US3773630A - Zinc electroplating baths - Google Patents

Zinc electroplating baths Download PDF

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Publication number
US3773630A
US3773630A US00105119A US3773630DA US3773630A US 3773630 A US3773630 A US 3773630A US 00105119 A US00105119 A US 00105119A US 3773630D A US3773630D A US 3773630DA US 3773630 A US3773630 A US 3773630A
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Prior art keywords
zinc
liter
baths
electroplating bath
bath
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Expired - Lifetime
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US00105119A
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English (en)
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F Popescu
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Individual
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Individual
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Classifications

    • 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
    • C25D3/22—Electroplating: Baths therefor from solutions of zinc
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04B—KNITTING
    • D04B15/00—Details of, or auxiliary devices incorporated in, weft knitting machines, restricted to machines of this kind
    • D04B15/88—Take-up or draw-off devices for knitting products

Definitions

  • the object of this invention is to remedy these disadvantages and, for this purpose, it relates to a process for obtaining brighteners for acid or neutral galvanic zincplating baths, and the brighteners which, added in small amounts (0.05 to 5 g./liter) to the aforementioned zincplating baths, enable very bright and uniform zinc deposits to be obtained, with a good power of penetration and having" high ductility and very low (or nonexistent) hydrogen absorption.
  • the products of the condensation of aromatic aldehydes and ketones with acetylenic alcohols, in the presence of hydrochloric acid as catalyzer, that is to say the acetals of aromatic aldehydes and ketones with acetylenic alcohols, are used as brighteners in acid or neutral zinc-plating baths.
  • addition agents are non-ionic or anionic wetting agents intended mainly to ensure dispersion of the brighteners in the zinc-plating electrolyte.
  • Electrolytic zinc-plating baths are made from a base of zinc salts, conductor salts, buffer salts and complexing salts, known in the technique, and contain as adjuvant, in accordance with this invention:
  • B one or more addition agents selected from among the non-ionic or anionic wetting agents made from ethylene oxide, in an amount of from 0.5 to 50 g./liter.
  • the radical R may be identical to or different from R depending on whether one or more alcohol ismade to react.
  • cinnamaldehyde C,,H -,Cl-l Cl-l-CHO ortho-hydroxybenzaldehyde C l-l (OH) (Cl-IO) .p-methoxybenzaldehyde C l-l (OCH (Cl-l0) piperonal CH;(CHO) 9. furfuraldehyde C H O-CHO l0. acetophenone C l-l CO CH ll. p-methoxyacetophone CH O (C H COCH l2. p-methylacetophenone CH (C H COCl-I l3.
  • the products in category A are prepared by making one mole of aromatic aldehyde react with two moles of acetylenic alcohol, using hydrochloric acid as catalyzer in the proportion of l of the total mixture.
  • the products are put into a reactor equipped with a system for agitation, reflux and heating, and the mixture is heated to 85 95C for 2 3 hours. After cooling, the product is washed with water and the dark-colored, insoluble liquid, which is the brightener proper, is separated by decantation.
  • the brightener may be mixed with varying proportions (preferably l/l) of an aliphatic alcohol or glycol, such as ethylic alcohol,
  • the condensation product of the benzaldehyde with the 2-methyl-3-butyne-2-0l is prepared by heating for 3 hours at 90C, under agitation and reflux, a mixture of 106 g. of benzaldehyde, 168g. of 2-methyl-3-butyne-2-ol, and 3 g. of hydrochloric acid. After cooling to the ambient temperature of the dark-colored liquid obtained, an equal volume of water is added, the mixture is well stirred and left to decant into a separating funnel. The aqueous phase is eliminated and the product is diluted in the proportion l/l with ethyl-glycol.
  • This solution may be used as a brightener in accordance with this invention. The brightener is added to the zinc-plating bath after all the other products have been added, invparticular the addition agents, and the electrolyte is stirred for several minutes to ensure that the brightener is well dispersed.
  • the role of the compounds in category B, the additional agents, is to effect a stable dispersion in the electrolyte of the brighteners, which are insoluble in water.
  • the addition agent improves the quality of the zinc deposits by making them more uniform and by preventing the formation of pores or pits.
  • the addition agents are non-ionic wetting agents with a predominantly hydrophilic chain, or anionic wetting agents, both types of wetting agents being manufactured by the various condensations of ethylene oxide.
  • types of wetting agents usable in association with brighteners in accordance with this invention are:
  • polyoxyethyl alkylphenols with a minimum of l5 moles of ethylene oxide (forlexample, nonyl phenoxypoly (ethylenoxy) ethanol with 20 moles of ethylene oxide):
  • I j a fatty polyoxyethyl alcohols with a minimumof 10 moles of ethylene oxide (for example, fatty polyoxyethyl tallo w alcoholswith 12 moles of ethylene oxide);
  • ether sulfates or fatty alcohols with a minimum of 5 moles of ethylene oxide for example, sodium laurylether sulfate with 6 moles of ethylene oxide.
  • the bright zinc-plating baths in accordance with this invention must contain at least one brightener from category A and at least one addition agent from category B.
  • the basic electrolyte is made up of a zinc salt, such as chloride, sulfate, fluoborate or zinc oxide (or a mixture of these salts), one or more zinc ion complexing agents, such as ammonium chloride or the polyhydroxycarboxylic compounds, and buffer substances such as boric acid and appropriate acids or bases (hydrochloric acid or ammonia) to obtain the baths optimal pH, which is from 4 to 5 for acid baths and from 7 to 7.5
  • a zinc salt such as chloride, sulfate, fluoborate or zinc oxide (or a mixture of these salts)
  • zinc ion complexing agents such as ammonium chloride or the polyhydroxycarboxylic compounds
  • buffer substances such as boric acid and appropriate acids or bases (hydrochloric acid or ammonia) to obtain the baths optimal pH, which is from 4 to 5 for acid baths and from 7 to 7.5
  • a preferred base composition in this invention is that wherein the zinc salt is chloride or zinc oxide which is in the presence of an excess of ammonium chloride and, possibly, ammonia, so as to obtain the formation of the probable formula complexes: Zn (Ni-1 C1 or Zn (NI-I4): C14.
  • EXAMPLE 1 Zinc chloride ZnCl,: g./liter Ammonium chloride Nl-LCI: 260 g./liter Citric acid C l-i 0 5 g./liter Nonyl phenoxypoly (ethylene oxide) ethanol with 20 moles of ethylene oxide: 10 g./liter Product of the condensation of the benzaldehyde with the 2-butyne-l .4 dihydric alcohol: 0.6 g./liter pH 4.2 4.5; temperature 20 30C; voltage 1 3 volts; cathode current density l-4 A/cm; anodes pure zinc (99.99
  • EXAMPLE 2 Zinc chloride ZnCl 60 g./liter Ammonium chloride Nl-LCI: 270 g./liter Nonyl phenoxypoly (ethylene oxide) ethanol with 30 moles of ethylene oxide: 8 g./liter Fatty polyoxyethyl tallow alcohol with 12 moles of ethylene oxide: 4 g./liter Product of thevcondensation of the benzaldehyde with the 2-propyne-l-ol: l g./liter Working conditions are the same as in Example 1.
  • Non-yl phenoxypoly (ethylene oxide) ethanol with 20 moles of ethylene oxide 10 g./liter
  • Product of the condensation of the benzaldehyde with the 2-propyne-l-0l 0.4 g/liter
  • Product of the condensation of the pmethoxybenzaldehyde with the 2-butyne-l.4 dihydric alcohol 0.2 g./liter pH 7.2 7.5; temperature 25 35C; cathode current density l-4 A/cm.
  • the deposits are bright and very ductile.
  • EXAMPLE 4 Zinc chloride ZnCl,: 70 g./liter Ammonium chloride NH,Cl: 260 g./liter Boric acid H 80 l g./liter Fatty polyoxyethyl alcohols with 11 moles of ethylene oxide: 8 g./liter Sodium lauryl-ether-sulfate with 6 moles of ethylene oxide: 2 g./liter Product of the condensation of the O-hydroxybenzaldehyde with the 2-methyl-3-butyne-2-ol: 0.5 g./liter Product of the condensation of the acetophenone with the 2-propyne-l-ol: 0.1 g./liter pH 4.5; temperature 25C; cathode current density 2-4 Alcm
  • the bright zinc-plating baths forming the object of this invention may be used industrially in zinc-plating installations by assembling or in casks. These baths may with advantage replace cyanide baths and enable new effects to be obtained through the greater brilliance of the
  • An aqueous zinc electroplating bath comprising, as a brightening agent for said bath, the combination of:
  • R is selected from the group consisting of phenyl, methyl phenyl, isopropyl phenyl, phenyl methyl, phenyl vinyl, hydroxy phenyl, methoxy phenyl, methylene dioxy phenyl, and furyl radicals;
  • R is selected from the group consisting of the methyl radical and hydrogen; and
  • R and R. are each selected from the group consisting of alkyne, methyl substituted alkyne, and hydroxy substituted alkyne radicals; and
  • an addition agent selected from the group consisting of nonionic and anionic wetting agents in an amount effective to reduce surface tension.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Textile Engineering (AREA)
  • Electroplating And Plating Baths Therefor (AREA)
US00105119A 1970-12-03 1971-01-08 Zinc electroplating baths Expired - Lifetime US3773630A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
FR7043547A FR2120246A5 (enExample) 1970-12-03 1970-12-03

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US3773630A true US3773630A (en) 1973-11-20

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US00105119A Expired - Lifetime US3773630A (en) 1970-12-03 1971-01-08 Zinc electroplating baths

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US (1) US3773630A (enExample)
FR (1) FR2120246A5 (enExample)
IT (1) IT941962B (enExample)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4284825A (en) * 1978-11-08 1981-08-18 Basf Aktiengesellschaft 4-Substituted benzaldehyde-dialkylacetal
WO1996020152A1 (de) * 1994-12-23 1996-07-04 Basf Aktiengesellschaft Salze aromatischer hydroxylverbindungen und deren verwendung als glanzbildner
WO2007020381A3 (en) * 2005-08-15 2007-05-03 Syngenta Participations Ag Process for the synthesis of mandipropamid and derivatives thereof

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4284825A (en) * 1978-11-08 1981-08-18 Basf Aktiengesellschaft 4-Substituted benzaldehyde-dialkylacetal
WO1996020152A1 (de) * 1994-12-23 1996-07-04 Basf Aktiengesellschaft Salze aromatischer hydroxylverbindungen und deren verwendung als glanzbildner
WO2007020381A3 (en) * 2005-08-15 2007-05-03 Syngenta Participations Ag Process for the synthesis of mandipropamid and derivatives thereof
US20090118532A1 (en) * 2005-08-15 2009-05-07 Syngenta Crop Protection, Inc. Process for the Synthesis of Mandipropamid and Derivatives Thereof
US8129560B2 (en) 2005-08-15 2012-03-06 Syngenta Crop Protection, Inc. Process for the synthesis of mandipropamid and derivatives thereof
TWI399363B (zh) * 2005-08-15 2013-06-21 Syngenta Participations Ag 方法

Also Published As

Publication number Publication date
FR2120246A5 (enExample) 1972-08-18
IT941962B (it) 1973-03-10

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