Stability of Carbides

At the high gas velocities required for measuring intrinsic rates at low eonversions away from equilibrium, the lack of back-diffusion of product gases may lead to oxidation of the nickel catalyst, as methane behaves as an inert in the Ni/NiO equilibrium (refer to Section 4.1). The problem is solved by addition of hydrogen to the feed. Axial dispersion also plays a signifieant role in determining the stability of carbide catalysts (refer to Section 4.1). 

Carbon content is usually about 0.15% but may be higher in bolting steels and hot-work die steels. Molybdenum content is usually between 0.5 and 1.5% it increases creep—mpture strength and prevents temper embrittlement at the higher chromium contents. In the modified steels, siUcon is added to improve oxidation resistance, titanium and vanadium to stabilize the carbides to higher temperatures, and nickel to reduce notch sensitivity. Most of the chromium—molybdenum steels are used in the aimealed or in the normalized and tempered condition some of the modified grades have better properties in the quench and tempered condition. 

AISI 321 and 347 are stainless steels that contain titanium and niobium iu order to stabilize the carbides (qv). These metals prevent iatergranular precipitation of carbides during service above 480°C, which can otherwise render the stainless steels susceptible to iatergranular corrosion. Grades such as AISI 316 and 317 contain 2—4% of molybdenum, which iacreases their creep—mpture strength appreciably. In the AISI 200 series, chromium—manganese austenitic stainless steels the nickel content is reduced iu comparison to the AISI 300 series. 

Figure 3.2 Chemical potential diagrams for the transport of silicon carbide by chlorine, showing that the much greater stability of SiCU than CCI4 makes this process very inefficient, while the use of HCl as the transporting gas can be operated under optimum conditions...

The expected oxidation mechanisms of carbides and silicides can be analysed from a thermodynamic viewpoint by a comparison of the relative stabilities... 

The C-C distance in CaC2 is close to that in ethyne (120.5 pm) and it has been suggested that the observed increase in the lanthanoid and actin-oid carbides results from a partial localization of the supernumerary electron in the antibonding orbital of the ethynide ion [C=C] (see p. 932). The effect is noticeably less in the sesquicarbides than in the dicarbides. The compounds EuC2 and YbC2 differ in their lattice parameters and hydrolysis behaviour from the other LnC2 and this may be related to the relative stability of Eu and Yb (p. 1237). 

Other potential applications are ceramic powders coated with their sintering aids, zirconia coated withyttria stabilizer, tungsten carbide coated with cobalt, or nickel, alumina abrasive powders coated with a relatively brittle second phase such as MgAl204 and plasma spray powders without the segregation of alloying elements. 

Both industry experience and research work indicate that postweld heat treatment (PWHT) of chromium-molybdenum steels in hydrogen service improves resistance to high temperature hydrogen attack. The PWHT stabilizes alloy carbides. This reduces the amount of carbon available to combine with hydrogen, thus improving high temperature hydrogen attack resistance. 

The addition of carbide stabilizers to steel reduces the tendency toward internal Assuring. Elements such as chromium, molybdenum, tungsten, vanadium, titanium, and niobium reduce the number of nucleation sites by forming more stable alloy carbides which resist breakdown by hydrogen and, therefore, decrease the propensity to form methane.9 The solid-line curves in Figure 1 reflect the increased resistance to internal attack when molybdenum and chromium are present. 

Titanium Carbide. Carbides of transition metals are known for their hardness, wear resistance and also for their high electrical conductivity, which makes them attractive as a refractory coating material for cutting tools or bearings. Only little work has been done on the electrochemical stability of transition metal carbides with the exception of TiC, where a corrosion and passivation mechanism was suggested by Hintermann et al. [119,120]. This mechanism was confirmed on amorphous TiC produced by metal-... 

In thick samples, a boron oxide/boron carbide crust has been detected on the surface of the polymer. This inorganic surface layer has a shielding effect on the inner polymer layers, further enhancing the thermal stability of the material. Poly(m-carborane-siloxane)s have therefore been considered as surface coatings for organic materials, providing protection from erosion effects. 

Schouten, S.C., Gijzeman, O.L., and Bootsma, G.A., Reaction of methane with nickel single crystal surfaces and the stability of surface nickel carbides, Bull. Soc. Chim. Belg., 88, 541,1979. 

The high-temperature stability of SiC-based ceramics is well-known, and therefore its composite materials have been investigated for application to high-tem-perature structural materials [19-21]. However, well-known SiC-based fibers and matrix-materials stained with alkali salt are easily oxidized at high temperatures in air [22]. This would be a serious problem when these materials are used near the ocean or in a combustion gas containing alkali elements. In particular, a silicon carbide fiber containing boron (a well-known sintering aid for SiC) over 1 wt% was extensively oxidized under the above condition. In this... 

Carbides have been studied for ORR in acidic media.219,220 Tungsten carbide was shown to be promising for ORR in acidic media,219 though WC has a corrosion problem in acidic systems.221 To increase the stability of the catalyst in PEM fuel cell conditions, tantalum was added to tungsten carbide.220 The Ta-WC catalyst was tested under fuel cell conditions and compared to WC. The corrosion resistance was markedly improved as well as the activity for ORR. It is thought that a Ta-W alloy acted as a stabilizer for the catalyst while WC remained the active site for ORR.220... 

Phosphoric Acid Fuel Cell (PAFC) Phosphoric acid concentrated to 100% is used for the electrolyte in this fuel cell, which operates at 150 to 220°C. At lower temperatures, phosphoric acid is a poor ionic conductor, and CO poisoning of the Pt electrocatalyst in the anode becomes severe. The relative stability of concentrated phosphoric acid is high compared to other common acids consequently the PAFC is capable of operating at the high end of the acid temperature range (100 to 220°C). In addition, the use of concentrated acid (100%) minimizes the water vapor pressure so water management in the cell is not difficult. The matrix universally used to retain the acid is silicon carbide (1), and the electrocatalyst in both the anode and cathode is Pt. 

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