• Corrosion Science and Technology
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• v.9 no.1
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• pp.20-28
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• 2010

According to the bipolar model, ion selectivity of some species in the passive film is important factor to control the passivation. An increase of cation selectivity of outer layer of the passive film can stabilize the film and improves the corrosion resistance. Therefore, the formation and roles of ionic species in the passive film should be elucidated. In this work, two types of solution (hydrochloric or sulfuric acid) were used to test high N and Mo-bearing stainless steels. The objective of this work was to investigate the formation of oxyanions in the passive film and the roles of oxyanions in passivation of stainless steel. Nitrogen exists as atomic nitrogen, nitric oxide, nitro-oxyanions (${NO_x}^-$), and N-H species, not nitride in the passive film. Because of its high mobility, the enriched atomic nitrogen can act as a reservoir. The formation of N-H species buffers the film pH and facilitates the formation of oxyanions in the film. ${NO_x}^-$ species improve the cation selectivity of the film, increasing the oxide content and film density. ${NO_x}^-$ acts similar to a strong inhibitor both in the passive film and at active sites. This facilitates the formation of chromium oxide. Also, ${NO_x}^-$ can make more molybdate and nitric oxide by reacting with Mo. The role of Mo addition on the passivation characteristics of stainless steel may differ with the test environment. Mo exists as metallic molybdenum, molybdenum oxide, and molybdate and the latter facilitates the oxide formation. When nitrogen and molybdenum coexist in stainless steel, corrosion resistance in chloride solutions is drastically increased. This synergistic effect of N and Mo in a chloride solution is mainly due to the formation of nitro-oxyanions and molybdate ion. Oxyanions can be formed by a 'solid state reaction' in the passive film, resulting in the formation of more molybdate and nitric oxide. These oxyanions improve the cation selectivity of the outer layer and form more oxide and increase the amount of chromium oxide and the ratio of $Cr_2O_3/Cr(OH)_3$ and make the film stable and dense.

• Korean Journal of Materials Research
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• v.25 no.9
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• pp.497-502
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• 2015

The hardenability of boron steel specimens with different molybdenum and chromium contents was investigated using dilatometry and microstructural observations, and then was quantitatively measured at a critical cooling rate corresponding to 90 % martensite hardness obtained from a hardness distribution plotted as a function of cooling rate. Based on the results, the effect of an austenitizing temperature on the hardenability and tensile properties was discussed in terms of segregation and precipitation behavior of boron atoms at austenite grain boundaries. The molybdenum addition completely suppressed the formation of pro-eutectoid ferrite even at the slowest cooling rate of $0.2^{\circ}C/s$, while the chromium addition did at the cooling rates above $3^{\circ}C/s$. On the other hand, the hardenability of the molybdenum-added boron steel specimens decreased with an increasing austenitizing temperature. This is associated with the preferred precipitation of boron atoms since a considerable number of boron atoms could be concentrated along austenite grain boundaries by a non-equilibrium segregation mechanism. The secondary ion mass spectroscopy results showed that boron atoms were mostly segregated at austenite grain boundaries without noticeable precipitation at higher austenitization temperatures, while they formed as precipitates at lower austenitization temperatures, particularly in the molybdenum-added boron steel specimens.

• Journal of the Korean Society for Heat Treatment
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• v.29 no.4
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• pp.181-189
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• 2016

The variation in microstructure and mechanical properties during heat treatment was examined in a series of 0.27% C-1.0% Si-1.5% Mn steels with chromium contents in the range of 0 to 1.0 wt%. It was found that chromium decreased the martensite packet size through the austenite grain refinement and increased tensile strength in the as-quenched steel, about 70 MPa per 1.0 wt%. The 0.27% C-1.0% Si-1.5% Mn-1.0% Cr steel showed tensile strength of 1700 MPa in the as-quenched steel. The 0.27% C-1.0% Si-1.5% Mn-1.0% Cr steel revealed a full martensitic structure after air cooling from $900^{\circ}C$ to room temperature, showing air hardening characteristics. Tempering at $150^{\circ}C$ slightly decreased the tensile strength and increased elongation, which is in a good agreement with impact toughness result.

• Corrosion Science and Technology
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• v.14 no.6
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• pp.313-324
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• 2015

Austenitic stainless steels have been widely used in many engineering fields because of their high corrosion resistance and good mechanical properties. However, welding or aging treatment may induce intergranular corrosion, stress corrosion cracking, pitting, etc. Since these types of corrosion are closely related to the formation of chromium carbide in grain boundaries, the alloys are controlled using methods such as lowering the carbon content, solution heat treatment, alloying of stabilization elements, and grain boundary engineering. This work focused on the effects of aging and UNSM (Ultrasonic Nano-crystal Surface Modification) on the intergranular corrosion of commercial 316L stainless steel and the results are discussed on the basis of the sensitization by chromium carbide formation and carbon segregation, residual stress, grain refinement, and grain boundary engineering.

• Journal of the Korean Society for Heat Treatment
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• v.19 no.2
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• pp.83-89
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• 2006

The surface phase changes, the hardness variations, the nitrogen contents and the corrosion resistances of 17-4 PH stainless steel have been investigated after nitrogen permeation(solution nitriding) at a temperature ranges from $1050^{\circ}C$ to $1150^{\circ}C$ The phases appeared at the nitrogen-permeated surface layer were shown to martensite plus austenite and austenite, depending on the variation of nitrogen and chromium contents. And the surface hardness was also depended on the phases appeared at the surface layer from 370 Hv to 220 Hv. The precipitates exhibited at the nitrogen-permeated surface layer were niobium nitride, niobium chromium nitride and carbo-nitride in the austenite and martensite matrices. The surface nitrogen contents were followed by the Cr contents of the surface layers, representing 0.55% at the temperatures of $1050^{\circ}C$ and $1150^{\circ}C$ respectively, and 0.96% at $1100^{\circ}C$ at the distances of $60{\mu}m$ from the outmost surface. From the comparison of the corrosion resistances between nitrogen-permeated and solution-annealed steels, nitrogen permeation remarkably improved the corrosion resistance in the solution of 1 N $H_2SO_4$ due to the increase of nitrogen content in the surface austenite phase.

• Proceedings of the KWS Conference
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• 2002.10a
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• pp.250-254
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• 2002

Intergranular corrosion of austenitic stainless steels is a conventional and momentous problem during welding and high temperature use. One of the major reasons for such intergranular corrosion is so-called sensitization, i.e., chromium depletion due to chromium carbide precipitation at grain boundaries. Conventional methods for preventing sensitization of austenitic stainless steels include reduction of carbon content in the material, stabilization of carbon atoms as non-chromium carbides by the addition of titanium, niobium or zirconium, local solution-heat-treatment by laser beam, etc. These methods, however, are not without drawbacks. Recent grain boundary structure studies have demonstrated that grain boundary phenomena strongly depend on the crystallographic nature and atomic structure of the grain boundary, and that grain boundaries with coincidence site lattices are immune to intergranular corrosion. The concept of "grain boundary design and control", which involves a desirable grain boundary character distribution, has been developed as grain boundary engineering. The feasibility of grain boundary engineering has been demonstrated mainly by thermomechanical treatments. In the present study, a thermomechanical treatment was tried to improve the resistance to the sensitization by grain boundary engineering. A type 304 austenitic stainless steel was pre-strained and heat-treated, and then sensitized, varying the parameters (pre-strain, temperature, time, etc.) during the thermomechanical treatment. The grain boundary character distribution was examined by orientation imaging microscopy. The intergranular corrosion resistance was evaluated by electrochemical potentiokinetic reactivation and ferric sulfate-sulfuric acid tests. The sensitivity to intergranular corrosion was reduced by the thermomechanical treatment and indicated a minimum at a small roll-reduction. The frequency of coincidence-site-lattice boundaries indicated a maximum at a small strain. The ferric sulfate-sulfuric acid test showed much smaller corrosion rate in the thermomechanically-treated specimen than in the base material. An excellent intergranular corrosion resistance was obtained by a small strain annealing at a relatively low temperature for long time. The optimum parameters created a uniform distribution of a high frequency of coincidence site lattice boundaries in the specimen where corrosive random boundaries were isolated. The results suggest that the thermomechanical treatment can introduce low energy segments in the grain boundary network by annealing twins and can arrest the percolation of intergranular corrosion from the surface.

• Corrosion Science and Technology
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• v.2 no.2
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• pp.59-67
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• 2003

Electrochemical potentiokinetic reactivation (EPR) tests are used to evaluate the degree of sensitization (DOS) of stainless steels and nickel base alloys. The validity of EPR test to detect DOS of these alloys, however, depends all the electrolyte composition employed. The existence of precipitates such as NbC, and TiC, etc. in the alloys also affects the reactivation behaviors of these alloys. In this investigation, the reactions involved during EPR processes are analyzed. In 0.5 M $H_2SO_4$+ 0.01 M KSCN electrolyte, a reactivation peak associated with the localized attack around NbC, different from that of intergranular corrosion, is observed for the solution annealed 347 SS. For solution annealed Alloy 600, matrix corrosion and localized attack around TiC with distinct anodic peaks appeared in the EPR curves are seen in the $H_2SO_4$+ KSCN electrolyte. With proper adjustment of elect rolyte composition, the contribution from intergranular corrosion, as a result of chromium carbide precipitation along the grain boundaries, can be distingui shed from the matrix and localized corrosion for the sensitized Alloy 600.

• Corrosion Science and Technology
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• v.5 no.5
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• pp.181-188
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• 2006

In this study, the characteristics of the experimentally produced high N-high Cr bearing stainless steels are discussed as a part of applications of materials for FGD (Fuel Gas Desulfurization) system of thermal power plants or for power plants using seawater as coolant. Corrosion resistance of developed alloys is especially investigated in detail. Corrosion characteristics of vacuum melted cast are shown to be superior to that of air melted one. From the viewpoint of CPT, It is estimated that the differences of corrosion resistance are $21.8^{\circ}C{\sim}24.6^{\circ}C$ at PRE 40 and $8^{\circ}C{\sim}12.4^{\circ}C$ at PRE 50, and the gaps becomes bigger as the PRE values are lower. In the evaluation of corrosion resistance in alloy A2501, Z3101, and A3301 according to Cr concentration, alloy A3301 shows a deviation from the general tendency in chloride solutions. It has relatively high PRE value as 48.6, but it has relatively poor pitting resistance. It is, however, difficult to observe a specific phase except ferrite in microstructure analysis and neither detects special phase such as sigma phase.

• Journal of the Korean Ceramic Society
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• v.24 no.6
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• pp.519-526
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• 1987

TiC was deposited onto several substrate steels by the Chemical Vapor Deposition technique from TiCl4-CH4-H2 gas mixtures in the horizontal resistance furnace. Deposition rates and morphologies of the coatings were investigated with the carbon contents. Deposition thickness increased linearly with the deposition time in the Presence of CH4 gas. The various interlayers of coating by EDS and X-ray Diffraction were proved as Cr7C3 and Fe3C. Chromium contents did not affect the preferred orientation of TiC deposit. The deposition was controlled by a mass transport and a surface reaction in case of 1 wt% C-5.25 wt% Cr steel irrespective of deposition temperature.

• Journal of Korea Foundry Society
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• v.30 no.4
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• pp.151-156
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• 2010

The high-strength low-alloy (HSLA) steels have low carbon contents (0.05~0.25% C) in order to produce adequate formability and weldability, and they have manganese contents up to 1.7%. Small quantities of silicon, chromium, nickel, copper, aluminum, molybdenum are used in various combinations. The results contained in this paper can provide the valuable information on the development of $-40^{\circ}C$ low temperature HSLA. Furthermore, the present experimental data will provide important database for casting steel materials of the offshore structure.