EP0570308B1 - Alloys of metals with high melting points, suitable for transformation into homogeneous and pure ingost, and preparation process of these alloys - Google Patents
Alloys of metals with high melting points, suitable for transformation into homogeneous and pure ingost, and preparation process of these alloys 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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- 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
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Classifications
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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
- C25C3/36—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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- Organic Chemistry (AREA)
- Electrolytic Production Of Metals (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
Description
La présente invention est relative à des alliages de métaux réfractaires aptes à la transformation en lingots homogènes et purs et à des procédés d'obtention des dits alliages.The present invention relates to alloys of refractory metals suitable for transformation into homogeneous and pure ingots and to processes for obtaining said alloys.
Elle concerne plus particulièrement les alliages formés à partir de métaux réfractaires ayant des températures de fusion différentes d'au moins 200°C, comme par exemple les alliages hafnium-zirconium, hafnium-titane, niobium-titane, niobiumzirconium, tantale-titane, tantale-zirconium, tantale-niobium, niobium-tantale-titane et niobium-titane-aluminium.It relates more particularly to 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.
Plus précisément, ces alliages ont des compositions pondérales telles que leur température de solidification commençante est inférieure d'au moins 150°C à la température de solidification du métal le moins fusible.More specifically, 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.
Ces alliages obtenus initialement sous forme plus ou moins divisée sont ensuite soumis à au moins une opération de fusion de façon à les transformer en lingots.These 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.
Ces lingots peuvent alors être laminés sous forme de tôles destinées à la fabrication de conteneurs de retraitement de combustibles nucléaires dans le cas des alliages Hf-Zr ou de ralentisseurs de neutrons dans le cas des alliages Hf-Ti ou encore de composés supraconducteurs ou de superalliages aéronautiques dans le cas de l'alliage Nb-Ti.These 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.
II est connu que de tels alliages peuvent être obtenus par différents procédés tels que :
- la coaluminothermie des oxydes qui a l'inconvénient de conduire à des alliages souillés par de l'aluminium et de l'oxygène et qui se présentent sous forme de blocs massifs qu'il faut concasser avant de les purifier par bombardement électronique et de les transformer en lingots.
- La coréduction des chlorures par un métal comme le sodium ou le magnésium qui donne lieu à la formation d'éponges fortement polluées par l'agent réducteur ainsi que par du fer et des ions chlorures et qu'il faut également concasser.
Pour améliorer la pureté et l'homogénéité de ce type d'alliage avant transformation en lingot, il est possible de procéder à un affinage électrolytique en milieu halogénure fondu par dépôt cathodique dudit alliage à l'état particulaire utilisé comme anode soluble. Ainsi selon FR 1216255 on peut obtenir par dépôt sur une cathode inerte un alliage de titane contenant de 1 à 10% de vanadium, sous forme de cristaux enchevêtrés avec moins de 0,03% d'oxygène, par électrolyse en milieu NaCI fondu d'une anode constituée par une éponge broyée de titane vanadium résultant de la coréduction par le sodium des chlorures métalliques correspondants. - La codéposition en phase vapeur qui fournit des whiskers très pyrophoriques, difficiles à manipuler qu'il faut compacter avant fusion.
- La mécano-synthèse ou cobroyage des métaux à allier qui aboutit à des particules de granulométrie relativement grossière et fortement polluées et à l'obtention lors de la fusion d'un produit hétérogène dû à la présence d'infondus du métal le moins fusible.
- the coaluminothermy of oxides which has the disadvantage of leading to alloys contaminated by aluminum and oxygen and which are in the form of massive blocks which must be crushed before being purified by electron bombardment and transforming them in ingots.
- The co-reduction of chlorides by a metal such as sodium or magnesium which gives rise to the formation of sponges highly polluted by the reducing agent as well as by iron and chloride ions and which must also be crushed.
To improve the purity and homogeneity of this type of alloy before transformation into an ingot, it is possible to carry out an electrolytic refining in a molten halide medium by cathodic deposition of said alloy in the particulate state used as soluble anode. Thus, according to FR 1216255, a titanium alloy containing 1 to 10% vanadium, in the form of crystals entangled with less than 0.03% oxygen, can be obtained by deposition on an inert cathode, by electrolysis in a molten NaCl medium of an anode consisting of a ground sponge of titanium vanadium resulting from the co-reduction by sodium of the corresponding metal chlorides. - Codeposition in the vapor phase which provides very pyrophoric whiskeys, difficult to handle which must be compacted before melting.
- Mechanical synthesis or co-grinding of the metals to be alloyed, which results in relatively coarse-grained and highly polluted particles and on obtaining during the melting of a heterogeneous product due to the presence of fuses of the least fusible metal.
Le but de l'invention est d'obtenir des alliages ayant une structure homogène au niveau du cristal élémentaire, une pureté améliorée par rapport à celle des produits de l'art antérieur et une granulométrie convenable afin qu'ils puissent être fondus intégralement et transformés en lingots dans lesquels cette homogénéité de structure et de pureté est maintenue.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.
L'invention est relative à des alliages de métaux réfractaires aptes à la transformation en lingots homogènes de pureté supérieure à 99,9% dont les températures de fusion diffèrent entre elles d'au moins 200°C et dont les proportions pondérales sont telles que pour chaque alliage la température de solidification commençante est inférieure de plus de 150°C à la température de solidification du métal le moins fusible se présentant sous forme d'agglomérats, caractérisés en ce que ces agglomérats de dimensions comprises entre 0,2 et 30mm sont composés de cristaux de surface spécifique comprise entre 0,005 et 0,2 m2/g, ayant une taille de 0,1 à 1 mm et dans lesquels les métaux sont à l'état de solution solide, c'est-à-dire qu'ils sont homogènes à l'échelle atomique et ne présentent tout au plus qu'un écart relatif de composition de 20% par rapport à la composition moyenne de l'alliage de sorte que cette homogénéité subsiste au cours de la fusion et confère aux lingots obtenus des propriétés identiques en tout point.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.
C'est là une différence importante avec les alliages obtenus par fusion d'un mélange des constituants où les infondus forment des zones macroscopiques pouvant atteindre des dimensions de plusieurs millimètres et où notamment quand il s'agit de métaux de densité très différente, il se produit des phénomènes de décantation importants.This is an important difference with the alloys obtained by melting a mixture of the constituents where the undesirable forms macroscopic zones which can reach dimensions of several millimeters and where in particular when metals of very different densities are involved, significant settling occurs.
De plus, ces cristaux et leurs agglomérats ont une taille et une surface spécifique telles qu'on évite les problèmes d'oxydation spontanée qui se posent quand cette surface est trop grande ou de mise en forme des produits avant fusion quand cette taille est trop grande, et telle qu'on favorise la dissolution dans le métal liquide. D'où l'absence de toute pollution de ces produits pas l'oxygène et le fer, en particulier lors des opérations de broyage, et la possibilité d'obtenir par fusion des lingots de grande pureté.In addition, 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.
De préférence, les cristaux ont une surface spécifique comprise entre 0,01 et 0,05 m2/g et les agglomérats ont des dimensions comprises entre 1,5 et 12mm car c'est à l'intérieur de ces fourchettes que les homogénéités et les puretés maxima sont obtenues.Preferably, 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.
L'invention concerne également des procédés d'obtention desdits alliages.The invention also relates to methods for obtaining said alloys.
Ces procédés sont basés sur la coélectrodéposition, c'est-à-dire le dépôt électrolytique simultané des éléments formant l'alliage.These methods are based on co-electrodeposition, that is to say the simultaneous electrolytic deposition of the elements forming the alloy.
Toutefois, la technique d'obtention de l'alliage varie en fonction de la différence de potentiel de dépôt de chacun des éléments de l'alliage.However, the technique for obtaining the alloy varies as a function of the difference in deposition potential of each of the elements of the alloy.
Une première technique est applicable aux métaux dont les potentiels de dépôt électrolytique sont très peu différents l'un de l'autre, c'est-à-dire quand ils présentent entre eux un écart inférieur à 0,5 volt tandis qu'une seconde technique est relative aux métaux dont la différence des potentiels de dépôt est au moins égale à cette valeur.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.
Dans le premier cas, qui concerne plus particulièrement les alliages hafnium-zirconium, le procédé d'obtention consiste à mettre en oeuvre une cellule d'électrolyse ignée contenant un bain de sels fondus à base de chlorures alcalins et d'au moins un ion fluorure en quantité comprise en poids entre 1,5 et 5% du poids du bain dans lequel sont au moins partiellement immergés une électrode de mesure en relation avec une électrode de référence qui servent à mesurer un potentiel de contrôle de l'électrolyse, un ensemble anodique muni d'un diaphragme à base de fibres de carbone et de graphite, une cathode à laquelle on applique une différence de potentiel continue par rapport audit ensemble, un injecteur de matière à électrolyser et de gaz inerte, caractérisé en ce que l'on introduit simultanément dans l'injecteur les métaux sous forme de chlorures gazeux dans des proportions correspondant à celles dudit alliage et en quantité telle que le rapport molaire du fluor contenu dans le bain à la quantité des métaux introduits soit compris entre 2,5 et 15, on note la valeur du potentiel de contrôle dit potentiel de consigne, on dépose à la cathode les métaux sous forme d'alliage tout en continuant à introduire les chlorures en proportion voulue dans l'injecteur et en quantité telle que le potentiel mesuré sur l'électrode de contrôle reste en valeur absolue voisin de la valeur absolue du potentiel de consigne.In the first case, which relates more particularly to hafnium-zirconium alloys, 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 potential is noted, the metals are deposited at the cathode in the form of an alloy while continuing to introduce the chlorides in desired proportion in the injector and in such quantity that the potential measured on the control electrode remains in absolute value close to the absolute value of the setpoint potential.
Ainsi, dans le cas où on veut obtenir des alliages de métaux dont les potentiels de dépôt diffèrent entre eux de moins de 0,5 volt, le procédé consiste à faire une électrolyse dans une cellule équipée d'un dispositif de contrôle.Thus, in the case where it is desired to obtain metal alloys whose deposition potentials differ from one another by less than 0.5 volts, the method consists in carrying out electrolysis in a cell equipped with a control device.
Un tel dispositif a déjà été décrit dans le brevet US 4567643. Il permet par le choix d'un rapport fluor/métal à déposer de mesurer avec une grande sensibilité un potentiel électrique qui est fonction de la concentration du bain en ions dudit métal. Ainsi, une concentration optimum ayant été déterminée, on peut noter le potentiel qui lui correspond. Ce potentiel va alors servir de référence et il suffit ensuite d'alimenter la cellule en chlorure de façon à maintenir ce potentiel constant pour être sûr d'avoir en permanence dans le bain la concentration voulue en ions métalliques dissous.
Le mérite de la demanderesse est d'avoir trouvé que ce dispositif était également utilisable dans le cas où on voulait mesurer de façon simultanée la concentration de plusieurs types d'ions.Such a device has already been described in US Pat. No. 4,567,643. It allows, by the choice of a fluorine / metal ratio to be deposited, to measure with great sensitivity an electrical potential which is a function of the concentration of the ion bath of said metal. Thus, an optimum concentration having been determined, one can note the potential which corresponds to it. This potential will then serve as a reference and it then suffices to supply the cell with chloride so as to maintain this constant potential to be sure to have permanently in the bath the desired concentration of dissolved metal ions.
The merit of the applicant is to have found that this device was also usable in the case where it was desired to simultaneously measure the concentration of several types of ions.
Dans ce procédé, on utilise également un ensemble anodique muni d'un diaphragme particulier et tel qu'il est décrit dans le brevet US 5064513.In this process, an anode assembly is also used, provided with a particular diaphragm and as described in US Pat. No. 5,064,513.
Ce diaphragme est constitué par des fibres de carbone noyées dans un matériau rigide à base de graphite et a la propriété de posséder une porosité de valeur déterminée ce qui permet une conduite plus facile de l'électrolyse et l'obtention d'un dépôt métallique de structure régulière.
Ici encore, le mérite de la demanderesse a été de montrer que ces avantages étaient atteints quand on met simultanément en oeuvre plusieurs types d'ions.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.
Here again, the merit of the Applicant has been to show that these advantages are achieved when several types of ions are used simultaneously.
Le procédé recourt également à un injecteur tel que celui qui est décrit dans le brevet français 2653139 et qui a pour effet de maintenir la concentration en poids du bain dans une fourchette restreinte et de l'ajuster de façon progressive et précise. Cela a l'avantage dans le cas présent de pouvoir maîtriser plus facilement les conditions d'obtention d'un dépôt où les proportions des différents métaux doivent être comprises dans des limites étroites.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.
La combinaison de ces différents moyens permet de conduire à l'électrolyse simultanée de plusieurs chlorures ainsi qu'au dépôt simultané des métaux de l'alliage suivant des proportions voulues et suivant une structure correspondant aux caractéristiques décrites ci-dessus.The combination of these different means allows the simultaneous electrolysis of several chlorides as well as the simultaneous deposition of the metals of the alloy in desired proportions and according to a structure corresponding to the characteristics described above.
Cependant, ce procédé n'est pas applicable quand les métaux à déposer présentent entre eux un écart de potentiel de dépôt supérieur ou égal à 0,5 volt comme par exemple dans le cas des alliages niobium-titane car il se produit alors un dépôt préférentiel du métal le moins électronégatif et donc un alliage dans lequel les éléments ne sont pas en proportion voulue. Il est donc nécessaire de trouver un autre procédé d'obtention.However, this process is not applicable when the metals to be deposited have a deposit potential difference greater than or equal to them. 0.5 volts as for example in the case of niobium-titanium alloys because there is then a preferential deposit of the least electronegative metal and therefore an alloy in which the elements are not in desired proportion. It is therefore necessary to find another process for obtaining it.
D'où l'idée de la demanderesse qui consiste à mettre le métal le plus électronégatif en solution dans le bain non pas par électrolyse de son halogénure mais, par électrodissolution du métal lui-même à partir d'une anode soluble.From where the idea of the applicant which consists in putting the most electronegative metal in solution in the bath not by electrolysis of its halide but, by electrodissolution of the metal itself starting from a soluble anode.
D'où le procédé d'obtention où on met en oeuvre une cellule d'électrolyse ignée contenant un bain de sels fondus à base de chlorures alcalins et d'au moins un ion fluorure en quantité comprise en poids entre 1 et 3% du poids du bain dans lequel sont immergés au moins partiellement une électrode de contrôle en relation avec une électrode de référence qui servent à mesurer un potentiel de contrôle, un ensemble anodique muni d'un diahragme à base de fibres de carbone et de graphite, une cathode de dépôt à laquelle on applique une différence de potentiel continue E1 par rapport audit ensemble, un injecteur de matière à électrolyser et de gaz inerte caractérisé en ce que l'on introduit dans le bain une électrode polarisée positivement constituée par le métal le plus électronégatif, et par l'injecteur polarisé négativement l'halogénure du métal le plus électropositif de l'alliage à déposer, on établit une différence de potentiel E2 positive entre ladite électrode et l'injecteur de sorte que du métal de l'électrode passe en solution dans le bain, on ajuste les concentrations en ions métalliques dans le bain de manière à avoir une proportion en relation avec celle de l'alliage désiré et une quantité telle que le rapport molaire du fluor contenu dans le bain à la quantité des métaux présents soit compris entre 2,5 et 15, on note la valeur du potentiel de contrôle dit potentiel de consigne, on dépose les métaux sous forme d'alliage à la cathode tout en continuant à introduire le chlorure dans l'injecteur et à maintenir la différence de potentiel E2 de manière que le potentiel mesuré sur l'électrode de contrôle reste en valeur absolue supérieur à la valeur absolue du potentiel de consigne et que E2 corresponde au passage d'au moins X/2 Faraday par mole de MClX introduit dans le bain où M est le métal le moins électronégatif et X sa valence et que E1 corresponde au passage d'au moins 1/2 Faraday par mole de MClX .Hence the process for obtaining where an igneous electrolysis cell is used 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 as to have a proportion in relation to that of the desired alloy and a quantity such that the molar ratio of fluorine contained in the bath to the quantity of metals present is between 2.5 and 15, the value of the control potential known as the reference potential is noted, the metals are deposited in the form of an alloy with the cathode while continuing to introduce chloride into the injector and maintain the potential difference E2 so that the potential measured on the control electrode remains in absolute value greater than the absolute value of the setpoint potential and that E2 corresponds to the passage of at least X / 2 Faraday per mole of MCl X introduced into the bath where M is the least electronegative metal and X its valence and that E1 corresponds to the passage of at least 1/2 Faraday per mole of MCl X.
Ainsi, commme dans le procédé précédent, l'invention consiste à combiner dans une même cellule d'électrolyse ignée l'enseignement des trois brevets cités plus haut mais, elle s'en différencie par le fait qu'au dépôt d'au moins un métal par réduction électrolytique de son halogénure est associé un dépôt obtenu à partir d"ions métalliques issus en partie d'une dissolution anodique.Thus, as in the previous method, 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.
Il est à noter que les métaux présentant un grand écart de leur potentiel de dépôt, il se produit une forte dissolution chimique de l'anode soluble dans le bain. Pour avoir la concentration voulue en ions dans le bain, il faut tenir compte de cet effet chimique et polariser plus ou moins cette anode et en même temps règler la préréduction de l'halogénure dans l'injecteur.It should be noted that since the metals have a large difference in their deposition potential, there is a strong chemical dissolution of the soluble anode in the bath. To have the desired concentration of ions in the bath, it is necessary to take account of this chemical effect and to polarize more or less this anode and at the same time regulate the prereduction of the halide in the injector.
D'où la nécessité, à la différence du procédé précédent de lier le potentiel E2 entre l'électrode soluble et l'injecteur à la quantité de chlorure introduit. Ainsi, on peut maîtriser la proportion d'ions dissous dans le bain et obtenir des alliages ayant la composition souhaitée.Hence the need, unlike the previous process, to link the potential E2 between the soluble electrode and the injector to the quantity of chloride introduced. Thus, it is possible to control the proportion of ions dissolved in the bath and to obtain alloys having the desired composition.
Ce type de procédé est également applicable au cas de deux métaux ayant des potentiels de dépôt proches mais comme la dissolution chimique est alors relativement faible, il faut polariser fortement l'anode soluble pour obtenir la concentration convenable dans le bain.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.
Les deux procédés conduisent à la formation sur la cathode d'un dépôt de cristaux facilement détachables où les éléments sont en solution solide et présentent les caractéristiques physiques définies plus haut.Both methods lead to the formation on the cathode of a deposit of easily detachable crystals where the elements are in solid solution and have the physical characteristics defined above.
Après séparation de la cathode, les dits cristaux sont lavés à l'eau pour éliminer les sels présents dans le bain puis mis sous forme de lingots par fusion à l'aide d'un moyen convenable tel que, par exemple, un four à arc, à induction, à bombardement d'électrons, à plasma inductif ou plasma d'arc.After separation of the cathode, 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.
L'invention sera mieux comprise à l'aide des figures ci-joint qui représentent :
- figure 1 : la vue suivant une coupe transversale d'une cellule d'électrolyse mise en oeuvre dans le cas de l'obtention d'alliages dont les éléments ont un écart de leur potentiel de dépôt < 0,5 volt.
- figure 2 : la vue suivant une coupe verticale d'une cellule d'électrolyse mise en oeuvre dans le cas de l'obtention d'alliages dont les éléments ont un écart de leur potentiel de dépôt supérieur ou égal à 0,5 volt.
- figure 3 : une macrographie d'un alliage Zr70Hf30 obtenu suivant l'art antérieur à partir d'éponge de zirconium et de cristaux électrolytiques de hafnium.
- figure 4 : une micrographie au grandissement 100 de l'alliage précédent.
- figure 5 : une micrographie au grandissement 3 du même alliage obtenu suivant l'art antérieur à partir d'éponge de zirconium et de copeaux de hafnium.
- figure 6 : une micrographie au grandissement 500 du même alliage obtenu suivant l'invention.
- figure 7 : une photographie de la section d'un lingot d'un alliage de Nb53Ti47 obtenu suivant l'art antérieur à partir d'éponge de titane et de copeaux de niobium.
- figure 8 : une photographie de la section d'un lingot du même alliage que celui de l'exemple précédent obtenu suivant l'invention.
- Figure 1: the view in cross section of an electrolysis cell used in the case of obtaining alloys whose elements have a difference in their deposition potential <0.5 volt.
- Figure 2: the view in a vertical section of an electrolysis cell used in the case of obtaining alloys whose elements have a difference in their deposition potential greater than or equal to 0.5 volts.
- FIG. 3: a macrography of a Zr 70 Hf 30 alloy obtained according to the prior art from zirconium sponge and hafnium electrolytic crystals.
- Figure 4: a magnification micrograph 100 of the previous alloy.
- Figure 5: a
magnification micrograph 3 of the same alloy obtained according to the prior art from zirconium sponge and hafnium chips. - FIG. 6: a micrograph at 500 magnification of the same alloy obtained according to the invention.
- Figure 7: a photograph of the section of an ingot of an alloy of Nb 53 Ti47 obtained according to the prior art from titanium sponge and niobium chips.
- Figure 8: a photograph of the section of an ingot of the same alloy as that of the previous example obtained according to the invention.
Sur la figure 1, on distingue une cuve 1 contenant un bain de sels fondus 2 fermée par un couvercle 3 percé d'ouvertures à travers lesquelles passent par l'intermédiaire de bagues 4 isolantes de l'électricité pour plonger partiellement dans le bain :
une anode 5 en carbone entouréepar un diaphragme 6 équipé d'une tubulure 7 par laquelle s'échappe l'halogène gazeux formé lors de l'électrolyse des halogénures et reliée au pôle positif d'une source de courant continu,un dispositif 8 d'alimentation en halogénures gazeux qui sont introduits dans le bain suivant le sens des flèches 9,une cathode 10 en acier sur laquelle se dépose l'alliage 11 et reliée au pôle négatif de la source de courant alimentant l'anode.une électrode 12 de mesure reliée à une électrode de référence non représentée.
- a
carbon anode 5 surrounded by adiaphragm 6 fitted with a tube 7 through which escapes the gaseous halogen formed during the electrolysis of the halides and connected to the positive pole of a direct current source, - a
device 8 for supplying gaseous halides which are introduced into the bath in the direction of thearrows 9, - a
steel cathode 10 on which thealloy 11 is deposited and connected to the negative pole of the current source supplying the anode. - a measuring
electrode 12 connected to a reference electrode not shown.
Sur la figure 2, on distingue une cellule d'électrolyse 21 contenant un bain 22 de sels fondus fermée par un couvercle 23 percé d'ouvertures à travers lesquelles passent par l'intermédiaire de bagues 24 en matière isolante pour plonger partiellement dans le bain :
une anode 25 en carbone entouréepar un diaphragme 26 équipé d'une tubulure 27 par laquelle s'échappe l'halogène gazeux qui se dégage au cours de l'électrolyse et reliée au pôle positif d'une source de courant continu,une électrode 28 consommable constituée par le métal le plus électronégatif de l'alliage à déposer et reliée au pôle positif d'une source de courant continu,- un dispositif 29 d'alimentation en halogénure du métal le moins électronégatif de l'alliage à déposer et qui est introduit dans le bain à l'état gazeux suivant les flèches 30 ; ce dispositif est relié au pôle négatif de la source de courant alimentant l'électrode consommable,
une cathode 31 sur laquelle se dépose l'alliage 32 à fabriquer et qui est reliée au pôle négatif de la source de courant alimentant l'anode 25.une électrode 33 de mesure reliée à une électrode de référence non représentée.
- a
carbon anode 25 surrounded by adiaphragm 26 fitted with atube 27 through which escapes the halogen gas which is released during the electrolysis and connected to the positive pole of a direct current source, - a
consumable electrode 28 consisting of the most electronegative metal of the alloy to be deposited and connected to the positive pole of a direct current source, - a device 29 for supplying the least electronegative metal of the alloy to be deposited with halide and which is introduced into the bath in the gaseous state according to the
arrows 30; this device is connected to the negative pole of the current source supplying the consumable electrode, - a
cathode 31 on which thealloy 32 to be produced is deposited and which is connected to the negative pole of the current source supplying theanode 25. - a measuring
electrode 33 connected to a reference electrode not shown.
Sur la figure 3, on distingue, indiquées par des flèches, des zones noires correspondant à des morceaux de hafnium infondus.In Figure 3, there are, indicated by arrows, black areas corresponding to pieces of unfounded hafnium.
Sur la figure 4, on distingue des zones blanches correspondant aux mêmes infondus.In FIG. 4, a distinction is made between white areas corresponding to the same unfounded.
Sur la figure 5, on voit des traits blancs qui représentent des restes de copeaux de hafnium infondus.In Figure 5, we see white lines representing the remains of unfounded hafnium chips.
Sur la figure 6, la structure de l'alliage est parfaitement homogène.In FIG. 6, the structure of the alloy is perfectly homogeneous.
Sur la figure 7, on distingue en noir les copeaux de niobium infondus.In Figure 7, we distinguish in black the unfused niobium shavings.
Sur la figure 8, on ne note aucune présence d'infondus.In FIG. 8, we do not note any presence of unfunded.
L'invention peut être illustrée à l'aide des exemples d'application suivants :The invention can be illustrated with the aid of the following application examples:
Dans une cellule d'électrolyse en Inconel 600 contenant un bain de sels fondus formé d'un mélange équimoléculaire de NaCl-KCl + 3,5% en poids de NaF porté à 720°C, la dite cellule étant équipée de :
- une anode en graphite entourée d'un diaphragme en fibres de carbone noyées dans du graphite suivant la technique décrite dans le brevet US 5064513,
- un dispositif d'alimentation en halogénures du type décrit dans le brevet français 2653139,
- une cathode de dépôt en acier,
- un dispositif de contrôle du potentiel par rapport à une électrode de référence du type décrit dans le brevet US 4657643,
- a graphite anode surrounded by a carbon fiber diaphragm embedded in graphite according to the technique described in patent US 5064513,
- a halide supply device of the type described in French patent 2,653,139,
- a steel deposition cathode,
- a device for checking the potential with respect to a reference electrode of the type described in US Pat. No. 4,676,643,
On a recueilli au cours de cinq opérations successives et avec un rendement Faraday moyen de 92%, 87,6 kg d'alliages dans lesquels les proportions en métaux étaient les suivantes :
Ces alliages se présentent sous la forme d'agglomérats ayant une taille moyenne de 10 mm et composés de cristaux de 3 mm de diamètre moyen ayant une surface spécifique de 0,03 m2/g dans lesquels les métaux étaient en solution solide.
Du point de vue pureté, ces alliages avaient pour composition :
- oxygène : 620 ppm
- carbone : < 10 ppm
- azote : < 10 ppm
- chlore : < 50 ppm
- fer : < 20 ppm
- chrome : < 10 ppm
- nickel : < 10 ppm.
From the purity point of view, these alloys had for composition:
- oxygen: 620 ppm
- carbon: <10 ppm
- nitrogen: <10 ppm
- chlorine: <50 ppm
- iron: <20 ppm
- chromium: <10 ppm
- nickel: <10 ppm.
Dans une cellule d'électrolyse présentant les mêmes caractéristiques que celles de l'exemple 1 sauf :
- une teneur en NaF de 2,5%,
- une température du bain de 725°C,
- la présence d'une électrode consommable en titane polarisée positivement et en relation électrique avec l'injecteur de chlorure polarisé négativement,
On a constaté que la concentration en ions Ti dans le bain se maintenait entre 1,5
- an NaF content of 2.5%,
- a bath temperature of 725 ° C.,
- the presence of a positively polarized titanium consumable electrode and in electrical connection with the negatively polarized chloride injector,
It was found that the concentration of Ti ions in the bath was maintained between 1.5 and 2.5% by weight with an average valence of between 2 and 2.3 while the concentration of Nb ions varied between 0.1 and 0 , 15% by weight for an average valence of between 3.4 and 3.7.
Pour une valence du titane égale à 2,15, le bilan matière met en évidence une attaque chimique complémentaire à l'attaque électrochimique et globalement représentée par
2 Nb5+ + 2e- = 2 Nb4+
Ti = Ti2+ + 2 e-
puis,
2 Nb4+ + Ti2+ = 2Nb(4-x)+ + Ti(2+2x)+.
For a valence of titanium equal to 2.15, the material balance highlights a chemical attack complementary to the electrochemical attack and generally represented by
2 Nb 5+ + 2e - = 2 Nb 4+
Ti = Ti 2+ + 2 e -
then,
2 Nb 4+ + Ti 2+ = 2Nb (4-x) + + Ti (2 + 2x) + .
Dans ces conditions, on a obtenu avec un rendement chlore de 95% et métal de 90% suivant un débit de 473 g/h un alliage contenant des cristaux de Nb-Ti en solution solide à 50% + ou - 10% atomique ayant une dimension moyenne de 0,5 mm et une surface spécifique de 0,02 m2/g sous forme d'agglomérats de 10 mm ayant la composition suivante :
oxygène : 500 ppm ; carbone : 20 ppm ; azote : < 20 ppm ; fer : < 20 ppm ; chrome < 10 ppm ; nickel < 10 ppm ; chlore < 100 ppm ; fluor < 10 ppm ; sodium : < 10 ppm ; potassium : < 10 ppm ; solde niobium et titane.Under these conditions, there was obtained with a chlorine yield of 95% and metal of 90% at a flow rate of 473 g / h an alloy containing crystals of Nb-Ti in solid solution at 50% + or - 10% atomic having a average dimension of 0.5 mm and a specific surface of 0.02 m 2 / g in the form of agglomerates of 10 mm having the following composition:
oxygen: 500 ppm; carbon: 20 ppm; nitrogen: <20 ppm; iron: <20 ppm; chromium <10 ppm; nickel <10 ppm; chlorine <100 ppm; fluorine <10 ppm; sodium: <10 ppm; potassium: <10 ppm; balance niobium and titanium.
L'invention trouve son application dans l'obtention d'alliages de métaux réfractaires de très grande pureté ayant une très bonne homogénéité à l'échelle microscopique.The invention finds its application in obtaining alloys of refractory metals of very high purity having very good homogeneity on the microscopic scale.
Claims (5)
- Refractory metal alloys capable of being formed into homogeneous ingots with a purity greater than 99.9 % which consist of refractory metals, the melting points of which differ from each other by at least 200°C and the mass proportions of which are such that for each alloy the temperature at which solidification starts is more than 150°C lower than the solidification temperature of the least fusible metal, being in the form of agglomerates, characterized in that these agglomerates with a size of 0.2 to 30 mm consist of crystals with a specific surface area of between 0.005 and 0.2 m2/g having a size of 0.1 to 1 mm and in which the metals are in a solid solution state, that is to say they are homogeneous on the atomic scale and have a composition which differs by no more than 20 % from the average composition of the alloy and that they are free from macroscopic zones of a mixture of unfused constituents.
- Alloys according to claim 1, characterized in that the crystals have a specific surface area of between 0.01 and 0.05 m2/g.
- Alloys according to claim 1, characterized in that the agglomerates are between 1.5 and 12 mm in size.
- Process for obtaining alloys according to claim 1, wherein the metals have deposition potentials which differ from each other by less than 0.5 volts and where a hot electrolytic cell (1) is used containing a bath (2) of molten salts based on alkali metal chlorides and at least one fluoride ion in a quantity by weight of between 1.5 % and 5 % of the weight of the bath in which are immersed at least partially a measuring electrode (12) in conjunction with a reference electrode which serve to measure an electrolysis control potential, an anode assembly (5) provided with a diaphragm (6) based on carbon and graphite fibres, a cathode (10) to which a continuous potential difference is applied with respect to the said assembly, an injector (8) for the material to be electrolysed and for inert gas, characterized in that metals in the form of gaseous chlorides are injected simultaneously into the injector in proportions corresponding to those of the said alloy and in a quantity such that the molar ratio of the fluorine contained in the bath to the quantity of metals introduced is between 2.5 and 15, the value of the control potential, the so-called index potential, is noted, metals are deposited at the cathode in the form of an alloy while continuing to introduce chlorides in the desired proportion into the injector and in a quantity such that the potential measured on the control electrode remains in absolute value close to the absolute value of the index potential.
- Process for obtaining alloys according to claim 1 wherein the metals have deposition potentials which differ from each other by at least 0.5 volts and where a hot electrolytic cell (21) is used containing a bath (22) of molten salts based on alkali metal chlorides and at least one fluoride ion in a quantity by weight of between 1 % and 3 % of the weight of the bath in which are immersed at least partially a control electrode (33) in conjunction with a reference electrode which serve to measure a control potential, an anode assembly (25) provided with a diaphragm (26) based on carbon and graphite fibres, a deposition cathode (31) to which a continuous potential difference El is applied with respect to the said assembly, an injector (29) for the material to be electrolysed and for inert gas, characterized in that a positively polarized electrode (28) consisting of the most electronegative metal of the alloy to be deposited is introduced into the bath and the halide of the most electropositive metal of the alloy to be deposited is introduced by means of the negatively polarized injector (29) and that a positive potential difference E2 is established between the said electrode and the injector such that the metal of the electrode (28) passes into solution in the bath, the concentrations of metal ions in the bath are adjusted so as to have a proportion with respect to that of the desired alloy and a quantity such that the molar ratio of fluorine contained in the bath to the quantity of metals present is between 2.5 and 15, the value of the control potential, the so-called index potential, is noted, the metals are deposited in the form of an alloy at the cathode while chloride continues to be introduced into the injector and the potential difference E2 continues to be maintained so that the potential measured on the control electrode remains in absolute value close to the absolute value of the index potential and that E2 corresponds to the passage of at least X/2 Faraday per mole of MClx introduced into the bath, where M is the least electronegative metal and X its valence and that El corresponds to the passage of at least ½ Faraday per mole of MClx.
Applications Claiming Priority (2)
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FR9206233 | 1992-05-12 | ||
FR929206233A FR2691169B1 (en) | 1992-05-12 | 1992-05-12 | REFRACTORY METAL ALLOYS SUITABLE FOR TRANSFORMATION INTO HOMOGENEOUS AND PURE INGOTS AND METHODS FOR OBTAINING SAID ALLOYS. |
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EP0570308A1 EP0570308A1 (en) | 1993-11-18 |
EP0570308B1 true EP0570308B1 (en) | 1996-12-27 |
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US (1) | US5372659A (en) |
EP (1) | EP0570308B1 (en) |
JP (1) | JP2863058B2 (en) |
AT (1) | ATE146828T1 (en) |
BR (1) | BR9301808A (en) |
DE (1) | DE69306853T2 (en) |
FR (1) | FR2691169B1 (en) |
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JP3582437B2 (en) * | 1999-12-24 | 2004-10-27 | 株式会社村田製作所 | Thin film manufacturing method and thin film manufacturing apparatus used therefor |
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 |
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US8171568B2 (en) | 2007-09-07 | 2012-05-01 | Freitas Robert A | Positional diamondoid mechanosynthesis |
CN101994045B (en) * | 2010-12-10 | 2012-07-11 | 西南铝业(集团)有限责任公司 | Aluminum-zirconium intermediate alloy and preparation method |
CN102268620A (en) * | 2011-08-01 | 2011-12-07 | 南昌大学 | Solid-solution treatment method of Al3Ti particle reinforced Al-Zn-Mg-Cu based aluminum alloys |
CN102212710B (en) * | 2011-08-02 | 2013-02-13 | 江苏中欧材料研究院有限公司 | Novel in-situ sub-micron multielement particle reinforced aluminum-base composite system and material |
CN102268621B (en) * | 2011-09-09 | 2013-03-20 | 西南铝业(集团)有限责任公司 | Production method of aluminium alloy bar |
CN102409270A (en) * | 2011-11-07 | 2012-04-11 | 内蒙古北方重工业集团有限公司 | Method for rolling large-sized aluminum alloy ring piece and performing solid solution treatment by using electric furnace |
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 (en) * | 2013-03-25 | 2016-01-20 | 上海大学 | A kind of method of niobium concentrate molten oxide electrolytic preparation ferrocolumbium |
CN104451317A (en) * | 2013-09-22 | 2015-03-25 | 北京有色金属研究总院 | Hafnium-base mixed metal material and iodination preparation method thereof |
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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DE1077878B (en) * | 1952-10-04 | 1960-03-17 | Norton Ges M B H Deutsche | Process for the production of zirconium, hafnium or mixtures of these metals by fused-salt electrolysis |
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US2985531A (en) * | 1959-06-05 | 1961-05-23 | Univ Ohio State Res Found | Niobium-zirconium base alloy |
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GB1095925A (en) * | 1965-12-02 | 1967-12-20 | Imp Metal Ind Kynoch Ltd | Hafnium alloys |
CH492793A (en) * | 1967-04-12 | 1970-06-30 | Starck Hermann C Fa | Production of alloys or mixtures of tantalum or niobium |
US3637374A (en) * | 1968-05-27 | 1972-01-25 | Fansteel Metallurgical Corp | Method of producing tungsten rhenium alloys by chemical vapor deposition |
JPS6052538A (en) * | 1983-08-31 | 1985-03-25 | Sumitomo Metal Ind Ltd | Method for melting zr alloy containing nb |
FR2579629B1 (en) * | 1985-03-28 | 1987-05-07 | Pechiney | METHOD FOR THE CONTINUOUS CONTROL OF THE METAL CONTENT DISSOLVED IN A MOLTEN SALT BATH AND ITS APPLICATION TO THE CONTINUOUS SUPPLY OF A SALT ELECTROLYSIS CELL |
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-
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- 1992-05-12 FR FR929206233A patent/FR2691169B1/en 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/en not_active Expired - Lifetime
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Title |
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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.) * |
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JP2863058B2 (en) | 1999-03-03 |
JPH0633161A (en) | 1994-02-08 |
EP0570308A1 (en) | 1993-11-18 |
BR9301808A (en) | 1994-03-01 |
DE69306853T2 (en) | 1997-05-07 |
FR2691169A1 (en) | 1993-11-19 |
FR2691169B1 (en) | 1994-07-01 |
DE69306853D1 (en) | 1997-02-06 |
US5372659A (en) | 1994-12-13 |
ATE146828T1 (en) | 1997-01-15 |
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