The Effect of Pulsed Current and Organic Additives on the Hydrogen Incorporation in Electroformed Copper Used in High Vacuum Applications
Authors: Lain Amador Lucia , Rolet Jason , Doche Marie-Laure , Massuti Ballester Pau , Gigandet Marie-Pierre , Moutarlier Virginie , Taborelli Mauro , Ferreira Leonel M.A. , Chiggiato Paolo , Hihn Jean-Yves 
Published: February 2020

The trend in electron accelerators design consists in approaching the poles of the steering magnets close to the electron beam. This implies reducing the bore hosting the vacuum chamber and using very small diameter vacuum pipes [1]. The application of functional thin films by physical vapour deposition in such small diameter chambers becomes then very difficult. A new approach relies on copper electroforming to build the vacuum chamber onto a pre-deposited thin film coating [2]. In this method, unlike the usual process, the pipe is built from the inside out. An aluminium mandrel is coated with a functional thin film first, then by a copper film and finally followed by a thick electroplated copper (1-3mm) structural layer. The replacement of high-purity copper parts by electroformed ones may nevertheless lead to the incorporation of various impurities among which hydrogen, which is generated by solvent reduction and thus trapped into the coating. The aim of the present study is the evaluation of the effect of two main triggers, namely polarization wave modulation and copper electrolyte composition by the addition of organic additives. For this purpose, transient curves in response to pulsed currents have been studied for various cathodic current densities. Two main patterns have been observed as shown in figure 1a in the absence of additive. At low current densities, i.e. below 50 A/dm2, the potential increases rapidly and reaches an average constant value. For higher current densities, two characteristic plateaux can be observed: the first one corresponds to the faradic reduction of copper below the diffusion limit, and the second one, at higher potential, is attributed to the diffusion-limited range that is well known for promoting the hydrogen generation. When adding 33 mg/L of d-xylose, it is possible to reach higher current densities before the occurrence of the transition between the faradic reduction of copper, near the electrode, and the diffusion-limited mechanism. The d-xylose acts clearly by inhibiting the hydrogen discharge. Thank to this, four singular situations have been identified on the curves (marked by the stars on figure 1). They correspond to four pulse sequences (40A/dm2, Ton=20 ms), (40A/dm2, Ton=80 ms), (70A/dm2, Ton=20 ms), (70A/dm2, Ton=80 ms), which were used to prepare samples for characterization in terms of hydrogen outgassing by Thermal Desorption Spectroscopy (TDS) and X-Ray Diffraction (XRD) measurements. TDS experiments show two peaks (figure 2), corresponding to the release of hydrogen trapped into the copper under different forms. The temperature of desorption of the first peak (around 420°C for a ramp of 10K/min) corresponds well to hydrogen interstitial diffusion in the copper deposit [3]. The nature of the second peak (around 600°C) is not yet understood.
[1] C. Steier, A. Anders, D. Arbelaez, J.M. Byrd, K. Chow, S. De Santis, R.M. Duarte, J.-Y. Jung, T.H. Luo, A. Madur, H. Nishimura, J.R. Osborn, G.C. Pappas, L.R. Reginato, D. Robin, F. Sannibale, D. Schlueter, C. Sun, C.A. Swenson, W.L. Waldron, E.J. Wallen and W. Wan, "Progress of the R&D towards a diffraction limited upgrade of the Advanced Light Source", in Proceedings of IPAC, Richmond, USA (2015), p. 1840.
[2] L. Lain Amador, P. Chiggiato, L. M.A Ferreira, V. Nistor, A. T. Perez Fontenla, M. Taborelli, W. Vollenberg, M-L Doche, J-Y Hihn “Development of copper electroformed vacuum chambers with integrated non-evaporable getter thin film coatings” Journal of Vacuum Science and Technology A, accepted.
[3] Y. Fukai “Formation of superabundant vacancies in M–H alloys and some of its consequences: a review” Journal of Alloys and Compounds 356–357 (2003) 270–273.

Figure 1