Mechanism of Saccharin Transformation to Metal Sulfides and Effect of Inclusions on Corrosion Susceptibility of Electroplated CoFe Magnetic Films

The electroplated magnetic alloys 1.0T Ni80Fe20, 1.6T Ni45Fe55, 2.4T Co40Fe60, obtained in the presence of saccharin, and sputtered magnetic alloys of the same composition showed dramatically different corrosion properties at pH 5.9. The higher corrosion susceptibility of electroplated magnetic alloys, known for many years, was generally attributed to sulfur inclusions into the deposit. However, there was no direct evidence of the structure of sulfur-containing molecules included in deposit. We have analyzed electroplated, EP-CoFe, and sputtered, SP-CoFe, magnetic films using electrochemical, secondary ion mass spectroscopy, X-ray photoelectron spectroscopy XPS, and high-pressure liquid chromatography HPLC techniques. The analysis of electroplated CoFe films obtained in the presence of saccharin revealed saccharin, benzamide, o-toluenbenzamide HPLC and metal sulfides XPS in EP-CoFe deposit. The proposed mechanism for saccharin transformation to metal sulfides involves four steps: i a reductive cleavage of C-S bond in saccharin giving rise to benzamido sulfinate, ii a desulfurization step leading to benzamide and sulfur dioxide, iii an electrochemical reduction of sulfur dioxide to hydrogen sulfide, and iv a reaction between H2 Sa nd M +2

[1]  D. Mockutė,et al.  The interaction of additives with the cathode in a mixture of saccharin, 2-butyne-1,4-diol and phthalimide during nickel electrodeposition in a Watts-type electrolyte , 2000 .

[2]  I. Tabaković,et al.  Roughness development in electrodeposited soft magnetic CoNiFe films in the presence of organic additives , 2003 .

[3]  P. Marcus,et al.  Segregation and adsorption of sulphur on Ni50Fe50(100) alloy: Studies of the surface composition and structure and of the effects on the passivation , 1986 .

[4]  I. Tabaković,et al.  Organic Additives in the Electrochemical Preparation of Soft Magnetic CoNiFe Films , 2000 .

[5]  J. Edwards Aspects of Addition Agent Behaviour , 1964 .

[6]  I. Tabaković,et al.  Effect of Magnetic Field on Electrode Reactions and Properties of Electrodeposited NiFe Films , 2003 .

[7]  W. Stickle,et al.  Handbook of X-Ray Photoelectron Spectroscopy , 1992 .

[8]  Shailesh Gadad,et al.  Oxygen Incorporation during the Electrodeposition of Ni, Fe, and Ni‐Fe Alloys , 1998 .

[9]  L. Shen,et al.  Electrodeposition of soft, high moment Co–Fe–Ni thin films , 2000 .

[10]  P. Marcus,et al.  The Dissolution and Passivation of a Single-Crystal Ni50Fe50 Alloy and the Influence of Sulfur Studied by Electron Spectroscopy for Chemical Analysis , 1986 .

[11]  Tetsuya Osaka,et al.  A soft magnetic CoNiFe film with high saturation magnetic flux density and low coercivity , 1998, Nature.

[12]  P. Marcus,et al.  Corrosion Mechanisms in Theory and Practice , 1995 .

[13]  G. Frankel,et al.  Pitting corrosion of electroplated permalloy films , 1993 .

[14]  P. Marcus,et al.  The sulphur-induced breakdown of the passive film and pitting studied on nickel and nickel alloys , 1989 .

[15]  P. Marcus,et al.  The antagonistic roles of chromium and sulphur in the passivation of NiCrFe alloys studied by XPS and radiochemical techniques , 1990 .

[16]  B. Popov,et al.  Galvanostatic Pulse and Pulse Reverse Plating of Nickel‐Iron Alloys from Electrolytes Containing Organic Compounds on a Rotating Disk Electrode , 1993 .

[17]  P. Marcus,et al.  The influence of sulphur on the dissolution and the passivation of a nickel-iron alloy—I. electrochemical and radiotracer measurements , 1984 .

[18]  R. Alkire,et al.  Role of Sulfide Inclusions on Localized Corrosion of Ni200 in NaCl Solutions , 2001 .

[19]  S. Rouvimov,et al.  Photoluminescence Intensity Analysis in Application to Contactless Characterization of Silicon Wafers , 2003 .

[20]  Hong Xu,et al.  Recent developments in high-moment electroplated materials for recording heads , 2005, IBM J. Res. Dev..

[21]  I. Tabaković,et al.  Composition, Structure, Stress, and Coercivity of Electrodeposited Soft Magnetic CoNiFe Films: Thickness and Substrate Dependence , 2002 .

[22]  Tetsuya Osaka,et al.  A high moment CoFe soft magnetic thin film prepared by electrodeposition , 2003 .

[23]  J. Edwards Radiotracer Study of Addition Agent Behaviour: 3—Incorporation of Sulphur in Nickel Deposited from Solutions Containing p-Toluenesulphonamide and Saccharin , 1962 .

[24]  P. Berçot,et al.  Effects of the structure of organic additives in the electrochemical preparation and characterization of CoFe film , 2002 .

[25]  T. Osaka,et al.  Corrosion Properties of Electroplated CoNiFe Films , 1999 .

[26]  J. Edwards Radiotracer Study of Addition Agent Behaviour: 4—Mechanism of Incorporation , 1964 .

[27]  T. Osaka,et al.  Influence of Crystalline Structure and Sulfur Inclusion on Corrosion Properties of Electrodeposited CoNiFe Soft Magnetic Films , 1999 .

[28]  L. Ricq,et al.  Influence of sodium saccharin on the electrodeposition and characterization of CoFe magnetic film , 2001 .

[29]  Lubomyr T. Romankiw,et al.  Batch-fabricated thin-film magnetic recording heads , 1970 .

[30]  T. Yokoshima,et al.  Effects of Saccharin and Thiourea on Sulfur Inclusion and Coercivity of Electroplated Soft Magnetic CoNiFe Film , 1999 .

[31]  C. Tsang,et al.  High Performance Write Head Using NiFe 45/55 , 1997 .