US2457152A - Electrodepositing composition and bath - Google Patents

Electrodepositing composition and bath Download PDF

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US2457152A
US2457152A US493755A US49375543A US2457152A US 2457152 A US2457152 A US 2457152A US 493755 A US493755 A US 493755A US 49375543 A US49375543 A US 49375543A US 2457152 A US2457152 A US 2457152A
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bath
tin
deposits
baths
per liter
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Raymond A Hoffman
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EIDP Inc
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EI Du Pont de Nemours and Co
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/30—Electroplating: Baths therefor from solutions of tin
    • C25D3/32—Electroplating: Baths therefor from solutions of tin characterised by the organic bath constituents used

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  • This invention relates to the electrodeposition of tin and is more particularly directed to tinplating compositions, tin-plating baths, and to processes for the electrodeposition of tin in the presence of a bath-soluble polyethercontaining a multiplicity of ether groups attached to aliphatic carbon atoms.
  • Tin-plating baths knownto the art are subject to disadvantages'which severely limit their usefulness.
  • Organic addition agents have been employed in attempts to improve the character of deposit obtained from such baths and while the addition agents eflect some refinement of crystal structure and some modification in appearance the tin electrodeposits are of limited usefulness and the baths from which they are made are diflicult and uneconomical to employ.
  • Tin electrodeposits produced from prior art baths are usually crystalline at even rather low current densities and athigher current densities the deposits are spongy. They are not adherent and many are so poorly adherent that they can easily be removed from the base metal by rubbing.
  • compositions, baths, and processes by the use of which there may be obtained tin deposits which are dense, adherent, and of good appearance. It is a further object to provide tin-plating baths. compositions, and processes by means of which there may be obtained deposits that can be readily brightened by fusion to a brilliant appearance and that can be subjected to lacquer baking operations without becoming discolored. Further objects of this invention will become apparent hereinafter.
  • this invention are attained by the use in a tin electrodepositing bath of a bath-soluble polyether containing a multiplicity of ether groups attached to aliphatic carbon atoms.
  • a bathsoluble polyether in tin electrodepositing baths one obtains deposits of a markedly improved ent invention in any tin-plating bath.
  • typical baths are given:
  • the following alkaline bath is of the type shown in the Oplinger Patent 1,841,978 and in the Wernlund et al. Patent 1,919,000.
  • Bath V The following bath is not verystable when used over long periods of time but it is given because it is frequently mentioned in the literature and it is markedly benefited by the use of polyethers according to the present invention.
  • the ratio of fluoride to stannous chloride must be carefully selected and related to the operating pH of the bath as more specifically described below.
  • the baths may be made up with stannous chloride and with an alkali fluoride, say sodium, potassium, or ammonium fluoride.
  • an alkali fluoride say sodium, potassium, or ammonium fluoride.
  • the concentration of stannous chloride may vary from about thirty-seven and one-half to one hundred and fifty grams per liter and the alkali fluoride may similarly vary from thirty-seven and one-half to one hundred and fifty grams per liter. More specifically, it is desired to maintain the concentration of the stannous chloride and the alkali fluoride between about sixty and one hundred grams per liter.
  • fluoride and SnCl is stanthan about grams per liter.
  • the pH of the formula is the maximum at which the bath is stable while the optimum pH for plating is within the range from about 1 to 5 and preferably the pH should be in the range from about 2 to 4.
  • a bath formulation that is stable at a given pH may also be stable at a lower pH but the'preferred ranges are those within which addition agents are generally most effective.
  • the acidity of the bath may be that which results from the bath constituents though adjustments of the pH may be made as desired.
  • the pH will fall within the range of about pH 1 to 5 while more specifically it is desired to have the pH from about 2 to 4.
  • pH as indicated above should have a value between 1 and 5 or, preferably, between 2 and 4.
  • the solution should be examined as to its potential. This can of course be done by making up a small amount of solution first rand then adjusting the entire bath composition in accordance with the findings. If the solution potential is below the values given for P in the above formulae, then it may be increased (made more negative) by increasing the MF/SnCl ratio; if the potential is too high it may be lowered by decreasing the MF/SnClz ratio. In adjusting the potential it will be noted that the potential increases with an increase in pH and decreases with a decrease in pH. Ordinarily potential will not be adjusted by changing the pH, though this means of adjustment is available if it is preferred to use some preselected ratio of MP to such.
  • the potential may be determined in any suitable manner as by connecting a potentiometer across a piece of tin metal and a ealomcl half cell in customary manner.
  • the static solution potential of tin against the bath is then obtained as volts after corrections are made for the calomel half cell.
  • the bath temperature is that customarily used for tin-plating baths, and deposits are obtained at room temperature. It is ordinarily preferred, however, to use the bath at a temperature from about 55 to 65 C. in order to secure the optimum quality of deposit over a broad current density range.
  • Organic addition agents may advantageously be employed in any of the foregoing baths to improve the appearance, and characteristics of tin deposits.
  • One or more organic addition agents may be used and there may be included in the bath, for instance, sulflte cellulose waste or a naphthol sulfonic acid.
  • Gelatin or glue may be used to advantage for some uses but it will be found that glue and certain other organic agents are not too satisfactory when the deposit is to be heat-fused or lacquer-baked.
  • Metal brighteners may also be included in any of the foregoing baths and there may be used small amounts of a soluble compound of the triad metals of the iron group including iron, cobalt,
  • the polyether may most conveniently be marketed in tin-plating compositions which contain some or all of the materials to be dissolved in water to make a tin-plating bath. Thus they may be sold in mixtures with tin compounds and any of the other bath components or additions as above described. Maintenance compositions may similarly be compounded with a polyether and other materials required for bath maintenance.
  • the polyethers should be bath-soluble. That is, they must be soluble enough to permit them to exercise an effect in the bath. They should be hydrophilic and even if they are very diflicultly soluble they may be added to a plating solution in a solvent or dispersed in other manners already well known to the art. Some of these polyethers behave very peculiarly in the bath in that they form stable suspensions which are effective. Apparently there is enough "bath-solubility for the agents to act. One very excellent agent, Igepal C," though it goes into solution very readily when simply added to the bath and is very effective therein, can nevertheless be separated from the bath by filtration.
  • any bath-soluble polyether may advantageously be employed for the modification of tin deposits according to the present invention it is preferred to use compounds containing a multiplicity of aliphatic ether groups. More specifically it is preferred to use compounds which contain a multiplicity of alkyleneoxy groups, -(CH2)n--O. the oxygen of which is attached to aliphatic carbon atoms.
  • R1 equals hydrogen, OH, or a monovalent organic radical
  • R4 equals hydrogen, OH, or a monovalent organic radical
  • Y equals a polyether group
  • R1 may be designated as hydrogen, OH, or a monovalent organic radical such as alkyl, alkoxy, aryl, aryloxy, aralkyl, alkaryl, acyl, amine, amido-, thioalkyl, and thioaryl.
  • R4 may represent any of the groups just mentioned for R1. It may be the same as Rt or it may be different in a given compound. In the formulas given hereafter an eifort will be made to let the letters of the above and the following formulas represent the same substituent groups and throughout the application numerous examples will be given of groups which may be used in the above. formula or in any of the following. It is to be noted that in Formula 2 where R1 is followed by X and in other similar formulas R1 would obviously not have the value OH.
  • polyalkylene oxides The preferred polyethers are of the class generally known. as polyalkylene oxides.
  • the formulae for polyalkylene oxides may be shown thus:
  • RlX RzO MR4 wherein X equals oxygen or NH, R1 equals hydrogen or a monovalent organic radical, R2 equals a bivalent hydrocarbon radical, preferably -CH2 or CH2CH:, R4 equals hydrogen, OH, or a monovalent organic radical, and wherein n is a whole number at least as great as 2.
  • X oxygen or NH
  • R1 hydrogen or a monovalent organic radical
  • R2 equals a bivalent hydrocarbon radical, preferably -CH2 or CH2CH:
  • R4 equals hydrogen, OH, or a monovalent organic radical
  • n is a whole number at least as great as 2.
  • amines such as decylamine, undccyla'mine, cetylamine. and diphenylamine.
  • alkylene oxides may be produced using such substituted lsocyclic compounds as ethylene oxide, propylene oxide, butylene oxide, butylene dioxide, cyclohexene oxide, glycide, epichlorhydrine, or the like.
  • the products are solid, semisolid, or even fluid materials which are soluble in water. These products. are generally believed to be composed of a plurality 'of alkylene groups linked together in linear configuration through ether. linkageaand to bear hy-- droxyl groups at the ends of the polymericchain.
  • a polyethylene oxide is represented by HO-(CHzCHzO-MCHzCHaOH (Staudinger, 10c. cit.) These polymers are sometimes called polyethylene. glycols. It is understood that these products are not intended to'cover cyclic dimers of alkylene oxides such as dioxan.
  • bath-soluble polyalkylene oxide may be employed for the modification of tinplatiug deposits it is preferred to use polymers having a molecular weight over about 400. Poly-.
  • Molecular weight Hydroxyl number wherein hydroxyl number has its usual meaning, 1. e., the number of milligrams of potassium hydroxide necessary to neutralize the acetic acid obtained'by the saponification of the acetylated compound from one gram of sample.
  • the amount of a polyether to employ for the modification of a tin electrodeposit and tinplating bath will depend upon the specific bath and upon the conditions of use and can best be determined in each particular instance by a few simple trials. It may be indicated that in general about .001 to 25 grams per liter of a polyether will be found to exercise a desirable modiflcation of a tin-plating deposit. More specifically with respect to the unsubstituted polyethylene oxides it may be suggested that from about 0.001 to 5 grams per liter will be satisfactory while more specifically from about 0.01 to 2 grams per liter will be found satisfactory.
  • reaction with aldehydes probably proceeds by an esterification reaction between equal molecular quantities of the aldehyde and ethylene oxide as follows:
  • n40 olnl on A phenol may be defined as an alcohol in which the hydroxyl group (or groups) is attached to an aromatic ring. They are therefore related to aliphatic alcohols, undergoing many of the same reactions and will react with ethylene oxide in an analogous manner.
  • Example 1 G./l. Stannous sulfate (SnSOr) 54 Sulfuric acid Carbowax 1500 .4 1.0
  • Ezamplel Carbowax 1500 was used in a tin-plating composition made according to the formula of Bath IV:
  • Example 5 Carbowax" 1500 was used in a tin-plating solution made according to the formula of Bath V:
  • the soft white waxy polyethylene oxide sold commercially under the trade name of Carbowax 1500 produced adherent sponge-free. deposits of tin that were ofa smooth matte-white texture over a plating range of from 5 to 100 noticeable physical change in the solution.
  • Example 2 A tin-plating bath according to the formula of Bath II was made as follows:
  • the Carbowax” 1500 in this bath produced deposits that were similar to those obtained from the bath of Example 1, effectively stopping the tendency to form sponge or crystalline deposits and producing an adherent, smooth white deposit over a wide current density range.
  • the physical appearance of the bath remained before its addition.
  • Example 3 A tin-plating composition according to the formula of Bath III was made up as follows:
  • Example 6 Carbowax 1500 was used in a tin-plating composition made according to the formula of Bath VI:
  • Example 7 Carbowax" 1500 was used in a tin-plating bath made according to the formula of Bath VII as follows:
  • the deposits obtained from this bath before adding Carbowax 1500 were simllarto those of the preceding bath. producing deposits that were i crystalline, poorly adherent, and scantily covered at current densities below 30 amps/sq. ft.
  • the addition of Carbowax 1500 eliminated the growth of tin crystals and produced adherent, smooth, matte-white deposits above 15 amps/sq. ft, The appearance of the bath was unchanged.
  • Example 8 Carbowax" 1500 was used in a tin-plating hath made accordin8 to the formula of Bath VIII, as
  • Example 9 Y Carbowax" 1500 was used in a tin-plating hath made according to the formula of Bath IX as follows:
  • Example 10 Apreferrgd composition was prepared according to the formula described under Bath 1:. as
  • Example 11 The foregoing examples from 1 to 10 inclusive were repeated using "Carbowax 4000, a fairly hard, white, waxy substance in place of "Carbowax” 1500. The results were about the same, using the same amount of material as described in each of the above examples.
  • Example 12 4 i small amount of foam was produced during eiec trolysis when these materials were present.
  • Example 14 The presence of 0.2 g./l. of Igepal C or C'IA in a bath made according to formula IX produced adherent, smooth, lustrous deposits over a current density range of from 3 to 120 amps/sq. ft. The increased throwing power obtained by use of this material was remarkable, producing deposits in very deep recesses. Fusion of the tin deposit resulted in an exceptionally smooth and brilliant surface comparable to tin plate that has been "hot dipped. Foaming was produced during passage of the current when this material was present.
  • Example 15 The cream colored, pasty solid sold commercially under the name of Emulphorf 0 or 0N,
  • Example 16 Emulphor ON was also used in the remaining nine tin-plating baths as described previously and was found to produce excellent deposits when present to the extent of from 0.1 to 5.0 g./1. Particularly good results were obtained from Bath IV and Bath X, the deposits being uniformly lustrous and adherent over the entire area of 9. Hull cell test plate, which indicates a current density range of from 3 to 120 amps/sq. ft. or greater. The deposits obtained could be readily flowbrightened by heating to the proper temperature and they closely resembled hot dippedtinplate in appearance. A small amount of foaming was noted during electrolysis.
  • Example 17 Peregal O is a honey colored liquid that is believed to be a polyethylene oxide made in accordance with U. S. Patent 1,970,578. When added to a bath prepared as described under Bath I, the deposits were like those described under Example 15. The optimum quantity appeared to be 1.0 g./l., larger amounts than this affording no further improvement in the deposits. A small amount of foaming was noted during electrolysis of the solution.
  • Example 18 Peregal O was also used in Baths II to X inclusive and was found to be as effective as Emulphor ON, when present to the extentof 0.1 to 5.0 g./1., the amount required depending largely upon the type of tin bath used. As in Example 16, particularly excellent results were obtained when this material was used in Bath IV and Bath X, the deposits being uniformly lustrous and adherent without sin of sponging over the entire area of .a Hullcell test plate. The deposits were easily "flow-brightened by fusing at the proper temperature and closely resembled "hot dipped" tinplate in appearance. A small amount of foaming was noted during passag of the current.
  • Example 19 The brown gummy product obtained by reacting polyvinyl alcohol with ethylene, oxide was j readily soluble in water and was added in the form of its aqueous solution to the plating baths described under Baths I, IV, V, and X. Smooth, lustrous, uniform deposits, that were adherent and free from sponge were obtained from these' 1 baths by the presence of from 1.0 to 2.0 g./l. of the above product. A slight brown tinge and slight foaming were noted when this material was i present. I
  • Example 20 The white pasty semi-solid material obtained by reacting cetyl alcohol with ethylene oxide disduced considerable foam when added to the plating baths, but produced semi-bright deposits up to 40 amps/sq. ft. in Baths III and IX and semibrightdeposits up to 80 amps. per sq. ft. in Bath X, the remainder of the depositsxbeing'mattewhite in all cases.
  • Example 21 The product formed by reacting phenol with ethylene oxide was an amber colored liquid that readily dissolved in the plating baths or in water. This material was particularly effective in preventing the formation of sponge or crystalline deposits and was further effective in producing smooth, lustrous, adherent deposits from such baths as I, IV, IX, and X. It was particularly efiective in Bath X, the deposits obtained being semi-bright, lustrous and readily flow-brightened by proper heating.
  • Example 23 was in some respects better than Emulphoi ON described in Examples and 16 since it did not-produce foam.
  • Example 24 Four. diflerent products were obtained by reacting octadecyl alcohol with ethylene oxide in the ratio of 1:9.1, 1:11.6, 1:17, and 1:20 respectively to form materials that were cream to light brown semi-solids in appearance. Since their effect was much the same they will be described jointly rather than separately. One or more of each product obtained was used in all ten of'the plating baths described to produce deposits that were smooth and matte-white in Baths I, II, III,
  • Example 25 The dark red liquid formed by reacting aniline and ethylene oxide was added to such baths as VIII, IX, and X in amounts of from 0.2 to 5 g./l. in which it dissolved to form clear and colorless solutions. as great as some of the better examples, but nevertheless was sufiicient to produce adherent matte-white deposits and greatly retarded the formation of sponge during electrolysis.
  • Example 26 The product obtained by reacting tannic acid and ethylene oxide in accordance with the teachbaths as I and X to the extent of from 0.1 to 10 g./l., produces smooth white adherent deposits rom Bath I Bath X.
  • Example 27 The colorless liquid obtained by reacting propylene oxide with octadecenyl' alcohol and which would probably conform to the formula:
  • cnuito cnomo ni was used in such baths as IV and X in amounts It was found to be somewhat insoluble since oily droplets were of from 0.1 to 3.0 grams per liter.
  • Hull cell test plate the adherence and covering power being noticeably improved by its presence.
  • nofcn-cmowz is predominantly nonaethylene glycol in which 12:9, although small amounts of higher and lower glycols are also present. It is a water white liquid having an effect similar to the effect of Carbowax 1500 and 4000 when'used in sufficiently large quantities, which is approximately ten times the quantity of Carbowax 4000, so that to obtain best results it is necessary to add from 1 to 20 g./l. of this material, depending upon the characteristics of the individual plating baths.
  • Example 29 I The materials known as Tweens" are exam- Its effect upon the deposits was not 1 and smooth lustrous deposits from 17 pics of polyoxyalkylene derivatives of hexitol anhydride partial long chain fatty acid esters whose starting materials are the hexahydric alcohols, mannitol and sorbitol. They are usually amber colored liquids or solids easily soluble in water and having a profound effect upon the type of deposit obtained from the various tinplating baths. When present to the extent of from 0.1 to 5.0 g./l. in Baths I to X, inclusive, the deposits obtainable are modified to such an extent as to permit the deposition of smooth, white, adherent deposits. They are particularly beneficial in bath x from which smooth, lustrous, adherent, sponge-free deposits may be obtained by the presence of 0.4 gl.
  • the Tweens used included those designated 20, 40, 60,-81, 80, 81, and 85.
  • a process for the electrodeposition of tin comprising effecting electrodeposition from an aqueous, tin-plating bath which contains a soluble tin compound, the process comprising eifecting electrodeposition in the presence of 0.001 to 25 grams per liter of a bath soluble polyalkyleneoxide of molecular weight over 400 as an addition agent.
  • the step. comprising 'eflecting electrodeposition from an aqueous. tin-plating bath which contains a soluble tin compound
  • the process comprising eflecting electrodeposition in the presence of 0.001 to 25 grams per liter of a bath-soluble polyalkylene oxide terminally substituted with a monovalent organic radical and having a molecular weight over 400 as an addition agent.
  • a process for the electrodeposition of tin comprising efiecting electrodeposition from an aqueous, tin-plating bath which contains a soluble tin compound, the process comprising effecting electrodeposition in the prestains a soluble tin compound, the process comprising eflecting electrodeposition in the presence of 0.001 to 25 grams per liter of a bath-soluble polyethylene oxide terminally substituted with a substituted isocyclic radical and having a molecular weight over 400 as an addition agent.
  • composition having a stannous chloride concentration of between about 37.5 and 150 grams per liter. and the bath satisfying the equation:
  • pH is equal to about 1 to 5
  • pH is equal to about 1 to 5
  • MP is alkali fluoride
  • a process for the electrodeposition of tin comprising effecting electrodeposition from an aqueous, tin-plating bath which contains a soluble tin compound; the process comprising effecting electrodeposition in the presence of 0.001 to 25 grams per liter of a bath soluble polyethylene oxide terminally substituted with a monovalent organic radical and having a molecular weight over 400 as an addition agent.
  • the pH is equal to about 1 to 5
  • It has a value from 0.1 to 1.0
  • MB is alkali fluoride
  • the mol ratio MF/SnClz is about from 2 to 12, the static solution. potential of tin in the bath being equal in volts to from -0.055 pH -0.265 to -0.055 pH -0.370.
  • a tin electrodepositing composition comprising an alakali fluoride, stannous chloride, and 0.001 to 25 grams per liter of a bath-soluble polyethylene oxide terminally substituted with a monovalent organic radical and having a molecular weight over 400 as an addition agent, the composition upon being dissolved in water being adapted to give a stannous chloride concentration of between about 37.5 and 150 grams per liter and satisfying the equation:
  • the pH is equal to about 1 to 5
  • MP is alkali fluoride
  • the mol ratio .MF/SnCh is about from 2 to 12
  • the static solution potential of tin in the bath being equal in volts to from 0.055 pH 0.265 to 12.
  • An aqueous, tin electrodepositing bath containing 'a soluble tin compound and 0.001 to 25 grams per liter of a bath-soluble polyalkylene oxide of a molecular weight over 400 as an addition agent.
  • a tin electrodepositing bath comprising an aqueous solution of an alkali fluoride, stannous chloride, and 0.001 to 25 grams per liter of a bathsoluble polyalkylene oxide of a molecular weight over 400 as an addition agent, the stannous chloride concentration being between about 37.5 and 150 grams per liter and the bath satisfying the equation:
  • MF alkali fluoride
  • the mol ratio MF/SnClz is about from 2 to 12, the static solution potential of tin in the bath being equal in volts to from 0.055 pH 0.265 to 0.055 pH 0.370.
  • the step comprising effecting electrodeposition from an aqueous bath which contains an alkali fluoride, stannous chloride, and 0.001to 25, grams per liter of a bath-soluble, unsubstituted polyethylene oxide having a molecular weight over 400 as an addition agent, the composition having a stannous chloride concentration of between about 37.5 and 150 grams per liter and the bath satisfying the equation:
  • pH is equal to about 1 to 5
  • R has a value from 0.1 to 1.0
  • MF is alkali fluoride
  • the mol ratio MF/SnClz is about from 2 to 12
  • polyethylene oxide having a molecular weight over 400 as an addition agent, the composition having astannous chloride concentration of between about 37.5 and grams per liter and the bath satisfying the equation:
  • polyethylene oxide having a molecular weight over 400 as an addition agent.
  • a tin electrodepositing bath comprising an aqueous solution of an alkali fluoride, stannous chloride,. and 0.001 to 25 grams per liter of a bath-soluble, unsubstituted polyethylene oxide of a molecular weight over 400 as an addition agent, the stannous chloride concentration being between about 37.5 and 150 grams per liter and the bath satisfying the equation: I
  • a process for the electrodeposition of tin the step comprising effecting electrodeposition from an aqueous, tin-plating bath which contains a soluble tin compound, the process comprising effecting electrodeposition in the presence of 0.001 to 25 grams per liter of a bathsoluble, unsubstituted polyethylene oxide having a molecular weight between 1500 and 9000 as an addition agent.
  • the step comprising eflecting electrodeposition from an aqueous bath which contains an alkali fluoride, stannous chloride, and 0.001 to 25 grams per liter of a bath-soluble, unsubstituted polyethylene oxide having a molecular weight between 1500 and 9000 as an addition agent, the composition having a stannous chloride concentration of, between about 37.5 and 150 grams per liter and the bath satisfying the equation:
  • pH is equal to about 1 to 5
  • MI is alkali fluoride
  • mol ratio MF/SnClz is about from 2 to 12
  • the static solution potential of tin in the bath beingequal in volts to from 0.055 pH 0.265 to 0.055 pH -0.370.
  • a tin electrodepositing bath comprising an aqueous solution of an alkali fluoride, stannous chloride, and 0.001 to 25 grams per liter of a bath-soluble, unsubstituted polyethylene oxide of 21 a molecular weight between 1500 and 9000 as an addition agent, the stannous chloride concentration being between about 37.5 and 150 grams per liter and the bath satisfying the equation:

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Cited By (20)

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US2734025A (en) * 1954-02-04 1956-02-07 Twatktnw att
US2758075A (en) * 1951-10-15 1956-08-07 Du Pont Electrodeposition of tin
US2791554A (en) * 1954-09-22 1957-05-07 Ann F Hull Method of electrodepositing zinc
US2828252A (en) * 1953-04-28 1958-03-25 Degussa Electrodeposition of bright zinc, copper, or nickel
US2842461A (en) * 1955-12-02 1958-07-08 Hauserman Co E F Lead coating process and material
US2860089A (en) * 1956-08-09 1958-11-11 R O Hull & Company Inc Method of electro depositing zinc
US2976169A (en) * 1958-02-12 1961-03-21 Du Pont Immersion deposition of tin
US3031400A (en) * 1960-05-27 1962-04-24 Ibm Preparation of superconductive tin by electrodeposition
US3860502A (en) * 1974-03-25 1975-01-14 United States Steel Corp Electrodeposition of tin
US4000047A (en) * 1972-11-17 1976-12-28 Lea-Ronal, Inc. Electrodeposition of tin, lead and tin-lead alloys
FR2409327A1 (fr) * 1977-11-16 1979-06-15 Dipsol Chem Bains d'electroplacage pour le depot brillant d'etain ou d'alliages d'etain
US4405663A (en) * 1982-03-29 1983-09-20 Republic Steel Corporation Tin plating bath composition and process
US4578158A (en) * 1983-11-01 1986-03-25 Nippon Steel Corporation Process for electroplating a metallic material with an iron-zinc alloy
EP0350387A3 (en) * 1988-07-06 1990-11-07 Technic, Inc. Additives for electroplating compositions and methods for their use
US4981564A (en) * 1988-07-06 1991-01-01 Technic Inc. Additives for electroplating compositions and methods for their use
US5538617A (en) * 1995-03-08 1996-07-23 Bethlehem Steel Corporation Ferrocyanide-free halogen tin plating process and bath
US5814202A (en) * 1997-10-14 1998-09-29 Usx Corporation Electrolytic tin plating process with reduced sludge production
WO2006057873A1 (en) * 2004-11-29 2006-06-01 Technic, Inc. Near neutral ph tin electroplating solution
CN102758228A (zh) * 2012-07-13 2012-10-31 深圳市华傲创表面技术有限公司 一种磺酸型半光亮纯锡电镀液
US9840785B2 (en) * 2014-04-28 2017-12-12 Samsung Electronics Co., Ltd. Tin plating solution, tin plating equipment, and method for fabricating semiconductor device using the tin plating solution

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US2828252A (en) * 1953-04-28 1958-03-25 Degussa Electrodeposition of bright zinc, copper, or nickel
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US5814202A (en) * 1997-10-14 1998-09-29 Usx Corporation Electrolytic tin plating process with reduced sludge production
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US20060113195A1 (en) * 2004-11-29 2006-06-01 George Hradil Near neutral pH tin electroplating solution
CN102758228A (zh) * 2012-07-13 2012-10-31 深圳市华傲创表面技术有限公司 一种磺酸型半光亮纯锡电镀液
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