US2734856A - Electrolytic method for refining titanium metal - Google Patents

Electrolytic method for refining titanium metal Download PDF

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US2734856A
US2734856A US2734856DA US2734856A US 2734856 A US2734856 A US 2734856A US 2734856D A US2734856D A US 2734856DA US 2734856 A US2734856 A US 2734856A
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C3/00—Electrolytic production, recovery or refining of metals by electrolysis of melts
    • C25C3/26—Electrolytic production, recovery or refining of metals by electrolysis of melts of titanium, zirconium, hafnium, tantalum or vanadium
    • C25C3/28—Electrolytic production, recovery or refining of metals by electrolysis of melts of titanium, zirconium, hafnium, tantalum or vanadium of titanium

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  • titanium tetrachloride titanium trichloride
  • titanium dichloride titanium trichloride
  • titanium dichloride an aqueous solution
  • reduced titanium compounds such as titanium dichloride and titanium trichloride are soluble whereas titanium tetrachloride is not.
  • titanium tetrachloride With such a variety of titanium compounds having different valence states, i. e. titanium tetrachloride, trichloride and dichloride, it is diilicult to refine impure titanium metal by such a process.
  • An object of this invention is to provide a method for refining impure or crude titanium metal by an electrolytic process which is simple and economical to operate.
  • a still further object of the instant invention is to provide an electrolytic refining process for the production of titanium metal which produces substantially pure and ductile titanium metal.
  • this invention contemplates a method for refining titanium metal which comprises passing electric current through an electrolytic cell having a cathode, and a molten halide salt electrolyte containing reduced titanium chlorides and employing impure titanium metal as the anode.
  • reduced titanium chlorides we mean titanium dichloride and titanium trichloride.
  • the titanium metal employed as the anode is composed of the impure or crude titanium metal to be refined.
  • the fused salt electrolyte should contain a concentration of from 0.1 to 5.0 molal reduced titanium chlorides of which at least 40% is titanium dichloride.
  • the refining process should be carried out by maintaining during the passage of said current an anode current density from 0.01 to 3.0 amperes per square centimeter, and a cathode current density of at least 0.1 ampere per square centimeter but not exceeding five times the numerical molality of the reduced titanium chlorides present in the electrolyte.
  • the electrolyte For refining impure titanium metal to produce ductile titanium metal of exceptional quality, it is desirable to have at least 70% of the reduced titanium chlorides in the electrolyte present as titanium dichloride, the re 2,734,856 Patented Feb. 14, 1956 mainder being titanium trichloride. Furthermore it is preferred in such instances to have present a concentration in said electrolyte of from 0.3 to 2.0 molal reduced titanium chlorides.
  • the anode current density preferably should be from 0.1 to 0.3 amperes per square centimeter and the cathode current density from 0.2 to 1.5 amperes per square centimeter during the passage of the current through the cell.
  • Fig. 1 is presented to illustrate more clearly in cross section the type of electrolytic cell which has been successfully used in refining titanium metal according to the instant invention.
  • the electrolytic cell consists of container 11 which is heated externally by gas flames 12 in furnace 13.
  • the halide salt electrolyte 14 is placed in the container.
  • a cathode 15 is inserted into the cell and extends down into the electrolyte.
  • cathode may be composed of any suitable material such as nickel.
  • the anode 16 consists of impure titanium metal which is to be refined.
  • the cell is further provided with vent 17 to permit the removal of any gaseous products.
  • anode is unimportant and substantially any sintered, pressed or solid form may be used. It is particularly desirable to consolidate as by sintering or pressing finely divided impure titanium metal to be refined into the form of a compacted mass, for instance rods, sheets, bars and the like. These compacted masses are then immersed into the fused salt bath as the anode.
  • many other methods may be used to prepare the anode for example, suspending the impure titanium metal in the fused salt bath by providing a container such as a metallic basket, e. g. one constructed of nickel or other suitable material in which the impure titanium metal may be placed.
  • Fig. 2 shows pieces of impure titanium metal 18 in such a metallic anode basket 16A.
  • the .halide salt electrolyte preferably comprises a molten halide mixture of alkali or alkaline earth metals or magnesium. It is particularly desirable to employ the chlorides of "said metals because of the economics involved. These halides may be employed singly or in combinations. Mixtures of these halides which form low melting point eutetics are most. convenient to em ploy.
  • the halide salt electrolyte should contain reduced titanium chlorides in concentration from 0.1 to 5.0 molal, of which at least 40% is titanium dichloride.
  • the halide salt electrolyte should contain reduced titanium chlorides in concentration from 0.1 to 5.0 molal, preferably from 0.3 to 2.0 molal, the reduced titanium chlorides being at least titanium dichloride. If the percentage of titanium dichloride is less than 40%, a titanium metal product is obtained which is no purer than the starting titanium metal and hence no refining is performed.
  • An atmosphere of argon or other inert gas is preferably maintained above the molten salt bath in order to prevent contamination of the titanium values by the outside atmosphere.
  • the impure titanium metal which acts as the anode is introduced into the fused salt bath which contains reduced titanium chlorides. An electric current is then passed through the cell. The impure titanium metal at the anode is then converted to solubilized titanium chlorides which are transferred through the salt bath bottom of the'cell. The titaniummetal at the anode 3 therefore is solubilized, transferred and subsequently deposited on the cathode in a purified state.
  • anode current density exceeds 3.0 amperes per square centimeter, there is too much opportunity for titanium dichloride present in the salt electrolyte to be converted to titanium trichloride which results in the titanium values being chlorinated instead of producing titanium metal.
  • the current densities of the electrodes are dependent on both the current passing through the cell and the effective electrode area, that is that portion of the surface area of the electrode at which electrolysis actually occurs. If the cathode current density is less than 0.1 ampere per square centimeter, titanium metal will not be deposited. If the maximum current density is exceeded, metals other than titanium, that is, those from the fused salt electrolyte will be deposited.
  • anode current density should be from 0.1 to 0.3 ampere per square centimeter and the cathode current density from 0.2 to 1.5 amperes per square centimeter.
  • EXAMPLE 1 An electrolytic cell of the type shown in Fig. 1 was used to refine impure titanium metal. A chloride salt electrolyte consisting of 7300 grams of strontium chloride and 2700 grams of sodium chloride was introduced into the cell and heated at a temperature of 700 C.
  • the electrolyte was charged with 1425 grams titanium dichloride and 463 grams titanium trichloride equivalent to a concentration of approximately 1.5 molal reduced titanium chlorides. About 75% of the total reduced titanium chlorides was titanium dichloride and the remainder titanium trichloride.
  • the impure titanium metal which was to be refined was compressed into the form of a solid cylindrical anode by sintering and the impure titanium metal anode was inserted into the electrolyte.
  • the impure titanium metal which had been prepared by the process described in U. S. Patent No. 2,205,854 had a Brinell hardness number of 361. A spectrographic analysis of the impure metal is reported in Table I.
  • An electric current of 65 amperes at an impressed voltage of 1.6 volts was then passed through the electrolytic cell.
  • the cell was run with a cathode current density of 1.0 ampere per square centimeter and an anode current density of 0.25 ampere per square centimeter.
  • the cell resistance was approximately 0.02 ohm.
  • the impure titanium metal at the anode was then converted to solubilized reduced titanium chlorides which were transferred through the fused saltelectrolyte to the cathode at which point they were electrolytically reduced to titanium metal which was deposited on the cathode.
  • the impurities which were present in the titanium metal forming the anode settled out as sludge material in the bottom of the cell.
  • the purified titanium metal which had deposited at the cathode was removed from the fused salt bath and leached with dilute hydrochloric acid. The metal was then washed with distilled water and dried at -60 C. The purified metal was then melted in an arc furnace to produce a metallic mass which had a Brinellhardness number of 204 and which was much purer than 4 the impure starting material as indicated by the spectrographic analysis also recorded in Table I.
  • impure titanium metal may be refined by passing electric current through an electrolytic cell in which the impure titanium metal acts as the anode and in which the molten salt electrolyte contains reduced titanium compounds. Furthermore it has been established that high purity ductile'titanium metal may be produced by an electrolytic refining process which is simple and economical to operate.
  • Method for refining titanium metal which comprises passing electric current through an electrolytic cell having an anode and a cathode and a molten halide salt electrolyte, employing impure titanium metal as the anode in said cell, said electrolyte being composed of at least one compound selected from the group consisting of the halide salts of alkali metals, alkaline earth metals, and magnesium, said electrolyte further containing soluble titanium compounds selected from the group consisting of titanium dichloride and titanium trichloride in concentration from 0.1 to 5.0 molal, said soluble titanium compounds comprising at least 40% titanium dichloride, and maintaining during the passage of said current an anode current density from 0.01 to 3.0 ampere per square centimeter, and a cathode current density in amperes per square centimeter ranging from 0.1 up to 5 times the numerical molality of the soluble titanium compounds.
  • Method for refining titanium metal which comprises passing an electric current through an electrolytic cell having an anode, cathode and a molten halide salt electrolyte, employing impure titanium metal as the anode in said cell, said electrolyte composed of at least one compound selected from the group consisting of the halide salts of alkali metals, alkaline earth metals, and magnesium, said electrolyte containing soluble titanium compounds selected from the group consisting of titanium dichloride and titanium trichloride in concentration from 0:3 to 2.0 molal, and maintaining during the passage of said current an anode current density from 0.1'to 0.3 amchloride.

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  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
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Description

Feb. 14, 1956 F. J. SCHULTZ ET AL ELECTROLYTIC METHOD FOR REFINING TITANIUM METAL Filed Oct. 18, 1951 INVENTORS Frank J. Schultz BY Thomas M. Buck RNEY United States PatentO ELECTROLYTIC METHOD FOR REFINING TITANIUM METAL Frank J. Schultz, Fords, and Thomas M. Buck, Plainfield, N. J., assignors to National Lead Company, New York, N. Y., a corporation of New Jersey Application October 18, 1951, Serial No. 251,902 3 Claims. (Cl. 204-64) It has been found that it is difiicult to refine elcctrolytically impure titanium metal since titanium is multi-valent and, therefore, forms a number of valence states in the electrolytic medium used for such a refining process.
For example, it is possible to formquadrivalent, trivalent,
and divalent compounds such as titanium tetrachloride, titanium trichloride, and titanium dichloride. Furthermore, an aqueous solution may not be used as the electrolytic medium because reduced titanium salts may react with water. With respect to using molten salt electrolytes, it has been found that reduced titanium compounds such as titanium dichloride and titanium trichloride are soluble whereas titanium tetrachloride is not. With such a variety of titanium compounds having different valence states, i. e. titanium tetrachloride, trichloride and dichloride, it is diilicult to refine impure titanium metal by such a process.
An object of this invention, therefore, is to provide a method for refining impure or crude titanium metal by an electrolytic process which is simple and economical to operate. A still further object of the instant invention is to provide an electrolytic refining process for the production of titanium metal which produces substantially pure and ductile titanium metal. These and other objects will become apparent from the following more complete description of the instant invention.
Broadly this invention contemplates a method for refining titanium metal which comprises passing electric current through an electrolytic cell having a cathode, and a molten halide salt electrolyte containing reduced titanium chlorides and employing impure titanium metal as the anode. By the term reduced titanium chlorides we mean titanium dichloride and titanium trichloride. The titanium metal employed as the anode is composed of the impure or crude titanium metal to be refined. The fused salt electrolyte should contain a concentration of from 0.1 to 5.0 molal reduced titanium chlorides of which at least 40% is titanium dichloride. The refining process should be carried out by maintaining during the passage of said current an anode current density from 0.01 to 3.0 amperes per square centimeter, and a cathode current density of at least 0.1 ampere per square centimeter but not exceeding five times the numerical molality of the reduced titanium chlorides present in the electrolyte.
For refining impure titanium metal to produce ductile titanium metal of exceptional quality, it is desirable to have at least 70% of the reduced titanium chlorides in the electrolyte present as titanium dichloride, the re 2,734,856 Patented Feb. 14, 1956 mainder being titanium trichloride. Furthermore it is preferred in such instances to have present a concentration in said electrolyte of from 0.3 to 2.0 molal reduced titanium chlorides. The anode current density preferably should be from 0.1 to 0.3 amperes per square centimeter and the cathode current density from 0.2 to 1.5 amperes per square centimeter during the passage of the current through the cell.
Fig. 1 is presented to illustrate more clearly in cross section the type of electrolytic cell which has been successfully used in refining titanium metal according to the instant invention. Referring to Fig. l, the electrolytic cell consists of container 11 which is heated externally by gas flames 12 in furnace 13. The halide salt electrolyte 14 is placed in the container. A cathode 15 is inserted into the cell and extends down into the electrolyte. The
cathode may be composed of any suitable material such as nickel. The anode 16 consists of impure titanium metal which is to be refined. The cell is further provided with vent 17 to permit the removal of any gaseous products.
The particular type of anode is unimportant and substantially any sintered, pressed or solid form may be used. It is particularly desirable to consolidate as by sintering or pressing finely divided impure titanium metal to be refined into the form of a compacted mass, for instance rods, sheets, bars and the like. These compacted masses are then immersed into the fused salt bath as the anode. However, many other methods may be used to prepare the anode for example, suspending the impure titanium metal in the fused salt bath by providing a container such as a metallic basket, e. g. one constructed of nickel or other suitable material in which the impure titanium metal may be placed. Fig. 2 shows pieces of impure titanium metal 18 in such a metallic anode basket 16A.
The .halide salt electrolyte preferably comprises a molten halide mixture of alkali or alkaline earth metals or magnesium. It is particularly desirable to employ the chlorides of "said metals because of the economics involved. These halides may be employed singly or in combinations. Mixtures of these halides which form low melting point eutetics are most. convenient to em ploy.
The halide salt electrolyte should contain reduced titanium chlorides in concentration from 0.1 to 5.0 molal, of which at least 40% is titanium dichloride. In order to make ductile metal orexceptional quality the halide salt electrolyte should contain reduced titanium chlorides in concentration from 0.1 to 5.0 molal, preferably from 0.3 to 2.0 molal, the reduced titanium chlorides being at least titanium dichloride. If the percentage of titanium dichloride is less than 40%, a titanium metal product is obtained which is no purer than the starting titanium metal and hence no refining is performed.
An atmosphere of argon or other inert gas is preferably maintained above the molten salt bath in order to prevent contamination of the titanium values by the outside atmosphere.
In order to carry out the process of the instant invention the impure titanium metal which acts as the anode is introduced into the fused salt bath which contains reduced titanium chlorides. An electric current is then passed through the cell. The impure titanium metal at the anode is then converted to solubilized titanium chlorides which are transferred through the salt bath bottom of the'cell. The titaniummetal at the anode 3 therefore is solubilized, transferred and subsequently deposited on the cathode in a purified state.
In operating the cell it is necessary to maintain current densities which fall within certain limits in order to refine impure titanium metal. It has been found that it is necessary to maintain an anode current density from 0.01 to 3.0 amperes per square centimeter and a cathode current density of at least 0.1 ampere per square centimeter but not in excess of five times the numerical molality of the reduced titanium chloride present in the electrolyte. If the anode current density is less than 0.01 ampere per square centimeter, the rate of titanium metal refined is excessively slow and therefore the throughput efliciencies are excessively low. 'If an anode current density exceeds 3.0 amperes per square centimeter, there is too much opportunity for titanium dichloride present in the salt electrolyte to be converted to titanium trichloride which results in the titanium values being chlorinated instead of producing titanium metal. The current densities of the electrodes are dependent on both the current passing through the cell and the effective electrode area, that is that portion of the surface area of the electrode at which electrolysis actually occurs. If the cathode current density is less than 0.1 ampere per square centimeter, titanium metal will not be deposited. If the maximum current density is exceeded, metals other than titanium, that is, those from the fused salt electrolyte will be deposited.
For ductile titanium metal of exceptional purity the anode current density should be from 0.1 to 0.3 ampere per square centimeter and the cathode current density from 0.2 to 1.5 amperes per square centimeter.
In order to describe more fully the invention, the following examples are presented:
EXAMPLE 1 An electrolytic cell of the type shown in Fig. 1 was used to refine impure titanium metal. A chloride salt electrolyte consisting of 7300 grams of strontium chloride and 2700 grams of sodium chloride was introduced into the cell and heated at a temperature of 700 C.
The electrolyte was charged with 1425 grams titanium dichloride and 463 grams titanium trichloride equivalent to a concentration of approximately 1.5 molal reduced titanium chlorides. About 75% of the total reduced titanium chlorides was titanium dichloride and the remainder titanium trichloride. The impure titanium metal which was to be refined was compressed into the form of a solid cylindrical anode by sintering and the impure titanium metal anode was inserted into the electrolyte. The impure titanium metal which had been prepared by the process described in U. S. Patent No. 2,205,854 had a Brinell hardness number of 361. A spectrographic analysis of the impure metal is reported in Table I.
An electric current of 65 amperes at an impressed voltage of 1.6 volts was then passed through the electrolytic cell. The cell was run with a cathode current density of 1.0 ampere per square centimeter and an anode current density of 0.25 ampere per square centimeter. The cell resistance was approximately 0.02 ohm.
The impure titanium metal at the anode was then converted to solubilized reduced titanium chlorides which were transferred through the fused saltelectrolyte to the cathode at which point they were electrolytically reduced to titanium metal which was deposited on the cathode. The impurities which were present in the titanium metal forming the anode settled out as sludge material in the bottom of the cell.
The purified titanium metal which had deposited at the cathode was removed from the fused salt bath and leached with dilute hydrochloric acid. The metal was then washed with distilled water and dried at -60 C. The purified metal was then melted in an arc furnace to produce a metallic mass which had a Brinellhardness number of 204 and which was much purer than 4 the impure starting material as indicated by the spectrographic analysis also recorded in Table I.
EXAMPLE it Another sample of impure titanium metal having a Brinell hardness number of 420 was refined electrolytically in the manner identical to that described in Example I. Again the impure titanium metal was sintered into the form of a cylindrical solid and the impure titanium metal anode inserted into the fused salt electrolyte. The operating conditions for this refining process were identical to those described in the previous example. The purified titanium metal which deposited at the cathode in this experiment was also melted into a metallic mass and had a Brinell hardness number of 212. The impure starting metal and the purified metal deposited at the cathode were analyzed spectrographically as reported in Table I.
Table l SPECTROGRAPHIC DATA It has been shown by the description and the examples presented above that impure titanium metal may be refined by passing electric current through an electrolytic cell in which the impure titanium metal acts as the anode and in which the molten salt electrolyte contains reduced titanium compounds. Furthermore it has been established that high purity ductile'titanium metal may be produced by an electrolytic refining process which is simple and economical to operate.
While this invention has been described and illustrated by the examples shown, it is not intended to be strictly limited thereto and other modifications and variations may be employed within the scope of the following claims.
We claim:
1. Method for refining titanium metal which comprises passing electric current through an electrolytic cell having an anode and a cathode and a molten halide salt electrolyte, employing impure titanium metal as the anode in said cell, said electrolyte being composed of at least one compound selected from the group consisting of the halide salts of alkali metals, alkaline earth metals, and magnesium, said electrolyte further containing soluble titanium compounds selected from the group consisting of titanium dichloride and titanium trichloride in concentration from 0.1 to 5.0 molal, said soluble titanium compounds comprising at least 40% titanium dichloride, and maintaining during the passage of said current an anode current density from 0.01 to 3.0 ampere per square centimeter, and a cathode current density in amperes per square centimeter ranging from 0.1 up to 5 times the numerical molality of the soluble titanium compounds.
2. Method for refining titanium metal which comprises passing an electric current through an electrolytic cell having an anode, cathode and a molten halide salt electrolyte, employing impure titanium metal as the anode in said cell, said electrolyte composed of at least one compound selected from the group consisting of the halide salts of alkali metals, alkaline earth metals, and magnesium, said electrolyte containing soluble titanium compounds selected from the group consisting of titanium dichloride and titanium trichloride in concentration from 0:3 to 2.0 molal, and maintaining during the passage of said current an anode current density from 0.1'to 0.3 amchloride.
References Cited in the file of this patent UNITED STATES PATENTS Weintraub Feb. I, 1910 Pyk June 26, 1951 6 FOREIGN PATENTS 635,267 Great Britain Apr. 5, 1950 81,510 Argentina Sept. 25, 1951 947,983 Germany July 16, 1935 OTHER REFERENCES Chemical Abstracts, v01. 35 (1941), page 3530, abstract of publication by Gratsianskii.
Transactions of The Electrochemical Society, vol. 87 (1945), pages 551-567, article by Kroll.

Claims (1)

1. METHOD FOR REFINING TITANIUM METAL WHICH COMPRISES PASSING ELECTRIC CURRENT THROUGH AN ELECTROLYTIC CELL HAVING AN ANODE AND A CATHODE AND A MOLTEN HALIDE SALT ELECTROLYTE, EMPLOYING IMPURE TITANIUM METAL AS THE ANODE IN SAID CELL, SAID ELECTROLYTE BEING COMPOSED OF AT LEAST ONE COMPOUND SELECTED FROM THE GROUP CONSISTING OF THE HALIDE SALTS OF ALKALI METALS, ALKALINE EARTH METALS, AND MAGNESIUM, SAID ELECTROLYTE FURTHER CONTAINING SOLUBLE TITANIUM COMPOUNDS SELECTED FROM THE GROUP CONSISTING OF TITANIUM DICHLORIDE AND TITANIUM TRICHLORIDE IN CONCENTRATION FROM 0.1 TO 5.0 MOLAL, SAID SOLUBLE TITANIUM COMPOUNDS COMPRISING AT LEAST 40% TITANIUM DICHLORIDE, AND MAINTAINING DURING THE PASSAGE OF SAID CURRENT AN
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Cited By (34)

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US2785066A (en) * 1955-06-07 1957-03-12 Chicago Dev Corp Solid plates of titanium and zirconium
US2786808A (en) * 1954-09-22 1957-03-26 Chicago Dev Corp Production of titanium
US2817631A (en) * 1956-03-23 1957-12-24 Chicago Dev Corp Refining titanium alloys
US2817630A (en) * 1954-02-04 1957-12-24 Chicago Dev Corp Methods of producing titanium and zirconium
US2821506A (en) * 1954-08-19 1958-01-28 Horizons Titanium Corp Purification of titanium and zirconium metal
US2874454A (en) * 1956-06-20 1959-02-24 Chicago Dev Corp Titanium group metals deposits
US2875038A (en) * 1955-02-16 1959-02-24 Chicago Dev Corp Method of producing crystalline metal
US2880149A (en) * 1956-07-09 1959-03-31 Horizons Titanium Corp Electrolytic process
US2881119A (en) * 1954-03-08 1959-04-07 Goldenberg Leo Titanium plating
US2887443A (en) * 1957-02-15 1959-05-19 Dow Chemical Co Arc-cathode production of titanium
US2901410A (en) * 1956-08-02 1959-08-25 Chicago Dev Corp Electro-refining titanium
US2905613A (en) * 1956-09-19 1959-09-22 Osaka Titanium Seizo Kabushiki Methods and apparatus for the electrolytic-refining of titanium metal or zirconium metal
US2909472A (en) * 1956-07-25 1959-10-20 Chicago Dev Corp Process for producing titanium crystals
US2909473A (en) * 1956-09-04 1959-10-20 Chicago Dev Corp Process for producing titanium group metals
US2913378A (en) * 1956-12-18 1959-11-17 Chicago Dev Corp Two-step electrorefining of titanium alloys
US2917440A (en) * 1953-07-24 1959-12-15 Du Pont Titanium metal production
US2920022A (en) * 1958-01-15 1960-01-05 Chicago Dev Corp Preparation of titanium-manganese alloys
US2927067A (en) * 1957-10-17 1960-03-01 Chicago Dev Corp Electrorefining of zirconium
US2935454A (en) * 1953-05-01 1960-05-03 Tokumoto Shin-Ichi Method of the electrodeposition of titanium metal
US2937128A (en) * 1956-07-25 1960-05-17 Horizons Titanium Corp Electrolytic apparatus
US2939823A (en) * 1957-09-26 1960-06-07 New Jersey Zinc Co Electrorefining metallic titanium
US2941931A (en) * 1958-12-22 1960-06-21 Chicago Dev Corp Compounds of zirconium and methods of preparing same
US2948663A (en) * 1957-01-15 1960-08-09 Chicago Dev Corp Composition of matter including titanium crystal intergrowths and method of making same
US2951795A (en) * 1958-06-09 1960-09-06 Chicago Dev Corp Production of polyvalent metals
US2955078A (en) * 1956-10-16 1960-10-04 Horizons Titanium Corp Electrolytic process
US2986503A (en) * 1956-03-20 1961-05-30 Sobertiz Soc De Brevets D Expl Production of titanium and zirconium by the electrolytic refining of their alloys
US2986502A (en) * 1954-09-14 1961-05-30 Goldenberg Leo Purification of titanium
US2994650A (en) * 1951-10-24 1961-08-01 Harvey L Slatin Preparation of pure metals from their compounds
DE1123482B (en) * 1958-05-09 1962-02-08 Ici Ltd Process and device for the electrolytic refining of titanium from titanium scrap
US3029193A (en) * 1954-11-23 1962-04-10 Chicago Dev Corp Electrorefining metals
US3036961A (en) * 1958-02-24 1962-05-29 Herasymenko Anna Electrolytic refinement of metals
US6086745A (en) * 1997-07-03 2000-07-11 Tsirelnikov; Viatcheslav I. Allotropic modification of zirconium and hafnium metals and method of preparing same
US20130164167A1 (en) * 2011-12-22 2013-06-27 Universal Technical Resource Services, Inc. System and method for extraction and refining of titanium
WO2018186922A2 (en) 2017-01-13 2018-10-11 Universal Technical Resource Services, Inc. Titanium master alloy for titanium-aluminum based alloys

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US2558627A (en) * 1948-03-19 1951-06-26 Pyk Sven Christian Method for the production of zirconium alloys
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Cited By (38)

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Publication number Priority date Publication date Assignee Title
US2994650A (en) * 1951-10-24 1961-08-01 Harvey L Slatin Preparation of pure metals from their compounds
US2935454A (en) * 1953-05-01 1960-05-03 Tokumoto Shin-Ichi Method of the electrodeposition of titanium metal
US2917440A (en) * 1953-07-24 1959-12-15 Du Pont Titanium metal production
US2817630A (en) * 1954-02-04 1957-12-24 Chicago Dev Corp Methods of producing titanium and zirconium
US2881119A (en) * 1954-03-08 1959-04-07 Goldenberg Leo Titanium plating
US2821506A (en) * 1954-08-19 1958-01-28 Horizons Titanium Corp Purification of titanium and zirconium metal
US2986502A (en) * 1954-09-14 1961-05-30 Goldenberg Leo Purification of titanium
US2786808A (en) * 1954-09-22 1957-03-26 Chicago Dev Corp Production of titanium
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