EP0492487B1 - Produit de protection temporaire de surfaces nues en argent et en cuivre contre le ternissement et procédé d'utilisation - Google Patents

Produit de protection temporaire de surfaces nues en argent et en cuivre contre le ternissement et procédé d'utilisation Download PDF

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Publication number
EP0492487B1
EP0492487B1 EP91121903A EP91121903A EP0492487B1 EP 0492487 B1 EP0492487 B1 EP 0492487B1 EP 91121903 A EP91121903 A EP 91121903A EP 91121903 A EP91121903 A EP 91121903A EP 0492487 B1 EP0492487 B1 EP 0492487B1
Authority
EP
European Patent Office
Prior art keywords
inhibitor
silver
water
emulsion
copper
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP91121903A
Other languages
German (de)
English (en)
Other versions
EP0492487A1 (fr
Inventor
Hermann Dr. Dipl.-Chem. Grossmann
Erwin Marka
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Doduco Contacts and Refining GmbH
Original Assignee
Doduco GmbH and Co KG Dr Eugen Duerrwaechter
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from DE19904041596 external-priority patent/DE4041596A1/de
Application filed by Doduco GmbH and Co KG Dr Eugen Duerrwaechter filed Critical Doduco GmbH and Co KG Dr Eugen Duerrwaechter
Publication of EP0492487A1 publication Critical patent/EP0492487A1/fr
Application granted granted Critical
Publication of EP0492487B1 publication Critical patent/EP0492487B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
    • C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
    • C23F11/16—Sulfur-containing compounds
    • C23F11/161—Mercaptans

Definitions

  • the invention is based on an agent for protecting bare silver surfaces against tarnishing, which contains, as a hydrophobic inhibitor, a long-chain aliphatic mercapto compound with at least 12 carbon atoms in the chain and water.
  • Silverware and silver-plated parts tarnish in an atmosphere containing hydrogen sulfide and turn brown to black due to the formation of silver sulfide.
  • an inorganic cover layer for example with rhodium or with silver chromate, which are applied by electrolytic processes.
  • silver surfaces by means of transparent lacquers or waxes, which are applied by dipping, spraying or vapor deposition.
  • a major disadvantage of these coatings is that they do change the external appearance of the silver, which is particularly disadvantageous for decorative objects. In applications in electrical engineering, especially in electrical contacts, such passivating coatings are not desirable because they greatly increase the electrical contact resistance.
  • a transparent, colorless, ideally monomolecular protective layer remains on the silver surface, which at least adheres to the goods until they are processed further or reach the consumer.
  • the disadvantage here is that the inhibitors are dissolved in halogenated hydrocarbons which are harmful to the environment.
  • the inhibitors which in turn are long-chain aliphatic compounds with SH group, namely mercapto compounds with 12 to 25 carbon atoms, in organic solvents such as glycols and / or Solve glycol ethers with a total of 4 or 5 carbon atoms and treat the silver surfaces to be protected with this solution.
  • organic solvents such as glycols and / or Solve glycol ethers with a total of 4 or 5 carbon atoms and treat the silver surfaces to be protected with this solution.
  • Glycols and glycol ethers have the advantage of being less harmful to the environment than halogenated hydrocarbons.
  • they have the disadvantage that they are flammable and that the vapors escaping from the treatment solution can form an explosive mixture, so that special precautions must be taken when working with such solutions.
  • DE-OS 39 05 850 In order to counteract the development of flammable or explosive gas mixtures, it is already known from DE-OS 39 05 850 not to dry the treated surfaces by letting the solvent evaporate. Rather, the solvent is removed from the treated surfaces by rinsing with aqueous solvents or with warm water with detergents. In order to reduce the evaporation rates, it is also known from DE-OS 39 05 850 to add water to the solution of the inhibitor in glycol or glycol ether. The glycol and the glycol ether dissolve in the water and are thereby diluted. However, care is taken to ensure that with this dilution the solubility limit of the inhibitor in the glycol or glycol ether is not exceeded so that there is no clouding or precipitation. The addition of water reduces the dangerousness of the glycol or the glycol ether, but does not eliminate it.
  • thiocarboxylic acids have been used as an additive to polishing pastes (DE-AS 1 279 428, claim 5).
  • Another, particularly significant disadvantage of thiocarboxylic acids is that water can attach to their hydrophilic carboxyl group, which ultimately enables the hydrogen sulfide from which the silver surface is to be protected to attack the silver surface, so that there is no protective layer which is impermeable to hydrogen sulfide receives.
  • the agent which is supposed to protect against tarnishing of the surface, should be applied as a film so uniform that the gloss of the surface is retained.
  • a precious metal cleaning and polishing bath is known from CH-A-478 925, which contains long-chain thiols as tarnishing protection, which are brought into solution by a primary alcohol as solubilizer.
  • a primary alcohol as solubilizer.
  • an alkylaryl polyglycol ether can also be present as an emulsifier.
  • a paste for cleaning and polishing tarnished silver is known, which among other things. contains a thiol and a non-ionic surfactant.
  • the present invention has for its object to provide a means for the temporary protection of bare silver surfaces, also in the field of electrical engineering, in particular in the case of electrical contacts, which can be handled easily and safely, even in immersion baths, and is environmentally compatible.
  • This object is achieved by an agent with the composition specified in claim 1.
  • a particularly suitable method for using this agent is the subject of claim 5.
  • Advantageous developments of the invention are the subject of the subclaims.
  • the agent according to the invention contains, as organic inhibitor substance, a hydrophobic aliphatic thio compound with at least 12 carbon atoms in the chain from the group of thio alcohols and their esterification products without hydrophilic carboxyl groups, the thio alcohols being particularly preferred. However, they are not dissolved in an organic solvent, but used in the form of an aqueous emulsion.
  • the emulsifier which is inevitably required to bring the selected inhibitors into an emulsion, is only incorporated in a negligible amount in the inhibitor film which forms on the silver surface which has been treated with the emulsion.
  • the emulsifier can be easily washed off by rinsing with water, while the passivating film of the inhibitor substance remains on the treated silver surface.
  • the silver surface is treated in the emulsion at a temperature which is above the melting point of the inhibitor substance.
  • the inhibitor substance is particularly readily distributed evenly thin on the surface to be passivated.
  • the subsequent rinsing of the surface is then carried out at a temperature below the melting point of the inhibitor substance, which has the advantage that it then adheres particularly firmly to the passivated surface.
  • the agent according to the invention is easy to handle. It contains neither an environmentally hazardous nor a flammable solvent, but only water as the carrier substance of the emulsion.
  • the sub-substances contained in the water, the inhibitor and the emulsifier, are biodegradable.
  • the agent according to the invention is easy to use. It can be marketed as a concentrate of the inhibitor and the emulsifier and can be made ready for use by the user by stirring it into water. It can be applied by dipping or spraying.
  • the goods to be treated are preferably immersed in the emulsion because the treatment times are then the shortest.
  • conventional devices such as in electroplating technology can be used, with the difference that there is no need for electrodes and that there are no problems with the disposal of the baths and rinsing water.
  • the agent according to the invention contains 2 to 20 g / l of the inhibitor.
  • the emulsifier is contained in the agent in an amount of 2 to 20 g / l.
  • an anionic or nonionic surfactant can be added to the agent.
  • Cationic surfactants are unsuitable.
  • inhibitors are selected which have at least 12 and preferably not more than 20 C atoms in the chain. With less than 12 carbon atoms, it is sometimes not possible to achieve a well-adhering protective coating, and in part there are strong odor nuisances. With more than 20 carbon atoms, the inhibitors become too solid in consistency and it becomes more difficult to produce a satisfactory emulsion.
  • the inhibitors can be emulsified very finely and with long-term stability and can be applied to the surfaces to be protected in a thin but dense layer.
  • Particularly suitable emulsifiers for this purpose are branched fatty alcohols having 9 to 20 carbon atoms, in particular having 10 to 15 carbon atoms, the branched fatty alcohols preferably being alkoxylated, in particular ethoxylated, with a degree of alkoxylation of 2 to 10.
  • the passivating agent when adjusted to a pH of 1-10, better 1-8, preferably 2-4, the emulsifier can be washed out of the deposited inhibitor layer practically completely with water, which is important for reliable surface protection is.
  • the emulsifier can be washed out of the deposited inhibitor layer practically completely with water, which is important for reliable surface protection is.
  • less inhibitor is washed out, which increases the protective effect and the lubricating effect; however, stains can appear on the surface, which can disturb the appearance of decorative surfaces.
  • Decorative surfaces are therefore preferably passivated with an agent whose pH is lower, preferably between 2 and 4, with sufficient inhibitor substance remaining even after washing out to form a tight protective layer. If the pH is above 10 there is a risk of the emulsion splitting.
  • the agent according to the invention is also suitable for passivating surfaces made of copper and copper alloys.
  • the water-emulsified inhibitor also absorbs very well on copper and copper-containing materials and protects the surface against the attack of sulfur compounds and against oxidation. The good solderability and the electrical properties are not impaired.
  • Examples of baths with which opaque and well-adhering coatings can be achieved on surfaces of silver and copper materials 1. Dissolved in one liter of deionized water: 2 - 20 g Inhibitor: Octadecanethiol 2 - 20 g Emulsifier: Branched fatty alcohol ethoxide with 8 to 16 carbon atoms (C8 - C16) and a degree of ethoxylation of 2 to 10 0.00 - 1 g
  • Surfactant Sodium lauryl ether phosphate pH 2 adjusted with a mineral acid Particularly suitable for silver and silver alloys. 2.
  • These baths are preferably used in such a way that the parts to be passivated are immersed in the approx. 40 ° C to 50 ° C warm baths. After 2 to 3 minutes, the surface of the parts is even and dense with the inhibitor wetted. The parts are then rinsed with cold water and then dried, preferably with hot air.
  • the effect of the tarnish protection layer on silver can be easily demonstrated with the help of a two percent sodium sulfide solution. Untreated silver parts tarnish immediately, treated parts remain bare over a longer period. The effect of the protective layer on copper was checked by passivating copper parts for several hours in a hydrogen sulfide atmosphere with 1 ppm H2S; the copper parts did not change color.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)

Claims (7)

  1. Produit assurant la protection provisoire, contre le ternissement, de surfaces brillantes d'argent et d'alliages d'argent, qui contient comme inhibiteur hydrophobe un composé thio aliphatique à longue chaîne ayant au moins un groupe SH et au moins 12 atomes de carbone dans la chaîne, choisi parmi l'ensemble comprenant les thio-alcools et leurs produits d'estérification, de l'eau et un émulsifiant soluble dans l'eau, à l'aide duquel l'inhibiteur est émulsifié dans l'eau, et qui est ajusté à un pH de 1 à 10, caractérisé en ce qu'il contient
    de 2 à 20 g/l de l'inhibiteur,
    de 2 à 20 g/l de l'émulsifiant,
    de 0 à 2 g/l d'un tensioactif anionique ou non ionique,
    le reste étant constitué d'eau, et que l'émulsifiant est choisi parmi l'ensemble comprenant les alcools gras ramifiés, alcoxylés - de préférence éthoxylés - ayant de 4 à 20 atomes de carbone et un degré d'alcoxylation de 2 à 10.
  2. Produit selon la revendication 1, caractérisé en ce qu'il est ajusté à un pH inférieure à 7, de préférence de 2 à 4.
  3. Produit selon la revendication 1, caractérisé en ce qu'il contient de 0,05 à 1 g/l du tensioactif.
  4. Produit selon l'une des revendications précédentes, caractérisé en ce qu'il ne contient pas, dans la chaîne, d'inhibiteurs ayant plus de 20 atomes de carbone.
  5. Procédé de passivation de surfaces brillantes d'argent et d'alliages d'argent, ou de surfaces brillantes de cuivre et d'alliages de cuivre, à l'aide d'une émulsion ayant la composition donnée dans les revendications 1 à 4, caractérisé en ce qu'on traite les surfaces à l'aide de l'émulsion à une température supérieure au point de fusion de l'inhibiteur, et qu'on rince ensuite les surfaces à une température inférieure au point de fusion de l'inhibiteur.
  6. Procédé selon la revendication 5, caractérisé en ce que les surfaces sont rincées à l'eau.
  7. Procédé selon la revendication 5 ou 6, caractérisé en ce qu'on sèche à l'air chaud les surfaces rincées.
EP91121903A 1990-12-22 1991-12-20 Produit de protection temporaire de surfaces nues en argent et en cuivre contre le ternissement et procédé d'utilisation Expired - Lifetime EP0492487B1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
DE4041596 1990-12-22
DE19904041596 DE4041596A1 (de) 1990-12-22 1990-12-22 Mittel zum zeitweiligen schutz von blanken silberoberflaechen gegen anlaufen und verfahren zu seiner anwendung
DE4124955 1991-07-27
DE4124955 1991-07-27

Publications (2)

Publication Number Publication Date
EP0492487A1 EP0492487A1 (fr) 1992-07-01
EP0492487B1 true EP0492487B1 (fr) 1996-03-20

Family

ID=25899756

Family Applications (1)

Application Number Title Priority Date Filing Date
EP91121903A Expired - Lifetime EP0492487B1 (fr) 1990-12-22 1991-12-20 Produit de protection temporaire de surfaces nues en argent et en cuivre contre le ternissement et procédé d'utilisation

Country Status (3)

Country Link
EP (1) EP0492487B1 (fr)
DE (1) DE59107581D1 (fr)
ES (1) ES2086471T3 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102005047843A1 (de) * 2005-10-05 2007-04-12 OTB Oberflächentechnik in Berlin GmbH & Co. Passivierungs- und Schmiermittel für Gold-, Silber- und Kupferoberflächen und Verfahren zu seiner Anwendung
CN104032289A (zh) * 2013-08-23 2014-09-10 珠海罗西尼表业有限公司 金及其合金表面耐腐蚀抗变色处理方法及其专用处理液
WO2021028440A1 (fr) 2019-08-13 2021-02-18 Saint-Gobain Glass France Réduction de la corrosion de fils d'argent sur un substrat de verre

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4333127A1 (de) * 1993-09-29 1995-03-30 Basf Ag Verfahren zum Schutz von lötfähigen Kupfer- und Kupferlegierungsoberflächen vor Korrosion
US7524535B2 (en) * 2004-02-25 2009-04-28 Posco Method of protecting metals from corrosion using thiol compounds
GB2412666B (en) * 2004-03-30 2008-10-08 Paul Gilbert Cole Water-based metal treatment composition
US7883738B2 (en) 2007-04-18 2011-02-08 Enthone Inc. Metallic surface enhancement
US10017863B2 (en) 2007-06-21 2018-07-10 Joseph A. Abys Corrosion protection of bronzes
TWI453301B (zh) 2007-11-08 2014-09-21 Enthone 浸鍍銀塗層上的自組分子
IT1398698B1 (it) * 2010-02-24 2013-03-08 Mesa S A S Di Malimpensa Simona E Davide E C Metodo per la protezione di superfici di argento e sue leghe dall'imbrunimento.
CN108315739B (zh) * 2018-02-10 2019-03-22 深圳市祥盛兴科技有限公司 一种化学抛光液及化学抛光工艺

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1347705A (fr) * 1961-09-28 1964-01-04 Minnesota Mining & Mfg Composition empêchant le ternissement des surfaces à base de cuivre
DE1282414B (de) * 1963-12-18 1968-11-07 Wmf Wuerttemberg Metallwaren Mittel zum Schutz von Silberwaren durch Passivieren ihrer Oberflaeche mittels organischer Thioverbindungen
US3398003A (en) * 1965-04-26 1968-08-20 Verle C. Smith Silver polish-tarnish retarder containing a dialkyl disulfide having from 8 to 20 carbon atoms in each alkyl radical
DE1546119A1 (de) * 1965-11-04 1970-03-12 Becker Hans Delu Fab Edelmetallreinigungs- und -polierbad mit Anlaufschutz
DE3905850A1 (de) * 1989-02-24 1990-08-30 Blasberg Oberflaechentech Verfahren zum schuetzen von blanken silberoberflaechen

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102005047843A1 (de) * 2005-10-05 2007-04-12 OTB Oberflächentechnik in Berlin GmbH & Co. Passivierungs- und Schmiermittel für Gold-, Silber- und Kupferoberflächen und Verfahren zu seiner Anwendung
CN104032289A (zh) * 2013-08-23 2014-09-10 珠海罗西尼表业有限公司 金及其合金表面耐腐蚀抗变色处理方法及其专用处理液
CN104032289B (zh) * 2013-08-23 2015-02-25 珠海罗西尼表业有限公司 金及其合金表面耐腐蚀抗变色处理方法及其专用处理液
WO2021028440A1 (fr) 2019-08-13 2021-02-18 Saint-Gobain Glass France Réduction de la corrosion de fils d'argent sur un substrat de verre

Also Published As

Publication number Publication date
DE59107581D1 (de) 1996-04-25
EP0492487A1 (fr) 1992-07-01
ES2086471T3 (es) 1996-07-01

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