Kühlwasserseitige Korrosionsbeständigkeit von metallischen Werkstoffen zur Handhabung von Schwefelsäure

Cooling water side corrosion resistance of high alloyed materials for handling of process side sulfuric acid The approved materials for use in sulfuric acid alloy 825 (German material No. 2.4858) and alloy 20 (German mater. No. 2.4660) have only a low resistance against localized corrosion in chloride containing water and are unsuitable for handling of sulfuric acid. The newly developed austenitic Cr-base alloy, alloy 33, (X1CrNiMoCuN 33-32-1, German mater. No. 1.4591) with 33 % Cr, 31 % Ni, 0,6 % Mo and 0.4 % N should have an excellent resistance against pitting and crevice corrosion additional to its high sulfuric acid resistance, too, because its Pitting Resistance Equivalent No. calculated according to PREN = %Cr + 3,3 · %Mo + 30%N runs to 50. Pitting and crevice corrosion properties of the alloy 33 are tested in comparison to those of reference materials in high chloride containing solutions (1M NaCl, artificial and modified sea water, 10% FeCl₃ · 6H₂O; 500 g/l CaCl₂ ). Pitting potentials and potentials of repassivation of pitting, critical temperatures of localized corrosion (FeCl₃-test, CaCl₂-test, artificial sea water), potentials of repassivation of crevice corrosion as well as depassivation pH values of crevice corrosion following Crolet have been determined. The results confirm that the localized corrosion behaviour of the alloy 33 corresponds to its PREN. With regard to pitting corrosion alloy 33 is comparable with the special stainless steel alloy 31 (mater. No. 1.4562), with regard to crevice corrosion it is comparable with alloy 926 (German mater. No. 1.4529).     

The corrosion behaviour of Fe-15Mn-7Si-9Cr-5Ni shape memory alloy

The corrosion behaviour of Fe-15Mn-7Si-9Cr-5Ni (mass%) shape memory alloy at 25 °C in 0.5 M H₂SO₄ and 3.5% NaCl solutions has been studied using potentiodynamic polarization and electrochemical impedance techniques. Three different microstructures viz., single-phase γ, γ-δ and γ-Fe₅Ni₃Si₂, were produced by heat-treating the alloy in different equilibrium phase fields. The corrosion behaviour in 0.5 M H₂SO₄ solution is almost same for all three microstructures, barring a slight difference in the passivation range. Although, the passivation current in 0.5 M H₂SO₄, is in the same range as that of SS 304, the critical current required for onset of passivation is almost three orders higher and the passivation range is much shorter. In 3.5% NaCl solution the corrosion behaviour of all three microstructures of the Fe-15Mn-7Si-9Cr-5Ni shape memory alloy was that of general dissolution without passivity or localized attack (pitting). The best corrosion resistance in both H₂SO₄ and NaCl solutions is shown by the single-phase γ microstructure.     

Development of EPR test technique for alloy 800

The degree of sensitization (DOS) of austenitic stainless steels and some nickel-based alloys (e.g., alloy 600) is evaluated by the electrochemical potentiokinetic reactivation (EPR) test. In this study a number of test solutions based on H₂SO₄ + KSCN composition have been evaluated to establish a reliable EPR test method for alloy 800. Different passivation (vertex) potentials are also tested. It has been shown that dilute test solutions with lower vertex potentials resulted in single loop (SL) and double loop (DL) EPR test methods that distinguished between different sensitized samples and also between sensitized and desensitized samples. It has been shown that an SL-EPR test in 1 M H₂SO₄ + 0.002 M KSCN (de-aerated) at 26 °C at a scan rate of 3 mV/s from a vertex potential of 700 mV_SCE (180 s hold time) gave results that matched with the DOS indicated by microstructures and the Huey test results. Similarly, the DL-EPR test in 1 M H₂SO₄ + 0.002 M KSCN (de-aerated) at 26 °C, forward scanning from the OCP to + 700 mV_SCE and then backward scanning from there to the OCP at a scan rate of 2 mV/s produced a good measure of DOS as indicated by the Huey test results. The effectiveness of the EPR test was ascertained by testing on alloy 800 containing Ti and Al (alloy 800 HT) and Nb (alloy 800 Nb).     

Effect of KSCN and its concentration on the reactivation behavior of sensitized alloy 600 in sulfuric acid solution

The effects of KSCN addition and its concentration on the reactivation behavior of sensitized Alloy 600 in an H₂SO₄ solution were investigated. Single-loop electrochemical potentiokinetic reactivation (SL-EPR), potentiostatic and potential decay tests were conducted in H₂SO₄+KSCN solutions, including intermittent adjustment of the electrolyte composition and concentration. The SL-EPR results showed that the maximum current densities of the reactivation peaks increased with an increase in KSCN concentration from 0 to 0.05 M in the 0.5 M H₂SO₄ solutions. A decrease in the peak current density was observed, however, if the KSCN concentration was increased to 0.5 M. The potentiostatic test results at +400 mV_SCE showed that sensitized Alloy 600 could be passivated in plain H₂SO₄ and KSCN solutions as well as in mixed H₂SO₄+KSCN solutions. Potentiostatic tests at +30 mV_SCE revealed that the presence of low KSCN concentrations made the passive film less stable in H₂SO₄ solutions, but it enhanced passivation at 0.5 M. The adsorption and desorption of SCN⁻ and its subsequent redox reaction at different concentrations was discussed in relation to the reactivation of passive film formed on sensitized Alloy 600.     

Untersuchung der Interkristallinen Korrosion bei Duplexstählen mit Thioacetamid als Aktivator im EPR-Verfahren

Investigation of intercristalline corrosion of duplex stainless steels using thioacetamid as an activator for EPR-test To evaluate susceptibility of the duplex stainless steel (DSS) X2CrNiMoN22-5-3 to intergranular attack (IGA) using doubleloop (DL)-EPR-test, thioacetamid (TA) instead of KSCN has been taken as activator. TA has to suppress selective ferrite corrosion by keeping up good IGA-detection. Solution annealed rolled samples were hold at 650°, 750° and 850° over 3 to 600 min. Conditions: 0.5 M H₂SO₄ + 0.01 M KSCN, 70° or 2.5 × 10^?4 to 1 × 10^?2 M TA; 50°, 60° and 70°. For test evaluation the ratio i_R/i_P respectively q_R/q_P, has been used in connection with research of microstructure. Using optimal parameters TA enables EPR-test to detect IGA on DSS produced by X- and α-phase precipitations. The mechanism of effect of TA is discussed.     

Über Elektrochemische Messungen zum Passivierungsverhalten austenitischer CrNi-Stähle in schwefelsauren Lösungen

Electrochemical measurements of passivation behaviour of austenitic CrNi steels in sulfuric acid solutions The determination of passivation current densities, passivation potentials and potentials of complete passivation of austenitic CrNi-and CrNiMo-stainles steels, using potentiodynamically measured current potential curves in 0.5 m H₂SO₄, is disturbed by means of the superposition of cathodic partial current potential curves. By addition of KSCN the measuring will be possible through poisoning the hydrogen evolution, that is why by the addition of KSCN both the total current potential curves and the partial current potential curves become identically with each other. The influence of an addition of KSCN in the range between 10⁻⁵ and 10⁻² mass-% on the anodic dissolution of austenitic CrNi- and CrNiMo-stainless steels in deaerated 0.5 m H₂SO₄ is studied by means of potentiodynamically measured polarization curves (0.02 V min⁻¹). It is proposed to determine these characteristics in deaerated 0.05 m or 0.5 m H₂SO₄ with an addition of KSCN of 10⁻⁴ mass-%, if the examinations should be comparable. These experimental conditions lead to real values of passivation current densities with excellent reproducibility.     

Corrosion behaviour of an alloy formed by inductive melting of a cobalt-based alloy and AISI 4140 steel

A bimetal of Co-based alloy/AISI 4140 steel was fabricated by induction melting. The microstructure of the Co-based alloy was examined and the influence of on the alloy of acid solutions, the temperature of these solutions, and the immersion time was investigated. The results show that the microstructure of Co-based alloy consisted of a Co-rich phase, a Cr-rich phase, and W₃CoB₃. In a solution of 20% HCl and 6% FeCl₃, the Co-rich phase was attacked to form porous channels but transformed to a Si-rich passivation film to prevent further attack in the solution of 72% H₂SO₄. Therefore, the relative corrosion resistance of Co-based alloy to acid solution is 72% H₂SO₄ > 20% HCl > 6% FeCl₃.     

Der Einfluß von Schwefeldioxid,Schwefelwasserstoff und Kohlenmonoxid auf die Lochkorrosion von austenitischen Chrom-Nickel-Stählen mit bis zu 4 Massen-% Molybdän in 1 M Natriumchlorid-Lösung

The Influence of SO₂, H₂S and CO on Pitting Corrosion of Austenitic Chromium-Nickel Stainless Steels with up to 4 wt. % Molybdenum in 1 M NaCl Active corrosion of chromium-nickel stainless steel X 5 CrNi 189 (AISI 304) in H₂SO₄ is stimulated by H₂S as well as by SO₂ (extension of the potential range of active corrosion, increase of the maximum corrosion rate in the active state and of the passivation current density), but is inhibited by CO (decrease of both maximum active corrosion rate and passivation current density). It is investigated whether likewise stimulating and inhibiting effects are valid also in case of pitting corrosion of austenitic stainless steels with molybdenum contents ranging from about zero (material no. 1.4301) to 4 wt. % (material no. 1.4449), tested in 1 M NaCl (ambient temperature) saturated with the gases mentioned above. The pitting corrosion behaviour of the materials investigated is judged by their pitting potentials measured by potentiostatically controlled experiments (testing time 24 hrs). The pitting potentials are compared with those measured in 1 M NaCl, N₂-bubbled. Pitting corrosion is stimulated by SO₂, CO and H₂S, with the stimulating efficacy increasing in the sequence given before. No stimulation is found only in 1 M NaCl, SO₂-bubbled,-with the highest Mocontent. In all other cases, stimulation of pitting corrosion increases with increasing Mo-content of the stainless steels. In coarse approximation, the critical limiting potentials of stable pitting in 1 M NaCl, bubbled with H₂S, SO₂ CO, correspond to the critical potentials of repassivating pitting corrosion found in N₂-bubbled 1 M NaCl. The chemical reactions and reaction products of SO₂ in aqueous solution are discussed. The nature of the stimulating component of the corrosive medium is not quite clear. The stimulating effects of SO₂ or one of its reaction products and of H₂S on pitting are in keeping with their stimulating effect on active corrosion of the steels investigated. The stimulating effect of CO, however, is in contradiction to the results expected and cannot be explained.     

Hochtemperaturkorrosion des 2.25Cr-1Mo-Stahls unter simulierten Müllverbrennungsbedingungen

High temperature corrosion of 2.25Cr-1Mo in simulated waste incineration environments The corrosion of the 2.25Cr-1Mo steel was investigated by thermogravimetry in He? O₂? HCl? SO₂ at 500°C with and without deposits, taken from a waste incinerator. Additions of 500 vppm HCl to He-O₂ without deposits lead to accelerated corrosion due to the formation of FeCl₂ at the metal/oxide interface, its evaporation and oxidation lead to Fe₂O₃ at the outer surface (“active oxidation”). SO₂ causes FeS₂ formation on the FeCl₂ which retards the corrosion process. Under deposits, accelerated corrosion was observed in He-O₂ due to the reaction of alkalichlorides of the deposits with the oxide scale to ferrate and chlorine, which causes active oxidation. In He? O₂? HCl occurs strongly accelerated corrosion, due to transformation of the sulfates in the deposits by reaction with HCl to alkalichlorides. Addition of SO₂ shifts this equilibrium to enhanced stability of the sulfates, thus the corrosion in He? O₂? HCl? SO₂ is reduced.     

Potentialabhängigkeit der Korrosion Mo-freier und Mo-haltiger Stähle in Calciumnitrat-Lösung und Natronlauge

Effect of potential on corrosion of Mo-free and Mo-bearing steels in solutions of calcium nitrate and sodium hydroxide The effect of potential on the corrosion behaviour of three low alloy steels with different carbon and molybdenum contents (0.08 C, 0.01 Mo; 0.08 C, 0.98 Mo; 0.18 C, 1.10 Mo) was investigated in boiling 60 wt.% Ca(NO₃)₂ solution (DIN 50 915) and in boiling concentrated NaOH solutions (20 and 35 wt.% NaOH) by potentiodynamic and chronopotentiostatic polarization measurements (i/E curves) and chronopotentiostatic mass loss measurements (corrosion rate v vs. potential E curves). In Ca(NO₃)₂ solution, i/E measurements give no information about the effect of potential on the anodic dissolution. For the materials investigated, v/E measurements indicate the existence of potential ranges with pronounced differences of the corrosion response. It can be differentiated between active, passive, and transpassive ranges, and also a potential range of secondary passivity was established. Transpassivity and secondary passivity are markedly pronounced with the molybdenum bearing steels but not with the steel free from molybdenum. There are no hints to the occurrence of intergranular attack in the specimens which are free from of internal and external mechanical stresses, whereas such hints could be derived from the shape of the i/E curves. Nevertheless, under mechanical stresses (constant load, CERT conditions) the materials are susceptible to intergranular SCC. The conception that intergranular SCC of low alloy steels in Ca(NO₃)₂ solution is connected with a break-through potential of grain boundary corrosion and hence is to be interpreted as an intergranular attack which, under mechanical stresses, runs in a modified form as SCC with intergranular crack path, cannot be maintained in such general terms. A pronounced active/passive behaviour is observed in NaOH. The effect of potential on anodic metal dissolution which is derived from v/E curve is also established by i/E measurements. For molybdenum bearing steels, the active potential range is somewhat extended to more positive potentials. Manifestations of localized attack, e.g., intergranular corrosion, do not occur. From the investigations, no hints to the cause of the deterioration of the resistance to intergranular SCC in caustic solutions by molybdenum can be derived.     

不锈钢电化学着黑色工艺与成膜机理研究

采用电化学着色法对不锈钢着黑色进行了研究,讨论了钝化处理、着色液组成等因素对着色的影响,测定了着色膜的耐磨性和耐蚀性,并根据着色膜的组成、微观结构分析了成膜机理.结果表明:钝化和封闭处理能明显提高着色膜的耐磨性和抗色变性;电化学分析表明在1 mol/L H2SO4溶液、3.5%NaC l溶液和10%NaOH溶液中,着色膜腐蚀电位比不锈钢基体分别正移1130、565和790 mV,且腐蚀电流密度都比相应介质中的小;扫描电镜和能谱结果显示膜层为封闭块状结构,着色膜主要成分是Fe、Cr、Mn等元素,封闭处理能明显减少其裂纹数目.该成膜反应机理为:1)不锈钢基体的溶解形成大量的M e2+;2)金属/溶液界面上的M e2+与Cr3+水解形成合金氧化膜沉积在基体表面上;3)电化学致密过程中4H2MoO4+2SO42-+4H+2(MoO)2SO4+6H2O+6[O]和M e+[O]=M eO反应是着色膜致密的主要原因.     

Interkristalline Korrosion von Auftragschweißungen einer FeCrNiSiMn-Legierung EB9/300rc

Intercrystalline corrosion of weld claddings of FeCrNiSiMn alloy type EB9/300rc The corrosion resistance against intercrystalline corrosion (IK) of weld claddings from the electrode EB9/300rc (alloy type FeCr18Ni8Si4Mn with ca. 18% δ-ferrite) has been investigated using electrochemical potentiodynamic reactivation (EPR) technique, the Straußtest, metallographic and microstructure analytical methods (REM, ESMA). In spite of the brittleness of the claddings investigated, the Straußtest failed in assessing sensitization of the (unbent) specimen. In the EPR double loop test in 0,5 M H₂SO₄ + 0,01 M KSCN at 30°C with a scan rate of 5 mV/s the extend of sensitization is indicated by the ratio of reactivation to passivation charge. Additional assessment of the microstructure of heat treated specimen enabled us to set up a grain disintegration diagram. Sensitization has been caused by precipitation of Cr-rich carbides and s?-phase at the grain boundaries and by decomposition of δ-ferrite followed by selective dissolution (?Ferritpfad”? corrosion). In the as welded state the claddings are not susceptible to IK.     

Einfluß von Passivierungs- und Kohlenstoffschichten auf austenitischen CrNiMo-Stählen auf die Beständigkeit gegen Lochfraß und Spannungsrißkorrosion

Effects of passivation and carbon films on austenitic CrNiMo steels on their piting and stress corrosion resistance The influence of passive film and combinations of a passivation and a carbon layer on the resistance to pitting and SCC of austenitic CrNiMo steels has been investigated in physiological sodium chloride solution (Tyrode solution) at pH 6.9 to 7.4 at 37 ± 1°C. The passive film was obtained after electrolytic polishing in H₃PO₄ + H₂SO₄ + C₆H₅NHCOCH₃ + oxalic acid + corrosion inhibitor CS by treatment with 40% nitric acid the carbon film was obtained by CVD. Impurities in the steel (non-metallic inclusions) and the different metallic phases were investigated and the chemical composition of the passive film was determined by quantitative analysis. The resistance to pitting of the steel with and without passive film was determined potentiodynamically in Tyrode's solution at 37 ± 1°C. The resistance to SCC was determined in Tyrode's solution at 37 ± 1°C, in neutral glycerole and in boiling magnesium chloride solution at 154 ± 1°C and evaluated in terms of K_σ and K_τ. The corrosion damage was investigated by optical and scanning electron microscopy. The investigations have revealed that the different surface conditions considerably improve the pitting and SCC resistance of the steels in the media used in this work, so that they make possible the use of these materials as surgical implants.     

Nachweis der IK-Beständigkeit von verschleißfesten Auftragschweißungen mit dem EPR-Verfahren und mit Salpetersäure-Flußsäurelösung

Investigation of the resistance against IGA of wearfacing weld claddings by using the EPR test and nitric-hydrofluoric acid solution The corrosion resistance against intergranular attack (IGA) of weld claddings from the electrode Tube S 17 8 Si (alloy type FeCrl8Ni8Si4Mn with ≤ 18% δ-ferrite) has been investigated using electrochemical potentiodynamic reactivation (EPR) technique, the nitric-hydrofluoric acid (SF) test according to ASTM A 262 practice D, metallographic and microstructure analytical methods (SEM, EDX). Samples produced by different welding techniques (shielded arc and open arc) and partly additional thermal treated have been investigated. In standardized SF-solution and in 2 M HNO₃ + 0.05 to 0.5 M HF at 30°C there is no correspondence between corrosion rate and IGA-susceptibility, possibly caused by inhibitive action of Fe-III-ions. SF etchants evaluate Cr-depleted zones and decomposed δ-ferrite. In the optimized EPR double loop test in 0.5 M H₂SO₄ + 0.01 M KSCN at 30°C the extend of sensitization is indicated by the ratio of reactivation to passivation charge with additional assessment of the microstructure. It is shown that the EPR-test in the evaluated manner is able to find out IGA at claddings up to 30% δ-ferrite. In the as-welded state all claddings are resistant. Treatments at 400°C resp. 450°C were tolerated up to at least 1000 resp. 100 h. Sensitization may be caused by precipitation of Cr-rich carbides and by decomposition of δ-ferrite, for IGA the amount and distribution of ferrite plays a decisive role.     

Inhibiting effects of butyl triphenyl phosphonium bromide on corrosion of mild steel in 0.5 M sulphuric acid solution and its adsorption characteristics

Butyl triphenyl phosphonium bromide (BuTPPB) has been evaluated as a corrosion inhibitor for mild steel in 0.5 M H₂SO₄ solutions using galvanostatic polarisation and potentiostatic polarisation measurements. The study was also complemented by infra red (IR) spectroscopy, scanning electron microscopy (SEM) and quantum chemical calculations. Galvanostatic polarisation measurements showed that the presence of BuTPPB in aerated 0.5 M H₂SO₄ solutions decreases corrosion currents to a great extent and the corrosion rate decreases with increasing inhibitor concentration at a constant temperature. At 298K, inhibition efficiency was found to be 94.5% for 10⁻⁷ M BuTPPB which increased to about 99% for the BuTPPB concentration of 10⁻² M. The effect of temperature on the corrosion behaviour of mild steel was studied at five different temperatures ranging from 298 to 338K. The polarisation curves clearly indicate that BuTPPB acts as a mixed type inhibitor. Adsorption of BuTPPB on the mild steel surface follows the Langmuir isotherm.Potentiostatic polarisation measurements showed that passivation was observed only for lower BuTPPB concentrations (10⁻⁵ and 10⁻⁷ mol l⁻¹) for the mild steel in 0.5 M H₂SO₄. IR and SEM investigations also confirmed the adsorption of BuTPPB on the mild steel surface in 0.5 M H₂SO₄ solutions. The molecular parameters obtained using PM3 semi-empirical method, were correlated with the experimentally measured inhibitor efficiencies.     

Stress corrosion cracking of weldments of AISI Type 316 stainless steel

The weldments of AISI Type 316 stainless steel prepared by the tungsten inert gas (TIG) and manual metal arc (MMA) welding processes, were tested in a boiling solution of 5 M NaCl + 0.15 M Na₂SO₄ (pH = 1.3) at an initial stress level of 200 MPa under the open circuit potential (OCP) and the impressed potential (IP) conditions using the constant load technique. Anodic polarisation above the critical cracking potential (CCP) which was determined by the OCP test, accelerated the stress corrosion cracking of both the weldments whereas slight cathodic polarisation below the CCP prevented it. The cracks initiated through pits in both the types of weldments under open circuit as well as impressed potential conditions. The TIG weldments cracked in the heat affected zone whereas the MMA weldments failed in the fusion zone at all potentials. At open circuit potential, the MMA weldments failed by the stress assisted dissolution of delta ferrite, while the TIG weldments failed by the TGSCC of austenite. On anodic polarisation, the MMA weldment failed by the dissolution of delta ferrite and intergranular SCC of austenite, while in the TIG weldments the cracks initiated and propagated in the intergranular mode in the austenite.     

Study for corrosion characteristics of ferritic stainless steel weld metal with respect to added contents of Ti and Nb

This paper identified the effects of Ti and Nb on pitting and intergranular corrosion resistance in a ferritic stainless steel weld metal of the automobile exhaust system. We fabricated 4 flux cored wires designed with 0–0.2 wt% Ti and 0–1.0 wt% Nb and performed Flux Cored Arc Welding. Through the potentiodynamic polarization test in 0.5M NaCl, we evaluated pitting resistance. And in order to evaluate the intergranular corrosion resistance, we observed microstructure after we performed DL-EPR test in 0.5M H₂SO₄+0.01M KSCN. As a result of the test, the specimen added with 0.2%Ti+1.0%Nb showed the highest pitting resistance. From observing the degree of sensitization and microstructure, the intergranular corrosion resistance was higher as the contents of Ti and Nb increased. And through EBSD we observed Cr carbide which affects the corrosion resistance.     

Poly(3‐octylthiophene) thermally treated as coating for corrosion protection of SS304 in sulfuric acid media

Poly(3‐octylthiophene) (P3OT) was synthesized by direct oxidation of the 3‐octylthiophene monomer using ferric chloride (FeCl₃) as an oxidant. Using the drop‐casting technique, P3OT coatings were deposited onto 304 type stainless steel electrodes. For the purpose of determining the effect of thermal annealing on the corrosion protection of stainless steel with P3OT coatings, the coated electrodes were thermally annealed for 30 h at two different temperatures, 55 and 100 °C. The corrosion behavior of P3OT coated stainless steel was investigated in 0.5 M sulfuric acid (H₂SO₄) at room temperature using potentiodynamic polarization curves (PPC), linear polarization resistance (LPR), and electrochemical impedance spectroscopy (EIS). The results indicated that the thermally treated P3OT coatings improved the corrosion resistance of the stainless steel in 0.5 M H₂SO₄. The best corrosion protection was obtained by the P3OT coating annealed at 100 °C. In order to study the temperature effect on the morphology of the coatings before and after the corrosive environment and compare it with corrosion protection, atomic force microscopy (AFM) and scanning electronic microscopy (SEM) were used.     

Corrosion behaviour of a new Ti‐6Al‐2Nb‐1Ta alloy in various solutions

A new Ti‐6Al‐2Nb‐1Ta alloy was obtained for to satisfy the mechanical and anticorrosion requirements in neutral corrosive environment. The corrosion behaviour of this new Ti‐6Al‐2Nb‐1Ta alloy in 0.1 M Na₂SO₄, 3% NaCl solutions and synthetic sea water was studied in this paper, using potentiodynamic and linear polarisation method, electrochemical impedance spectroscopy (EIS) and monitoring of the open circuit potentials. The structure of the alloy represents an α + β uniform structure with un‐oriented grains. From the potentiodynamic polarisation curves it resulted that the studied alloy is self‐passivated in all three solutions having a very good and very easy tendency to passivation. The most favourable values of the electrochemical parameters were registered in 0.1 M Na₂SO₄ solution due to its reduced corrosivity. EIS measurements proved the improvement of the passive layer resistance with the immersion time. An electric equivalent circuit with two time constants was fitted. The values of the polarisation resistances showed very good protective capacities which improved in time. The open circuit potentials have the general tendency to ennoble in time, suggesting the thickening of the passive films and the increase of their protective capacities.     

The effect of heat treatment on the corrosion resistance of 440C stainless steel in 20% HNO<Subscript>3</Subscript> + 2.5% Na<Subscript>2</Subscript>Cr<Subscript>2</Subscript>O<Subscript>7</Subscript> solution

The effect of heat treatment on the corrosion resistance of 440C stainless steel was investigated in a 20% HNO₃ + 2.5% Na₂Cr₂O₇ solution using electrochemical noise (ECN) measurements, electrochemical impedance spectroscopy (EIS), and scanning electron microscopy (SEM) examinations. The noise resistance (Rn), which has been found to be inversely related to the localized corrosion rate, was measured to be 5.7E + 08 Ω-cm², 4.2E + 08 Ω-cm², and 3.7E + 04 Ω-cm² for the oil-quenched, air-quenched, and vacuum furnace cooled (VFC) samples, respectively, after 1200 s exposures. The Rn for all heat treat conditions stabilized within a range of 1.0E + 07 Ω-cm² to 3.2E + 08 Ω-cm² after 2 h exposures. The EIS response showed a polarization resistance (R _p) on the order of 6.6E + 04 Ω-cm², 5.3E + 04 Ω-cm², and 1.1E + 04 Ω-cm² for the oil-quenched, air-quenched, and VFC samples, respectively, after 2 h exposures. The EIS data are in good agreement with ECN data and indicate that after longer exposures, general corrosion mechanisms dominate and the corrosion rates are comparable. SEM examinations of specimens subjected to 1200 s exposures revealed that severity of pitting and intergranular corrosion damage was consistent with trends in the Rn data. Specifically, the electrochemical noise data as well as SEM examinations of specimens revealed a higher localized corrosion resistance of the hardened specimens during the early stages of passivation. This greater resistance to localized corrosion can be attributed to an increased stability of the natural passive film resulting from a higher concentration of chromium atoms in solution for the martensite phase.