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EP0362351B1 - Procédé pour préparer un alliage fritté ODS et alliage obtenu par ce procédé - Google Patents

Procédé pour préparer un alliage fritté ODS et alliage obtenu par ce procédé Download PDF

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Publication number
EP0362351B1
EP0362351B1 EP89904067A EP89904067A EP0362351B1 EP 0362351 B1 EP0362351 B1 EP 0362351B1 EP 89904067 A EP89904067 A EP 89904067A EP 89904067 A EP89904067 A EP 89904067A EP 0362351 B1 EP0362351 B1 EP 0362351B1
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EP
European Patent Office
Prior art keywords
alloy
oxide
base metal
sintered
strength
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.)
Expired - Lifetime
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EP89904067A
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German (de)
English (en)
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EP0362351A1 (fr
Inventor
Wolfgang GLÄTZLE
Udo Gennari
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Metallwerk Plansee GmbH
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Metallwerk Plansee GmbH
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/10—Alloys containing non-metals
    • C22C1/1078—Alloys containing non-metals by internal oxidation of material in solid state
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/04—Making non-ferrous alloys by powder metallurgy
    • C22C1/05—Mixtures of metal powder with non-metallic powder
    • C22C1/051—Making hard metals based on borides, carbides, nitrides, oxides or silicides; Preparation of the powder mixture used as the starting material therefor
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C32/00—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ
    • C22C32/001—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with only oxides
    • C22C32/0015—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with only oxides with only single oxides as main non-metallic constituents
    • C22C32/0031—Matrix based on refractory metals, W, Mo, Nb, Hf, Ta, Zr, Ti, V or alloys thereof

Definitions

  • the invention relates to a method for producing a ductile, high-strength oxide dispersion-hardened sintered alloy from a base metal with a high melting point (T M ), without fractions, or optionally with fractions of substitution mixed crystal phase that do not have a lasting effect on the alloy properties, in which a metal oxide powder as dispersoid is used to powder the base metal is mixed in, using oxides of metals which have greater formation energies than the oxides of the base metal at temperatures ⁇ 0.5 T M.
  • dispersoids are understood to mean those particles which are generally built into the metallic base matrix continuously and which do not react with the base metal or dissolve at higher temperatures and are not built into the base lattice as a substitute metal. Oxides, carbides and nitrides are used in particular as dispersoids.
  • the dispersoids are usually introduced into the powder of the base metal by impregnating the powder with a dispersoid suspension or else by mixing powdered dispersoids.
  • DE-AS 12 32 353 describes a process for the production of refractory metals, preferably containing metal oxides, by sintered metallurgical processes.
  • the invention there begins with the knowledge that oxides introduced into the powder as colloidal solutions coagulate during sintering, that is to say from the originally fine distribution they form larger oxide particles and thus represent the cause of the high sensitivity to breakage of the sintered material, in particular during further processing .
  • the process feature essential to the invention according to DE-AS 12 32 353 is now based on lowering the sintering temperature compared to the usual standard, in order to reduce the mobility of the introduced oxide particles by diffusion by introducing sintering aids in the form of "other non-harmful metal additives" to the sintered good, which melt at lower temperatures than the oxide and thus enable a kind of liquid phase sintering ("liquid or pasty phase already at temperatures at which no sintering occurs yet.
  • sintering has ended before the oxide particles - due to lack of movement in the sintered body - become closed have clustered harmful particles ", column 1, lines 51-52, column 2, lines 16-20).
  • the oxide particles are largely held where they were introduced in the form of the colloidal solution.
  • Dispersoids introduced in this way can be further homogenized by "mechanical alloying".
  • the aim of mechanical alloying is to distribute the dispersoids as homogeneously as possible even within the individual metal powder grains.
  • dispersion-hardened alloys consist, by definition, of incorporating particles which do not react or alloy with the basic matrix as dispersoids.
  • dispersoids with a melting point that is generally well above the alloy sintering temperature are generally used in the sintered metallurgical processes for producing dispersion alloys.
  • the dispersoids are in a solid phase during the entire manufacturing process.
  • oxide dispersion alloys of metals with high melting points by melt metallurgy, in particular by melting in an arc.
  • the second phase meaning the carbides, nitrides and / or oxides contained in the base matrix (base metal) after melting, forms a solution with the base matrix.
  • the second phase should remain in solution during cold working and should only be excreted homogeneously and finely by aging annealing.
  • the achievable quality is documented by examples and in the form of strength properties compiled in tables.
  • the means of substitution mixed crystal alloying and the precipitation hardening according to column 1, line 65 of the description, are used together with the means of dispersion hardening to increase the mechanical properties of such alloys.
  • the strengths achieved thus result from two or three processes running side by side that increase strength and hardness.
  • alloys produced using this process can have relatively high strengths, but at the same time only low ductility at room temperature (see e.g. BVG Grigorovich and EN Sheftel 'Met. Sci. And Heat Treatment 24 (7-8), p. 472, (1983)
  • US Pat. No. 3,181,946 describes a niobium-based alloy which contains 0.25-0.5% oxygen and / or 1-3% zirconium and / or titanium, the weight ratio oxygen to titanium or zirconium being 3: 1 up to 12: 1 is enough.
  • Material hardening is achieved there by oxide dispersion hardening and, according to the examples given, to a certain extent also by interstitially dissolved oxygen and by alloying niobium with titanium and / or zirconium. It is pointed out there that higher proportions of interstitially dissolved oxygen in the niobium cause great brittleness.
  • the object of the present invention is to develop a more economical process for the production of ODS sintered alloys with high ductility and strength properties using a base metal with a high melting point.
  • the strength values of alloys produced by known metallurgical processes, both in the deformed and in the recrystallized state, should at least be achieved without substitution mixed crystal formation and classic precipitation of a second metal or compound phase being used as a means of increasing the strength.
  • the process should be able to control the degree of dispersion hardening very precisely.
  • the ductility of the alloy should also be sufficiently large for subsequent cold forming of the material.
  • the properties of a single metallic element such as its corrosion behavior and the radiation physical properties, should be preserved as far as possible unaffected by foreign elements and at the same time the mechanical strength of the metals compared to the high-purity phase, with or without deformation hardening, should be significantly increased.
  • Oxide dispersion-hardened sintered alloys which can be produced by one of the processes mentioned, are disclosed in claims 4-6.
  • the method can only be applied to a limited number of alloys.
  • the metals with high melting points are primarily those of the V. and VI. Subgroup of the periodic table suitable. Due to the free negative energy of formation, only a limited number of oxides can be used for the desired dispersion hardening.
  • table Solution metal Solution metal oxide and hard temperature-resistant metal oxide Approximate values of the negative free oxide formation energy at 25 o C in kilojoules per gram atom of oxygen silicon SiO2 403 kJ titanium TiO2 424 kJ Zircon ZrO2 512 kJ aluminum Al2O3 529 kJ beryllium BeO 584 kJ Thorium ThO2 613 kJ chrome Cr2O3 348 kJ magnesium MgO 572 kJ manganese MnO 365 kJ MnO2 233 kJ Lanthanum La2O3 580 kJ hafnium HfO2 566 kJ barium BaO 529 kJ strontium SrO 560 kJ calcium CaO 605 kJ yttrium Y2O3 60
  • the concentration of the oxide in the base metal essentially determines the respective temperature at which the individual processes according to the invention take place or become dominant over the others.
  • the total oxygen content in the sintered material should preferably be set so that just the stoichiometrically necessary amount remains for the formation of the oxide, which is strictly only valid for the sinterling center due to a diffusion-controlled concentration profile.
  • the oxygen content will be set lower, ie sub-stoichiometric, in order to prevent the oxide from precipitating too quickly and, as a rule, coarse-grained when cooling after the annealing treatment - at the expense of a slight reduction in strength.
  • the sintering and annealing process can take place both by direct sintering and by indirect sintering.
  • the direct sintering process the sintered material is heated by direct current passage.
  • the necessary water cooling of the connections enables the sintered goods to cool down particularly quickly when the sintering process has ended.
  • the re-excretion in the form of the finest, homogeneously distributed oxide particles will already take place during cooling or during a subsequent aging annealing.
  • the rate of cooling plays an important role here, and more so the higher the oxide concentration in the alloy.
  • Directly sintered material can be quenched particularly quickly to low temperatures. By heating the alloy, e.g. B. before the extrusion as the first forming process, the precipitation of the oxide particles is occasionally made possible or completed.
  • the oxide dispersion alloy according to the invention In order to carry out mechanical shaping processes, in particular cold forming by forging, rolling or hammering, the oxide dispersion alloy according to the invention must have sufficient ductility in addition to high strength. It is therefore important to determine the strength properties of the alloy according to the invention by choosing the dispersoid concentration, but especially by the Controlled control of the solution annealing according to the invention so that it can be brought as close as possible to a just tolerable limit value.
  • the alloy consists of niobium or tantalum as the base metal and, in addition to small amounts of dissolved oxygen, contains 0.2-1.5% by weight oxides using one or more of the metals Ti, Zr, Hf, Ba, Sr, Ca, Y, La.
  • niobium alloy which contains 0.2-1% by weight of TiO2, whereby in addition to small amounts of interstitially dissolved oxygen, TiO2 is present in the basic matrix as a finely divided dispersoid in the basic matrix.
  • TiO2 is present in the basic matrix as a finely divided dispersoid in the basic matrix.
  • Another preferred niobium alloy contains 0.2-1.5% by weight of ZrO2.
  • the metal component of the decomposing oxide should evaporate out of the alloy much more easily when the alloy material is melted. It therefore has no possibility of being distributed comparatively homogeneously in the base metal.
  • the sintering has been carried out at comparatively substantially lower temperatures than according to the present invention. This ensured that the oxide particles distributed in the compact remain as unchanged and stationary as possible at their place of introduction.
  • the feasibility of the annealing treatment according to the invention to the extent that was actually possible was surprising. According to the prevailing doctrine, there was a fear that at the annealing or sintering temperatures according to the invention, in addition to the oxides of the base metal, the dissolved oxide metals would also evaporate at high rates from the sintered body surface. Because taking into account the boundary conditions to be fulfilled for the oxide formation energies, the melting points of the oxide metals can be significantly below the annealing temperatures which are respectively desirable according to the present invention and, in preferred embodiments, are also below the annealing temperatures.
  • a major advantage of the method according to the invention is its economy. Insofar as dispersion alloys previously produced by melt metallurgy were produced using roughly comparable annealing processes, the entire production process was significantly more cost-intensive with significantly lower solidifications. B. melting and repeated remelting of the oxides in the casting by means of arc melting.
  • a significant economic advantage of the method according to the invention is based on the integration of the annealing treatment according to the invention in the generally required sintering process.
  • Niobium and tantalum alloys produced by the method according to the invention therefore considerably expand the field of application in implant medicine.
  • a promising application of alloys according to the inventive method is in pipe systems for alkali metal cooling circuits, for. B. in nuclear power plants.
  • An alloy niobium - 0.5 wt.% TiO2 is produced according to the inventive method.
  • 3980 g of niobium powder with an average particle size of 10 ⁇ m and an oxygen content of ⁇ 1000 ppm are mixed homogeneously with 20g TiO2 powder agglomerate with an average particle size of 0.25 ⁇ m for 1 hour.
  • the powder mixture is then hydrostatically compressed to 80% of the theoretical density at approx. 2000 bar.
  • the compact thus obtained is slowly heated in a high vacuum (better 1 x 10 ⁇ 5 mbar) and finally sintered at a temperature of 2100 o C for 12 hours.
  • Table 1 shows two sets of tensile strengths at room temperature 800 o C, 1000 o C and 1200 o C, specifically for the deformed sample and for the sample subsequently recrystallized at 1400 o C for 1 hour. In addition to the tensile strengths, the table also contains associated elongation values.
  • the alloy has excellent ductility. This manifests itself on the one hand in the good processability and also in a very low value of approx. -50 o C for the transition temperature, in a high notched impact strength of approx. 135 J / cm2 at room temperature and in a high elongation at break of> 10% deformed material.
  • An oxide dispersion-strengthened niobium-1 TiO2 alloy was produced by the process described in Example 1. For this purpose, the TiO2 was weighed in twice as high as in Example 1.
  • Example 2 In contrast to Example 1, a partial excretion of the TiO2 could already be observed in this case during the cooling after the sintering and reaction annealing process.
  • the titanium still in solution was almost completely excreted as TiO2.
  • the higher TiO2 content in the alloy caused a higher resistance to deformation, so that the samples were advantageously annealed before the individual steps of cold forming in order to achieve a more uniform structure.
  • Example 2 After the process steps listed in Example 1, a niobium-0.5 ZrO2 alloy was produced.
  • the powder compact was further processed by means of direct sintering, especially with a view to rapid cooling of the sintered material after the sintering and annealing process.
  • the sintering temperature was increased to 2300 o C to ensure on the one hand that the components of the ZrO2 go completely into solution, but on the other hand to set the total oxygen content of the sample somewhat lower and thus too fast and comparatively to prevent rough re-excretion of the oxide when the sample cools after the sintering process. Measures known per se ensured rapid cooling of the sintered product.
  • the heating or aging temperature was increased by 100 o C to 1100 o C before the first hot forming process.
  • the further process steps were carried out in accordance with Example 1.
  • the tensile strengths and elongation values obtained in the formed as well as in the recrystallized state are listed in Table 1 under item 4.
  • the results according to the invention can only be compared to a limited extent with the cited literature values, because on the one hand the deformation process of the samples according to the cited prior art is not described in detail and because On the other hand, based on the description details given there, it can be assumed that in addition to the oxide dispersion precipitates, the alloy also contains significant proportions of oxide metals of the dispersion oxides in the basic matrix and has an alloy effect which increases strength. From a purely qualitative point of view, however, it can be stated that, according to the prior art, it is not possible to achieve high strength values comparable with the present invention.
  • Patent 3,181,946 hot deformed RT 506 29 871 307 19th 982 251 14 1204 185 20th 4th Nb-0.5 ZrO2 deformed RT 760 11 recist.
  • RT 450 32 5 Nb-1 Zr (Niobium TMS-AIME) deformed RT 350-550 5-15 recist.
  • RT 290 35 800 190 18th 1000 135 32 1200 90 77 6 Nb-1 Zr 0.25 0
  • hot deformed RT 530 16 982 312 17th 1093 224 26 7 Niobium; purely deformed RT 300-550 2-15 recist.
  • an alloy tantalum - 0.5% by weight TiO 2 is produced, the higher melting point of the tantalum having to be taken into account in some process parameters.
  • the sintering temperature is 2300 o C compared to the usual approx. 2600 o C. This achieves an approximately stoichiometric oxygen concentration corresponding to the titanium concentration introduced.
  • the lower sintering density due to the lower sintering temperature is completely sufficient for complete compression during the subsequent extrusion.
  • the aging annealing for the separation of the finest TiO2 particles takes place here preferably at 1100 o C. Due to the high heat resistance of tantalum, extrusion is carried out at 1200 o C. Cold forming is then carried out using profile rollers and rotary hammers - a total of approx. 80% forming.
  • Table 1 shows in item 8 the tensile strengths and elongation values obtained in turn on 8 mm test specimens in the deformed state and after recrystallization.
  • the high recrystallization temperature (1600 o C / 1 h) leads to a clear coarsening of the TiO2 dispersoids and thus to a weakening of the dispersion hardening compared to the cold-formed material.
  • the combination of work hardening and dispersion hardening results in particularly high strengths while maintaining sufficient ductility. For comparison, values of pure tantalum with 82% deformation are given in position 9, the production steps and process parameters corresponding to the above.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Powder Metallurgy (AREA)
  • Manufacture Of Alloys Or Alloy Compounds (AREA)

Abstract

Procédé pour préparer un alliage fritté ductile, à résistance élevée, renforcé par dispersion d'oxyde, à partir d'un métal réfractaire. Jusqu'à présent, la dispersion d'oxyde ne jouait qu'un rôle secondaire par rapport à d'autres procédés d'augmentation de la résistance. Ledit procédé permet d'obtenir de manière économique des matériaux métalliques d'une résistance que l'on n'avait jusqu'à présent pas pu obtenir par dispersion d'oxyde et d'une ductilité plus élevée qu'avec les techniques habituelles. On peut ainsi limiter les composants étrangers métalliques ou non métalliques des alliages frittés à des teneurs relativement faibles en matières dispersées et, éventuellement, en oxygène résiduel dissous. Le procédé consiste en un traitement de recuit ciblé et nécessite un choix ciblé du métal de base et du produit de dispersion d'oxyde correspondant. Les matériaux ainsi obtenus sont utilisés en particulier lorsqu'il faut des éléments métalliques à résistance et ductilité élevées et à teneur en composants étrangers aussi faible que possible, par exemple en médecine humaine, où la résistance à la corrosion et la compatibilité avec l'organisme sont particulièrement importantes, ou dans le domaine nucléaire, pour éviter des réactions néfastes entre particules.

Claims (6)

  1. Procédé de fabrication d'un alliage fritté ductile à haute résistance, durci par dispersion d'oxydes, à partir d'un métal de base à haut point de fusion (TM) où la teneur en phases cristallines mélangées de substitution est nulle ou sans effet défavorable sur les propriétés de l'alliage, dans lequel un comprimé de poudre d'oxyde métallique est additionné à la poudre du métal de base en tant que matière dispersée, en employant des oxydes de métaux dont les énergies de formation sont supérieures à celle des oxydes du métal de base à des températures < 0,5 TM,
       caractérisé en ce que
       un comprimé de poudre formé à l'aide du mélange de poudre pendant le processus de frittage est fritté à des températures situées dans la plage de 0,7 à 0,9 TM selon la séquence de processus suivants:
    - l'oxyde introduit se détruit et/ou est réduit par le métal de base, les composants qui en résultent passent en solution dans le métal de base
    - les composants dissous sont finement divisés par suite d'une diffusion dans le métal de base
    - une fraction de l'oxygène total qui se trouve dans l'alliage s'évapore de façon contrôlée à partir de la surface du corps fritté,
       et en ce que les matières dispersées d'oxydes sont séparées de la solution d'une manière contrôlée pendant le refroidissement de l'alliage fritté à la fin du processus de frittage ou lors d'un recuit de précipitation qui le suit.
  2. Procédé selon la revendication 1 caractérisé en ce que l'alliage fritté est fabriqué par frittage direct du comprimé de poudre.
  3. Procédé selon la revendication 1 ou 2, caractérisé en ce qu'une fraction de l'oxygène s'évapore de la surface du corps fritté sous forme d'oxyde du métal de base.
  4. Alliage fritté durci par dispersion d'oxydes, qui peut être fabriqué par un procédé selon l'une des revendications 1 à 3, caractérisé en ce que cet alliage se compose du métal de base niobium ou tantale et contient, en plus de petites quantités d'oxygène dissout, 0,2 à 1,5 % en poids d'oxydes, en employant un ou plusieurs des métaux Ti, Zr, Hf, Ba, Sr, Ca, Y, La.
  5. Alliage fritté durci par dispersion d'oxydes selon la revendication 4, caractérisé en ce qu'il s'agit d'un alliage de niobium à 0,2 à 1% en poids de TiO₂.
  6. Alliage fritté durci par dispersion d'oxydes selon la revendication 4, caractérisé en ce qu'il s'agit d'un alliage de niobium à 0,2 à 1,5 % en poids de ZrO₂.
EP89904067A 1988-04-14 1989-04-13 Procédé pour préparer un alliage fritté ODS et alliage obtenu par ce procédé Expired - Lifetime EP0362351B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
AT963/88 1988-04-14
AT0096388A AT391435B (de) 1988-04-14 1988-04-14 Verfahren zur herstellung einer odssinterlegierung
PCT/EP1989/000396 WO1989009840A1 (fr) 1988-04-14 1989-04-13 Procede pour preparer un alliage fritte ods

Publications (2)

Publication Number Publication Date
EP0362351A1 EP0362351A1 (fr) 1990-04-11
EP0362351B1 true EP0362351B1 (fr) 1994-12-07

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Country Link
US (1) US5049355A (fr)
EP (1) EP0362351B1 (fr)
JP (1) JPH03500188A (fr)
AT (1) AT391435B (fr)
DE (1) DE58908731D1 (fr)
WO (1) WO1989009840A1 (fr)

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JPS61136640A (ja) * 1984-12-04 1986-06-24 Toyota Motor Corp 酸化還元反応を利用した合金の製造方法
EP0290820B1 (fr) * 1987-05-13 1994-03-16 Mtu Motoren- Und Turbinen-Union MàœNchen Gmbh Procédé de préparation d'alliages métalliques renforcés par dispersion

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WO1989009840A1 (fr) 1989-10-19
DE58908731D1 (de) 1995-01-19
AT391435B (de) 1990-10-10
JPH03500188A (ja) 1991-01-17
US5049355A (en) 1991-09-17
ATA96388A (de) 1990-04-15
EP0362351A1 (fr) 1990-04-11

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