EP3159435B1 - Supplement pour electrolyte d'alliage argent-palladium - Google Patents

Supplement pour electrolyte d'alliage argent-palladium Download PDF

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Publication number
EP3159435B1
EP3159435B1 EP15190885.2A EP15190885A EP3159435B1 EP 3159435 B1 EP3159435 B1 EP 3159435B1 EP 15190885 A EP15190885 A EP 15190885A EP 3159435 B1 EP3159435 B1 EP 3159435B1
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EP
European Patent Office
Prior art keywords
silver
palladium
electrolyte
acid
concentration
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EP15190885.2A
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German (de)
English (en)
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EP3159435A1 (fr
Inventor
Bernd Weyhmueller
Alexander Peters
Uwe Manz
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Umicore Galvanotechnik GmbH
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Umicore Galvanotechnik GmbH
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Priority to EP15190885.2A priority Critical patent/EP3159435B1/fr
Priority to PL15190885T priority patent/PL3159435T3/pl
Priority to TW105132420A priority patent/TW201728787A/zh
Priority to US15/767,234 priority patent/US20190071789A1/en
Priority to PCT/EP2016/075096 priority patent/WO2017067985A1/fr
Priority to CN201680061439.2A priority patent/CN108350592A/zh
Priority to JP2018520151A priority patent/JP2018535318A/ja
Priority to EP16784879.5A priority patent/EP3365478A1/fr
Priority to KR1020187014301A priority patent/KR20180072774A/ko
Publication of EP3159435A1 publication Critical patent/EP3159435A1/fr
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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
    • C25D3/56—Electroplating: Baths therefor from solutions of alloys
    • C25D3/64—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of silver
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C5/00—Alloys based on noble metals
    • C22C5/06—Alloys based on silver
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D7/00—Electroplating characterised by the article coated
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01H—ELECTRIC SWITCHES; RELAYS; SELECTORS; EMERGENCY PROTECTIVE DEVICES
    • H01H1/00—Contacts
    • H01H1/02—Contacts characterised by the material thereof
    • H01H1/021—Composite material
    • H01H1/023—Composite material having a noble metal as the basic material

Definitions

  • the present invention relates to an electrolyte containing suitable reducing agents for adjusting the composition of silver-palladium layers. Furthermore, these reducing agents contribute to the improvement of the layered appearance and the increase in the brightness (L value, CIE-Lab) of the deposited layers.
  • the present invention also discloses a process for the electrodeposition of silver-rich silver-palladium alloys.
  • Electrical contacts are installed today in virtually all electrical devices. Their application ranges from simple plug-in connectors to safety-relevant, sophisticated switch contacts in the communications sector, for the automotive industry or the aerospace industry. Here are required by the contact surfaces good electrical conductivities, low and long-term stable contact resistance, and good corrosion and wear resistance with the lowest possible insertion forces.
  • plug contacts are often coated with a hard gold alloy layer consisting of gold-cobalt, gold-nickel or gold-iron. These layers have good wear resistance, good solderability, low and long-term stable contact resistance and good corrosion resistance. Due to the rising gold price is looking for cheaper alternatives.
  • silver-rich silver alloys As a replacement for the hard gold coating, the coating with silver-rich silver alloys (hard silver) has proven to be advantageous. Also due to their high electrical conductivity and good oxidation resistance, silver and silver alloys are among the most important contact materials in electrical engineering. These silver alloy layers have, depending on the metal to be alloyed, similar layer properties as the previously used hard gold layers or layer combinations such. Palladium-nickel with gold flash. In addition, the price of silver is relatively low compared to other precious metals, especially hard gold alloys.
  • a limitation for the use of silver is, for example, the lower corrosion resistance of silver in sulfur and chlorine atmospheres compared to hard gold.
  • tarnish made of silver sulfide are in addition to the visible surface change usually no great danger, since silver sulfide is semiconducting, soft and easily displaced by the wiping mating process with sufficient contact forces.
  • start-up layers of silver chloride are non-conductive, hard and not easily displaceable.
  • a higher proportion of silver chloride in the tarnish layer leads to problems with the contact properties ( Literature: Marjorie Myers: Overview of the Use of Silver in Connector Applications; Interconnect & Process Technology, Tyco Electronics Harrisburg, Feb. 2009 ).
  • the US 3,980,531 discloses a cyanide-free electrolyte for the electrodeposition of alloys containing gold, silver and / or palladium.
  • the baths contain a thiosulphate, a sulphite and a borate or phosphate.
  • the deposition of the alloys takes place in the slightly acidic to strongly alkaline pH range.
  • the electrolyte may contain salts of base metals such as arsenic or cadmium.
  • the deposition takes place at current densities of 0.1 to 5 A / dm 2 .
  • the composition of the deposited alloy depends on the concentrations of the metal salts used and the current density used. The appearance of the alloys varies from matt to high gloss. Due to the use of arsenic or cadmium, this electrolyte is no longer up-to-date due to applicable regulations (REACH).
  • the US 6,251,249 B1 discloses electrolytes for the deposition of precious metals on solids. These electrolytes are free of iodides and contain the noble metal to be deposited in the form of alkanesulfonates, alkanesulfonamides and / or alkanesulfonimides. Furthermore, the electrolytes contain an organosulfur compound and / or a carboxylic acid.
  • the deposition of the noble metals is preferably carried out in a temperature range of 20 ° C to 60 ° C.
  • the pH can be between 0 and 12.
  • the electrolytes are suitable for electroless and electrolytic depositions of noble metal layers as well as for dip plating.
  • the examples in the US 6,251,249 B1 refer exclusively to dip plating and deposit either silver or palladium but no silver-palladium alloy. There is no information on the electrolytic deposition of silver-palladium alloys and their nature.
  • EP 0 065 100 A1 is a galvanic, palladium sulfite and an acid-containing palladium electrolyte described.
  • the electrolyte contains sulfuric and / or phosphoric acid and can be used at 20 ° C to 40 ° C. 80 to 95% of the palladium content is added as palladium sulfate, the remainder as palladium sulfite.
  • EP 0 065 100 A21 no statements on the deposition of palladium alloys.
  • the DE 10 2013 215 476 B3 discloses a cyanide-free, acidic and aqueous electrolyte for deposition of silver-palladium alloys.
  • the electrolyte contains a selenium or tellurium compound, urea and / or at least one amino acid and a sulfonic acid.
  • This electrolyte allows the deposition of predominantly silver-containing silver-palladium alloys over a large current density range.
  • semi-matt alloy coatings can be made with this electrolyte.
  • the generated layers show a distinct brownish color.
  • the electrolyte shows a significant dependence of the alloy composition on the applied current density.
  • the alloy can only be influenced by concentration shift of the alloy metals or by variation of the electrolyte temperature during the deposition.
  • electrolytes which are superior in practical use to prior art electrolytes.
  • electrolytes should have sufficiently high stability and allow stable and light alloy compositions to be deposited over as wide a current density range as possible can. It is also important to be able to easily adjust the alloy composition.
  • the electrolytes should remain fully functional even after high current density loading, and the deposits made with these electrolytes should be homogeneous and advantageous for use in contact materials.
  • the composition of the deposited alloy 90 ⁇ 3 wt .-% silver, 10 ⁇ 3 wt .-% palladium and 0 - 3 wt .-% tellurium and / or selenium.
  • Claim 9 relates to a preferred method for the deposition of silver-palladium alloys, in which the electrolyte according to the invention is used.
  • Claims 10 to 12 relate to preferred embodiments of the subject method.
  • the electrolytes according to the invention are suitable as replacement material for hard gold alloys in contact materials.
  • the palladium content in the layer can be easily adjusted by the added reducing agents (brightener additives), depending on the amount of reducing agent added. As the concentration of the reducing agents increases, the palladium content in the deposited layer increases.
  • the electrolyte of the invention exhibits a comparatively high stability, which makes it appear particularly advantageous in industrial applications. With the present electrolyte, high-quality electrical contact materials can advantageously also be produced in frame and high-speed coating systems.
  • the electrolyte preferably contains only the constituents specified above.
  • the electrolyte according to the invention can be used in a current density range of 0.1 to 100 A / dm 2 .
  • a current density range of 0.5 to 20 A / dm 2 is preferred.
  • homogeneous silver-palladium alloy layers in the present invention are meant those layers whose appearance is uniform in color and layer properties. Layer properties are gloss, brightness, hardness and corrosion resistance.
  • the silver-palladium alloy layers are homogeneous in two respects. On the one hand, the silver-palladium alloy layer deposited on a specific electrically conductive substrate is homogeneous according to the above definition.
  • the appearance of the deposited silver-palladium alloys is homogeneous when depositing layers of the same electrolyte, without change of electrolyte composition, temperature and motion, on a plurality of the same electrically conductive substrates at different current densities, which have the same alloy composition and optical appearance have, regardless of the current density, the deposited layers are homogeneous in this case.
  • L * a * b * measurement according to CIEL * a * b (www.cielab.de), where the L * value is the brightness indicates.
  • the brightness values (L * values) of the silver-palladium alloy layers according to the invention are between 80 and 90 L * a * b * (measuring device X-Rite SP62, type of light D65 / 10).
  • the reflectivity is increased by 5 to 40% from the starting value as a function of the applied current density and the concentration of the reducing agent due to the addition of the reducing agents.
  • the reflectivity was measured with the BYK Gardner - mirror TRI-gloss meter. The measurement was carried out at 20 ° incidence and 20 ° angle of incidence of the light beam) in accordance with EN ISO 7668.
  • the gloss measurement of surfaces is known to the person skilled in the art and can be described, for example, in US Pat. Series Electroplating and Surface Treatment. Testing of Functional Metallic Layers, Chap. 4.3: Gloss and Reflection Measurement on Surfaces ", Eugen G. Leuze-Verlag, Saulgau, 1, 1997 Edition, pp. 117-125 "be looked up.
  • Galvanic baths are solutions containing metal salts from which electrochemical metallic precipitates (coatings) can be deposited on substrates (objects). Frequently, such galvanic baths are also referred to as “electrolytes”. Accordingly, the cyanide-free and aqueous electroplating baths of the present invention will hereinafter be referred to as "electrolytes”.
  • the electrolyte according to the invention for the electrolytic deposition of light, homogeneous and predominantly silver-containing silver-palladium alloys and the process for depositing such silver-palladium alloys are explained below, the invention encompassing all embodiments listed below individually and in combination with one another.
  • the metal compounds that can be added to the electrolyte are generally known to those skilled in the art.
  • the silver compound contained in the electrolyte according to the invention is advantageously a silver salt which is soluble in this electrolyte.
  • the silver salts are preferably selected from the group consisting of silver methanesulfonate, silver carbonate, silver sulfate, silver phosphate, silver pyrophosphate, silver nitrate, silver oxide, silver lactate, silver fluoride, silver bromide, silver chloride, silver iodide, silver azide, silver sulfide and silver sulfate.
  • Silver nitrate, silver carbonate, silver methanesulfonate, silver chloride and silver oxide are particularly preferably used in the electrolyte according to the invention.
  • the expert should be guided by the sentence that as few additional substances as possible should be added to the electrolyte. Therefore, the skilled person will most preferably choose as the silver salt to be added the silver methanesulfonate, the silver carbonate or the silver oxide. In the concentration of the silver compound used, the skilled person will have to orientate to the limits given above.
  • the silver compound is preferably present in the electrolyte in a concentration of 1 to 300 g / l of silver, more preferably 2 to 100 g / l of silver, and most preferably between 4 to 15 g / l of silver.
  • the palladium compound to be used is preferably used as the electrolyte-soluble salt or soluble complex.
  • the palladium compound used here is selected from the group consisting of palladium hydroxide, Palladium chloride, palladium sulfate, palladium pyrophosphate, palladium nitrate, palladium phosphate, palladium bromide, palladium P salt (diamminedinitritopalladium (II), palladium glycinates, palladium acetates, tetramminepalladium (II) chloride, tetramminepalladium (II) bromide, palladium methanesulfonate, diamminedinitropalladium (II) chloride, diamminedinitropalladium (II) bromide, diamminedinitropalladium (II) sulfate, potassium di-oxalatopalladate, palladium iodide
  • the palladium compound is added to the electrolyte in a concentration as indicated above.
  • the palladium compound is preferably used in a concentration of 0.1-100 g / l of palladium, and the concentration is very preferably 2-20 g / l of palladium in the electrolyte.
  • the electrolyte according to the invention is aqueous.
  • the silver and palladium compounds to be used are preferably salts soluble in the electrolyte or soluble complexes.
  • the terms "soluble salt” and “soluble complex” therefore refer to those salts and complexes which dissolve in the electrolyte at the working temperature.
  • the working temperature is the temperature at which deposition of the silver-palladium alloy takes place.
  • a substance is considered to be soluble if at least 0.002 g / l of this substance dissolves in the electrolyte at the working temperature.
  • the deposited alloys which contain silver, palladium and selenium and / or tellurium, have a composition which comprises 70-99% by weight of silver, 1-30% by weight of palladium and 0.1-5% by weight of selenium and / or tellurium. The sum of the proportions of silver, palladium and selenium and / or tellurium is 100 wt .-%. According to the invention, the concentrations of the metals to be deposited in the electrolyte in the above-mentioned frame so that a silver-rich alloy results.
  • an alloy is desired in which the silver has a concentration of 70-99% by weight, more preferably 80-95% by weight and most preferably 87-94% by weight.
  • the palladium content of the alloys according to the invention is 1 to 30% by weight, preferably 5 to 20% by weight and more preferably 6 to 13% by weight.
  • the selenium or tellurium content of the alloy according to the invention is 0.1-5 wt .-%, preferably 0.5 to 4 wt .-% and particularly advantageously 1-3 wt .-%.
  • alloys according to the invention which contain silver, palladium and selenium and / or tellurium are referred to as "silver-palladium alloys”.
  • the selenium or tellurium compound which is used in the electrolyte can be selected appropriately by the person skilled in the art within the scope of the above-indicated concentration. As a preferred concentration range, a concentration of between 0.002 and 10 g / l of tellurium and / or selenium and most preferably between 0.1 and 5 g / l of tellurium and / or selenium can be selected.
  • the concentration data relate to the total amount of tellurium and selenium in the electrolyte. Suitable selenium and tellurium compounds are those in which selenium or tellurium are present in the oxidation states +4 or +6.
  • Selenium and tellurium compounds in the electrolyte are advantageously used in which selenium or tellurium in the oxidation state +4 are present.
  • the selenium and tellurium compounds are particularly preferably selected from tellurites, selenites, telluric acid, selenious acid, telluric acid, selenic acid, selenocyanates, tellurocyanates and selenate, and also tellurate.
  • tellurium compound over selenium compounds is generally preferred.
  • Very particular preference is given to adding the tellurium to the electrolyte in the form of a salt of the telluric acid, for example in the form of potassium tellurite.
  • the electrolyte according to the invention contains a compound selected from the group of urea, urea derivatives, thiourea, thiourea derivatives and mixtures thereof and / or one or more ⁇ -amino acids which serve as a complexing agent for the palladium and contribute to increasing the stability of the present electrolyte.
  • Urea derivatives are selected from dimethylurea, ethyleneurea, N, N'-dimethylpropyleneurea and N- (2-hydroxyethyl) ethyleneurea.
  • Thiourea derivatives are, for example, 3-S-isothioroniumpropanesulfonate and N-ethylthiourea.
  • component d) of the electrolyte according to the invention i. the complexing agent for the palladium to urea.
  • the one or more ⁇ -amino acids are selected from the group consisting of alanine, aspartic acid, cysteine, glutamine, glutamic acid, glycine, lysine, leucine, methionine, phenylalanine, phenylglycine, proline, serine, tyrosine and valine.
  • those amino acids are used which have only alkyl groups in the variable radical.
  • the ⁇ -amino acid is selected from alanine, glycine and valine. Very particularly preferred is the use of glycine and / or alanine.
  • Urea, urea derivatives, thiourea, thiourea derivatives and mixtures thereof are used in a concentration of 0.05 to 2 mol / l, preferably 0.2 to 1.5 mol / l, based on the total amount of urea and urea derivatives in the electrolyte.
  • the concentration of the one or more ⁇ -amino acids in the electrolyte according to the invention is 0.005 to 0.5 mol / l, preferably 0.01 to 0.2 mol / l. In the case of ⁇ -amino acids, these concentrations refer to the total amount of ⁇ -amino acid or ⁇ -amino acids, regardless of whether the electrolyte contains one or more ⁇ -amino acids.
  • the electrolyte according to the invention is used in an acidic pH range. Optimal results can be achieved at pH values in the electrolyte of ⁇ 2.
  • the person skilled in the art knows how to adjust the pH of the electrolyte. He will be guided by the idea of introducing as few additional substances into the electrolyte as possible, which may have a negative effect on the deposition of the corresponding alloy.
  • the pH is determined solely by the addition of the sulfonic acid. Strongly acidic deposition conditions then preferably result in which the pH is less than 1 and, where appropriate, even up to 0.1 in borderline cases can also reach up to 0.01. In the optimal case, the pH is around 0.3-0.6.
  • At least one sulfonic acid in a concentration of 0.25-4.75 mol / l is used in the electrolyte according to the invention, the concentration being based on the total amount of the sulfonic acids used.
  • the concentration is preferably 0.5-3 mol / l and most preferably 0.8-2.0 mol / l.
  • the at least one sulfonic acid serves on the one hand to establish a corresponding pH in the electrolyte. On the other hand, their use leads to a further stabilization of the electrolyte according to the invention.
  • the upper limit of the sulfonic acid concentration is due to the fact that at too high a concentration only silver is deposited.
  • sulfonic acid As sulfonic acid, sulfonic acids known in principle to those skilled in the art for use in electroplating can be used.
  • sulfonic acids are selected from the group consisting of ethanesulfonic acid, propanesulfonic acid, benzenesulfonic acid, methanesulfonic acid used. They can be used individually or as mixtures. Very particular preference is given to mentioning propanesulfonic acid and methanesulfonic acid in this context. Most preferably, methanesulfonic acid is used.
  • the at least one reducing agent is selected from formic acid, oxalic acid, ascorbic acid, hydrazine, urotropin, salts and / or esters of sulfurous acid, gaseous sulfites, sulfinic acids and their salts and / or esters, formaldehyde, sodium formaldehyde sulfoxylate, benzaldehyde, benzaldehyde derivatives, hydroxybenzenes and their esters , Polyphenols and their esters, phenolsulfonic acids and their salts and / or esters and glutathione and its salts and / or esters.
  • the reducing agent is selected from hydroxybenzenes, Na-formaldehydsulfoxylat and ascorbic acid.
  • the reducing agent is selected from salts and / or the esters of sulfurous acid.
  • the sulphurous acid salts can be sulphites or hydrogen sulphites.
  • the sulfites and hydrogen sulfites are lithium, sodium, potassium or ammonium salts.
  • the linear or branched acyclic alkyl groups having 1 to 10 carbon atoms are selected from methyl, ethyl, n-propyl, isopropyl, 1-butyl, 2-butyl, tert-butyl, 1-pentyl, 2-pentyl, 3-pentyl, 3-methylbutyl, 2,2-dimethylpropyl and all isomers of hexyl, heptyl, octyl, nonyl and decyl. It is known to the person skilled in the art that cyclic alkyl groups must contain at least three carbon atoms.
  • Cyclic alkyl groups in the context of the present invention advantageously include propyl, butyl, pentyl, hexyl, heptyl, and octyl rings.
  • a cyclic alkyl group in the context of the present invention is selected from the said ring-shaped alkyl groups which carry no further substituents, and from the said ring-shaped alkyl groups, which in turn are bonded to one or more acyclic alkyl groups.
  • the bonding of the cyclic alkyl group to the oxygen atom according to the above formula may be via a cyclic or an acyclic carbon atom of the cyclic alkyl group.
  • Cyclic alkyl groups according to the above definition of the term "alkyl group” also contain a maximum of 10 carbon atoms. If one of the radicals R 1 and R 2 is an aryl group, this is selected from among phenyl, naphthyl and anthracenyl.
  • Gaseous sulfites are SO 2 gas which is introduced into the electrolyte.
  • Benzaldehyde derivatives are selected from benzaldehydesulfonic acid, their salts and esters, e.g. Benzaldehyde-2-sulfonic acid sodium salt, dimethylaminobenzaldehyde, 3-chlorobenzaldehyde, 4-chlorobenzaldehyde, 2-methoxybenzaldehyde, 2-methylbenzaldehyde, 2-nitrobenzaldehyde, 3,5-dibromobenzaldehyde, 3-nitrobenzaldehyde and 3,5-dimethoxybenzaldehyde.
  • Benzaldehyde derivatives are selected from benzaldehydesulfonic acid, their salts and esters, e.g. Benzaldehyde-2-sulfonic acid sodium salt, dimethylaminobenzaldehyde, 3-chlorobenzaldehyde, 4-chlorobenzaldehyde, 2-methoxybenzaldehyde, 2-methyl
  • Hydroxybenzenes are selected from phenol, catechol, resorcinol, hydroquinone, pyrogallol, hydroxyquinone and phloroglucin.
  • the at least one reducing agent is a salt of an organic compound
  • a single acidic hydrogen atom or several or all may be replaced by sodium, potassium, lithium or ammonium ions. If more than one acidic hydrogen atom is replaced by sodium, potassium, lithium or ammonium ions, these cations may be identical or different.
  • the at least one reducing agent may further be an ester of an organic compound.
  • esters are the condensation products of an alcohol and a carboxylic acid. Accordingly, esters of alcohols according to the above list of suitable reducing agents are condensation product of one of the abovementioned alcohols and a carboxylic acid R4-COOH, and esters of carboxylic acids according to the above list are condensation products of one of the abovementioned carboxylic acids with an alcohol R5-OH.
  • R 4 and R 5 are here selected from linear or branched acyclic alkyl groups having 1 to 10 carbon atoms, cyclic alkyl groups having 3 to 10 carbon atoms, aryl or benzyl groups, these groups being defined as described above for R 1 and R 2.
  • At least one reducing agent selected from salts and / or esters of sulfurous acid and gaseous sulfites.
  • the at least one reducing agent is contained in the electrolyte in a concentration of 1 to 100 mmol / l, advantageously in a concentration of 5-30 mmol / l, this concentration refers to the total amount of the above-mentioned reducing agent in the electrolyte.
  • the electrolyte of the invention further contains at least one sulfonic acid in a concentration of 0.25 to 4.75 mol / l.
  • the concentration is preferably 0.5 to 3 mol / l and most preferably 0.8 to 2.0 mol / l.
  • the at least one sulfonic acid serves on the one hand to establish a corresponding pH in the electrolyte. On the other hand, their use leads to a further stabilization of the electrolyte according to the invention.
  • the upper limit of the sulfonic acid concentration is due to the fact that at too high a concentration only silver is deposited.
  • sulfonic acids are selected from the group consisting of methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid and benzenesulfonic acid. Very particular preference is given to mentioning methanesulfonic acid and propanesulfonic acid in this context. Most preferably, methanesulfonic acid is used.
  • the electrolyte according to the invention further contains a surfactant.
  • This surfactant is selected from anionic and nonionic surfactants. Examples thereof are polyethylene glycol adducts, fatty alcohol sulfates, alkyl sulfates, alkyl sulfonates, aryl sulfonates, alkylaryl sulfonates and heteroaryl sulfonates, betaines, fluorosurfactants and their salts and derivatives.
  • Suitable surfactants are known to the person skilled in the art, for example from N. Kanani: Galvanotechik, Hanser-Verlag, Kunststoff-Vienna, 2000, p.
  • the electrolyte according to the invention has a surface tension of greater than or equal to 70 mN / m. If a surfactant is added, its concentration is advantageously chosen so that the surface tension of the electrolyte drops to a value less than or equal to 50 mN / m. The surface tension can be measured with a bubble pressure tensiometer.
  • the present invention relates to a process for the electrolytic deposition of predominantly silver-containing silver-palladium layers of an electrolyte according to the invention, wherein an electrically conductive substrate is immersed in the electrolyte and between an anode in contact with the electrolyte and the substrate as a cathode established a current flow.
  • an electrically conductive substrate is immersed in the electrolyte and between an anode in contact with the electrolyte and the substrate as a cathode established a current flow.
  • the temperature which prevails during the deposition of the silver-palladium alloy can be chosen at will by the person skilled in the art. It will orientate itself on a sufficient deposition rate and applicable current density range on the one hand and on the other hand on economic aspects or the stability of the electrolyte. It is advantageous to set a temperature of 25 ° C to 75 ° C in the electrolyte, preferably between 30 ° C and 65 ° C. Most preferably, the use of the electrolyte at temperatures of 45 ° C to 55 ° C.
  • the current density established during the deposition process in the electrolyte between the cathode and the anode can be selected by one skilled in the art in accordance with the efficiency and the quality of the deposition.
  • the current density in the electrolyte is set to 0.1 to 100 A / dm 2 , depending on the application and coating system type.
  • the current densities can be increased or decreased by adjusting the system parameters such as the structure of the coating cell, flow rates, anode, cathode ratios, etc.
  • the electrolyte according to the invention is an acidic type.
  • the pH should preferably be ⁇ 2, more preferably ⁇ 1. It may be that with respect to the pH of the electrolyte during the electrolysis fluctuations occur. In a preferred embodiment of the subject method, the person skilled in the art therefore proceeds in such a way that he controls the pH during the electrolysis and, if necessary, sets it to the desired value.
  • anodes When using the electrolyte, various anodes can be used. Soluble or insoluble anodes are also suitable, as is the combination of soluble and insoluble anodes. If a soluble anode is used, it is particularly preferred if a silver anode is used.
  • Preferred insoluble anodes are those made of a material selected from the group consisting of platinized titanium, graphite, iridium-transition metal mixed oxide and special carbon material ("Diamond Like Carbon" DLC) or combinations of these anodes.
  • Mixed oxide anodes of iridium-ruthenium mixed oxide, iridium-ruthenium-titanium mixed oxide or iridium-tantalum mixed oxide are particularly preferably used for carrying out the invention. Very particular preference is given to using platinum-titanium anodes. Others can be added Cobley, AJ et al. (The use of insoluble anodes in Acid Sulphate Copper Electrodeposition Solutions, Trans. IMF, 2001, 79 (3), pp. 113 and 114 ) being found.
  • the present invention provides a silver-palladium alloy electrolyte with an added reducing agent for alloying and brightening, and for the electrodeposition of silver-palladium layers, and a corresponding method.
  • the electrolyte contains at least one reducing agent for alloy adjustment and lightening: By adding the at least one reducing agent, the palladium content of the deposited silver-palladium alloy can be adjusted.
  • the deposited alloys according to the invention have a composition which contains 70-99% by weight of silver, 1-30% by weight of palladium and 0.1-5% by weight of selenium and / or tellurium. wherein the sum of the proportions of silver, palladium and selenium and / or tellurium is 100 wt .-%.
  • the electrolyte according to the invention leads to a more homogeneous deposition compared to conventional silver-palladium alloy electrolytes.
  • Layers deposited from conventional silver palladium electrolytes have L * values of 67-78, depending on the applied current density. With the new electrolyte system according to the invention, significantly higher L * values of the deposited layers, uniform over the applied current density range, are achieved. These are between 80 and 90, depending on the reducing agent used.
  • the palladium content of the deposited layers was determined by means of an X-ray fluorescence analysis method (RFA, XRF) (Fischerscope XDV-SDD, software WIN-FTM version 6.28-S-PDM). Measurement results of palladium content: Content of Na formaldehyde sulfoxylate [g / l] Current density [A / dm2] Pd content [% by weight] 0 1 4.2 0 2 3.2 0 3 3.0 0.95 1 5,7 0.95 2 3.5 0.95 3 3.4 4.7 1 9.1 4.7 2 6.8 4.7 3 5.4
  • the brightness of the deposited layers was measured in terms of the L * value according to CIEL * a * b. Measurement results: Content of Na formaldehyde sulfoxylate [g / l] Current density [A / dm2] Brightness [L *] 0 1 78.3 0 2 73.4 0 3 73.0 0.95 1 73.6 0.95 2 83.0 0.95 3 80.5 4.7 1 75.6 4.7 2 77.2 4.7 3 78.8
  • the palladium content of the deposited layers was determined by an X-ray fluorescence analysis method (RFA). Measurement results of palladium content: Ascorbic acid content [g / l] Current density [A / dm2] Pd content [% by weight] 0 1 3.8 0 2 2.9 0 3 2.7 0.14 1 4.2 0.14 2 3.1 0.14 3 2.7 0.42 1 5.3 0.42 2 3.6 0.42 3 3.3
  • the brightness of the deposited layers was measured in terms of the L * value according to CIEL * a * b. Measurement results
  • the palladium content of the deposited layers was determined by an X-ray fluorescence analysis method (RFA). Measurement results of palladium content: Hydroquinone content [g / l] Current density [A / dm2] Pd content [% by weight] 0 1 1.4 0 2 2.9 0 3 2.8 0.5 1 6.8 0.5 2 5.5 0.5 3 6.0 1.0 1 16.8 1.0 2 15.0 1.0 3 14.4
  • the brightness of the deposited layers was measured in terms of the L * value according to CIEL * a * b. Measurement results
  • the palladium content of the deposited layers was determined by an X-ray fluorescence analysis method (RFA). Measurement results of palladium content: Sodium sulphite content [g / l] Current density [A / dm2] Pd content [% by weight] 0 1 6.2 0 2 4.9 0 3 3.5 1.0 1 10.0 1.0 2 8.1 1.0 3 8.1 2.0 1 15.6 2.0 2 12.3 2.0 3 11.7
  • the brightness of the deposited layers was measured in terms of the L * value according to CIEL * a * b. Measurement results

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Claims (12)

  1. Électrolyte exempt de cyanure, acide et aqueux pour le dépôt électrolytique d'alliages d'argent-palladium clairs, contenant surtout de l'argent, qui présente les constituants suivants sous forme dissoute :
    a) un composé d'argent à une concentration en argent de 1 à 300 g/L ;
    b) un composé de palladium à une concentration en palladium de 0,1 à 100 g/L ;
    c) un composé de tellure et/ou de sélénium à une concentration en tellure et/ou en sélénium de 0,002 à 10 g/L par rapport à la quantité totale de tellure et de sélénium dans l'électrolyte ;
    d) de l'urée et/ou des dérivés d'urée à une concentration de 0,05 à 1,5 mole/L, par rapport à la quantité totale d'urée et de dérivés d'urée dans l'électrolyte, et/ou un ou plusieurs acides α-aminés choisis parmi le groupe constitué par l'alanine, l'acide aspartique, la cystéine, la glutamine, l'acide glutamique, la glycine, la lysine, la leucine, la méthionine, la phénylalanine, la phénylglycine, la proline, la sérine, la tyrosine et la valine à une concentration de 0,005 à 0,5 mole/L, par rapport à la quantité totale d'acides aminés dans l'électrolyte ;
    e) au moins un acide sulfonique à une concentration de 0,25 à 4,75 moles/L, par rapport à la quantité totale des acides sulfoniques,
    caractérisé en ce que l'électrolyte présente en outre
    f) au moins un agent réducteur, choisi parmi le groupe acide formique, acide oxalique, acide ascorbique, hydrazine, urotropine, sels et/ou esters de l'acide sulfureux, sulfites gazeux, acides sulfiniques et leurs sels et/ou esters, formaldéhyde, formaldéhydesulfoxylate de sodium, benzaldéhyde, dérivés du benzaldéhyde, hydroxybenzènes et leurs esters, polyphénols et leurs esters, acides phénolsulfoniques et leurs sels et/ou esters et glutathion ainsi que ses sels et/ou esters à une concentration de 1 à 100 mmoles/L, par rapport à la quantité totale de ces agents réducteurs.
  2. Électrolyte selon la revendication 1, caractérisé en ce que le composé d'argent est choisi parmi le nitrate d'argent, le carbonate d'argent, le méthanesulfonate d'argent, le chlorure d'argent et l'oxyde d'argent.
  3. Électrolyte selon l'une quelconque des revendications 1 et 2, caractérisé en ce que le composé de palladium est choisi parmi l'hydroxyde de palladium, le chlorure de palladium, le glycinate de palladium, le méthanesulfonate de palladium et le sulfate de palladium.
  4. Électrolyte selon l'une quelconque des revendications 1 à 3, caractérisé en ce que les composés de sélénium et/ou de tellure sont choisis parmi les tellurites, les sélénites, l'acide tellureux, l'acide sélénieux, l'acide tellurique et le sélénate ainsi que le tellurate.
  5. Électrolyte selon l'une quelconque des revendications 1 à 4, caractérisé en ce que l'acide α-aminé est choisi parmi l'alanine, la glycine et la valine.
  6. Électrolyte selon l'une quelconque des revendications 1 à 4, caractérisé en ce le constituant d) est l'urée.
  7. Électrolyte selon l'une quelconque des revendications 1 à 6, caractérisé en ce que ledit au moins un acide sulfonique est choisi parmi l'acide éthanesulfonique, l'acide propanesulfonique, l'acide benzènesulfonique, l'acide méthanesulfonique.
  8. Électrolyte selon l'une quelconque des revendications 1 à 7, caractérisé en ce que ledit au moins un agent réducteur est choisi parmi les hydroxyphénols, l'acide ascorbique et les sels et/ou les esters de l'acide sulfureux.
  9. Procédé de dépôt électrolytique de couches d'argent-palladium contenant surtout de l'argent, à partir d'un électrolyte selon les revendications 1 à 8, caractérisé en ce qu'un substrat électriquement conducteur est plongé dans l'électrolyte et un courant s'établit entre l'anode en contact avec l'électrolyte et le substrat en tant que cathode.
  10. Procédé selon la revendication 9, caractérisé en ce que la température de l'électrolyte est de 25 à 70 °C.
  11. Procédé selon l'une quelconque des revendications 9 et 10, caractérisé en ce que l'intensité du courant pendant l'électrolyse est située entre 0,5 et 20 A/dm2.
  12. Procédé selon l'une quelconque des revendications 9 à 11, caractérisé en ce que le pH pendant l'électrolyse est ajusté en permanence à une valeur < 2.
EP15190885.2A 2015-10-21 2015-10-21 Supplement pour electrolyte d'alliage argent-palladium Not-in-force EP3159435B1 (fr)

Priority Applications (9)

Application Number Priority Date Filing Date Title
EP15190885.2A EP3159435B1 (fr) 2015-10-21 2015-10-21 Supplement pour electrolyte d'alliage argent-palladium
PL15190885T PL3159435T3 (pl) 2015-10-21 2015-10-21 Dodatek do elektrolitów do stopu srebro-palladowego
TW105132420A TW201728787A (zh) 2015-10-21 2016-10-06 用於銀鈀合金電解質之添加劑
PCT/EP2016/075096 WO2017067985A1 (fr) 2015-10-21 2016-10-19 Additif pour électrolytes d'alliage argent-palladium
US15/767,234 US20190071789A1 (en) 2015-10-21 2016-10-19 Additive for silver-palladium alloy electrolytes
CN201680061439.2A CN108350592A (zh) 2015-10-21 2016-10-19 用于银钯合金电解质的添加剂
JP2018520151A JP2018535318A (ja) 2015-10-21 2016-10-19 銀−パラジウム合金電解質用添加物
EP16784879.5A EP3365478A1 (fr) 2015-10-21 2016-10-19 Additif pour électrolytes d'alliage argent-palladium
KR1020187014301A KR20180072774A (ko) 2015-10-21 2016-10-19 은-팔라듐 합금 전해질을 위한 첨가물

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP15190885.2A EP3159435B1 (fr) 2015-10-21 2015-10-21 Supplement pour electrolyte d'alliage argent-palladium

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EP3159435A1 EP3159435A1 (fr) 2017-04-26
EP3159435B1 true EP3159435B1 (fr) 2018-05-23

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EP15190885.2A Not-in-force EP3159435B1 (fr) 2015-10-21 2015-10-21 Supplement pour electrolyte d'alliage argent-palladium
EP16784879.5A Withdrawn EP3365478A1 (fr) 2015-10-21 2016-10-19 Additif pour électrolytes d'alliage argent-palladium

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EP (2) EP3159435B1 (fr)
JP (1) JP2018535318A (fr)
KR (1) KR20180072774A (fr)
CN (1) CN108350592A (fr)
PL (1) PL3159435T3 (fr)
TW (1) TW201728787A (fr)
WO (1) WO2017067985A1 (fr)

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CN110770371A (zh) * 2017-05-23 2020-02-07 萨克森爱德美塔尔有限责任公司 贵金属盐制剂、其生产方法及用于电镀的用途
DE102019106004B4 (de) * 2019-03-08 2023-11-30 Umicore Galvanotechnik Gmbh Additiv für die cyanidfreie Abscheidung von Silber
JP7405827B2 (ja) * 2018-08-21 2023-12-26 ウミコレ・ガルファノテフニック・ゲーエムベーハー 銀の非シアン系析出用電解質
DE102018126174B3 (de) * 2018-10-22 2019-08-29 Umicore Galvanotechnik Gmbh Thermisch stabile Silberlegierungsschichten, Verfahren zur Abscheidung und Verwendung
US11242609B2 (en) 2019-10-15 2022-02-08 Rohm and Hass Electronic Materials LLC Acidic aqueous silver-nickel alloy electroplating compositions and methods
DE102020109818A1 (de) * 2020-04-08 2021-04-22 Doduco Solutions Gmbh Elektrischer Steckverbinder zum Anschließen eines Elektrofahrzeugs an eine Ladestation
CN111455360A (zh) * 2020-05-06 2020-07-28 广东工业大学 一种化学镀钯还原剂及化学镀钯液

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Publication number Publication date
EP3365478A1 (fr) 2018-08-29
CN108350592A (zh) 2018-07-31
PL3159435T3 (pl) 2018-10-31
US20190071789A1 (en) 2019-03-07
WO2017067985A1 (fr) 2017-04-27
JP2018535318A (ja) 2018-11-29
TW201728787A (zh) 2017-08-16
KR20180072774A (ko) 2018-06-29
EP3159435A1 (fr) 2017-04-26

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