US3576724A - Electrodeposition of rutenium - Google Patents
Electrodeposition of rutenium Download PDFInfo
- Publication number
- US3576724A US3576724A US757762A US3576724DA US3576724A US 3576724 A US3576724 A US 3576724A US 757762 A US757762 A US 757762A US 3576724D A US3576724D A US 3576724DA US 3576724 A US3576724 A US 3576724A
- Authority
- US
- United States
- Prior art keywords
- ruthenium
- bath
- complex
- ammonium
- solution
- 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
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/082—Compounds containing nitrogen and non-metals and optionally metals
- C01B21/083—Compounds containing nitrogen and non-metals and optionally metals containing one or more halogen atoms
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G55/00—Compounds of ruthenium, rhodium, palladium, osmium, iridium, or platinum
- C01G55/002—Compounds containing, besides ruthenium, rhodium, palladium, osmium, iridium, or platinum, two or more other elements, with the exception of oxygen or hydrogen
-
- 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
- C25D3/50—Electroplating: Baths therefor from solutions of platinum group metals
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/74—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by peak-intensities or a ratio thereof only
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/82—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by IR- or Raman-data
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/42—Magnetic properties
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
- C01P2006/82—Compositional purity water content
Definitions
- Ruthenium complex compounds are produced in which the anion has the general formula [Ru N(H O) Y wherein Y is a chloro or bromo group, at equals 2, 3 or 4, x+y equals 10 and z equals 5 x, and the cation is most advantageously monovalent, for example, ammonium, lithium, sodium or potassium.
- a plating bath is prepared using the ruthenium complex compounds in aqueous acidic solution and the plating bath is employed in the electrodeposition of ruthenium.
- the present invention relates to novel ruthenium compounds, to methods for the preparation thereof, and particularly to the use of such compounds in the electrodeposition of ruthenium.
- Ruthenium has attractive properties as an electrical contact material (a low contact resistance at temperatures up to 600 C. 1100 F.) and resistance to welding at these temperatures). In the electrodeposited condition ruthenium has a high hardness of from 900 DPN to 1300 DPN. Such electrodeposits of ruthenium are valuable as coatings for electrical contacts, for example, those in reed switches, and for other surfaces requiring good resistance to wear.
- ruthenium is electrodeposited cathodically from a fused electrolyte.
- the electrolyte consists of a fused mixture of sodium and potassium cyanides that has been charged with ruthenium by alternating current electrolysis be tween ruthenium electrodes.
- This process gives satisfactory coherent coatings of up to 0.005 inch thick but has the disadvantage that a temperature of about 500 C. must be used to maintain the bath in a molten condition.
- Ruthenium has also been electrodeposited commercially in processes employing a ruthenium nitrosyl sulfamate electrolyte. This electrolyte has produced deposits having satisfactory characteristics, but it operates at a relatively low cathode efficiency, and it is difiicult to prepare reproducibly on a large scale, that is, in baths containing more than 200 grams of ruthenium. Too, this process (and others) is subject to sludge deposition during use. In any event, as far as we are aware, etforts to improve the cathode efiiciency and the batch size of plating baths using the ruthenium nitrosyl sulfama-te electrolyte have not been entirely successful.
- ruthenium complex compound can be made which, in aqueous acidic solution, provides an electroplating bath which can be produced in batches which contain relatively large amounts of ruthenium and from which ruthenium may be electrodeposited with a relatively high cathode efiiciency.
- Still another object of this invention is the preparation of novel ruthenium complex compounds which are soluble in water.
- ruthenium is electrodeposited from an aqueous acidic solution of a soluble ruthenium complex compound.
- the plating solutions are prepared using novel ruthenium coordination compounds in which ruthenium is present in an anionic complex of the following general formula:
- the coordination number of ruthenium is 6.
- the nitrogen atom satisfies one position for each ruthenium atom and the remaining 10 positions are filled by laquo groups and chloro or bromo groups.
- x+y is 10.
- the ruthenium atoms are tetravalent and therefore the total positive charge due to ruthenium is 8.
- the compounds in accordance with the invention advantageously contain anions having the formula: [Ru N(H O) Y
- the compounds are, most advantageously, salts of monovalent cations, in particular ammonium, lithium, sodium or potassium salts.
- suitable compounds are ammonium salts of the general formula [Ru N(H O) Y (NH).
- the ammonium salt of the bis-aquo-chloro complex is prepared by heating an aqueous solution of ruthenium chloride with excess sulphamic acid for long enough to hydrolyze the sulphamate.
- the ammonium salt of the complex is then obtained from the reaction mixture.
- To obtain the solid compound it is usually necessary first to saturate the solution by evaporation followed by cooling, preferably to about 0 C., e.g. with ice or ice-cold water.
- the compound may then be separated by filtration and should be washed with ice-cold water to free it from highly water-soluble impurities, such as sulphuric acid and ammonium sulphate and chloride.
- Ruthenium chloride is often supplied commercially in hydrochloric acid solution. Care should be taken to avoid excessive amounts of hydrochloric acid in the initial reaction mixture since this can lead to the formation of compounds other than the desired complex. We find it advantageous when using commercial solutions of ruthenium chloride in hydrochloric acid first to evaporate the solution to obtain a concentration of g. of ruthenium in 300 ml. of acid solution.
- hydrochloric acid helps to prevent bisulphate groups, for example, from entering the complex as ligands in place of the chloro groups.
- Such liganding of bisulphate groups may occur in the absence of suflicient chloride ion since high concentrations of ammonium bisulphate and sulphuric acid may form in the reaction mixture.
- at least 3 ml. of concentrated hydrochloric acid should be added for each gram of ruthenium. The addition is best made 3 after concentrating the reaction mixture and allowing it to cool since otherwise upleasant fuming may occur.
- ammonium salts are much preferred for use in plating baths, particularly because of their case of preparation, other salts such as the lithium, sodium or potassium salts mentioned above herein, may have other specific advantages, e.g., have greater solubility, thus enabling a higher ruthenium concentration to be employed in the bath.
- both the ammonium and other salts of a particular complex may be used as the starting material for the preparation of another complex containing different ligands. Such a preparation has been described in Example IV. Such substitution of ligands is well known in coordination chemistry.
- ruthenium can be satisfactorily electrodeposited from acidic aqueous solutions of our novel ruthenium compounds in which ruthenium is present in the aforedescribed anionic complex of general formula [Ru N(H O) Y Baths for the electrodeposition of ruthenium can be obtained by dissolving the ruthenium complex in water and adding an appropriate acid to adjust the pH to 4 or less.
- the acid used to effect the adjustment of pH obviously should not cause the breakdown of the complex.
- the complex used is of the formula: [Rll2N(H2O)2Cl8] (NH the addition of hydrochloric acid or sulphuric acid is suitable.
- the complex is of the formula [Ru N(H O) Br (NH the addition of hydrobromic 'acid is then suitable.
- the pH of the bath solution is too low, the deposition of ruthenium takes place at a low cathode current efficiency, while if the pH is too high the resulting ruthenium deposit is black. Increasing the pH still further leads to the formation of a brownish deposit on the cathode that is not metallic ruthenium.
- the pH should be from 0.5 to 4 and beneficially it is from 1.5 to 2.5.
- ammonium salts e.g., ammonium chloride or ammonium bromide, may be added to increase the conductivity.
- the plating bath conveniently contains from 5 to 20 grams per liter (g./l. hereinafter) of ruthenium. With lower ruthenium concentrations frequent replenishment of the bath is required. Although higher concentrations of ruthenium up to the limit of solubility of the compounds may be used, there is no practical advantage in doing so. Moreover, losses of ruthenium from the bath by drag-out are increased, and the capital cost of the bath becomes unnecessarily high. Agitation of the bath is desirable at ruthenium contents exceeding 20 g./l.
- Suitable insoluble anodes for use in plating from the baths are of platinum and platinized titanium.
- the temperature of the bath is advantageously from 50 C. to 70 C. or 75 C., since plating takes place more slowly at lower temperatures, while higher temperatures lead to excessive losses by evaporation. Moreover, at temperatures below 50 C. the baths can only be operated within a limited range of current densities, since the cathode etficiency is found to fall off rapidly as the current density is increased above 1 ampere per square decimeter (A./dm. Thus, if only a slow rate of deposition is required the baths may be used at temperatures down to room temperature, but the current density should not exceed 1.5 A./dm. at room temperature if satisfactory deposits are to be obtained. At 50 C.
- plating may be performed with current densities in the range of 0.5 to 4 A./dm. and at 70 C. in the range of 0.5 to 10 A./dm. provided that at current densities above 4 A./dm. the pH of the solution is in the range 0.5 to 1.
- current densities lower than 0.25 A./dm. the rate of deposition is very low, while higher current densities than the maxima indicated lead to loss of efficiency and ultimately to burning of the deposit.
- the cathode efficiency of a bath containing 10 g./l. of ruthenium is generally at least 75%, calculated for tetravalent ruthenium.
- the baths are readily replenished by the addition of the solid ruthenium complex compound.
- the pH tends to decrease during operation of the bath, but it is readily adjusted by the addition of dilute ammonium hydroxide solution.
- the solid compounds may be recovered by evaporating the solution to low volume and cooling. The solid is then washed free from unwanted salts, e.g., ammonium salts, with ice-cold water, and redissolved for further use.
- EXAMPLE VI Baths were prepared by dissolving the aquo-chloro complex [Ru N(H Cl ](N'H (taken from Sample A) in water to give ruthenium concentrations of g./l. and g./l. To each bath 5 g./l. of ammonium chloride was added to increase the conductivity and the pH was adjusted to pH 2.5 by the addition of hydrochloric acid. The baths were then used at 50 C. to deposit ruthenium on copper cathodes that had been given a flash coating of gold, using platinum anodes. The current density was varied, and the cathode efficiency and plating rate observed under each set of conditions are shown in Table I.
- a bath was prepared by dissolving sutficient of the aquo-bromo complex of formula in water to give a ruthenium concentration of 10 g./l. Dilute hydrobromic acid was added to adjust the pH to 2.5. The bath was then used at 70 C. to deposit ruthenium on gold-flashed copper cathodes, using platinum anodes. At a current density of 1.0 A./dm. a deposit of ruthenium 2.5 microns thick was obtained in 20 minutes.
- the cathode current efliciency was close to During electrodeposition, 'With some combinations of bath composition and operating conditions it is found that evolution of undesirable products may occur at the anode. In particular, this tendency is favored by high concentrations of ammonium chloride or bromide accumulated in the bath, a low pH, and a high anode current density.
- the product evolved if any, depends on the bath composition. For instance, from baths prepared from compounds containing [R-u N(H O) Cl anion, nitrogen trichloride and intermediate products, possibly mixed with other compounds, are evolved. The amounts of nitrogen trichloride and other compounds liberated are small and under the conditions of operation of the baths, particularly at the higher temperatures, tend readily to decompose.
- This evolution of undesirable products at the anode may be suppressed or even wholly eliminated by adding sulphamic acid or a soluble sulphamate to the bath.
- the evolution at the anode can be suppressed by the addition of other mild reducing agents compatible with the bath, e.g., ethanol.
- other mild reducing agents compatible with the bath e.g., ethanol.
- great care must be taken in the choice of such reducing agents since they may themselves affect the bath or be oxidized to undesirable compounds.
- urea could possibly enter the anionic complex and co-ordinate with the ruthenium, replacing some other ligands
- ethanol may be oxidized, first to acetaldehyde and then to acetic acid and it may be desired to avoid such oxidation products.
- sulphamic acid or a soluble sulphamate we prefer to add sulphamic acid or a soluble sulphamate.
- ammonium sulphamate since the addition of sulphamic acid lowers the pH, which must then be restored by the addition of ammonium hydroxide, so that the net effect is the same. Sulphamates of cations that might adversely affect the plating, must, of course, be avoided.
- a further advantage of adding sulphamate is that it increases the conductivity of the bath.
- the proportions are from 1 to 2 parts by weight of ammonium sulphamate for each part of ruthenium in the ruthenium compound added.
- Baths to which sulphamate is added may be operated Without the evolution of undesirable anode products under a wider range of conditions than sulphamate-free baths.
- they may be used at a higher acidity than pH 1, e.g. down to pH 0.5 or lower, though this may not be desirable since it may lead to corrosion of the surface being plated.
- the rate of hydrolysis of the sulphamate is increased and more frequent additions of sulphamate are required.
- the bath compositions and operating conditions for sulphamate-free baths are also satisfactory when the baths contain sulphamate.
- An advantageous bath composition contains initially 12 g./l. of ruthenium added as the aquo-chloro complex,
- ammonium sulphamate has a pH of 1.5 to 2.0 and is operated at 70 C.
- EXAMPLE IX By way of example, a bath containing 5 g./1. of ruthenium was prepared by dissolving some of the aquochloro complex (Sample A) in distilled water that had been acidified to pH 2.5 to 3 by means of hydrochloric acid. The temperature was raised to 70 C. and the pH adjusted to 1.5 to 2 by means of a further addition of hydrochloric acid. Ruthenium was deposited from this bath at 70 C. on to a copper cathode that had been given a flash coating of gold, using a platinized titanium anode, a cathode current density of 1.0 A. dm. and an anode current density of 0.2 A./dm.
- the bath was periodically replenished with ruthenium when its ruthenium content had fallen to 4 g./l., by the addition of the solid aquo-chloro complex, and the pH was maintained at 1.5 to 2 by means of dilute aqueous ammonium hydroxide.
- ruthenium had been deposited, evolution of nitrogen trichloride at the anode became noticeable.
- An addition of 10 g./l. of ammonium sulphamate was then made to the bath, which immediately suppressed the nitrogen trichloride evolution. No further evolution was observed when plating was continued until a total of 7 g./l. of ruthenium had been deposited, when the run was discontinued. During this further plating, one gram of ammonium sulphamate was added to the bath for each gram of ruthenium added during its periodical replenishment.
- the deposits obtained from the baths of the invention are bright up to a thickness of about 2-3 microns. As plating proceeds to greater thicknesses, surface cracking becomes apparent, and at still greater thicknesses the deposits a-re matt and grey. If desired, small amounts of 'conventional organic stress-relieving agents that are compatible with the bath may be added.
- the high cathode efiiciency of the baths results in substantial freedom from gassing at the cathode, and the deposits are therefore almost free from streaking and pitting.
- L represents the aquo, chloro or bromo ligands.
- a bath for the electrodeposition of ruthenium comprising an acidic aqueous solution of a complex ruthenium compound having a cation selected from the group consisting of ammonia, hydrogen, lithium, sodium and potassium, the ruthenium being present in the form of an anionic complex of the formula [Ru N(H O) Y wherein Y is a member selected from the chloro and bromo groups, said solution having a pH of about 0.5 to 4 and containing from 5 to 20 grams per liter of ruthenium.
- a process for electrodepositing ruthenium to provide a hard and Wear resistant surface which comprises cathodically depositing ruthenium from the aqueous acidic bath of claim 1 while maintaining the bath at a temperature in the range from C. to C. and the current density in the range from 0.25 to 10 amperes per square decimeter.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Electroplating And Plating Baths Therefor (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB4747767 | 1967-10-18 | ||
GB20908/68A GB1244309A (en) | 1967-10-18 | 1967-10-18 | Electrodeposition of ruthenium |
GB5642867 | 1967-12-12 |
Publications (1)
Publication Number | Publication Date |
---|---|
US3576724A true US3576724A (en) | 1971-04-27 |
Family
ID=27257929
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US757762A Expired - Lifetime US3576724A (en) | 1967-10-18 | 1968-09-05 | Electrodeposition of rutenium |
Country Status (9)
Country | Link |
---|---|
US (1) | US3576724A (fr) |
JP (1) | JPS4927960B1 (fr) |
BE (1) | BE722559A (fr) |
CH (2) | CH505208A (fr) |
DE (1) | DE1803524A1 (fr) |
FR (1) | FR1602538A (fr) |
GB (1) | GB1244309A (fr) |
NL (1) | NL6814650A (fr) |
SE (1) | SE354877B (fr) |
Cited By (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3793162A (en) * | 1971-12-17 | 1974-02-19 | Int Nickel Co | Electrodeposition of ruthenium |
US4082624A (en) * | 1976-12-03 | 1978-04-04 | Bell Telephone Laboratories, Incorporated | Articles electrodeposited with ruthenium and processes of producing such articles |
US4082625A (en) * | 1976-06-08 | 1978-04-04 | The International Nickel Company, Inc. | Electrodeposition of ruthenium |
US4297178A (en) * | 1979-04-10 | 1981-10-27 | The International Nickel Company, Inc. | Ruthenium electroplating and baths and compositions therefor |
US5693427A (en) * | 1995-12-22 | 1997-12-02 | Baldwin Hardware Corporation | Article with protective coating thereon |
US5783313A (en) * | 1995-12-22 | 1998-07-21 | Baldwin Hardware Corporation | Coated Article |
DE19741990C1 (de) * | 1997-09-24 | 1999-04-29 | Degussa | Elektrolyt zur galvanischen Abscheidung von spannungsarmen, rißfesten Rutheniumschichten, Verfahren zur Herstellung und Verwendung |
EP1975282A1 (fr) * | 2007-03-28 | 2008-10-01 | Umicore Galvanotechnik GmbH | Electrolyte et procédé de séparation de couches décoratives et techniques en ruthénium noir |
WO2012171856A2 (fr) | 2011-06-17 | 2012-12-20 | Umicore Galvanotechnik Gmbh | Électrolyte et son utilisation pour le dépôt de revêtements de ruthénium noir et revêtements obtenus en utilisant ledit électrolyte |
RU2538492C1 (ru) * | 2013-08-06 | 2015-01-10 | Александр Владимирович Ермаков | Способ изготовления катодной обкладки танталового объемно-пористого конденсатора |
CN107021464A (zh) * | 2017-06-07 | 2017-08-08 | 王晓波 | 一种[μ‑氮‑双(四氯一水合钌)]酸钾的合成方法以及电子元器件表面镀钌的方法 |
CN113106507A (zh) * | 2021-04-15 | 2021-07-13 | 电子科技大学 | 一种用于微纳沟槽和盲孔填充的电镀钌镀液及配制方法 |
EP3964610A1 (fr) | 2020-09-08 | 2022-03-09 | IWG Ing. W. Garhöfer Gesellschaft m. b. H. | Bain d'électrodéposition pour revêtements palladium-ruthénium |
CN116874042A (zh) * | 2023-08-28 | 2023-10-13 | 中铁建发展集团有限公司 | 钌/污泥基生物炭/泡沫镍阴极材料制备方法及其产品与应用 |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5775191A (en) * | 1980-10-18 | 1982-05-11 | Kurita Water Ind Ltd | Air diffuser |
-
1967
- 1967-10-18 GB GB20908/68A patent/GB1244309A/en not_active Expired
-
1968
- 1968-09-05 US US757762A patent/US3576724A/en not_active Expired - Lifetime
- 1968-10-04 CH CH1464270A patent/CH505208A/fr not_active IP Right Cessation
- 1968-10-04 CH CH1484868A patent/CH498775A/fr not_active IP Right Cessation
- 1968-10-14 NL NL6814650A patent/NL6814650A/xx unknown
- 1968-10-17 DE DE19681803524 patent/DE1803524A1/de active Pending
- 1968-10-17 FR FR1602538D patent/FR1602538A/fr not_active Expired
- 1968-10-18 BE BE722559D patent/BE722559A/xx unknown
- 1968-10-18 SE SE14088/68A patent/SE354877B/xx unknown
-
1971
- 1971-09-02 JP JP46067799A patent/JPS4927960B1/ja active Pending
Cited By (20)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3793162A (en) * | 1971-12-17 | 1974-02-19 | Int Nickel Co | Electrodeposition of ruthenium |
US4082625A (en) * | 1976-06-08 | 1978-04-04 | The International Nickel Company, Inc. | Electrodeposition of ruthenium |
US4082624A (en) * | 1976-12-03 | 1978-04-04 | Bell Telephone Laboratories, Incorporated | Articles electrodeposited with ruthenium and processes of producing such articles |
US4297178A (en) * | 1979-04-10 | 1981-10-27 | The International Nickel Company, Inc. | Ruthenium electroplating and baths and compositions therefor |
US5693427A (en) * | 1995-12-22 | 1997-12-02 | Baldwin Hardware Corporation | Article with protective coating thereon |
US5783313A (en) * | 1995-12-22 | 1998-07-21 | Baldwin Hardware Corporation | Coated Article |
DE19741990C1 (de) * | 1997-09-24 | 1999-04-29 | Degussa | Elektrolyt zur galvanischen Abscheidung von spannungsarmen, rißfesten Rutheniumschichten, Verfahren zur Herstellung und Verwendung |
US6117301A (en) * | 1997-09-24 | 2000-09-12 | Degussa-Huls Aktiengesellschaft | Electrolyte for the galvanic deposition of low-stress, crack-resistant ruthenium layers |
EP1975282A1 (fr) * | 2007-03-28 | 2008-10-01 | Umicore Galvanotechnik GmbH | Electrolyte et procédé de séparation de couches décoratives et techniques en ruthénium noir |
WO2008116545A1 (fr) * | 2007-03-28 | 2008-10-02 | Umicore Galvanotechnik Gmbh | Électrolyte et procédé de dépôt de couches décoratives et techniques de ruthénium noir |
WO2012171856A2 (fr) | 2011-06-17 | 2012-12-20 | Umicore Galvanotechnik Gmbh | Électrolyte et son utilisation pour le dépôt de revêtements de ruthénium noir et revêtements obtenus en utilisant ledit électrolyte |
DE102011105207A1 (de) | 2011-06-17 | 2012-12-20 | Umicore Galvanotechnik Gmbh | Elektrolyt und seine Verwendung zur Abscheidung von Schwarz-Ruthenium-Überzügen und so erhaltene Überzüge |
DE102011105207B4 (de) * | 2011-06-17 | 2015-09-10 | Umicore Galvanotechnik Gmbh | Elektrolyt und seine Verwendung zur Abscheidung von Schwarz-Ruthenium-Überzügen und so erhaltene Überzüge und Artikel |
RU2538492C1 (ru) * | 2013-08-06 | 2015-01-10 | Александр Владимирович Ермаков | Способ изготовления катодной обкладки танталового объемно-пористого конденсатора |
CN107021464A (zh) * | 2017-06-07 | 2017-08-08 | 王晓波 | 一种[μ‑氮‑双(四氯一水合钌)]酸钾的合成方法以及电子元器件表面镀钌的方法 |
CN107021464B (zh) * | 2017-06-07 | 2019-10-15 | 王晓波 | 一种[μ-氮-双(四氯一水合钌)]酸钾的合成方法以及电子元器件表面镀钌的方法 |
EP3964610A1 (fr) | 2020-09-08 | 2022-03-09 | IWG Ing. W. Garhöfer Gesellschaft m. b. H. | Bain d'électrodéposition pour revêtements palladium-ruthénium |
CN113106507A (zh) * | 2021-04-15 | 2021-07-13 | 电子科技大学 | 一种用于微纳沟槽和盲孔填充的电镀钌镀液及配制方法 |
CN116874042A (zh) * | 2023-08-28 | 2023-10-13 | 中铁建发展集团有限公司 | 钌/污泥基生物炭/泡沫镍阴极材料制备方法及其产品与应用 |
CN116874042B (zh) * | 2023-08-28 | 2024-05-07 | 中铁建发展集团有限公司 | 钌/污泥基生物炭/泡沫镍阴极材料制备方法及其产品与应用 |
Also Published As
Publication number | Publication date |
---|---|
NL6814650A (fr) | 1969-04-22 |
JPS4927960B1 (fr) | 1974-07-22 |
BE722559A (fr) | 1969-04-18 |
FR1602538A (fr) | 1970-12-21 |
SE354877B (fr) | 1973-03-26 |
CH505208A (fr) | 1971-03-31 |
DE1803524A1 (de) | 1969-05-22 |
GB1244309A (en) | 1971-08-25 |
CH498775A (fr) | 1970-11-15 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US3480523A (en) | Deposition of platinum-group metals | |
US3576724A (en) | Electrodeposition of rutenium | |
US2525942A (en) | Electrodepositing bath and process | |
US3161575A (en) | Copper pyrophosphate electroplating solutions | |
US2693444A (en) | Electrodeposition of chromium and alloys thereof | |
US2250556A (en) | Electrodeposition of copper and bath therefor | |
TWI507571B (zh) | 藉由電鑄法但不使用有毒金屬或類金屬而獲致黃金合金沉積的方法 | |
US2160321A (en) | Electrodeposition of tungsten alloys | |
US3864227A (en) | Method for the electrolytic refining of copper | |
US3616332A (en) | Process for recovering silver from scrap materials and electrolyte composition for use therein | |
US1465034A (en) | Process for the electrolytic deposition of copper | |
US2075623A (en) | Zinc plating | |
US4297178A (en) | Ruthenium electroplating and baths and compositions therefor | |
US3793162A (en) | Electrodeposition of ruthenium | |
Reid et al. | Electrodeposition of ruthenium | |
US3855089A (en) | Process for the electrolytic refining of heavy metals | |
US2984603A (en) | Platinum plating composition and process | |
US4082625A (en) | Electrodeposition of ruthenium | |
US2577365A (en) | Rhodium plating | |
US3772167A (en) | Electrodeposition of metals | |
US4297179A (en) | Palladium electroplating bath and process | |
US4377450A (en) | Palladium electroplating procedure | |
US2489523A (en) | Electrodeposition of tin or lead-tin alloys | |
US1991995A (en) | Platinum metal ammino cyanide plating bath and process for electrodeposition of platinum metal therefrom | |
US3347757A (en) | Electrolytes for the electrodeposition of platinum |