Dokumentenidentifikation EP0625593 16.09.1999
EP-Veröffentlichungsnummer 0625593
Titel Verfahren zur Schlammverringerung bei der Zinnplattierung in Säurebädern
Anmelder LeaRonal, Inc., Freeport, N.Y., US
Erfinder Thomson, Donald, Northport, NY 11768, US;
Luke, David A., Macclesfield, Cheshire SK10 2ED, GB;
Mosher, Claudia, Amityfille, NY 11701, US
Vertreter HOFFMANN · EITLE, 81925 München
DE-Aktenzeichen 69419964
Vertragsstaaten AT, BE, CH, DE, DK, ES, FR, GB, GR, IE, IT, LI, LU, MC, NL, PT, SE
Sprache des Dokument En
EP-Anmeldetag 19.05.1994
EP-Aktenzeichen 941077729
EP-Offenlegungsdatum 23.11.1994
EP date of grant 11.08.1999
Veröffentlichungstag im Patentblatt 16.09.1999
IPC-Hauptklasse C25D 3/30
IPC-Nebenklasse C25D 3/60   

Technical Field

The present invention relates to electroplating solutions for reducing the amount of oxidation of stannous tin ions in an electroplating solutions containing same.

Background Art

Electroplating baths containing divalent tin are used widely in industry for plating tin and/or tin alloys onto basis metals. These baths are acidic and are mainly based on acids such as sulfuric, phenolsulphonic, fluoroboric, methane sulfonic, or a combination of hydrochloric and hydrofluoric. In all of these baths, a common problem has been the formation of a sludge during operation that results in a loss of divalent tin and excessive clean-up costs. This sludge occurs because, during the plating process, divalent tin has a tendency to become oxidized to tetravalent tin by oxidation at the anode or by oxygen which is introduced into the bath from the surrounding air. Tetravalent tin thus becomes soluble stannic acid which accumulates in the bath to eventually form β stannic acid which is not soluble and which precipitates to form the undesirable sludge. In order to prevent the formation of this sludge, tin must remain in the divalent state.

When plating tin from these solutions onto strip steel using insoluble anodes, the problem is multiplied even further. Oxygen is liberated at these insoluble anodes to further oxidize divalent tin to its tetravalent state. U.S. Patent No. 4,181,580 describes a process for plating strip steel using insoluble anodes and a method for replenishing tin. Divalent tin is replenished in these plating installations by separately dissolving metallic tin granules in a fluidized bed of acidic plating bath into which oxygen is fed to dissolve the metallic tin. The tin enriched solution is returned to the plating bath thereby replenishing the tin which has been plated out. Excess oxygen in the tin dissolving cell described in this patent can also react with divalent tin to form tetravalent tin; therefore, tin plating machines of this type are particularly subject to formation of tin sludge.

In normal plating installations using soluble anodes and cathode rod agitation, the sludge problem can be minimized. However, when rapid pumping of the solution is used in high speed plating machines, the inclusion of substantial amounts of air into the bath accelerates the oxidation of divalent tin by the oxygen which is present in the air. The sludge problem therefore exists somewhat in normal tin plating installations, is worsened in high speed plating installations, and is further worsened in strip steel machines that use insoluble anodes and tin dissolving cells.

Attempts have been made in the art to minimize sludge formation in these divalent tin baths. A paper by J. McCarthy entitled "Oxidation Characteristics of Tin-Plating Electrolytes," which appeared in the July 1960 issue of Plating magazine, discussed studies of tin oxidation by bubbling oxygen into various tin solutions. U.S. Patent Nos. 5,094,726 and 5,066,367 disclose methods and solutions for limiting sludge using alkyl sulfonic acid based tin solutions in combination with reducing agents or antioxidants to prevent a buildup of tin4+. Dihydroxybenzene reducing agents were disclosed to be very effective for this purpose. A recent paper by Chi Pong Ho of the Nanfang Metallurgical Institute appearing in Vol. 24 #1 of Materials Protection (January 1991) describes the use of reducing agents based on vanadium pentoxide in divalent tin sulfate-sulfuric acid solutions to limit sludge formation.

Tin plating onto steel strip using acid solutions also results in a continual build-up of iron in the plating bath. The iron content can continue to build until its concentration reaches as high as about 30 g/l. Although the iron interferes only slightly in the tin deposition process, it causes a rapid acceleration of tin sludge formation and a decrease in rate of dissolution of metallic tin in the dissolving cell described above. Any antioxidant used to prevent tin sludge formation in strip plating installations should maintain its usefulness in the presence of this iron buildup in the bath.

Chemical Abstract number 88:81098e discloses a tin plating solution comprising Sn(II) ions, sulphate ions, and at least one additive selected form fluoro complexes, Fe ions, Ti ions, Cr ions, Sb ions, V ions and C6-18 alkylamines. The additives are present in order to stabilize the solution against air oxidation.

Chemical Abstract number 91:99172w discloses a tin plating solution comprising Sn(II) ions, sulphate ions, BF4- ions and a small amount of a salt of Ti. The salt of Ti is present as a stabilizer.

Chemical Abstract No. 84:113539k discloses a tin electroplating bath comprising SnSO4, cresolsulfonic acid, K2TiO(C2O4)2.H2O, beta-napthol, sulphuric acid and gelatin.

Summary of the Invention

The present invention provides a solution for use in the electroplating of tin or tin alloys comprising: a basis solution of an organic sulfonic acid or a salt thereof; divalent tin ions; and an antioxidant compound in an amount effective to assist in maintaining the tin ions in the divalent state,

   characterised in that the antioxidant compound is a vanadium, tantalum, zirconium or tungsten compound.

The preferred amount of antioxidant compound ranges from about 0.025 to 5 g/l. Generally, the antioxidant compound is added to the solution as an oxide or a solution soluble compound.

These antioxidant compounds are highly effective when used in a basis solution which comprises an alkane sulfonic acid, an alkanol sulfonic acid, an alkane sulfonate, an alkanol sulfonate, phenol sulfonic acid or a phenol sulfonate. If desired, these solutions may also contain at least one or more of a wetting agent, a brightener, or divalent lead ions to improve or enhance electroplating performance or the resultant deposit characteristics.

The antioxidant compound is added in an amount effective to assist in maintaining the tin ions in the divalent state. Also, this compound may be added to an electroplating solution which contains iron ion contamination.

Detailed Description of the Invention

It has been found that the addition of certain multivalent metal compounds into divalent tin or tin alloy alkyl or alkylol sulfonic acid plating baths results in a substantially reduced rate of tin sludge formation. This is particularly true in high speed plating installations that pump the solution rapidly to provide a high agitation rate thereby introducing air into the plating bath. The improvement caused by the above combination is very significant, particularly in those installations that use insoluble anodes and a tin metal dissolving cell. The multivalent compounds that are effective are those based on vanadium, tantalum, zirconium and tungsten.

The preferred metal compounds are those that are readily soluble in the plating bath, are relatively inexpensive, and readily available in commercial quantities. Typical of the preferred compounds are those of vanadium whose valences are 5+, 4+, 3+, and 2+. Any vanadium compound can be used provided it can form the required ions in solution and is not harmful to the bath. Examples of useful vanadium compounds are vanadium pentoxide (V2O5), vanadium sulfate VOSO4, and sodium vanadate. If vanadium pentoxide (V2O5), previously dissolved in acid, is added to a tin plating bath, the existing V5+ reacts with tin2+ and becomes reduced to V4+, V3+, and V2+, primarily by reacting with tin2+ and metallic tin anodes. The dominant ions in solution are believed to be V4+, V3+ and V2+. If tin2+ becomes oxidized to tin4+, it quickly reverts back to tin2+ by reacting with V2+ and V3+ which then becomes V4+. V4+ then reacts with tin anodes to regenerate V2+ and V3+.

The other components of the electroplating baths are generally known to one of ordinary skill in the art.

The tin compounds useable are those which are soluble in the basis solution. The desired alloying metals can be added in any form which is soluble in or compatible with the basis solution. When sulfonic acids are used, the metals are preferably added in the form of sulfonate or sulfonic acid salts.

The acids which can be used in the invention are mentioned above and illustrated in the following examples. Alkane sulfonic acids containing 1-7 carbon atoms; alkylol sulfonic acids containing 1-7 carbon atoms, aromatic sulfonic acids, such as phenol sulfonic acid, alone or in combination, are suitable for use as the basis solution. Methane sulfonic acid, and "Ferrostan" (i.e., phenol sulfonic acid) are the most preferred. Salts or other derivatives of these acids can also be used, provided that the solution is sufficiently acidic and can retain all necessary components in solution. The pH range of these solutions will generally be less than 5, preferably 2-3 or less.

Any of a wide variety of surfactants can be included in the electroplating solutions of the invention. Since much of the electrodeposited tin is accomplished using high speed electroplating processes and equipment, it is preferred to utilize wetting agents or surfactants which are substantially non-foaming. Typical surfactants of this type can be found in U.S. Patents 4,880,507 and 4,994,155.

When high speed electroplating is not necessary, any of the wetting agents or surfactants of U.S. Patent 4,701,244 can be used. Of those surfactants, the higher cloud point materials are preferred. In addition, the solutions of the invention can contain brighteners, leveling agents or any other additives (such as bismuth compounds or acetaldehyde) which are known to those persons skilled in the art to improve the performance of the electroplating process or the properties of the resulting electrodeposit. The '244 patent discloses such surfactants and other additives.

The amounts of these surfactants or other additives are not critical and optimum amounts will vary depending on the particular agent selected for use and the particular bath in which it is used. Generally, about 0.05 to 10 ml/1 of the wetting agents give excellent results with pure tin and 60/40 tin-lead alloy baths. Higher amounts could be used but there is no particular reason to do so. As the lead content of the bath is increased, additional amounts of these wetting agents may have to be employed.

The electroplating solution can be prepared by placing tin or tin and lead compounds in an excess of the selected acid, adjusting the acid content to the required pH, adding the appropriate wetting agent and antioxidant compound, removing undissolved matter by filtration, and then diluting with water to the final desired volume. The electroplating solution is generally operated at ambient temperatures, although agitation and elevated temperatures are desirable for high speed electroplating. When the electroplating step is conducted under high speed conditions, the agitation and solution turnover due to pumping action maintains the oxygen content of the solution at or near its maximum concentration, thus promoting the tendency of to oxidize tin2+ to tin4+. Under these conditions, the use of the present antioxidants is most important to maintain tin as tin2+.

Various alloys can be produced depending on the relative tin and alloying metal ratios employed in the solutions. For plating a 60-40 tin-lead alloy, for example, 20 g/l of tin metal and 10 g/l of lead metal can be used. Other ratios can be routinely determined by one of ordinary skill in the art.


The scope of the invention is further described in connection with the following examples which are set forth for the purposes of illustration only and are not to be construed as limiting the scope of the invention in any manner.

In order to determine whether a material is capable of reducing sludge in a given tin solution, a laboratory setup of the tin dissolving cell utilizing oxygen with a fluidized bed of tin granules described in U.S. Patent 4,181,580 was constructed. The solution containing the antioxidant is pumped at a rapid rate through a bed of metallic tin granules and oxygen is fed into the solution. The rate of pumping was adjusted to a level capable of keeping the bed fluid with no settling of the metallic tin granules. The result is very rapid mixing of the oxygenated solution with the tin. This method of test is similar to that used by J. McCarthy described above except that a vastly increased oxygen flow is used with very thorough mixing of the oxygenated solution.

The tin solutions used in the above apparatus were the following: Acid Tin2+ g/l Free acid g/l 1) Sulfuric 30 15 (Sulfate) 2) Phenolsulfonic 30 15 (Ferrostan) 3) Methylsulfonic 30 15 (MSA)

All tests were made at ambient temperature, with a constant oxygen flow of 283 × 103 cm3/hr. at 345 kPa (10 cu. ft./hr. at 50 psi), and the same level of pumping to produce the same fluidized bed. The same amount and size of tin granules was used to begin each test, the same volume of solution was used each time in the same apparatus, and the time for each test was 16 hours.

Examples 1-16

A number of electrolytes containing various antioxidants were prepared and tested as noted above. The sulfate baths, those baths which did not contain an antioxidant, and those baths which contained conventional antioxidants (i.e., examples 1-3 and 8-16) were included for comparison purposes. The test results appear in Table 1. Example - Bath Antioxidant (g/l) Dissolved Iron (g/l) Tin IV rate of buildup (g/h) 1-sulfate none 0 54.6 2-sulfate V2O5 - 0.5 g/l 0 30.5 3 - MSA none 0 5.83 4 - MSA V2O5 - 0.5 g/l 0 0 5 - MSA V2O5 - 0.5 g/l 5 0 6 - MSA V2O5 - 0.5 g/l 10 0.36 7 - MSA V2O5 - 0.5 g/l 20 7.83 8 - MSA Catechol - 1 g/l 0 0 9 - MSA Catechol - 1 g/l 5 1.35 10 - MSA Catechol - 1 g/l 10 2.80 11 - MSA Catechol - 1 g/l 20 9.90 12-Ferrostan None 0 0 13-Ferrostan None 3 1.35 14-Ferrostan None 5.7 2.89 15-Ferrostan None 13 2.91 16-Ferrostan None 20 28.7

The sulfate bath used by the Nanfang Metallurgical Institute described earlier, developed tin4+ at a disastrous rate in this test and an unusually high amount of sludge was formed. When 0.5 g/l of V2O5 was added to this bath, there was an improvement; however, the amount of sludge and amount of tin4+ generated was still completely unacceptable. Iron was not added to the bath in this test since it would only have made matters worse, as indicated by all other tests containing iron. Although the use of V2O5 in the Nanfang sulfate bath showed improvement in their tests, its use in strongly oxygenated solutions was of little value. Note the extremely high rate of tin4+ build-up in the sulfate bath test results even with the addition of V2O5. The results indicate that the sulfate bath would be impractical for use in high-speed tin plating, even if V2O5 is added.

The combination of V2O5 with MSA (examples 4-7) showed a remarkable improvement. This combination was capable of reducing the amount of tin2+ buildup to essentially zero. When iron was added to the bath, this build-up remained very close to zero even with an iron content of 10 g/l. The bath containing a very high iron content of 20 g/l showed an increase tin4+ build-up which shows the harmful effect of iron in the bath, even with vanadium present.

The prior art tin baths containing MSA plus a catechol antioxidant (examples 8-11) behaved similarly to the MSA bath with vanadium, but was much worse than the MSA-vanadium bath when iron was added. These improved results with vanadium compared with catechol in the iron-containing MSA baths proved the unexpected superiority of vanadium as an antioxidant in the MSA bath.

The Ferrostan bath containing stannous sulfate and phenolsulfonic acid does not normally contain an additional antioxidant since phenolsulfonic acid is itself known to be a reducing agent or antioxidant. These baths behaved similarly to the MSA plus catechol bath when iron was added in increasing amounts up to 10 g/l. When 20 g/l iron was present in the tests of both the MSA and Ferrostan baths, the build-up of tin4+ in the Ferrostan bath became excessive by comparison to the MSA. The Ferrostan bath thus remains commercially feasible only when iron is periodically removed from production baths to minimize its harmful effects relating to sludge formation.

Examples 17-28

Additional tests were performed using the method of McCarthy. In these tests, the same amount of oxygen was bubbled into each flask under test containing tin granules plus the solution being tested. The major difference between the two test methods is the amount of oxygen bubbling into the test solutions and the time of test. The McCarthy test was run for 7 days at ambient temperature and oxygen flowed at 5.66 × 103 cm3/hr. (0.2 cu. ft./hr.).

To compare the utility of the antioxidants in organic sulfonic acid solutions with that in other divalent tin acid solutions, tests were also performed using tin in the "Halogen" tin bath based on hydrofluoric and hydrochloric acids, used in present day production for high speed plating. Without an antioxidant, the baths exhibited the same sludge problems exhibited by MSA and Ferrostan solutions. Tantalum, tungsten, zirconium, chromium, and molybdenum were also used as additional examples of multivalent ions which perform similar to vanadium and which demonstrate antioxidant qualities when iron was present in the plating solution.

The Halogen bath contained the following components: Stannous chloride 75 g/l Sodium fluoride 30 g/l Sodium bifluoride 45 g/l Sodium chloride 50 g/l pH 3.2 - 3.6

The bath was formulated with an antioxidant in accordance with the present invention. Tantalum was added as tantalum chloride, vanadium as vanadium sulfate, tungsten as sodium tungstate, zirconium as zirconium sulfate, chromium as chromium sulfate, and molybdenum as molybdenum chloride. The amount of metal used as an antioxidant in each solution was 0.28 g/l.

The Ferrostan bath was the same as that in the previous test.

Ten g/l of dissolved iron was added to some test solutions and 20 g/l of dissolved iron to others in order to simulate production baths containing iron. The bubbling oxygen test results are shown in Table 2.

Results show that vanadium, tantalum, zirconium, and tungsten are effective as antioxidants to reduce tin4+ buildup in the presence of oxygen. Chromium and molybdenum are far less effective. The baths in which the antioxidants are effective are organic sulfonic acid based baths such as methyl sulfonic acid and phenolsulfonic acid. Results with the Halogen bath were poor, showing that the antioxidants are not effective in these baths when they contain iron. The Halogen baths are successful in production since iron, which accelerates tin4+ buildup, is constantly being removed from solution and is not permitted to build up to any appreciable amount.

The useful quantities of these multivalent metal antioxidants can vary from about 0.025 g/l of metal in solution to about 5 g/l. Their effectiveness is apparent in very low concentrations with increasing effectiveness with increasing concentration until about 1 g/l. Above 1 g/l, there is only slight improvement. Generally, the multivalent metals either do not co-deposit at all with the metal being plated or they may only be detected in the deposit in trace amounts. Example - Bath Antioxidant (one g/l) Dissolved Iron (g/l) % Divalent Sn lost to form Sn IV 17* - MSA none 10 20.9 18 - MSA vanadium 10 16.4 19 - MSA tantalum 10 15.9 20*-Ferrostan none 10 28.2 21-Ferrostan vanadium 10 15.5 22*-Halogen none 10 95 23*-Halogen vanadium 10 95 24 - MSA zirconium 20 31.8 25 - MSA vanadium 20 30.7 26 - MSA tungsten 20 40.4 27* - MSA molybdenum 20 95 28* - MSA chromium 20 68
Comparative Example

  1. Lösung zur Verwendung beim Galvanisieren von Zinn oder Zinnlegierungen, umfassend: eine Basislösung aus einer organischen Sulfonsäure oder einem Salz davon; zweiwertige Zinnionen; und eine Oxidationsinhibitorverbindung in einer Menge, die wirksam ist, um die Aufrechterhaltung der Zinnionen im zweiwertigen Zustand zu unterstützen, dadurch gekennzeichnet, dass die Oxidationsinhibitorverbindung eine Vanadium-, Tantal-, Zirkonium- oder Wolframverbindung ist.
  2. Lösung gemäss Anspruch 1, umfassend ca. 0,025 bis 5 g/&litre; der Oxidationsinhibitorverbindung.
  3. Lösung gemäss Anspruch 1, worin die Oxidationsinhibitorverbindung ein Oxid oder eine in der Lösung lösliche Verbindung ist.
  4. Lösung gemäss Anspruch 1, worin die Basislösung eine Alkansulfonsäure oder ein Alkansulfonat umfasst.
  5. Lösung gemäss Anspruch 1, worin die Basislösung Phenolsulfonsäure oder ein Phenolsulfonat umfasst.
  6. Lösung gemäss Anspruch 1, die zusätzlich wenigstens ein Benetzungsmittel, ein Glanzmittel und zweiwertige Bleiionen umfasst.
  7. Lösung gemäss Anspruch 6, worin das Benetzungsmittel eines ist, das im wesentlichen nicht-schäumend ist.
  8. Lösung gemäss Anspruch 1, die zusätzlich eine Eisenionen-Verunreinigung einschliesst.
  9. Lösung gemäss Anspruch 1, worin der Sauerstoffgehalt an oder nahe seiner maximalen Konzentration in der Lösung ist.
  1. A solution for use in the electroplating of tin or tin alloys comprising: a basis solution of an organic sulfonic acid or a salt thereof; divalent tin ions; and an antioxidant compound in an amount effective to assist in maintaining the tin ions in the divalent state,

       characterised in that the antioxidant compound is a vanadium, tantalum, zirconium or tungsten compound.
  2. A solution according to Claim 1, comprising about 0.025 to 5 g/l of the antioxidant compound.
  3. A solution according to Claim 1, wherein the antioxidant compound is an oxide or a solution soluble compound.
  4. A solution according to Claim 1, wherein the basis solution comprises an alkane sulfonic acid or alkane sulfonate.
  5. A solution according to Claim 1, wherein the basis solution comprises phenol sulfonic acid or a phenol sulfonate.
  6. A solution according to Claim 1, further comprising at least one of a wetting agent, a brightener, and divalent lead ions.
  7. A solution according to Claim 6, wherein the wetting agent is one which is substantially non-foaming.
  8. A solution according to Claim 1, which further includes iron ion contamination.
  9. A solution according to Claim 1, wherein the oxygen content is at or near its maximum concentration in the solution.
  1. Solution destinée à être utilisée pour la galvanoplastie d'étain ou d'alliages d'étain comprenant : une solution de base d'un acide sulfonique organique ou d'un sel de celui-ci; des ions étain divalents; et un composé anti-oxydant en une quantité efficace pour aider à maintenir les ions étain à l'état divalent,

       caractérisée en ce que le composant anti-oxydant est un composé de vanadium, de tantale, de zirconium ou de tungstène.
  2. Solution selon la revendication 1, comprenant environ 0,025 à 5 g/l du composé anti-oxydant.
  3. Solution selon la revendication 1, dans laquelle le composé anti-oxydant est un oxyde ou un composé soluble dans la solution.
  4. Solution selon la revendication 1, dans laquelle la solution de base comprend un acide alcane-sulfonique ou un alcanesulfonate.
  5. Solution selon la revendication 1, dans laquelle la solution de base comprend de l'acide phénolsulfonique ou un phénolsulfonate.
  6. Solution selon la revendication 1, comprenant en outre au moins un des éléments constitués par un agent mouillant, un brillanteur, et des ions plomb divalents.
  7. Solution selon la revendication 6, dans laquelle l'agent mouillant est un agent mouillant qui est essentiellement non moussant.
  8. Solution selon la revendication 1, qui comprend en outre des ions fer comme impuretés.
  9. Solution selon la revendication 1, dans laquelle la teneur en oxygène est à sa concentration maximale ou au voisinage de celle-ci dans la solution.

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