Optimisation of Thiourea Concentration in a Decorative Copper Plating Acid Bath Based on Methanesulfonic Electrolyte

Fabbri, Lorenzo; Giurlani, Walter; Mencherini, Giulia; De Luca, Antonio; Passaponti, Maurizio; Piciollo, Emanuele; Fontanesi, Claudio; Caneschi, Andrea; Innocenti, Massimo

doi:10.3390/coatings12030376

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Optimisation of Thiourea Concentration in a Decorative Copper Plating Acid Bath Based on Methanesulfonic Electrolyte

^1,2

^1,3,*

¹,

¹,

¹,

²,

⁴

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and

Massimo Innocenti

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Department of Chemistry “Ugo Schiff”, University of Florence, Via della Lastruccia 3, 50019 Sesto Fiorentino, Italy

LEM s.r.l. Socio Unico, Via L. Valiani 55, 52021 Bucine, Italy

National Interuniversity Consortium of Materials Science and Technology (INSTM), Via G. Giusti 9, 50121 Florence, Italy

⁴

Department of Engineering “Enzo Ferrari”, University of Modena and Reggio Emilia, Via Università 4, 41121 Modena, Italy

⁵

Department of Engineering, University of Florence, Via di S. Marta 3, 50139 Florence, Italy

⁶

Center for Colloid and Surface Science (CSGI), Via della Lastruccia 3, 50019 Sesto Fiorentino, Italy

⁷

National Research Council-Organometallic Compounds Chemistry Institute (CNR-ICCOM), Via Madonna del Piano 10, 50019 Sesto Fiorentino, Italy

Authors to whom correspondence should be addressed.

Academic Editor: Véronique Vitry

Coatings 2022, 12(3), 376; https://doi.org/10.3390/coatings12030376

Received: 23 February 2022 / Revised: 9 March 2022 / Accepted: 10 March 2022 / Published: 12 March 2022

(This article belongs to the Special Issue Electrodeposition, Characterization and Application of Metal and Alloy Films)

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Abstract

The role of thiourea as an organic additive in the nucleation and growth mechanism was studied for copper deposition and its application in the decorative electroplating and fashion accessory industries. The bath was designed to reduce the environmental and ecological impacts using methanesulfonic acid as electrolyte as an alternative to alkaline cyanide baths. We evaluated the nucleation and growth mechanism of copper exploiting voltametric and chronoamperometric measurements with a brightener concentration ranging from 0 to 90 ppm. We used the Scharifker–Hills model to estimate the type of nucleation mechanism after progressive addition of thiourea. Scanning electron microscope was employed for surface analysis and morphological characterisation of the nuclei. We verified that progressive nucleation is a key step in the obtainment of a shiny and homogeneous copper film, but an excess of thiourea could cause parasitic adsorption reactions on the surface of the substrate. X-ray fluorescence spectroscopy was used for the thickness determination of the copper deposits and the electrodeposition efficiency correlated to thiourea concentration. Finally, the optimal concentration of thiourea was assessed to be 60 ppm for the used formulation of copper plating. View Full-Text

Keywords: electroplating; copper electrodeposition; thiourea; nitrilotriacetic acid; hydroquinone; plating additive; methanesulfonic acid; nucleation and growth; decorative applications; plating industry

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MDPI and ACS Style

Fabbri, L.; Giurlani, W.; Mencherini, G.; De Luca, A.; Passaponti, M.; Piciollo, E.; Fontanesi, C.; Caneschi, A.; Innocenti, M. Optimisation of Thiourea Concentration in a Decorative Copper Plating Acid Bath Based on Methanesulfonic Electrolyte. Coatings 2022, 12, 376. https://doi.org/10.3390/coatings12030376

AMA Style

Fabbri L, Giurlani W, Mencherini G, De Luca A, Passaponti M, Piciollo E, Fontanesi C, Caneschi A, Innocenti M. Optimisation of Thiourea Concentration in a Decorative Copper Plating Acid Bath Based on Methanesulfonic Electrolyte. Coatings. 2022; 12(3):376. https://doi.org/10.3390/coatings12030376

Chicago/Turabian Style

Fabbri, Lorenzo, Walter Giurlani, Giulia Mencherini, Antonio De Luca, Maurizio Passaponti, Emanuele Piciollo, Claudio Fontanesi, Andrea Caneschi, and Massimo Innocenti. 2022. "Optimisation of Thiourea Concentration in a Decorative Copper Plating Acid Bath Based on Methanesulfonic Electrolyte" Coatings 12, no. 3: 376. https://doi.org/10.3390/coatings12030376

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Optimisation of Thiourea Concentration in a Decorative Copper Plating Acid Bath Based on Methanesulfonic Electrolyte

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