US3170856A - Method and device for producing hyperpure gallium - Google Patents
Method and device for producing hyperpure gallium Download PDFInfo
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- US3170856A US3170856A US141381A US14138161A US3170856A US 3170856 A US3170856 A US 3170856A US 141381 A US141381 A US 141381A US 14138161 A US14138161 A US 14138161A US 3170856 A US3170856 A US 3170856A
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- gallium
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- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 title claims description 40
- 229910052733 gallium Inorganic materials 0.000 title claims description 40
- 238000000034 method Methods 0.000 title claims description 20
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 21
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 18
- 238000001556 precipitation Methods 0.000 claims description 9
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 6
- 229910052736 halogen Inorganic materials 0.000 claims description 6
- 150000002367 halogens Chemical group 0.000 claims description 6
- 239000008096 xylene Substances 0.000 claims description 6
- 239000002635 aromatic organic solvent Substances 0.000 claims description 4
- 239000003792 electrolyte Substances 0.000 description 15
- 210000002445 nipple Anatomy 0.000 description 12
- 238000005868 electrolysis reaction Methods 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000000243 solution Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000007670 refining Methods 0.000 description 4
- 238000011109 contamination Methods 0.000 description 3
- 239000011356 non-aqueous organic solvent Substances 0.000 description 3
- XOYLJNJLGBYDTH-UHFFFAOYSA-M chlorogallium Chemical compound [Ga]Cl XOYLJNJLGBYDTH-UHFFFAOYSA-M 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229910005540 GaP Inorganic materials 0.000 description 1
- 229910005542 GaSb Inorganic materials 0.000 description 1
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- -1 for example Substances 0.000 description 1
- 150000002258 gallium Chemical class 0.000 description 1
- 150000002259 gallium compounds Chemical class 0.000 description 1
- SRVXDMYFQIODQI-UHFFFAOYSA-K gallium(iii) bromide Chemical compound Br[Ga](Br)Br SRVXDMYFQIODQI-UHFFFAOYSA-K 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
- C25C1/22—Electrolytic production, recovery or refining of metals by electrolysis of solutions of metals not provided for in groups C25C1/02 - C25C1/20
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
Definitions
- dram-s9 My invention relates to a method and apparatus for the production of hyperpure gallium, such as required for the production of electronic semiconductors from gallium compounds, for example, GaP, GaAs, GaSb, or as required for use as doping or contact substance for semiconductor bodies. Hyperpure gallium is also used, for example, in high-temperature thermometers and as a metallic heat-exchange liquid in cooling systems.
- I employ as electrolyte for electrolytic precipi tation, the solution of a gallium complex of the type Ga(GaX in a non-aqueous organicsolvent, wherein X denotes a halogen element, which as used herein is understood to be chlorine, bromine and iodine.
- non-aqueous organic solvent particularly suitable as the non-aqueous organic solvent are benzene, toluene and xylene, and as gallium complexes are Ga(GaCl Ga(GaBr.,) and Ga(GaI
- the purifying effect obtained by virtue of the invention is not mainly predicated upon a refining action as known from the electrolysis of aqueous solutions or molten salt, but is rather predominantly based upon the insolubility of many metal halides in the organic solvents to be employed. This results in a considerable advantage over the just-mentioned known methods, namely the fact that the131-fying action does not depend upon the separation potential so'that relatively high cell voltages can be used trolyte results in the precipitationof gallium.
- gallium bromide complex An example of the technique is given by the production of gallium bromide complex.
- Commercially available gallium metal is heated in a flow of nitrogen laden with Table 2 Concentration of the foreign elements of the anodic Ga in p.p.m. (10- (percent) the foreign elements of the oath odicallyprecipitated Gain p.p.m. (10- percent) Element Not detectable.
- the purifying effect can Because of the insolubility of many metal- 7 Concentration of Table 3 Concentration'of the foreign elements of Element the'twice cathodically precipitated Ga in p.p.m. (IO-t Percent) Pb- Not detectable. Fe. ,Do.
- the drawing shows a schematic and sectional view of an electrolysis device for performing the above-described method.
- the anode is formed by molten gallium located at 1 on the bottom of the electrolytic cell. Current is supplied to the anode by a platinum wire 2 which is immersed at its lower end into the molten gallium.
- the cathode is denoted by 3 and a collector funnel by 4.
- the funnel 4 is connected with a receiving vessel 5 through a capillary 6.
- the electrolyte 7 covers the anode 1 and forms part of a thermosiphon system which serves to maintain the electrolyte in circulation.
- This system comprises the two legs 8 and 9 which are interconnected by transverse portion 13. Leg 9 is surrounded by a cooler 19.
- Leg 8 has its lower end widened to form an inverted funnel portion at 11 above the cathode 3 and in upwardly spaced relation to the funnel 4.
- a reflux condenser 712 Connected to the circulation system of the electrolyte is a reflux condenser 712.
- the suction nipple of the reflux condenser 12 is denoted by 14.
- the nipple 14 is closed by a protective cover 15 during operation of the device.
- a stopcock is provided at 16.
- the cell vessel is further provided at 17 with a conical ground nipple through which the anode current-supply lead enters into the vessel.
- the nipple 17 also serves to supply the vessel with electrolyte.
- purified gallium 19 is sealed by a stoppered ground nippie 18.
- Conically ground junctions at 21 connect the lower portion of the electrolytic cell with the upper portion that contains the above-described entire electrolytecirculating system.
- the quantity of cathode gallium required for starting the process is supplied through the receiving vessel 5 so that the capillary 6 and the receiving funnel 4 are filled with gallium.
- the anode gallium l is supplied through the central nipple 17 in a quantity adequate to bring the level of the anode gallium to a height of at most a few millimeters below the lower end of the tube 9.
- the electrolyte is filled into the vessel through the same nipple 17. Since the electrolyte must not be subjected to moisture, the filling must be done in a sealed container through a siphon or pump with the aid of a dry inert gas, for example, nitrogen.
- the electrolyte for example, is composed of 50% by weight of Ga(GaBr and 50% benzene.
- nipple 17 With nipple 17 open, the electrolyte is inducted through V the suction nipple 14 up to the stopcock 16. Thereafter, the stopcock 16 is closed, the suction line removed from nipple 14, and the protective cap 15 placed over nipple 14. Simultaneously, the condensers and 12 are put into operation, the anode current supply lead 2 is inserted, thus closing the opening of the nipple i7, and the cathode 3 is inserted through nipple 20. A voltage of from about to about v. is applied to the cell between cathode and anode. This results in the flow of an average current value of about 0.4 amp. Precipitation of about 1 g./hour of hyper-pure gallium takes place with a current yield of about 100%. I
- the device operates practically automatically, continuously and free of maintenance over a long period of time.
- the platinum wire of the cathode The receiving vessel 5 for the involves the thermosiphon principle.
- the precipitation is preferably carried out with a high cathode current density which preferably should not be below 200 amperes/decimeter This is aided by the fact that the cathode surface is very small in comparison with the anode surface.
- the gallium becomes precipitated as a fine pulverulent metal.
- This powder is suitable, for example, for the production of gallium containing semiconducting sinter materials, which have been recently employed for thermoelectric purposes.
- the circulatory system prevents the occurrence of a solid bottom body of Ga(GaX on top of the anode gallium. Such a body would considerably increase the ohmic resistance of the cell and, for the same cell voltage, would result in a reduction of the current density.
- the method of producing hyperpure gallium for electronic purposes by electrolytic precipitation which comprises using a solution of a gallium complex of the type Ga(GaX wherein X is a halogen, in a non-aqueous organic solvent.
- the method of producing hyperpure gallium for electronic purposes by electrolytic precipitation which comprises using a solution of a gallium complex of the type Ga(GaXr) wherein X is a halogen, in a non-aqueous aromatic organic solvent selected from the group consisting of benzene, toluene and xylene.
- the method of producing hyperpure gallium for electronic purposes by electrolytic precipitation which comprises using a solution of a gallium complex of the type Ga(GaX wherein X is a halogen, in a non-aqueous aromatic organic solvent selected from the group consisting of: benzene, toluene and xylene, and adjusting the current density above 200 amperes/square decimeter to precipitate gallium at the cathode in liquid form.
- the method of producing hyperpure gallium for electronic purposes by electrolytic precipitation which comprises using a solution of a gallium complex of the type Ga(GaBr in a non-aqueous aromatic organic solvent selected from the group consisting of benzene, toluene and xylene, and adjusting the current density below 200 amperes/square decimeter to precipitate gallium at the cathode in pulverulent form.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
- Electrolytic Production Of Metals (AREA)
Description
Feb. 23, 1965 LEIBENZEDER METHOD AND DEVICE FOR PRODUCING HYPERPURE GALLIUM Filed Sept. 28. 1961 United States Patent 7 4 Claims. dram-s9 My invention relates to a method and apparatus for the production of hyperpure gallium, such as required for the production of electronic semiconductors from gallium compounds, for example, GaP, GaAs, GaSb, or as required for use as doping or contact substance for semiconductor bodies. Hyperpure gallium is also used, for example, in high-temperature thermometers and as a metallic heat-exchange liquid in cooling systems.
Various methods have become known for extreme purification of gallium. Past investigations have mainly been directed to refinement of gallium by electrolytic processes. Among the known refining methods are the precipitation from aqueous medium, as well as the molten-bath electrolysis. The first-mentioned method has only a slight purifying effect, in contrast to molten-bath electrolysis which afford-a high purity of the separated gallium, this purity being dependent to a great extent upon accurate control of electric potentials.
It is an object of my invention to devise a method and apparatus for the production of hyperpure gallium on electrolytic principles in which the refining action is independent, Within a wide range, of accurately constant potentials and, under otherwise comparable conditions, permits a considerable increase in yield by operation at increased electrolytic cell voltages.
To achieve these objects and in accordance with my invention, I employ as electrolyte for electrolytic precipi tation, the solution of a gallium complex of the type Ga(GaX in a non-aqueous organicsolvent, wherein X denotes a halogen element, which as used herein is understood to be chlorine, bromine and iodine. Particularly suitable as the non-aqueous organic solvent are benzene, toluene and xylene, and as gallium complexes are Ga(GaCl Ga(GaBr.,) and Ga(GaI The purifying effect obtained by virtue of the invention is not mainly predicated upon a refining action as known from the electrolysis of aqueous solutions or molten salt, but is rather predominantly based upon the insolubility of many metal halides in the organic solvents to be employed. This results in a considerable advantage over the just-mentioned known methods, namely the fact that the puir-fying action does not depend upon the separation potential so'that relatively high cell voltages can be used trolyte results in the precipitationof gallium. This Was all the less expectablea's the above-mentioned complexes have a salt-like structure. In fact, however, it has been found'that, for example, a solubility of Ga(GaCl and Ga(GaBr in benzene at 20 C. is approximately 1200 g./liter, and is only slightly less than. the solubility in toluene and xylene. The specific electric conductivities (S in ohm" cmr of the electrolytes used according to the invention is indicated in the following Table 1.
3,170,856 Patented Feb. 23, 1965 Table 1 Concentratlon in per- S at S at cent by 22 C. 40 0. weight 52. 4 0.05 0. 07 Gawaoh) i 57. 32
Another advantage over the methods heretofore known resides in the production of the electrolyte. The preparation of the gallium complex to be employed according to the invention is efiected' in known manner through the reduction of GaX (wherein X denotes a halogen element) with gallium in accordance with the following reaction equations:
An example of the technique is given by the production of gallium bromide complex. Commercially available gallium metal is heated in a flow of nitrogen laden with Table 2 Concentration of the foreign elements of the anodic Ga in p.p.m. (10- (percent) the foreign elements of the oath odicallyprecipitated Gain p.p.m. (10- percent) Element Not detectable.
By a second refining operation, the purifying effect can Because of the insolubility of many metal- 7 Concentration of Table 3 Concentration'of the foreign elements of Element the'twice cathodically precipitated Ga in p.p.m. (IO-t Percent) Pb- Not detectable. Fe. ,Do.
A2 D0. Ha D0. Cu -Dc. Si Do. Zn Do. Me 0.0s,
As is further aparent fro m the apparatus described hereinafter, the above-mentioned extreme purity of the refined product is obtained withthe minimum in equipmentand with a good yield per unit of time.
When perform-ingthe methodaccording to my inven-' tion, it is significant that no gas development occurs during the electrolysis so that the process can be carried in a completely closed vessel. This excludes the danger of contamination from the ambient atmosphere. In the electrolytic cells, the contamination can also be avoided to a great extent because the electrolysis can be performed at a temperature of about 50 C., and the electrolyte is only slightly aggressive. To further describe the invention, reference is made to the drawing and the specific example hereinbelow.
The drawing shows a schematic and sectional view of an electrolysis device for performing the above-described method. The anode is formed by molten gallium located at 1 on the bottom of the electrolytic cell. Current is supplied to the anode by a platinum wire 2 which is immersed at its lower end into the molten gallium. The cathode is denoted by 3 and a collector funnel by 4. The funnel 4 is connected with a receiving vessel 5 through a capillary 6. The electrolyte 7 covers the anode 1 and forms part of a thermosiphon system which serves to maintain the electrolyte in circulation. This system comprises the two legs 8 and 9 which are interconnected by transverse portion 13. Leg 9 is surrounded by a cooler 19. Leg 8 has its lower end widened to form an inverted funnel portion at 11 above the cathode 3 and in upwardly spaced relation to the funnel 4. Connected to the circulation system of the electrolyte is a reflux condenser 712. The suction nipple of the reflux condenser 12 is denoted by 14. To prevent contamination, the nipple 14 is closed by a protective cover 15 during operation of the device. A stopcock is provided at 16. The cell vessel is further provided at 17 with a conical ground nipple through which the anode current-supply lead enters into the vessel. The nipple 17 also serves to supply the vessel with electrolyte. purified gallium 19 is sealed by a stoppered ground nippie 18. Conically ground junctions at 21 connect the lower portion of the electrolytic cell with the upper portion that contains the above-described entire electrolytecirculating system.
The quantity of cathode gallium required for starting the process is supplied through the receiving vessel 5 so that the capillary 6 and the receiving funnel 4 are filled with gallium. The anode gallium l is supplied through the central nipple 17 in a quantity suficient to bring the level of the anode gallium to a height of at most a few millimeters below the lower end of the tube 9. Thereafter, the electrolyte is filled into the vessel through the same nipple 17. Since the electrolyte must not be subjected to moisture, the filling must be done in a sealed container through a siphon or pump with the aid of a dry inert gas, for example, nitrogen. The electrolyte, for example, is composed of 50% by weight of Ga(GaBr and 50% benzene.
With nipple 17 open, the electrolyte is inducted through V the suction nipple 14 up to the stopcock 16. Thereafter, the stopcock 16 is closed, the suction line removed from nipple 14, and the protective cap 15 placed over nipple 14. Simultaneously, the condensers and 12 are put into operation, the anode current supply lead 2 is inserted, thus closing the opening of the nipple i7, and the cathode 3 is inserted through nipple 20. A voltage of from about to about v. is applied to the cell between cathode and anode. This results in the flow of an average current value of about 0.4 amp. Precipitation of about 1 g./hour of hyper-pure gallium takes place with a current yield of about 100%. I
Aside from the addition of the anode gallium and the removal of the cathodically precipitated gallium, the device operates practically automatically, continuously and free of maintenance over a long period of time. After starting the process, .the platinum wire of the cathode The receiving vessel 5 for the involves the thermosiphon principle.
Gil
becomes coated with gallium melt, until a drop of gallium is formed at the lower end and drips into the collecting funnel 4. This is repeated continually.
The precipitation is preferably carried out with a high cathode current density which preferably should not be below 200 amperes/decimeter This is aided by the fact that the cathode surface is very small in comparison with the anode surface.
However, if the cathode current density is considerably lowered below the above-mentioned amount, then, according to another embodiment of the invention, the gallium becomes precipitated as a fine pulverulent metal. This powder is suitable, for example, for the production of gallium containing semiconducting sinter materials, which have been recently employed for thermoelectric purposes.
The performance of the electrolyte circulation system That is, the electrolyte heated by the heating bath rises in the leg 8 and passes through the cooled leg 9 back to the lower portion of the electrolytic cell. This affords a relatively simple design despite the required complete sealing of the electrolytic cell. By mounting the cathode at the input funnel 11 of the circulation leg 8, a considerable quantity of loules heat which occurs in the vicinity of the cathode in the electrolyte is advantageously used to amplify the thermosiphon effect.
The circulatory system prevents the occurrence of a solid bottom body of Ga(GaX on top of the anode gallium. Such a body would considerably increase the ohmic resistance of the cell and, for the same cell voltage, would result in a reduction of the current density.
I claim:
1. The method of producing hyperpure gallium for electronic purposes by electrolytic precipitation, which comprises using a solution of a gallium complex of the type Ga(GaX wherein X is a halogen, in a non-aqueous organic solvent.
2. The method of producing hyperpure gallium for electronic purposes by electrolytic precipitation, which comprises using a solution of a gallium complex of the type Ga(GaXr) wherein X is a halogen, in a non-aqueous aromatic organic solvent selected from the group consisting of benzene, toluene and xylene.
3. The method of producing hyperpure gallium for electronic purposes by electrolytic precipitation, which comprises using a solution of a gallium complex of the type Ga(GaX wherein X is a halogen, in a non-aqueous aromatic organic solvent selected from the group consisting of: benzene, toluene and xylene, and adjusting the current density above 200 amperes/square decimeter to precipitate gallium at the cathode in liquid form.
4. The method of producing hyperpure gallium for electronic purposes by electrolytic precipitation, which comprises using a solution of a gallium complex of the type Ga(GaBr in a non-aqueous aromatic organic solvent selected from the group consisting of benzene, toluene and xylene, and adjusting the current density below 200 amperes/square decimeter to precipitate gallium at the cathode in pulverulent form.
References Cited in the file of'this patent UNITED STATES PATENTS 2,440,238 Alley et a1 Apr. 27, 1948 2,928,731 Gebauhr Mar. 15, 1960 2,952,589 Ziegler et al Sept. 30, 1960 2,985,568 Ziegler et al May 23, 1961 2,998,374 Crantors Aug. 29, 1961 3,007,858 Braithwaite Nov, 7, 1961 FOREIGN PATENTS 126,270 I Russia June .4, 1959
Claims (1)
- 3. THE METHOD OF PRODUCING HYPERPURE GALLIUM FOR ELECTRONIC PURPOSES BY ELECTROLYTIC PRECIPITATION, WHICH COMPRISES USING A SOLUTION OF A GALLIUM COMPLEX OF THE TYPE GA(GAX4) WHEREIN X IS A HALOGEN, IN A NON-AQUEOUS AROMATIC ORGANIC SOLVENT SELECTED FROM THE GROUP CONSISTING OF BENZENE, TOLUENE AND XYLENE, AND ADJUSTING THE
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US370749A US3170861A (en) | 1961-09-28 | 1964-05-06 | Apparatus for producing hyperpure gallium |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DES70729A DE1141461B (en) | 1960-09-30 | 1960-09-30 | Method and device for the electrolytic production of high-purity gallium |
DES85697A DE1183249B (en) | 1960-09-30 | 1963-06-15 | Method and device for the electrolytic production of high-purity gallium |
Publications (1)
Publication Number | Publication Date |
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US3170856A true US3170856A (en) | 1965-02-23 |
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Family Applications (2)
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US141381A Expired - Lifetime US3170856A (en) | 1960-09-30 | 1961-09-28 | Method and device for producing hyperpure gallium |
US375211A Expired - Lifetime US3325380A (en) | 1960-09-30 | 1964-06-15 | Method and apparatus for electrolytically producing highly pure gallium |
Family Applications After (1)
Application Number | Title | Priority Date | Filing Date |
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US375211A Expired - Lifetime US3325380A (en) | 1960-09-30 | 1964-06-15 | Method and apparatus for electrolytically producing highly pure gallium |
Country Status (7)
Country | Link |
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US (2) | US3170856A (en) |
AT (1) | AT249389B (en) |
CH (2) | CH409415A (en) |
DE (2) | DE1141461B (en) |
FR (2) | FR1306202A (en) |
GB (2) | GB913325A (en) |
NL (1) | NL6403726A (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3897317A (en) * | 1974-06-24 | 1975-07-29 | Texas Instruments Inc | Process for making hyperpure gallium |
Citations (6)
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US2440238A (en) * | 1942-12-09 | 1948-04-27 | Harold R Alley | Means for producing mercury electrolytically from acid solutions |
US2928731A (en) * | 1955-09-06 | 1960-03-15 | Siemens Ag | Continuous process for purifying gallium |
US2952589A (en) * | 1956-04-09 | 1960-09-13 | Karl Ziegler | Purification of aluminum |
US2985568A (en) * | 1954-11-26 | 1961-05-23 | Ziegler | Electrolytic process for the production of metal alkyls |
US2998374A (en) * | 1959-02-09 | 1961-08-29 | Goodyear Tire & Rubber | Container linings |
US3007858A (en) * | 1959-05-06 | 1961-11-07 | Nalco Chemical Co | Preparation of organo metallic compounds |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3170857A (en) * | 1963-03-28 | 1965-02-23 | Siemens Ag | Method for producing gallium, particularly for semiconductor purposes |
-
1960
- 1960-09-30 DE DES70729A patent/DE1141461B/en active Pending
-
1961
- 1961-08-08 CH CH929261A patent/CH409415A/en unknown
- 1961-09-28 GB GB34991/61A patent/GB913325A/en not_active Expired
- 1961-09-28 US US141381A patent/US3170856A/en not_active Expired - Lifetime
- 1961-09-29 FR FR874595A patent/FR1306202A/en not_active Expired
-
1963
- 1963-06-15 DE DES85697A patent/DE1183249B/en active Pending
-
1964
- 1964-03-18 CH CH353164A patent/CH478246A/en not_active IP Right Cessation
- 1964-04-08 NL NL6403726A patent/NL6403726A/en unknown
- 1964-04-16 AT AT334564A patent/AT249389B/en active
- 1964-06-11 FR FR977958A patent/FR86816E/en not_active Expired
- 1964-06-12 GB GB24618/64A patent/GB1013997A/en not_active Expired
- 1964-06-15 US US375211A patent/US3325380A/en not_active Expired - Lifetime
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
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US2440238A (en) * | 1942-12-09 | 1948-04-27 | Harold R Alley | Means for producing mercury electrolytically from acid solutions |
US2985568A (en) * | 1954-11-26 | 1961-05-23 | Ziegler | Electrolytic process for the production of metal alkyls |
US2928731A (en) * | 1955-09-06 | 1960-03-15 | Siemens Ag | Continuous process for purifying gallium |
US2952589A (en) * | 1956-04-09 | 1960-09-13 | Karl Ziegler | Purification of aluminum |
US2998374A (en) * | 1959-02-09 | 1961-08-29 | Goodyear Tire & Rubber | Container linings |
US3007858A (en) * | 1959-05-06 | 1961-11-07 | Nalco Chemical Co | Preparation of organo metallic compounds |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3897317A (en) * | 1974-06-24 | 1975-07-29 | Texas Instruments Inc | Process for making hyperpure gallium |
Also Published As
Publication number | Publication date |
---|---|
AT249389B (en) | 1966-09-26 |
NL6403726A (en) | 1964-12-16 |
US3325380A (en) | 1967-06-13 |
DE1141461B (en) | 1962-12-20 |
GB1013997A (en) | 1965-12-22 |
DE1183249B (en) | 1964-12-10 |
FR1306202A (en) | 1962-10-13 |
CH409415A (en) | 1966-03-15 |
CH478246A (en) | 1969-09-15 |
GB913325A (en) | 1962-12-19 |
FR86816E (en) | 1966-04-22 |
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