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The di-atomic H gas reacts with the steel and is dissolved into it in atomic form
as per the Sieverts law. The solubility of H in steels is strongly dependent on
crystal structure, temperature and composition.
1. Effect of Temperature
As the temperature of steel will be more, greater is the solubility of hydrogen
in the melt.
H2 (g) =2 [H] (dissolved in steel)
The following equation represents equilibrium constant in the above reaction.
K = [ppm H]/ (pH2)
The temperature dependence of K in iron in equilibrium with pH2 = 1 atm is as
follows for alpha, delta (bcc) iron, gamma (fcc) iron, and liquid iron (liquid) are
given by the following equations.
Log K (alpha, delta) = -1418/T+ 1.628
Log K (gamma) = -1182/T+ 1.628
Log K (liquid) = -1900/T+ 2.423
Where the temperature T is in degrees Kelvin.
The solubility of H in steel increases with temperature, ranging from less than
1ppm at room temperature to about 8 ppm at 704 deg C.
2. Effect of Composition
C normally improves the solubility of H, but the situation is rather complex at
high temperatures due to the formation of methane (CH4). Manganese (Mn) also
has a complex effect which may be based on crystal structure. Silicon (Si) and
aluminium (Al) lower H solubility. Chromium (Cr) in contents up to 10 %
increases H solubility, but higher concentration of Cr decreases it. The effect is
explained in terms of crystal structure, since about 10 % Cr closes the g-loop and
higher concentrations cause the steel to be fully ferritic up to the melting point.
Nickel (Ni) increases the solubility of H and in this case the solubility of H is
proportional to the content of Ni. Molybdenum (Mo) has no effect on H solubility.
Tungsten (W) decreases H solubility. Vanadium (V), titanium (Ti), niobium (Nb),
zirconium (Zr) and tantalum (Ta) all increase the solubility of H particularly at
low and moderate temperatures.
Cold working of steels has no effect on the solubility of H in pure iron, but the
presence of carbides results into a marked increase in the solubility. This is
because of H migrating to and collecting in the internal voids formed next to
carbide and inclusion particles. Thus, when a cold worked steel is annealed, some,
but not all, of the H is removed by diffusion.
3.
Since oxygen acts as a surface active element and retards the rate of hydrogen
absorption in liquid iron. It is important to note that it is not the oxygen in
solution in the bulk metal but the oxygen at the bubble surface which
determines the kinetics of the hydrogen reaction. Presence of low oxygen
content facilitates a high hydrogen pickup in accordance with reaction given
below
H2O = 2[H] + [O]
The rate of hydrogen pickup is controlled by the liquid phase mass transfer for
lower values and by chemical kinetics for higher values of the oxygen
concentration. Depending upon the type of tapping, this oxygen would react
with the liquid iron or the alloy elements in the melt. Consequently the oxygen
concentration at the bubble-liquid metal interface is what affects the reaction
kinetics.
Equation 1
The water vapour formed dissociates on the liquid steel surface causing
hydrogen pickup by the following reaction
H2O (g) = 2[H] + [O]
Equation 2