Surface oxidation rate

Consider, for example, a carbon surface burning in a concentration of oxygen in the free stream specified by pmox. The burning is at a steady mass rate. Then the concentration of oxygen at the surface is some value mos. If the surface oxidation rate follows first-order kinetics, as Frank-Kamenetskii [21] assumed,... 

The modification with allylamine could be expected to not only reduce the surface oxidation rate but also maintain an efficient electronic transition feature that facilitates blue emission. The optical properties show significant size dependence due to the quantum confinement effect. The increase in the number of allylamine molecules could only result in a slight red shift of emission spectra. 

In characterizing HTC, X-Ray Diffraction is a very useful and reliable technique for indexing patterns of phases leading to phase identification in the corrosion product known as surface scale. In fact, this high temperature phenomenon is different from the mst layer formation (in the presence of moisture) since it virtually occurs in dry gaseous environments or molten salts, hi certain cases, HTC may be an internal oxidation process when oxygen diffusion is faster than the surface oxidation rate. 

Examination of oven-aged samples has demonstrated that substantial degradation is limited to the outer surface (34), ie, the oxidation process is diffusion limited. Consistent with this conclusion is the observation that oxidation rates are dependent on sample thickness (32). Impact property measurements by high speed puncture tests have shown that the critical thickness of the degraded layer at which surface fracture changes from ductile to brittle is about 0.2 mm. Removal of the degraded layer restores ductiHty (34). Effects of embrittled surface thickness on impact have been studied using ABS coated with styrene—acrylonitrile copolymer (35). 

A typical oxidation is conducted at 700°C (113). Methyl radicals generated on the surface are effectively injected into the vapor space before further reaction occurs (114). Under these conditions, methyl radicals are not very reactive with oxygen and tend to dimerize. Ethane and its oxidation product ethylene can be produced in good efficiencies but maximum yield is limited to ca 20%. This limitation is imposed by the susceptibiUty of the intermediates to further oxidation (see Figs. 2 and 3). A conservative estimate of the lower limit of the oxidation rate constant ratio for ethane and ethylene with respect to methane is one, and the ratio for methanol may be at least 20 (115). 

This is essentially a corrosion reaction involving anodic metal dissolution where the conjugate reaction is the hydrogen (qv) evolution process. Hence, the rate depends on temperature, concentration of acid, inhibiting agents, nature of the surface oxide film, etc. Unless the metal chloride is insoluble in aqueous solution eg, Ag or Hg ", the reaction products are removed from the metal or alloy surface by dissolution. The extent of removal is controUed by the local hydrodynamic conditions. 

Because the reaction takes place in the Hquid, the amount of Hquid held in the contacting vessel is important, as are the Hquid physical properties such as viscosity, density, and surface tension. These properties affect gas bubble size and therefore phase boundary area and diffusion properties for rate considerations. Chemically, the oxidation rate is also dependent on the concentration of the anthrahydroquinone, the actual oxygen concentration in the Hquid, and the system temperature (64). The oxidation reaction is also exothermic, releasing the remaining 45% of the heat of formation from the elements. Temperature can be controUed by the various options described under hydrogenation. Added heat release can result from decomposition of hydrogen peroxide or direct reaction of H2O2 and hydroquinone (HQ) at a catalytic site (eq. 19). 

In neutral and alkaline environments, the magnesium hydroxide product can form a surface film which offers considerable protection to the pure metal or its common alloys. Electron diffraction studies of the film formed ia humid air iadicate that it is amorphous, with the oxidation rate reported to be less than 0.01 /rni/yr. If the humidity level is sufficiently high, so that condensation occurs on the surface of the sample, the amorphous film is found to contain at least some crystalline magnesium hydroxide (bmcite). The crystalline magnesium hydroxide is also protective ia deionized water at room temperature. The aeration of the water has Httie or no measurable effect on the corrosion resistance. However, as the water temperature is iacreased to 100°C, the protective capacity of the film begias to erode, particularly ia the presence of certain cathodic contaminants ia either the metal or the water (121,122). 

At ambient temperatures beryUium is quite resistant to oxidation highly poHshed surfaces retain the brilliance for years. At 700°C oxidation becomes noticeable in the form of interference films, but is slow enough to permit the working of bare beryUium in air at 780°C. Above 850°C oxidation is rapid to a loosely adherent white oxide. The oxidation rate at 700°C is paraboHc but may become linear at this temperature after 24—48 hours of exposure. In the presence of moisture this breakaway oxidation occurs more rapidly and more extensively. BeryUium oxide [1304-56-9] BeO, forms rather than beryUium nitride [1304-54-7] Be2N2, but in the absence of oxygen, nitrogen attacks beryUium above 900°C. 

The classifications in Table 16-3 are intended only as a rough guide. For example, a carbon molecular sieve is truly amorphous but has been manufactured to have certain structural, rate-selective properties. Similarly, the extent of hydrophobicity of an activated carbon will depend on its ash content and its level of surface oxidation. 

What of the corrosion resistance of new turbine-blade alloys like DS eutectics Well, an alloy like NiaAl-NisNb loses 0.05 mm of metal from its surface in 48 hours at the anticipated operating temperature of 1155°C for such alloys. This is obviously not a good performance, and coatings will be required before these materials are suitable for application. At lower oxidation rates, a more insidious effect takes place - preferential attack of one of the phases, with penetration along interphase boundaries. Obviously this type of attack, occurring under a break in the coating, can easily lead to fatigue failure and raises another problem in the use of DS eutectics. 

The aforementioned inconsistencies between the paralinear model and actual observations point to the possibility that there is a different mechanism altogether. The common feature of these metals, and their distinction from cerium, is their facility for dissolving oxygen. The relationship between this process and an oxidation rate which changes from parabolic to a linear value was first established by Wallwork and Jenkins from work on the oxidation of titanium. These authors were able to determine the oxygen distribution in the metal phase by microhardness traverses across metallographic sections comparison of the results with the oxidation kinetics showed that the rate became linear when the metal surface reached oxygen... 

Theories of the oxidation of tantalum in the presence of suboxide have been developed by Stringer. By means of single-crystal studies he has been able to show that a rate anisotropy stems from the orientation of the suboxide which is precipitated in the form of thin plates. Their influence on the oxidation rate is least when they lie parallel to the metal interface, since the stresses set up by their oxidation to the pentoxide are most easily accommodated. By contrast, when the plates are at 45° to the surface, complex stresses are established which create characteristic chevron markings and cracks in the oxide. The cracks in this case follow lines of pores generated by oxidation of the plates. This behaviour is also found with niobium, but surprisingly, these pores are not formed when Ta-Nb alloys are oxidised, and the rate anisotropy disappears. However, the rate remains linear it seems that this is another case in which molecular oxygen travels by sub-microscopic routes. 

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