Bond metal/oxide

FIGURE 22.14 Schematic diagram for corrosion of ionic bonding metal oxide MO in aqueous solution as a function of solution pH and interfacial potential Ac >h vmo = corrosion rate of MO. 

Table 12 gives surface energies for a number of materials. The plastics which are difficult to bond all have low surface energies, and can only be adequately bonded after surface treatment. Clean surfaces of the other polymers are all readily bonded. Metal oxides all have very high surface energies. 

Chemisoq)tion bonding to metal and metal oxide surfaces has been treated extensively by quantum-mechanical methods. Somoijai and Bent [153] give a general discussion of the surface chemical bond, and some specific theoretical treatments are found in Refs. 154-157 see also a review by Hoffman [158]. One approach uses the variation method (see physical chemistry textbooks) ... 

NL Li O. Thick film resistors are also made from transition-metal oxide soHd solutions. Glass-bonded Bi... 

Aluminum, the most common material used for contacts, is easy to use, has low resistivity, and reduces surface Si02 to form interfacial metal-oxide bonds that promote adhesion to the substrate. However, as designs reach submicrometer dimensions, aluminum, Al, has been found to be a poor choice for metallization of contacts and via holes. Al has relatively poor step coverage, which is nonuniform layer thickness when deposited over right-angled geometric features. This leads to keyhole void formation when spaces between features are smaller than 0.7 p.m. New collimated sputtering techniques can extend the lower limit of Al use to 0.5-p.m appHcations. 

Ketenes can react in several ways with organometaUic compounds and complexes. They can add as ligands to coordinated metals forming stable ketene, ketenyl, and ketenyfldene complexes. Ketenes can be inserted into metal—hydride, metal—alkyl, metal—OR, and metal—NR2 bonds, react with metal—oxide complexes, and with coordinated Hgands. This chemistry has been reviewed (9,51). 

Figure 17 summarizes the avadable sol—gel processes (56). The process on the right of the figure involves the hydrolysis of metal alkoxides in a water—alcohol solution. The hydrolyzed alkoxides are polymerized to form a chemical gel, which is dried and heat treated to form a rigid oxide network held together by chemical bonds. This process is difficult to carry out, because the hydrolysis and polymerization must be carefully controlled. If the hydrolysis reaction proceeds too far, precipitation of hydrous metal oxides from the solution starts to occur, causing agglomerations of particulates in the sol. 

An extremely wide variety of catalysts, Lewis acids, Brmnsted acids, metal oxides, molecular sieves, dispersed sodium and potassium, and light, are effective (Table 5). Generally, acidic catalysts are required for skeletal isomerization and reaction is accompanied by polymerization, cracking, and hydrogen transfer, typical of carbenium ion iatermediates. Double-bond shift is accompHshed with high selectivity by the basic and metallic catalysts. 

Ethjl Silicate-Bonded Investments. These investments are mixtures of powder and Uquid. The powder consists of refractory particles of sUica glass, crystobahte, and other metal oxides plus magnesium oxide. The Uquid is a hydrated sUica, tetrasUicic acid [10193-36-9] Si [OH], that is suppUed in a stabUized form it can be developed by mixing ethyl sUicate [78-10 ] denatured ethyl alcohol [64-17-5] and hydrochloric acid [7647-01 -OJ. The binding of the powder is accompUshed by the formation of a sUica gel according to the reaction ... 

Carboxylated polymers such as AF use similar but not identical compounds. The higher strength, especially hot bond strength, is due to the interaction of the carboxyl groups on the polymer chain with the metal oxides. The crystallization rate of AF is low and does not contribute to bond strength. Manufacture of adhesive compounds from AF is more demanding than manufacture of those from AD. 

With decreasing amounts of metal oxide, the degree of polymerisation increases. Chains of linked tetrahedra form, like the long chain polymers with a -C-C- backbone, except that here the backbone is an -Si-O-Si-O-Si- chain (Fig. 16.4c). Two oxygens of each tetrahedron are shared (there are two bridging oxygens). The others form ionic bonds between chains, joined by the MO. These are weaker than the -Si-O-Si- bonds which form the backbone, so these silicates are fibrous asbestos, for instance, has this structure. 

The isocyanates are believed to aid wetting of metals by interacting with the metal oxides and hydroxides (M-OH) present on the surface. The isocyanates can then react with water to form a rigid polyurea network which interacts at the metal surface through hydrogen bonding. The isocyanates also react to form hard segments , which will be explained shortly. 

At elevated temperatures where titanium alloys could be the adherend of choice, a different failure mechanism becomes important. The solubility of oxygen is very high in titanium at high temperatures (up to 25 at.%), so the oxygen in a CAA or other surface oxide can and does dissolve into the metal (Fig. 12). This diffusion leaves voids or microcracks at the metal-oxide interface and embrittles the surface region of the metal (Fig. 13). Consequently, bondline stresses are concentrated at small areas at the interface and the joint fails at low stress levels [51,52]. Such phenomena have been observed for adherends exposed to 600°C for as little as 1 h or 300°C for 710 h prior to bonding [52] and for bonds using... 

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