EP0313484A1 - Tungsten-nickel-iron high-density alloys with very high mechanical properties, and process for manufacturing these alloys - Google Patents
Tungsten-nickel-iron high-density alloys with very high mechanical properties, and process for manufacturing these alloys Download PDFInfo
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- EP0313484A1 EP0313484A1 EP88420358A EP88420358A EP0313484A1 EP 0313484 A1 EP0313484 A1 EP 0313484A1 EP 88420358 A EP88420358 A EP 88420358A EP 88420358 A EP88420358 A EP 88420358A EP 0313484 A1 EP0313484 A1 EP 0313484A1
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- 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
- C22C1/045—Alloys based on refractory metals
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- 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
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C27/00—Alloys based on rhenium or a refractory metal not mentioned in groups C22C14/00 or C22C16/00
- C22C27/04—Alloys based on tungsten or molybdenum
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/16—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of other metals or alloys based thereon
- C22F1/18—High-melting or refractory metals or alloys based thereon
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- the invention relates to heavy tungsten-nickel-iron alloys with very high mechanical characteristics and to a process for manufacturing said alloys.
- the subject of the present invention is heavy alloys with a density of between 15.6 and 18 containing by weight between 80 and 99% of tungsten, as well as nickel and iron in a Ni / Fe weight ratio greater than or equal to 1.5. and possibly other elements such as molybdenum, titanium, aluminum, manganese, cobalt, rhenium, which have very high mechanical characteristics and in particular a breaking strength of up to 2000 MPa for a at least 1% elongation.
- these heavy alloys are characterized in that they have a structure where the ⁇ phase of tungsten has the form of butterfly wings with dislocation cells of dimensions between 0.01 and 1 ⁇ m and the phase ⁇ of the binder has an average free path of less than 15 ⁇ m.
- nickel-iron tungsten alloys have a structure formed of pure tungsten nodules more or less spherodized during sintering constituting the ⁇ phase, these nodules being surrounded by a ⁇ phase composed of the three elements of the alloy which acts as a binder between said nodules.
- the Applicant has found that to develop very high mechanical characteristics, the tungsten alloys had to have a particular structure.
- free mean path here is meant the average of the distances which in a given direction separates two successive zones of phase ⁇ .
- the invention also relates to a method for manufacturing alloys having such a structure and in which the value of the desired mechanical characteristics can be adjusted at will and in particular reaching a tensile strength close to 2000 MPa.
- This process includes the steps already known and consisting in: - use powders of each element of the alloy, each of them having a FISHER diameter of between 1 and 15 ⁇ m - mixing said powders in proportions corresponding to the composition of the desired alloy - compressing said powders in the form of compacts - sinter the compacts between 1490 and 1650 ° C for 2 to 5 hours - treat the sintered compacts under vacuum between 1000 and 1300 ° C - subject the compacts thus obtained to at least one wrought pass.
- the invention consists of a succession of cycles which are all the more numerous when it is desired to reach structures corresponding to the highest values of the mechanical characteristics.
- three cycles make it possible to reach a breaking strength of between 1400 and 1450 MPa, while at the end of four cycles, it is close to values of 1850 MPa.
- Each of these cycles comprises in order a step of wrought-out carried out by hammering, for example, so as to develop a certain reduction rate of surface of the sintered compact between 10 and 50% followed by an annealing treatment by passage in an oven heated to a temperature below 1300 ° C under an inert atmosphere for 4 to 20 hours.
- the wrought rates are lower and the temperatures higher than during the cycles later.
- the suitable degree of wrought work is achieved by making at least two successive passes in the hammer hammer, for example, before carrying out the heat treatment.
- FIG. 1 the nodular structure of the ⁇ phase of tungsten and the ⁇ phase of binder, the mean free path of which is close to 20 ⁇ m, are observed in white.
- Figure 2 we see the formation of butterfly wings while the mean free path drops to around 10 to 14 ⁇ m.
- FIG. 3 the trend observed in FIG. 2 is accentuated and the mean free path is in the range 3 to 7 ⁇ m.
- FIG. 4 the rupture of the alloy is essentially internodular and cupular at the level of the ⁇ phase.
- FIGS. 5 and 6 corresponding to test pieces with characteristics superior to those of FIG. 4, it can be seen that the global rupture mode becomes transnodular with rare internodular rupture initiations.
- FIG. 7 At the level of the microstructure of the ⁇ phase, states of substructures are developed.
- FIG. 7 there is a restoration structure with rearranged cells of size 0.4 to 0.8 ⁇ m.
- Figure 8 we observe the polygonized step, step necessary for the transition to the highest characteristics.
- Figure 9 we see a typical structure of the highest characteristics with development of dislocation microcells from 0.05 to 0.01 ⁇ m.
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Abstract
Description
L'invention est relative à des alliages lourds de tungstène-nickel-fer à très hautes caractéristiques mécaniques et à un procédé de fabrication desdits alliages.The invention relates to heavy tungsten-nickel-iron alloys with very high mechanical characteristics and to a process for manufacturing said alloys.
L'homme de l'art sait que les matériaux destinés à la confection de masses d'équilibrage, d'écrans d'absorption de vibrations et de rayonnements de projectiles ayant une grande capacité de perforation X, α,β, γ, de projectiles ayant une grande capacité de perforation doivent avoir une masse spécifique relativement importante.A person skilled in the art knows that the materials intended for making up balancing masses, screens for absorbing vibrations and radiation from projectiles having a large perforation capacity X, α, β, γ, projectiles with a large perforation capacity must have a relatively large specific mass.
C'est pourquoi on recourt pour leur fabrication à des alliages dits "lourds" contenant principalement du tungstène réparti de façon homogène dans une matrice métallique formée généralement par des éléments de liaison tels que le nickel et le fer. Ces alliages ont le plus souvent une teneur en tungstène en poids comprise entre 90 et 98 % et une densité de 15,6 à 18. Ils sont obtenus essentiellement par la métallurgie des poudres, c'est-à-dire que leur composants sont mis en oeuvre à l'état pulvérulent, comprimés pour leur conférer la forme appropriée, frittés et stabilisés pour leur donner une tenue mécanique et éventuellement soumis à une opération de corroyage et de traitement thermique pour qu'ils acquièrent des caractéristiques mécaniques : résistance, allongement et dureté qui conviennent à l'usage qui en sera fait.This is why recourse is made, for their manufacture, to so-called "heavy" alloys containing mainly tungsten distributed homogeneously in a metallic matrix generally formed by connecting elements such as nickel and iron. These alloys most often have a tungsten content by weight of between 90 and 98% and a density of 15.6 to 18. They are obtained essentially by powder metallurgy, that is to say that their components are put in the pulverulent state, compressed to give them the appropriate shape, sintered and stabilized to give them mechanical strength and possibly subjected to a wrinkling and heat treatment operation so that they acquire mechanical characteristics: strength, elongation and hardness suitable for the use that will be made of it.
L'enseignement de tels alliages est donné par exemple par l'USP 3 979 234 qui décrit un procédé de fabrication d'alliage de W-Ni-Fe dans lequel:
- on prépare un mélange homogène de poudres contenant en poids 85-96 % W, le reste étant du nickel et du fer dans un rapport pondéral Ni/Fe de 5,5 à 8,2
on comprime le mélange sous forme de compactés
- on fritte les compactés dans une atmosphère réductrice à une température d'au moins 1200°C et au-dessous de la température d'apparition d'une phase liquide pendant une durée suffisante pour obtenir un produit ayant une densité d'au moins 95 % de la densité théorique
on chauffe le produit à une température comprise entre 0,1 et 20°C au-dessus de la température d'apparition d'une phase liquide pendant le temps suffisant pour faire apparaître une phase liquide mais insuffisante pour obtenir la déformation du produit
- on recuit sous vide le produit entre 700 et 1420°C pendant un temps suffisant pour le dégazer
on l'usine aux dimensions souhaitées, opération qui peut être précédée par au moins une passe de corroyage pour en augmenter la résistance.The teaching of such alloys is given for example by USP 3,979,234 which describes a process for manufacturing W-Ni-Fe alloys in which:
- A homogeneous mixture of powders containing by weight 85-96% W is prepared, the rest being nickel and iron in a Ni / Fe weight ratio of 5.5 to 8.2
the mixture is compressed in the form of compacts
- The compacts are sintered in a reducing atmosphere at a temperature of at least 1200 ° C and below the temperature of appearance of a liquid phase for a sufficient time to obtain a product having a density of at least 95 % of theoretical density
the product is heated to a temperature between 0.1 and 20 ° C above the temperature of appearance of a liquid phase during sufficient time to show a liquid phase but insufficient to obtain the deformation of the product
- the product is annealed under vacuum between 700 and 1420 ° C for a time sufficient to degas it
it is factory at the desired dimensions, an operation which can be preceded by at least one wrought pass to increase its resistance.
Dans ces conditions, on obtient, par exemple, un produit présentant, après un corroyage conduisant à une réduction de surface de 31 %, une résistance à la rupture RM de 1220 MPa, une limite élastique R 0,2 de 1180 MPa, un allongement A de 7,8 % et une dureté Rockwell C : HRc de 41.
Ces caractéristiques sont suffisantes pour certains usages mais, pour des applications de plus haute sollicitation, elles s'avèrent très nettement insuffisantes car des niveaux de résistance à la rupture supérieures à 1600 MPa et pouvant aller jusqu'à 2000 MPa sont maintenant recherchés.Under these conditions, one obtains, for example, a product having, after a wrinkling leading to a surface reduction of 31%, a breaking strength RM of 1220 MPa, an elastic limit R 0.2 of 1180 MPa, an elongation A of 7.8% and a Rockwell C: HRc hardness of 41.
These characteristics are sufficient for certain uses but, for applications of higher stress, they prove to be very clearly insufficient because levels of resistance to rupture higher than 1600 MPa and being able to go up to 2000 MPa are now sought.
La présente invention a pour objet des alliages lourds de densité comprise entre 15,6 et 18 contenant en poids entre 80 et 99 % de tungstène, ainsi que du nickel et du fer dans un rapport pondéral Ni/Fe supérieur ou égal à 1,5 et éventuellement d'autres éléments tels que le molybdène, le titane, l'aluminium, le manganèse, le cobalt, le rhénium, qui présentent de très hautes caractéristiques mécaniques et notamment une résistance à la rupture pouvant aller jusqu'à 2000 MPa pour un allongement d'au moins l %.The subject of the present invention is heavy alloys with a density of between 15.6 and 18 containing by weight between 80 and 99% of tungsten, as well as nickel and iron in a Ni / Fe weight ratio greater than or equal to 1.5. and possibly other elements such as molybdenum, titanium, aluminum, manganese, cobalt, rhenium, which have very high mechanical characteristics and in particular a breaking strength of up to 2000 MPa for a at least 1% elongation.
Selon l'invention, ces alliages lourds sont caractérisés en ce qu'ils présentent une structure où la phase α de tungstène a la forme d'ailes de papillon avec des cellules de dislocation de dimensions comprises entre 0,01 et 1 µm et la phase γ du liant a un libre parcours moyen inférieur à 15 µm.According to the invention, these heavy alloys are characterized in that they have a structure where the α phase of tungsten has the form of butterfly wings with dislocation cells of dimensions between 0.01 and 1 μm and the phase γ of the binder has an average free path of less than 15 µm.
Il est connu de l'homme de l'art que les alliages tungstène nickel-fer ont une structure formée de nodules de tungstène pur plus ou moins sphérodisés au frittage constituant la phase α , ces nodules étant entourés par une phase γ composée des trois éléments de l'alliage qui joue le rôle de liant entre lesdits nodules.It is known to those skilled in the art that nickel-iron tungsten alloys have a structure formed of pure tungsten nodules more or less spherodized during sintering constituting the α phase, these nodules being surrounded by a γ phase composed of the three elements of the alloy which acts as a binder between said nodules.
La demanderesse a trouvé que pour développer de très hautes caractéristiques mécaniques, les alliages de tungstène devaient présenter une structure particulière.The Applicant has found that to develop very high mechanical characteristics, the tungsten alloys had to have a particular structure.
Ainsi, du point de vue morphologique, si on examine sur une éprouvette obtenue à partir de ces alliages une surface transversale à la direction de corroyage, on constate que :
- la phase α n'a plus une forme sphérodisée mais plutôt celle d'ellipsoïdes accolés deux à deux au voisinage de l'une des extrémités de leur grand axe de manière à former entre lesdits axes un angle aigu, disposition plus communément appelée "ailes de papillon"
- la phase γ de liant a un libre parcours moyen qui décroît au fur et à mesure que la résistance à la rupture, notamment, augmente. Ainsi, en-dessous de 15 µm on atteint des valeurs supérieures à 1600 MPa.Thus, from the morphological point of view, if one examines on a test piece obtained from these alloys a surface transverse to the direction of working, one notes that:
- the α phase no longer has a spherodized shape but rather that of ellipsoids joined two by two in the vicinity of one of the ends of their major axis so as to form between said axes an acute angle, an arrangement more commonly called "wings" butterfly "
- The binder γ phase has an average free path which decreases as the breaking strength, in particular, increases. Thus, below 15 µm, values greater than 1600 MPa are reached.
On entend ici par libre parcours moyen, la moyenne des distances qui dans une direction donnée sépare deux zones successives de phase γ .By free mean path here is meant the average of the distances which in a given direction separates two successive zones of phase γ.
Du point de vue microstructure, par prélèvement de lames minces, on constate la présence dans la phase α de cellules de dislocation de dimensions comprises entre 0,01 et 1 µm qui vont décroissant à mesure que les caractéristiques mécaniques augmentent. Suivant cette augmentation, on observe également une désorientation de ces cellules les unes par rapport aux autres. On pense que ce sont ces cellules qui confèrent à ces alliages la plasticité nécessaire à leur déformation. De plus, l'examen sur une éprouvette de la surface parallèle à la direction de corroyage fait apparaître une texture fibreuse d'autant plus prononcée que les caractéristiques mécaniques sont élevées. Ces fibres sont caractérisées par une orientation particulière répondant, suivant les indices de Miller, à la direction < 110 > pour les pôles 
Par ailleurs, l'accroissement des caractéristiques mécaniques au-delà de 1500 MPa passe par une polygonisation de la phase α. Complémentairement, se développe un réseau de précipitation de la phase γ dans le domaine de contiguité des nodules de la phase α .Furthermore, the increase in mechanical characteristics beyond 1500 MPa requires a polygonization of the α phase. In addition, a γ phase precipitation network develops in the domain of contiguity of the nodules of the α phase.
L'invention a également pour objet un procédé de fabrication d'alliages ayant une telle structure et dans lequel on peut régler à volonté la valeur des caractéristiques mécaniques souhaitées et notamment atteindre une résistance à la rupture voisine de 2000 MPa.The invention also relates to a method for manufacturing alloys having such a structure and in which the value of the desired mechanical characteristics can be adjusted at will and in particular reaching a tensile strength close to 2000 MPa.
Pour y parvenir, elle a mis au point un traitement des alliages permettant de favoriser la déformation plastique de la phase α sachant que celleci est normalement fragile mais qu'elle a une haute limite élastique.To achieve this, it has developed a treatment for alloys allowing to favor the plastic deformation of the α phase knowing that this is normally fragile but that it has a high elastic limit.
Ce procédé comporte les étapes déjà connues et consistant à :
- mettre en oeuvre des poudres de chaque élément de l'alliage, chacune d'elles ayant un diamètre FISHER compris entre 1 et 15 µm
- mélanger lesdites poudres dans des proportions correspondant à la composition de l'alliage souhaité
- comprimer lesdites poudres sous forme de compactés
- fritter les compactés entre 1490 et 1650°C pendant 2 à 5 heures
- traiter les compactés frittés sous vide entre 1000 et 1300°C
- soumettre les compactés ainsi obtenus à au moins une passe de corroyage.This process includes the steps already known and consisting in:
- use powders of each element of the alloy, each of them having a FISHER diameter of between 1 and 15 μm
- mixing said powders in proportions corresponding to the composition of the desired alloy
- compressing said powders in the form of compacts
- sinter the compacts between 1490 and 1650 ° C for 2 to 5 hours
- treat the sintered compacts under vacuum between 1000 and 1300 ° C
- subject the compacts thus obtained to at least one wrought pass.
Mais ce qui le caractérise, c'est que l'on fait subir aux compactés après traitement sous vide au moins trois cycles d'opérations comprenant chacun un corroyage suivi d'un traitement thermique.But what characterizes it is that the compacts are subjected after vacuum treatment to at least three cycles of operations each comprising a working followed by a heat treatment.
Ainsi, l'invention consiste en une succession de cycles qui sont d'autant plus nombreux que l'on veut atteindre des structures correspondant aux plus hautes valeurs des caractéristiques mécaniques.
Ainsi trois cycles permettent d'atteindre une résistance à la rupture comprise entre 1400 et 1450 MPa, tandis qu'au bout de quatre cycles on avoisine des valeurs de 1850 MPa.
Chacun de ces cycles comporte dans l'ordre une étape de corroyage réalisée par martelage, par exemple, de manière à développer un certain taux de réduction de surface du compacté fritté compris entre 10 et 50 % suivie d'un traitement de recuit par passage dans un four chauffé à une température inférieure à 1300°C sous une atmosphère inerte pendant 4 à 20 heures.Thus, the invention consists of a succession of cycles which are all the more numerous when it is desired to reach structures corresponding to the highest values of the mechanical characteristics.
Thus, three cycles make it possible to reach a breaking strength of between 1400 and 1450 MPa, while at the end of four cycles, it is close to values of 1850 MPa.
Each of these cycles comprises in order a step of wrought-out carried out by hammering, for example, so as to develop a certain reduction rate of surface of the sintered compact between 10 and 50% followed by an annealing treatment by passage in an oven heated to a temperature below 1300 ° C under an inert atmosphere for 4 to 20 hours.
De préférence, au cours des deux premiers cycles, les taux de corroyage sont plus faibles et les températures plus élevées qu'au cours des cycles ultérieurs.
Lors du quatrième cycle, le taux de corroyage convenable est atteint en pratiquant au moins deux passes successives dans la marteleuse, par exemple, avant d'effectuer le traitement thermique.Preferably, during the first two cycles, the wrought rates are lower and the temperatures higher than during the cycles later.
During the fourth cycle, the suitable degree of wrought work is achieved by making at least two successive passes in the hammer hammer, for example, before carrying out the heat treatment.
L'invention peut être illustrée à l'aide des planches de dessins ci-jointes et qui représentent pour un alliage contentant en poids 93 % de tungstène, 5 % de nickel et 2 % de fer :
- - fig. 1,2,3, les structures sous un grossissement de 200 de coupes transversales d'éprouvettes ayant respectivement une résistance à la rupture de 1100, 1540 et 1850 MPa
- - fig. 4,5,6, des microstructures de faciès de rupture en traction obtenues à partir des mêmes éprouvettes sous des grossissements respectifs de 1000-1000-2600.
- - fig. 7,8,9, des microstructures obtenues par observation au microscope électronique de lames minces sous des grossissements respectifs de 35.000, 30.000 et 60.000, mettant en évidence l'état spécifique de la phaseα permettant d'atteindre les caractéristiques souhaitées.
- - fig. 1,2,3, the structures under a magnification of 200 of transverse sections of test pieces having respectively a breaking strength of 1100, 1540 and 1850 MPa
- - fig. 4,5,6, microstructures of tensile fracture facies obtained from the same test pieces under respective magnifications of 1000-1000-2600.
- - fig. 7,8,9, microstructures obtained by observation with an electron microscope of thin sections at respective magnifications of 35,000, 30,000 and 60,000, highlighting the specific state of the α phase making it possible to achieve the desired characteristics.
Sur la figure 1, on observe en blanc la structure nodulaire de la phase α de tungstène et la phase γ de liant dont le libre parcours moyen est voisin de 20 µm.
Sur la figure 2, on constate la formation d'ailes de papillon tandis que le libre parcours moyens s'abaisse aux environs de 10 à 14 µm.
Sur la figure 3, la tendance constatée sur la figure 2 s'accentue et le libre parcours moyen se situe dans la fourchette 3 à 7 µm.
Sur la figure 4, la rupture de l'alliage est essentiellement internodulaire et cupulaire au niveau de la phase γ.
Sur les figures 5 et 6 correspondant à des éprouvettes de caractéristiques supérieures à celles de la figure 4, on constate que le mode de rupture global devient transnodulaire avec de rares initiations de rupture internodulaires. Au niveau de la microstructure de la phase α des états de sous structures sont développés.
Sur la figure 7, on remarque une structure de restauration avec des cellules réarrangées de taille 0,4 à 0,8 µm.
Sur la figure 8, on observe l'étape polygonisée, étape nécessaire au passage aux plus hautes caractéristiques.
Sur la figure 9, on voit une structure typique des plus hautes caractéristiques avec développement de microcellules de dislocation de 0,05 à 0,01 µm.In FIG. 1, the nodular structure of the α phase of tungsten and the γ phase of binder, the mean free path of which is close to 20 μm, are observed in white.
In Figure 2, we see the formation of butterfly wings while the mean free path drops to around 10 to 14 µm.
In FIG. 3, the trend observed in FIG. 2 is accentuated and the mean free path is in the range 3 to 7 μm.
In FIG. 4, the rupture of the alloy is essentially internodular and cupular at the level of the γ phase.
In FIGS. 5 and 6, corresponding to test pieces with characteristics superior to those of FIG. 4, it can be seen that the global rupture mode becomes transnodular with rare internodular rupture initiations. At the level of the microstructure of the α phase, states of substructures are developed.
In FIG. 7, there is a restoration structure with rearranged cells of size 0.4 to 0.8 μm.
In Figure 8, we observe the polygonized step, step necessary for the transition to the highest characteristics.
In Figure 9, we see a typical structure of the highest characteristics with development of dislocation microcells from 0.05 to 0.01 µm.
L'invention peut être illustrée à l'aide de l'exemple d'application suivantThe invention can be illustrated using the following application example
On a mélangé des poudres élémentaires de diamètre FISHER comprises entre 1,4 et 10 µm de manière à obtenir un produit ayant la composition en poids suivante : W 93 % - Ni 5 % - Fe 2 %.
Après compression isostatique sous une pression de 230 MPa, les compactés de diamètre 90 mm et de longueur 500 mm ont été frittés dans un four à passage à une température de 1490°C pendant 5 heures puis maintenus sous vide partiel pendant 25 heures dans un four chauffé entre 900 et 1300°C.
Les produits ainsi obtenus ont alors été traités suivant l'invention.
Les conditions particulières dans lesquelles ont été effectués les cycles ainsi que les caractéristiques mécaniques Rm (résistance à la rupture), RO,2 (résistance à 0,2 % d'allongement), A (allongement) HV30(dureté Vickers) et HRc (dureté Rockwell) obtenues aux différents cycles de traitement ont été rassemblés dans le tableau suivant:
After isostatic compression under a pressure of 230 MPa, the compacts with a diameter of 90 mm and a length of 500 mm were sintered in a pass-through oven at a temperature of 1490 ° C for 5 hours then kept under partial vacuum for 25 hours in an oven heated between 900 and 1300 ° C.
The products thus obtained were then treated according to the invention.
The particular conditions under which the cycles were carried out as well as the mechanical characteristics Rm (resistance to rupture), RO, 2 (resistance to 0.2% elongation), A (elongation) HV30 (Vickers hardness) and HRc ( Rockwell hardness) obtained at the different treatment cycles have been collated in the following table:
On constate donc que la résistance à la rupture augmente fortement quand on augmente le nombre de cycles et que l'allongement demeure suffisant pour permettre la transformation de l'alliage.It is therefore found that the breaking strength increases sharply when the number of cycles is increased and that the elongation remains sufficient to allow the transformation of the alloy.
Claims (7)
- on met en oeuvre des poudres de chaque élément ayant un diamètre FISHER compris entre 1 et 15 µm
- on mélange lesdites poudres dans des proportions correspondant à la composition de l'alliage souhaité
- on comprime lesdites poudres sous forme de compactés
- on fritte les compactés à une température comprise entre 1490 et 1650°C pendant 2 à 5 heures
- on traite les compactés frittés sous vide entre 1000 et 1300°C
- on les soumet à au moins une passe de corroyage
caractérisé en ce que l'on fait subir au compactés après traitement sous vide au moins trois cycles d'opérations comprenant chacun un corroyage suivi d'un traitement thermique.5. Method for manufacturing alloys according to claim 1, in which:
- powders of each element having a FISHER diameter of between 1 and 15 μm are used
- Said powders are mixed in proportions corresponding to the composition of the desired alloy
- said powders are compressed in the form of compacts
- the compacts are sintered at a temperature between 1490 and 1650 ° C for 2 to 5 hours
- the sintered compacts are treated under vacuum between 1000 and 1300 ° C
- they are subjected to at least one currying pass
characterized in that the compacts are subjected to after vacuum treatment at least three cycles of operations each comprising a working followed by a heat treatment.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AT88420358T ATE73174T1 (en) | 1987-10-23 | 1988-10-20 | TUNGRAM-NICKEL-IRON HEAVY METAL ALLOYS WITH VERY HIGH MECHANICAL PROPERTIES AND PROCESSES FOR THE PRODUCTION OF THESE ALLOYS. |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR8715315 | 1987-10-23 | ||
| FR8715315A FR2622209B1 (en) | 1987-10-23 | 1987-10-23 | HEAVY DUTIES OF TUNGSTENE-NICKEL-IRON WITH VERY HIGH MECHANICAL CHARACTERISTICS AND METHOD OF MANUFACTURING SAID ALLOYS |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0313484A1 true EP0313484A1 (en) | 1989-04-26 |
| EP0313484B1 EP0313484B1 (en) | 1992-03-04 |
Family
ID=9356493
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP88420358A Expired - Lifetime EP0313484B1 (en) | 1987-10-23 | 1988-10-20 | Tungsten-nickel-iron high-density alloys with very high mechanical properties, and process for manufacturing these alloys |
Country Status (21)
| Country | Link |
|---|---|
| US (2) | US4938799A (en) |
| EP (1) | EP0313484B1 (en) |
| JP (1) | JPH01142048A (en) |
| KR (1) | KR950008693B1 (en) |
| CN (1) | CN1019318B (en) |
| AT (1) | ATE73174T1 (en) |
| AU (1) | AU606759B2 (en) |
| BR (1) | BR8805467A (en) |
| CA (1) | CA1340011C (en) |
| DE (1) | DE3868843D1 (en) |
| DK (1) | DK587288A (en) |
| EG (1) | EG19412A (en) |
| ES (1) | ES2032336T3 (en) |
| FR (1) | FR2622209B1 (en) |
| GR (1) | GR3003967T3 (en) |
| IL (1) | IL88062A (en) |
| IN (1) | IN171726B (en) |
| PT (1) | PT88821B (en) |
| SG (1) | SG73092G (en) |
| YU (1) | YU47632B (en) |
| ZA (1) | ZA887893B (en) |
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| EP0396185A1 (en) * | 1989-05-03 | 1990-11-07 | Metallwerk Plansee Gesellschaft M.B.H. | Process for preparing semi-finished creep resistant products from high melting metal |
| US5462576A (en) * | 1993-06-07 | 1995-10-31 | Nwm De Kruithoorn B.V. | Heavy metal alloy and method for its production |
| EP2372296A1 (en) | 2010-03-30 | 2011-10-05 | Nexter Munitions | Kinetic energy penetrator |
| EP2372295A1 (en) | 2010-03-30 | 2011-10-05 | Nexter Munitions | Penetrator with stepped profile |
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| US6136105A (en) * | 1998-06-12 | 2000-10-24 | Lockheed Martin Corporation | Process for imparting high strength, ductility, and toughness to tungsten heavy alloy (WHA) materials |
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| US6447715B1 (en) * | 2000-01-14 | 2002-09-10 | Darryl D. Amick | Methods for producing medium-density articles from high-density tungsten alloys |
| EP1134539A1 (en) * | 2000-02-07 | 2001-09-19 | Halliburton Energy Services, Inc. | High performance powdered metal mixtures for shaped charge liners |
| KR100363395B1 (en) * | 2000-04-17 | 2002-12-02 | 국방과학연구소 | Fabrication process of micro-crystalline tungsten heavy alloy by mechanical alloying and rapid two-step sintering |
| KR100390173B1 (en) * | 2000-12-28 | 2003-07-10 | 주식회사 래피더스 | Method for manufacturing high ductile tungsten based heavy alloy having an excellent oxidation resistance |
| US7217389B2 (en) * | 2001-01-09 | 2007-05-15 | Amick Darryl D | Tungsten-containing articles and methods for forming the same |
| FR2830022B1 (en) * | 2001-09-26 | 2004-08-27 | Cime Bocuze | HIGH POWER SINTERED TUNGSTEN BASE ALLOY |
| US6749802B2 (en) | 2002-01-30 | 2004-06-15 | Darryl D. Amick | Pressing process for tungsten articles |
| WO2003064961A1 (en) * | 2002-01-30 | 2003-08-07 | Amick Darryl D | Tungsten-containing articles and methods for forming the same |
| KR100467393B1 (en) * | 2002-07-13 | 2005-01-24 | 주식회사 풍산 | W-heavy alloy penetrator producing accumulation fragmentation effect & Method of manufacuring of same |
| US7000547B2 (en) | 2002-10-31 | 2006-02-21 | Amick Darryl D | Tungsten-containing firearm slug |
| US7059233B2 (en) * | 2002-10-31 | 2006-06-13 | Amick Darryl D | Tungsten-containing articles and methods for forming the same |
| EP1633897A2 (en) * | 2003-04-11 | 2006-03-15 | Darryl Dean Amick | System and method for processing ferrotungsten and other tungsten alloys articles formed therefrom and methods for detecting the same |
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| CN107058841B (en) * | 2017-06-29 | 2018-12-21 | 浙江创特新材科技有限公司 | A kind of high mechanical strength tungsten alloy material and preparation method thereof |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| DE1558821A1 (en) * | 1967-03-25 | 1970-06-04 | Hermsdorf Keramik Veb | Process for the production of ductile semi-finished products |
| US3979234A (en) * | 1975-09-18 | 1976-09-07 | The United States Of America As Represented By The United States Energy Research And Development Administration | Process for fabricating articles of tungsten-nickel-iron alloy |
| EP0073384A1 (en) * | 1981-08-27 | 1983-03-09 | GTE Products Corporation | Frangible tungsten penetrator |
| EP0209632A2 (en) * | 1985-07-10 | 1987-01-28 | GTE Products Corporation | Method for producing an elongate tungsten article |
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| FR2225980A5 (en) * | 1969-10-28 | 1974-11-08 | Onera (Off Nat Aerospatiale) | |
| US3888636A (en) * | 1971-02-01 | 1975-06-10 | Us Health | High density, high ductility, high strength tungsten-nickel-iron alloy & process of making therefor |
| US3988118A (en) * | 1973-05-21 | 1976-10-26 | P. R. Mallory & Co., Inc. | Tungsten-nickel-iron-molybdenum alloys |
| US4090875A (en) * | 1973-10-01 | 1978-05-23 | The United States Of America As Represented By The Department Of Energy | Ductile tungsten-nickel-alloy and method for manufacturing same |
| JPS5913037A (en) * | 1982-07-09 | 1984-01-23 | Sumitomo Electric Ind Ltd | Production of w-ni-fe sintered alloy |
| DE3336516C2 (en) * | 1983-10-07 | 1985-09-05 | Bayerische Metallwerke GmbH, 7530 Pforzheim | Lining and allocation for hollow, flat and projectile cargoes |
| JP2531623B2 (en) * | 1986-02-12 | 1996-09-04 | 三菱マテリアル株式会社 | Manufacturing method of W-based sintered alloy flying body having high toughness |
| US4851042A (en) * | 1987-05-12 | 1989-07-25 | Rensselaer Polytechnic Institute | Hardness and strength of heavy alloys by addition of tantalum |
| US4762559A (en) * | 1987-07-30 | 1988-08-09 | Teledyne Industries, Incorporated | High density tungsten-nickel-iron-cobalt alloys having improved hardness and method for making same |
-
1987
- 1987-10-23 FR FR8715315A patent/FR2622209B1/en not_active Expired - Lifetime
-
1988
- 1988-09-29 IN IN680/MAS/88A patent/IN171726B/en unknown
- 1988-10-05 US US07/253,506 patent/US4938799A/en not_active Expired - Lifetime
- 1988-10-17 CA CA000580392A patent/CA1340011C/en not_active Expired - Fee Related
- 1988-10-17 IL IL88062A patent/IL88062A/en not_active IP Right Cessation
- 1988-10-20 DE DE8888420358T patent/DE3868843D1/en not_active Expired - Lifetime
- 1988-10-20 ES ES198888420358T patent/ES2032336T3/en not_active Expired - Lifetime
- 1988-10-20 JP JP63265202A patent/JPH01142048A/en active Granted
- 1988-10-20 AT AT88420358T patent/ATE73174T1/en not_active IP Right Cessation
- 1988-10-20 EP EP88420358A patent/EP0313484B1/en not_active Expired - Lifetime
- 1988-10-20 CN CN88107568A patent/CN1019318B/en not_active Expired
- 1988-10-21 ZA ZA887893A patent/ZA887893B/en unknown
- 1988-10-21 PT PT88821A patent/PT88821B/en not_active IP Right Cessation
- 1988-10-21 DK DK587288A patent/DK587288A/en not_active Application Discontinuation
- 1988-10-21 YU YU197388A patent/YU47632B/en unknown
- 1988-10-21 AU AU24088/88A patent/AU606759B2/en not_active Ceased
- 1988-10-21 BR BR8805467A patent/BR8805467A/en not_active IP Right Cessation
- 1988-10-22 KR KR1019880013866A patent/KR950008693B1/en not_active IP Right Cessation
- 1988-10-24 EG EG54888A patent/EG19412A/en active
-
1990
- 1990-03-07 US US07/489,510 patent/US4960563A/en not_active Expired - Lifetime
-
1992
- 1992-03-05 GR GR910401849T patent/GR3003967T3/el unknown
- 1992-07-16 SG SG730/92A patent/SG73092G/en unknown
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| DE1558821A1 (en) * | 1967-03-25 | 1970-06-04 | Hermsdorf Keramik Veb | Process for the production of ductile semi-finished products |
| US3979234A (en) * | 1975-09-18 | 1976-09-07 | The United States Of America As Represented By The United States Energy Research And Development Administration | Process for fabricating articles of tungsten-nickel-iron alloy |
| EP0073384A1 (en) * | 1981-08-27 | 1983-03-09 | GTE Products Corporation | Frangible tungsten penetrator |
| EP0209632A2 (en) * | 1985-07-10 | 1987-01-28 | GTE Products Corporation | Method for producing an elongate tungsten article |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0396185A1 (en) * | 1989-05-03 | 1990-11-07 | Metallwerk Plansee Gesellschaft M.B.H. | Process for preparing semi-finished creep resistant products from high melting metal |
| US5051139A (en) * | 1989-05-03 | 1991-09-24 | Schwarzkopf Development Corporation | Process for the manufacture of semi-finished products or preformed parts made of refractory metals and resistant to thermal creep |
| US5462576A (en) * | 1993-06-07 | 1995-10-31 | Nwm De Kruithoorn B.V. | Heavy metal alloy and method for its production |
| EP2372296A1 (en) | 2010-03-30 | 2011-10-05 | Nexter Munitions | Kinetic energy penetrator |
| EP2372295A1 (en) | 2010-03-30 | 2011-10-05 | Nexter Munitions | Penetrator with stepped profile |
| FR2958392A1 (en) * | 2010-03-30 | 2011-10-07 | Nexter Munitions | PENETRATEUR WITH KINETIC ENERGY WITH STAGE PROFILE. |
Also Published As
| Publication number | Publication date |
|---|---|
| US4938799A (en) | 1990-07-03 |
| PT88821B (en) | 1993-01-29 |
| ES2032336T3 (en) | 1993-02-01 |
| IN171726B (en) | 1992-12-19 |
| FR2622209A1 (en) | 1989-04-28 |
| CN1019318B (en) | 1992-12-02 |
| EG19412A (en) | 1995-01-31 |
| AU2408888A (en) | 1989-04-27 |
| DK587288A (en) | 1989-04-24 |
| FR2622209B1 (en) | 1990-01-26 |
| ZA887893B (en) | 1989-07-26 |
| US4960563A (en) | 1990-10-02 |
| CN1033651A (en) | 1989-07-05 |
| EP0313484B1 (en) | 1992-03-04 |
| GR3003967T3 (en) | 1993-03-16 |
| DK587288D0 (en) | 1988-10-21 |
| YU197388A (en) | 1990-08-31 |
| KR890006843A (en) | 1989-06-16 |
| IL88062A (en) | 1992-09-06 |
| IL88062A0 (en) | 1989-06-30 |
| JPH0468371B2 (en) | 1992-11-02 |
| CA1340011C (en) | 1998-08-25 |
| KR950008693B1 (en) | 1995-08-04 |
| JPH01142048A (en) | 1989-06-02 |
| BR8805467A (en) | 1989-07-04 |
| SG73092G (en) | 1992-10-02 |
| ATE73174T1 (en) | 1992-03-15 |
| YU47632B (en) | 1995-12-04 |
| AU606759B2 (en) | 1991-02-14 |
| DE3868843D1 (en) | 1992-04-09 |
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