EP0570308B1 - Legierungen aus Metall mit hohen Schmelzpunkten geeignet für die Umwandlung in homogene und rein Blöcke, und Herstellungsverfahren dieser Legierungen - Google Patents
Legierungen aus Metall mit hohen Schmelzpunkten geeignet für die Umwandlung in homogene und rein Blöcke, und Herstellungsverfahren dieser Legierungen Download PDFInfo
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- EP0570308B1 EP0570308B1 EP93420192A EP93420192A EP0570308B1 EP 0570308 B1 EP0570308 B1 EP 0570308B1 EP 93420192 A EP93420192 A EP 93420192A EP 93420192 A EP93420192 A EP 93420192A EP 0570308 B1 EP0570308 B1 EP 0570308B1
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- metals
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- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 62
- 239000000956 alloy Substances 0.000 title claims abstract description 62
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 56
- 239000002184 metal Substances 0.000 title claims abstract description 56
- 150000002739 metals Chemical class 0.000 title claims abstract description 30
- 230000008018 melting Effects 0.000 title claims description 8
- 238000002844 melting Methods 0.000 title claims description 8
- 230000009466 transformation Effects 0.000 title description 5
- 238000002360 preparation method Methods 0.000 title 1
- 230000008021 deposition Effects 0.000 claims abstract description 17
- 239000013078 crystal Substances 0.000 claims abstract description 13
- 150000003839 salts Chemical class 0.000 claims abstract description 9
- 239000006104 solid solution Substances 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims description 22
- 238000005868 electrolysis reaction Methods 0.000 claims description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 13
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 10
- 150000004820 halides Chemical class 0.000 claims description 10
- 150000001805 chlorine compounds Chemical class 0.000 claims description 9
- 229910002804 graphite Inorganic materials 0.000 claims description 9
- 239000010439 graphite Substances 0.000 claims description 9
- 229910052731 fluorine Inorganic materials 0.000 claims description 8
- 239000011737 fluorine Substances 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- 239000003870 refractory metal Substances 0.000 claims description 6
- 238000007711 solidification Methods 0.000 claims description 6
- 230000008023 solidification Effects 0.000 claims description 6
- 229910021645 metal ion Inorganic materials 0.000 claims description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- 239000000243 solution Substances 0.000 claims description 3
- 239000000470 constituent Substances 0.000 claims description 2
- 229910001092 metal group alloy Inorganic materials 0.000 claims description 2
- 229910018957 MClx Inorganic materials 0.000 claims 2
- 229910001514 alkali metal chloride Inorganic materials 0.000 claims 2
- 229910020012 Nb—Ti Inorganic materials 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 150000003841 chloride salts Chemical class 0.000 abstract 2
- 238000000151 deposition Methods 0.000 description 13
- 239000010955 niobium Substances 0.000 description 12
- 150000002500 ions Chemical class 0.000 description 10
- 229910052726 zirconium Inorganic materials 0.000 description 10
- 241000243142 Porifera Species 0.000 description 9
- 239000010936 titanium Substances 0.000 description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 229910052735 hafnium Inorganic materials 0.000 description 6
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 230000004927 fusion Effects 0.000 description 5
- 229910052758 niobium Inorganic materials 0.000 description 5
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- 229910052708 sodium Inorganic materials 0.000 description 5
- 229920000049 Carbon (fiber) Polymers 0.000 description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 4
- 241000287107 Passer Species 0.000 description 4
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000004917 carbon fiber Substances 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 3
- 229910001275 Niobium-titanium Inorganic materials 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 238000001000 micrograph Methods 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- RJSRQTFBFAJJIL-UHFFFAOYSA-N niobium titanium Chemical compound [Ti].[Nb] RJSRQTFBFAJJIL-UHFFFAOYSA-N 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- 229910052720 vanadium Inorganic materials 0.000 description 3
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 241001080024 Telles Species 0.000 description 2
- 229910001069 Ti alloy Inorganic materials 0.000 description 2
- 229910001093 Zr alloy Inorganic materials 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- INIGCWGJTZDVRY-UHFFFAOYSA-N hafnium zirconium Chemical compound [Zr].[Hf] INIGCWGJTZDVRY-UHFFFAOYSA-N 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- -1 niobium-titanium-aluminum Chemical compound 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- YHBDIEWMOMLKOO-UHFFFAOYSA-I pentachloroniobium Chemical compound Cl[Nb](Cl)(Cl)(Cl)Cl YHBDIEWMOMLKOO-UHFFFAOYSA-I 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 229910003865 HfCl4 Inorganic materials 0.000 description 1
- 229910019804 NbCl5 Inorganic materials 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910001362 Ta alloys Inorganic materials 0.000 description 1
- 229910007926 ZrCl Inorganic materials 0.000 description 1
- 229910007932 ZrCl4 Inorganic materials 0.000 description 1
- JODOMBGKVAIYRQ-UHFFFAOYSA-N [Nb].[Ta].[Ti] Chemical compound [Nb].[Ta].[Ti] JODOMBGKVAIYRQ-UHFFFAOYSA-N 0.000 description 1
- VSTCOQVDTHKMFV-UHFFFAOYSA-N [Ti].[Hf] Chemical compound [Ti].[Hf] VSTCOQVDTHKMFV-UHFFFAOYSA-N 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 230000002925 chemical effect Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- PDPJQWYGJJBYLF-UHFFFAOYSA-J hafnium tetrachloride Chemical compound Cl[Hf](Cl)(Cl)Cl PDPJQWYGJJBYLF-UHFFFAOYSA-J 0.000 description 1
- 229910001055 inconels 600 Inorganic materials 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 229910001338 liquidmetal Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910001510 metal chloride Inorganic materials 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- RHDUVDHGVHBHCL-UHFFFAOYSA-N niobium tantalum Chemical compound [Nb].[Ta] RHDUVDHGVHBHCL-UHFFFAOYSA-N 0.000 description 1
- XTLMLBGRGAHTQE-UHFFFAOYSA-N niobium zirconium Chemical compound [Zr].[Nb].[Nb].[Nb] XTLMLBGRGAHTQE-UHFFFAOYSA-N 0.000 description 1
- 239000003758 nuclear fuel Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- BUKHSQBUKZIMLB-UHFFFAOYSA-L potassium;sodium;dichloride Chemical compound [Na+].[Cl-].[Cl-].[K+] BUKHSQBUKZIMLB-UHFFFAOYSA-L 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000012958 reprocessing Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 229910000601 superalloy Inorganic materials 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- VSSLEOGOUUKTNN-UHFFFAOYSA-N tantalum titanium Chemical compound [Ti].[Ta] VSSLEOGOUUKTNN-UHFFFAOYSA-N 0.000 description 1
- GFNGCDBZVSLSFT-UHFFFAOYSA-N titanium vanadium Chemical compound [Ti].[V] GFNGCDBZVSLSFT-UHFFFAOYSA-N 0.000 description 1
- 230000001131 transforming effect Effects 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 235000015041 whisky Nutrition 0.000 description 1
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 1
Images
Classifications
-
- 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
- C25C3/36—Alloys obtained by cathodic reduction of all their ions
Definitions
- the present invention relates to alloys of refractory metals suitable for transformation into homogeneous and pure ingots and to processes for obtaining said alloys.
- alloys formed from refractory metals having different melting temperatures of at least 200 ° C. such as for example the hafnium-zirconium, hafnium-titanium, niobium-titanium, niobiumzirconium, tantalum-titanium, tantalum alloys -zirconium, tantalum-niobium, niobium-tantalum-titanium and niobium-titanium-aluminum.
- these alloys have weight compositions such that their starting solidification temperature is at least 150 ° C. lower than the solidification temperature of the least fusible metal.
- alloys obtained initially in more or less divided form are then subjected to at least one operation of fusion so as to transform them into ingots.
- ingots can then be rolled in the form of sheets intended for the manufacture of nuclear fuel reprocessing containers in the case of Hf-Zr alloys or of neutron retarders in the case of Hf-Ti alloys or else of superconductive compounds or superalloys aeronautics in the case of the Nb-Ti alloy.
- the object of the invention is to obtain alloys having a homogeneous structure at the level of the elementary crystal, an improved purity compared to that of the products of the prior art and a suitable particle size so that they can be fully melted and transformed. in ingots in which this homogeneity of structure and purity is maintained.
- the invention relates to alloys of refractory metals suitable for transformation into homogeneous ingots of purity greater than 99.9%, the melting temperatures of which differ from each other by at least 200 ° C. and whose weight proportions are such that for each alloy the starting solidification temperature is more than 150 ° C lower than the solidification temperature of the least meltable metal in the form of agglomerates, characterized in that these agglomerates of dimensions between 0.2 and 30mm are composed crystals with a specific surface of between 0.005 and 0.2 m 2 / g, having a size of 0.1 to 1 mm and in which the metals are in the form of a solid solution, that is to say that they are homogeneous on the atomic scale and at most have a relative deviation of composition of 20% from the average composition of the alloy so that this homogeneity remains during the melting and gives the ingots obtained identical properties at all points.
- these crystals and their agglomerates have a size and a specific surface such that the problems of spontaneous oxidation which arise when this surface is too large or of shaping of the products before fusion when this size is too large are avoided. , and such that the dissolution in the liquid metal is promoted. Hence the absence of any pollution of these products, not oxygen and iron, in particular during grinding operations, and the possibility of obtaining ingots of high purity ingots.
- the crystals have a specific surface of between 0.01 and 0.05 m 2 / g and the agglomerates have dimensions of between 1.5 and 12mm because it is within these ranges that the homogeneities and the maximum purities are obtained.
- the invention also relates to methods for obtaining said alloys.
- the technique for obtaining the alloy varies as a function of the difference in deposition potential of each of the elements of the alloy.
- a first technique is applicable to metals whose electrolytic deposition potentials are very little different from each other, that is to say when they have a difference between them less than 0.5 volt while a second technique relates to metals whose difference in deposition potentials is at least equal to this value.
- the obtaining process consists in using an igneous electrolysis cell containing a bath of molten salts based on alkali chlorides and at least one fluoride ion in an amount between 1.5 and 5% by weight of the weight of the bath in which a measurement electrode is at least partially immersed in relation to a reference electrode which are used to measure a potential for controlling electrolysis, an anode assembly provided with a diaphragm based on carbon fibers and graphite, a cathode to which a difference in continuous potential is applied with respect to said assembly, an injector of material to be electrolyzed and of inert gas, characterized in that one introduces simultaneously in the injector the metals in the form of gaseous chlorides in proportions corresponding to those of said alloy and in an amount such as the molar ratio of fluorine contained in the bath at the quantity of metals introduced is between 2.5 and 15, the value of the control potential known as the reference
- the method consists in carrying out electrolysis in a cell equipped with a control device.
- an anode assembly is also used, provided with a particular diaphragm and as described in US Pat. No. 5,064,513.
- This diaphragm is formed by carbon fibers embedded in a rigid graphite-based material and has the property of having a porosity of determined value which allows easier conduct of the electrolysis and obtaining a metallic deposit of regular structure.
- the merit of the Applicant has been to show that these advantages are achieved when several types of ions are used simultaneously.
- the method also uses an injector such as that described in French patent 2653139 and which has the effect of maintaining the weight concentration of the bath within a limited range and of adjusting it gradually and precisely.
- This has the advantage in the present case of being able to more easily control the conditions for obtaining a deposit where the proportions of the different metals must be included within narrow limits.
- an igneous electrolysis cell containing a bath of molten salts based on alkali chlorides and at least one fluoride ion in an amount between 1 and 3% by weight of the bath in which are at least partially immersed a control electrode in relation to a reference electrode which are used to measure a control potential, an anode assembly provided with a diahragm based on carbon fibers and graphite, a cathode of deposit to which a continuous potential difference E1 is applied with respect to said assembly, an injector of material to be electrolyzed and of inert gas characterized in that a positively polarized electrode consisting of the most electronegative metal is introduced into the bath, and by the negatively polarized injector the halide of the most electropositive metal of the alloy to be deposited, a positive potential difference E2 is established between ladi te electrode and the injector so that the metal of the electrode goes into solution in the bath, the concentrations of metal ions in the bath are adjusted so
- the invention consists in combining the teaching of the three patents mentioned above in the same igneous electrolysis cell, but it differs from it in that at the filing of at least one metal by electrolytic reduction of its halide is associated with a deposit obtained from metal ions resulting in part from an anodic dissolution.
- This type of process is also applicable to the case of two metals having close deposition potentials but since the chemical dissolution is then relatively low, it is necessary to strongly polarize the soluble anode to obtain the suitable concentration in the bath.
- said crystals are washed with water to remove the salts present in the bath and then formed into ingots by fusion using a suitable means such as, for example, an arc furnace , induction, electron bombardment, inductive plasma or arc plasma.
- a suitable means such as, for example, an arc furnace , induction, electron bombardment, inductive plasma or arc plasma.
- the invention finds its application in obtaining alloys of refractory metals of very high purity having very good homogeneity on the microscopic scale.
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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 Metals (AREA)
- Manufacture And Refinement Of Metals (AREA)
Claims (5)
- Legierungen hochschmelzender Metalle mit Eignung zur Umwandlung in homogene Blöcke einer Reinheit über 99,9 %, die aus hochschmelzenden Metallen zusammengesetzt sind, deren Schmelztemperaturen voneinander um wenigstens 200 °C verschieden sind und deren Gewichtsanteile derart sind, daß für jede Legierung die Erstarrungsbeginntemperatur mehr als 150 °C unter der Erstarrungstemperatur des am wenigsten schmelzbaren Metalls ist, und die eine Form von Agglomeraten aufweisen,
dadurch gekennzeichnet,
daß diese Agglomerate von Abmessungen im Bereich von 0,2 bis 30 mm aus Kristallen einer spezifischen Oberfläche im Bereich von 0,005 bis 0,2 m2/g mit einer Größe von 0,1 bis 1 mm zusammengesetzt sind, wobei in ihnen die Metalle im Festlösungszustand sind, d.h. daß sie im atomaren Maßstab homogen sind und höchstens eine Relativzusammensetzungsabweichung von 20 % bezüglich der mittleren Zusammensetzung der Legierung aufweisen und daß sie frei von makroskopischen Gemischzonen ungeschmolzener Bestandteile sind. - Legierungen nach dem Anspruch 1,
dadurch gekennzeichnet,
daß die Kristalle eine spezifische Oberfläche im Bereich von 0,01 bis 0,05 m2/g haben. - Legierungen nach dem Anspruch 1,
dadurch gekennzeichnet,
daß die Agglomerate eine Abmessung im Bereich von 1,5 bis 12 mm haben. - Verfahren zur Herstellung von Legierungen nach dem Anspruch 1, bei dem die Metalle Abscheidungspotentiale haben, die sich untereinander um weniger als 0,5 Volt unterscheiden, und wo man eine Schmelzflußelektrolysezelle (1) einsetzt, die ein Bad (2) von geschmolzenen Salzen auf Basis von Alkalimetallchloriden und wenigstens eines Fluoridions in einer Menge von 1,5 bis 5 Gew.% des Gewichts des Bades enthält, in das wenigstens teilweise eine Meßelektrode (12) in Beziehung mit einer Bezugselektrode, die zum Messen eines Steuerpotentials der Elektrolyse dienen, eine mit einem Diaphragma (6) auf Basis von Fasern aus Kohlenstoff und Graphit ausgestattete Anodeneinheit (5), eine Kathode (10), an die man eine gleichbleibende Potentialdifferenz bezüglich dieser Einheit anlegt, und ein Injektor (8) für zu elektrolysierendes Material und Inertgas eingetaucht sind,
dadurch gekennzeichnet,
daß man gleichzeitig in den Injektor die Metalle in Form gasförmiger Chloride in denen der Legierung entsprechenden Anteilen und in solcher Menge einführt, daß das Molverhältnis des im Bad enthaltenen Fluors zur Menge der eingeführten Metalle im Bereich von 2,5 bis 15 ist, man den Einstellpotential genannten Wert des Steuerpotentials feststellt und man bei Fortsetzung des Einführens der Chloride in den Injektor in gewolltem Anteil und in solcher Menge, daß das an der Steuerelektrode gemessene Potential im Absolutwert nahe dem Absolutwert des Einstellpotentials bleibt, an der Kathode die Metalle in Legierungsform abscheidet. - Verfahren zur Herstellung von Legierungen nach dem Anspruch 1, bei dem die Metalle Abscheidungspotentiale haben, die sich untereinander um wenigstens 0,5 Volt unterscheiden, und wo man eine Schmelzflußelektrolysezelle (21) einsetzt, die ein Bad (22) von geschmolzenen Salzen auf Basis von Alkalimetallchloriden und wenigstens eines Fluoridions in einer Menge von 1 bis 3 Gew.% des Gewichts des Bades enthält, in das wenigstens teilweise eine Steuerelektrode (33) in Beziehung mit einer Bezugselektrode, die zum Messen eines Steuerpotentials dienen, eine mit einem Diaphragma (26) auf Basis von Fasern aus Kohlenstoff und Graphit ausgestattete Anodeneinheit (25), eine Abscheidekathode (31), an die man eine gleichbleibende Potentialdifferenz El bezüglich dieser Einheit anlegt, und ein Injektor (29) für zu elektrolysierendes Material und Inertgas eingetaucht sind,
dadurch gekennzeichnet,
daß man in das Bad eine positiv polarisierte, aus dem elektronegativsten Metall der abzuscheidenden Legierung bestehende Elektrode (28) und durch den negativ polarisierten Injektor (29) das Halogenid des elektropositivsten Metalls der abzuscheidenden Legierung einführt und daß man eine positive Potentialdifferenz E2 zwischen dieser Elektrode und dem Injektor derart einrichtet, daß Metall der Elektrode (28) im Bad in Lösung geht, man die Konzentrationen an Metallionen im Bad derart einstellt, um ein Verhältnis in Beziehung mit dem der gewünschten Legierung und eine solche Menge zu haben, daß das Molverhältnis des im Bad enthaltenen Fluors zur Menge der vorhandenen Metalle im Bereich von 2,5 bis 15 liegt, man den Einstellpotential genannten Wert des Steuerpotentials feststellt und man bei Fortsetzung des Einführens des Chlorids in den Injektor und des Haltens der Potentialdifferenz E2 derart, daß das an der Steuerelektrode gemessene Potential im Absolutwert nahe dem Absolutwert des Einstellpotentials bleibt und daß E2 dem Durchgang von wenigstens X/2 Faraday je Mol von in das Bad eingeführtem MClx entspricht, wobei M das am wenigsten elektronegative Metall ist und x seine Wertigkeit ist, und daß E1 dem Durchgang von wenigstens 1/2 Faraday je Mol von MClx entspricht, an der Kathode die Metalle in Legierungsform abscheidet.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR9206233 | 1992-05-12 | ||
| FR929206233A FR2691169B1 (fr) | 1992-05-12 | 1992-05-12 | Alliages de metaux refractaires aptes a la transformation en lingots homogenes et purs et procedes d'obtention des dits alliages. |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0570308A1 EP0570308A1 (de) | 1993-11-18 |
| EP0570308B1 true EP0570308B1 (de) | 1996-12-27 |
Family
ID=9430049
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP93420192A Expired - Lifetime EP0570308B1 (de) | 1992-05-12 | 1993-05-11 | Legierungen aus Metall mit hohen Schmelzpunkten geeignet für die Umwandlung in homogene und rein Blöcke, und Herstellungsverfahren dieser Legierungen |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US5372659A (de) |
| EP (1) | EP0570308B1 (de) |
| JP (1) | JP2863058B2 (de) |
| AT (1) | ATE146828T1 (de) |
| BR (1) | BR9301808A (de) |
| DE (1) | DE69306853T2 (de) |
| FR (1) | FR2691169B1 (de) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3582437B2 (ja) * | 1999-12-24 | 2004-10-27 | 株式会社村田製作所 | 薄膜製造方法及びそれに用いる薄膜製造装置 |
| US20030227068A1 (en) * | 2001-05-31 | 2003-12-11 | Jianxing Li | Sputtering target |
| US6833058B1 (en) * | 2000-10-24 | 2004-12-21 | Honeywell International Inc. | Titanium-based and zirconium-based mixed materials and sputtering targets |
| US20040123920A1 (en) * | 2002-10-08 | 2004-07-01 | Thomas Michael E. | Homogenous solid solution alloys for sputter-deposited thin films |
| US20130178627A1 (en) | 2011-07-21 | 2013-07-11 | Robert A. Freitas, JR. | Methods, Systems and Workpieces Using Mechanosynthesis |
| US10308514B2 (en) | 2007-09-07 | 2019-06-04 | Cbn Nano Technologies Inc. | Systems and methods for the manufacture of atomically-precise products |
| US9244097B1 (en) | 2007-09-07 | 2016-01-26 | Robert A. Freitas, JR. | Mechanosynthetic tools for a atomic-scale fabrication |
| US8171568B2 (en) | 2007-09-07 | 2012-05-01 | Freitas Robert A | Positional diamondoid mechanosynthesis |
| CN101994045B (zh) * | 2010-12-10 | 2012-07-11 | 西南铝业（集团）有限责任公司 | 一种铝锆中间合金的制备方法 |
| CN102268620A (zh) * | 2011-08-01 | 2011-12-07 | 南昌大学 | 一种Al3Ti颗粒增强Al-Zn-Mg-Cu基铝合金的固溶处理方法 |
| CN102212710B (zh) * | 2011-08-02 | 2013-02-13 | 江苏中欧材料研究院有限公司 | 一种原位亚微米多元颗粒增强铝基复合新体系及材料 |
| CN102268621B (zh) * | 2011-09-09 | 2013-03-20 | 西南铝业（集团）有限责任公司 | 一种铝合金棒材生产方法 |
| CN102409270A (zh) * | 2011-11-07 | 2012-04-11 | 内蒙古北方重工业集团有限公司 | 一种大型铝合金环件轧制和电炉固溶处理方法 |
| US9676677B2 (en) | 2013-02-28 | 2017-06-13 | Robert A. Freitas, JR. | Build sequences for mechanosynthesis |
| US10197597B2 (en) | 2013-02-28 | 2019-02-05 | Cbn Nano Technologies Inc. | Build sequences for mechanosynthesis |
| CN103160863B (zh) * | 2013-03-25 | 2016-01-20 | 上海大学 | 一种铌精矿熔融氧化物电解制备铌铁合金的方法 |
| CN104451317A (zh) * | 2013-09-22 | 2015-03-25 | 北京有色金属研究总院 | 一种铪基混合金属材料及其碘化制备方法 |
| US10067160B2 (en) | 2016-11-16 | 2018-09-04 | CBN Nano Technologies, Inc. | Sequential tip systems and methods for positionally controlled chemistry |
| US11708384B2 (en) | 2016-05-12 | 2023-07-25 | Cbn Nano Technologies Inc. | Systems and methods for mechanosynthesis |
| US10072031B1 (en) | 2016-05-12 | 2018-09-11 | CBN Nano Technologies, Inc. | Systems and methods for mechanosynthesis |
| US10822229B2 (en) | 2016-11-16 | 2020-11-03 | Cbn Nano Technologies Inc. | Systems and methods for mechanosynthesis |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1077878B (de) * | 1952-10-04 | 1960-03-17 | Norton Ges M B H Deutsche | Verfahren zur Herstellung von Zirkonium, Hafnium oder von Gemischen dieser Metalle durch Schmelzflusselektrolyse |
| FR1216255A (fr) * | 1957-03-20 | 1960-04-25 | Internat Metallurg Corp | Perfectionnements à l'obtention de métaux polyvalents |
| US2985531A (en) * | 1959-06-05 | 1961-05-23 | Univ Ohio State Res Found | Niobium-zirconium base alloy |
| NL302728A (de) * | 1963-02-18 | |||
| GB1095925A (en) * | 1965-12-02 | 1967-12-20 | Imp Metal Ind Kynoch Ltd | Hafnium alloys |
| CH492793A (de) * | 1967-04-12 | 1970-06-30 | Starck Hermann C Fa | Herstellung von Legierungen oder Gemischen des Tantals bzw. Niobs |
| US3637374A (en) * | 1968-05-27 | 1972-01-25 | Fansteel Metallurgical Corp | Method of producing tungsten rhenium alloys by chemical vapor deposition |
| JPS6052538A (ja) * | 1983-08-31 | 1985-03-25 | Sumitomo Metal Ind Ltd | Ζｒ基Νｂ合金の溶解法 |
| FR2579629B1 (fr) * | 1985-03-28 | 1987-05-07 | Pechiney | Procede de controle en continu de la teneur en metal dissous dans un bain de sels fondus et son application a l'alimentation continue d'une cellule d'electrolyse en sels dudit metal |
| FR2634938B1 (fr) * | 1988-07-28 | 1990-09-21 | Cezus Co Europ Zirconium | Procede de fabrication d'un element metallique absorbeur de neutrons et element obtenu |
| FR2643653B1 (fr) * | 1989-02-28 | 1991-05-03 | Cezus Co Europ Zirconium | Diaphragme pour electrolyse en bain de sels fondus d'halogenures de metaux |
| EP0396821B1 (de) * | 1989-05-08 | 1994-06-15 | Sumitomo Metal Industries, Ltd. | Legierung auf Zirkon-Basis mit erhöhter Beständigkeit gegen Korrosion durch Salpetersäure und mit guter Kriechbeständigkeit |
| FR2653139B1 (fr) * | 1989-10-17 | 1991-12-13 | Cezus Co Europ Zirconium | Procede et dispositif d'introduction d'au moins un halogenure a l'etat liquide ou gazeux dans le bain d'une cellule d'electrolyse ignee. |
-
1992
- 1992-05-12 FR FR929206233A patent/FR2691169B1/fr not_active Expired - Fee Related
-
1993
- 1993-05-11 US US08/059,287 patent/US5372659A/en not_active Expired - Fee Related
- 1993-05-11 EP EP93420192A patent/EP0570308B1/de not_active Expired - Lifetime
- 1993-05-11 BR BR939301808A patent/BR9301808A/pt not_active IP Right Cessation
- 1993-05-11 AT AT93420192T patent/ATE146828T1/de not_active IP Right Cessation
- 1993-05-11 DE DE69306853T patent/DE69306853T2/de not_active Expired - Fee Related
- 1993-05-12 JP JP5110465A patent/JP2863058B2/ja not_active Expired - Lifetime
Non-Patent Citations (1)
| Title |
|---|
| CHEMICAL ABSTRACTS, vol. 86, no. 8, 21 Février 1977, Columbus, Ohio, US; abstract no. 48583, 'Alloys by electrolysis' page 336; colonne 1; & SU-A-533 677 (VOLEINIK ET AL.) * |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2863058B2 (ja) | 1999-03-03 |
| JPH0633161A (ja) | 1994-02-08 |
| EP0570308A1 (de) | 1993-11-18 |
| BR9301808A (pt) | 1994-03-01 |
| DE69306853T2 (de) | 1997-05-07 |
| FR2691169A1 (fr) | 1993-11-19 |
| FR2691169B1 (fr) | 1994-07-01 |
| DE69306853D1 (de) | 1997-02-06 |
| US5372659A (en) | 1994-12-13 |
| ATE146828T1 (de) | 1997-01-15 |
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