Carbide phases

Fig. 16. Iron—iron carbide phase diagram (1). See text.

Low—medium alloy steels contain elements such as Mo and Cr for hardenabiHty, and W and Mo for wear resistance (Table 4) (7,16,17) (see Steel). These alloy steels, however, lose their hardness rapidly when heated above 150—340°C (see Fig. 3). Furthermore, because of the low volume fraction of hard, refractory carbide phase present in these alloys, their abrasion resistance is limited. Hence, low—medium alloy steels are used in relatively inexpensive tools for certain low speed cutting appHcations where the heat generated is not high enough to reduce their hardness significantly. 

Mechanical properties depend on the alloying elements. Addition of carbon to the cobalt base metal is the most effective. The carbon forms various carbide phases with the cobalt and the other alloying elements (see Carbides). The presence of carbide particles is controlled in part by such alloying elements such as chromium, nickel, titanium, manganese, tungsten, and molybdenum that are added during melting. The distribution of the carbide particles is controlled by heat treatment of the solidified alloy. 

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. 

Samples were tested on in a melt of salts (75% Na SO, 25% NaCl) at 950°C in an air atmosphere for 24 hours. Micro X-rays spectrum by the analysis found that the chemical composition of carbides of an alloy of the ZMI-3C and test alloys differs noticeably. In the monocarbide of phase composition of an alloy of the ZMI-3C there increased concentration of titanium and tungsten is observed in comparison with test alloys containing chemical composition tantalum. The concentration of more than 2% of tantalum in test alloys has allowed mostly to deduce tungsten from a mono carbide phase (MC) into solid solution. Thus resistance of test alloys LCD has been increased essentially, as carbide phase is mostly sensitive aggressive environments influence. The critical value of total molybdenum and tungsten concentration in MC should not exceed 15%. 

In the case of TiC, preferential evaporation of titanium leads to a change in the stoichiometry of the compound towards the carbon-rich end, the excess carbon being left diffuses into the carbide phase, and so the flux ratio of the two elements changes widi time until congruent vaporization is achieved. 

In the kinetics of formation of carbides by reaction of the metal widr CH4, the diffusion equation is solved for the general case where carbon is dissolved into tire metal forming a solid solution, until the concentration at the surface reaches saturation, when a solid carbide phase begins to develop on the free surface. If tire carbide has a tirickness at a given instant and the diffusion coefficient of carbon is D in the metal and D in the carbide. Pick s 2nd law may be written in the form (Figure 8.1)... 

Table 1. Formation of filled nanocapsules. Elements in shadowed boxes are those which were encapsulated so far. M and C under the chemical symbols represent that the trapped elements are in metallic and carbide phases, respectively. Numbers above the symbols show references.

The final section of the volume contains three complementary review articles on carbon nanoparticles. The first by Y. Saito reviews the state of knowledge about carbon cages encapsulating metal and carbide phases. The structure of onion-like graphite particles, the spherical analog of the cylindrical carbon nanotubes, is reviewed by D. Ugarte, the dominant researcher in this area. The volume concludes with a review of metal-coated fullerenes by T. P. Martin and co-workers, who pioneered studies on this topic. 

Now to complete the solution of the problem one would need to know the solution laws for iron, and a small amount of nickel, in each of these carbide phases, since equilibrium requires that and a , in the segregated carbide must be 0-74 and 0-08 respectively as well as a., being 0-18. At present nothing is known about these laws except that the metal atoms might well be randomly distributed in the carbide phase, in which case, as an example. 

The quadrupole doublet has an isomer shift corresponding to iron in the ferric or Fe " state. After reduction in H2 at 675 K the catalyst consists mainly of metallic iron, as evidenced by the sextet, along with some unreduced iron, which gives rise to two doublet contributions of Fe " and Fe " in the centre. The overall degree of iron reduction, as reflected by the relative area under the bcc ion sextet, is high. Fischer-Tropsch synthesis at 575 K in CO and FI2 converts the metallic iron into the Flagg carbide, Fe5C2. The unreduced iron is mainly present as Fe ". Exposure of the carburized catalyst to the air at room temperature leaves most of the carbide phase unaltered but oxidizes the ferrous to ferric iron. 

To verify that steady state catalytic activity had been achieved, the catalyst was allowed to operate uninterrupted for approximately 8 hours. The catalyst was then removed from the reactor and the surface investigated by XPS. The results are shown in Figure 2c. The two major changes in the XPS spectrun were a shift in the iron 2p line to 706.9 eV and a new carbon Is line centered at 283.3 eV. This combination of iron and carbon lines indicates the formation of an iron carbide phase within the XPS sampling volume.(J) In fact after extended operation, XRD of the iron sample indicated that the bulk had been converted to FecC2 commonly referred to as the Hagg carbide.(2) It appears that the bulk and surface are fully carbided under differential reaction conditions. 

At an Ni(110)-O surface exhibiting a (3 x 1) structure (0.3 ML of oxygen), benzene adsorption at room temperature induces a compression of the (3 x 1) added-row to a (2 x 1) structure. There was no evidence for a direct reaction between the surface oxygen and benzene, but on heating to 600 K the oxygen is removed (as CO) and the surface is clean, other than areas of a p(4 x 5)C carbidic phase.41... 

Jefferson s studies of the pyroxenoids has added greatly to our application of the way in which, through the intermediary of planar - or planar and Kinke - faults one structure is converted into another (45). And Audier, Jones and Bowen (46) have revealed how unit cell strips of Fe C may be accommodated as extended defects in the Fe C structure. Both these carbidic phases can be readily identified by HREM at the interface of iron catalysts used for the disproportionation of CO (to yield C j+CC ). 

For the development of a selectivity model it is helpful to have a picture of the surface of the catalyst to ht the explanation of how the product spectrum is formed. The fundamental question regarding the nature of the active phase for the FT and water-gas shift (WGS) reactions is still a controversial and complex topic that has not been resolved.8 Two very popular models to describe the correlations between carbide phase and activity are the carbide9 and competition models.10 There are also proposals that magnetite and metallic iron are both active for the FT reaction and carbides are not active11. These proposals will not be discussed in detail and are only mentioned to highlight the uncertainty that is still present on the exact phase or active site responsible for the FT and WGS reactions. 

Supported nanoparticles (1-1.5 nm) based on Ru4Pt2 entities have been obtained by using a Ru4Pt2(CO)i8 precursor on carbon black and fullerene soot [63]. XANES analysis showed differences between the interaction of nanoparticles with both carbon black and fullerene supports. In particular, a change in the electronic properties of the nanoparticles on fullerene is proposed this change was related to a strong interaction between the nanoparticle and a surface-atom, probably via the formation of a Ru-carbide phase. 

Upon prolonged exposure to temperatures above SOO F, the carbide phase of steel may be converted to graphite. Permissible, but not recommended for prolonged use above SOO F. 

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