The Structure of Poly-molybdate Ions and It's Relevance to the Electroplating of Molybdenum Alloy

聚钼酸根离子的结构及其与钼合金电镀的关系

• 批准号: 09305052
• 负责人: AWAKURA Yasuhiro
• 金额: $ 21.57万
• 依托单位: KYOTO UNIVERSITY
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (A)
• 财政年份: 1997
• 资助国家: 日本
• 起止时间: 1997 至 1999
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-09305052/
• 关键词: Electroplated Mo-Ni alloy; Induced codeposition; Poly-molybdate ion; Atomic structure; X-ray diffraction; Factor analysis; Small angle x-ray scattering; Molybdenum complex; 合金電析; ラマンスペクトル; 誘起共析; Ni-Mo合金; 平衡定数; 錯体生成; めっき; X線異常散乱; 因子分析; クエン

Structures of poly-molybdate ions in acid Ni-Mo aqueous solutions have been investigated by the anomalous x-ray scattering (AXS), EXAFS, small angle x-ray scattering, and factor analysis methods. In a solution containing only molybdenum ions, molybdenum ions form a poly-molybdate ion consisting of seven edge-sharing MoO6 octahedra. In a solution containing both Mo and Ni ions, there exists another poly-molybdate ion consisting of 6 edge-sharing MoO6 surrounding a Ni ion. The coordination number of Mo-Mo pairs decreases by half by adding citric ions. This indicates that the large ply-molybdate ion is decomposed to smaller molybdate ions due to formation of citric complexes. This is also confirmed by the SAXS measurements. Since molybdenum-nickel alloys are not electrodeposited from the solutions without citric ions, we expect that the decomposition of large poly-molybdate ions in the solution is closely related with the mechanism of the induced codeposition of molybdenum and nickel alloy.

用异常x射线散射（AXS）、EXAFS、小角x射线散射和因子分析等方法研究了Ni-Mo酸性水溶液中多钼酸盐离子的结构。在只含钼离子的溶液中，钼离子形成由七个共用边的MoO6八面体组成的多钼酸盐离子。在同时含有Mo和Ni离子的溶液中，在Ni离子周围存在另一种由6个共边MoO6组成的多钼酸盐离子。柠檬酸离子的加入使Mo-Mo对的配位数降低了一半。这表明，由于形成柠檬酸配合物，大的钼酸盐离子被分解成较小的钼酸盐离子。SAXS的测量结果也证实了这一点。由于没有柠檬酸离子的溶液中不能电沉积钼镍合金，因此我们认为，溶液中大量多钼酸离子的分解与钼镍合金诱导共沉积的机理密切相关。

项目成果

E.Matsubara et al.: "Structural Study of Poly-Molybdate Ions in Acid Mo-Ni Aqueuous Solutions"Special Issue of Jpn. J. Appl. Phys.. Supp.38-1. 576-581 (1999)

E.Matsubara 等：“酸性钼镍水溶液中多钼酸根离子的结构研究”日本特刊。

E.Matsubara and K.Shinoda: "Structural Study of Poly-Molybdate lons in Acid Mo-Ni Aqueuous Solutions, The 2nd Int'l Conf. on Synchrotron Radiation in Materials Science, Kobe, Japan, Oct. 3-Nov. 3 (1998)"Special lssue of Jpn. J.Appl. Phys.. Suppl. 38-1. 57

E.Matsubara 和 K.Shinoda：“酸性钼镍水溶液中聚钼酸盐的结构研究”，第二届材料科学同步辐射国际会议，日本神户，10 月 3 日至 11 月 3 日（

E.Matsubara et al.: "Structural study of poly-molybdate ions in acid Mo-Ni aqueous solutions" Jpn.J.Appl.Phys.(to be published). (1999)

E.Matsubara 等人：“酸性 Mo-Ni 水溶液中聚钼酸根离子的结构研究”Jpn.J.Appl.Phys.（待出版）。

K.Murase et: "Determination of Molybdenum(VI) Species and Composition In Ni-Mo Alloy Plating. Baths by Factor Analysis of Raman Spectra"J. Electrochem. Soc.. 147. (2000)

K.Murase 等人：“通过拉曼光谱因子分析测定 Ni-Mo 合金镀液中的钼 (VI) 形态和成分”J。

E.Matsubara et al.: "Structural studies of aqueous solutions by the anomalous x-ray scattering method" High Temp.Mater.Proc.17. 133-143 (1998)

E.Matsubara 等人：“通过反常 X 射线散射法对水溶液进行结构研究”High Temp.Mater.Proc.17。