Development of a hydrothermal deposition process for applying zirconia coatings on BWR materials for IGSCC mitigation

An in situ hydrothermal deposition process is being developed to apply a film of zirconia (ZrO₂) onto interior surface of 304 stainless steel and Alloy 600 as a potential method for mitigating intergranular stress corrosion cracking (IGSCC) in boiling water reactors (BWRs). The coating process is discussed. The obtained zirconia coatings are adherent. Monoclinic ZrO₂ is the dominant phase when ZrO(ClO₄)₂ was the oxidant; tetragonal ZrO₂ became the dominant phase when ZrO(NO₃)₂ was the oxidant. A preliminary experiment did not measure significantly lower values of the electrochemical potential (ECP), relative to the uncoated specimen over a wide range of dissolved oxygen in 265 °C water.     

Unusual oxidation behaviour of Zr50Cu50 alloy at high temperatures

The oxidation of Zr₅₀Cu₅₀ alloy at 500-700 °C is characterized by preferential oxidation of zirconium, while the excess of copper is accumulated at the alloy-oxide interface forming the Zr₁₄Cu₅₁ phase. The strong reaction at 800 and 850 °C resulted in the total corrosion of the specimens in 21 and 15 h, respectively. The oxidation at elevated temperatures showed an anomalous decrease of the oxygen consumption rate in the temperature range 930-1000 °C, corresponding to the preferentially oriented crystallites of ZrO₂ in the oxide scale at 900 and 1000 °C. The oxide layer consists of ZrO₂ and CuO in the whole temperature interval of the oxidation. The reaction kinetics obeys a parabolic rate law. An activation energy of 92.0 ± 0.3 kJ/mol has been estimated.     

The influence of relative humidity and temperature on the acetic acid vapour-induced atmospheric corrosion of lead

The acetic-acid induced atmospheric corrosion of lead was studied at 22.0 °C and 30-95% RH and at 4 °C and 95% RH. The samples were exposed to synthetic air with careful control of relative humidity, temperature, acetic acid concentration (170 ppb) and flow conditions. Reference exposures were carried out in clean humid air. Samples were analysed by gravimetry, ion chromatography, quantitative carbonate analysis, ESEM and XRD. Traces of acetic acid vapour strongly accelerate the atmospheric corrosion of lead. The corrosion rate is only weakly dependent on relative humidity in the range 95-50% RH. The accumulated amount of acetate is independent of RH in the range 95-40%. Lead corrosion in humid air in the presence of acetic acid vapour exhibits a negative correlation with temperature. The crystalline corrosion products formed on lead in the presence of acetic acid vapour were lead acetate oxide hydrate (Pb(CH₃COO)₂ · 2PbO · H₂O) and massicot (β-PbO) together with plumbonacrite (Pb₁₀O(CO₃)₆(OH)₆) or hydrocerussite (Pb₃(CO₃)₂(OH)₂). The transformation of lead acetate oxide hydrate into hydrocerussite and vice versa was also studied. The mechanism of corrosion is addressed, and the implications of this study for combating the corrosion of lead organ pipes in historical organs are discussed.     

Corrosion study of HK-40m alloy exposed to molten sulfate/vanadate mixtures using the electrochemical noise technique

Corrosion performance of HK-40m alloy obtained from electrochemical noise technique and polarization curves during 24 h of exposure in high sulfate (80 mol% Na₂SO₄-20 mol% V₂O₅) and high vanadate (80 mol% V₂O₅-20 mol% Na₂SO₄) molten salts at 700 °C are reported. Electrochemical noise signals were analyzed in the time and frequency domain. A statistical analysis obtaining the resistance noise, the current standard deviation and the localization index are presented as well as the determination of corrosion rates. Corrosion rates were supported by X-ray diffraction analysis of corrosion products and scanning electron microscopy analysis of corroded samples. Results from optical microscope examination of the corroded samples showed that HK-40m alloy suffered inter-granular corrosion when was exposed to the high vanadate salt, whereas exposed to the high sulfate salt, HK-40m corroded through a mixed corrosion process. A corrosion mechanism of HK-40m alloy was obtained together with the corrosion rate, showing the different behavior when exposing the alloy to a high vanadate and high sulfate molten salts.     

Transient and steady state crack growth kinetics for stress corrosion cracking of a cold worked 316L stainless steel in oxygenated pure water at different temperatures

The stress corrosion cracking (SCC) growth kinetics for a cold worked 316L stainless steel was continuously monitored in high purity water at different temperatures and dissolved oxygen (DO) levels under a K (or K_max) of 30 MPa m^0.5. The total SCC test time was more than 8000 h to make sure the steady state crack growth rate under each test condition could be reached. Crack growth rate (CGR) increases with increasing temperature in the range 110-288 °C. A typical intergranular-cracking mode is identified. Depending on the previous test condition, especially the temperature, three kinds of crack growth kinetics, i.e., increasing with testing time then becoming steady, being constant during the whole period, or decreasing with test time then becoming steady, are identified and discussed. Time-dependent and testing history-dependent crack growth modes were confirmed in two series of tests in 2 ppm DO and 7.5 ppm DO pure water. The apparent activation energies are calculated and compared with other data in different environments under different applied loading levels for understanding the cracking mechanism.     

Corrosion loss of mild steel in high temperature hard freshwater

This paper presents an interpretation of corrosion loss data for mild steel coupons exposed for up to 2.6 years to freshwater under a range of dissolved oxygen levels and temperatures 50-60 °C. The water total alkalinity was 0.5-0.6 mmol/l and pH 8.7-9.2. It is shown herein that the data is consistent with the early stages of the corrosion loss model proposed earlier for steel exposed to seawater, brackish water or freshwaters in the usual environmental range of 0-30 °C. The new data was found to be consistent with the effect of dissolved oxygen and the effect of water hardness on the model.     

Mechanisms of corrosion layer formation during zirconium immersion in a (Fe)-bearing glass melt

The kinetics and mechanism of pure zirconium corrosion in an iron-bearing borosilicate glass melt are investigated from 1230 to 1418 °C. The influence of immersion time and temperature on the corrosion layer morphologies is discussed. The corrosion mechanism is a multi-step process and is described using the Zr-Si-O-B phase diagram. Boron and silicon species contained in the melt are reduced at the zirconium contact and ZrSi_sB_b intermetallic compounds are formed while the Zr substrate is oxidized into ZrO_x. When the local melt fO₂ value induces the Fe⁰ precipitation, complex ZrSi_sB_bFe_f compounds are formed. The last step consists in the oxidation of ZrO_x into ZrO₂.     

Oxidation and corrosion of silicon nitride ceramics with different sintering additives at 1200 and 1500 °C in air, water vapour, SO2 and HCl environments - A comparative study

The effect of different sintering additives on the high temperature oxidation and corrosion behaviour of silicon nitride based ceramics was investigated. Comparative tests were conducted at 1200 and 1500 °C in air, in water vapour, and with the highly corrosive gases HCl and SO₂. Si₃N₄ was prepared with MgO, Al₂O₃, Y₂O₃ and Al₂O₃ + Y₂O₃ sintering additives. Hot pressed discs were tested for a total time of up to 128 h. The electrically conductive ceramic composites Si₃N₄ + TiN and Si₃N₄ + MoSi₂ were also tested under the same conditions. The effects that the different corrosion environments have on the different ceramics are presented. SEM studies of the oxidised ceramics show the direct transformation of Si₃N₄ grains into SiO₂ through a reaction interface layer.     

H2S and O2 influence on the corrosion of carbon steel immersed in a solution containing 3 M diethanolamine

Aqueous solutions with 3 mol L⁻¹ (M) diethanolamine (DEA) concentration are extensively used in the gas processing industry to remove acid gases. However, the degradation of the DEA and the formation of heat-stable salts (HSS) lead to severe corrosion problems. Even worse, equipment corrosion can be magnified by the unavoidable presence of sulphide acid and dissolved oxygen as a result of hydrocarbon (natural gases and crude oil) processing. The aim of this work is to study the combined corrosion effects of DEA, sulphide acid and oxygen on carbon steel. Electrochemical methods revealed that in the 3 M DEA medium without oxygen, corrosion processes are modulated by adsorbed DEA film formation. Furthermore, it was shown that the addition of oxygen and 15 × 10⁻³ mol L⁻¹ (15 mM) H₂S produced the formation of an adherent film on the carbon steel surface. Chemical analyses by EDAX revealed a homogeneous film of corrosion products composed of iron oxide and sulphide formed in DEA solution containing O₂ and H₂S, respectively. Equivalent circuits were used to estimate the parameters associated with ion diffusion through the formed corrosion films. The results showed that the presence of H₂S induced the formation of thin iron sulphide films that provide protective properties to the metal. It is concluded that the presence of oxygen in a sweetening plant should be avoided as DEA degradation can be produced with the subsequent decrease in chelating process efficiency and the increase in corrosion problems.     

The influence of CO2, AlCl3 · 6H2O, MgCl2 · 6H2O, Na2SO4 and NaCl on the atmospheric corrosion of aluminum

The influence of salt deposits on the atmospheric corrosion of high purity Al (99.999%) was studied in the laboratory. Four chloride and sulfate-containing salts, NaCl, Na₂SO₄, AlCl₃ · 6H₂O and MgCl₂ · 6H₂O were investigated. The samples were exposed to purified humid air with careful control of the relative humidity (95%), temperature (22.0 °C), and air flow. The concentration of CO₂ was 350 ppm or <1 ppm and the exposure time was four weeks. Under the experimental conditions all four salts formed aqueous solutions on the metal surface. Mass gain and metal loss results are reported. The corroded surfaces were studied by ESEM, OM, AES and FEG/SEM equipped with EDX. The corrosion products were analyzed by gravimetry, IC and grazing incidence XRD. In the absence of CO₂, the corrosivity of the chloride salts studied increases in the order MgCl₂ · 6H₂O < AlCl₃ · 6H₂O < NaCl. Sodium chloride is very corrosive in this environment because the sodium ion supports the development of high pH in the cathodic areas, resulting in alkaline dissolution of the alumina passive film and rapid general corrosion. The low corrosivity of MgCl₂ · 6H₂O is explained by the inability of Mg²⁺ to support high pH values in the cathodic areas. In the presence of carbon dioxide, the corrosion induced by the salts studied exhibit similar rates. Carbon dioxide strongly inhibits aluminum corrosion in the presence of AlCl₃ · 6H₂O and especially, NaCl, while it is slightly corrosive in the presence of MgCl₂ · 6H₂O. The corrosion effects of CO₂ are explained in terms of its acidic properties and by the precipitation of carbonates. In the absence of CO₂, Na₂SO₄ is less corrosive than NaCl. This is explained by the lower solubility of aluminum hydroxy sulfates in comparison to the chlorides. The average corrosion rate in the presence of CO₂ is the same for both salts. The main difference is that sulfate is less efficient than chloride in causing pitting of aluminum in neutral or acidic media.     

The initial stage of pitting corrosion on coated steels investigated by photon rupture in chloride containing solutions

A photon rupture method, film removal by a focused pulse of pulsed Nd-YAG laser beam irradiation, has been developed to enable oxide film stripping at extremely high rates without contamination from the film removal tools. In the present study, Zn-55mass%Al alloy and Al-9mass%Si alloy-coated steel specimens covered with protective nitrocellulose film were irradiated with a focused pulse of a pulsed Nd-YAG laser beam at a constant potential in 0.5 kmol m⁻³ H₃BO₃-0.05 kmol m⁻³ Na₂B₄O₇ (pH = 7.4) with 0.01 kmol m⁻³ of chloride ions to investigate the initial stage of localized corrosion. At low potentials, oxide films on both coated alloys were reformed after the nitrocellulose films were removed by this method. The oxide film formation kinetics follows an inverse logarithmic law, in agreement with Cabrera-Mott theory. However, at high potentials, localized corrosion producing corrosion products occurs at the area where nitrocellulose film was removed. Nevertheless, when the applied potential is less noble, the dissolution current of the Zn-55mass%Al-coated steel samples is higher than that of Al-9mass%Si-coated samples.     

Pitting corrosion mechanism of Type 304 stainless steel under a droplet of chloride solutions

Pitting corrosion of Type 304 stainless steel under drops of MgCl₂ solution has been investigated to clarify the rusting mechanism in marine atmospheres. A pitting corrosion test was performed under the droplets with various combinations of the diameter and thickness (height) by exposure to a constant relative humidity. Probability of occurrence of pitting corrosion decreased with decreasing the diameter and thickness. Pitting corrosion progressed only when the [Cl⁻] exceeded 6 M (RH < 65%). In almost cases, there was a small hole (∼10 μm diameter) in the center of a single pit, which may be the trace of an inclusion particle like MnS dissolved out. The pitting corrosion mechanism of Type 304 under droplets containing chloride ions has been proposed.     

Effect of nitrogen addition on the stress corrosion cracking behavior of 904 L stainless steel welds in 288 °C deaerated water

This paper concerns with the effect of nitrogen addition to 904 L stainless steel (SS) welds on their stress corrosion cracking (SCC) behavior in high temperature (288 °C) and high pressure (1050 psi) water of high oxygen content (100 ppb) and high conductivity (2.5 μS/cm). For this study, 316 L SS base plate TIG welded with 904 L SS filler wire and with nitrogen contents of 0.027, 0.058 and 0.095 wt.% were used. Flat pin-loaded tensile specimens were fabricated from transverse welds, with the weld in the gauge length. Slow strain rate tests (SSRT) were carried out at a strain rate of 2.2 × 10⁻⁶ s⁻¹. The study shows that the samples, when tested in air, failed at the weld fusion zone for 0.027 and 0.058 wt.% N and at the base metal for 0.095 wt.% N. In the environment, the samples failed in the base metal except the one with least nitrogen content (0.027 wt.%). With nitrogen addition, as the failure location shifted to the base alloy, the weld seemed to acquire SCC resistance and became even more resistant than the base alloy.     

Environmental effects on the stress corrosion cracking susceptibility of 3.5NiCrMoV steels in high temperature water

Constant elongation rate tests (CERTs) were carried out to investigate the effects of environmental factors of dissolved oxygen and temperature on the stress corrosion cracking (SCC) susceptibility of 3.5NiCrMoV turbine steels. Tests were conducted in pure water of various dissolved oxygen concentrations at temperatures of 50 °C-200 °C in the range of strain rates from 5 × 10⁻⁸/s to 1 ×  10⁻⁶/s. Dissolved oxygen significantly affected the SCC susceptibility of turbine steels in water. The SCC susceptibility of the turbine steels increases as the dissolved oxygen concentration in water increases. The elongation of the turbine steels tested in aerated water at 150 °C at a strain rate of 1 × 10⁻⁷/s decreased to half of that of the steels tested in deaerated water in the same test condition. And the SCC susceptibility of the steels increased with decreasing strain rate, and with increasing temperature. The increase of the SCC susceptibility of the turbine steels in the higher dissolved oxygen environment is considered to be due to the higher content of dissolved oxygen enhancing the reduction reactions of oxygen on the metal surfaces (cathode) and accelerating the dissolution rate at the crack tips (anode) by galvanic attack of an aeration cell.     

Notched tensile tests of cold-rolled 304L stainless steel in 40 wt.% 80 °C MgCl2 solution

The effects of cold-rolling (20% thickness reduction) and sensitization treatment (600 °C/10 h) on the microstructure, tensile properties and susceptibility to stress corrosion cracking of 304 stainless steel in 80 °C MgCl₂ (40 wt.%) solution were investigated. The increase in hydrogen traps, which retarded hydrogen diffusion to the strained region, accounted for the low loss in notched tensile strength (NTS) of such a cold-rolled specimen, as compared to the solution-treated specimen in the corrosive environment. By contrast, the high NTS loss of sensitized specimens in MgCl₂ solution was attributed mainly to the formation of stress-induced martensite near grain boundary regions.     

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.     

Copper corrosion inhibition in O2-saturated H2SO4 solutions

Corrosion inhibition of copper in O₂-saturated 0.50 M H₂SO₄ solutions by four selected amino acids, namely glycine (Gly), alanine (Ala), valine (Val), or tyrosine (Tyr), was studied using Tafel polarization, linear polarization, impedance, and electrochemical frequency modulation (EFM) at 30 °C. Protection efficiencies of almost 98% and 91% were obtained with 50 mM Tyr and Gly, respectively. On the other hand, Ala and Val reached only about 75%. Corrosion rates determined by the Tafel extrapolation method were in good agreement with those obtained by EFM and an independent chemical (i.e., non-electrochemical) method. The chemical method of confirmation of the corrosion rates involved determination of the dissolved Cu²⁺, using ICP-AES (inductively coupled plasma atomic emission spectrometry) method of chemical analysis. Nyquist plots exhibited a high frequency depressed semicircle followed by a straight line portion (Warburg diffusion tail) in the low-frequency region. The impedance data were interpreted according to two suitable equivalent circuits. The kinetics of dissolved O₂ reduction and hydrogen evolution reactions on copper surface were also studied in O₂-saturated 0.50 M H₂SO₄ solutions using polarization measurements combined with the rotating disc electrode (RDE). The Koutecky-Levich plot indicated that the dissolved O₂ reduction at the copper electrode was an apparent 4-electron process.     

Corrosion behavior of alumina ceramics in aqueous HCl and H2SO4 solutions

The corrosion behavior of cold isostatically pressed (CIP) high purity alumina ceramics in aqueous HCl and H₂SO₄ solutions with various concentrations has been studied simultaneously at room temperature (25 °C). Corrosion tests were also performed with 0.65 mol/l HCl and 0.37 mol/l H₂SO₄ solutions at 40, 55 and 70 °C for 48 h. Chemical stability was monitored by determining the amount of Al³⁺, Mg²⁺, Ca²⁺, Na⁺ Si⁴⁺ and Fe³⁺ ions eluted in different concentrations of HCl and H₂SO₄ solutions by means of atomic absorption spectrometry (AAS). By increasing the concentration from 0.37 to 6.5 mol/l, it was notified that the corrosion susceptibility in HCl and H₂SO₄ solutions for the CIP alumina specimens at room temperature decreases.     

Influence of oxygen ion irradiation on the corrosion aspects of Ti-5%Ta-2%Nb alloy and oxide coated titanium

The corrosion resistance of Ti-5%Ta-2%Nb alloy and DOCTOR (double oxide coating on titanium for reconditioning) coated titanium by O⁵⁺ ion irradiation were compared and investigated for their corrosion behaviour. O⁵⁺ ion irradiations were carried out at a dose rate of 1 × 10¹⁷, 1 × 10¹⁸ and 1 × 10¹⁹ ions/m² at 116 MeV. The surface properties and corrosion resistance were evaluated by using scanning electron microscopy (SEM), atomic force microscopy (AFM), energy dispersive X-ray (EDX), glancing-angle X-ray diffraction (GXRD) and electrochemical testing methods. The results of electrochemical investigations in 11.5 N HNO₃ indicated that the open circuit potential (OCP) of DOCTOR coated titanium is nobler than Ti-5%Ta-2%Nb alloy. The potentiodynamic polarization study of Ti-5%Ta-2%Nb alloy and DOCTOR coated specimen indicated decrease in passive current density with increase in ion doses (1 × 10¹⁷ to 1 × 10¹⁹ ions/m²) indicating decrease in anodic dissolution. Nyquist arc behaviour in the electrochemical impedance study substantiated the enhancement in oxide layer stability by O⁵⁺ ion irradiation. AFM results revealed that the DOCTOR coated Ti surface was dense without gross voids, and the surface roughness decreased by O⁵⁺ ion irradiation, but increased after corrosion test. EDX and GXRD patterns of DOCTOR coated Ti sample indicated that the coating was mainly composed of rutile TiO₂. Based on the above results, the O⁵⁺ ion irradiation effect on corrosion behavior of Ti-5%Ta-2%Nb alloy and DOCTOR coated titanium are discussed in this paper.     

Influence of ion-bombardment-energy on thin zirconium oxide films prepared by dual frequency oxygen plasma sputtering

Thin ZrO₂ films were prepared using dual frequency oxygen reactive plasma sputtering for wear-resistance coating of ceramics products. Influences of ion-bombardment-energy E_i were investigated for improvement of film characteristics. The results revealed that the deposition rate and the hardness of the prepared ZrO₂ thin films gradually increased with increasing E_i for E_i < 220-250 eV and then decreased, whereas the water-contact-angle on ZrO₂ thin films was about 90 °, having a good water-repellent nature.