EP0570308A1 - 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 PDF

Info

Publication number: EP0570308A1
Authority: EP; European Patent Office
Prior art keywords: metals; bath; potential; alloys; alloy
Prior art date: 1992-05-12
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.): Granted

Application number

EP93420192A

Other languages

English (en)

French (fr)

Other versions

EP0570308B1 (de

Inventor

Airy Pierre Lamaze

Christophe Mennetrier

Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)

Compagnie Europeenne du Zirconium Cezus SA

Original Assignee

Compagnie Europeenne du Zirconium Cezus SA

Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)

1992-05-12

Filing date

1993-05-11

Publication date

1993-11-18

1993-05-11 Application filed by Compagnie Europeenne du Zirconium Cezus SA filed Critical Compagnie Europeenne du Zirconium Cezus SA

1993-11-18 Publication of EP0570308A1 publication Critical patent/EP0570308A1/de

1996-12-27 Application granted granted Critical

1996-12-27 Publication of EP0570308B1 publication Critical patent/EP0570308B1/de

2013-05-11 Anticipated expiration legal-status Critical

Status Expired - Lifetime legal-status Critical Current

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Classifications

- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- 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 meltable 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% whose melting temperatures are different 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 fusible metal, characterized in that they are in the form of agglomerates of dimensions between 0.2 and 30 mm and compounds crystals with a specific surface 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 the form of a solid solution.
the alloys according to the invention are characterized by crystals where the metals are in solid solution, that is to say that they are homogeneous on the atomic scale and have at most only a relative difference of composition of 20% relative to 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 as we favor the dissolution in liquid metal. Hence the absence of any pollution of these products by 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 m2 / g and the agglomerates have dimensions of between 1.5 and 12 mm 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 of less than 0.5 volts while a second technique is relative to metals, the difference of the deposit potentials of which 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 comprised by weight between 1.5 and 5% of the weight of the bath in which are at least partially immersed a measurement electrode in relation to a reference electrode which are used to measure an electrolysis control potential, an anode assembly provided with a diaphragm based on carbon fibers and graphite, a cathode to which a continuous potential difference with respect to said assembly, an injector of material to be electrolyzed and of inert gas characterized in that the metals are simultaneously introduced into the injector in the form of gaseous chlorides in proportions corresponding to those of said alloy and in an amount such that the molar ratio of the fluorine contained in the bath to the amount of metals introduced is understood between 2.5 and 15, the value of the control potential known as the reference potential is noted
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 made up of 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 concentration by weight of the bath within a restricted 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.
this method is not applicable when the metals to be deposited have a deposit potential difference greater than or equal to 0.5 volts, such as, for example, in the case of niobium-titanium alloys, since a preferential deposit then occurs. the least electronegative metal and therefore an alloy in which the elements are not in the desired proportion. It is therefore necessary to find another process for obtaining it.
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 diaphragm 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 an electrode consisting of the most electronegative metal of the is introduced into the bath alloy to be deposited and by the injector the halide of the most electropositive metal of the alloy to be deposited, a positive potential difference E2 is established between said electrode and the in jector so that the metal of the electrode passes into solution in the bath, the concentrations of metal ions in the bath are adjusted so as to have a proportion in
the invention consists in combining in a same igneous electrolysis cell the teaching of the three patents mentioned above, 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.
alloys are in the form of agglomerates having an average size of 10 mm and composed of crystals of 3 mm in average diameter having a specific surface of 0.03 m2 / g in which the metals were in solid solution. 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. or a purity (Zr + Hf) greater than 99.9%.
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)

EP93420192A 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 Expired - Lifetime EP0570308B1 (de)

Applications Claiming Priority (2)

Application Number	Priority Date	Filing Date	Title
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.
FR9206233		1992-05-12

Publications (2)

Publication Number	Publication Date
EP0570308A1 true EP0570308A1 (de)	1993-11-18
EP0570308B1 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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CN103160863A (zh) *	2013-03-25	2013-06-19	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
WO2024227680A2 (en)	2023-05-04	2024-11-07	Rolex Sa	Article made of binary ti-hf or zr-hf alloy comprising a dark oxide layer

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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
US9244097B1 (en)	2007-09-07	2016-01-26	Robert A. Freitas, JR.	Mechanosynthetic tools for a atomic-scale fabrication
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
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
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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
US10197597B2 (en)	2013-02-28	2019-02-05	Cbn Nano Technologies Inc.	Build sequences for mechanosynthesis
US9676677B2 (en)	2013-02-28	2017-06-13	Robert A. Freitas, JR.	Build sequences for mechanosynthesis
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
US10072031B1 (en)	2016-05-12	2018-09-11	CBN Nano Technologies, Inc.	Systems and methods for mechanosynthesis
US11708384B2 (en)	2016-05-12	2023-07-25	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 (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
DE1226311B (de) *	1963-02-18	1966-10-06	Union Carbide Corp	Verfahren zum elektrolytischen Abscheiden von Zirkonium, Hafnium, Vanadium, Niob, Tantal, Chrom, Molybdaen oder Wolfram oder ihrer Legierungen
FR1565784A (de) *	1967-04-12	1969-05-02
US3637374A (en) *	1968-05-27	1972-01-25	Fansteel Metallurgical Corp	Method of producing tungsten rhenium alloys by chemical vapor deposition

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1992
- 1992-05-12 FR FR929206233A patent/FR2691169B1/fr not_active Expired - Fee Related
1993
- 1993-05-11 BR BR939301808A patent/BR9301808A/pt not_active IP Right Cessation
- 1993-05-11 US US08/059,287 patent/US5372659A/en not_active Expired - Fee Related
- 1993-05-11 DE DE69306853T patent/DE69306853T2/de not_active Expired - Fee Related
- 1993-05-11 AT AT93420192T patent/ATE146828T1/de not_active IP Right Cessation
- 1993-05-11 EP EP93420192A patent/EP0570308B1/de not_active Expired - Lifetime
- 1993-05-12 JP JP5110465A patent/JP2863058B2/ja not_active Expired - Lifetime

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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
DE1226311B (de) *	1963-02-18	1966-10-06	Union Carbide Corp	Verfahren zum elektrolytischen Abscheiden von Zirkonium, Hafnium, Vanadium, Niob, Tantal, Chrom, Molybdaen oder Wolfram oder ihrer Legierungen
FR1565784A (de) *	1967-04-12	1969-05-02
US3637374A (en) *	1968-05-27	1972-01-25	Fansteel Metallurgical Corp	Method of producing tungsten rhenium alloys by chemical vapor deposition

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number	Priority date	Publication date	Assignee	Title
CN103160863A (zh) *	2013-03-25	2013-06-19	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
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
WO2024227680A2 (en)	2023-05-04	2024-11-07	Rolex Sa	Article made of binary ti-hf or zr-hf alloy comprising a dark oxide layer

Also Published As

Publication number	Publication date
FR2691169B1 (fr)	1994-07-01
JPH0633161A (ja)	1994-02-08
FR2691169A1 (fr)	1993-11-19
DE69306853D1 (de)	1997-02-06
EP0570308B1 (de)	1996-12-27
DE69306853T2 (de)	1997-05-07
US5372659A (en)	1994-12-13
ATE146828T1 (de)	1997-01-15
JP2863058B2 (ja)	1999-03-03
BR9301808A (pt)	1994-03-01

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EP0570308B1 (de)	1996-12-27	Legierungen aus Metall mit hohen Schmelzpunkten geeignet für die Umwandlung in homogene und rein Blöcke, und Herstellungsverfahren dieser Legierungen
JPH0475301B2 (de)	1992-11-30
CA2020494C (fr)	2001-09-18	Procede d'obtention d'uranium a partir d'oxyde et utilisant une voie chlorure
LU86090A1 (fr)	1987-04-02	Procede pour preparer du tantale ou du niobium affins
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