EP4146848A1 - Électrolyte à base d'argent pour le dépôt de couches de dispersion d'argent - Google Patents

Électrolyte à base d'argent pour le dépôt de couches de dispersion d'argent

Info

Publication number
EP4146848A1
EP4146848A1 EP22755083.7A EP22755083A EP4146848A1 EP 4146848 A1 EP4146848 A1 EP 4146848A1 EP 22755083 A EP22755083 A EP 22755083A EP 4146848 A1 EP4146848 A1 EP 4146848A1
Authority
EP
European Patent Office
Prior art keywords
electrolyte
silver
amount
graphite
group
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.)
Granted
Application number
EP22755083.7A
Other languages
German (de)
English (en)
Other versions
EP4146848B8 (fr
EP4146848B1 (fr
Inventor
Uwe MANTZ
Alexander Peters
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.)
Umicore Galvanotechnik GmbH
Original Assignee
Umicore Galvanotechnik GmbH
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
Application filed by Umicore Galvanotechnik GmbH filed Critical Umicore Galvanotechnik GmbH
Publication of EP4146848A1 publication Critical patent/EP4146848A1/fr
Application granted granted Critical
Publication of EP4146848B1 publication Critical patent/EP4146848B1/fr
Publication of EP4146848B8 publication Critical patent/EP4146848B8/fr
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

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
    • C25D3/46—Electroplating: Baths therefor from solutions of 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
    • 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
    • C25D7/06—Wires; Strips; Foils
    • C25D7/0614—Strips or foils

Definitions

  • the present invention is directed to a silver electrolyte and a corresponding method for the electrodeposition of silver onto conductive substrates.
  • the silver electrolyte is characterized by certain additives that help to prevent foaming of the electrolyte without negatively affecting the electrodeposition.
  • Electrical contacts are installed in practically all electrical devices today. Their application ranges from simple connectors to safety-relevant, demanding switching contacts in the communications sector, for the automotive industry or aerospace technology. Good electrical conductivity, low and long-term stable contact resistance, as well as good corrosion and wear resistance with the lowest possible insertion forces are required from the contact surfaces.
  • 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 price of gold, cheaper alternatives are being sought.
  • silver and silver alloys are among the most important contact materials in electrical engineering. These silver layers have similar layer properties to the hard gold layers or layer combinations used up until now, such as palladium-nickel with gold flash. In addition, the price of silver is relatively low compared to other precious metals, especially hard gold alloys.
  • Silver electrolytes are used to coat substrates with silver and to produce contact surfaces. These are mostly cyanide-containing or cyanide-free silver-containing solutions that are used for electrochemical, in particular galvanic, silvering of surfaces. Silver electrolyte solutions can in this case a wide variety of other additives such as grain refiners, dispersants, brighteners or include solid components. The conductivity, the contact resistance and the coefficient of friction are particularly relevant for applications in the electrical and electronics sector, in particular for plugs and plug-in and switching contacts.
  • DE102018005352A1 also describes cyanide-containing silver electrolytes for producing contact surfaces into which solid components are dispersed as a dry lubricant. These solids should be built into the silver layer as highly dispersed and well distributed as possible. The aim is to ensure the highest possible self-lubricating properties of the silver layer by uniformly dispersing solid components (Arnet, R. et al, Silberdispersions füre mitslubricating properties, Galvanotechnik 2021, Vol.
  • the problem is that the known silver electrolytes tend to form foam (total volume increase of the electrolyte approx. 40%), especially when using high electrolyte movements, for example when using dispersing devices.
  • high electrolyte movements are necessary for a high applicable current density and thus rapid deposition. In the coating process, this disrupts, among other things: a) the uniform incorporation of the solid into the silver layer; b) due to loss of electrolyte due to the foam escaping from the process vessel; and c) by marbling effects on the surface of the parts due to adhering foam when extending and lifting the parts; and thus leads to unfavorable products or process problems.
  • the object of the present invention is therefore to indicate a possibility with which foam formation is maximally suppressed in such electrolytes during the deposition of silver and at the same time the homogeneous deposition of a silver dispersion layer is not adversely affected as far as possible.
  • an aqueous silver electrolyte for the galvanic deposition of silver layers on conductive substrates, which has the following components: a) at least one soluble silver compound; b) free cyanide in an amount of 20 - 200 g/L; c) at least one gloss additive in an amount of 0.2 - 10 g/l; d) at least one wetting agent in an amount of 0.1 - 15 ml/L; e) at least one solid component in an amount of 2-200 g/L; where the electrolyte additionally has: f) at least one defoamer in an amount of 0.2-20 g/l, it is surprisingly easy to achieve the objectives set.
  • the electrolyte During the deposition of silver layers from the electrolyte according to the invention, the electrolyte must be kept in constant motion in order to prevent sedimentation of the solid components and to ensure the highest possible current density. Foam formation is reliably prevented/reduced as far as possible with the defoamers. It is also surprising that the addition of appropriate defoamers does not have a significant negative effect on the layer composition (solids incorporation) and the desired properties of the silver layer, such as contact resistance.
  • defoamers from the Group consisting of polyethers (BASF Pluriol® E series), fatty alcohol alkoxylates (BASF Degressal® SD20), phosphoric acid esters (BASF Degressal® SD40) and alkyl polyglycol ether carboxylic acid (CLARIANT COL® 100).
  • defoamers based on polyethers is particularly advantageous.
  • These are commercially available under various trade names, eg Pluriol® series E200 to E 9000, the numerical designation corresponding to the average molecular weight of the substance. It has also proven advantageous if the polyalkylene glycols used, in particular polyethylene glycol, have a higher average molecular weight greater than 200 g/mol, preferably at least 400 g/mol.
  • the average molar mass of the polyethylene glycols used is very preferably between 1000 and 9000 g/mol and very particularly preferably between 4000 and 8000 g/mol.
  • the amount of defoamer in the electrolyte can be determined by a person skilled in the art. It varies between 0.2 and 20 g/l, preferably 1 and 10 g/l and very preferably between 1 and 5 g/l.
  • brightening additives are substances which shift the grain size of the silver deposit to smaller grain sizes.
  • Brightening additives selected from the group consisting of substituted and unsubstituted mononuclear arylsulfonic acids and thioalkylcarboxylic acids and thiocarbamides have proven to be such.
  • Particularly preferred in this context are arylsulfonic acids such as phenolsulfonic acid and benzenesulfonic acid, toluenesulfonic acid.
  • thiolactic acid, thiobarbituric acid and 1-phenyl-1H-tetrazole-5-thione in particular have also proven advantageous.
  • the brightening additives are used in the electrolyte according to the invention in a concentration of 0.2-10 g/l, preferably 0.5-10 g/l and very preferably 1.0-5 g/l.
  • naphthalene sulfonic acid, naphthalene sulfonic acid derivatives (eg naphthalene sulfonic acid condensation products with aldehydes) or mixtures thereof are present in the electrolyte according to the invention.
  • Na or K Salts of arylsulfonic acids in which the aryl moiety is a benzene ring such as benzenesulfonic acid.
  • the aryl radical can optionally be substituted.
  • the polyether-based defoamers mentioned above in particular polyethylene glycol ether, the latter mean that, despite high current densities and the resulting high electrolyte movement, only little foam occurs and the solid components can be dispersed so well in the silver deposit (see examples).
  • solid component means a component that is not in solution but is present in the electrolyte as a solid.
  • solid components can be used which are mentioned in this respect in DE102018005352A1.
  • These are preferably those selected from the group consisting of graphite, graphite fluoride, graphite oxide, coated graphite, graphene, carbon black, fullerenes, diamond, Al2O3, cubic boron nitride, or mixtures thereof, preferably graphite, graphite fluoride, graphite oxide, Al2O3 coated graphite or mixtures thereof, more preferably graphite, graphite oxide or mixtures thereof and even more preferably graphite.
  • the manner of a suitable preparation of the substances is adequately described in the literature and has only a minor influence, if any, on the invention described here.
  • the solid component is dispersed in the electrolyte, in particular physically dispersed.
  • the amount of solid component used can be determined by the person skilled in the art at his discretion. As a rule, the concentration here is 2-200 g/l, preferably 20-150 g/l and very preferably 80-130 g/l.
  • the mean particle diameter (d50 of the Q3 distribution) is measured in accordance with ISO 13320-1 (latest version on the filing date) using a Tornado dry dispersion module from Beckmann.
  • the mean particle size (d50) indicates that 50% of the particles of a solid component have a smaller diameter than the specified value.
  • Wetting agents are also present in the electrolyte. Those skilled in the art know how to select these. Typically, ionic and non-ionic surfactants are used as wetting agents, such as, for example, polyethylene glycol adducts, fatty alcohol sulfates (e.g.
  • the wetting agent contains a linear or branched chain alkyl sulfate having C3-Ci5 alkyl groups which may be unsubstituted or optionally substituted, and more preferably a linear or branched chain alkyl sulfate having C3-Ci2 alkyl groups which may be unsubstituted or optionally substituted.
  • the wetting agents can also be present in the form of their salts, eg sodium salt, potassium salt.
  • their salts eg sodium salt, potassium salt.
  • Very particularly preferred in this context are those selected from the group consisting of 2-ethylhexyl sulfate sodium salt, lauryl ether sulfate sodium salt, sodium monoalkyl sulfates such as sodium tetradecyl sulfate, sodium dodecyl sulfate, sodium ethylhexyl sulfate, sodium decyl sulfate, sodium octyl sulfate, and mixtures thereof , used.
  • the content of the at least one wetting agent is between 0.1 and 15 ml/L, preferably between 0.2 and 10 ml/L, more preferably between 0.5 and 7 ml/L and even more preferably between 1 and 6 ml/L.
  • salts containing Se or Te can also be present in the electrolyte.
  • the selenium or tellurium compound used in the electrolyte can be chosen accordingly by a specialist. Suitable selenium and tellurium compounds are those in which selenium or tellurium is present in the +4 or +6 oxidation state in the form of an anion. Selenium and tellurium compounds in which selenium or tellurium is present in the +4 oxidation state are advantageously used in the electrolyte.
  • the selenium and tellurium compounds are particularly preferably selected from tellurites, selenites, parturic acid, selenious acid, telluric acid, selenic acid, selenocyanates, tellurocyanates and selenate, and also tellurate.
  • the use of selenium compounds is generally preferred over tellurium compounds.
  • the addition of selenium to the electrolyte in the form of a salt of selenious acid, for example in the form of potassium selenite, is very particularly preferred. Addition as potassium selenocyanate is extremely preferred.
  • the amount of these compounds in the electrolyte can be selected according to the expert will. It will be in the range of 0.1 mg - 500 mg/l, preferably 0.5 mg - 100 mg and very preferably between 0.5 mg - 10 mg/l based on selenium or tellurium.
  • the electrolyte also contains a certain amount of free cyanide.
  • This is preferably supplied to the electrolyte in the form of a water-soluble salt of hydrocyanic acid.
  • the alkali metal salts are advantageous, and potassium cyanide is very particularly preferably used.
  • the amount of free cyanide in the electrolyte can be adjusted according to values known to those skilled in the art. As a rule, the free cyanides are present in the electrolyte in a concentration of 20-200 g/l, preferably 80-180 g/l and very preferably 100-150 g/l (in each case based on the CN ion).
  • the cyanide salt used can also serve as a conducting salt.
  • Another essential component of the electrolyte is the silver to be deposited in dissolved form. According to the expert, this can be introduced into the electrolyte in the form of a water-soluble salt. Suitable as such are those from the group consisting of silver methanesulfonate, silver carbonate, silver phosphate, silver pyrophosphate, silver nitrate, silver oxide, silver lactate, silver fluoride, silver bromide, silver chloride, silver iodide, silver thiocyanate, silver thiosulfate, silver hydantoins, silver sulfate, silver cyanide and alkali metal silver cyanide. Potassium silver cyanide is particularly advantageous in this context.
  • the silver salts are used in an initial concentration in the electrolyte of between 2-200 g/l, preferably 10-100 g/l and very preferably 20-50 g/l (in each case based on the Ag metal).
  • ions can also be present dissolved in the electrolyte in low concentrations.
  • these are those that lead to a harder layer (so-called hard silver) compared to the deposition of a pure silver layer.
  • These ions are selected from the group consisting of Sb, Bi, In, Sn, W, Mo, Pb, As, Cu, Ni. These will generally be present in a concentration of 0.001-30 g/l, preferably 0.01-20 g/l and very preferably 0.1-10 g/l (in each case based on the corresponding metal).
  • the subject matter of the present invention is also a process for the galvanic deposition of silver layers on conductive substrates, in which an electrically conductive substrate is immersed in the electrolyte according to the invention and a current flow is established between an anode in contact with the electrolyte and the substrate as cathode.
  • the temperature that prevails during the deposition of the dispersion layer can be selected by the person skilled in the art at will, or the temperature adjusts itself due to external influences (frictional heat from dispersing modules). It will depend on a sufficient deposition rate and the applicable current density range on the one hand and on the other hand based on economic aspects or the stability of the electrolyte. It is advantageous to set a temperature of the electrolyte of 10°C to 70°C, preferably 15°C to 40°C and particularly preferably 20°C to 30°C.
  • the pH of the electrolyte can be adjusted as required by a person skilled in the art. However, he will be guided by the idea of introducing as few additional substances into the electrolyte as possible that could adversely affect the deposition of the corresponding layer. In a very particularly preferred embodiment, the pH is therefore adjusted solely by adding a base. All compounds that are suitable for a corresponding application can serve as such for the person skilled in the art. He preferably uses alkali metal hydroxides, oxides or carbonates.
  • the electrolyte according to the invention is preferably adjusted to a basic pH range of >8 during the electrolysis. Optimum results can be achieved at pH values in the electrolyte of 8-13, more preferably 9-11.
  • the pH can be adjusted as required by a person skilled in the art. However, he will be guided by the idea of introducing as few additional substances into the electrolyte as possible that could adversely affect the deposition of the corresponding layer. In a very particularly preferred embodiment, the pH is therefore adjusted solely by adding a base. All compounds that are suitable for a corresponding application can serve as such for the person skilled in the art. There may be fluctuations in the pH value of the electrolyte during electrolysis. In a preferred embodiment of the present method, the person skilled in the art therefore proceeds in such a way that he monitors the pH value during the electrolysis and, if necessary, adjusts it to the desired value. The expert knows how to proceed here.
  • the current density which is established between the cathode and the anode in the electrolyte according to the invention during the deposition process according to the invention can be selected by a person skilled in the art in accordance with the efficiency and quality of the deposition.
  • the current density in the electrolyte is set to 0.2 to 100 A/dm 2 depending on the application and the type of coating. If necessary, they can Current densities can be increased or reduced by adjusting the system parameters such as the structure of the coating cell, flow rates, anode and cathode conditions, etc.
  • a current density of 0.2-50 A/dm 2 , preferably 1-10 A/dm 2 and very particularly preferably 1-5 A/dm 2 is advantageous.
  • pulsed direct current or reverse pulse plating can also be used.
  • the current flow is interrupted for a certain period of time (pulse plating) or the current flow is reversed.
  • pulse plating in the form of current interruptions and reverse pulse plating for silver graphite dispersion deposition is described in the literature (Arnet, R. et al, silver dispersion layers with self-lubricating properties, Galvanotechnik 2021, vol. 1, p. 21 ff .).
  • the electrolyte according to the invention and the method according to the invention can be used for the galvanic deposition of silver layers, preferably for technical applications, for example electrical plug connections and printed circuit boards. Coating in continuous systems can also be used for technical applications.
  • Layer thicknesses in the range from 0.1 to 100 ⁇ m are typically deposited in rack operation, in particular for technical applications with current densities in the range from 0.5 to 50 A/dm 2 .
  • layers up to 200 ⁇ m or even 500 ⁇ m thick are sometimes deposited in continuous systems.
  • the current densities are in the range given above.
  • anodes can be used when using the electrolyte. Soluble or insoluble anodes are just as suitable as the combination of soluble and insoluble anodes. If a soluble anode is used, it is particularly preferred if a silver anode is used (DE1228887, Practical Galvanotechnik, 5th edition, Eugen G. Leuze Verlag, p. 342f, 1997).
  • the insoluble anodes used are preferably those made from a material selected from the group consisting of platinized titanium, graphite, stainless steel, mixed metal oxides, glassy carbon anodes and special carbon material (“diamond-like carbon” DLC) or combinations of these anodes.
  • Insoluble anodes made of platinized titanium or titanium coated with mixed metal oxides are advantageous, the mixed metal oxides preferably being selected from iridium oxide, ruthenium oxide, tantalum oxide and mixtures thereof.
  • Iridium transition metal oxide Mixed oxide anodes particularly preferably mixed oxide anodes of iridium-ruthenium mixed oxide, iridium-ruthenium-titanium mixed oxide or iridium-tantalum mixed oxide, are used for the implementation of the invention. More can be found at Cobley, AJ et al. (The use of insoluble anodes in Acid Sulphate Copper Electrodeposition Solutions, Trans IMF, 2001, 79(3), p. 113 and 114).
  • Suitable electrically conductive substrates are those which can be coated with the electrolyte according to the invention in the basic pH range. These are preferably substrates containing precious metals or less precious substrates, such as nickel or copper surfaces. According to the invention, the silver layer is preferably deposited on a nickel or nickel alloy layer or on a copper or copper alloy layer.
  • Suitable substrate materials that are used to advantage here are copper-based materials such as pure copper, brass, bronze (e.g. CuSn, CuSnZn) or special copper alloys for connectors such as alloys with silicon, beryllium, tellurium, phosphorus or iron-based materials such as iron or Stainless steel or nickel or a nickel alloy such as NiP, NiW, NiB, gold or silver.
  • the substrate materials can also be multi-layer systems that have been coated galvanically or with another coating technique. This also applies, for example, to iron materials that have been nickel- or copper-plated and then optionally gold-plated, pre-palladium-plated, pre-platinized or coated with pre-silver.
  • the intermediate layers for nickel plating or copper plating can also be made of appropriate alloy electrolytes - e.g. NiP, NiW, NiMo, NiCo, NiB, Cu, CuSn, CuSnZn, CuZn, etc.
  • Another substrate material can be a wax core that is pre-coated with conductive silver lacquer (electroforming).
  • electrolyte is understood to mean the aqueous solution which is placed in a corresponding vessel and used for the electrolysis with an anode and a cathode under current flow. The only exception here is the solid component used.
  • the electrolyte according to the invention is aqueous. Except for the added solid components and possibly insoluble heterogeneous defoamers, the compounds used in the electrolyte are soluble in the electrolyte.
  • the terms "soluble” refers to those compounds that dissolve in the electrolyte at the working temperature.
  • the working temperature is the temperature at which the electrolytic deposition takes place.
  • a substance is considered soluble if at least 1 mg/l of this substance dissolves in the electrolyte at the working temperature.
  • the electrolyte according to the invention is stable over the long term. Coatings suitable for the application described are obtained by combining the brightening additives described for the deposition of silver and the use of a defoamer. These have sufficiently low contact resistances and also retain an astonishingly high level of surface integrity and therefore low contact resistances even after many plugging and rubbing processes in contact circuits. This was not to be expected from the available state of the art.
  • Electrolyte composition aqueous A
  • Electrolyte composition aqueous B aqueous B
  • Anodes soluble fine silver anodes

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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)
  • Electroplating And Plating Baths Therefor (AREA)

Abstract

La présente invention concerne un électrolyte à base d'argent et un procédé correspondant pour le dépôt galvanique d'argent sur des substrats conducteurs. L'électrolyte en argent est caractérisé par des additifs déterminés qui contribuent à empêcher un moussage de l'électrolyte sans influer négativement sur le dépôt électrolytique.
EP22755083.7A 2021-07-21 2022-07-20 Électrolyte à base d'argent pour le dépôt de couches de dispersion d'argent Active EP4146848B8 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102021118820.2A DE102021118820A1 (de) 2021-07-21 2021-07-21 Silber-Elektrolyt
PCT/EP2022/070294 WO2023001868A1 (fr) 2021-07-21 2022-07-20 Électrolyte à base d'argent pour le dépôt de couches de dispersion d'argent

Publications (3)

Publication Number Publication Date
EP4146848A1 true EP4146848A1 (fr) 2023-03-15
EP4146848B1 EP4146848B1 (fr) 2024-04-10
EP4146848B8 EP4146848B8 (fr) 2024-07-24

Family

ID=82939917

Family Applications (1)

Application Number Title Priority Date Filing Date
EP22755083.7A Active EP4146848B8 (fr) 2021-07-21 2022-07-20 Électrolyte à base d'argent pour le dépôt de couches de dispersion d'argent

Country Status (7)

Country Link
EP (1) EP4146848B8 (fr)
JP (1) JP2024526925A (fr)
KR (1) KR20240031423A (fr)
CN (1) CN117677733A (fr)
DE (1) DE102021118820A1 (fr)
PL (1) PL4146848T3 (fr)
WO (1) WO2023001868A1 (fr)

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1228887B (de) 1961-10-26 1966-11-17 Riedel & Co Verfahren zum galvanischen Abscheiden von Silber-Antimon- oder Silber-Wismut-Legierungen hoher Haerte
DE2543082C3 (de) 1975-09-26 1979-06-28 Siemens Ag, 1000 Berlin Und 8000 Muenchen Cyanidischer Silberelektrolyt und Verfahren zur galvanischen Abscheidung von Silber-Graphit-Dispersionsüberzügen und seine Anwendung
DE4010346A1 (de) 1990-03-28 1991-10-02 Siemens Ag Verfahren zum aufbringen von silber-graphit-dispersionsueberzuegen
KR101074744B1 (ko) * 2002-11-28 2011-10-19 신꼬오덴기 고교 가부시키가이샤 전해 은도금액
DE10346206A1 (de) 2003-10-06 2005-04-28 Bosch Gmbh Robert Kontaktoberflächen für elektrische Kontakte
DE102008030988B4 (de) 2008-06-27 2010-04-01 Siemens Aktiengesellschaft Bauteil mit einer Schicht, in die CNT (Carbon Nanotubes) eingebaut sind und Verfahren zu dessen Herstellung
DE102015102453A1 (de) 2015-02-20 2016-08-25 Heraeus Deutschland GmbH & Co. KG Bandförmiges Substrat zur Herstellung von Chipkartenmodulen, Chipkartenmodul, elektronische Einrichtung mit einem derartigen Chipkartenmodul und Verfahren zur Herstellung eines Substrates
CN105297095A (zh) 2015-12-14 2016-02-03 南昌航空大学 一种纯银层/银石墨复合层的功能性镀层及制备方法
DE102018005352A1 (de) 2018-07-05 2020-01-09 Dr.-Ing. Max Schlötter GmbH & Co KG Silberelektrolyt zur Abscheidung von Dispersions-Silberschichten und Kontaktoberflächen mit Dispersions-Silberschichten

Also Published As

Publication number Publication date
DE102021118820A1 (de) 2023-01-26
KR20240031423A (ko) 2024-03-07
EP4146848B8 (fr) 2024-07-24
JP2024526925A (ja) 2024-07-19
CN117677733A (zh) 2024-03-08
EP4146848B1 (fr) 2024-04-10
PL4146848T3 (pl) 2024-07-01
WO2023001868A1 (fr) 2023-01-26

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