Factors affecting solubility of Hydrogen in Steel:

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.

Effect of Oxygen content

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.

4. Effect of Sulphur content

Like oxygen, sulphur also retards the rate of H2O reaction with the liquid
iron because of its surface active property. Its pronounced effect on the
hydrogen absorption can be seen in highly deoxidized steel. When the
oxygen content of the liquid metal is very low, it is susceptible to
significant hydrogen pickup, however, presence of a high sulphur level
prevents hydrogen absorption due to its surface active property.

Sources of Hydrogen in Steel:

1. Hydrogen pickup from Ca (OH)2
CaO is an important addition during steelmaking operations, especially
during ladle metallurgy. Hydrated lime which exists as Ca(OH)2 was found to
be a source of hydrogen. Under experimental conditions in this study, about 2
percent of the hydrogen present in the hydroxide was found to go into liquid
metal. This low value is possibly because Ca(OH)2 has a decomposition
temperature of 811 K which is low as compared to steelmaking temperature
of more than 1800 K. Consequently most of the water vapour dissociated from
the hydroxide escapes into the atmosphere before it could further dissociate
and enter as hydrogen into the melt. Hydrogen pickup in steel primarily occurs
from the dissociation of water. Calcium oxide is added to adjust slag
chemistry, to facilitate inclusion removal and for desulfurization during the
secondary steelmaking. Due to the moist atmospheric conditions, lime can
become hydrated to form calcium hydroxide. This hydrated lime when added
to the liquid melt decomposes according to the reaction

Ca(OH)2 (s) = CaO (s) + H2O (g)

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

2. Hydrogen Pickup from Carburizers

Addition of metallurgical coke, having close to 0.2 % hydrogen content, to
medium carbon steel did not result in any hydrogen pickup by the melt. A possible
explanation is the loss of more than 40% of the hydrogen in the form of volatiles
upon heating this coke to steelmaking temperatures. Petroleum coke, on the other
hand, caused a hydrogen pickup proportional to the amount of coke addition. A
total hydrogen recovery of about 10% was registered from these additions. The
effect of metallurgical coke addition on the hydrogen content of low carbon steel
was investigated in a trial at Electro-Nite. The hydrogen partial pressure values
measured by HYDRIS were used to obtain the actual hydrogen concentration.

3. Hydrogen Pickup during Tapping

Hydrogen pickup occurs from the air bubble entrainment during the tapping.
Sometime Computational Fluid Dynamic software, used to compute the total
interfacial area of the bubbles in contact with the liquid metal. Mixed control
models, incorporating liquid phase mass transfer and chemical kinetics in
series, were mainly used to calculate the hydrogen pickup for different
operating conditions. Different models found to predict the hydrogen pickup
value ranging from 0.5 to 8 ppm respectively for different oxygen and sulphur
content in the metal and partial pressure of water vapour in the atmosphere.
The amount of moisture in the air will depend on the temperature and the
relative humidity. Hence, for any given temperature, the water vapour partial
pressure will be the product of the relative humidity and the saturated vapour
pressure. For instance, on a typical summer day when the relative humidity is
as high as 80%, the water vapour pressure will be around 0.04 atmospheres
while on a winter day for a relative humidity of 30% the vapour pressure is
less than 0.01 atmospheres. Nonetheless high moisture content in the ambient
atmosphere is a favourable condition for a higher hydrogen pickup.