Corrosion Science 46 (2004) 14 www.elsevier.

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Letter

Stress corrosion cracking of 18 carat gold

 G.S. Duo
a

a,b,*

, S.B. Farina a, J.R. Galvele

a,b

Departamento Materiales, Comisin Nacional de Energa Atmica, Avda Libertador 8250, o o Gral Paz 1499, 1650 San Martn, Buenos Aires, Argentina b Consejo Nacional de Investigaciones Cientcas y Tcnicas, 1033, Argentina e Received 11 April 2003; accepted 20 May 2003

Abstract Due to the so-called parting limit in gold alloys there is a general belief that coppergold alloys with a gold content above 4045 a/o (atomic %) are immune to stress corrosion cracking (SCC) in aqueous solutions. In the present work it is reported that, by an adequate choice of the corrosive environment, it is possible to produce intergranular SCC in AuCu alloy of 18 carat gold, equivalent to Au 50 a/o, in aqueous solutions. 2003 Elsevier Ltd. All rights reserved.
Keywords: Gold alloy; Stress corrosion cracking; Exchange current density

As shown by Graf [1,2] CuAu alloys are susceptible to stress corrosion cracking (SCC) in a wide variety of aqueous environments. The SCC susceptibility changes with the alloy composition. Graf reported that starting from almost pure copper, by increasing the gold content, the SCC susceptibility increased, up to a value of around 30 a/o (atomic %) gold. For higher gold contents the SCC susceptibility of the Au Cu alloys started to decrease, and it vanished completely above approximately 45 a/o gold. This gold concentration, above which no SCC is found is coincident with the so called parting limit. Graf reported SCC failure times, as a function of the AuCu alloy composition, for the following environments [1,2]: oxygenated ammonia solution, 2% FeCl3 solution, concentrated HCl, 2% H2 CrO4 solution, concentrated HNO3 , 2% PtCl2 solution, and aqua regia. No SCC had been observed for AuCu

Corresponding author. Address: Departamento Materiales, Comisin Nacional de Energa Atmica, o o Avda Libertador 8250, Gral Paz 1499, 1650 San Martn, Buenos Aires, Argentina. Tel.: +54-11-6772-7403; fax: +54-11-6772-7388. E-mail address: duo@cnea.gov.ar (G.S. Du ). o 0010-938X/$ - see front matter 2003 Elsevier Ltd. All rights reserved. doi:10.1016/S0010-938X(03)00132-X

G.S. Du et al. / Corrosion Science 46 (2004) 14 o

alloys, with gold contents above the parting limit, in aqueous solutions, and Grafs conclusion was [1]: . . . Thus on the noble metal side of a homogeneous solid solution system with a noble metal as an alloying component, no stress corrosion cracking will occur. The conclusions reached by Graf received generalized acceptance. Nevertheless, after working with silver rich AgCd alloys it was considered that the case of gold rich AuCu alloys deserved a new analysis. The experience with silver rich AgCd alloys [3,4] showed that SCC could be induced in these alloys under certain experimental conditions. It was found that to produce SCC in silver rich AgCd alloys the environment had to contain dissolved Ag ions, and the specimens had to be kept at the Ag/Ag equilibrium potential. Galvele and Du [5] correlated the specic aco tion of the Ag ions on the SCC susceptibility in these alloys to the exchange current density between the noble metal of the alloy and the metal ions present in the solution. The experience with the silver rich AgCd alloys suggested that AuCu alloys, with gold contents above the parting limit, as it was the case with 18 carat goldcopper alloy, could also be susceptible to SCC if tested in aqueous chloride solutions containing Au3 ions at the Au/Au3 equilibrium potential. To test this possibility, 0.08 cm diameter 18 carat gold wire samples were used. The chemical composition of the alloy (in w/o) was: Cu 22.8%; Ag 0.05%; Cd < 0.001% and Au balance. The composition of the samples was equivalent to Au 52.5Cu 47.5 a/o. The specimens were degreased with acetone, annealed for two hours in argon at 700 C and water-quenched. Prior to the measurements, the surface of the samples was again degreased with acetone and dried with hot air. The mechanical properties of the wires measured after heat treatment was: yield strength (r0:2 ) 463 5 MPa, ultimate tensile strength (rUTS ) 528 5 MPa and elongation to rupture 5.4%. After mechanical tests in air, the fracture surfaces of the samples showed exclusively ductile fracture. For the SCC evaluation the constant potential slow strain rate tests (SSRT) were used. The straining experiments were performed with a modied Hounseld tensometer at an initial strain rate of 4.7 106 s1 . The cell used in the wire straining tests was described in a previous publication [6]. The solutions used were 0.06 M AuCl3 and 0.006 M AuCl3 adjusted with KCl in order to maintain a total chloride concentration equal to 1 M. To avoid the hydrolysis of the AuCl3 a few drops of conc. HCl were added to the solutions. The solutions were prepared with analytical grade reagents and deionized water (Resistivity 18 MX cm). The tests were performed at the equilibrium potential for Au $ Au3 + 3e reaction, by means of a pure gold wire as a reference electrode, and maintaining the potential with a LYP M9 potentiostat at 0.00 VAu=Au3 . All the experiments were carried out at room temperature. The wires were strained to rupture. After fracture, the specimens were observed with a Philips SEM 500 scanning electron microscope. The crack propagation rate was calculated by dividing the length of the brittle zone, in the fracture surface, by the failure time. A total of six constant potential SSRT was performed, and in all cases SCC was found. The failure time in 0.006 M AuCl3 was 141 21 min, and in 0.06 M AuCl3 was 137 10 min, while in air the failure time was 246 16 min. In all cases, in AuCl3 solutions, the fracture surface showed typical intergranular cracks. Fig. 1

G.S. Du et al. / Corrosion Science 46 (2004) 14 o

Fig. 1. Fracture surface of an 18 carat gold wire strained to rupture at 0.00 VAu=Au3 in a 0.06 M AuCl3 + 0.92 M KCl solution. Strain rate: 4.7 106 s1 .

shows the fracture surface of an 18 carat gold wire strained at 0.00 VAu=Au3 in a 0.06 M AuCl3 + 0.92 M KCl solution. The crack propagation rate values measured ranged from 2.2 108 up to 3.5 108 m/s. All the samples tested in air, Fig. 2, showed typical ductile fracture surface.

Fig. 2. Fracture surface of an 18 carat gold wire strained to rupture in air. A typical ductile failure is observed.

G.S. Du et al. / Corrosion Science 46 (2004) 14 o

The conclusion from the present work is that, contrary to Grafs statement [1] AuCu alloys with over a 45 a/o gold content could show SCC if the environment and the experimental conditions are appropriately chosen.

Acknowledgements The present research has been supported by the Consejo Nacional de Investigaciones Cientcas y Tcnicas, Argentina, and by the FONCYT, Secretara de e Ciencia y Tecnologa, Argentina. References
[1] L. Graf, Stress corrosion cracking in homogeneous, non-supersaturated alloys containing noble or no noble metals, in: R.W. Staehle, A.J. Forty, D. van Rooyen (Eds.), Fundamental Aspects of Stress Corrosion Cracking, NACE, Houston, TX, 1969, pp. 187201. [2] L. Gra, The causes and the mechanism of stress corrosion cracking of homogeneous nonsupersaturated alloys as derived from experimental work with alloys containing noble metal components, in: J.C. Scully (Ed.), The Theory of Stress Corrosion Cracking in Alloys NATO, Scientic Aairs Division, Brussels, 1971, pp. 399417. [3] M.L. Montoto, G.S. Du, J.R. Galvele, Corros. Sci. 36 (1994) 1805. o [4] M.L. Montoto, G.S. Du, J.R. Galvele, Corros. Sci. 43 (2001) 755. o [5] J.R. Galvele, G.S. Du, Corros. Sci. 39 (1997) 605. o [6] J.R. Galvele, S.M. de De Micheli, I.L. Muller, S.B. de Wexler, I.L. Alanis, Critical potential for localized corrosion of aluminum, in: R.W. Staehle, B.F. Brown, J. Kruger, A. Agrawal (Eds.), Localized Corrosion, NACE, Houston, TX, 1974, pp. 580599.