Tin Plating from the Pyrophosphate Bath

Vaid, J.; Char, T.L. Rama

doi:10.1149/1.2428562

Cited by 18 publications

(9 citation statements)

References 7 publications

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“…Early observations have also shown that tin plating could generally also be carried out with aqueous solutions of tin(II) salts containing pyrophosphate . − In secondary literature of the early 19th century, it has been mentioned that, already in 1850, the “Roseleur solutions” obtained from stannous chloride and sodium pyrophosphate were found to be a potential source for tin plating. , This method was tested again by Vaid and Rama Char, who used the solution obtained from stannous pyrophosphate and sodium pyrophosphate, and reported “a complex being formed” . Because both copper(II) and zinc(II) also form soluble complexes with pyrophosphate in an intermediate pH region, the same system was applied in the electrodeposition of bronzes.…”

Section: Introductionmentioning

confidence: 99%

“…10,11 This method was tested again by Vaid and Rama Char, who used the solution obtained from stannous pyrophosphate and sodium pyrophosphate, and reported "a complex being formed". 8 Because both copper(II) 12 and zinc(II) 13 also form soluble complexes with pyrophosphate in an intermediate pH region, the same system was applied in the electrodeposition of bronzes.…”

Section: ■ Introductionmentioning

confidence: 99%

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Pyrophosphate Complexation of Tin(II) in Aqueous Solutions as Applied in Electrolytes for the Deposition of Tin and Tin Alloys Such as White Bronze

2012

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Electrodeposition of tin and tin alloys from electrolytes containing tin(II) and pyrophosphates is an important process in metal finishing, but the nature of the tin pyrophosphate complexes present in these solutions in various pH regions has remained unknown. Through solubility and pH studies, IR and (31)P and (119)Sn NMR spectroscopic investigations of solutions obtained by dissolving Sn(2)P(2)O(7) in equimolar quantities of either Na(4)P(2)O(7)·10H(2)O or K(4)P(2)O(7) the formation of anionic 1:1 complexes {[Sn(P(2)O(7))]}(n)(2n-) has now been verified and the molecular structures of the monomer (n = 1) and the dimer (n = 2) have been calculated by density functional theory (DFT) methods. Whereas the alkali pyrophosphates Na/K(4)P(2)O(7) give strongly alkaline aqueous solutions (pH ∼13), because of partial protonation of the [P(2)O(7)](4-) anion, the [Sn(P(2)O(7))](2-) anion is not protonated and the solutions of Na/K(2)[Sn(P(2)O(7))] are almost neutral (pH ∼8). The monomeric dianion appears to have a ground state with C(2v) symmetry with the Sn atom in a square pyramidal coordination and the lone pair of electrons in the apical position, while the dimer approaches C(2) symmetry with the Sn atoms in a rhombic pyramidal coordination, also with a sterically active lone pair. A comparison of experimental and calculated IR details favors the monomer as the most abundant species in solution. With an excess of pyrophosphate, 3:2 and 2:1 complexes (P(2)O(7)):(Sn) are first formed, which, in the presence of more pyrophosphate, undergo rapid ligand exchange on the NMR time scale. The structure of the 2:1 complex [Sn(P(2)O(7))(2)](6-) was calculated to have a pyramidal complexation by two 1,5-chelating pyrophosphate ligands. Neutralization of these alkaline solutions by sulfuric or sulfonic acids (H(2)SO(4), MeSO(3)H), as also practiced in electroplating, appears to afford the tin(II) hydrogen pyrophosphates [Sn(P(2)O(7)H)](-) and [Sn(H(2)P(2)O(7))](0). The molecular structures of the mononuclear model units have also been calculated and were shown to have an unsymmetrical complexation and to feature trigonal pyramidal (pseudotetrahedral) coordination. NMR observations have shown that, contrary to the results obtained for Sn(II) compounds, Sn(IV) as present in K(2)SnO(3) or its hydrated form (K(2)Sn(OH)(6)) does not form a pyrophosphate complex in aqueous solution near pH 7. There is also no interference of sulfite.

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Section: Introductionmentioning

confidence: 99%

Section: ■ Introductionmentioning

confidence: 99%

Pyrophosphate Complexation of Tin(II) in Aqueous Solutions as Applied in Electrolytes for the Deposition of Tin and Tin Alloys Such as White Bronze

2012

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“…The continuous electrodeposition of tin was conducted on the resulting 3DC1, employing a pyrophosphate bath 10 (0.25 M Sn 2 P 2 O 7 + 1 M K 4 P 2 O 7 ) as the basic tin plating bath, together with polyethylene glycol (mean molecular weight 600: PEG600) and formaldehyde (HCHO) as additives.…”

Section: Methodsmentioning

confidence: 99%

Communication—Fabrication of a Uniformly Tin-Coated Three-Dimensional Copper Nanostructured Architecture by Electrodeposition

Arai

Munkhbat

Nishimura

2015

J. Electrochem. Soc.

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A three-dimensional copper nanostructure architecture (3DC1) coated uniformly with a tin film was fabricated by electrodeposition. In these trials, a pyrophosphate bath was used for tin plating, and the effects of polyethylene glycol and formaldehyde additives on the morphology of the deposited tin were investigated. Relatively large tin particles were electrodeposited in an inhomogeneous manner over the 3DC1 surface when using a plating bath without additives. In contrast, 3DC1 coated with a uniformly thick tin film was fabricated by employing a bath with the additives. have been widely researched. Among these potential uses, the application of 3D copper nanostructured architectures as current collectors in lithium ion battery anodes is one of the most attractive. Consequently, numerous studies have investigated possible tin-based lithium ion battery anodes, including nanoporous copper formed by de-alloying aluminum from an Al-Cu alloy, 4 nanoporous copper generated by electrodeposition using hydrogen bubbles as a template 5-7 and copper nanopillars fabricated by electrodeposition through a porous alumina membrane.8 Although these 3D copper nanostructured architectures are very effective at improving electrode functions, their manufacture requires many steps and is therefore complex. In contrast, our group has previously developed a very straightforward electrodeposition method for the fabrication of these architectures, in which an organic additive is simply added to the electrodeposition bath.9 This process of making 3D copper nanostructure architectures by one-step electrodeposition (the resulting products henceforth being designated as 3DC1) can be expected to have practical applications in the manufacture of various objects, such as current collectors for tin-based lithium ion battery anodes. To ensure the high performance of such anodes, the uniformity of the tin film on the 3DC1 substrate is important. Unfortunately, in general, it is difficult to form metal films with uniform thicknesses on uneven substrates such as 3DC1 by electrodeposition.In this study, therefore, the conditions associated with the electrodeposition of tin on 3DC1 were examined with the aim of fabricating uniformly tin-coated 3DC1. Experimental3DC1 was fabricated on a pure copper plate (JIS C1201P) with an exposed surface area of 10 cm 2 (3.3 × 3 cm) using a plating bath (0.85 M CuSO 4 · 5H 2 O + 0.55 M H 2 SO 4 + 3 × 10 −4 M polyacrylic acid (mean molecular weight 5000; PA-5000)) under galvanostatic conditions (1 A dm −2 ) without agitation at 25• C. 9 The amount of charge applied was 38 C (3.8 C cm −2 ). The continuous electrodeposition of tin was conducted on the resulting 3DC1, employing a pyrophosphate bath 10 (0.25 M Sn 2 P 2 O 7 + 1 M K 4 P 2 O 7 ) as the basic tin plating bath, together with polyethylene glycol (mean molecular weight 600: PEG600) and formaldehyde (HCHO) as additives. 11 * Electrochemical Society Active Member. z E-mail: araisun@shinshu-u.ac.jpThe composition of the tin plating bath with additives was 0.25 M S...

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“…There are a number of pyrophosphate baths available in the literature [42]. These types of baths containing P 2 O 2 2-is considered as one of the most stable systems and is widely used for Sn plating [59,60]. However, its use is limited in literature due to one disadvantage, that it requires more control and maintenance than the other plating baths.…”

Section: Pyrophosphate Bathsmentioning

confidence: 99%

“…These baths require more control of the electrodeposition parameters. Normally chelating agents and organic additives such as triethanolamine, sodium gluconate, 1, 4-hydroxybenzene, and Triton X-100 have been added in pyrophosphate baths [42,59,60,61,81,82]. The additives are active only up to a certain concentration and have a beneficial effect on the microstructure of the deposits by increasing the cathodic polarization.…”

Section: Additivesmentioning

confidence: 99%

Pulse Electroplating of Ultrafine Grained Tin Coating

Sharma¹,

Das²,

Das³

2015

Electroplating of Nanostructures

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In the electronic packaging industries, soldering materials are essential in joining various microelectronic networks. Solders assure the reliability of joints and protect the microelectronic packaging devices. They provide electrical, thermal, and mechanical continuity among various interconnections in an electronic device. The service performance of all the electronic appliances depends on high strength and durable soldering materials. Lead-containing solders are in use for years, resulting in an extensive database for the reliability of these materials. However, due to toxicity and legislations, lead-free solders are now being developed. As tin (Sn) is the major component of solders, this chapter presents the detailed results and discussion about the metallurgical overview of Sn, synthesis, and characterization of pulse electrodeposited pure tin finish from different aqueous solution baths. The experiments on pulse electrodeposition such as common tin plating baths employed, their chemical compositions, rationale behind their selection and their characterization by bath conductivity and cathodic current efficiency, microstructures, and tin whisker growth are discussed. Further, the effect of pulse electrodeposition parameters such as current density, additive concentration, pH, duty cycle, frequency, temperature, and stirring speed on microstructural characteristics of the coating obtained from sulfate bath and their effect on grain size distribution have been presented.

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Tin Plating from the Pyrophosphate Bath

Cited by 18 publications

References 7 publications

Pyrophosphate Complexation of Tin(II) in Aqueous Solutions as Applied in Electrolytes for the Deposition of Tin and Tin Alloys Such as White Bronze

Pyrophosphate Complexation of Tin(II) in Aqueous Solutions as Applied in Electrolytes for the Deposition of Tin and Tin Alloys Such as White Bronze

Communication—Fabrication of a Uniformly Tin-Coated Three-Dimensional Copper Nanostructured Architecture by Electrodeposition

Pulse Electroplating of Ultrafine Grained Tin Coating

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