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EDTA electrolytes for the deposition of antimony coatings

https://doi.org/10.21285/achb.997

EDN: IUCBBE

Abstract

Antimony coatings serve as a cost-effective alternative to tin in manufacturing printed circuit boards, a replacement for toxic cadmium in protecting steel components from marine corrosion, and a means of producing protective-decorative coatings with high reflectivity. These coatings also find application in semiconductor contacts, lithium-ion battery production, and other applications. This review examines the compositions and key process characteristics of aqueous solutions used for the electrochemical and electroless deposition of antimony coatings. These compositions contain the EDTA ion [(OOCCH2)2NCH2CH2N(CH2COO)2]4-, which functions as a ligand, thereby binding antimony(+3) into complexes. EDTA-based electrolytes are characterized by high throwing power and their ability to yield high-quality, bright, and corrosion-resistant antimony coatings. A typical formulation, for instance, operates at a pH of 0.5–0.7 and contains 50–70 g/dm3 antimony trichloride, 20–30 g/dm3 disodium ethylenediaminetetraacetate dihydrate, 3.5–4.5 g/dm3 of OP-10 additive, and 1.5–2.5 g/dm3 of leveling agent A. Under operating conditions of 18–25 °C and a cathode current density of 1.5–5.0 A/dm2, these electrolytes yield light, silvery, bright, and relatively hard coatings. The deposition process is carried out with a current efficiency of 97.6–100.0% and a rate of 18.0–19.2 µm/h. The obtained coatings, with a thickness of up to 100 µm, possess a defective rhombohedral structure. The throwing power of the electrolyte under these conditions is 76–81%. A further advantage of these electrolytes is their relatively low toxicity. In addition, the review summarizes literature data on the complex formation of antimony(+3) with the EDTA ion in aqueous solution and on the structures of crystalline antimony(+3) ethylenediaminetetraacetates.

About the Author

E. G. Afonin
Kaluga Research Institute of Telemechanical Devices
Russian Federation

Evgeniy G. Afonin, Cand. Sci. (Chemistry), Senior Researcher

4, Кarl Marx St., Kaluga, 248000



References

1. Bartl D., Mudrokh O. Chemical and electrochemical processing of metals. Мoscow: Mashgiz; 1961, 712 p. (In Russian).

2. Korovin N.V. New coatings and electrolytes in galvanotechnics. Moscow: Metallurgizdat; 1962, 135 p. (In Russian).

3. Solovyeva Z.A., Solodkova L.N. Electrodeposition of antimony and its alloys. In: Itogi nauki i tekhniki. Elektrokhimiya = Results of science and technology. Electrochemistry. Moscow: All-Union Institute of Scientific and Technical Information; 1972, vol. 8, p. 215-271. (In Russian).

4. Bryngelsson H., Eskhult J., Edström K., Nyholm L. Electrodeposition and electrochemical characterization of thick and thin coatings of Sb and Sb/Sb 2 O 3 particles for Li-ion battery anodes. Electrochimica Acta. 2007;53(3):1062-1073. DOI: 10.1016/j.electacta.2007.02.009.

5. Howard J.S., Adams Jr. E., Grover T.E., Carpenter N. Improvement in electroplating with antimony. Patent USA, no. 100038; 1870.

6. Betts A.G. Process of electrodepositing of antimony. Patent USA, no. 792307; 1905.

7. Marino Q., Bowen C. An electrolytic process for coating iron or steel with lead or antimony or an alloy of lead and antimony. Patent GB, no. 130302; 1919.

8. Ghosh J.C., Kappana A.N. Electrodeposition of antimony. The Journal of Physical Chemistry. 1924;28(2):149-160. DOI: 10.1021/j150236a005.

9. Bloom M.C. Improvements in or relating to the electrodeposition of antimony. Patent GB, no. 559164; 1942.

10. Bloom M.C. Electrodeposition of antimony. Patent USA, no. 2389131; 1945.

11. Chester A.E. Method of electroplating. Patent USA, no. 2515192; 1950.

12. Little J.D. Electrodeposition of antimony. Patent USA, no. 2683114; 1954.

13. Karash W.P. Electrodeposition of antimony. Patent USA, no. 2711010; 1955.

14. Burnside D.G. Antimony plating. Patent USA, no. 2715096; 1955.

15. Du Rose A.H. Electrodeposition of antimony. Patent USA, no. 2721836; 1955.

16. Smart C.F. Improvements in or relating to the electrodeposition of lead and antimony and alloys thereof. Patent GB, no. 737713; 1955.

17. Smart C.F. Electrodeposition of antimony and antimony alloys. Patent USA, no. 2750333; 1956.

18. Ehrhardt R.A. Electrodeposition with antimony. Patent USA, no. 2753299; 1956.

19. Smart C.F. Antimony plating bath. Patent USA, no. 2779725; 1957.

20. Du Rose A.H. Alkaline antimony plating. Patent USA, no. 2801959; 1957.

21. Du Rose A.H. Heterocyclic nitrogen compound containing antimony plating solutions and process. Patent USA, no. 2813065; 1957.

22. Smart C.F. Antimony plating bath. Patent USA, no. 2817629; 1957.

23. Breining E.R., Nixon F., Vincent W.R. Antimony plating bath and process. Patent USA, no. 2823176; 1958.

24. Schaer G.R. Antimony plating process. Patent USA, no. 2918414; 1959.

25. Schaer G.R. Antimony plating process. Patent USA, no. 2918415; 1959.

26. Gevorkyan V.М. Method of antimony electrodeposition on metals. Author′s certificate no. 142489, USSR; 1961. (In Russian).

27. Shibleva T.G., Povetkin V.V., Zakharov M.S. Structure and properties of antimony electrodeposited from solutions containing trilone B. Zashchita metallov. 1985;6:974-976. (In Russian).

28. Sadana Y.N., Singh J.P., Kumar R. Electrodeposition of antimony and antimony alloys – a review. Surface Technology. 1985;24(4):319-353. DOI: 10.1016/0376-4583(85)90053-6.

29. Abd El Rehim S.S., Awad A., El Sayed A. Electroplating of antimony and antimony-tin alloys. Journal of Applied Electrochemistry. 1987;17:156-164. DOI: 10.1007/BF01009142.

30. Shibleva T.G., Povetkin V.V., Zakharov M.S. Electrolyte for antimony deposition. Author′s certificate no. 1220387, USSR; 1996. (In Russian).

31. Shibleva T.G., Povetkin V.V. Electrodeposition of antimony from trilonate solutions. ChemChemTech. 2001;44(6):127-129. (In Russian).

32. Aoun C.M. Electroplating solution for plating antimony and antimony alloy coatings. Patent USA, no. 6409906; 2002.

33. Ro B., Arai T., Yamamoto T. Electroplating bath of antimony or its alloys. Patent JP, no. 5142571; 2013.

34. A kind of antimony electroplating solution and preparation method thereof. Patent no. 109778259, CN; 2020.

35. Kulikova D.I. Specific features of electric deposition of antimony from aqueous solutions. Herald of Technological University. 2020:23(12):9-11. (In Russian). EDN: ONQQOH.

36. Bhat T.R., Iyer R.K. Studies on EDTA complexes: V. Antimony(III) and bismuth(III) EDTA system. Zeitschrift für anorganische und allgemeine Chemie. 1965;335(5-6):331-336. DOI: 10.1002/zaac.19653350513.

37. Wang E., Chang J. Polarographic study of antimony(III) complex with ethylenediaminetetra-acetic acid. Acta Chimica Sinica. 1965;31(1):18-28.

38. Anderegg G., Malik S. Complexone XVIII. The complexes of trivalent antimony with polyaminocarboxylates. Helvetica Chimica Acta. 1970;53(3):564-569. (In German). DOI: 10.1002/hlca.19700530313.

39. Özer U.Y., Bogucki R.F. Equilibrium studies of antimony(III) chelates in aqueous solution. Journal of Inorganic and Nuclear Chemistry. 1971;33(12):4143-4153. DOI: 10.1016/0022-1902(71)80514-6.

40. Anderegg G. Critical survey of stability constants of EDTA complexes. Oxford – New York – Toronto – Sydney – Paris – Frankfurt: Pergamon Press; 1977, 42 p.

41. Wang E. Polarographic electrode process of antimony(III) complexes with complexones. Collection of Czechoslovak Chemical Communications. 1982;47(12):3243-3251. DOI: 10.1135/cccc19823243.

42. Filella M., May P.M. Critical appraisal of available thermodynamic data for the complexation of antimony(III) and antimony(V) by low molecular mass organic ligands. Journal of Environmental Monitoring. 2005;7(12):1226-1237. DOI: 10.1039/B511453E.

43. Kolbe F., Mattusch J., Wennrich R., Weiss H., Sorkau E., Lorenz W., et al. Analytical investigations of antimony-EDTA complexes and their use in speciation analysis. Fresenius Environmental Bulletin. 2012;21(11c):3453-3458.

44. Kita I., Uehiro T., Iwamoto T., Ouchi A., Yoshino Y. Molecular structure of ethylenediamine-N,N,N’,N’-tetraacetato complex of antimony(III): HSb(C10H12N2O8)•2H2O. Chemistry Letters. 1976;5(4):333-334. DOI: 10.1246/cl.1976.333.

45. Shimoi M., Orita Y., Uehiro T., Kita I., Iwamoto T., Ouchi A., et al. The structure of (Hydrogen ethylenediaminetetraacetato)antimony(III) dihydrate Sb(C10H13N2O8)•2H2O. Bulletin of the Chemical Society of Japan. 1980;53(11):3189-3194. DOI: 10.1246/bcsj.53.3189.

46. Mistryukov V.E., Sergeev A.V., Mikhailov Yu.N., Shchelokov R.N. Synthesis and crystal structure of (CN3H6)[Sb(EDТА)]•2H2O. Koordinatsionnaya khimiya. 1987;13(8):1129-1131. (In Russian).

47. Xie Z., Hu S. Crystal structure of sodium ethylenediaminetetraacetatoantimony(III) trihydrate Na[Sb(EDTA)]•3H2O. Chinese Journal of Structural Chemistry. 1991;10(2):129-131.

48. Marrot B., Brouca-Cabarrecq C., Mosset A. LiSb(edta)(H2O): a convenient precursor to LiSbS2 and LiSbO3. Journal of Materials Chemistry. 1996;6(5):789-793. DOI: 10.1039/JM9960600789.

49. Davidovich R.L., Logvinova V.B., Kaydalova T.A. Antimony(III) ethylenediaminetetraacetate complex compounds with mono and double charged cations. Koordinatsionnaya khimiya. 1998;24(6):424-430. (In Russian).

50. Marrot B., Brouca-Cabarrecq C., Mosset A. [CaSb2(EDTA)2(H2O)8]n: synthesis, crystal structure, and thermal behavior. Journal of Chemical Crystallography. 1998;28:447-452. DOI: 10.1023/A:1021716605217.

51. Fun H.K., Raj S.S.S., Razak I.A., Ilyukhin A.B., Davidovich R.L., Huang J.W., et al. Aminoguanidinum (ethylenediamine-N,N,N’,N’-tetraacetato)antimonite(III) monohydrate. Acta Crystallographica Section C. 1999;55:905-907. DOI: 10.1107/S0108270199002310.

52. Ilyukhin A.B., Davidovich R.L. Effect of a cation on stereochemical activity of lone electron pair in structures of ethylenediaminetetraacetatoantimonates(III), Cat[Sb(EDTA)]•xH2O[Cat+ = Cs, NMe4, 1/2{H2en}, NH4, Tl, K, 1/2Mn, 1/2Cd, or NH3CH2CH2COOH]. Crystallography Reports. 1999;44(2):204-213.

53. Ilyukhin A.B., Poznyak A.L. Stereochemical activity of a lone electron pair in antimony(III) and bismuth(III) chelates: crystal structures of Ca[Sb(Edta)]2•8H2O and Ba{[Bi(Edta)]2H2O}•H2O. Crystallography Reports. 2000;45(1):56-63. DOI: 10.1134/1.171137.

54. Davidovich R.L. Сomplexonates of antimony(III) and bismuth(III). Vladivostok: Dalnauka; 2003, 192 p. (In Russian).

55. Hu S., Chen M. Study on the secondary bonding and coordination polyhedra in crystal of antimony(III) complexonate family. Acta Physico-Chimica Sinica. 2005;21(6):646-652. DOI: 10.3866/PKU.WHXB20050614.

56. Shen J., Jiang Q.-Y., Zhong G.-Q., Jia Y.-Q., Yu K.-B. Synthesis, crystal structure and thermal decomposition of a novel 3D heterometallic Sb(III)-Pr(III) complex [Sb2-μ4-(EDTA)2Pr(H2O)5]NO3•4H2O. Acta Chimica Sinica. 2007;65(16):1588-1592.

57. Zhong G.Q., Shen J., Jiang Q.Y., Jia Y.Q., Chen M.J., Zhang Z.P. Synthesis, characterization and thermal decomposition of SbIII-M-Sb III type trinuclear complexes of ethylenediamine-N,N,N’,N’-tetraacetate (M: Co(II), La(III), Nd(III), Dy(III)). Journal of Thermal Analysis and Calorimetry. 2008;92:607-616. DOI: 10.1007/s10973-007-8579-5.

58. Zhong G., Shen J., Jiang Q., Yu K. Synthesis and structural determination of a novel heterometallic complex [Sb2(EDTA)2-μ4-Co(H2O)2]•5,15H2O. Chinese Journal of Chemistry. 2011;29(12):2650-2654. DOI: 10.1002/cjoc.201100394.

59. Shen J., Jin B., Jiang Q., Zhong G., Hu Y., Huo J. Synthesis, characterization, and magnetic properties of heterometallic trinuclear complex with Sb(III) and Ho(III). Inorganica Chimica Acta. 2012;385:158-163. DOI: 10.1016/j.ica.2012.01.045.

60. Shen J., Jin B., Jiang Q.-Y., Znong G.-Q., Hu Y.-M., Huo J.-C. Edta-linked 5p-4f trinuclear heterometallic complex: syntheses, X-ray structure and luminescent properties. Journal of Coordination Chemistry. 2012;65(17):3040-3049. DOI: 10.1080/00958972.2012.709628.

61. Wu Z.-X., Zhong G.-Q. Synthesis and characterization of the trinuclear heterometallic complex [Sb2(edta)2Gd(H2O)4]NO3•3H2O. Journal of Synthetic Crystals. 2013;42(8):1707-1711.

62. Shen J., Jin B., Jiang Q.-Y., Zhong G.-Q., Hu Y.-M., Huo J.-C. Synthesis, structures, luminescent and magnetic properties of heterometallic 5p-4f compounds with ethylenediaminetetraacetate. Zeitschrift für anorganische und allgemeine Chemie. 2013;639(1):89-95. DOI: 10.1002/zaac.201200401.

63. Li D., Zhong G.-Q. Synthesis and crystal structure of the bioinorganic complex [Sb(Hedta)]•2H2O. Bioinorganic Chemistry and Applications. 2014:461605. DOI: 10.1155/2014/461605.

64. Liu T., Yang R.-G., Zhong G.-Q. Synthesis, structural characterization, and antibacterial activity of novel erbium(III) complex containing antimony. Bioinorganic Chemistry and Applications. 2018:4313197. DOI: 10.1155/2018/4313197.

65. Berezin N.B., Gudin N.V., Filippova A.G., Chevela V.V., Mezhevich Zh.V., Yakhyaev E.D., et al. Electrodeposition of metals and alloys from aqueous solutions of complex compounds. Kazan: Kazan State Technological University; 2006, 276 p. (In Russian).

66. Berezin N.B., Berezina T.N. General regularities of cathode recovery of metal complexes and their anodic formation. Butlerovskie soobshcheniya. 2009;17(6):1-12. (In Russian). EDN: NCZXAB.

67. Gudin N.V. Role of structural factors in the deposition of metals from solutions of complexes. Herald of Technological University. 2016:19(9):10-18. (In Russian). EDN: VVVKLP.

68. Qi Y., Liu X., Wang W. Electrochemical reduction of Bi(III)/Sb(III)/Te(IV) with EDTA and tartaric acid in sulfuric acid solution. Journal of the Electrochemical Society. 2019;166:D719. DOI: 10.1149/2.0641914jes.

69. Senda A., Takano Y., Nakagawa T. Formation of antimony film by electroless plating. Journal of the Surface Finishing Society of Japan. 1992;43(6):589-594. (In Japanese). DOI: 10.4139/sfj.43.589.

70. Periferakis A., Caruntu A., Periferakis A.-T., Scheau A.-E., Badarau I.A., Caruntu C., et al. Availability, toxicology and medical significance of antimony. International Journal of Environmental Research and Public Health. 2022;19(8):4669. DOI: 10.3390/ijerph19084669.


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For citations:


Afonin E.G. EDTA electrolytes for the deposition of antimony coatings. Proceedings of Universities. Applied Chemistry and Biotechnology. 2025;15(3):294-304. (In Russ.) https://doi.org/10.21285/achb.997. EDN: IUCBBE

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