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DOI : 10.2240/azojomo0296

Influences of Cr Addition on Internal Oxidation of Ni(Al) Solid Solution

Makoto Nanko and Katsumi Uemura

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AZojomo (ISSN 1833-122X) Volume 6 November 2010

Topics Covered

Abstract
Keywords
Introduction
Experimental Procedure
Results & Discussion
Conclusions
References
Contact Details

Abstract

Ni - 5 mol%Al alloys with 0.5 mol%Cr addition were prepared by an arc-melting process. Oxidation process was conducted at temperature ranging from 1000 to 1200°C with Co/CoO buffer to avoid oxidation of Ni. In oxidation at 1000 and 1100°C, Al2O3 rod-like precipitates were formed with small amount of coarse Cr2O3 rod- like precipitates being heterogeneously in the internal oxidation zone. Al2O3 rod-like precipitates seem to be covered by Cr2O3. Oxidizing at 1200°C, (Al,Cr)2O3 rod-like precipitates were formed homogeneously. Morphology of internal oxidation zone implies nuclear formation of Cr2O3 in internal oxidation zone consisting of Al2O3 precipitates does not occur homogeneously at lower oxidation temperatures.

Keywords

Internal oxidation, Ni(Al) solid solution, Cr, Al2O3, Nano-rod array

Introduction

Recently nano-rod array structures have received great attention for high-tech applications such as electronics, optics and optoelectronics [1-6]. Their components and devices were produced by applying various semiconductor production processes such as vapor phase processing [6-12] and etching processes [13-16]. These production processes of nano-rod array structures require expensive equipments such as vacuum chambers. Also, oxide ceramic materials for nano-rod array structure are limited, such as ZnO, TiO2 and SiO2. The template techniques, the direct nano-rod array fabrication by selective deposition in a mold with the nano-pore array, have been also applied to fabricate nano-rod array structures [1, 5, 17-19]. Bonding strength to the substrate and mechanical strength of their ceramic rods produced by their processes are not so high. The nano ceramic rods produced by their processes were just loosely adhered to the substrate.

Internal oxidation is an oxidation mode where the oxide precipitates were formed in the alloy inside. In high-temperature oxidation/corrosion resistance, internal oxidation is very important because chemical composition of alloys may degrade alloy performance. On the other hand, internal oxidation has been applied to fabricate oxide-dispersion strengthen alloys [20]. In cases of Ni(Al) alloys, precipitates of internal oxidation have rod-like or needle-like shapes perpendicular to the alloy surface [21-24]. The oxide morphology of the internally oxidized zone (referred to as IOZ) of these alloys can be applied to prepare nano-rod array after removing Ni in the IOZ. The author’s group has proposed a unique production process for oxide nano-rod array structure using internal oxidation of Ni(Al) alloys [25]. Nano-rod array structures were successfully fabricated by internal oxidation and electropolishing of dilute Ni(Al) alloys. Because the nano-rods are embedded in the substrate, high holding strength of these nano-rods are expected in comparison with the conventional nano-rod array structures prepared by the vapor deposition or etching processes.

When small amount of Cr is added into Ni(Al) solid solution, Cr would be oxidized after formation of Al2O3 precipitates. Because Cr2O3 has the same crystal structure with a- Al2O3, Cr-doped Al2O3 precipitates (i.e., ruby) may be obtained. In the present paper, internal oxidation behavior of Ni(Al) solid solution with small amount of Cr was discussed in order to fabricate Cr- doped Al2O3 nano-rod array structures.

Experimental Procedure

Ni - 5 mol%Al alloys with 0.5 mol%Cr addition (5Al-0.5Cr) were prepared by an arc-melting process. Ni – 5 mol%Al alloys (5Al) were also prepared for comparison. The alloys were annealed at 1300°C for 12 h in vacuum. The alloys were cut and polished in mirror finishing with diamond slurry. The samples were ultrasonically washed in ethanol and dryed at room temperature in laboratory air. Oxidation process was conducted at temperature ranging from 1000 to 1200°C in vacuum with Co/CoO buffer to avoid oxidation of Ni. Electropolishing process with sulphuric acid solution with constant 4 V was applied to the oxidized samples for exposing oxide precipitates on the alloy surface. Microstructure of oxidized samples was observed by scanning electron microscopy (SEM). Phase identification of the oxide precipitates was conducted for electropolished surface by using X-ray diffraction (XRD).

Results & Discussion

Figures 1 – 3 show cross-sectional views of 5Al and 5Al-0.5Cr oxidized at 1000, 1100 and 1200°C, respectively. Rod-like oxide precipitates were developed in 5Al and 5Al-0.5Cr. However oxide rod orientation was sometimes at random, in particular, the Cr added ones. Coarse precipitates were often observed in 5Al-0.5Cr oxidized at 1000 and 1100°C.

Figure 1. Cross-sectional views of samples oxidized at 1000°C.

Figure 2. Cross-sectional views of samples oxidized at 1100°C.

Figure 3. Cross-sectional views of samples oxidized at 1200°C.

Figure 4 shows XRD patterns of 5Al and 5Al-0.5Al oxidized at temperature ranging from 1000 to 1200°C. Oxide products in 5Al consists of mainly θ-Al2O3 at 1000°C. With incrasing oxidation temperature, α- Al2O3 becomes predominat in 5Al. Oxide products in 5Al-0.5Al Cr consists of mainly α-Al2O3 at 1000°C. Cr addition leads to faster θ/α transformation. Because Cr2O3 is the same crystal structure with α-Al2O3, Cr2O3 would act as a catalyst for the θ/α-transformation.

Figure 4. XRD patterns of samples oxidized at various temperatures. (a) 5Al and (b) 5Al-0.5Cr.

Figure 5 shows high magnification images of oxide precipitates oxidized at 1100°C (a) and 1200°C (b). Oxide Precipitates formed at 1100°C consist of dark grains covered partially by a light gray one. Although Al2O3 was detected in all of the oxidized samples by XRD, the oxide precipitates consist of Al2O3, probably, covered by Cr2O3 at low temperatures. On the other hand, oxide precipitates in the sample oxidized at 1200°C have the uniform contrast as shown in Fig. 5 (b). Cr2O3 would be dissolved into Al2O3 grains immideatly.

Figure 5. High magnification images of cross section of the 5Al-0.5Cr oxidized at 1100°C (a) and 1200°C (b).

In internal oxidation of 5Al-0.5Cr, Al is oxidized on the front of the internal oxidation and then Cr is oxidized in internal oxidation zone consisiting of Al2O3 precipetates in Ni(Cr) solid solution materix, because affinity of Al to oxygen is higher than that of Cr. However their oxygen partial pressures in the equilibrium of Cr/Cr2O3 and Al/Al2O3 are much lower than that of the oxidation atmosphere, that is, Co/CoO equilibrium. The area in which only Al is oxidized internally is negligible. At high temperatures such as 1200° C, interdiffusion between Al2O3 and Cr2O3 is so fast that their solid soution is formed immidiately. Figure 6 shows a schematic drawing of the oxide precipitates in the IOZ of 5Al-0.5Cr.

Figure 6. A schematic drawing of internal oxidation of Ni(Al, Cr) solid solution.

Nano-rod array structure can be obtained by using internal oxidation of Ni(Al, Cr) solid solution. Figure 7 shows SEM images of nano-rod structure on Ni(Al, Cr) solid solution. IOZ prepared at 1000 and 1100°C sometime consists of larger oxide precipitates. Nano-rod array structure fabricated at 1200°C was more homogeneous than ones made at lower temperatures. (Al,Cr)2O3 nano-rod array can be produced by using Ni(Al, Cr) solid solution oxidized at high temperatures such as 1200°C.

Figure 7. SEM images of nano-rod array structure on 5Al-0.5Cr by internal oxidaiton and electropolishing.

Conclusions

Internal oxidation of Ni - 5 mol%Al alloys with 0.5 mol%Cr addition was studied for preparing nano-rod array structure by using internal oxidation and electropolishing. In oxidation at 1000 and 1100°C, Al2O3 rod-like precipitates were formed with small amount of coarse Cr2O3 containing rod-like precipitates being heterogeneously in the internal oxidation zone. Fine rod precipitates were most likely comprised of Al2O3 grains covered by Cr2O3. Oxidizing at 1200°C, (Al,Cr) 2O3 rod-like precipitates were formed homogeneously. Morphology of internal oxidation zone implies nuclear formation of Cr2O3 in internal oxidation zone with Al2O3 precipitates does not occur homogeneously at lower temperatures. Nano-rod array structure can be obtained successfully on Ni(Al, Cr) solids solution by using internal oxidation and electropolishing.

References

1. D. Routkevitch, A. A. Tager, J. Haruyama, D. Almawlawi, M. Moskvits and J. M. Xu., “Naonlithographic Nano- Wire Arrays: Fabrication, Physics and Device Applications”, IEEE Trans. Electron Devices, 43 (1996) 1646-1658.
2. S. Y. Lin, E. Chow, V. Hietala, P. R. Villeneuve and J. D. Joannopoulos, “Experimental Demonstration of Guiding and Bending of Electromagnetic Waves in a Photonic Crystal”, Science, 282 (1998) 274-276.
3. N. Beermann, L. Vayssieres, S. E. Lindquist and A. Hagfeldz, “Controlled Aqueous Chemical Growth of Oriented Three- Dimensional Crystalline Nanorod Arrays: Application to Iron(III) Oxides”, J. Electrochem. Soc., 147 (2000) 2456-2461.
4. M. H. Huang, S. Mao, H. Feick, H. Yan, Y. Wu, H. Kind, E. Weber, R. Russo and P. Yang, “Room-Temperature Ultraviolte Nanowire Nanolasers”, Science, 292 (2001) 1897-1899.
5. C. Jamois, R. B. Wehrsphn, L. C. Andreani, C. Hermann, O. Hess and U. Gösele, “Silicon-Based Two-Dimentional Crystal Waveguides”, Photonics and Nanostructures –Fundamentals and Applications, 1 (2003) 1-13.
6. Y. Xia, P. Yang, Y. Sun, Y. Wu, B. Mayers, B. Gates, Y. Yin, F. Kim and H. Yan, “One-Dimensional Nanostuructures: Synthesis, Characterization, and Applications”, Adv. Mater., 15 (2003) 353-389.
7. M. Satoh, N. Tanaka, Y. Ueda, S. Ohshio and H. Saitoh, “Epitaxial Growth of Zinc Oxide Whiskers by Chemical-Vapor Deposition under Atmospheric Pressure”, Jpn. J. Appl. Phys., 38 (1999) L586-589.
8. Y. B. Seung, W. S. Hee, W. N. Chan and J. Park, “Synthesis of Blue-Light-Emmiting ZnGa2O4 Nanowires using Chemical Vapor Deposition”, Chem. Com., 10 (2004) 1834-1835.
9. H. Ham, G. Shen, J.H. Cho, T. J. Lee, S. H. Seo and C.J. Lee, “Vertically Aligned ZnO Nanowires Produced by a Catalyst- free Thermal Evaporation Method and their Field Emission Properties”, Chem. Phys. Lett., 404 (2005) 69-73.
10. M. Guo, P. Diao, Y. J. Ren, B. Wang and S. M. Cai, “Preparation and Characterization of Highly Oriented ZnO Single Crystal Submicrorod Arrays”, Acta Phys. Chim. Sin., 19 (2003) 478-480.
11. Y. S. Park, S. H. Lee, J. E. Oh, C. M. Park and T. W. Kang, “Self-Assembled GaN Nano-rods Grown Directly on (111) Si Substrates: Dependence on Growth Conditions”, J. Crystal Growth, 282 (2005) 313-319.
12. N. Takahashi, Y. Matsumoto and T. Nakamura, “Investigations of Structure and Morphjology of the AlN Nano-Pillar Crystal Films Prepared by Halide Chemical Vapor Deposition under Atmospheric Pressure”, J. Phys. Chem. Solids, 67 (2006) 665-668.
13. Z. Yuan, H. Huang and S. Fan, “Regular Alumina Nanopillar Arrays”, Adv. Mater., 14 (2002) 303-306.
14. H. W. Huang, C. C. Kao, T. H. Hsueh, C. C. Yu, C. F. Lin, J. T. Chu, H. C. Kuo and S. C. Wang, “Fabrication of GaN-based Nanorod Light Emitting Diodes using Self-Assemble Nickel Nano-Mask and Inductively Coupled Plasma Reactive Ion Etching”, Mate. Sci. Eng., 113B (2004) 125-129.
15. Y. Ando, Y. Nishibayadhi and A. Sawabe, “"Nano-rods" of Single Crystalline Diamond”, Dia. Related Mater., 13 (2005) 633- 637.
16. S. Choi, H. Park, S. Lee and K. H. Koh, “Fabrication of Graphite Nanopillars and Nanocones by Reaction Ion Etching”, Thin Solid Films, 513 (2006) 31-35.
17. X. Zhang, B. Yao, L. Zhao, C. Liang, L. Zhang and Y. Mao, “Electrochemical Fabrication of Single-Crystalline Anatase TiO2 Nanowire Arrays”, J. Electrochem. Soc., 148 (2001) G398-400.
18. S. Yamabi, H. Imai and K. Awazu, “Biomimetic Approach for Exact Control of TiO2 Periodic Microstructure”, Chem. Lett., 2002 (2002) 714-715.
19. Y. Maio and S. S. Wong, “General, Room-Temperature Method for the Synthesis of Isolated as Well as Arrays of Single- Crystalline ABO4-Type Nanorods”, J. Am. Chem. Soc., 126 (2004) 15245-15252.
20. B. Ralph, H. C. Yuen and W. B. Lee, “The Processes of Metal Matrix Composites - an Overview”, J. Mater. Proc. Technol., 63 (1997) 339-353.
21. J. S. Wolf, J. W. Weeton and J. C. Freehe, “Observations of Internal Oxidation in Six Nickel-base Alloy Systems”, Sci. Tech. Aerospace Rept., 3 (1965) 2042-2043.
22. H. M. Hindam and W. W. Smeltzer, “Growth and Microstructure of α-Al2O3 on β-NiAl”, J. Electochem. Soc., 127 (1980) 1630-1635.
23. F. H. Stott, G. C. Wood, Y. Shida, D. P. Whittle and B. D. Bastow, “The Morphological and Structural Development of Internal Oxides in Nickel-Aluminum Alloys at High Temperatures”, Oxid. Met., 18 (1982) 127-146.
24. F. H. Stott, G. C. Wood, D. P. Whittle, B. D. Bastow, Y. Shida and A. Martinez-Villafane, “The Transport of Oxygen to the Advancing Internal Oxide Front During Internal Oxidation of Nickel-Base Alloys at High Temperatures”, Solid State Ionics, 12 (1984) 365-374.
25. M. Nanko, K Uemura and K Takeda, “Rod Array Structure Produced by Using Internal Oxidation of Dilute Ni(Al) Alloys”, ECS Trans., 3 [14] (2006) 3-12.

Contact Details

Makoto Nanko and Katsumi Uemura
Department of Mechanical Engineering, Nagaoka University of Technology
Kamitomioka, Nagaoka, Niigata 940-2188, JAPAN

E-mail : [email protected]

This paper was also published in print form in "Advances in Technology of Materials and Materials Processing", 12[1] (2010) 13-18.

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