US3904493A - Gold sulfite baths containing organophosphorus compounds - Google Patents

Gold sulfite baths containing organophosphorus compounds Download PDF

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US3904493A
US3904493A US386798A US38679873A US3904493A US 3904493 A US3904493 A US 3904493A US 386798 A US386798 A US 386798A US 38679873 A US38679873 A US 38679873A US 3904493 A US3904493 A US 3904493A
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gold
bath
sulfite
group
free
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Salvatore Losi
Pierre Lalanne
Rene Henzi
Erwin Marka
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Oxy Metal Industries Corp
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Oxy Metal Industries Corp
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
    • C07H11/00—Compounds containing saccharide radicals esterified by inorganic acids; Metal salts thereof
    • C07H11/04—Phosphates; Phosphites; Polyphosphates
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
    • 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
    • C25D3/48—Electroplating: Baths therefor from solutions of gold
    • 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
    • C25D3/56—Electroplating: Baths therefor from solutions of alloys
    • C25D3/62—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of gold

Definitions

  • the present invention concerns the use of organophosphorus compounds in sulfite baths for the electrodeposition of gold and gold alloys as additives for improving the performances and theoperating conditions of said baths.
  • the invention also concerns the sulfite baths for the electrodeposition of gold and gold alloys which contain at least one of said organophosphorus compounds.
  • the invention also concerns the process of depositing coatings of gold and gold alloys the electrolysis of gold and gold alloys sulfite baths containing said organophosphorus compounds.
  • organophosphorus additives will often, relatively slight variations of current density result in the formation of foggy deposits,nburns, pittings or colour changes, particularly when depositing gold alloys.
  • the present additives are stable water-soluble organic compounds of phosphorusof valency fouror five comprising at least one P atom having up to four bonds identical or different chosen among PR and POR and having connected to the possibly free remaining valencies thereof substituents selected among 0 and OH free or salified with alkali metals, NHf, earth-alkali metals or the metals which participate to the electrodeposition of the gold and its alloys.
  • R comprise monovalent or divalent organic radicals. In said second alternative, they can either be connected together in cyclic form or bridge with at least another phosphorus atom.
  • R can denote the following substituents v l.
  • a monoor polycyclic aromatic radical which can be substituted by linear, branched or cyclic aliphatic groups and which can comprise, as well as the substituent groups, at least one function like (1 above.
  • a radical as under l above further comprising at least one aromatic or heterocyclic substituent containing at least one N, O or S, said substituents themselves comprising or not functions as under l above.
  • a radical as described under (1) to (4) which is connected to a tetravalent P atom and a function of which having a labile proton is under anionic form to balance with the positive cationic charge of the phosphorus atom.
  • the number of carbon atoms of each substituent R is preferably comprised between I and 30 although this number can be exceeded in some cases.
  • Quaternary phosphonium compounds R P X X being an anion derived from an organic or inor ganic acid or an anionic function of one of the R groups (X can be derived for instance from H 50 HCl', CH COOH, CI COOH, etc.).
  • Ph'osphinic acids R PO(OH) free or esterified.
  • the phosphorus compounds which are preferably used as additives in sulfite baths for the electrodeposition of gold and gold alloys are phosphonic acids, phosphinic acids or mixed phosphono-phosphinic acids, their salts and their ester derivatives. Consequently, they can comprise one or seeral phosphorus atoms and the acid functions thereof can be free, salified or esterified partially or completely. It has been found that in many cases phosphoric and phosphonic esters are as active or more active than the correspnding free acids when added to the present gold baths and this observation is very surprising and completely unexpected.
  • the present additives can be classified in a more de- 6 tailed manner as follows 1.
  • chain A may have inserted in the main part thereof or in the side branches one or several hetero-functions, e.g. O and NR.
  • R and R are selected among hydrogen and linear or branched alkyl radicals halogenated or not having I to 6 C atoms, e.g. CH C H C H iso- C H CICH CICH CHCI, (CICH )2CH, etc., CH COOH and CH SO H free, salified or esterified. Furthermore, R and R can constitute together with the N atom a 5 to 6 links heterocycle. R has the same meaning as R or R but also comprises alkylene bridges connected to a possible second N atom of A.
  • R and R represent the same substituents as R and R but further comprise a (CH ),,,PO H group free, salified or esterified (m l or 2).
  • R comprises the same substituents as R and. in addition, a CH PO H group free, salified or esterified.
  • R represents a halogen (Cl, Br or I) or an OH (free or etherified); R" represents H, halogens or C to C linear or branched alkyl or alkenyl groups which may be substituted or unsubstituted by at least one group selected among OH, CN, halogens (Cl, Br or 1),
  • acid groups such as COOH, SO -,H and PO H free. salified or esterified and oxygen.
  • A, B. R and R are defined as above and A is preferably a linear or branched alkyl radical which may or not be substitued by halogens (Cl, Br or I), OH or NRR R' and R being defined as above.
  • ester and ether functions are preferably derived from lower alkanols which may be halogenated or not, e. g. methanol, ethanol, propanol, isopropanol, butanol, isobutanol, CICH OH, Cl CHOI-I, ClCH --ClCHOH, (ClCH -CHOH, etc.
  • organophosphorus compounds which are useful according to the invention are listed below as non limitative examples.
  • the acid functions have been generally represented in the free state but it is understood that such functions can actually be salified or esterified as mentioned above.
  • This list of compounds which is far from being exhaustive is followed by references relative thereto, e.g. to the preparation thereof. Some of these references also comprise other compounds which can be used according to the invention and which are in accord with formulae, l) to (5) above.
  • the present compounds were initially obtained as esters, the latter were hydrolized by usual means, e. g. by I boiling with aqueous mineral acid or alkali.
  • ester was preferably used as an additive in gold electroplating baths.
  • Free acidic functions were esterified by usual means, e.g. by boiling with an alcohol in the presence or in the absence of a catalyst such as H HCl, BF etc.
  • Sulfite baths for the electrodeposition of gold and gold alloys in which the present additives are particularly useful are known from the men skilled in the art. Such baths are described for instance in Swiss Patent No 506,628 and British Patent No 1,134,615. These baths contain the gold as a sulfite of gold or a gold sulfite complexed with an amine, the concentration of which can vary, for instance, from 0.5 to 30 g of metal /I. They generally contain alkali or ammonium sulfites the quantity of which can vary from 1 to 150 g/l, chelateing or complexing agents such as water-soluble organic acids and hydroxyacids, e.g.
  • metals the following ones can be mentioned Fe, Co, Ni, Zn, Cd, Sn, Cu, Bi, Ga, In, Pb, Mn, Mo, Ag, Tl, Zr, V, W and, in some cases, the precious metals of the platinum group.
  • Said metal ions are introduced into the present baths as watersoluble salts, chelates or complexes well known in the electroplating art (see for example The Metal Finishing Guidebook Directory, Metals and Plastics Publ., Inc., Westwood, N..I., U.S.A.).
  • the sulfates, sulfites, citrates or carbonates of said metals, complexed or not with the above described complexing agents, are used preferably when soluble in water.
  • the amount of said metals in the present baths can vary between wide limits depending on the composition and the carat of the alloys to be plated. It can be comprised, for instance, between 0.5 and 150 g/l. However, these limits are not critical and it is possible to have concentrations below or above said limits in some cases. Thus, when the metals are used only as brightening agents, very small quantities can be effective, e.g. in the order of only 1 to 500 mg/l.
  • the present bathscan also contain mineral or or ganic acids and bases as well as buffers so that the pH can be maintained between operating limits according to usual means.
  • acids are H HCl, H SO HCOOI-I and others.
  • bases are NaOI-I, KOH, LiOH and others.
  • buffers are citrate, borate and phthalate buffers.
  • the pH of said baths are generally comprised between about 5 and l 1; however, a given bath may have rather narrow operative pH limits.
  • the sulfite baths for the electrodeposition of gold and gold alloys operate at current densities generally comprised between rather' narrow limits.
  • the optimal current density at C is about 1 A/dm in such case, it is not advisable to operate at densities 20 more or less than the average value as defective coatings might be produced (burns or alloy composition variations).
  • the effective quantities of the compounds useful according to the invention can vary between wide limits. These quantities depend, naturally, on the chemical structure of the phosphorus compound considered, that is on the nature and the number of the functional groups and, presumably, on their orientation. In some cases, a few mg/l, e.g. I to 2 mg/l are sufficient; in other cases higher concentrations, e.g. of the order of 10 to g/l or even up to the limit of solubility in the bath can be desirable and advantageous.
  • the present additives can be incorporated to the baths, depending on the case, as the pure substances or a ready prepared solutions in water or water-soluble liquids such as alcohol, acetone or others.
  • non esterified forms of the present additives are used, it is generally immaterial that they should be added into the baths as the free acids or as the alkali salts thereof with the condition, of course, that the final pH of the bath be adjusted to the required value with an acid or a base, e.g. H 80 or NaOI-I.
  • Table 1 shows the composition of a few sulfite gold and gold alloy baths wherein the present organophosphorus additives are very useful.
  • organic monoor polyacids egv sehacic, stearic. linolcic. etc. organic compound having at least one trivalent nitrogen atom. e.g. nicotinic acid. dipyridyl.
  • Au is present as gold sulfitc or gold sulfite complexed with an amine. e.g. en.
  • Cu. Cd. Ni, Zn. Sb are present as water-soluble compounds (mineral or organic acid salts. complex salts. e.g. with en) on ethylene diamine.
  • ED'IA ethylene diamine tetraacctic acid tetrztsodium salt; disodium salt.
  • EXAMPLES l to 18 A sulfite bath for the electrodeposition of an Au-Cu- Cd alloy having a white to yellow-white colour was pre pared by mixing the following ingredients at the concentrations indicated.
  • EDTA means ethylene diamine tetraacetic acid or the alkali salts thereof.
  • Concentration Au (as gold sulfite) 6 g/l Cd (as EDTA complcxed sulfate) 12 g/l Ni (as EDTA complexed sulfate) 3 g/l Cu (as EDTA complcxed sulfate) 0.06 g/l EDTA (free) g/l N21 80 30 g/l pH (NaOH) 9,7 10
  • crating conditions could be varied only very slightly without experiencing difficulties. Indeed, when the current density was increased 0.] or 0.2 A/dm (that is up to 0.6 or 0.7 A/dm the platings started to burn. In addition, the levelling action was poor. that is the action of hiding originally produced defects (e.g. burns) by the freshly deposited layers of alloy: for instance, it was noted that when burns were intentionally produced by increasing the current density and thereafter the current was reduced to normal (0.5 A/dm the bums remained present even at much higher coating thickness. It should also be noted that operating the above bath below 0.5 A/dm may be inconvenient as the colour of the deposit becomes yellower.
  • the differences resulting from the presence of the additive on the quality of the platings and on the operating conditions were recorded.
  • the main parameters which were checked were the levelling power defined as above, the surface condition of the deposit (gloss) and the limits of variations of the current density during plating without producing defective coatings.
  • Example 2 The results obtained (Examples of compounds 1 to 18) plus control are recorded in Table 2 which also shows the concentration of each of the additives used.
  • the composition of the plated alloy was about l819 carat 20 Cd and 23 Cu).
  • organo-phosphorus additives used in Examples 1 to 18 can be prepared as follows (the temperatures are in degrees Centigrades).
  • Dimethylacetylphosphonate Diphosphonomethane Ref.: .1. Chem. Soc. 1947, 1465. A mixture of diiodomethane (142.5 g, 0.53 mole) and triethylphosphite 157 g, 0.94 mole) was heated progressively from to C, in the course of 5 hrs, in a flask provided 65 with a reflux condenser having an intermediate outlet tube for collecting volatile distillates.
  • Phosphonoacetic acid (Hydroxycarbonylmethane phosphonic acid) Ref.: C.A. 41, 700.
  • Sodium ethoxide (27.2 g, 0.4 mole) was added to a solution of diethylphosphite (55.2 g, 0.4 mole) in 200 ml of anhydrous xylene.
  • ethyl bromoacetate 66.8 g, 0.4 mole
  • Diethyl 2-hydroxyethanephosphonate 14. Diethyl N-butylacetamidophosphonate Ref.: Canadian Patent No. 509.034. Under strong cooling, butyl isocyanate (25 g) was slowly dropped into a solution of sodium (0.4 g) in diethylphosphite (34.5 g), so as to maintain the temperature below 5C. After standing overnight the crystallized product was filtered off; yield 12.5 g, m.p. 3233C.
  • a bath for the electrodeposition of gold alloys was prepared by dissolving the following ingredients in water In grcdicnts Concentration Au (as sulfitc) 4 g/l Ni (as NiSOroH O) 12 g/l Cd (as CdSO,) 10.6 g/l Cu (as DTPA complex) 0.05 g/l Nat- S0 g/l Citric acid 25 g/l Disodium EDTA'2H. l 15 g/l pH (NaOH or H 80 9.5
  • FIGS. 1 to 7 show the results obtained.
  • curve (a) represents the behaviour of the above bath without additives (control); whereas curve (b) expresses the effect of the additive.
  • the position and the shape of these curves indicate that, in general, the effect of the organophosphorus additives is to pro prise a rightwise displacement of the curve and to make it steeper. This trend correlates with a standardization action on the electrodeposition potentials of the various metals of the plated gold alloy.
  • the composition of this alloy was about 18 carat and about 20 Cd.
  • FIG. I concerns the additive of Example 1
  • FIG. 2 concerns the additive of Example 5
  • FIG. 3 concerns the additive of Example 6
  • FIG. 4 concerns the additive of Example 12
  • FIG. 5 concerns the additive of Example 13
  • FIG. 6 concerns the additive of Example 18
  • FIG. 7 concerns, for comparative purposes, the tetraacid (HO) POC(CH )Ol-IPO(OH) which corresponds to the additive of Example 18.
  • an aqueous electroplating bath for the deposi tion of gold or a gold alloy from a sulfite complex.
  • the improvement comprising including from 1 mg/l up to the solubility limit of, the bath of an ester of an organophosphorus compound of the formula wherein R represents Cl, Br, I, or a free or esterified OH group; R represents H, halogens or C to C linear or branched alkyl or alkenyl groups which may be substituted by a group selected from the group consisting of OH, CN, Cl, Br, 1, COOH, SO H and PO H which can be free. salified or esterified, and carbonyl groups; and wherein the acid functions are at least partially esterified with lower alcohols of l to 6 carbon atoms.
  • ester functions are derived from the group consisting of the lower halogenated and non halogenated alcohols.
  • a process for obtaining a gold or gold alloy deposit on a conductive surface comprising immersing the surface in the bath of claim 1 and electrolyzing said bath with the surface as cathode.
  • an aqueous electroplating bath which comprises as the main ingredient for the deposition of gold and gold alloys 0.5 to 30 g/l of gold as sulfite, l to 150 g/l of alkali metal or ammonium sulfite, 0.1 to g/l of chelating agents selected among organic acids and hydroxyacids and dior polyamines free or substituted by acetic groups, 0 to g/l of at least one metal acting as a brightening agent or as an alloying metal with the gold present as a salt or water-soluble chelate, enough acids, bases or buffers for maintaining the bath at an approximately constant pH in the range of pH 5 to l 1 during electrolysis, the improvement comprising in cluding from 1 mg/l up to the solubility limit of the bath of an ester of an organophosphorus compound of the formula (HO) OPCRR" PO(OH) wherein R represents Cl, Br, I, or a free or esterified OH group; R represents, H, hal

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CH1197572A CH555894A (fr) 1972-08-10 1972-08-10 Utilisation de derives organophosphores dans les bains sulfitiques pour l'electrodeposition de l'or et des alliages d'or.
CH1138873 1973-08-06

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Cited By (25)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4012294A (en) * 1972-08-10 1977-03-15 Oxy Metal Industries Corporation Gold sulfite baths containing organophosphorous compounds
US4029696A (en) * 1976-04-09 1977-06-14 Benckiser-Knapsack Gmbh N-hydroxy alkane amino alkane diphosphonic acids, process of producing same, and compositions for and method of using same
US4197172A (en) * 1979-04-05 1980-04-08 American Chemical & Refining Company Incorporated Gold plating composition and method
US4212708A (en) * 1979-06-05 1980-07-15 Belikin Alexandr V Gold-plating electrolyte
US4246103A (en) * 1976-05-14 1981-01-20 Bayer Aktiengesellschaft Propane-1,3-diphosphonic acids for conditioning water
US4253920A (en) * 1980-03-20 1981-03-03 American Chemical & Refining Company, Incorporated Composition and method for gold plating
DE3244092A1 (de) * 1981-12-14 1983-06-23 American Chemical & Refining Co., Inc., 06720 Waterbury, Conn. Waessriges bad zur galvanischen abscheidung von gold und verfahren zur galvanischen abscheidung von hartgold unter seiner verwendung
US4579720A (en) * 1965-08-24 1986-04-01 Plains Chemical Development Co. Chelation
US4670107A (en) * 1986-03-05 1987-06-02 Vanguard Research Associates, Inc. Electrolyte solution and process for high speed gold plating
US4802990A (en) * 1987-07-30 1989-02-07 Inskeep Jr Eugene L Solution and method for dissolving minerals
US5277790A (en) * 1992-07-10 1994-01-11 Technic Incorporated Non-cyanide electroplating solution for gold or alloys thereof
US5438048A (en) * 1990-12-20 1995-08-01 Leiras Oy Methylenebisphosphonic acid derivatives
WO2001038609A1 (en) * 1999-11-29 2001-05-31 Enthone-Omi Inc. METHOD OF PRODUCING AuCuGa ALLOY COATING USING ELECTROLYSIS, AND ALLOYS PRODUCED BY SUCH A METHOD
US6319387B1 (en) * 1998-06-30 2001-11-20 Semitool, Inc. Copper alloy electroplating bath for microelectronic applications
US6365033B1 (en) 1999-05-03 2002-04-02 Semitoof, Inc. Methods for controlling and/or measuring additive concentration in an electroplating bath
US20020084195A1 (en) * 1998-05-01 2002-07-04 Chen Linlin Automated chemical management system executing improved electrolyte analysis method
US20020112970A1 (en) * 1998-05-01 2002-08-22 Graham Lyndon W. Automated chemical management system having improved analysis unit
US20030047108A1 (en) * 2001-06-29 2003-03-13 Katsunori Hayashi Displacement gold plating solution
US6576114B1 (en) 1995-11-03 2003-06-10 Enthone Inc. Electroplating composition bath
US6592736B2 (en) 2001-07-09 2003-07-15 Semitool, Inc. Methods and apparatus for controlling an amount of a chemical constituent of an electrochemical bath
USRE38931E1 (en) * 1998-05-01 2006-01-10 Semitool, Inc. Methods for controlling and/or measuring additive concentration in an electroplating bath
US6991710B2 (en) 2002-02-22 2006-01-31 Semitool, Inc. Apparatus for manually and automatically processing microelectronic workpieces
US20110076219A1 (en) * 2009-09-25 2011-03-31 Cytec Technology Corp. Preventing or reducing scale in wet-process phosphoric acid production
CN102272043A (zh) * 2009-01-06 2011-12-07 纳尔科公司 酸性条件中沉淀物形态和沉淀特性的改变
ITFI20130057A1 (it) * 2013-03-18 2014-09-19 Bluclad S R L Soluzione per l¿elettrodeposizione di una lega di oro e la lega da essa derivante.

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CH632533A5 (fr) * 1979-06-14 1982-10-15 Aliprandini P Procede pour le depot galvanoplastique d'un alliage d'or.
CN113571698B (zh) * 2021-09-23 2021-12-28 中南大学 一种碳点调控的金属硒化物/碳复合材料及其制备方法和应用

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US3057789A (en) * 1959-02-26 1962-10-09 Paul T Smith Gold plating bath and process
US3475292A (en) * 1966-02-10 1969-10-28 Technic Gold plating bath and process
US3666640A (en) * 1971-04-23 1972-05-30 Sel Rex Corp Gold plating bath and process
US3672969A (en) * 1970-10-26 1972-06-27 Lea Ronal Inc Electrodeposition of gold and gold alloys
US3770596A (en) * 1972-07-21 1973-11-06 Auric Corp Gold plating bath for barrel plating operations

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US3057789A (en) * 1959-02-26 1962-10-09 Paul T Smith Gold plating bath and process
US3475292A (en) * 1966-02-10 1969-10-28 Technic Gold plating bath and process
US3672969A (en) * 1970-10-26 1972-06-27 Lea Ronal Inc Electrodeposition of gold and gold alloys
US3666640A (en) * 1971-04-23 1972-05-30 Sel Rex Corp Gold plating bath and process
US3770596A (en) * 1972-07-21 1973-11-06 Auric Corp Gold plating bath for barrel plating operations

Cited By (36)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4579720A (en) * 1965-08-24 1986-04-01 Plains Chemical Development Co. Chelation
US4012294A (en) * 1972-08-10 1977-03-15 Oxy Metal Industries Corporation Gold sulfite baths containing organophosphorous compounds
US4029696A (en) * 1976-04-09 1977-06-14 Benckiser-Knapsack Gmbh N-hydroxy alkane amino alkane diphosphonic acids, process of producing same, and compositions for and method of using same
US4100067A (en) * 1976-04-09 1978-07-11 Benckiser-Knapsack Gmbh. Method for sequestering metal ions
US4246103A (en) * 1976-05-14 1981-01-20 Bayer Aktiengesellschaft Propane-1,3-diphosphonic acids for conditioning water
US4197172A (en) * 1979-04-05 1980-04-08 American Chemical & Refining Company Incorporated Gold plating composition and method
US4212708A (en) * 1979-06-05 1980-07-15 Belikin Alexandr V Gold-plating electrolyte
US4253920A (en) * 1980-03-20 1981-03-03 American Chemical & Refining Company, Incorporated Composition and method for gold plating
DE3244092A1 (de) * 1981-12-14 1983-06-23 American Chemical & Refining Co., Inc., 06720 Waterbury, Conn. Waessriges bad zur galvanischen abscheidung von gold und verfahren zur galvanischen abscheidung von hartgold unter seiner verwendung
US4670107A (en) * 1986-03-05 1987-06-02 Vanguard Research Associates, Inc. Electrolyte solution and process for high speed gold plating
US4802990A (en) * 1987-07-30 1989-02-07 Inskeep Jr Eugene L Solution and method for dissolving minerals
US5438048A (en) * 1990-12-20 1995-08-01 Leiras Oy Methylenebisphosphonic acid derivatives
US5277790A (en) * 1992-07-10 1994-01-11 Technic Incorporated Non-cyanide electroplating solution for gold or alloys thereof
US6576114B1 (en) 1995-11-03 2003-06-10 Enthone Inc. Electroplating composition bath
US20020112970A1 (en) * 1998-05-01 2002-08-22 Graham Lyndon W. Automated chemical management system having improved analysis unit
US6899805B2 (en) 1998-05-01 2005-05-31 Semitool, Inc. Automated chemical management system executing improved electrolyte analysis method
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NL7311108A (enExample) 1974-02-12
FR2253106A1 (enExample) 1975-06-27
FR2253106B1 (enExample) 1976-11-19
DE2340462C3 (de) 1978-10-12
DE2340462A1 (de) 1974-02-28
IT994135B (it) 1975-10-20
ES417762A1 (es) 1976-06-16
CH555894A (fr) 1974-11-15
GB1447058A (en) 1976-08-25
DE2340462B2 (de) 1978-02-02

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