechanical and corrosion properties are improved. Another important alloy is steel, which is an alloy between iron (>50%) and other alloying elements such as carbon. 

Monel and nickel are the preferred materials of constmction for cylinders and deHvery systems however, copper, brass, steel, and stainless steel can be used at room temperature, providing that these metals are cleaned, dried, and passivated with a fluoride film prior to use. Studies have shown that fluorine passivation of stainless steel and subsequent formation of an iron fluoride layer prior to WF exposure prevents reaction between the WF and the stainless steel surface (23). 

Anodes. Lead—antimony (6—10 wt %) alloys containing 0.5—1.0 wt % arsenic have been used widely as anodes in copper, nickel, and chromium electrowinning and metal plating processes. Lead—antimony anodes have high strength and develop a corrosion-resistant protective layer of lead dioxide during use. Lead—antimony anodes are resistant to passivation when the current is frequendy intermpted. 

An especially insidious type of corrosion is localized corrosion (1—3,5) which occurs at distinct sites on the surface of a metal while the remainder of the metal is either not attacked or attacked much more slowly. Localized corrosion is usually seen on metals that are passivated, ie, protected from corrosion by oxide films, and occurs as a result of the breakdown of the oxide film. Generally the oxide film breakdown requires the presence of an aggressive anion, the most common of which is chloride. Localized corrosion can cause considerable damage to a metal stmcture without the metal exhibiting any appreciable loss in weight. Localized corrosion occurs on a number of technologically important materials such as stainless steels, nickel-base alloys, aluminum, titanium, and copper (see Aluminumand ALUMINUM ALLOYS Nickel AND nickel alloys Steel and Titaniumand titanium alloys). 

Electroforrning is the production or reproduction of articles by electro deposition upon a mandrel or mold that is subsequendy separated from the deposit. The separated electro deposit becomes the manufactured article. Of all the metals, copper and nickel are most widely used in electroforming. Mandrels are of two types permanent or expendable. Permanent mandrels are treated in a variety of ways to passivate the surface so that the deposit has very Httie or no adhesion to the mandrel, and separation is easily accompHshed without damaging the mandrel. Expendable mandrels are used where the shape of the electroform would prohibit removal of the mandrel without damage. Low melting alloys, metals that can be chemically dissolved without attack on the electroform, plastics that can be dissolved in solvents, ate typical examples. 

Silt, sand, concrete chips, shells, and so on, foul many cooling water systems. These siliceous materials produce indirect attack by establishing oxygen concentration cells. Attack is usually general on steel, cast iron, and most copper alloys. Localized attack is almost always confined to strongly passivating metals such as stainless steels and aluminum alloys. 

Metals which owe their good corrosion resistance to the presence of thin, passive or protective surface films may be susceptible to pitting attack when the surface film breaks down locally and does not reform. Thus stainless steels, mild steels, aluminium alloys, and nickel and copper-base alloys (as well as many other less common alloys) may all be susceptible to pitting attack under certain environmental conditions, and pitting corrosion provides an excellent example of the way in which crystal defects of various kinds can affect the integrity of surface films and hence corrosion behaviour. 

Previous considerations of pitting have been largely confined to metals and alloys that have a strong tendency to passivate, but since the pitting of copper has a number of unusual features it is appropriate to consider it in some detail. Reference to the potential-pH diagram for the Cu-H O (Section 4.2) system shows that in neutral solutions at the potentials encountered in oxygenated waters the stable form of copper is Cu O, and the corrosion resistance of copper thus depends upon whether or not the CU2O forms a protective film. 

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