Brass stress corrosion

R.P.M. Procter, G.N. Stevens, Formation of cuprous oxide films on a a-brass stress-corrosion fracture surfaces, Corros. Sci. 15 (1975) 349—359. 

Brasses are susceptible to dezincification in aqueous solutions when they contain >15 wt% zinc. Stress corrosion cracking susceptibiUty is also significant above 15 wt % zinc. Over the years, other elements have been added to the Cu—Zn base alloys to improve corrosion resistance. For example, a small addition of arsenic or phosphoms helps prevent dezincification to make brasses more usefiil in tubing appHcations. 

Admiralty Brass and Naval Brass are 30 and 40% zinc alloys, respectively, to which a 1% tin addition has been added. Resistance to dezincification of Cu—Zn alloys is increased by tin additions. Therefore, these alloys are important for thein corrosion resistance in condenser tube appHcations. In these, as weU as the other higher zinc compositions, it is common to use other alloying additives to enhance corrosion resistance. In particular, a small amount (0.02—0.10 wt %) of arsenic (C443), antimony (C444), or phosphoms (C445) is added to control dezincification. When any of these elements are used, the alloy is referred as being "inhibited." For good stress corrosion resistance, it is recommended that these alloys be used in the fiiUy annealed condition or in the cold worked plus stress reHef annealed condition. 

Conditions that favor dezincification include stagnant solutions, especially acidic ones, high temperatures, and porous scale formation (2). Additions of small amounts of arsenic, antimony, or phosphoms can increase the resistance to dezincification. These elements are, however, not entirely effective in preventing the dezincification of the two-phase (cc—P) brasses because dezincification of the P-phase is not prevented (31). Another area of corrosion concern involves appHed or residual stresses from fabrication that can lead to EIC of brasses in the form of stress-corrosion cracking. 

Virtuallv evety alloy system has its specific environment conditions which will prodiice stress-corrosion cracking, and the time of exposure required to produce failure will vary from minutes to years. Typical examples include cracking of cold-formed brass in ammonia environments, cracking of austenitic stainless steels in the presence of chlorides, cracking of Monel in hydrofluosihcic acid, and caustic embrittlement cracking of steel in caustic solutions. 

Brasses with up to 15 percent Zn are ductile but difficult to machine. Machinability improves with increasing zinc up to 36 percent Zn. Brasses with less than 20 percent Zn have corrosion resistance eqmvalent to that of copper but with better tensile strengths. Brasses with 20 to 40 percent Zn have lower corrosion resistance and are subject to dezincincation and stress-corrosion cracking, especially when ammonia is present. 

Bronzes are somewhat similar to brasses in mechanical properties and to high-zinc brasses in corrosion resistance (except that bronzes are not affected by stress cracking). Aluminum and silicon bronzes are very popiilar in the process industries because they combine good strength with corrosion resistance. 

Finally, any living organism dies. Decomposition may generate ammonia at local concentrations high enough to produce stress-corrosion cracking of brass condenser tubes (Fig. 6.1). 

Figure 6.1 Stress-corrosion cracking of a brass condenser tube caused by ammonia from decomposing slime masses lodged on internal surfaces.

Figure 9.4 Both longitudinal and transverse stress-corrosion cracks on a brass heat exchanger tube that had been exposed to ammonia. Note the branching of the cracks.

Other examples of metallurgy decisions are red brass versus admiralty tubes with fresh water on the tubeside and suspected stress corrosion cracking conditions on the shellside, and stainless steel versus carbon steel with chlorides present. A good metallurgist should be brought in when these kinds of decisions are needed. 

Season Cracking—stress corrosion cracking of brass. 

Single-phase a-brasses are susceptible to stress-corrosion cracking in the presence of moist ammonia vapour or certain ammonium compounds Here the predominant metallurgical variable is alloy composition, and in... 

A survey of the literature (see pages 1.114 to 1.117) shows that numerous workers in the field of corrosion have used potential-pH diagrams in order to throw more light on the mechanism of a corrosion process. As an example, some consideration will be given to the stress corrosion of a-brass, which also serves to illustrate diagrams of the type where in... 

Leidheiser, H. and Kissinger, R., Chemical Analysis of the Liquid Within a Propagating Stress Corrosion Crack in 70 30 Brass Immersed in Concentrated NH4OH , Corrosion, 28, 218... 

Lynes, W., Intergranular Corrosion of Alpha-brass and Some Effects of Stress , Corrosion, 21, 125 (1965)... 

Nitrogen compounds These also arise from both natural and synthetic sources. Thus ammonia is formed in the atmosphere during electrical storms, but increases in the ammonium ion concentration in rainfall over Europe in recent years are attributed to increased use of artiflcial fertilisers. Ammonium compounds in solution may increase the wettability of a metaland the action of ammonia and its compounds in causing season cracking , a type of stress-corrosion cracking of cold-worked brass, is well documented. 

Many of the alloys of copper are more resistant to corrosion than is copper itself, owing to the incorporation either of relatively corrosion-resistant metals such as nickel or tin, or of metals such as aluminium or beryllium that would be expected to assist in the formation of protective oxide films. Several of the copper alloys are liable to undergo a selective type of corrosion in certain circumstances, the most notable example being the dezincification of brasses. Some alloys again are liable to suffer stress corrosion by the combined effects of internal or applied stresses and the corrosive effects of certain specific environments. The most widely known example of this is the season cracking of brasses. In general brasses are the least corrosion-resistant of the commonly used copper-base alloys. 

Failure of copper alloys may occur by cracking due to the combined influence of tensile stress and exposure to a corrosive environment. When the stresses are produced in components during manufacture the trouble is usually known as season cracking and failures of brass components due to this form of stress corrosion have been known for many years ... 

Only certain specific environments appear to produce stress corrosion of copper alloys, notably ammonia or ammonium compounds or related compounds such as amines. Mercury or solutions of mercury salts (which cause deposition of mercury) or other molten metals will also cause cracking, but the mechanism is undoubtedly differentCracks produced by mercury are always intercrystalline, but ammonia may produce cracks that are transcrystalline or intercrystalline, or a mixture of both, according to circumstances. As an illustration of this, Edmundsfound that mercury would not produce cracking in a stressed single crystal of brass, but ammonia did. 

Alloys containing only a few per cent of zinc may fail if the stresses are high and the environment sufficiently corrosive. Most types of brass, besides the plain copper/zinc alloys, appear to be susceptible to stress corrosion. An extensive investigation of the effect of additions to 70/30 brass was carried out by Wilson, Edmunds, Anderson and Peirce , who found that about 1% Si was markedly beneficial. Other additions were beneficial under some circumstances and none of the 36 additions tested accelerated stress-corrosion cracking. Further results are given in later papers ... 

Investigations into the effects of arsenic and phosphorus in single-phase brasses on their susceptibility to intergranular attack and stress-corrosion cracking in seawater have shown that the normal addition of arsenic to... 

However, whilst the effects of change in alloy composition upon stress-corrosion cracking susceptibility in the present context may be partly due to their effect upon stacking-fault energy, this does not constitute a complete explanation, since alloying may have significant effects upon electrochemical parameters. The effect of the zinc content of brasses upon their filming characteristics has already been mentioned, while in more recent... 

It is hardly surprising that the preparation of surfaces of plain specimens for stress-corrosion tests can sometimes exert a marked influence upon results. Heat treatments carried out on specimens after their preparation is otherwise completed can produce barely perceptible changes in surface composition, e.g. decarburisation of steels or dezincification of brasses, that promote quite dramatic changes in stress-corrosion resistance. Similarly, oxide films, especially if formed at high temperatures during heat treatment or working, may influence results, especially through their effects upon the corrosion potential. 

Copper and silver tarnish readily in sulphide atmospheres, and copper in contact with sulphur-vulcanised rubber will sometimes react with the sulphur, devulcanising it in the process. The growth of conducting sulphide whiskers on silver is noteworthy as these whiskers may give rise to short circuits across silver-plated contacts. Ammonia has little effect on most metals, but traces will tarnish many copper alloys and cause stress-corrosion cracking of certain stressed brasses. 

Season Cracking cracking resulting from the combined effect of corrosion and stress, which is usually confined to the stress-corrosion cracking of brass in ammoniacal environments. 

Certain internal chemical treatments employed also need strict control to avoid risks of adverse chemical reaction and resultant corrosion. In particular, nitrogen-containing chemicals such as hydrazine and amines require effective monitoring to limit the concentration of ammonia release into steam because the presence of ammonia may, under certain conditions, cause stress corrosion cracking of copper and brasses. 

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