Effect of CO2 on the stability of steels with 1% and 13% Cr in saline water

In engineering storage sites for Carbon Sequestration the CO₂-induced corrosion of injection pipe steels is a relevant safety issue when emission gasses are compressed in deep geological layers. The reliability of the steels suitable for the geological onshore CCS-site (Carbon Capture and Storage) at Ketzin, Germany, is demonstrated in laboratory experiments in equivalent corrosive environment (T = 60 °C, p = 1-60 bar, aquifer water, CO₂-flow rate of 3 L/h, 700-8000 h exposure time). Corrosion kinetics and microstructures were characterized using specimens of the heat treated steel 42CrMo4 (1.7225) used for casing, and specimens of the martensitic stainless injection-pipe steel X46Cr13 (1.4034).     

Characterization of Corrosion Product Layers from CO2 Corrosion of 13Cr Stainless Steel in Simulated Oilfield Solution

The influence of temperature and flow rate on the characterization and mechanisms of corrosion product layers from CO₂ corrosion of 13Cr stainless steel was carried out in simulated oilfield solution. Cyclic potentiodynamic polarization method as well as weight loss tests in autoclave were utilized to investigate pitting corrosion behavior at various temperatures. Weight loss tests were performed at 100 and 160 °C under dynamic and static flow conditions. At the same time, the significant pitting parameters such as E _corr, E _pit, E _pp, ∆E, and I _pass in cyclic polarization curves at various temperatures were analyzed and compared for revealing the pitting behavior of 13Cr stainless steel. The surface measurement techniques such as SEM, XRD, and XPS were used to detect the corrosion product layers. The results showed that both temperature and flow rate had significant effects on characterization of corrosion product layers or passive films formed on 13Cr stainless steel in CO₂ corrosion system. At high temperature, lots of pits were formed at the localized corrosion areas of metal surfaces. Corrosion rates under the condition of 5 m/s were higher than those under the static condition regardless of the test temperatures.     

High temperature naphthenic acid corrosion and sulphidic corrosion of Q235 and 5Cr1/2Mo steels in synthetic refining media

The corrosion of Q235 and 5Cr1/2Mo steels in synthetic refining media containing naphthenic acid and/or sulphur compounds was studied to evaluate naphthenic acid corrosion (NAC), sulphidic corrosion (SC), and their interaction. Corrosion dependencies on the test duration, temperature, total acid number (TAN) and content of sulphur compound were assessed. Specimens after NAC and SC tests were characterized by SEM/EDX, and XRD. It is found that in liquid phase of media containing only naphthenic acid and at temperature about 230 °C, 5Cr1/2Mo and Q235 steels have almost the same NAC rate, and above 230 °C, 5Cr1/2Mo has a higher NAC rate than Q235 has due to the higher NAC activation energy (63.2 kJ mol⁻¹) of 5Cr1/2Mo than that of Q235 (54.0 kJ mol⁻¹), indicating that increasing temperature accelerates NAC rate of 5Cr1/2Mo more than that of Q235. In oil containing only dimethyl disulphide, the growth of SC film follows parabolic kinetics, and the film of Q235 grows faster than that of 5Cr1/2Mo while SC rate of Q235 is higher than that of 5Cr1/2Mo. In oil containing both naphthenic acid and dimethyl disulphide, 5Cr1/2Mo has a lower corrosion rate than Q235 has. On the basis of “naphthenic acid corrosion index” (NACI), the benefits of 5Cr1/2Mo over Q235 should ascribe to that the pseudo-passive film for 5Cr1/2Mo has better NAC resistance than that for Q235. This is close related to the existing of additional chromium sulphide (Cr₅S₈) on the pseudo-passive film of 5Cr1/2Mo, in contrast with the pyrrhotite (Fe₇S₈) and troilite (FeS) on the film of Q235.     

Towards improved integrated properties in FeCrPCB bulk metallic glasses by Cr addition

Fe-based soft-magnetic metallic glasses (MGs) of Fe_80−xCr_xP₉C₉B₂ (x = 0, 2, 5, 8 and 16 at.%) with high glass-forming ability (GFA), good soft-magnetic properties and high corrosion resistance are fabricated. With the addition of Cr to FePC-based alloys, the GFA and saturation magnetization (M_s) slightly decrease while the corrosion resistance effectively increases. The Fe–Cr–P–C–B BMGs exhibit good GFA and fully glassy rods can be produced up to 1.8 and 1.5 mm in diameter for the 2 and 5 at.% Cr added alloys, respectively. The alloys with 2 and 5 at.% Cr addition also show good soft-magnetic properties featured by high M_s of 1.16 and 1.04 T, low coercivity of 2.7 and 2.2 A/m, respectively. Besides, the corrosion behavior of the alloys was studied by immersion tests and potentiodynamic polarization measurements. It was found that the addition of Cr efficiently enhances the corrosion resistance of Fe–Cr–P–C–B alloys and the glassy alloy with 5 at.% Cr addition exhibits better corrosion resistance in comparison with the stainless steel SUS304 in 3 mass% NaCl solution. The combination of large GFA, good soft-magnetic properties, high corrosion resistance as well as low cost makes the Fe–Cr–P–C–B alloys as promising soft-magnetic and anti-corrosive materials for industrial applications.     

Application of polyaniline to galvanic anodic protection on stainless steel in H2SO4 solutions

A stand-alone polyaniline (PANI) film electrode was made and then applied to protect 1Cr13 stainless steel (a type of stainless steel typically used in China, 0–15% C, 13% Cr) from corrosion in highly acidic solution, up to 5 M H₂SO₄. The stand-alone PANI electrode and 1Cr13 were coupled to study their galvanic interactions. PANI is a cathode while 1Cr13 is an anodic. The results indicate that PANI with a certain area can quickly passivate the stainless steel and effectively maintain the steady passive state for a long period of time. This specific method of PANI preventing 1Cr13 from corrosion is called galvanic anodic protection (GAP). Moreover, the efficiency, mechanism, and security of GAP were discussed. The results demonstrate that the stand-alone PANI electrode may have a potential application to galvanic anodic protection on stainless steel in highly corrosive H₂SO₄ solutions.     

Investigation on carbon dioxide corrosion behaviour of HP13Cr110 stainless steel in simulated stratum water

The carbon dioxide corrosion behaviour of HP13Cr110 stainless steel in simulated stratum water is studied by potentiodynamic curve and electrochemical impedance spectroscopy (EIS); the micro-structure and composition of the corrosion scale formed at high-temperature and high-pressure are analyzed by scanning electron microscopy (SEM), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). The results show that 13Cr stainless steel is in passive state in the stratum water, the passive current density increases and the passive potential region decreases with increasing temperature. The corrosion scale formed at high-temperature and high-pressure is mainly composed of iron/chromium oxides and a little amount of FeCO₃.     

CORROSION OF 1Cr13 STAINLESS STEEL IN SOILS

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Electrochemical and Sulfide Stress Corrosion Cracking Behaviors of Tubing Steels in a H2S/CO2 Annular Environment

The electrochemical and sulfide stress corrosion cracking (SSCC) behaviors of 13Cr stainless steel and P110 steel were investigated in a simulated acidic annular environment with low-temperature and high-pressure H₂S/CO₂ using electrochemical methods, U-bend immersion tests, and scanning electron microscopy. In the solution containing high pressure CO₂, 13Cr, and P110 steels exhibited general corrosion and severe pitting, respectively. Compared with sweet corrosion, additional H₂S in the solution enhanced the corrosion of 13Cr steel but inhibited the corrosion of P110 steel. By contrast, in a solution containing 4 MPa CO₂ and different $ {P}_{{{\text{H}}_{ 2} {\text{S}}}}$ (0-0.3 MPa), the susceptibility of both 13Cr stainless steel and P110 steel toward SSCC was significantly promoted by increases in H₂S partial pressure. The 13Cr stainless steel exhibited higher susceptibility toward SSCC than P110 steel under a H₂S/CO₂ environment but lower susceptibility under a pure CO₂ environment.     

Corrosion of low-temperature nitrided molybdenum-bearing stainless steels

Austenitic stainless steels with up to 6.1 wt.% Mo were nitrided at 425 °C and examined in 0.1 M Na₂SO₄ without and with chlorides at pH 3.0 and 6.5. Nitrided steels exhibited an increased resistance to pitting, but at pH 3.0 they had a decreased resistance to general corrosion. After corrosion at pH 3.0 surface films contained chromium nitrides and oxides of Mo, Cr and Fe. It is proposed that the improved pitting resistance of nitrided steels is associated with the initially accelerated dissolution which leads to the accumulation of corrosion resistant CrN and of oxidised steel components.     

Microstructure and corrosion resistance of Cr/Cr2N multilayer film deposited on the surface of depleted uranium

Depleted uranium is widely used in national defence and nuclear energy fields. However, the inferior corrosion resistance limits its application. A Cr/Cr₂N film was prepared by magnetron sputtering on the uranium to improve its corrosion resistance. The Cr/Cr₂N film exhibits modulation structure. The introduction of the Cr/Cr₂N increases the corrosion potential; the corresponding current density decreases about three orders of magnitude. After polarization corrosion, the surface morphology of the Cr/Cr₂N-coated on uranium keeps integrated. Only a thin layer of film (∼40 nm) is oxidized. The Cr/Cr₂N film shows great potential in improving oxidation and corrosion resistance of depleted uranium.     

氮元素对2Cr13不锈钢CO2腐蚀产物膜结构和电化学性能的影响

利用高温高压釜进行2Cr13不锈钢的高温高压CO2腐蚀实验,用扫描电镜（SEM）和X射线光电子谱（XPS）分析腐蚀产物膜的形貌和成分,电化学交流阻抗谱测试腐蚀产物膜对2Cr13不锈钢电极过程影响,失重法评价两种2Cr13不锈钢CO2均匀腐蚀速率．结果表明：含氮钢的腐蚀产物膜结构比较疏松,腐蚀膜中的Cr2O3被CrN和Na3CrO4部分替代,并且含有较多的Fe3O4和α—FeOOH,其膜的电阻值比不含氮的2Cr13钢的小,腐蚀速率较大．     

Korrosion von Stahl vom Typ 03Cr18Ni13Mo2,5 und 02Cr25Ni22Mo2N bei der Harnstoffsynthese

Corrosion of steels type 03Cr18Ni13Mo2.5 and 02Cr25Ni22Mo2N in urea processing environment Long-term corrosion tests with the steel types 03Cr18Ni3Mo2.5 having different chemical compositions and chemical purity, and 02Cr25Ni22Mo2N have been carried out for up to 112517 and 64 699 h, respectively, in the urea manufacture environment. According to the results the first steel is a suitable material of construction for the high pressure parts of urea plant, provided its chromium content is higher than 18%. This quality meets requirements of urea grade steels. The steel 02Cr25Ni22Mo2N is even more corrosion resistant, but its use may be critical because of the high nickel content. A mathematical model has been developed for the weight loss-time-dependence and the results have been extrapolated to up to 1.5 ·10⁵h.     

Accelerated corrosion of five commercial steels under a ZnCl2-KCl deposit in a reducing environment typical of waste gasification at 673-773 K

The corrosion of five Fe-Cr commercial steels containing 0-18 wt.% Cr at 673-773 K has been studied in a reducing H₂-HCl-CO₂ atmosphere under a ZnCl₂-KCl deposit typical of waste gasification environments. In comparison with the behavior of the same steels in a similar gas mixture without salt deposit, all steels suffered from accelerated corrosion induced by the salt and formed porous scales with poor adherence to the underlying steels. Some Cl was detected close to the steels/scale interface, indicating that Cl-containing species were able to go through the scale down to the metal matrix. Even though the corrosion rates generally decreased with increasing Cr content, the high-Cr stainless steel SS304 was still unable to provide a good corrosion resistance against the ZnCl₂-KCl deposit. The reaction mechanisms are discussed on the basis of thermodynamic considerations and of the “active oxidation” model.     

Corrosion behavior of steel under wet and dry cycles containing Cr ion

The corrosion behavior of mild steel has been investigated during the wet and dry cyclic transitions containing Cr³⁺ ion added as sulfate in order to gain a better understanding of the influence of Cr on the atmospheric corrosion of steels. The corrosion rate during drying is greatly suppressed by the existence of Cr³⁺ ion in the electrolyte covered with the surface. Lower corrosion rates are observed during drying even if the surface have been polarized to negative potentials below −200 mV_SHE during the wet corrosion conditions in which the surface-covered electrolyte contains Cr³⁺ ion. This corrosion behavior is identical to the case of Cr-containing steel for the wet and dry cyclic transitions without the addition of Cr³⁺ ion. The composition of rust layer after the wet and dry cyclic transitions is composed of α-FeOOH, γ-FeOOH and Fe_3−δO₄ for both cases of non-Cr³⁺ and Cr³⁺-containing condition, and no significant difference in the mass fraction of the above rust substances between two conditions is observed by means of Mössbauer spectroscopy. The only difference in the rust layer is that the rust formed under the wet and dry cyclic transitions containing Cr³⁺ ion contains a certain amount of Cr near the steel/rust interface. Those results suggest that the role of Cr during the wet and dry cyclic transitions is the inhibition of the rust reduction and the formation of Fe²⁺-state intermediate by the existence of Cr in the rust layer. This can lead to the inhibition of the oxygen reduction during drying.     

The behavior of chromium and molybdenum in the propagation process of localized corrosion of steels

In order to clarify the effect of Cr and Mo on the propagation of localized corrosion of steels, the electrochemical behavior of pure chromium and molybdenum and of some stainless steels was studied under conditions similar to those existing inside occluded corrosion cells of steels. Oxygen-free FeCl₂ and/or CrCl₃ solutions were used for experiments. The surface films formed in these conditions were analyzed by means of AES and XPS. Cr is passive if the pH value >ca. 1.8 and Cr may retard the propagation of localized corrosion of steels in its early stage. The hydrolysis of Cr³⁺ may change the pH to even lower values. At such low pH and high Cl^? concentrations, Cr is active in the potential range of interest for localized corrosion of steels. Mo is passive under these more acidic conditions and the passivity of Mo in this potential range is attributed to the formation of a film of MoO₂ (or hydrated oxide), which is extremely thin but very protective. Mo is thus effective to retard the propagation of localized corrosion of steels in its more advanced stage.     

Electrochemical Corrosion Investigations on Anaerobic Treated Distillery Effluent

Present study is focused on the corrosivity of anaerobic treated distillery effluent and corrosion performance of mild steel and stainless steels. Accordingly, electrochemical polarization tests were performed in both treated distillery and synthetic effluents. Polarization tests were also performed in synthetic solutions and it was observed that Cl^? and K⁺ increase whereas SO₄ ^?, PO₄ ^?, NO₃ ^?, and NO₂ ^? decrease the corrosivity of effluent at alkaline pH. Further, comparison in corrosivity of distillery and synthetic effluents shows the former to be less corrosive and this is assigned due to the presence of amino acids and melanoidins. Mild steel experienced to have the highest corrosion rate followed by stainless steels—304L and 316L and lowest in case of SAF 2205. Relative corrosion resistance of stainless steels is observed to depend upon Cr, Mo, and N content.     

Interfacial morphology and corrosion resistance of Fe–B cast steel containing chromium and nickel in liquid zinc

The interfacial morphology and corrosion resistance of low carbon Fe–B cast steels in zinc bath at 520 °C were investigated. The results show Fe–B cast steel containing high Cr and Ni exhibits the best corrosion resistance to liquid zinc. The corrosion layers are composed of Γ-Fe₃Zn₁₀, δ-FeZn₁₀, ξ-FeZn₁₃ and η-Zn. The corrosion behaviour of Fe–B cast steels includes the following processes: the preferential leach and dissolution of Cr and Ni, the formation of Fe–Zn compounds controlled by zinc atom diffusion, and the spalling of borides without the supporting role of α-(Fe, Cr) matrix corroded by liquid zinc.     

Stress corrosion cracking of 13% Cr martensitic steels in sodium chloride solutions in the presence of thiosulphate

The stress corrosion cracking (SCC) susceptibility of 13% Cr martensitic (UNS S42000) and supermartensitic (UNS S41125) steels in sodium chloride solutions in the presence of thiosulphate was evaluated by slow strain rate tests (SSRT). The tests were performed in 5% sodium chloride solutions buffered at pH 2.7, 3.5, 4.5 and 6.0 in the absence and presence of thiosulphate in a concentration range between 10⁻⁶ and 10⁻³ M, at 25 ± 0.1 °C. The electrochemical behaviour of the two steels in the different solutions was determined by recording the anodic and cathodic polarisation curves. 13% Cr martensitic steel showed SCC in 5% sodium chloride solutions with pH ≤ 4.5 in the presence of 3 × 10⁻⁶ M thiosulphate. Decreasing the chloride ion concentration from 50 to 10 g/l, the critical concentration of thiosulphate to provoke SCC susceptibility increased from 3 × 10⁻⁶ to 1 × 10⁻⁵ M. The resistance to SCC of the supermartensitic steel was higher than that of the martensitic steel. The critical concentration of thiosulphate to induce SCC on the supermartensitic steel were 1 × 10⁻⁵ M at pH 2.7 and 1 × 10⁻⁴ M at pH 3.5. At pH ≥ 4.5 the supermartensitic steel did not crack. The anodic and cathodic polarisation curves evidenced the influence of the thiosulphate on the corrosion and the activation effect on the steels. The SCC of the two steels was attributed to hydrogen embrittlement produced by sulphur and hydrogen sulphide formed by dismutation and reduction of thiosulphate.     

Intergranular corrosion of Ti-stabilized 11 wt% Cr ferritic stainless steel for automotive exhaust systems

Intergranular corrosion (IGC) of type 409L ferritic stainless steel (FSS) was investigated. A free-exposure corrosion and a double loop electrochemical potentiokinetic reactivation (DL-EPR) tests were conducted to examine IGC of the FSS. IGC occurred in the specimens aged at the temperature range of 400–600 °C that has the sensitization nose located around 600 °C. The critical I_r/I_a value was determined to be about 0.03 above which IGC occurred. Based on the analysis of the intergranular precipitates by an energy dispersive spectroscopy (EDS) and a transmission electron microscopy (TEM), IGC was induced by the Cr depletion zone formation due to Cr segregation around intergranular TiC.     

13Cr系列不锈钢在模拟井下介质中的CO2腐蚀研究

根据某油田不同井况条件,配制不同井下模拟溶液,用高温高压釜研究了4种不同成分的13Cr马氏体不锈钢在不同温度、Cl^-浓度和CO₂分压下的腐蚀行为,对腐蚀性能进行了评价,用SEM,EDS,XRD和XPS等方法对腐蚀产物的形貌与成分进行了观察分析。结果表明,随着温度的升高及Cl^-浓度和CO₂分压的增大,13Cr系列不锈钢的腐蚀速率均相应增大,腐蚀速率由高到低的排序为13Cr-0>13Cr-1>M13Cr>S13Cr;其腐蚀产物膜的形貌与结构也有明显差异。