EP0082210B1 - Procédé pour la dissolution sélective du molybdène en présence de tungstène - Google Patents

Procédé pour la dissolution sélective du molybdène en présence de tungstène Download PDF

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Publication number
EP0082210B1
EP0082210B1 EP81110588A EP81110588A EP0082210B1 EP 0082210 B1 EP0082210 B1 EP 0082210B1 EP 81110588 A EP81110588 A EP 81110588A EP 81110588 A EP81110588 A EP 81110588A EP 0082210 B1 EP0082210 B1 EP 0082210B1
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EP
European Patent Office
Prior art keywords
molybdenum
tungsten
acid
oxygen
dissolving
Prior art date
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.)
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Application number
EP81110588A
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German (de)
English (en)
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EP0082210A1 (fr
Inventor
Károly Dr. Dipl. Chem. Vadasdi
László Dr. Dipl. Chem. Bartha
András Dr. Dipl. Chem. Kiss
Tivadar Dr. Dipl. Chem. Ing. Millner
Endre Tekula
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.)
Mta Mueszaki Fizikai Kutato Intezete
Magyar Tudomanyos Akademia Muszaki Fizikai Kutato Intezete
Original Assignee
Mta Mueszaki Fizikai Kutato Intezete
Magyar Tudomanyos Akademia Muszaki Fizikai Kutato Intezete
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Priority to EP81110588A priority Critical patent/EP0082210B1/fr
Priority to DE8181110588T priority patent/DE3169917D1/de
Priority to AT81110588T priority patent/ATE12661T1/de
Publication of EP0082210A1 publication Critical patent/EP0082210A1/fr
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F1/00—Etching metallic material by chemical means
    • C23F1/10—Etching compositions
    • C23F1/14—Aqueous compositions
    • C23F1/16—Acidic compositions
    • C23F1/26—Acidic compositions for etching refractory metals

Definitions

  • the invention relates to a method for the selective dissolution of molybdenum in the presence of tungsten, in particular for the selective dissolution of the molybdenum core wire from tungsten spirals produced on a molybdenum core wire.
  • the tungsten wire is usually formed by winding or winding onto a molybdenum core wire to form a single or multiple spiral, then these tungsten spirals are heated on the molybdenum core in a protective gas to about 1500 ° C. until the Mechanical stresses in the tungsten wire have largely disappeared, which means that after the chemical dissolution of the molybdenum core, i. H. after its removal, the tungsten coils no longer change their intended original dimensions to any significant extent (do not shrink) and, when heated for the first time without a core to the temperature of the incandescent body, also lose none of their geometric uniformity and correctness.
  • the tungsten wire is spiraled, e.g. H.
  • small groove-like depressions are pressed into the surface of the molybdenum core, d. H. that the tungsten in this product does not come into contact with the molybdenum along a line but on a considerable part of the surface, which is why when heated together to around 1500 ° C, a clearly detectable amount of molybdenum in significant concentration in the surface parts of the tungsten wire that touch the molybdenum core, diffuses.
  • a disadvantage of this known method is that the weight loss of the tungsten spirals of different sizes made of tungsten wires of different thicknesses, which is brought about by loosening the molybdenum core wire with the mixture of nitric acid, sulfuric acid and water, is on average about 4% by weight, so it is still increasing is high, and in particular that its spread is large.
  • This weight loss and its dispersion are due in part to the fact that the composition and temperature of the mixture do not change uniformly with each individual dissolution process, and in part to the fact that the surface part of the spirals made of tungsten wires of different thickness, which comes into contact with the molybdenum, comes into play various masses of molybdenum absorbs from the molybdenum core wire and the tungsten / molybdenum alloys formed in the surface are sensitive to the chemical effect of the mixture dissolving the molybdenum core to varying degrees.
  • nitric acid inevitably produces large amounts of nitrogen oxides during the dissolution of the core and that the so-called nitrous gas consisting of them is an extremely caustic and very harmful product, the neutralization (binding) of which is known to be one only with a great deal of effort and also only a very incompletely solvable task.
  • Another disadvantageous feature of this process is that the recovery of the valuable molybdenum trioxide content (MoOa content) of the exhausted solution mixture can only be achieved with end-of-solution products that count as impermissible impurities in living water.
  • MoOa content molybdenum trioxide content
  • DE-OS No. 2234494 describes a method for dissolving the wire mandrel, for example made of molybdenum, a filament or spool of tungsten in a solution containing nitric acid and water, which in addition to the nitric acid as acids also contains sulfuric acid, hydrochloric acid and / or May contain phosphoric acid and contains an inhibitor against the generation of gaseous nitrogen oxides, known.
  • this known method also has the disadvantage that it has to be used with a solution of nitric acid with its disadvantages, albeit to a lesser extent, as is the case, for example, in p. 10, lines 14 to 16 (in example 4) and p.
  • DE-OS No. 2425379 describes a solution which consists only of hydrogen peroxide and water for etching molybdenum.
  • a solution which consists only of hydrogen peroxide and water for etching molybdenum.
  • DE-AS No. 2359558 also describes the use of hydrogen peroxide together with nitric acid or an acid mixture containing nitric acid as disadvantageous. Because of the fact that the hydrogen peroxide is not selective with respect to molybdenum in the presence of tungsten, it is not surprising that DE-OS No.
  • 2425379 does not speak of the presence of tungsten, but rather of the etching Molybdenum restricted.
  • other standard etching agents such as hydrochloric acid and sulfuric acid, are mentioned as the state of the art at that time, but only in relation to the etching of molybdenum , d. H. without the presence of tungsten, although its use is also discouraged for molybdenum etching.
  • DE-OS No. 2532773 discloses a solvent made of nitric acid, optionally together with sulfuric acid or hydrochloric acid, hydrogen peroxide and various organic hydrogen peroxide stabilizers, the purpose of use also being to remove molybdenum cores from tungsten filaments.
  • this known method also has the disadvantage that it is imperative to use nitric acid in the solvent.
  • DE-OS No. 2848475 discloses solvents for dissolving metals from sulfuric acid, hydrogen peroxide and monohydroxy- or dihydroxy-substituted cycloparaffins or alkylcycloparaffins as activators, optionally together with copper ions.
  • solvents for dissolving metals from sulfuric acid, hydrogen peroxide and monohydroxy- or dihydroxy-substituted cycloparaffins or alkylcycloparaffins as activators, optionally together with copper ions.
  • the use for the selective dissolution of molybdenum in the presence of tungsten is not even hinted at, rather the etching of copper in the production of printed circuits is specified as a special embodiment.
  • 3597290 is the etching of copper plates in the production of printed circuits.
  • Table II on page 14 of DE-OS No. 2848475 also shows in particular how unfavorable that the solvent containing no substituted cycloparaffin or alkylcycloparaffin was as stabilizer, in that the hydrogen peroxide decomposed rapidly.
  • lines 17 to 20 of DE-OS No. 2848475 it is pointed out that silver ions in hydrogen peroxide / sulfuric acid etching solutions do not yet promote the etching rate to the extent that this would be desirable.
  • dissolved molybdenum is recovered from spent mixed acid pickling solutions in such a way that they are combined with ammonium hydroxide solution Adjusted pH from about 1.5 to 3, the resulting solution is heated to a temperature of less than about 95 ° C with stirring and then filtered.
  • a disadvantage of this method is, however, that the ammonium molybdate formed is difficult to filter off and the waste water is additionally contaminated by the ammonium salts formed.
  • the invention is based on the object, while eliminating the disadvantages of the prior art, a method for the selective dissolution of molybdenum in the presence of tungsten, in particular for the selective dissolution of the molybdenum core wire of tungsten spirals produced on a molybdenum core wire, in which the weight loss of the tungsten is less than in the case of the is known methods and no harmful and polluting substances are created.
  • the invention relates to a method for the selective dissolution of molybdenum in the presence of tungsten, in particular for the selective dissolution of the molybdenum core wire of tungsten spirals made on a molybdenum core wire, with an acidic solution of 1 or more oxygen in a compound (s) having a peroxide-oxygen bond, which is characterized in that that dissolving with an acidic solution that does not contain nitric acid in the presence of 1 promotes more compound (s) of 1 or more of the elements iron, copper, thallium, silver, lead, chromium, nickel, bismuth, tellurium, ger , Titan, Vana-. dium, manganese and cadmium which dissolve the peroxide oxygen bond as catalyst (s) which selectively accelerate or accelerate the dissolution of the molybdenum.
  • Hydrogen peroxide and / or 1 or more peracid (s), persalt (s) and / or other peroxides (other peroxide) (superoxides [superoxide]) are or are preferably used as the compound (s) having oxygen in a peroxide-oxygen bond.
  • the use of hydrogen peroxide is particularly preferred. This is advantageously used in the form of a 30% solution.
  • the concentration of the hydrogen peroxide or other solvent containing peroxide to the size of the specific surface of the molybdenum body, e.g. B. to choose the thickness of the molybdenum core wire, that is, to determine the most suitable concentration experimentally, and to regulate the severity of the chemical solution process with drop metering.
  • the oxygen-bonded oxygen compound can be added dropwise to an acidic solution of the catalyst or catalysts containing the body containing the tungsten and the molybdenum, which selectively accelerates or accelerates the dissolution of the molybdenum.
  • An essential element of the invention is the discovery of catalysts which practically do not increase the dissolution rate of the tungsten in acidic solutions of 1 or more oxygen in compound (s) containing peroxide-oxygen bond, such as hydrogen peroxide solutions, but the dissolution of the molybdenum under the same conditions Accelerate orders of magnitude and thus enable the molybdenum core to be loosened at a practically usable rate even without other solvents in such a way that the tungsten spiral suffers a smaller weight loss than previously, mostly 1 to 2% by weight, which is insignificant for the spiral quality.
  • iron compound (s) in particular iron (III) compounds, very particularly iron (III) chloride, are preferably in the form of its hexahydrate.
  • the rate of dissolution of the molybdenum can be varied within wide limits. Concentrations thereof of 0.1 to 6, in particular 0.2 to 4,% by weight are preferably used.
  • the compound (s) whose acidity is adjusted with an inorganic or organic acid other than nitric acid can be used.
  • the compound (s) whose acidity is adjusted to a pH of -0.5 to +2.0 with an acid other than nitric acid is used. It was found that very favorable practical solution conditions can be achieved as a result. Mineral acids other than nitric acid, especially sulfuric acid and / or hydrochloric acid, and / or overchloric acid can suitably serve as acids for this purpose, the use of sulfuric acid is particularly preferred. Of the organic acids, the use of acetic acid and / or tartaric acid is preferred. Acid concentrations of 0.5 to 3, in particular 1 to 3,% by weight are preferably used.
  • the advantages of the method according to the invention can be further increased if the dissolution of the molybdenum in the presence of an inhibitor, i.e. H. of a substance that prevents the tungsten from attacking.
  • the acidic solution of 1 or more oxygen in a peroxide-oxygen bond is one which also contains 1 or more perchlorate (s) and / or overchloric acid or 1 or more chromate (s) and / or contains chromic acid as an inhibitor (s) to prevent the tungsten from dissolving.
  • overchloric acid this can also serve to adjust the acidity.
  • the speed of the process of dissolving the molybdenum according to the process according to the invention is sensitive to the temperature of the dissolving mixture.
  • the temperature is advantageously kept below 45, in particular at 25 to 35, very particularly at 25 to 30 ° C. With such temperatures of the dissolving mixture, the dissolution rate of the tungsten can namely be kept at a negligible value. It turned out to be useful to regulate the temperature of the dissolving mixture by constant cooling.
  • the dissolution process is carried out in a closed system under excess pressure, as a result of which the loss of peroxide oxygen, which occurs as a result of the spontaneous decomposition of the hydrogen peroxide or the other compound (s) having a peroxide-oxygen bond, is reduced.
  • a particular advantage of the method according to the invention also lies in the fact that when it is carried out not only no nitrous gases are produced, but also, as the end product of the solution, an exhausted solution which is available for recovering the molybdenum trioxide content and which in the process is not harmful to living water and contains only difficult to remove solutes, can be obtained.
  • Example 1 There were spirals of the type described in Example 1 in the amount also described in this in 300 cm 3 of a solution which 1% by weight iron (III) sulfate (Fe 2 [SO 4 ] 3 ) and 2% by weight overchloric acid contained, introduced. With water cooling, 500 cm 3 of a 30% hydrogen peroxide solution were added dropwise at such a rate that the temperature of the solution did not exceed 35 ° C. After the dissolution of the molybdenum had ended, the tungsten spirals were treated as described in Example 1. The surface of the spirals was polished. Their weight loss was 2% by weight and their weight spread matched that of the original spirals.
  • Example 1 Spirals of the type described in Example 1 were used in the amount also described in 500 cm 3 of a solution which contained 0.1% by weight of thallium (III) sulfate (TI 2 [SO 4 ] 3 ) and 0.02% by weight .-% copper (11) sulfate (CuS0 4 ) and 3 wt .-% sulfuric acid, introduced. While cooling, 30% hydrogen peroxide was added to the solution at such a rate that the temperature of the solution did not exceed 35 ° C. After the molybdenum triggering reaction had ended (about 30 min), the spirals were separated and treated as described in Example 1. The weight loss was determined to be 3% by weight.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Catalysts (AREA)
  • Manufacture And Refinement Of Metals (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)

Claims (9)

1. Procédé de dissolution sélective du molybdène en présence de tungstène, en particulier de dissolution sélective de l'armature centrale en fil de molybdène de spirales en tungstène réalisées sur une armature centrale en fil de molybdène, à l'aide d'une solution acide, caractérisé en ce que l'on réalise la dissolution en utilisant une solution acide d'un ou de plusieurs composés contenant de l'oxygène sous la forme d'une liaison oxygène dans un groupe peroxyde, en partie connus en eux-mêmes pour la dissolution non sélective du molybdène en même temps que du tungstène, en présence d'un ou de plusieurs composés d'un ou de plusieurs des éléments fer, cuivre, thallium, argent, plomb, chrome, nickel, bismuth, tellure, cérium, titane, vanadium, manganèse et cadmium comme catalyseur(s) qui accélère(nt) sélectivement la dissolution du molybdène.
2. Procédé selon la revendication 1, caractérisé en ce que l'on utilise, comme composé(s) comportant de l'oxygène sous la forme d'un groupe peroxyde, le peroxyde d'hydrogène et/ou un ou plusieurs peracides, persels et/ou autres peroxydes.
3. Procédé selon l'une des revendications 1 ou 2, caractérisé en ce qu'on utilise comme catalyseur qui accélère sélectivement la dissolution du molybdène le chlorure de fer (III).
4. Procédé selon l'une des revendications 1 à 3, caractérisé en ce qu'on utilise comme solution acide d'un ou de plusieurs composés contenant de l'oxygène sous la forme d'un groupe peroxyde une solution dont l'acidité a été ajustée à l'aide d'un acide, à une valeur de pH comprise entre -0,5 et +2,0.
5. Procédé selon l'une des revendications 1 à 4, caractérisé en ce qu'on utilise comme solution acide d'un ou de plusieurs composés contenant de l'oxygène sous la forme d'un groupe pexoxyde un composé dont l'acidité a été ajustée d'acides sulfurique, chlorhydrique, perchlorique, acétique et/ou tartrique.
6. Procédé selon l'une des revendications 1 à 5, caractérisé en ce que l'on utilise comme solution acide d'un ou de plusieurs composés contenant de l'oxygène sous la forme d'un groupe peroxyde une solution qui contient aussi un ou plusieurs perchlorates et/ou de l'acide perchlorique ou un ou plusieurs chromates et/ou de l'acide chromique comme inhibiteur(s) pour empêcher la dissolution du tungstène.
7. Procédé selon l'une des revendications 1 à 6, caractérisé en ce que l'on maintient la température en dessous de 45° C.
8. Procédé selon l'une des revendications 1 à 7, caractérisé en ce que l'on maintient la température entre 25 et 35° C.
9. Procédé selon l'une des revendications 1 à 8, caractérisé en ce que l'on opère dans un système fermé, sous une surpression.
EP81110588A 1981-12-18 1981-12-18 Procédé pour la dissolution sélective du molybdène en présence de tungstène Expired EP0082210B1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
EP81110588A EP0082210B1 (fr) 1981-12-18 1981-12-18 Procédé pour la dissolution sélective du molybdène en présence de tungstène
DE8181110588T DE3169917D1 (en) 1981-12-18 1981-12-18 Method of selectively dissolving molybdenum in the presence of tungsten
AT81110588T ATE12661T1 (de) 1981-12-18 1981-12-18 Verfahren zum selektiven loesen von molybdaen in gegenwart von wolfram.

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP81110588A EP0082210B1 (fr) 1981-12-18 1981-12-18 Procédé pour la dissolution sélective du molybdène en présence de tungstène

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EP0082210A1 EP0082210A1 (fr) 1983-06-29
EP0082210B1 true EP0082210B1 (fr) 1985-04-10

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AT (1) ATE12661T1 (fr)
DE (1) DE3169917D1 (fr)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4548791A (en) * 1983-09-30 1985-10-22 American Chemical & Refining Company, Inc. Thallium-containing composition for stripping palladium
EP0138531B1 (fr) * 1983-10-06 1988-01-27 Olin Corporation Procédé pour le nettoyage de matériaux à base de cuivre et pour la régénération de la solution de nettoyage

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5045742A (fr) * 1973-08-27 1975-04-24
DE2359558C2 (de) * 1973-11-29 1975-11-13 Hitachi, Ltd., Tokio Verfahren zum Verhindern der Bildung von Stickstoffmonoxid bei der Ausätzung eines Molybdänkernes aus einer Wolframdrahtwendel
US3945865A (en) * 1974-07-22 1976-03-23 Dart Environment And Services Company Metal dissolution process
US4174253A (en) * 1977-11-08 1979-11-13 Dart Industries Inc. Dissolution of metals utilizing a H2 O2 -H2 SO4 solution catalyzed with hydroxy substituted cycloparaffins
DE2933430A1 (de) * 1979-08-17 1981-03-26 Patent-Treuhand-Gesellschaft für elektrische Glühlampen mbH, 81543 München Verfahren zur rueckgewinnung von molybdaen und mischsaeure aus verbrauchten mischsaeurebeizloesungen

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Publication number Publication date
DE3169917D1 (en) 1985-05-15
ATE12661T1 (de) 1985-04-15
EP0082210A1 (fr) 1983-06-29

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