Seasonal variations in corrosion rate and runoff rate of copper roofs in an urban and a rural atmospheric environment

This paper summarizes the results from an extensive field exposure program implemented to study possible seasonal dependencies of copper corrosion rates and runoff rates. Two-year exposures in one urban and one rural environment were performed at four different starting seasons. An extensive multi-analytical approach was undertaken of all exposed samples.Seasonal differences in corrosion product formation was observed during the first month of exposure and attributed mainly to differences in relative humidity conditions. Seasonal differences in corrosion rate at the rural site could be discerned throughout the whole two-year exposure, again, mainly attributed to differences in relative humidity. No seasonal effect could be observed at the urban site indicating that other parameters influenced the corrosion kinetics at this site. While corrosion rates exhibit a continuous decrease with exposure time, the yearly runoff rates are independent of time. Depending on starting months the yearly copper runoff rates ranged from 1.1 to 1.7 g m⁻² y⁻¹ for the urban site, and from 0.6 to 1.0 g m⁻² y⁻¹ for the rural site. These seasonal variations were primarily attributed to differences in precipitation quantity and environmental characteristics. Runoff rates are significantly lower than corrosion rates as long as the adhering copper patina is growing with exposure time.A full risk assessment requires not only information on the total amount of copper in the runoff, but also on its chemical speciation. Under present conditions, 70–90% of all copper in runoff water collected immediately after leaving the surface is present as the most bioavailable form, the hydrated cupric ion, Cu(H₂O)₆²⁺.     

Electrochemical characterization of the different surface states formed in the corrosion of carbon steel in alkaline sour medium

In this study the different surface states that manifest in the corrosion process of 1018 carbon steel in alkaline sour environment, solution prepared specifically to mimic the sour waters occurring in the catalytic oil refinery plants of the Mexican Oil Company (PEMEX) (0.1 M (NH₄)₂S and 10 ppm NaCN at pH 9.2) were prepared and characterized. The surface states of the carbon steel were formed by treating the surface with cyclic voltammetry at different switching potentials (E_λ+), commencing at the corrosion potential (E_corr=−0.890 V vs sulfate saturated electrode, SSE). The surface states thus obtained were characterized using electrochemical impedance spectroscopy and scanning electron microscopy techniques. It was found that for E_λ+=−0.7 and −0.6 V vs SSE a first product of corrosion formed, characterized by a high passivity. Moreover, it was very compact (with a thickness of 0.047 μm). However, at more anodic potentials (E_λ+>−0.5 V vs SSE) a second corrosion product with non-protective properties (porous with a thickness of 0.4 μm and very active) was observed. The diffusion of atomic hydrogen (H⁰) was identified as the slowest step in the carbon steel corrosion process in the alkaline sour media. The H⁰ diffusion coefficients in the first and second products that formed at the carbon steel–sour medium interface were of the order of 10⁻¹⁵ and 10⁻¹² cm²/s respectively.     

Untersuchungen zum Einfluß von Polyphosphat auf das Korrosionsverhalten von Kupfer in Elektrolytlösungen

Experiments on the effect of polyphosphate on the corrosion behaviour of copper in electrolytic solutions Gravimetric experiments in a circulating equipment were performed on the effect of Graham salt on the corrosion behaviour of copper in electrolytic solutions by means of a high confounded 2^7?4-fractional factorial. The composition of copper samples: 99.7% Cu, 0.002% Bi, 0.005% Sb, 0.01% As, 0.05% Fe, 0.2% Ni, 0.01% Pb, 0.05% Sn, 0.01% S. The aqueous electrolytic solutions contained hydrogencarbonate-, sulphate-, chloride-, nitrate-, manganese-, calcium ions and Graham salt. It appears that Graham salt is unsuitable for the inhibition of copper corrosion. The polyphosphate promotes corrosion. Chloride-, nitrate-, sulphate- und manganese ions also increase corrosion rate whereas it is decreased by hydrogencarbonate ions. Increase of temperature also causes a decrease of corrosion rate. An existing danger of contact corrosion induced by copper cannot be removed by addition of Graham salt if copper and carbon steel, respectively galvanized steel are installed together in equipments of plant water.     

The corrosion inhibition of copper in hydrochloric acid solutions by a tripeptide compound

The efficiency of glutathione as a non-toxic corrosion inhibitor for copper in 0.5 M HCl has been studied by using the weight-loss technique, cyclic voltammetry, electrochemical impedance spectroscopy (EIS) and potentiodynamic polarization. Maximum protection efficiency reaches about 92.7% for glutathione at 10 mM concentration level. Results obtained from potentiodynamic polarization and impedance measurements are in good agreement. The adsorption of glutathione on copper surface follows Langmuir isotherm. The adsorption free energy of glutathione on copper (−32 kJ mol⁻¹) reveals a strong physical adsorption of the inhibition on the metal surface.     

2-Amino-5-ethyl-1,3,4-thiadiazole as a corrosion inhibitor for copper in 3.0% NaCl solutions

2-Amino-5-ethyl-1,3,4-thiadiazole (AETDA) has been evaluated as a corrosion inhibitor for copper in 3.0% NaCl solutions using weight loss, pH, potentiodynamic polarization, potentiostatic current–time, and electrochemical impedance spectroscopic (EIS) measurements. The study was also complemented by scanning electron microscopy (SEM) and energy dispersive X-ray (EDX) investigations. Weight loss measurements gave an inhibition efficiency of about 60% with 1.0 × 10⁻³ M AETDA present, increasing to about 97% at the AETDA concentration of 5.0 × 10⁻³ M. Potentiodynamic polarization measurements showed that the presence of AETDA in de-aerated, aerated and oxygenated 3.0% NaCl solutions decreases cathodic, anodic, and corrosion currents to a great extent and shifts the corrosion potential slightly towards more negative values. Potentiostatic current–time measurements, SEM and EDX investigations also confirmed that the protection of the copper surface is achieved by strong adsorption of AETDA molecules. EIS measurements revealed that the surface and the charge transfer resistances increase upon increasing the AETDA concentration. Results together showed clearly that AETDA is a good mixed-type inhibitor for copper corrosion and its inhibition efficiency increases in the order of oxygenated > aerated > de-aerated 3.0% NaCl solutions.     

Tribology of thermal sprayed WC–Co coatings

This paper looks at the tribology of thermal sprayed WC–Co based coatings and covers the high energy air–sand erosion resistance and slurry jet impingement erosion performance, dry and wet sliding tribology of thermal spray WC–Co based coatings as well as the abrasion and abrasion–corrosion of these coatings. The tribological and tribo-corrosion performance of the coatings will be related to their mechanical and corrosion properties as well as deposition parameters, microstructure and actual composition. For example, the anisotropic microstructure of thermally sprayed WC–Co–Cr coatings, in particular the low fracture toughness in a direction parallel to the substrate, has been observed to affect the nature of crack formation under 200 μJ air–solid particle erosion conditions. Voids and occasionally other microstructural features (i.e., cobalt lakes, splat boundaries, interfacial inclusions) in the coating act as crack initiation sites. The erosion rate was dominated by cracks within 5 μm of the surface and was relatively insensitive to total length of cracks, showing a near-surface damage front controls the erosion rate and this region is coincident with the region of maximum shear stress induced by erodent impacts. Optimisation of the deposition parameters of HVOF 86WC–10Co–4Cr coatings show an improvement in erosion resistance of more than 50% over the conventional D-gun applied coating of identical nominal composition. The variation in the slurry erosion performance of the thermally sprayed coatings is also linked to directional fracture toughness and crack propagation paths which are influenced by the presence of pores, inhomogeneous carbide distributions and substrate grit blast remnants. The influence of slurry jet angle is more pronounced under 0.4 μJ energy conditions where maximum erosion occurred at 90° and the minimum at 30° in contrast to 7 μJ slurry erosion rates which were independent of jet angle. This reflects the lower levels of fluctuating stresses imparted to the coating during low energy slurry impacts leading to the impact angle having a greater effect on sub critical crack growth rate than for higher energy conditions.The abrasion resistance of these coatings was found comparable to sintered cermets of the same composition. The synergistic effects between micro and macro abrasion and corrosion for detonation gun (D-gun) sprayed WC–10Co–4Cr coatings are shown to be significant and depend on the environment. The size effect of the abradant relative to the microstructure and splat size is important as well as the propensity for the various phases to passivate to control corrosion levels. Comparisons between exposed and freshly polished coating surfaces in strong NaOH solutions (pH 11) show that significantly lower wear rates were seen for the exposed surface due to a negative wear–corrosion synergy due to selective phase removal and the effects of localised passivation.Dry and wet sliding wear resistance of these coatings is shown to be high (wear rates of 10⁻¹⁶–10⁻¹⁸ m³/Nm) with modest coefficient of friction levels between 0.2 and 0.5. The presence of oxides on the binder phases appears to influence the friction and wear levels. Wear appears to be by carbide ejection and/or by tribo-chemical processes.     

Corrosion behavior and surface characterization of tantalum implanted TiNi alloy

TiNi shape memory alloy has been modified by Ta plasma immersion ion implantation technology to improve corrosion resistance. The results of the polarization tests show that the corrosion resistance of TiNi alloy in Ringer's solution at 310 K has been improved by the Ta ion implantation and the Ta/TiNi sample with a moderate incident dose of 1.5 × 10¹⁷ ions/cm² exhibits the best corrosion resistance ability. The surface characterization and chemical composition of the Ta/TiNi samples were determined by Auger electron spectroscopy (AES), Atomic force microscopy (AFM) and X-ray photoelectron spectroscopy (XPS) methods. AFM images reveal that compact aggregates of nano-grains uniformly disperse on the surface of the Ta/TiNi samples. AES and XPS analyses on the Ta/TiNi sample show that the component of the surface layer is mainly composed of TiO₂ and Ta₂O₅, which is benefit to the corrosion resistance ability and biocompatibility.     

铸铁在海水中的腐蚀行为

报告了18种铸铁在天然海水和流动海水中的腐蚀试验结果,总结了它们在海水中的腐蚀行为,普通铸铁在天然海水及流动海水中的腐蚀速度与碳钢接近,低合金铸铁在海水中的腐蚀行为与普通铸铁相似。CrSbCu铸铁在海水中的腐蚀比普通铸铁轻,添加Ni,Ni-Cr,Ni-Cr-Mo,Ni－Cr-Cu,Ni-Cr-Re,Cu-Sn-Re,Cu-Cr,Cu-Al等的低合金铸铁在海水中的腐蚀速度与普通铸铁无明显差别,加入少量Ni,Cr,Mo,Cu,Sn,Sb,Re等合金元素可减小铸铁在海洋大气区的腐蚀速度,高镍铸铁在天然海水及流动海水中的腐蚀均较轻。     

Hydrogen permeable Ta–Ti–Ni duplex phase alloys with high resistance to hydrogen embrittlement

Crystal structures, microstructures and hydrogen permeability Φ of as-cast Ta–TiNi alloys on the line connecting the compositions of the primary (Ta, Ti) and the ternary eutectic phases have been investigated to find out highly hydrogen permeable duplex phases alloys with high resistance to the hydrogen embrittlement. The alloys on this line show microstructures of (1) the eutectic {(Ta, Ti) + TiNi} phase, (2) the primary (Ta, Ti) phase + the eutectic {(Ta, Ti) + TiNi} phase, and (3) the (Ta, Ti) solid solution, although a little amount of unidentified (impurity) phases are included in these samples. The value of Φ increases with increasing Ta content and the volume fraction of the primary (Ta, Ti) phase, which indicates that the primary phase contributes mainly to the hydrogen permeation. The Ta₅₆Ti₂₃Ni₂₁ alloy, containing the 61 vol.% primary phase, shows the highest Φ of 2.18 × 10⁻⁸ mol H₂ m⁻¹ s⁻¹ Pa^−0.5 at 673 K, which is 1.3 times higher than that of the previous most high Φ alloy (Ta₅₃Ti₂₈Ni₁₉). The more Ta-rich alloys on this line, i.e., containing a small amount of the eutectic phase, are broken down by the hydrogen embrittlement, suggesting that the eutectic phase suppresses the hydrogen embrittlement.     

Corrosion behaviour and catalytic effectiveness of Pb–Ca–Sn,RuO2–IrO2/Ti and IrO2–Ta2O5/Ti anodes for copper electrowinning

Abstract

The dependence of the corrosion rate on cell current density (CD) for three anode materials (Pb–Ca–Sn, RuO₂–IrO₂/Ti and IrO₂–Ta₂O_5/Ti) in a laboratory scale copper electrowinning cell has been studied by means of short term weight loss tests, scanning electron microscopy observations and energy dispersive spectroscopy analysis. The lead anodes (Pb–Ca–Sn) corroded at all the studied cell CDs, and their corrosion rate increased with increasing cell CD. The precious metal oxide anodes (RuO₂–IrO₂ and IrO₂–Ta₂O₅) only exhibited corrosion at the highest tested cell CD (1000 A m^?2), and their corrosion rates were about a quarter of the lead corrosion rate at the same cell CD. The electrocatalytic properties of the three anode materials were characterised by means of potentiodynamic experiments. The overall results pointed to IrO₂–Ta₂O₅/Ti as the best anode material of choice, although plant tests would be required before deciding on any specific commercial use.     

Open circuit potentials of metallic chromium and austenitic 304 stainless steel in aqueous sulphuric acid solution and the influence of chloride ions on them

Open circuit potential measurements and cyclic voltammetry of chromium and 304 stainless steel in deaerated aqueous H₂SO₄ solution of pH 1, without and containing NaCl in the concentration range 1–4 M revealed that chromium exhibits two stable open circuit potentials both having the character of a Wagner–Traud corrosion potential. One, E_corr.1, was established on the passive surface formed by previously exposing Cr to air or by potentiostatic passivation in a controlled manner, and the second one, E_corr.2, at the bare Cr surface obtained by prolonged cathodic activation. There was a small difference in the E_corr.1 values depending on the properties of the passive layer. Addition of NaCl accelerates to some extent, the hydrogen evolution reaction on the passive surface, while the same reaction on the bare surface was somewhat inhibited by NaCl. On the other hand, presence of NaCl accelerates the anodic reaction on the bare surface, and it activates the dissolution of the passive layer so that the passivation currents increase with addition of NaCl. This effect is so large that at concentrations of NaCl larger than 3 M, the destruction of the passive layer was so fast that in a matter of seconds the Cr is activated, and the only stable corrosion potential observed was E_corr.2. No pitting of Cr in the presence of NaCl was observed up to the transpassive potentials. 304 stainless steel could not be activated in sulphuric acid solution, and its open circuit potential, unlike the corrosion potential of the 400 types of stainless steel, was established by the hydrogen evolution reaction on the passive steel surface. The small anodic peak often observed on 304 stainless steel if the metal had been cathodically pre-treated is a pseudo-peak due to the anodic oxidation of hydrogen absorbed inside the metal. This finding should be elaborated more in recommendations (e.g. ASTM standards) for the application of electrochemical corrosion rate measurement to 304 stainless steel corrosion. Addition of NaCl activates the anodic dissolution of steel with the current of the passivation peak being proportional to the NaCl concentration. Unlike chromium, austenitic 304 stainless steel achieves only one corrosion potential in sulphuric acid, both in the presence and absence of NaCl, with the value of ca. −0.200 to −0.350 V (SCE) in the absence and −0.450 V (SCE) in the presence of NaCl, when steel corrodes as the active metal.     

Corrosion evaluation and surface characterization of the corrosion product layer formed on Cu-6Sn bronze in aqueous Na2SO4 solution

The binary bronze alloy Cu-6Sn corrosion, and formation and properties of corrosion product layer (patinas) during 12 days of exposure to 15 mM Na₂SO₄ aqueous solution were investigated by a range of diverse experimental techniques. For the reasons of comparison, some techniques were applied, in parallel, to copper. Gravimetric measurements revealed lower corrosion rates of bronze than those of copper, probably caused by the presence of tin compounds in the corrosion product layer. Cyclic voltammetry results showed that the oxidation processes on bronze are affected by the formation of tin oxide species. Electrochemical impedance spectroscopy showed that, as opposed to copper which produced only two time constants, bronze corrosion resistance was dominated by the additional high-frequency time constant representing redox processes occurring at the corrosion product surface. SEM, ATR FTIR and PIXE results suggest that Cu-6Sn bronze corrosion in 15 mM Na₂SO₄ solution was impeded by the formation of two-layered structure of corrosion products that formed due to selective dissolution of copper at the layer/solution interface, leaving the outer layer enriched in highly corrosion resistant Sn oxi/hydrohide species.     

Surface tension isotherms of a free surface and grain boundaries in the Cu-Sn system

Surface tension of pure copper and its alloys with Sn has been measured at 1000°C in a hydrogen atmosphere. Surface tension of a free surface equaled 1.81 N/m for pure copper, and 1.55, 1.38, and 1.28 N/m for the alloys with 0.05, 0.22, and 0.33 at % Sn, respectively; surface tension at grain boundaries equaled 0.5 N/m for pure copper, and 0.36, 0.3, and 0.23 N/m for the alloys, respectively. Based on these data, the concentration dependence of tin absorption at a free surface and grain boundaries has been calculated. Parameters of Sn absorption at grain boundaries and a free surface of copper have been compared with those of Sb and Bi.     

Effect of tin on the corrosion behavior of low-alloy steel in an acid chloride solution

This study examined the effect of Sn addition ranging from 0 to 0.1 wt.% on the electrochemical properties of low-alloy steel using electrochemical techniques in an acid chloride solution and surface analysis techniques. The potentiodynamic test showed the active corrosion behavior of all specimens and the corrosion rate decreased with increasing Sn addition. EIS showed that the Sn-containing steels had higher rust layer resistance. These results confirmed that the interaction of Sn with Cu and Sb improves the corrosion resistance of low-alloy steel due to the formation of the continuous tin oxide, copper oxide and antimony oxide layer.     

Studies on leaching of metals from solders due to corrosion

Leaching of Ag, Cd, Cu, Pb, Sn, Sb and Zn from 50/50 Pb/Sn, 95/5 Sn/Sb and 96/4 Sn/Ag soldered copper plates into distilled, tap and well waters as a function of contact time under static conditions was done. Ag, Cd and Sb were not leached to significant extent. Significant amounts of tin were leached especially into tap and well waters. The amount of copper leached from soldered samples was in general less than the amount leached from blank copper samples. The amount of Zn leached was by far less than the drinking water quality limit (5 mg/L). The amount of Pb leached from nonleaded solders was less than 10 μg/L and exceeded 10 μg/L in the case of Pb/Sn solder. Surface analysis by X-ray photoelectron spectroscopy and electron microprobe techniques of Pb/Sn solder samples showed the presence of Pb and Sn oxides. The results fit into galvanic corrosion scheme of the solder surface.     

The effects of temperature and hydrodynamics on the CO2 corrosion of 13Cr and 13Cr5Ni2Mo stainless steels in the presence of free acetic acid

This paper describes the effects of temperature and hydrodynamics on the CO₂ corrosion of two stainless steels in the presence of free acetic acid. The experimental set-up developed in this work was able to evaluate the corrosion behavior of 13Cr and 13Cr5Ni2Mo stainless steels in static conditions with a flow velocity of 1 m s⁻¹ at temperatures of 125, 150 and 175 °C. Electrochemical tests of impedance and linear polarization resistance have been carried out, as well as mass loss tests and surface analysis.     

Effect of Benzotriazole on the dissolution of copper single crystal planes in dilute sulphuric acid

The kinetics of the dissolution of copper single crystal planes in aerated 0·1N H₂SO₄ containing various concentrations (10⁻⁶−10⁻²M) of Benzotriazole have been studied. The dissolution rates which were controlled by surface reaction, were a function of the temperature, crystallographic orientation and the concentration of Benzotriazole. The stabilities of the crystal planes were in the order (100) > (110) > (111). At 7·5 × 10⁻³M Benzotriazole, Cu-Benzotriazole film appeared on the surface, bringing mechanical passivity. Benzotriazole acted as cathodic inhibitor at low concentrations and anodic inhibitor at high concentrations. The corrosion potentials of the crystal planes were in the order (100) > (110) > (111) at all concentrations of benzotriazole.     

The site occupancies of alloying elements in TiAl and Ti3Al alloys

The site occupancies of V, Cr, Mn, Fe, Ni, Zr, Nb, Mo, Ta, Ga and Sn (1–5 at.%) in TiAl alloys with different compositions, and in Ti₃Al with the compositions of Ti–26 at.%Al–(1–2 at.%)X, were measured by the atom location channelling enhanced microanalysis (ALCHEMI) method. For TiAl alloys, the results show that Zr, Nb and Ta atoms invariably occupy Ti sites, while Fe, Ni, Ga and Sn atoms occupy Al sites, the alloy composition having no significant influence on their site preference. By contrast, the site preference of V, Cr, and Mn changes considerably with alloy composition (the Ti/Al ratio in particular), the probability of these elements substituting for Ti decreasing in the above order. For quaternary Ti–Al–V–Cr alloys, the site occupancies of V and Cr do not show much mutual influence. In general, with increasing atomic number, elements in the same period show increasing tendency to substitute for Al, as is the tendency to substitute for Ti for elements in the same group of the periodic table. For Ti₃Al alloys, Ga and Sn atoms occupy Al sites, while V, Cr, Mn, Zr, Nb, Mo and Ta atoms occupy Ti sites, the site preference of V, Cr, Mn and Mo in TiAl alloys being different from that in Ti₃Al. The experimental results are interpreted in terms of a Bragg–Williams-type model and bond-order data obtained from electronic structure calculation. Qualitative agreement between the model and measurements is reached.     

Effect of ternary alloying elements on the shape memory behavior of Ti–Ta alloys

The effect of ternary alloying elements (X = V, Cr, Fe, Zr, Hf, Mo, Sn, Al) on the shape memory behavior of Ti–30Ta–X alloys was investigated. All the alloying elements decreased the martensitic transformation temperatures. The decrease in the martensitic transformation start (M_s) temperature due to alloying was affected by the atomic size and number of valence electrons of the alloying element. A larger number of valence electrons and a smaller atomic radius of an alloying element decreased the M_s more strongly. The effect of the alloying elements on suppressing the aging effect on the shape memory behavior was also investigated. It was found that the additions of Sn and Al to Ti–Ta were effective in suppressing the effect of aging on the shape memory behavior, since they strongly suppress the formation of ω phase during aging treatment. For this reason the Ti–30Ta–1Al and Ti–30Ta–1Sn alloys exhibited a stable high-temperature shape memory effect during thermal cycling.