Citation: ZHENG Jing-Wu, LU Guo-Ying, QIAO Liang, JIANG Li-Qiang, JIANG Mei-Yan. Copper Electrodeposition from Non-Cyanide Alkaline Baths Containing Methylene Diphosphonic Acid as a Complexing Agent[J]. Acta Physico-Chimica Sinica, ;2011, 27(01): 143-148. doi: 10.3866/PKU.WHXB20110118 shu

Copper Electrodeposition from Non-Cyanide Alkaline Baths Containing Methylene Diphosphonic Acid as a Complexing Agent

1.
College of Chemical Engineering and Materials Science, Zhejiang University of Technology, Hangzhou 310032, P. R. China

Received Date: 20 July 2010
Available Online: 2 December 2010
Fund Project: 浙江省自然科学基金(Y406406)资助项目 (Y406406)

A cyanide-free alkaline copper deposition bath was developed using methylene diphosphonic acid (MDPA, H₄L) as a complexing agent for Cu²⁺. The plating bath was investigated using potentiometric titrations, voltammetric curves, and polarization curves. The potentiometric titration gave dissociation constants for MDPA of: pK₁=1.86, pK₂=2.65, pK₃=6.81, pK₄=9.04, and the stability constants were: pK_ML= 10.65, pK_ML₂ = 5.59, pK_ML₃ = 2.50. Three different complex species were present in the bath as the pH increases: Cu(H₃L)₂, [Cu(H₃L)(H₂L)]^-, and [Cu(H₂L)₂]^2-. MDPA was found to be more likely to form complex species with Cu²⁺ than 1-hydroxyethylene-1,1-diphosphonic acid (HEDPA) from pH 7 to pH 10. At pH 9, [Cu(H₃L)(H₂L)]^- and [Cu(H₂L)₂]^2- were reduced to Cu at the cathode. Compared with the HEDPA system at 10 °C the peak potential shifted to more negative values and the rate of diffusion was faster.
- Non-cyanide bath,
- Methylene diphosphonic acid,
- Copper electrodeposition,
- pH potentiometric titration,
- 1-Hydroxyethylene-1,1-diphosphonic acid
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