Hydrogen in Steels | Hydrogen | Steelmaking

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STEEL IN HYDROGEN
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  Hydrogen in Steels Abstract:  The control of hydrogen content in steels is an important task of steelmakers because of its generallydetrimental effects on processing characteristics and service performance of steel products. Just a few partsper million of hydrogen dissolved in steel can cause hairline cracks (flakes), hydrogen embrittlement,hydrogen blistering and loss of tensile ductility, particularly in large steel castings ingots, blooms and slabs.Hydrogen has been and always will be a source of various problems within steel production because of itsgenerally detrimental effects on processing characteristics and service performance of steel products. If thehydrogen content of the molten steel exceeds the solubility limit of hydrogen in solid iron, the hydrogen will berejected during solidification, and this leads to pinhole formation and porosity in steel. Just a few parts per million of hydrogen dissolved in steel can cause hairline cracks (flakes), hydrogen embrittlement, hydrogenblistering and loss of tensile ductility, particularly in large steel castings ingots, blooms and slabs. Thermodynamic considerations  According to Sievert's law, a di-atomic gas reacts with a metal and is dissolved into atomic form. In the case of hydrogen solubility, data are summarized by the following equations and are shown graphically in Fig 1.½H 2(G) = [H] (dissol. in metal) (1)The equilibrium constant of reaction (1) is:K= [ppm H] / ( p H2 ) ½ (2) Figure 1: Solubility of Hydrogen in pure iron or low-alloy steel at 1 atm pressure of H 2 The temperature dependence of K in iron in equilibrium with p H2 = 1 atm is as follows for  α , δ (bcc) iron, γ (fcc)iron and liquid iron ( I ) are given by the following equations: log K α,δ = -1418/T+ 1.628 (3) log K γ = -1182/T+ 1.628 (4) log K I = -1900/T+ 2.423 (5)where the temperature T is in degrees Kelvin.During rapid cooling of a heavy-section steel casting, e.g. thick slab or bloom, there will be little diffusion of  H  out of casting. Because of the hydrogen solubility decreases with a decreasing temperature, there will be a buildup of H 2 pressure in the steel matrix during rapid cooling. For the limiting case of no hydrogen diffusion, the H 2    pressures will be as shown below in the steel containing 2, 4 and 8 ppm H. Table 1: Build up of H 2 pressure in the steel matrix during rapid cooling Temperature, °CH 2 pressure, atm2 ppm H4 ppm H8 ppm H γ14000.0580.230.90γ11000.120.481.90γ9000.230.923.70α9000.582.339.30α7001.837.3029.2α50010.441.6166.5 Hydrogen pickup Numerous sources of hydrogen exist during the melting, the ladle processing and the casting operations.Hydrogen pickup in the steel is primarily due to the water associated with the slagmaking materials and as animpurity in the alloy additions and the carburizers. Hydrogen is generally not a problem in the BOF steelmakingexcept in the bottom blown converters (Q-BOP) where natural gas (CH 4 ), used as a tuyere coolant, is the major source of hydrogen.The lime, e.g. calcium oxide (CaO), is an important addition during steelmaking operations, especially duringladle metallurgy to adjust slag chemistry, to facilitate inclusion removal and for desulphurization of steels. Due tothe moist atmospheric conditions, lime can become hydrated to form calcium hydroxide. This hydrated limewhen added to the liquid melt decomposes according to the reactionCa(OH) 2 (s) = CaO(s) + H 2 O(g) (6)The water vapor formed dissociates on the liquid steel surface causing hydrogen pickup by the followingreactionH 2 O(g) = 2[H] + [O] (7)Figure 2, 3 and 4 show results of experiments performed in laboratory and on the industrial scale to investigatethe effect of both calcium hydroxide and coke addition on the hydrogen content in carbon steels. All figures show the variation of hydrogen pickup as a function of additional Ca(OH) 2 and coke. In Figure 2showed results where is the Ca(OH) 2 was added on top of the liquid metal while in Figure 3 showed results of case that the calcium hydroxide was added along with the CaO-Al 2 O 3 slag. Figure 4 shows the effect of metallurgical coke addition on the hydrogen content of low carbon steel.  Figure 2: Hydrogen pickup due to Ca(OH) 2 addition on the top of the slag Figure 3: Hydrogen pickup due to Ca(OH) 2 addition along with the CaO-Al 2 O 3 slag  Figure 4: Change in the hydrogen content of the liquid metal as a function of coke addition for 90 tone heat As a follow up of these trials it can be seen that the hydrogen pickup increases in steel with both addition of limee.g. Ca(OH) 2 and coke. The capacity of the melt to absorb the hydrogen decreases as the hydrogen content inthe melt approaches the equilibrium value. The capacity to absorb hydrogen increases as the steel isdeoxidized.The control of hydrogen content in steels is an important task of steelmakers during BOF and EAF steelmaking.The control of the pickup of hydrogen must include the use of inputs with low moisture or hydrogen content,avoidance of late addition of lime during smelting process, minimization of carry over slag, efficient degassing atdeep vacuum and intense purging, recarburization with low hydrogen pet coke, control of ladle slag basicity etc.
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