Research article
Transformation of amorphous passive oxide film on Zr65Cu17.5Ni10Al7.5 metallic glass ribbons

https://doi.org/10.1016/j.jallcom.2022.167265Get rights and content

Highlights

  • Tg = 374 °C and Tx = 461 °C lead to a large supercooled region of 87 °C.

  • Upon linear sweep voltammetry of Zr-MG ribbon hydronium ions react with ZrO2 layer.

  • Stable corrosion potential & corrosion current density of 1.00 mAcm–2 were recorded.

  • Crystalline ZrO2 composition turns into a fully amorphous Zr-rich oxide layer.

  • 1.33 %wt. hydrogen absorption capacity was recorded at 400 °C under 6 MPa.

Abstract

Zr-based metallic glass with favorable properties and a stable surface oxide layer is foreseen as an alternative material for water/nuclear reactor pressure systems. The high stability of Zr65Cu17.5Ni10Al7.5 metallic glass (MG) in anodic and cathodic regions within 0.5 M H2SO4 solution is evidenced by the negligible shift in the corrosion potential upon linear sweep voltammetry cycles. The recorded passivation current density of 15 mA cm–2 is very similar to 430 stainless steel. The formation of an amorphous Zr-rich oxide phase and slight dissolution of the native ZrO2 layer are confirmed by scanning transmission electron microscopy – energy dispersive X-ray analysis, which result from the interaction of hydronium ions (H3O+) with the oxide layer during linear polarization. Furthermore, promising hydrogen absorption of the produced Zr-based MG ribbons (1.33 %wt, non-reversible) by Sieverts-type apparatus were recorded at 400 °C and under 6 MPa, which evidences that this alloy can minimize the hydrogen evolution within the chamber due to the coverage with an oxide film and thereby prevent accidents.

Introduction

Amorphous materials have become widespread due to a set of their unique magnetic, mechanical and thermophysical properties, as well as high corrosion resistance and catalytic activity [1], [2], [3], [4]. The properties of these materials are associated with the absence of long-range order of atoms in their structure. The interaction of amorphous materials with hydrogen is one of the most promising areas of research since existing materials that absorb hydrogen, such as palladium, have high costs and are also prone to hydrogen embrittlement. At the same time, amorphous materials are able to transport hydrogen as efficiently as crystal analogs [5], [6]. Previous studies of the sorption properties of multicomponent and amorphous materials by electrochemical and pressure gas isotherms methods show matching results [7], [8].

Zirconium-based alloys are among the most promising amorphous materials with relatively high glass-forming ability [9], [10]. These alloys are very easy to synthesize due to the low critical cooling rate and wide temperature range of the supercooled liquid [11]. Zirconium alloys, in general, have unique thermophysical and mechanical properties, and they are also capable of absorbing a relatively large amount of hydrogen (1.4 H/M) [12], [13], [14], [15]. It is also extremely promising to create amorphous copper-zirconium alloys interacting with hydrogen in a corrosive environment [12], [16], [17], [18], [19], [20].

Alloy selection for accident tolerant fuel cladding in commercial light water reactors has prime importance where the U.S. Department of Energy Office of Nuclear Energy does extensive research to generate less hydrogen and heat than the conventional alloys [21]. In fact, the U.S. nuclear navy zirconium was used as a cladding material because of its higher transparency to neutrons compared to uranium, making the reactors more robust in submarine applications [22], [23]. Various improved Zr-based cladding alloys and/or their oxide forms that significantly improve resistance to waterside corrosion and hydrogen absorption have been developed to increase the economic efficiency and safety of nuclear power plants, and a few improved Zr-based alloys have already been introduced in commercial nuclear power plants [24], [25], [26], [27], [28], [29], [30], [31]. In addition to these properties, the dimensional stability (irradiation void or swelling resistance) of the fuel rod and fuel assembly during irradiation is a potential concern. Several state-of-the-art Zr-based alloys were confirmed by X-ray line analysis. Model and first-principles calculations were utilized to suffice the use of these alloys in fuel cladding systems [32], [33], [34], [35]. Compared to the existing crystalline metallic alloys, metallic glasses including Zr-based ones were proven to have relatively superior corrosion resistance due to the robust passive oxide formation [36], [37], [38], [39], [40].

In order to assess the adequateness of these state-of-the-art amorphous metallic alloys for extreme environments, the passive oxide layer on the material surface has to be analyzed. In this article, the electrochemical stability of the quaternary Zr-base metallic glass (MG) system, Zr65Cu17.5Ni10Al7.5 was investigated. The potentiodynamic polarization studies in different acidic solutions have confirmed the very low corrosion current density of this alloy within 10–5-10–6 A cm–2 [41]. This type of MG exhibits a remarkable compression and bending plasticity under quasi-static loading at room temperature along with a high elastic limit of 2.2 % [42]. Moreover, Zr65Cu17.5Ni10Al7.5 BMGs can be superplastically deformed into high-performance complex micro amorphous components due to the extensive supercooled liquid region, the difference between the crystallization and glass transition, above 100 °C [43]. We first determined the passivation kinetics of the oxide film present on the amorphous zirconium ribbons in an acidic medium using linear sweep voltammetry (LSV). The influence of LSV on the microstructure and composition was evaluated by high-angle annular dark-field imaging (HAADF) and energy dispersive X-ray (EDX) in scanning transmission electron microscopy (STEM). Furthermore, the hydrogen gas absorption properties of these alloys were investigated in a Sieverts-type apparatus. The thermal properties of the as-spun ribbons and the formation of the new phases after gas absorption are determined by differential scanning calorimetry (DSC) and X-ray diffraction (XRD), respectively.

Section snippets

Synthesis of metallic glass ribbons

The ingots of Zr65Cu17.5Ni10Al7.5 alloy were fabricated by induction melting (Diavac Ltd., Yachiyo, Chiba, Japan) in an argon atmosphere by arc melting from mixtures of pure Zr, Cu, Ni, Al (purity of each element used was ≈ 99.9 %). The metallic glass ribbons were prepared by single copper roller melt spinning. After vacuuming below 10–3 Pa, high purity argon up to the pressure of 5 kPa was applied. The vacuum prior to melt spinning is in the typical evacuation levels (10–2 to 10–3 Pa) in the

Structural and thermal analyses

The X-ray diffractogram shows that the as-spun tape is completely amorphous without traces of crystallization indicated by the diffuse peaks (Fig. 1a and b). The DSC trace depicted in Fig. 1c shows a typical glass transition Tg (350 °C) and crystallization temperature, Tx (461 °C), measured from their onset. For metallic glass and other glasses, Tg is where the relatively hard and brittle glassy state starts to transform into a viscous state as the temperature increases further, whereas Tx

Conclusion

This study discusses the electrochemical and structural behavior of a quaternary Zr65Cu17.5Ni10Al7.5in an acidic environment. The X-ray diffraction pattern reveals its globally amorphous nature in its as-spun state. A clear Tg = 350 °C and Tx = 461 °C were determined from their onset points, leading to a large supercooled region of 111 °C. The electrodes submerged in a 0.5 M H2SO4 were polarized at potentials from –0.8–0.6 V with potential increments of 0.2 V at each scan. A very stable

CRediT authorship contribution statement

Baran Sarac: Conceptualization, Data curation, Methodology, Investigation, Formal Analysis, Writing – original draft. Askar Kvaratskheliya: Investigation, Formal Analysis, Writing – review & editing. Vladislav Zadorozhnyy: Methodology, Investigation,Formal Analysis, Writing-Original Draft, Funding Acquisition. Yurii P. Ivanov: Methodology, Data curation,Investigation,Formal Analysis, Writing-Original Draft, Funding Acquisition. Lixia Xi:Writing – review & editing,Funding Acquisition. Semen

Declaration of Competing Interest

The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.

Acknowledgments

This work was supported by the Ministry of Science and Higher Education of the Russian Federation in the framework of the federal academic leadership program Priority 2030 under increase competitiveness program of NUST "MISiS" (grant number К1-2022-032). Y.P.I. acknowledges the support from the European Research Council (ERC) under the Advanced Grant “ExtendGlass single bond Extending the range of the glassy state: Exploring structure and property limits in metallic glasses” (Grant ERC-2015-ADG-695487),

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