electrochemical-characterization-of-al86ce10tm4-tmfe-co-ni-and-cu-amor

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Electrochemical Characterizaton of Al86Ce10TM4 TMFe Co Ni and Cu Amorphous Alloys Jianqi Zhang 1 Yichao Fu 2 Tian Zhang 1 August Chang 3 Wenwen Li 1 Pengzhong Shi 1 Na Na 1 Chenyuan Chang 1 Jiyu Jia 1 Dianchen Feng 1 Xuemei Wang 1 Yinfeng Zhao 1 Tao Li 1 Yongchang Huang 4 and Shengli An 1 1 Inner Mongolia University of Science and Technology Baotou 014010 P R China 2 Hohai University Nanjing 210098 P R China 3 University of Wisconsin-Madison Madison Wisconsin 53706 USA 4 Shanghai Jiaotong University Shanghai 200240 P R China Corresponding author: Jianqi Zhang Inner Mongolia University of Science and Technology Baotou 014010 P R China E-mail: jzhang82imust.cn Received date: January 29 2020 Accepted date: February 11 2020 Published date: February 18 2020 Citaton: Zhang J Fu Y Zhang T Chang A Li W et al. 2020 Electrochemical Characterizaton of Al86Ce10TM4 TMFe Co Ni and Cu Amorphous Alloys. Insights Anal Electrochem Vol 6 No.1:2. Copyright: © 2020 Zhang J et al. This is an open-access artcle distributed under the terms of the Creatve Commons Atributon License which permits unrestricted use distributon and reproducton in any medium provided the original author and source are credited. Abstract Electrochemical behavior of Al86Ce10TM4 TMFe Co Ni and Cu amorphous alloys was studied. The amorphous alloys exhibit corrosion resistance and mechanical hardness substantally higher than the traditonal Al alloys on merit of electrochemical homogeneity self-passivatng and latce strengthening of the amorphous matrix. Annealing crystallizaton of the amorphous alloys can furthermore promote these propertes signifcantly due to the added efect of metallic nano-crystals tessellated in the amorphous matrix in mechanisms of ant-corrosion enhancement and precipitate hardening. The oxide flms grown on the amorphous alloys at 630°C in statc air provide superior corrosion resistance due to the resilient blockage of the oxide layers to the environment. The results manifest amorphous Al86Ce10TM4 TMFe Co Ni and Cu alloys present distnguished electrochemical and mechanical propertes and thus have potental aerospace and defence applicatons in terms of their mechanical strength 8001200 MPa high temperature endurance 300420°C and ant-oxidaton 630°C and corrosion resistance 10-610-8 A/cm2. Keywords: Amorphous Alloys Al-Ce-TM Devitrifcaton Oxidaton Corrosion Introducton Over the past three decades since Poon 1 and Inoue 2 reported Al-based amorphous alloys with high tensile strength and good ductlity in 1988 the Al-based amorphous alloys have allured great interest in terms of their peculiar mechanical propertes in comparison to traditonal Al alloys 3-5. Investgatons on glass forming ability thermal stability devitrifcaton microstructure and property 6-12 have become the centered topics thus far. Besides superior mechanical performance electrochemical behavior of the Al-based amorphous alloys has also become the focused study as corrosion resistance is always taken regard as one of the major criteria for practcal applicatons under variant environments such as land sea or space. Quite a few reports have been published in the past years 13-16. In this communicaton we aim to summarize our research regarding the electrochemical characterizaton of the Al86Ce10TM4 TMFe Co Ni and Cu alloys in amorphous state through devitrifcaton process and to the oxide layers formed by high temperature oxidaton. Experimental Amorphous Al86Ce10TM4 TMFe Co Ni and Cu tapes were fabricated by melt-spin method. All the as-spun tapes were 40 μm thick and 4 mm wide. The morphology compositon and structure were examined by transmission electron microscope scanning electron microscope and energy dispersive spectroscopy and X-ray difracton. Devitrifcaton of the as-spun tapes was studied by diferental scanning calorimeter and carried out at designated temperatures under fowing high- purity argon 1718. Oxidaton was conducted at 630°C in statc air. The mechanical and electrochemical behaviors of the alloys and oxide flms were measured using an indentaton tester and a Solartron electrochemical interface. All measurements were repeated fve tmes and the average values were utlized as the fnal results with the uncertainty estmates determined by the least square method. Mini Review iMedPub Journals www.imedpub.com DOI: 10.36648/2470-9867.6.1.2 Insights in Analytical Electrochemistry ISSN 2470-9867 Vol.6 No.1:2 2020 © Copyright iMedPub | This article is available from: http://electroanalytical.imedpub.com/ 1

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Results and Discussion Figure 1 illustrates the potentodynamic polarizatons of the as-spun Al86Ce10TM4 TM Fe Co Ni and Cu alloys measured in 3.56 wt.NaCl aqueous soluton. The measured parametric data are summarized in Table 1. The as-spun alloys have been identfed to be a full amorphous matrix embedded with short range ordered SRO quasi-crystalline clusters 1718. Compared to pure Al or the traditonal Al alloys such as AA 2024 AA 6061 and AA 7075 4 the as-spun amorphous alloys not only exhibit enhanced mechanical hardness Hv but also improved corrosion resistance. As compared to the parametric data of pure Al the corrosion Ecorr and pitng Epit potentals of the amorphous Al86Ce10TM4 TM Fe Co Ni and Cu alloys are more noble while the passivaton current density Ipass dwindles and localized corrosion susceptbility ∆Erep drops except Al86Ce10Cu4. The higher mechanical hardness of the amorphous alloys than the traditonal crystalline counterparts relies essentally on the amorphous matrix of the former whose disordered and tortured atomic latces generate lots of internal stress and strain making the amorphous matrix tougher than the crystalline ones. In additon the amorphous matrix are further strengthened by solute Ce and TM and precipitaton SRO clusters hardening conferring the amorphous matrix superior hardness to the crystalline alloys. The excellent electrochemical behavior should be also ascribed to the amorphous matrix that is not only natvely self-passivatng but also electrochemically homogeneous ofering peculiar resistance to generalized and localized corrosions. To inspect how devitrifcaton of the amorphous matrix in associaton with the mechanical and electrochemical performance evolves the as-spun alloys were annealed at designated temperatures the frst crystallizaton onset and end temperatures and the second crystallizaton onset temperature for which polarizaton curves are marked in black red and blue respectvely for 15 minutes in Ar atmosphere 1718. Figure 2 depicts the electrochemical polarizatons of the post-annealed alloys with the measured data provided in Table 1. Figure 1: Electrochemical polarizatons of the as-spun amorphous Al86Ce10TM4 TM Fe a Co b Ni c and Cu d alloys in 3.56 wt. NaCl soluton. Annealing usually spurs nucleaton and growth of metallic nano-crystals that are precipitated in the amorphous matrix generatng a composite texture consistng of both glassy phase and crystalline precipitates tll the matrix develops into full polycrystalline phases. As seen from Figure 2 the electrochemical characterizaton evolves with the annealing crystallizaton process and both corrosion resistance and mechanical hardness rise initally up to a maximum value corresponding to an ideal texture with uniformly distributed nano-crystals tessellated in amorphous matrix then falls Insights in Analytical Electrochemistry ISSN 2470-9867 Vol.6 No.1:2 2020 2 This article is available from: http://electroanalytical.imedpub.com/

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monotonously to the value as the traditonal Al polycrystalline alloys. Table 1: Electrochemical data and hardness measured from the as-spun post-annealed and post-oxidized Al86Ce10TM4 TM Fe Co Ni and Cu alloys. Alloys T oC Ecorr Icorr Ipass Epit Erep ∆ Erep ∆ Epass Hv VSCE μA/cm2 μA/cm2 VSCE VSCE VSCE VSCE MPa Pure Al 17 25 -1.10 ± 0.04 0.4 ± 0.2 1.5 ± 0.3 -0.74 ± 0.01 -1.14 ± 0.00 0.40 ± 0.01 0.36 ± 0.02 - 25 -0.87 ± 0.01 0.08 ± 0.00 0.64 ± 0.05 -0.38 ± 0.01 -0.45 ± 0.01 0.07 ± 0.02 0.49 ± 0.02 863 ± 17 Al86Ce10Fe 4 304 -0.91 ± 0.02 0.03 ± 0.01 0.02 ± 0.01 -0.66 ± 0.02 -0.86 ± 0.02 0.20 ± 0.02 0.25 ± 0.02 1165 ± 20 Anneal 350 -0.85 ± 0.02 0.02 ± 0.01 0.03 ± 0.02 -0.75 ± 0.02 -0.88 ± 0.01 0.13 ± 0.03 0.10 ± 0.03 984 ± 16 420 -0.93 ± 0.01 0.02 ± 0.01 0.08 ± 0.02 -0.77 ± 0.01 -0.86 ± 0.02 0.09 ± 0.03 0.16 ± 0.02 1033 ± 18 10 h -0.75 ± 0.06 8.0 ± 0.3 8.5 ± 0.3 -0.75 ± 0.02 -0.82 ± 0.05 0.07 ± 0.06 0.55 ± 0.02 848 ± 30 20 h -0.75 ± 0.05 4.0 ± 0.1 6.0 ± 0.3 -0.74 ± 0.03 -0.78 ± 0.04 0.04 ± 0.04 0.41 ± 0.05 707 ± 28 50 h -0.79 ± 0.04 4.6 ± 0.1 6.0 ± 0.3 -0.78 ± 0.02 -0.72 ± 0.02 0.06 ± 0.02 0.42 ± 0.02 650 ± 18 Al86Ce10Fe 4 100 h -0.75 ± 0.10 0.7 ± 0.2 5.0 ± 0.3 -0.75 ± 0.05 -0.73 ± 0.06 0.02 ± 0.02 0.45 ± 0.04 559 ± 24 630oC 200 h -0.73 ± 0.08 1.9 ± 0.4 7.0 ± 0.2 -0.73 ± 0.04 -0.78 ± 0.04 0.05 ± 0.03 0.42 ± 0.03 612 ± 18 oxidation 1000 h -0.73 ± 0.06 2.0 ± 0.2 1.0 ± 0.3 -0.73 ± 0.02 -0.79 ± 0.03 0.06 ± 0.02 0.67 ± 0.02 646 ± 24 2000 h -0.75 ± 0.04 2.0 ± 0.2 2.0 ± 0.2 -0.75 ± 0.03 -0.78 ± 0.02 0.03 ± 0.03 0.65 ± 0.03 806 ± 18 25 -0.71 ± 0.00 0.8 ± 0.2 1.0 ± 0.2 -0.44 ± 0.02 -0.45 ± 0.01 0.01 ± 0.03 0.27 ± 0.02 762 ± 20 Al86Ce10Co 4 284 -0.67 ± 0.03 0.3 ± 0.1 1.0 ± 0.2 -0.63 ± 0.02 -0.78 ± 0.02 0.15 ± 0.04 0.04 ± 0.02 1186 ± 18 Anneal 300 -0.68 ± 0.02 0.6 ± 0. 2 10 ± 2 -0.63 ± 0.02 -0.78 ± 0.02 0.15 ± 0.02 0.05 ± 0.02 1167 ± 16 370 -0.66 ± 0.03 1.0 ± 0.2 10 ± 2 -0.63 ± 0.02 -0.80 ± 0.02 0.17 ± 0.04 0.03 ± 0.02 1053 ± 15 25 -0.54 ± 0.02 0.10 ± 0.08 0.8 ± 0.3 -0.38 ± 0.02 -0.43 ± 0.02 0.05 ± 0.04 0.16 ± 0.02 809 ± 16 Al86Ce10Ni 4 250 -0.46 ± 0.02 0.08 ± 0.02 0.3 ± 0.1 -0.35 ± 0.02 -0.50 ± 0.02 0.15 ± 0.04 0.11 ± 0.02 1066 ± 22 Anneal 300 -0.55 ± 0.03 0.05 ± 0.02 0.3 ± 0.2 -0.38 ± 0.02 -0.50 ± 0.02 0.12 ± 0.04 0.17 ± 0.02 912 ± 16 380 -0.71 ± 0.02 3.0 ± 0.6 - - - - - 840 ± 18 10 h -0.78 ± 0.04 8.0 ± 0.3 8.0 ± 0.3 -0.77 ± 0.05 -0.77 ± 0.03 0.00 ± 0.02 0.33 ± 0.02 1030 ± 18 Al86Ce10Ni 4 20 h -0.79 ± 0.02 8.0 ± 0.3 9.0 ± 0.3 -0.76 ± 0.03 -0.69 ± 0.02 0.07 ± 0.02 0.34 ± 0.03 942 ± 22 630 oC 50 h -0.78 ± 0.03 8.0 ± 0.3 8.0 ± 0.4 -0.77 ± 0.02 -0.78 ± 0.04 0.01 ± 0.01 0.33 ± 0.02 542 ± 20 oxidation 100 h -0.76 ± 0.02 6.0 ± 0.3 7.0 ± 0.3 -0.78 ± 0.04 -0.78 ± 0.04 0.00 ± 0.02 0.32 ± 0.04 476 ± 16 200 h -0.77 ± 0.03 2.2 ± 0.3 5.5 ± 0.3 -0.78 ± 0.02 -0.78 ± 0.02 0.00 ± 0.02 0.32 ± 0.02 576 ± 22 25 -0.62 ± 0.01 1.0 ± 0.2 20 ± 8 -0.54 ± 0.04 -0.65 ± 0.03 0.11 ± 0.07 0.08 ± 0.02 715 ± 11 Al86Ce10Cu 4 219 -0.65 ± 0.02 0.2 ± 0.1 10 ± 2 -0.55 ± 0.02 -0.75 ± 0.02 0.2 ± 0.04 0.10 ± 0.02 1020 ± 18 Anneal 270 -0.73 ± 0.02 4.0 ± 0.8 20 ± 4 -0.70 ± 0.02 -0.74 ± 0.02 0.04 ± 0.04 0.03 ± 0.02 880 ± 15 Insights in Analytical Electrochemistry ISSN 2470-9867 Vol.6 No.1:2 2020 © Copyright iMedPub 3 350 -0.67 ± 0.03 4.0 ± 1.0 40 ± 10 -0.63 ± 0.03 -0.89 ± 0.02 0.26 ± 0.04 0.04 ± 0.02 720 ± 14

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Figure 2: Electrochemical polarizatons of the post-annealed Al86Ce10TM4 TMFe a Co b Ni c and Cu d alloys in 3.56 wt. NaCl soluton. This encourages exploring what are the ideally optmized textures bearing the best mechanical and electrochemical propertes and what mechanisms are laid on such textures with the unique propertes. From Figure 2 and Table 1 even higher mechanical hardness and corrosion resistance can be achieved afer amorphous matrix be annealed at peculiar temperatures for a certain of tme e.g. Al86Ce10Co4 annealed at temperature between 304420°C Al86Ce10Co4 at 284370°C Al86Ce10Ni4 at 250-300°C and Al86Ce10Cu4 at 219°C for 15 min respectvely. The increment in mechanical hardness for the post- annealed alloys over their full amorphous texture relies on the fact that the precipitate hardening by sediment of metallic nano- crystals in the amorphous matrix is an added strengthening contributed to the amorphous matrix. On the other hand the improvement of electrochemical corrosion resistance for the post-annealed alloys over their amorphous matrix stands by the added ant-corrosion enhancement from the metallic nano-crystalline precipitates because majority of the precipitates are FCC-Al and Al11Ce3 nano-crystals which are natvely high self-passivatng and corrosion resistant 18-22. Further devitrifcaton via annealing passing over the ideal textures incurs coarsening of the polycrystalline precipitates thus both mechanical hardness and corrosion resistance diminish not only because the larger-sized crystals lesson the strengthening efects but arises distnct electrochemical inhomogeneites between the polycrystalline phases. As a consequence understanding the devitrifcaton process can greatly help to design fabricate and engineer ideal structures for advanced materials. Insights in Analytical Electrochemistry ISSN 2470-9867 Vol.6 No.1:2 2020 4 This article is available from: http://electroanalytical.imedpub.com/

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Figure 3: Polarizaton curves of the oxide flms grown on as- spun Al86Ce10Fe4 at 630 °C in statc air for a 10 b 200 c 1000 and d 2000 hours. We have discussed the electrochemical behavior of the Al86Ce10TM4 TMFe Co Ni and Cu amorphous alloys and their crystallizatons. As discussed annealing results in devitrifcaton of the amorphous matrix once crystallizaton rides over the ideal texture mechanical and electrochemical propertes fall and fnally stay at the full polycrystalline state. How the alloys behave under high temperature oxidaton and how the oxide flms perform under corrosion environment. The as-spun Al86Ce10TM4 TMFe and Ni amorphous alloys were oxidized at 630°C in statc air for up to 2000 hours. Electrochemical polarizatons of the oxide flms grown on the alloys are present in Figures 3 and 4 respectvely. The measured electrochemical data and mechanical hardness are tabulated in Table 1. As seen from Figures 3 and 4 the oxides grown on the alloys at 630°C exhibit great blocking efect and resistance to corrosion in that corrosion current densites Icorr and Ipass rate low as 10-6 A/cm2 passivaton regions ∆Epass span to 300-600 mV and susceptbility to localized corrosion ∆Erep are minor in 0-70 mV. The electrochemical behavior of the oxide flms grown on the alloys shows much beter corrosion resistance than the own alloys given the alloys are annealed at the same temperatures for the same period of tme. The thickness of the oxide flms grows with oxidaton tme and the thicken oxide flms present higher corrosion resistance than the thinner indicatng the growing oxide flms tend to be more compact inert and resistant to corrosion. Figure 4: Polarizaton curves of the oxide flms grown on as- spun Al86Ce10Ni4 at 630°C in statc air for a 10 b 50 c 100 and d 200 hours. Conclusion Electrochemical behavior of the as-spun post-annealed and post-oxidized Al86Ce10TM4 TMFe Co Ni and Cu alloys was investgated. The corrosion resistance and mechanical hardness of the amorphous alloys are substantally higher than the traditonal Al alloys on merit of the uniqueness of the amorphous textures. Devitrifcaton enables to raise the propertes signifcantly to the maximum values by ideally precipitatng uniformly-distributed nanocrystals in the amorphous matrix. The oxide flms grown on the alloys present good corrosion resistance. The results manifest the amorphous Al86Ce10TM4 TMFe Co Ni and Cu alloys exhibit corrosion resistance and mechanical hardness much superior to the traditonal Al alloys in terms of mechanical strength 8001200 MPa high temperature endurance 300420°C oxidaton 630°C and corrosion resistance 10-610-8 A/cm2 of the former comparing to the strength 550 MPa temperature endurance 200°C and corrosion resistance 10-6A/cm2 of the later therefore mark potental values for aerospace and natonal defence. Acknowledgements This work was supported by Natonal Natural Science Foundaton of China under the grants of NNSF Nos. 50642034 20963006 51061012 51161014 and 51761035 the Ministry of Science and Technology of China under the grant No. of 2012DFA51260 and the Inner Mongolia Key Natural Science Foundaton of China under the grant No. of 2017ZD03. The authors gratefully acknowledge the above fnancial supports. References 1. He Y Poon SJ Shifet J 1988 Synthesis and propertes of metallic glasses. J Aluminum Science 241: 1640–1642. Insights in Analytical Electrochemistry ISSN 2470-9867 Vol.6 No.1:2 2020 © Copyright iMedPub 5

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