Matrix cobalt

Appllca.tlons. The principal appHcations of nickel-base superalloys are in gas turbines, where they are utilized as blades, disks, and sheet metal parts. Abcraft gas turbines utilized in both commercial and military service depend upon superalloys for parts exposed to peak metal temperatures in excess of 1000°C. Typical gas turbine engines produced in the United States in 1990 utilized nickel and cobalt-base superalloys for 46% of total engine weight (41). However, programs for future aerospace propulsion systems emphasize the need for lightweight materials having greater heat resistance. For such apphcations, intermetallics matrix composites and ceramic composites are expected to be needed. 

Table 13 is a representative Hst of nickel and cobalt-base eutectics for which mechanical properties data are available. In most eutectics the matrix phase is ductile and the reinforcement is britde or semibritde, but this is not invariably so. The strongest of the aHoys Hsted in Table 13 exhibit ultimate tensile strengths of 1300—1550 MPa. Appreciable ductiHty can be attained in many fibrous eutectics even when the fibers themselves are quite britde. However, some lamellar eutectics, notably y/y —5, reveal Htde plastic deformation prior to fracture. 

A more extensive comparison of many potential turbine blade materials is available (67). The refractory metals and a ceramic, sHicon nitride, provide a much higher value of 100 h stress—mpture life, normalised by density, than any of the cobalt- or nickel-base aHoys. Several intermetaHics and intermetaUic matrix composites, eg, aHoyed Nb Al and MoSi —SiC composites, also show very high creep resistance at 1100°C (68). Nevertheless, the superaHoys are expected to continue to dominate high temperature aHoy technology for some time. 

Cemented Carbides. Cemented carbides contain mostiy tungsten carbide and lesser amounts of other hard-metal components, embedded in a matrix of cobalt (see Carbides, cemented carbides). 

Fig. 5. Micrographs of the microstructure of fully hardened and tempered tool steels produced by the powder metallurgy technique, showing uniform distribution and fine carbide particles in the matrix, (a) M-42 (see Table 6) and (b) cobalt-free AlSl T-15 having a higher concentration of fine carbide...

Cemented tungsten carbides also find use as a support for polycrystalline diamond (PCD) cutting tips, or as a matrix alloy with cobalt, nickel, copper, and iron, ia which diamond particles are embedded. These tools are employed ia a variety of iadustries including mineral exploration and development oil and gas exploration and production and concrete, asphalt, and dimension stone cutting. 

Pure metallic cobalt has a soHd-state transition from cph (lower temperatures) to fee (higher temperatures) at approximately 417°C. However, when certain elements such as Ni, Mn, or Ti are added, the fee phase is stabilized. On the other hand, adding Cr, Mo, Si, or W stabilizes the cph phase. Upon fcc-phase stabilization, the energy of crystallographic stacking faults, ie, single-unit cph inclusions that impede mechanical sHp within the fee matrix, is high. 

The abrasion resistance of cobalt-base alloys generally depends on the hardness of the carbide phases and/or the metal matrix. For the complex mechanisms of soHd-particle and slurry erosion, however, generalizations cannot be made, although for the soHd-particle erosion, ductihty may be a factor. For hquid-droplet or cavitation erosion the performance of a material is largely dependent on abiUty to absorb the shock (stress) waves without microscopic fracture occurring. In cobalt-base wear alloys, it has been found that carbide volume fraction, hence, bulk hardness, has Httie effect on resistance to Hquid-droplet and cavitation erosion (32). Much more important are the properties of the matrix. 

Carbide-based cermets have particles of carbides of tungsten, chromium, and titanium. Tungsten carbide in a cobalt matrix is used in machine parts requiring very high hardness such as wire-drawing dies, valves, etc. Chromium carbide in a cobalt matrix has high corrosion and abrasion resistance it also has a coefficient of thermal expansion close to that of steel, so is well-suited for use in valves. Titanium carbide in either a nickel or a cobalt matrix is often used in high-temperature applications such as turbine parts. Cermets are also used as nuclear reactor fuel elements and control rods. Fuel elements can be uranium oxide particles in stainless steel ceramic, whereas boron carbide in stainless steel is used for control rods. 

A model similar to that of the iron complex 31 was proposed for the cobalt species synthesized as a result of co-condensation of cobalt vapors with pyrrole in vacuum. A frozen matrix formed is subsequently warmed to room temperature (89JA3881). An oligomer or a polymer results, in which a- and ir-donor functions are realized simultaneously. The model proposed differs from that for the iron pyrrolyl complex by inclusion of the Co—Co bonds to attain the 18-electron configuration. 

The metal concentration, matrix, and temperature effects that favor clustering of the cobalt group of metal atoms have been assessed by... 

Ozin, Hanlan, and Power, using optical spectroscopy (49,121). In view of the marked temperature-effect observed for the cobalt system, we shall focus on this cluster system here. Evidence for cobalt-atom aggregation at the few-atom extreme first came from a comparison of the optical data for Co Ar — 1 10 mixtures recorded at 4.2 and 12 K (see Fig. 4). A differential of roughly 8 K in this cryogenic-temperature regime was sufficient to cause the dramatic appearance of an entirely new set of optical absorptions in the regions 320-340 and 270-280 nm (see Fig. 4). Matrix variation, from Ar, to Kr, to Xe, helped clarify atom-cluster, band-overlap problems (see Fig. 5). 

On photolyzing CoziCOg in the matrix (20), a number of photoproducts could be observed. The results of these experiments are summarized in Scheme 4, which illustrates the various species formed. Of particular interest is the formation of Co2(CO)7 on irradiation of Co2(CO)g in CO (254 nm), as this species had not been characterized in the metal-atom study of Hanlan et al. (129). Passage of Co2(CO)g over an active, cobalt-metal surface before matrix isolation causes complete decomposition. On using a less active catalyst, the IR spectrum of Co(CO)4 could be observed. An absorption due to a second decomposition product, possibly Co2(CO)g, was also noted. 

A current area of interest is the use of AB cements as devices for the controlled release of biologically active species (Allen et al, 1984). AB cements can be formulated to be degradable and to release bioactive elements when placed in appropriate environments. These elements can be incorporated into the cement matrix as either the cation or the anion cement former. Special copper/cobalt phosphates/selenates have been prepared which, when placed as boluses in the rumens of cattle and sheep, have the ability to decompose and release the essential trace elements copper, cobalt and selenium in a sustained fashion over many months (Chapter 6). Although practical examples are confined to phosphate cements, others are known which are based on a variety of anions polyacrylate (Chapter 5), oxychlorides and oxysulphates (Chapter 7) and a variety of organic chelating anions (Chapter 9). The number of cements available for this purpose is very great. 

The SOMO in these radicals is expected from extended Hiickel MO calculations27-29 to be primarily cobalt 3dyz in character. In the Cs symmetry of the radicals, dyz belongs to the a" representation and d-hybridization is possible only with dxy. Assuming that such hybridization is negligible, the g-matrix... 

It is relatively easy to understand the significance of the non-coincident matrix axes in these cases. For the Co2C2 cluster, the C2v molecular symmetry permits a specific prediction of the possible matrix axis orientations. The g-matrix principal axes must be coincident with the molecular symmetry axes. The two cobalt nuclei are located in a reflection plane (which we label xz) so that symmetry requires the y-axis to be a principal axis for all three matrices. The other two axes may be rotated, relative to the molecular x- and z-axes, by /J. (Since the two nuclei are symmetrically equivalent, the rotations must be equal and opposite.)... 

Nickel carbonyl radicals show an even greater tendency than cobalt carbonyls to cluster in a krypton matrix. Three binuclear nickel carbonyls have been detected by EPR spectroscopy in the products of y-irradiated Ni(CO)4 in Kr, yet no mononuclear species has been positively identified (65). 13C hyperfine structure has... 

The cobalt(II)15 and zinc(II)16 complexes of phthalocyanine(Pc), octcyano-Pc, and tetrasulfon-ato-Pc incorporated in poly(4-vinylpyridine-co-styrene) or Nafion films coated on graphite have also been examined as catalytic devices for dihydrogen electrogeneration in phosphate buffer. These catalytic systems were strongly suggested to be dominated by the electron transfer within the polymer matrix. The best catalytic film is that constituted of the nonsubstituted Con-Pc complex in poly(4-vinylpyridine-co-styrene), giving a turnover number of 2 x 10s h-1 at an applied potential of —0.90 V vs. Ag Ag Cl. 

The composition of the codeposition bath is defined not only by the concentration and type of electrolyte used for depositing the matrix metal, but also by the particle loading in suspension, the pH, the temperature, and the additives used. A variety of electrolytes have been used for the electrocodeposition process including simple metal sulfate or acidic metal sulfate baths to form a metal matrix of copper, iron, nickel, cobalt, or chromium, or their alloys. Deposition of a nickel matrix has also been conducted using a Watts bath which consists of nickel sulfate, nickel chloride and boric acid, and electrolyte baths based on nickel fluoborate or nickel sulfamate. Although many of the bath chemistries used provide high current efficiency, the effect of hydrogen evolution on electrocodeposition is not discussed in the literature. 

Tominaga et al. [682,683] studied the effect of ascorbic acid on the response of these metals in seawater obtained by graphite-furnace atomic absorption spectrometry from standpoint of variation of peak times and the sensitivity. Matrix interferences from seawater in the determination of lead, magnesium, vanadium, and molybdenum were suppressed by addition of 10% (w/v) ascorbic acid solution to the sample in the furnace. Matrix effects on the determination of cobalt and copper could not be removed in this way. These workers propose a direct method for the determination of lead, manganese, vanadium, and molybdenum in seawater. 

Cobalamin, 25 803 folic acid and, 25 802 Cobalt (Co), 7 207-228. See also Co-base superalloys 60Co isotope 60Co nucleus Fe-Ni-Co alloys Dicobalt octacarbonyl Tetracobalt dodecacarbonyl analysis, 7 215-216 in ceramic-matrix composites, 5 554t coke formation on, 5 266 colloidal suspensions, 7 275 economic aspects, 7 214-215 effect on copper resistivity, 7 676t environmental concerns, 7 216 health and safety factors, 7 216-218 in M-type ferrites, 11 66, 69 occurrence, 7 208... 

M(CxC) matrix, 32 290-291, 311-313 Measurements, interpretation of, in experimental catalysis, 2 251 Mechanism see also specific types cobalt catalysis, 32 342-349 dehydrocyclization, 29 279-283 rhodium catalysis, 32 369-375 ruthenium catalysis, 32 381-387 space, 32 280... 

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