US3371020A - Process for the electrodeposition of metals - Google Patents

Process for the electrodeposition of metals Download PDF

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US3371020A
US3371020A US418118A US41811864A US3371020A US 3371020 A US3371020 A US 3371020A US 418118 A US418118 A US 418118A US 41811864 A US41811864 A US 41811864A US 3371020 A US3371020 A US 3371020A
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melt
metal
temperature
deposited
metals
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John E Perry
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Union Carbide Corp
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Union Carbide Corp
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Priority to US418118A priority Critical patent/US3371020A/en
Priority to DE19651483347 priority patent/DE1483347A1/de
Priority to GB51108/65A priority patent/GB1134217A/en
Priority to BE673322D priority patent/BE673322A/xx
Priority to FR41048A priority patent/FR1460990A/fr
Priority to CH1721065A priority patent/CH450858A/fr
Priority to AT1124165A priority patent/AT271033B/de
Priority to NL6516263A priority patent/NL6516263A/xx
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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
    • C25D3/66—Electroplating: Baths therefor from melts

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  • this invention relates to an improved process capable of yielding dense, fine grain, structurally coherent plates of refractory metals, alloys and compounds of metals of the group: zirconium, hafnium, vanadium, columbium, tantalum, chromium, molybdenum and tungsten.
  • this invention relates to an improved process useful in the electroplating and electroforming of refractory metals, alloys and the like wherein undesirable roughness and irregularities in the surface of the plated deposit are largely eliminated.
  • This process comprises electrolyzing an electrolytic system comprising an electrically conductive base material as a cathode, an anode, and an electrolytic melt having no appreciable concentration of chlorides, bromides, and oxides and consisting essentially of a base melt of at least one fluoride selected from the group consisting of the fluorides of potassium, rubidium, and cesium and at least one fluoride of other elements higher in the 3,371,020 Patented Feb.
  • an object of this invention to provide a novel process wherein the aforementioned disadvantages are largely eliminated. It is an object of this invention to provide a novel, improved process for the electrodeposition of metals. A further object of this invention is to provide an improved process for the electrodeposition of metals from an electrolytic system onto a cathode base material wherein roughness and irregularities in the plated deposit are largely eliminated. Another object is to provide an improved process for the electrodeposition of refractory metals, alloys and compounds thereof at temperatures as high as 600 C. and higher.
  • the present invention relates to an improved process for the electrodeposition of metals, particularly refractory metals and alloys and compounds one or more of the following objects will the practice of the instant invention. It
  • the improvement comprises heating the zone above and around the gas-electrolyte interface to a temperature at least up to about the liquidus temperature of the electrolyte whereby any circulation due to thermal currents generated by temperature differences within the bath is minimized.
  • FIGURE 1 depicts a cell for fused salt electrodeposition surrounded by thermal insulation and equipped with electrolyte resistance heaters 11 and heat shields 12. The zone above and around the gaselectrolyte interface is heated by gas zone resistance heaters 13 in accordance with the teachings of this invention.
  • FIGURE 2 depicts temperature profiles taken on a typical cell which was provided with means for applying heat to the upper walls of the cell sufficient to equalize or at least compensate for heat loss from the melt surface. This was accomplished by the use of additional heaters and heat shields around the gas zone of the cell. Profile a represents the temperatures obtained when the gas zone was not heated and is typical of the temperature variations experienced in fused salt electrodeposition cells. Profile b represents the temperatures experienced in a fused salt electrodeposition cell when the gas zone was heated in accordance with improved process of the present invention to provide a substantially constant temperature throughout the melt Zone.
  • any heat loss is predominantly from the top surface of the melt.
  • the heat loss from the surface of a fused salt bath is 100 or more times the heat loss from the insulated sides.
  • the rate of heat loss at an electrolysis temperature of 775 to 800 C. has been found to be 8.0 kilowatts per square foot of bath surface.
  • temperature measurements as a function of depth of electrolyte have shown no variation in temperature except in the top six inches of the bath.
  • the objectives of this invention are achieved when the zone surrounding the gas-melt interface is heated to a temperature sufiicient to substantially reduce or eliminate circulation within the melt due to thermal currents generated by temperature differences.
  • the zone is heated to at least about the liquidus temperature of the electrolytic melt.
  • the liquidus temperature of the melt can be defined as that temperature at which the first solid material forms as the melt is slowly cooled.
  • the liquidus temperature will, of course, be dependent upon the particular composition of the electrolytic melt and hence, will vary for different metals, alloys, or compounds thereof.
  • the zone above and around the gas-melt interface is heated to a temperature such that the difference between the lower and upper portions of the electrolytic melt is less than about 10 C., and more preferably less than about 2 C.
  • the zone is heated to a temperature at which the gas zone and electrolytic melt are substantially in thermal equilibrium.
  • the method by which the heating of the zone surrounding the gas-melt interface is effected is not necessarily critical and a variety of means can be employed.
  • electrical resistance heaters can be arranged around the periphery of the gas zone and gas-melt interface if desired.
  • Heat shields are also usually employed at the top of the gas zone to further reduce heat loss and maintain substantially a thermal equilibrium at the gas-melt interface.
  • the improved process of this invention is applicable to any electrodeposition procedure wherein the temperature differences within the bath are of sufficient magnitude to cause thermal pumping, i.e., circulation of the electrolyte.
  • the process is particularly applicable to the electrodeposition of refractory metals by a recently discovered technique wherein roughness and imperfections in the electrodeposited plate were encountered. This recently discovered technique represents a marked technological advance in the production of highly corrosion resistant equipment for both industrial and military needs.
  • the process utilizes an electrolytic melt which contains only fluorides. If other anions, such as chlorides, bromides or oxides are present as more than minor impurities, the metal deposit will be in the form of a powder or dendrites.
  • Interdependent factors which must be adjusted in the process to produce a dense coherent deposit are the proportions of the various fluorides in the electrolytic melt, the electrolyzing current density, and the melt temperature. It has been noted that each of these factors always depend somewhat on the particular metal of the other interdependent factors and on the particular metal being deposited. However, these limits can be readily determined for any given electrolytic system by simply adjusting one or more of the variables and observing the nature of the resulting deposit.
  • the electrolytic melt consists of at least one fluoride of the metal to be deposited and the base melt, i.e., the melt without any fluorides of the metal to be deposited.
  • the base melt is at least one fluoride selected from the fluorides of potassium, rubidium, and cesium and at least one fluoride of other elements higher in the electromotive series than the metal to be deposited.
  • the exact composition of the base melt required to produce dense coherent deposits depends not only on the particular temperature and current density employed, but also on the particular metal being deposited.
  • the base melt should contain between about 10 and about weight percent, preferably between about 30 and about 75 weight percent, of at least one fluoride selected from the group consisting of the fluorides of potassium, rubidium, and cesium.
  • the balance of the base melt for these metals consists of at least one fluoride of other elements higher in the electromotive series than the metal to be deposited.
  • One preferred base melt which can be used to deposit any of the subject metals is the eutectic composition of the fluorides of lithium, sodium, and potassium, which consists of 29.25 weight percent, LiF, 11.70 weight percent NaF, and 59.05 weight percent KF and has a melting point of about 454 C.
  • Other suitable base melts for the various metals are described below in the specific examples.
  • the concentration of the fluoride of the metal to be deposited in the electrolytic melt depends on the particular base melt, temperature, and current density employed and,
  • the fluoride of the metal to be deposited should be dissolved in the base melt in a concentration between about 5 and about 30 weight percent, preferably between about 5 and about weight percent, based on the simple metal fluoride, and the concentration should be maintained within the range throughout the electrolyzing process.
  • the melt should contain between about 1 and about 33 weight percent, preferably between 3 and 10 weight percent, tungsten metal.
  • molybdenum is deposited, the melt should contain between about 1 and about weight percent, preferably between 3 and 10 weight percent, molybdenum metal.
  • suitable concentrations of metal fluoride are 8 weight percent for chromium and hafnium, and 10 weight percent for vanadium, all based on the simple metal fluoride.
  • the metal fluoride employed may be simple or complex; but if a complex fluoride is used, its cation must be higher in the electromotive series than the metal to be deposited, and its anion must not contain oxygen.
  • Typical useful metal fluorides are the simple fluorides and double fluorides such as potassium hex'afluozirconate potassium hexafluovanadate potassium heptafluocolumbate potassium heptafluotantalate potassium hexafluochromate and potassium hexafluomolybdate Where the solubility of the particular metal fluoride employed is very low, it may be fixed in the melt by reduction with the appropriate metal.
  • tungsten or molybdenum metal in the deposition of tungsten or molybdenum it is preferred to place tungsten or molybdenum metal in the electrolytic bath and then introduce gaseous tungsten hexafluoride or molybdenum hexafluoride, which are insoluble, into the bath through a graphite bubbler.
  • the tungsten or molybdenum metal reduces the insoluble hexafluoride gas to a soluble fluoride, from which the tungsten or molybdenum is electrolytically deposited.
  • the process deposits four of the subject metals (zirconium, hafnium, tantalum, and chromium) from their highest stable valence states in the particular system under consideration, i.e., 4+ for Zirconium and hafnium, 5+ for tantalum and 3+ for chromium.
  • the other metals are deposited from valence states below the highest stable state, i.e., 3+ for vanadium and molybdenum and 4+ for columbium and tungsten.
  • a compound of the metal in the appropriate valence state may be prepared externally and added to the electrolytic melt. Alternatively, the metal ion may be reduced in situ in the melt.
  • the tungsten is preferably reduced to a lower valence state by contactingthe gaseous tungsten hexafluoride with tungsten metal in the melt and further reduction accomplished by electrolysis.
  • the electrodeposition step should be carried out in an inert, nonoxidizing atmosphere such as argon, neon, helium, or the like, or under vacuum conditions. If an inert gas is employed, it may be at a pressure above or below atmospheric pressure, as long as it is substantially inert with respect to the melt and the metal.
  • the container for the melt may be made of any material which has no deleterious effect on the melt or the deposited metal and is not attacked by the melt during operation.
  • the operating limits for the electrolyzing temperature and current density depend on the particular melt employed and on the metal being deposited. Also, the uppermost limit for the current density generally decreases as the concentration of the plating metal fluoride in the melt decreases. Of course, the temperature of the electrolyte must always be above the melting point of the particular melt employed. For example, zirconium can be deposited at a cathode current density of 5 to 40 ma./cm.
  • tantalum can be deposlted at a cathode current density of 5 to ma/emfl, preferably 40 ma./cm. and a temperature of 700 to 850 C., preferably 800 C.; columbium at 5 to 100 ma./cm. preferably 50 ma./cm. and 675 to 850 C., preferably 770 C.; hafnium at 20 ma./cm. and 750 C.; vanadium at 40 met/cm. and 770 C.; chromium at 25 to 60 ma./ cm. and 800 to 840 C.; molybdenum at 2 to 200 ma./ cm.
  • a wide variety of electrically conductive materials and alloys are available for use as the base material (cathode).
  • the only limitations on the base material for this particular process are that it be not excessively reactive with the melt and that it not melt at or below the operating temperature. For example, satisfactory deposits are obtained on stainless steel, graphite, nickel, and copper.
  • the actual choice of a particular base material and the pretreatment to be given to it in any specific case depend on several factors. Among such factors are the type of metal to be deposited, the geometry of the article to be plated, and the dimensional tolerances required in the plate-d article. In large-scale operations in which the deposited metal is to be removed from the base material, reusable base materials are preferred.
  • the source of the metal to be deposited in the subject electrolytic system may be either the anode or the electrolytic melt, and the type of anode used depends on whether the anode or the melt is to be the source of metal.
  • any of the subject metals can be deposited by using a soluble anode which must be composed in whole or in part of the metal to be plated.
  • Such anode materials include rods, plates, r-ondels, chunks, or other discrete particles of the particular metal to be deposited. If a particulate anode material is used, it can be held in place by a suitable mesh retainer, such as nickel.
  • an insoluble, soluble, or gaseous anode may be used, depending on the particular metal to be deposited.
  • An insoluble anode such as graphite or carbon, may be used in the electrowinning of any of the metals which are deposited from their maximum stable valence states, i.e., zirconium, hafnium, tantalum, and chromium. With the insoluble anode, the applied voltage must be at least as high as the breakdown potential of the melt.
  • any of the subject metals may be electrowon by using a gaseous hydrogen anode or a soluble anode containing an active metal selected from the group consisting of lithium, sodium, potassium, magnesium, calcium, and aluminum.
  • the applied voltage need not be as high as the breakdown potential of the melt, but only sufiicient to overcome the resistance of the electrolyte and the very small polarization of the electrode.
  • the melt is gradually diluted by active metal fluoride formed at the anode and by deposition of refractory metal at the cathode; thus, for continuous operation, it is best that the melt be recirculated through an external station where the active metal fluoride is removed and refractory metal fluoride added.
  • the gaseous hydrogen anode is generally preferred for electrowinning applica- C.
  • the hydrogen anode is also preferred over the insoluble anode because the anodic product is hydrogen fluoride, which is less corrosive than the fluorine gas which is produced at the insoluble anode.
  • the hydrogen anode permits the use of less expensive and more readily available construction materials for containers, barriers, baflles, and other cell components.
  • the melt Since the concentration of the fluoride of the metal to be deposited decreases during electrowinning, the melt must be replenished with the plating metal fluoride so that the concentration of that fluoride in the melt is con tinuously maintained within the required range.
  • the concentration of the plating metal fluoride in the melt should be maintained between about and about 30 weight percent.
  • the metal deposits produced by this particular process are dense, fine grain, structurally coherent plates, as opposed to the layers of compacted powders or dendritic growths produced heretofore.
  • Metal deposits have a density of at least 98 percent of the theoretical density of the metal deposited, and are generally mechanically deformable without breaking and substantially free of non-metallic impurities.
  • There seems to be no limit on the thickness of the deposits which can be produced by this process and dense coherent plates of more than 0.5 inch thickness have been obtained.
  • One of the advantages of this process is that it can produce metal foils.
  • a metal foil is distinguished from a film in that a foil is capable of maintaining a structurally coherent shape Without a substrate for support, whereas a film is incapable of maintaining a structurally coherent shape without a substrate for support.
  • the aforesaid process may be used to electrofine any of the subject metals. This is achieved by making an anode from compounds or alloys wherein one of these metals is present as one of the major constituents, placing the anode in the aforedescribed bath containing a fluoride of the metal, and cathodically depositing the pure metal. This process is also useful for separating the various metals from each other.
  • the process may also be used to electroplate or electroclad any of the subject metals on a base material of any desired shape. Because of its unusual throwing power, this process is especially useful for depositing metal on intricately shaped base materials or on internal surfaces.
  • this process produces a metal deposit which is bonded to the substrate by atomic attractive forces. Each initially deposited atom of the coating is in intimate contact with the surface atoms of the substrate.
  • the bonding in roll cladding is attained by mechanical means where on a molecular scale there are only a few isolated points of contact.
  • this process may be used to electroform articles of any desired shape.
  • the manner in which the electroformed article is separated from the base material depends on the nature of the base material, the shape of the formed article, and whether the base material is to be reused.
  • a nickel base can be dissolved in nitric acid or mechanically removed by chipping or drilling.
  • a graphite base is usually removed mechanically by chipping or drilling.
  • a base made of Hastelloy C can be easily removed from the deposited metal by simply pulling the base away from the metal.
  • the process may be used not only to deposit the pure metals, but also to deposit various alloys or compounds of the subject metals. This may be accomplished by introducing into the melt the respective fluorides of the materials required to make the desired alloys or compounds, or
  • dense structurally coherent plates of zirconium di boride can be deposited by electrolyzing a melt consisting of .a base melt containing between about 10 and about weight percent at least one fluoride selected from the group consisting of the fluorides of potassium, rubidium, and cesium, and a balance of at least one fluoride of other elements higher in the electromotive series than zirconium, and boron; about 5 to 30 weight percent as a fluoride of zirconium, based on the simple fluoride; and about 5 to 11 weight percent boron trifluoride present in the melt as a fluoroborate.
  • Suitable base melts for the deposition of zirconium diboride are the eutectic composition of the fluorides of lithium, sodium, and potassium; the eutectic composition of the fluorides of potassium and lithium; and the eutectic composition of the fluorides of potassium and sodium.
  • the boron trifluoride may be provided by bubbling gaseous boron trifluoride (BP into a melt containing potassium fluoride; the boron trifluoride and the potassium fluoride then react within the melt to form potassium fluoroborate (KBF so that the boron trifluoride is actually present in the melt as a fluoroborate.
  • the melt may be formed directly from KBE; as a starting material, such as by mixing together appropriate proportions of KBF NaBF and K ZrF
  • the boron trifluoride could also be added by other suitable chemically equivalent starting materials.
  • the electrodisposition of zirconium diboride is carried out at temperatures of 700 to 900 C., preferably 775 to 875 C., and cathode current densities of 5 to 350 ma./cm. preferably 150 to 200 ma./cm.
  • the anode used in the deposition of zirconium diboride preferably contains a major amount of Zirconium The following examples are illustrative:
  • Example I Tantalum was plated onto a copper rod cathode from a bath consisting of the eutectic composition of LiF, NaF, and KP and containing 15 weight percent tantalum fluoride.
  • the electrolysis was carried out at a melt temperature of 775 C. and a cathode current density of 30 ma./cm. Although the top of the cell was covered by a heat shield and the cell otherwise insulated, no attempt was made to apply additional heat to the gas zone above the melt. Temperature profiles taken on the cell indicated that the difference between the lower and upper portion of the melt was greater than 50 C.
  • the resulting plate on the cathode was identified as tantalum and had a density of 16.6 grams/cm. (the theoretical density of tantalum), a hardness of DPH, and was structurally coherent. However, a careful inspection of the plated tantalum surface revealed roughness and irregularities.
  • the electrodeposition was then repeated under the aforementioned conditions with the exception that additional heaters were placed around the gas zone and gasmelt interface.
  • the gas zone was heated to provide a substantially constant temperature throughout the melt zone. Temperaure profiles taken on the cell indicated that the temperature in the melt zone varied only by a few degrees and this was confined to the top 1 to 2 inches of melt.
  • the resulting plates were smooth and free of roughness and bumps and superior to those produced by the first process wherein no additional heat was employed.
  • Example 11 Columbium was plated onto a copper rod cathode from a bath consisting of the eutectic composition of LiF, NaF, and KP and containing 10 weight percent tantalum fluoride.
  • the electrolysis was carried out at a melt temperature of 775 C. and a cathode current density of 50 ma./cm.
  • the top of the cell was covered by a heat shield and the cell otherwise insulated, no attempt was made to apply additional heat to the gas zone above the meltQTemperature profiles taken on the cell indicated that the difference between the lower and upper portion of the melt was greater than 50 C.
  • the resulting plate on the cathode was identified as columbiurn and was structurally coherent. However, a careful inspection of the plated columbium surface revealed roughness and irregularities.
  • the electrodeposition was then repeated under the aforementioned conditions with the exception that additional heaters were placed around the gas zone and gasmelt interface.
  • the gas zone was heated to provide a substantially constant temperature throughout the melt zone.
  • Temperature profiles taken on the cell indicated that the temperatures in the melt zone varied only by a few degrees and this was confined to the top 1 to 2 inches of melt.
  • the resulting plates were smooth and free of roughness and bumps and superior to those produced by the first process where no additional heat was employed;
  • Example III Tungsten was plated onto a copper rod cathode from a bath consisting of the eutectic composition of LiF, NaF, and KP and containing 15 weight percent tantalum fluoride. The electrolysis was carried out at a melt temperature of 775 C. and a cathode current density of 30 ma./cm.
  • the electrodeposition was then repeated under the aforementioned conditions with the exception that additional heaters were placed around the gas zone and gasmelt interface.
  • the gas zone was heated to provide a substantially constant temperature throughout the melt zone.
  • Temperature profiles taken on the cell indicated that the temperature in the melt zone varied only by a few degrees and this was confined to the top 1 to 2 inchesof melt.
  • the resulting plates were smooth and free of roughness and bumps and superior to those produced by the first process wherein no additional heat was employed.
  • an electrodeposition process wherein metals, alloys and compounds thereof, are deposited in an electrolytic system on an electrically conductive cathode base material, said electrolytic system comprising (1) a gas zone and (2) an electrolyte zone heated by heating means and having temperature differentials within said electrolyte zone suflicient to cause circulation of said electrolyte, the improvement which comprises heating said gas zone using heating means separate from the heating means of said electrolyte zone to a temperature at least up to about the liquidus temperature of said electrolyte whereby said circulation is minimized.
  • an electrodeposition process wherein metals, alloys and compounds thereof, are deposited in an electrolytic system on an electrically conductive cathode base material, said electrolytic system comprising (1) an inert gas zone and (2) an electrolytic melt zone heated by heating means and having temperature differentials within said melt sufficient to cause circulation of said melt, the improvement which comprises heating said gas zone using 10 heating means separate from the heating means of said electrolytic melt at least to a temperature at which said inert gas zone and said electrolytic melt are substantially isothermal, whereby said circulation is minimized.
  • said electrolytic melt having temperature differentials within said melt suflicient to cause circulation of said melt;
  • the improvement which comprises heating said gas zone using heating means separate from the heating means of said electrolytic melt at least to a temperature at which said inert gas zone and said electrolytic melt are substantially isothermal, whereby said circulation is minimized.
  • said electrolytic melt having temperature differentials within said melt suflicient to cause circulation of said melt;
  • the improvement which comprises heating said gas zone using heating means separate from the heating means of said electrolytic melt at least to a temperature wherein the difference between the lower and upper portions of said electrolytic melt is less than about 10 0, whereby said circulation is minimized.
  • bromides and oxides consisting essentially of (a) a base melt of at least one fluoride selected from the group consisting of the fluorides of potassium, rubidium and cesium and at least one fluoride of other elements higher in the electromotive series than metal to be deposited, and
  • said electrolytic melt having temperature differentials within said melt suificient to cause circula tion of said melt;
  • the improvement which comprises heating said gas zone using heating means separate from the heating means of said electrolytic melt at least to a temperature wherein the difference between the lower and upper portions of said electrolytic melt is less than about 2 C., whereby said circulation is minimized.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
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US418118A 1964-12-14 1964-12-14 Process for the electrodeposition of metals Expired - Lifetime US3371020A (en)

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Application Number Priority Date Filing Date Title
US418118A US3371020A (en) 1964-12-14 1964-12-14 Process for the electrodeposition of metals
DE19651483347 DE1483347A1 (de) 1964-12-14 1965-11-24 Verfahren zum elektrolytischen Abscheiden von Metallen
GB51108/65A GB1134217A (en) 1964-12-14 1965-12-02 Improved process for the electrodeposition of metals, alloys or compounds thereof from molten electrolytes
FR41048A FR1460990A (fr) 1964-12-14 1965-12-06 Procédé de dépôt électrolytique
BE673322D BE673322A (de) 1964-12-14 1965-12-06
CH1721065A CH450858A (fr) 1964-12-14 1965-12-14 Procédé de dépôt électrolytique de métaux, d'alliages et de composés métalliques
AT1124165A AT271033B (de) 1964-12-14 1965-12-14 Elektrolytisches Abscheidungsverfahren
NL6516263A NL6516263A (de) 1964-12-14 1965-12-14

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BE (1) BE673322A (de)
CH (1) CH450858A (de)
DE (1) DE1483347A1 (de)
FR (1) FR1460990A (de)
GB (1) GB1134217A (de)
NL (1) NL6516263A (de)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20040262163A1 (en) * 2003-06-24 2004-12-30 Sumitomo Electric Industries, Ltd. Molten salt bath for electroforming and method of manufacturing metal product using the same
CN111339581A (zh) * 2018-12-18 2020-06-26 通用电气公司 形成电铸构件的方法及相关系统
CN111511964A (zh) * 2017-12-15 2020-08-07 高木幹晴 镀覆覆膜的晶粒的微细化方法

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1758149C2 (de) * 1968-04-10 1974-07-25 Vereinigte Aluminium-Werke Ag, 5300 Bonn Vorrichtung zur Verbesserung des Wärmehaushalts von Aluminium-Elektrolysezellen neuzeitlicher Bauart mit vorgebrannten, kontinuierlichen Anoden
DE3340294C2 (de) * 1983-11-08 1985-09-19 Degussa Ag, 6000 Frankfurt Vorrichtung und Verfahren zur Schmelzflußelektrolyse von Alkalimetallhalogeniden

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1984745A (en) * 1931-04-22 1934-12-18 Bergwerksgesellschaft Georg Von Giesches Erben Electrodeposition of zinc
US2424179A (en) * 1941-10-15 1947-07-15 Robert J Mcnitt Method and apparatus for purifying a molten light metal by precipitation of impurities

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1984745A (en) * 1931-04-22 1934-12-18 Bergwerksgesellschaft Georg Von Giesches Erben Electrodeposition of zinc
US2424179A (en) * 1941-10-15 1947-07-15 Robert J Mcnitt Method and apparatus for purifying a molten light metal by precipitation of impurities

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20040262163A1 (en) * 2003-06-24 2004-12-30 Sumitomo Electric Industries, Ltd. Molten salt bath for electroforming and method of manufacturing metal product using the same
CN111511964A (zh) * 2017-12-15 2020-08-07 高木幹晴 镀覆覆膜的晶粒的微细化方法
CN111339581A (zh) * 2018-12-18 2020-06-26 通用电气公司 形成电铸构件的方法及相关系统
CN111339581B (zh) * 2018-12-18 2024-02-02 通用电气公司 形成电铸构件的方法及相关系统

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AT271033B (de) 1969-05-27
GB1134217A (en) 1968-11-20
DE1483347A1 (de) 1969-03-13
FR1460990A (fr) 1966-12-02
BE673322A (de) 1966-04-01
NL6516263A (de) 1966-06-15
CH450858A (fr) 1968-04-30

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