Papers to be presented at Eurocor '77

Abstract

Despite numerous studies on atmospheric corrosion of copper and copper based alloys, the corrosion induced release processes of individual alloy constituents suffer from significant knowledge gaps. This investigation comprises metal release rate measurements of copper, zinc and tin from some copper based alloys including brass (20 wt-%Zn) and bronze (6 wt-%Sn), and their pure alloying metals, copper, zinc and tin. Data have been generated during a 2·5 year urban field exposure in Stockholm, Sweden and parallel laboratory investigations in a specially designed rain chamber using artificial rain. Brass shows significantly lower annual release rates of both copper and zinc compared to pure metal sheets of its alloy constituents. Zinc is preferentially released compared to copper. Dezincification of brass occurs both at field and laboratory conditions, a process influenced by rain characteristics. Alloying with tin does not largely reduce the release rate of copper from bronze compared to pure copper. No measurable amount of tin is released from the bronze surface.     

Role of alloyed copper on corrosion resistance of austenitic stainless steel in H2S–Cl− environment

Corrosion test, surface analysis and thermodynamic calculation were carried out in the H₂S–Cl⁻ environments to clarify the role of alloyed Cu on the corrosion resistance of austenitic alloys. The alloyed Cu improved pitting corrosion resistance in the H₂S–Cl⁻ environment. The surface film of Cu-containing alloy indicated double layer consists of copper sulfide and chromium oxide, and the copper sulfide was able to exist stably compared to iron sulfide and nickel sulfide. It is concluded that the copper sulfide would enhance the formation of chromium oxide film which improve the pitting corrosion resistance in the H₂S–Cl⁻ environment.     

Kondensatorrohre aus Kupferwerkstoffen Richtlinien für Werkstoffauswahl und Betriebsbedingungen

Condenser tubes made of copper materials

• 1 Today, the copper alloys most generally used for condenser tubes are CuZn28Sn (Special brass 71 — Admiralty brass) CuZn20Al (Special brass 76 — Aluminium brass), as well as the copper-nickel alloys CuNi10Fe and CuNi30Fe. The high corrosion resistance of these materials is due to the electropositive normal potential of their base metal — copper — and to their ability to form a highly adhesive, protective sealing film. To counteract the dezinzification of copper-zinc condenser tube materials, alloying with arsenic or phosphorus is indispensable, and generally resorted to.
• 2 The properties of normal-type cooling waters and the phenomena of tube corrosion are discussed. In practice, the only difficulties are likely to arise if polluted waters are used. Especially at the time of commissioning, the tubes must be kept free of polluted water so as to ensure the formation of a dense and firm protective film.
• 3 The reaction of the tube material to the cooling water depends mainly on the p_H-value, on the carbonate, chloride and oxygen contents, and on the temperature and flow rate of the water.
• 4 The following practice rules are advised: For fresh water (containing less than 0.1 pC matter in dissolution) and flow rates exceeding 1.4 metres pr. second, tubes consisting of CuZn20Al or of a copper-nickel alloy should be used so as to avoid erosion-corrosion. If the sea water is greatly polluted, it is advisable — especially at flow rates around or above 3 metres pr. second — to use tubes consisting of CuNi10Fe or CuNi30Fe.

     

Hochlegierte korrosionsbeständige Stähle für Chemie‐, Energie‐ und Meerestechnik – Rückblick und Ausblick

High‐alloyed corrosion resistant steels for the chemical process industry, power engineering and marine technology – past and future Today's most common high‐alloyed corrosion resistant steels are in their majority characterised by very low contents of carbon and sulphur and, in many cases, by substantial amounts of nitrogen as an alloying constituent. Their broad use in the chemical process industry, power generation and marine technology has become possible when new metallurgical processes for steel making had been introduced in the 1960s. The time before had seen mainly stabilised grades, being highly alloyed with copper in many cases, which have disappeared to a large extent in our days. The superferritic grades (ferritic steels with ≥ 25% chromium) had been the materials of great expectations in the 1970s, but have found a very limited application only in the chemical industry since then, e.g. for the handling of hot concentrated sulphuric acid, due to the high risks of low ductility cracking of these materials at greater wall thickness. These risks can be managed better if the highly alloyed ferritic phase is present in a finely dispersed compound with an austenitic phase where the ferritic part is adding its advantages, higher strength and resistance to stress corrosion cracking, to the duplex compound. This can result in low weight and corresponding cost saving. The application of the corrosion resistant duplex grades will expand further as much as users will better learn the special requirements of manufacturing of these materials and to take advantage of their unique properties. However, the most important alloy developments since the 1960s have been seen in the field of the austenitic stainless steels being highly alloyed with chromium, molybdenum and nitrogen. Especially the austenitic 6% Mo grades as e.g. X1NiCrMoCuN25‐20‐7 – alloy 926 (1.4529) have found many applications in chemical process industry, power generation and marine technology. Higher alloyed grades as e.g. X1NiCrMoCu32‐28‐7 – alloy 31 (1.4562) are excelling in extraordinary resistance to corrosion by acids and pitting attack. In addition today's upper limits of alloying austenitic corrosion resistant grades have been explored with grade X1CrNiMoCu33‐32‐1 – alloy 33 (1.4591) for chromium additions up to about 33% and with grade X1NiCrSi24‐9‐7 – alloy 700 Si (1.4390) for additions of silicon up to about 7%, providing a high corrosion resistance mainly in oxidising acids. When considering the prospects of further development of the corrosion resistant duplex grades the ferritic phase within these materials is both offering chances and setting limits. The high‐alloyed austenitic corrosion resistant steels have a potential being unexplored so far in the alloy range where molybdenum and nitrogen are becoming more prominent compared to the chromium content.     

Stress corrosion cracking of copper and silver, specific effect of the metal cations

Based on stress corrosion cracking (SCC) studies on brass, and on Ag-Cd alloys (a model alloy used to reproduce the behaviour of brass), it was found that both pure copper and pure silver are susceptible to SCC in 1 M copper(II) nitrate and in 1 M silver nitrate aqueous solutions, at the equilibrium potentials for the reactions: Cu²⁺+2e⁻↔Cu and Ag⁺+e⁻↔Ag, respectively. The results were analysed under the light of recent developments in surface science. It was concluded that the same SCC mechanism that operates in brass and in Ag-Cd alloys should be operating during SCC of pure copper and pure silver, under equivalent experimental conditions.     

Kommen oberflächliche Deckschichten und Materialversprödungen als Ursachen für das Auftreten von Spannungsrißkorrosion in Betracht

Could surface layers and material embrittlement be among the causes of stress corrosion cracking? Neither the hypothesis claiming rupture of the surface layer nor the embrittlement theory yield a sufficiently consistent explanation of the susceptibility to stress corrosion cracking, since the latter can occurr even in the absence of such layers (e.g. brass in copper nitrate and copper tetrammine salts). An indispensable condition for stress corrosion cracking to occurr is the possibility that cathodically active zones are formed by corrosion products at crevices and cracks; such active zones amy be formed e.g. by Cu₂O or by dissolved and redeposited noble metals. This phenomenon would also account for the specific action of certain agens: local formation or deposition of corrosion products which are not dissolved again (as e.g. noble metals may be dissolved with complex formation). The susceptibility to stress corrosion cracking is increased by mixed crystal formation, because this process enhances reactivity at grain boundaries, inner defects and creeping zones. In the case of alloys containing no noble metals, however, it is difficult, to predict susceptibility to stress corrosion cracking.     

Stress corrosion cracking of noble metals and their alloys in solutions containing cations of the noble metal: Review of observations relevant to competing models of SCC

The stress corrosion cracking of Ag, Au and Cu-base alloys, and of pure Ag and Cu, has been studied by J.R. Galvele and others. These authors used solutions that contained the cation of the more-noble metal, so that the tested specimen was at or close to its equilibrium potential in the given solution. The opportunity is taken to review the history of this far-from-new observation and some of its implications. The role of the exchange current density in such cracking is discussed. Observations of Sieradzki and Torchio are used to suggest that in alloys such as brass, SCC is favoured by low,nothigh,surfacemobility, in line with the film-induced cleavage model, which requires very fine nanoporosity at the crack tip - such a favourable condition can only be achieved if dealloying is either very fast or occurs under conditions of low surface mobility. Observations of very slow intergranular SCC in pure metals under dynamic loading are interesting, but not really suggestive of mechanistic continuity with the dramatic mixed-mode cracking that occurs under static loading in brass or AuAg alloys. Torchio’s observations on brass U-bends in CuSO₄ solutions of various pH and Cu²⁺ concentrations are particularly hard to interpret using the surface mobility model.     

Pitting and crevice corrosion of superaustenitic stainless steels

Superaustenites are mainly used in offshore applications, oil production and chemical industry. Most important types of localised corrosion of these steels are pitting and crevice corrosion. Investigated materials were N08028, S31254 and three modified alloys. Chromium content of investigated alloys varied between 20 and 27%, molybdenum between 3.2 and 6.0%, nitrogen between 0.1 and 0.36% and copper between 0 and 1.1%. For means of comparison stainless steel AISI 316L has been included in the study. Pitting and crevice corrosion of these highly corrosion resistant steels has been investigated by use of standardized tests. Critical pitting temperature and critical crevice temperatures were determined according to ASTM G 48, Methods C and D, respectively. Electrochemical measurements for determination of pitting potentials were done according to ASTM G 61 as well as for determination of critical pitting temperatures according to ASTM G 150. Results are presented as function of MARC (Measure of alloying for resistance to corrosion) defined by Speidel since linear correlation coefficients were higher when compared to conventional PREN. Results obtained by different testing methods must not be compared directly. Every test however is sensitive to microstructural defects like precipitations and segregations that decrease corrosion resistance. The higher alloyed a material is, the higher is its tendency to form microstructural defects, and the more difficult is it to reach its theoretical corrosion resistance at given chemical composition.     

Einfluss der Halbzeugform auf die Korrosionsbeständigkeit hochlegierter Ni‐Cr‐Mo‐Werkstoffe

Effect of semi‐finished products on the corrosion resistance of high‐alloyed Ni‐Cr‐Mo materials The corrosion resistance of different semi‐finished products of six superaustenitic steels and nickel based alloys in the condition of delivery was investigated in some typical standard corrosion tests. The resistance of sheets, plates, strips, seamless tubes and welded tubes to intercrystalline corrosion was tested according to ASTM G 28 methods A and B, as well the resistance to pitting corrosion according to ASTM G 48 method C. The nickel based alloys 625, C‐276 and alloy 59 are resistant to the FeCl₃‐test according to ASTM G 48 method C and therefore a differentiation of these types in regard to their localized corrosion resistance was achieved only in the more aggressive ‘Green‐Death’‐solution. The laboratory experiments confirmed that the corrosion resistance is identical for all semi‐finished products and that it shows only a slight dependence of the surface condition of the materials tested. Additionally, some typical industrial and practical applications of the six high performance materials are presented to demonstrate the excellent corrosion resistance in the manufactured condition.     

High temperature corrosion properties of ionic liquids

The corrosion behaviour of several metals and metal alloys (copper, nickel, AISI 1018 steel, brass, Inconel 600) exposed to a typical ionic liquid, the 1-butyl-3-methyl-imidazolium bis-(trifluoromethanesulfonyl) imide, ([C₄mim][Tf₂N]), has been investigated by electrochemical and weight-loss methods. Corrosion current densities have been determined by extrapolation from Tafel plots and by polarization resistance measurements and 48 h immersion tests were performed at 150, 250, 275 and 325 °C. Room temperature results show low corrosion current densities (0.1-1.2 μA/cm²) for all the metals and alloys investigated. At 70 °C, the corrosion current for copper dramatically increases showing a strongly dependence on temperature. At 150 °C copper shows significant weight-loss while nickel, AISI 1018, brass and Inconel do not. At higher temperatures (?275 °C), the copper sample crumbles and localized corrosion occurs for the other metals and alloys.     

Stress corrosion cracking of pure copper in dilute ammoniacal solutions

Studies of the stress corrosion cracking (SCC) of 99.999% copper and Cu-Zn alloys containing up to 10 wt%Zn in NH₄OH solution were made with varying concentrations (0.03–0.07 M) and temperatures (40–70°C). Stress corrosion cracking occurs on pure copper and all of the alloys under the condition in which thick tarnish film (Cu₂O oxide film) forms. The path of cracking is transgranular for pure copper and alloys containing < 1.3 wt%Zn, but intergranular for alloys containing > 1.3 wt%Zn. Crack propagation rates and times-to-failure estimated by the tarnish rupture theory, utilizing experimentally determined values of the fracture strain of film and the creep rate of specimens during SCC tests, are in good agreement with those observed under constant load.     

灰铸铁不同合金化同等强度下的加工性能对比研究

制备了用多元合金添加剂(含RE、Cr、Mn、Si、Fe)合金化和Cu合金化的具有相同抗拉强度的2种灰铸铁,对比研究了2种灰铸铁的加工性能.结果表明,具有同强度的2种灰铸铁的布氏硬度和珠光体基体硬度基本相同,但多元合金添加剂合金化灰铸铁的断面敏感性较小,加工性能好,在切削深度分别为1.5、1.75、2.0mm的条件下,其主切削力比Cu合金化灰铸铁的分别降低了23.0％、55.0％和55.2％.     

The resistance to stress corrosion cracking of some Cr–Ni–Fe austenitic steels and alloys

Abstract

Stress-corrosion cracking testing by a variety of methods has been carried out in chloride and caustic environments on a series of Cr–Ni–Fe austenitic steels and alloys containing between 10 and 25 % of chromium and 15 and 45% of nickel. Limited testing has also been carried out on alloys containing additions of molybdenum and copper. The tests have confirmed that increasing the nickel content reduces the susceptibility of Cr–Ni–Fe alloys to stress-corrosion cracking in chloride solutions. Chromium content also affects cracking susceptibility but to a lesser degree. Stress corrosion susceptibility in caustic solutions is affected by these alloying elements in a different way. The results are discussed in relation to currently proposed theories of stress-corrosion cracking.     

铋黄铜组织及性能的研究

与铅黄铜相比,铋黄铜对人体和环境无害,可代替铅黄铜用于许多工程领域。日本、德国等国家都开发了铋黄铜,并研究了铋黄铜的切削性能、力学性能和耐蚀性能。近年来,我国也开展了铋黄铜的研究工作,研究了不同含铋量黄铜的显微组织、力学性能、耐脱锌腐蚀性能,特别是切削性能。结果表明,铋黄铜的组织主要为α相和β相,铋以单质形式存在于晶界和相界;铋黄铜的切削性能与铅黄铜相近;铋能明显改善黄铜的耐脱锌腐蚀性能。目前,铋黄铜的某些性能尚未完全达到铅黄铜的水平,价格也较昂贵,有待进一步研究。     

Mechanism of Stress Corrosion Cracking of Al–Li Alloys

G.V. Akimov's concepts of the corrosion–electrochemical properties of aluminum alloys containing lithium are developed. It is found that binary Al–Li alloys are insusceptible to stress corrosion cracking, even though their dissolution rate under normal conditions can increase by up to 30 times because of the selective dissolution of lithium. The interaction of dislocations with phases formed upon heat treatments is demonstrated to play a determining role in the stress corrosion cracking of all the basic aluminum–lithium alloys, namely Al–Li, Al–Li–Cu, Al–Li–Cu–Mg, and Al–Li–Mg alloys. The stress corrosion cracking of both binary aluminum–lithium alloys and alloys which are in addition alloyed with copper and magnesium has mainly a dislocation–electrochemical mechanism. The effect of electrochemical factors is well represented by the difference in the magnitude between the pitting initiation potential and the repassivation potential.     

Laboratory‐simulated fuel‐ash corrosion of superheater tubes in coal‐fired ultra‐supercritical‐boilers

The corrosion behaviour of a number of Ni‐base alloys of different composition together with a highly‐alloyed austenitic stainless steel has been investigated with and without coating of the samples with alkali‐containing synthetic coal ash. The effects of various parameters have been studied, namely the Cr content (from 20 to 28 mass % Cr), the test temperature (700 and 775°C), the SO₂ content in the gas (1 vol% and 0.25 vol % SO₂) and the alkali sulphate content of the ash (10 and 30 mass%). The results can be explained on the basis of the differences in corrosion mechanisms resulting primarily from the composition of the alloys tested.     

Effect of platinum group metal addition on microstructure and corrosion behaviour of Ti–47·5 at-%Al

Plain and alloyed titanium aluminides of composition Ti–47·5 at-%Al were prepared with the addition of 1·0 at-% platinum group metals (PGMs). The as cast alloys were subjected to potentiodynamic scans in 5, 15 and 25 wt-%HCl solutions at room temperature, and the PGM containing alloys were assessed for their abilities to spontaneously passivate by cathodic modification. Plain titanium aluminide had a duplex microstructure consisting of lamellar (α₂ and γ alternating lamellae) and γ-TiAl phase grains. The introduction of 1·0 at-%PGMs (platinum, palladium and iridium) led to the formation of a new phase, developing more in the γ-TiAl phase grains and a general improvement of corrosion resistance by increasing the corrosion potential to nobler values. Platinum group metal additions to plain TiAl resulted in the corrosion potentials falling in the passive region of plain TiAl, indicating spontaneous passivation of PGM alloyed TiAl in 5 and 15 wt-%HCl solutions. In 25 wt-%HCl solution, the addition of PGMs shifted the cathodic process in the transpassive or active region of plain TiAl, resulting in either case in the dissolution of the alloy due to the absence of an extended passivation region. The cathodic modification of PGM alloyed TiAl occurred as a result of PGM accumulation on the surface of the TiAl alloys, which simultaneously improved the hydrogen evolution efficiency and inhibited anodic dissolution.     

Stress corrosion cracking and selective corrosion of copper-zinc alloys for the drinking water installation

Despite a generally good corrosion resistance to tap and industrial water, many brass taps and fittings have failed in the past by stress corrosion cracking (SCC) and selective corrosion (dezincification or preferred removal of a phase). The experimental investigations of the present study clarify the influence of the ammonia concentration on the two types of corrosion. Notched specimens made of the alloys CuZn39Pb3, CuZn40Pb2, CuZn37, CuZn36Pb2As and CuZn21Si3P are polarized anodically in pure tap water and tap water with realistic ammonia concentrations (15 and 30 ppm) under a simultaneous mechanical loading condition. The influence of stress and of the third alloying elements lead and arsenic are investigated and evaluated. The experiments show that the ammonia additions significantly increase the risk of dezincification of the α-β-brasses. The arsenic in the CuZn36Pb2As alloy avoids dezincification, but enhances the risk of SCC. The rate of selective corrosion and SCC consistently increases with increase in tensile stress.     

The effect of small additions of Zr, Cr, Mg, Al, and Si on the oxidation of 6∶4 brass

The oxidation behavior of 60%Cu-40%Zn brass having small amounts of Zr, Cr, Mg, Al, and Si was studied between 873 and 1043 K in air. The alloying element of Mg was harmful, while other alloying elements were beneficial to oxidation resistance. Particularly, the simultaneous addition of Al and Si decreased the oxidation rate drastically. During oxidation, Zr formed ZrO₂ Cr formed CuCr₂O₄, Mg formed MgO, Al formed Al₂CuO₄, and Si formed amorphous SiO₂. These oxides were incorporated in the oxide scale composed predominantly of ZnO. The oxide scales formed on all the tested alloys were prone to cracking, wrinkling, and spallation.     

Fracture Behavior and Characterization of Lead-Free Brass Alloys for Machining Applications

The stricter environmental, health, and safety regulations address the harmful effects of lead and provide the driving force for the development of lead-free brass alloys. Conventional leaded brass rods are widely used in several manufacturing sectors (i.e., fabrication of hydraulic components, fittings, valves, etc.) due to their superior workability in extrusion and drawing as well as their superior machinability. As machinability performance involves shear and dynamic fracture processes evolved under high strain-rate conditions, the understanding of the mechanical behavior/microstructure interaction is critical in order to successfully tailor candidate lead-free alloys for improved machinability without compromising the reliability of manufactured components. In this work, the mechanical behavior under static and dynamic loading of three lead-free brass alloys (CW510L-CW511L-C27450) in comparison to a conventional leaded brass alloy (CW614N) was studied. The fractographic evaluation of the texture of conjugate fracture surfaces was performed to identify the involved fracture mechanisms and their relation to the alloy microstructure. It was shown that the CW510L lead-free brass alloy is a potential candidate in replacing conventional CW614N leaded brass, combining high tensile strength and fracture toughness, due to the prevalence of the β-intermetallic phase in the alloy microstructure.