EP0456591A1 - Copper-based spinodal alloys and process for their preparation - Google Patents
Copper-based spinodal alloys and process for their preparation Download PDFInfo
- Publication number
- EP0456591A1 EP0456591A1 EP91420149A EP91420149A EP0456591A1 EP 0456591 A1 EP0456591 A1 EP 0456591A1 EP 91420149 A EP91420149 A EP 91420149A EP 91420149 A EP91420149 A EP 91420149A EP 0456591 A1 EP0456591 A1 EP 0456591A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- finished product
- alloy
- semi
- substrate
- process according
- 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.)
- Withdrawn
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
- B22D23/00—Casting processes not provided for in groups B22D1/00 - B22D21/00
- B22D23/003—Moulding by spraying metal on a surface
-
- 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
- C22C1/0425—Copper-based alloys
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C9/00—Alloys based on copper
- C22C9/06—Alloys based on copper with nickel or cobalt as the next major constituent
-
- 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
- C22F1/08—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of copper or alloys based thereon
-
- 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
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
- C23C4/12—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the method of spraying
- C23C4/123—Spraying molten metal
Definitions
- the invention relates to the field of copper, nickel and tin alloys with spinodal decomposition and their manufacturing process.
- American patent n ° 4052204 describes compositions of Cu Ni Sn alloys which may contain Fe, Zn, Mn, Zr, Nb, Cr, Al, Mg. Furthermore, a selective composition of Sn and Ni makes it possible, according to American patent n ° 4090890, to obtain a band resistant to folding.
- US Patent No. 4,260,432 describes a composition of Cu Ni Sn alloy with Mo, Nb, Ta, V, Fe comprising hot or cold shaping, intermediate annealing followed by quenching, shaping cold and final income.
- European patent n ° 079755 describes a process for manufacturing a Cu Ni Sn alloy, which may contain other elements in small quantities, such as Fe, Mg, Mn, Mo, Nb, Ta, V, Al, Cr, Si, Zn, Zr and using a powder metallurgy technique previously obtained by atomization and which comprises a step of compacting the powders to form a strip, a step of sintering, cooling, cold rolling with intermediate annealing followed by quenching, a final annealing followed by quenching and a tempering step.
- a powder metallurgy technique previously obtained by atomization and which comprises a step of compacting the powders to form a strip, a step of sintering, cooling, cold rolling with intermediate annealing followed by quenching, a final annealing followed by quenching and a tempering step.
- the subject of the invention is the economical industrial manufacture of finished or semi-finished products based on Cu Ni Sn alloys with spinodal decomposition, which may contain other minor addition elements, not presenting any tin segregation ; it also relates to a process for manufacturing all of the products demanded by the market for this type of alloy regardless of their shape or size, by combining in a single step the rapid solidification of the liquid metal and obtaining blank (semi-finished product) suitable for hot and cold processing.
- the object of the invention is to improve the machinability to the point of allowing the industrial manufacture of parts which hitherto could not have been with this type of alloy.
- the weight composition of Ni is between 8 and 16% and that of Sn between 4 and 10%.
- niobium-titanium coming from superconductive cables nickel-titanium vaning alloy with shape memory
- an alloy is prepared in the liquid state, based on Cu, Ni, Sn with Ti and possibly Pb, by melting in an induction furnace provided with a crucible made of silicon carbide , of a mixture in the proportions of the nominal composition of the alloy, of electrolytic copper at 99.99% of copper by weight, of electrolytic nickel at 99.92% of nickel by weight and of electrolytic tin at 99, 9% tin by weight and containing very little carbon (C ⁇ 0.002%), as well as titanium, preferably in the form of recycling metal for economic reasons.
- the fusion is done under cover of good quality charcoal, previously ignited, up to 1280 or 1300 ° C to be sure that all the nickel is melted.
- the electrolytic grade tin is then introduced using a graphite bell, in the proportion corresponding to the nominal composition of the alloy which it is desired to manufacture. If necessary, lead is added in the same way and wait 20 minutes for the temperature to reach 1100-1200 ° C.
- the free titanium is measured in the bath; in fact, titanium intervenes in the process itself on the one hand as a decarburization agent for nickel so that, if the nickel supplied was of lower quality, therefore of greater carbon content, a greater quantity of Ti would be transformed into insoluble titanium carbide; titanium also acts as a deoxidizing agent in the bath, the titanium oxide also being insoluble in the bath.
- the determination of the free Ti makes it possible to precisely adjust the composition of the Ti bath by introducing Ti in the form of a Cu-Ti master alloy to obtain the nominal Ti content. We wait another 10 min and we clean the alloy before pouring. The liquid alloy (after possible filtration) is ready to be transformed into a semi-finished product by spray-deposition.
- spray-deposition is meant a process in which the molten metal is divided in the form of fine liquid droplets which are then directed and agglomerated on a substrate so as to form a massive and coherent deposit containing a low closed porosity.
- This deposit can be in the form of billets, trays, plates, tubes whose geometry is controlled, or of blanks of various shapes ready for example to be forged, which we will denote by the general term of "semi-finished product".
- This deposit can be separated from the substrate which serves as a support and in this case, the semi-finished product consists only of alloy based on Cu Ni Sn; it can also be kept integral with the substrate so as to obtain, after transformation, a multilayer composite with an alloy part based on Cu Ni Sn and a part made of material constituting said support.
- the material of said support is preferably based on copper, aluminum, stainless steel.
- spray-deposition a technique of this type is referred to as "spray-deposition" by the Anglo-Saxons; it is described in the following patent applications: GB-B-1379261, GB-B-1472939, GB-B-1548616, GB-B-1599392, GB-A-2172827, EP-A-225080, EP-A- 225732, WOA-87-03012.
- the transformation of the semi-finished products uses, alone or in combination, the known means of deformation of the metal, such as, according to the geometric characteristics of the semi-finished product, hot rolling, cold rolling, hot spinning, drawing, forging, wire drawing.
- Another processing method is hot forging when massive parts are needed.
- the semi-finished product is generally passed over a lathe to bring its outer surface in the form of a cylinder of revolution with precise dimensions.
- the implementation annealing is a so-called “flash” annealing, that is to say comprising a very rapid rise in temperature; this temperature is between 450 ° C. and a temperature slightly lower than that of the liquidus, for example that of the liquidus reduced by 30 ° C. This temperature is preferably between 650 and 850 ° C.
- very rapid rise we mean an ascent rate which can range from 50 ° C per minute for semi-finished products of larger cross section to 500 ° C per second for semi-finished products of smaller cross section, such as wires of small cross section.
- the practical means for carrying out the flash annealing of the invention are either known in themselves, or adaptable from known means.
- flash annealing is preferably obtained with a continuous process as opposed to the process discontinuous by "batch", the semi-finished product itself being either continuous (strip) or discontinuous (tray, plate).
- a second important parameter is the actual heating technique: calories can be provided by an external source to the semi-finished product, by radiation, convection or conduction; this family of techniques is called “indirect heating” and is represented by electric resistance ovens, gas ovens with radiation or direct action of the flame on the product to be treated, ovens with salt bath or with fluidized bed .
- calories are generated within the semi-finished product during processing, according to techniques known as "direct heating” such as heating by Joule effect or by induction.
- Annealing is always followed by rapid quenching, carried out according to known means; in fact, if the cooling rate were too low, it could start to harden by spinodal decomposition, undesirable at this stage.
- the product obtained is subjected to a heat treatment of tempering, at an average temperature between 200 and 400 ° C, which ensures hardening by spinodal decomposition.
- the spinodal decomposition is influenced by the local tin content so that it is essential to obtain finished products of hardness and more generally of homogeneous mechanical characteristics, to maintain, until the final tempering phase, a homogeneous tin distribution.
- the means used in the invention make it possible to keep both the tin and the lead in the finely dispersed state.
- the invention makes it possible to obtain, on an industrial scale and economically, machinable products based on Cu Ni Sn of hardness high and homogeneous.
- the process developed by the applicant can also be applied to other copper alloys. It is of great interest to obtain copper alloys free of segregation, in particular in the case of alloys having a wide solidification interval, such as bronzes and particularly those based on Cu and Sn.
- composition of this billet was:
- the bar is thus qualified for the manufacture of connectors.
- This plate was then cold rolled to 1 mm thick.
- the product obtained is therefore a composite of 0.5 mm of copper intimately bound to 0.5 mm of Cu15Ni8Sn.
- the product was used to manufacture connectors, in which the electric current is conducted by copper while the elasticity and resistance to stress relaxation is ensured by the Cu15Ni8Sn alloy. .
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Plasma & Fusion (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Conductive Materials (AREA)
Abstract
Description
L'invention concerne le domaine des alliages de cuivre, nickel et étain à décomposition spinodale et leur procédé de fabrication.The invention relates to the field of copper, nickel and tin alloys with spinodal decomposition and their manufacturing process.
Ces alliages de cuivre, dans lesquels le durcissement dû à la solution solide est renforcé par un décomposition spinodale pouvant même aboutir à un durcissement par précipités, ont fait l'objet de nombreuses recherches car ils peuvent remplacer avantageusement les alliages cuivre-beryllium.These copper alloys, in which the hardening due to the solid solution is reinforced by a spinodal decomposition which can even lead to hardening by precipitates, have been the subject of much research because they can advantageously replace the copper-beryllium alloys.
Ainsi, le brevet américain n° 3937638 décrit des compositions d'alliage Cu Ni Sn et leur procédé d'obtention qui comporte une phase d'homogénéisation à 800°, une mise en forme à chaud et à froid avec des recuits intermédiaires à 800° C suivis de trempe, la mise en forme à froid finale étant suivie d'un revenu vers 300° C.Thus, American patent n ° 3937638 describes Cu Ni Sn alloy compositions and their production process which includes a homogenization phase at 800 °, hot and cold shaping with intermediate annealing at 800 ° C followed by quenching, the final cold shaping being followed by tempering at around 300 ° C.
Le brevet américain n° 4052204 décrit des compositions d'alliages Cu Ni Sn pouvant contenir du Fe, Zn, Mn, Zr, Nb, Cr, Al, Mg. Par ailleurs une composition sélective en Sn et Ni permet, selon le brevet américain n° 4090890, d'obtenir de la bande résistant au pliage.American patent n ° 4052204 describes compositions of Cu Ni Sn alloys which may contain Fe, Zn, Mn, Zr, Nb, Cr, Al, Mg. Furthermore, a selective composition of Sn and Ni makes it possible, according to American patent n ° 4090890, to obtain a band resistant to folding.
Le brevet américain n° 4260432 décrit une composition d'alliage Cu Ni Sn avec du Mo, Nb, Ta, V, Fe comportant une mise en forme à chaud ou à froid, des recuits intermédiaires suivis d'une trempe, une mise en forme à froid et un revenu final.US Patent No. 4,260,432 describes a composition of Cu Ni Sn alloy with Mo, Nb, Ta, V, Fe comprising hot or cold shaping, intermediate annealing followed by quenching, shaping cold and final income.
Les procédés décrits dans ces brevets américains relèvent de ce qu'il est convenu d'appeler la métallurgie classique, c'est-à-dire l'obtention de l'ébauche par fusion et coulée-solidification.The processes described in these American patents fall under what is known as conventional metallurgy, that is to say obtaining the blank by melting and casting-solidification.
Dans le cas des alliages Cu Ni Sn, l'inconvénient de ces procédés est inhérent à la forme même du diagramme d'équilibre des trois constituants Cu, Ni et Sn, qui présente un large intervalle de solidification conduisant à une ségrégation importante de l'étain incompatible avec l'obtention de propriétés mécaniques homogènes dans tout l'alliage. Des traitements thermiques de longue durée sont donc décrits pour compenser les effets néfastes de cette ségrégation, mais, comme cela est indiqué dans le brevet européen n° 079755, si ces traitements sont valables à l'échelle du laboratoire, leur efficacité n'a jamais été démontrée à l'échelle industrielle.In the case of Cu Ni Sn alloys, the drawback of these methods is inherent in the very form of the balance diagram of the three constituents Cu, Ni and Sn, which has a wide solidification interval leading to significant segregation of the tin incompatible with obtaining homogeneous mechanical properties throughout the alloy. Long-term heat treatments are therefore described to compensate for the harmful effects of this segregation, but, as indicated in European patent No. 079755, if these treatments are valid on a laboratory scale, their effectiveness has never has been demonstrated on an industrial scale.
Par ailleurs, on connaît aussi un procédé de coulée continue de barres à partir d'un bain de métal liquide. Dans ce procédé, il faut, pour lutter contre la ségrégation de l'étain, imposer une grande vitesse de solidification avec de forts débits d'eau de refroidissement de la lingotière en graphite, ce qui rend le procédé peu économique et le limite à la fabrication de produits de faible section ; quant aux additions métalliques spécifiques telles que celles de V, Nb, Ta, proposées pour limiter les conséquences de la ségrégation de l'étain, elles sont coûteuses et peu efficaces.Furthermore, a method is also known for continuously casting bars from a bath of liquid metal. In this process, it is necessary, in order to combat the segregation of tin, to impose a high rate of solidification with high flow rates of cooling water from the graphite ingot mold, which makes the process uneconomical and limits it to the manufacture of small section products; as for the specific metallic additions such as those of V, Nb, Ta, proposed to limit the consequences of tin segregation, they are costly and not very effective.
Par contre, le brevet européen n° 079755 décrit un procédé de fabrication d'un alliage Cu Ni Sn, pouvant contenir d'autres éléments en faible quantité, tels que Fe, Mg, Mn, Mo, Nb, Ta, V, Al, Cr, Si, Zn, Zr et utilisant une technique de métallurgie des poudres préalablement obtenues par atomisation et qui comporte une étape de compactage des poudres pour former une bande, une étape de frittage, de refroidissement, de laminage à froid avec recuits intermédiaires suivis de trempe, un recuit final suivi d'une trempe et d'une étape de revenu.On the other hand, European patent n ° 079755 describes a process for manufacturing a Cu Ni Sn alloy, which may contain other elements in small quantities, such as Fe, Mg, Mn, Mo, Nb, Ta, V, Al, Cr, Si, Zn, Zr and using a powder metallurgy technique previously obtained by atomization and which comprises a step of compacting the powders to form a strip, a step of sintering, cooling, cold rolling with intermediate annealing followed by quenching, a final annealing followed by quenching and a tempering step.
Ce procédé de métallurgie des poudres décrit dans ce brevet européen d'une part ne permet que l'obtention d'un produit fini limité à un produit laminé mince tel que ruban, bande, tôle, d'autre part conduit à des alliages de prix de revient élevé à cause des deux étapes successives d'obtention de la poudre et du compactage.This powder metallurgy process described in this European patent on the one hand only allows obtaining a finished product limited to a thin laminated product such as tape, strip, sheet metal, on the other hand leads to price alloys high cost due to the two successive stages of obtaining the powder and compaction.
Finalement, compte tenu de tous ces problèmes, cette famille d'alliages n'a pas encore connu de véritable essor industriel et commercial.Finally, given all these problems, this family of alloys has not yet experienced real industrial and commercial growth.
L'invention a pour objet la fabrication industrielle économique de produits finis ou semi-finis à base d'alliages de Cu Ni Sn à décomposition spinodale, pouvant comporter d'autres éléments mineurs d'addition, ne présentant pas de ségrégation de l'étain ; elle a aussi pour objet un procédé permettant de fabriquer l'ensemble des produits demandés par le marché pour ce type d'alliage quelle que soit leur forme ou leur taille, en combinant en une seule étape la solidification rapide du métal liquide et l'obtention d'ébauche (demi-produit) apte à être transformée à chaud et à froid.The subject of the invention is the economical industrial manufacture of finished or semi-finished products based on Cu Ni Sn alloys with spinodal decomposition, which may contain other minor addition elements, not presenting any tin segregation ; it also relates to a process for manufacturing all of the products demanded by the market for this type of alloy regardless of their shape or size, by combining in a single step the rapid solidification of the liquid metal and obtaining blank (semi-finished product) suitable for hot and cold processing.
Enfin, l'invention a pour objet l'amélioration de l'usinabilité au point de permettre la fabrication industrielle de pièces qui ne pouvaient l'être jusqu'à présent avec ce type d'alliage.Finally, the object of the invention is to improve the machinability to the point of allowing the industrial manufacture of parts which hitherto could not have been with this type of alloy.
L'invention concerne un procédé de fabrication d'un produit fini constitué, au moins en partie, d'un alliage à base de cuivre, de nickel et d'étain, ayant subi une décomposition spinodale, caractérisé en ce que :
- a) on prépare un bain liquide de l'alliage à base de Cu Ni Sn contenant en outre du titane, ou tout autre élément décarburant et affinant, et éventuellement du plomb
- b) on forme un demi-produit par pulvérisation-dépôt de cet alliage sur un substrat servant de support
- c) on transforme ce demi-produit, dont une partie peut être constituée dudit substrat, avec, quand nécessaire, un recuit "flash" suivi d'une trempe rapide
- d) on soumet le produit obtenu après transformation du demi-produit à un traitement thermique de revenu de façon à réaliser la décomposition spinodale de la partie dudit produit constituée d'alliage à base de Cu Ni Sn, et à obtenir ainsi un produit fini.
- a) a liquid bath of the alloy based on Cu Ni Sn is prepared, containing furthermore titanium, or any other decarburizing and refining element, and optionally lead
- b) a semi-finished product is formed by spray-deposition of this alloy on a substrate serving as a support
- c) transforming this semi-finished product, part of which may consist of said substrate, with, when necessary, "flash" annealing followed by rapid quenching
- d) the product obtained after transformation of the semi-finished product is subjected to an annealing heat treatment so as to carry out the spinodal decomposition of the part of the said product consisting of Cu Ni Sn-based alloy, and thus to obtain a finished product.
Les alliages à base de Cu Ni Sn selon l'invention ont la composition pondérale suivante :
- Ni
- de 0,5 à 35 %
- Sn
- de 3 à 13 %
- Ti
- de 0,005 à 0,5 %
- Pb
- jusqu'à 0,5 %
- Impuretés
- jusqu'à 0,5 %
- Cu
- reste
- Or
- 0.5 to 35%
- Sn
- from 3 to 13%
- Ti
- from 0.005 to 0.5%
- Pb
- up to 0.5%
- Impurities
- up to 0.5%
- Cu
- rest
De préférence la composition pondérale de Ni est comprise entre 8 et 16% et celle de Sn entre 4 et 10%.Preferably, the weight composition of Ni is between 8 and 16% and that of Sn between 4 and 10%.
Selon l'invention, il est particulièrement avantageux sur le plan économique, pour assurer la teneur en Ti dans l'alliage, d'utiliser des métaux de recyclage : le niobium-titane venant de câbles supraconducteurs, le nickel-titane vanant d'alliage à mémoire de forme, le fer-titane et le manganèse-titane venant d'alliage du stockage de l'hydrogène sous forme d'hydrures.According to the invention, it is particularly advantageous from the economic point of view, to ensure the Ti content in the alloy, to use recycling metals: niobium-titanium coming from superconductive cables, nickel-titanium vaning alloy with shape memory, iron-titanium and manganese-titanium coming from alloy of the storage of hydrogen in the form of hydrides.
Selon une première étape de l'invention, on prépare un alliage à l'état liquide, à base de Cu, Ni, Sn avec du Ti et éventuellement du Pb, par fusion au four à induction muni d'un creuset en carbure de silicium, d'un mélange dans les proportions de la composition nominale de l'alliage, de cuivre électrolytique à 99,99 % de cuivre en poids, de nickel électrolytique à 99,92 % de nickel en poids et d'étain électrolytique à 99,9 % d'étain en poids et contenant très peu de carbone (C < 0,002 %), ainsi que du titane, préférentiellement sous forme de métal de recyclage pour des raisons économiques.According to a first step of the invention, an alloy is prepared in the liquid state, based on Cu, Ni, Sn with Ti and possibly Pb, by melting in an induction furnace provided with a crucible made of silicon carbide , of a mixture in the proportions of the nominal composition of the alloy, of electrolytic copper at 99.99% of copper by weight, of electrolytic nickel at 99.92% of nickel by weight and of electrolytic tin at 99, 9% tin by weight and containing very little carbon (C <0.002%), as well as titanium, preferably in the form of recycling metal for economic reasons.
La fusion se fait sous couverte de charbon de bois de bonne qualité, préalablement enflammé, jusqu'à 1280 ou 1300° C pour être sûr que tout le nickel est fondu. On introduit alors l'étain de qualité électrolytique à l'aide d'une cloche en graphite, dans la proportion correspondant à la composition nominale de l'alliage que l'on veut fabriquer. On ajoute éventuellement le plomb de la même façon et on attend 20 minutes pour que la température atteigne 1100-1200°C. On dose le titane libre dans le bain; en effet, le titane intervient dans le procédé lui-même d'une part comme agent de décarburation du nickel de sorte que, si le nickel approvisionné était de qualité moindre, donc de teneur plus grande en carbone, une plus grande quantité de Ti serait transformée en carbure de titane insoluble ; le titane intervient aussi comme agent de désoxydation du bain, l'oxyde de titane étant également insoluble dans le bain. Le dosage du Ti libre permet d'ajuster avec précision la composition du bain en Ti en introduisant du Ti sous forme d'alliage-mère Cu-Ti pour obtenir la teneur nominale en Ti. On attend encore 10 min et on décrasse l'alliage avant verse. L'alliage liquide (après filtration éventuelle) est prêt à être transformé en demi-produit par pulvérisation-dépôt. On peut envisager aussi un affinage de bain liquide par injection de gaz ou par passage sous vide.The fusion is done under cover of good quality charcoal, previously ignited, up to 1280 or 1300 ° C to be sure that all the nickel is melted. The electrolytic grade tin is then introduced using a graphite bell, in the proportion corresponding to the nominal composition of the alloy which it is desired to manufacture. If necessary, lead is added in the same way and wait 20 minutes for the temperature to reach 1100-1200 ° C. The free titanium is measured in the bath; in fact, titanium intervenes in the process itself on the one hand as a decarburization agent for nickel so that, if the nickel supplied was of lower quality, therefore of greater carbon content, a greater quantity of Ti would be transformed into insoluble titanium carbide; titanium also acts as a deoxidizing agent in the bath, the titanium oxide also being insoluble in the bath. The determination of the free Ti makes it possible to precisely adjust the composition of the Ti bath by introducing Ti in the form of a Cu-Ti master alloy to obtain the nominal Ti content. We wait another 10 min and we clean the alloy before pouring. The liquid alloy (after possible filtration) is ready to be transformed into a semi-finished product by spray-deposition. One can also consider a refining of liquid bath by injection of gas or by passage under vacuum.
Par pulvérisation-dépôt on entend un procédé dans lequel le métal fondu est divisé sous forme de fines gouttelettes liquides qui sont ensuite dirigées et agglomérées sur un substrat de manière à former un dépôt massif et cohérent contenant une faible porosité fermée. Ce dépôt peut se présenter sous la forme de billettes, plateaux, plaques, tubes dont la géométrie est contrôlée, ou d'ébauches de formes diverses prêtes par exemple à être forgées, que nous désignerons par le terme général de "demi-produit".By spray-deposition is meant a process in which the molten metal is divided in the form of fine liquid droplets which are then directed and agglomerated on a substrate so as to form a massive and coherent deposit containing a low closed porosity. This deposit can be in the form of billets, trays, plates, tubes whose geometry is controlled, or of blanks of various shapes ready for example to be forged, which we will denote by the general term of "semi-finished product".
Ce dépôt peut être séparé du substrat qui sert de support et dans ce cas, le demi-produit est constitué seulement d'alliage à base de Cu Ni Sn ; on peut aussi le garder solidaire du substrat de manière à obtenir, après transformation, un composite multicouches avec une partie en alliage à base de Cu Ni Sn et une partie en matériau constituant ledit support. Dans ce cas le matériau dudit support est de préférence à base de cuivre, d'aluminium, d'acier inox.This deposit can be separated from the substrate which serves as a support and in this case, the semi-finished product consists only of alloy based on Cu Ni Sn; it can also be kept integral with the substrate so as to obtain, after transformation, a multilayer composite with an alloy part based on Cu Ni Sn and a part made of material constituting said support. In this case the material of said support is preferably based on copper, aluminum, stainless steel.
Il existe de nombreuses variantes du procédé de pulvérisation-dépôt ; une technique de ce type est désignée sous le nom de "spray-deposition" par les anglo-saxons ; elle est décrite dans les demandes de brevets suivants : GB-B-1379261, GB-B-1472939, GB-B-1548616, GB-B-1599392, GB-A-2172827, EP-A-225080, EP-A-225732, WOA-87-03012.There are many variations of the spray-deposition process; a technique of this type is referred to as "spray-deposition" by the Anglo-Saxons; it is described in the following patent applications: GB-B-1379261, GB-B-1472939, GB-B-1548616, GB-B-1599392, GB-A-2172827, EP-A-225080, EP-A- 225732, WOA-87-03012.
L'intérêt du procédé de pulvérisation-dépôt appliqué aux alliages de l'invention est multiple :
- il évite la ségrégation de l'étain puisque la solidification se fait à l'échelle des gouttelettes, donc dans un volume de quelques centaines de micron-cube et ceci de façon très rapide ; par contre, et par opposition avec la métallurgie des poudres classique, le refroidissement se fait plus lentement, permettant ainsi une meilleure homogénéïsation de l'alliage. Les conséquences de cette répartition uniforme de l'étain dans la masse de l'alliage sont dues à l'absence de formation de dendrites de solidification grossières ; la décomposition spinodale et donc la dureté de l'alliage final est favorisée par une répartition régulière de l'étain.
- dans le cas de l'alliage au plomb, le plomb est en solution solide dans le cuivre liquide, mais totalement insoluble dans le cuivre solide. Ainsi, avec le procédé selon l'invention, le plomb se met hors solution au sein de chaque gouttelette sans risque de coalescence entre gouttelettes voisines : on obtient ainsi une très fine dispersion de plomb qu'aucun autre procédé ne peut assurer pour ce type d'alliage et qui est à l'origine de l'excellente aptitude à l'usinage de l'alliage objet de l'invention.
On obtient ainsi un alliage homogène à la fois en Sn et en Pb sans une phase coûteuse d'homogénéisation. Il faut noter que le traitement d'homogénéisation de la métallurgie classique, s'il permet de réduire partiellement la ségrégation de l'étain, provoque en même temps une coalescence rédhibitoire du plomb. D'ailleurs, c'est la raison pour laquelle le brevet US n° 4260432 impose une teneur maximale en plomb de 0,005 % et la norme ASTM n° B-740-87 limite pour les alliages Cu Ni Sn la teneur en plomb à une valeur inférieure à 0,02 %. - le procédé conduit à un demi-produit de faible porosité, de densité apparente supérieure à 95 % de la densité théorique et généralement comprise entre 99 et 100 %. La porosité résiduelle est une porosité fermée sans effet néfaste qui disparaît pour l'essentiel lors de la transformation du demi-produit.
- it avoids the segregation of tin since solidification takes place at the droplet scale, therefore in a volume of a few hundred micron-cubes and this very quickly; on the other hand, and in opposition with conventional powder metallurgy, the cooling takes place more slowly, thus allowing better homogenization of the alloy. The consequences of this uniform distribution of tin in the mass of the alloy are due to the absence of formation of coarse solidification dendrites; the spinodal decomposition and therefore the hardness of the final alloy is favored by a regular distribution of the tin.
- in the case of the lead alloy, the lead is in solid solution in liquid copper, but completely insoluble in solid copper. Thus, with the process according to the invention, the lead goes out of solution within each droplet without the risk of coalescence between neighboring droplets: this gives a very fine dispersion of lead which no other process can provide for this type of alloy which is at the origin of the excellent machinability of the alloy object of the invention.
A homogeneous alloy is thus obtained in both Sn and Pb without an expensive homogenization phase. It should be noted that the homogenization treatment of conventional metallurgy, if it makes it possible to partially reduce the segregation of tin, at the same time causes a crippling coalescence of lead. Moreover, this is the reason why US patent n ° 4260432 imposes a maximum lead content of 0.005% and the ASTM standard n ° B-740-87 limits for Cu Ni Sn alloys the lead content to a value less than 0.02%. - the process leads to a semi-product of low porosity, with an apparent density greater than 95% of the theoretical density and generally between 99 and 100%. The residual porosity is a closed porosity with no harmful effect which essentially disappears during the transformation of the semi-finished product.
Selon l'invention, la transformation des demi-produits utilise, seuls ou en combinaison, les moyens connus de déformation du métal, tels que, selon les caractéristiques géométriques du demi-produit, le laminage à chaud, le laminage à froid, le filage à chaud, l'étirage, le forgeage, le tréfilage.According to the invention, the transformation of the semi-finished products uses, alone or in combination, the known means of deformation of the metal, such as, according to the geometric characteristics of the semi-finished product, hot rolling, cold rolling, hot spinning, drawing, forging, wire drawing.
Le mode le plus courant de transformation est le passage, après réchauffage, dans une presse à filer ; on peut alors obtenir de nombreuses formes différentes : barre, fil, méplat, profilé, tube.The most common mode of transformation is the passage, after reheating, in a spinning press; many different shapes can then be obtained: bar, wire, flat, profile, tube.
Il est souhaitable d'avoir un rapport de filage élevé (> 20) pour corroyer et densifier totalement l'alliage.It is desirable to have a high spinning ratio (> 20) to fully wrought and densify the alloy.
Un autre mode de transformation est le forgeage à chaud lorsque l'on a besoin de pièces massives.Another processing method is hot forging when massive parts are needed.
Dans les deux cas, le demi-produit est généralement passé sur un tour pour amener sa surface extérieure à la forme d'un cylindre de révolution aux cotes précises.In both cases, the semi-finished product is generally passed over a lathe to bring its outer surface in the form of a cylinder of revolution with precise dimensions.
Durant la transformation des demi-produits, particulièrement lors de transformation à froid, il est généralement nécessaire de réaliser un ou plusieurs recuits intermédiaires suivis de trempe afin d'augmenter la ductilité de l'alliage et de pouvoir poursuivre sa transformation.During the transformation of the semi-finished products, particularly during cold transformation, it is generally necessary to carry out one or more intermediate anneals followed by quenching in order to increase the ductility of the alloy and to be able to continue its transformation.
Selon l'invention, le recuit de mise en oeuvre est un recuit dit "flash", c'est-à-dire comportant une montée très rapide en température ; cette température est comprise entre 450° C et une température légèrement inférieure à celle du liquidus, par exemple celle du liquidus diminuée de 30° C. Cette température est comprise de préférence entre 650 et 850° C. Par "montée très rapide" nous entendons une vitesse de montée qui peut aller de 50° C par minute pour les demi-produits en cours de transformation de plus grande section à 500° C par seconde pour les demi-produits de plus petite section, tels que des fils de faible section. Les moyens pratiques pour réaliser le recuit flash de l'invention sont soit connus en eux-mêmes, soit adaptables à partir de moyens connus. Ils se distinguent souvent par un premier paramètre important qui est le caractère continu/discontinu du procédé ; le recuit "flash" est de préférence obtenu avec un procédé continu par opposition au procédé discontinu par "batch", le demi-produit pouvant être lui-même soit continu (bande), soit discontinu (plateau, plaque).According to the invention, the implementation annealing is a so-called "flash" annealing, that is to say comprising a very rapid rise in temperature; this temperature is between 450 ° C. and a temperature slightly lower than that of the liquidus, for example that of the liquidus reduced by 30 ° C. This temperature is preferably between 650 and 850 ° C. By "very rapid rise" we mean an ascent rate which can range from 50 ° C per minute for semi-finished products of larger cross section to 500 ° C per second for semi-finished products of smaller cross section, such as wires of small cross section. The practical means for carrying out the flash annealing of the invention are either known in themselves, or adaptable from known means. They are often distinguished by a first important parameter which is the continuous / discontinuous nature of the process; "flash" annealing is preferably obtained with a continuous process as opposed to the process discontinuous by "batch", the semi-finished product itself being either continuous (strip) or discontinuous (tray, plate).
Un deuxième paramètre important est la technique de chauffage proprement dite : les calories peuvent être apportées par une source extérieure au demi-produit, par rayonnement, convection ou conduction ; cette famille de techniques est dite à "chauffage indirect" et est représentée par les fours électriques à résistance, les fours à gaz à rayonnement ou à action directe de la flamme sur le produit à traiter, les fours à bain de sel ou à lit fluidisé. Dans une deuxième famille de techniques, les calories sont générées au sein même du demi-produit en cours de traitement, selon des techniques dites à "chauffage direct" comme le chauffage par effet joule ou par induction.A second important parameter is the actual heating technique: calories can be provided by an external source to the semi-finished product, by radiation, convection or conduction; this family of techniques is called "indirect heating" and is represented by electric resistance ovens, gas ovens with radiation or direct action of the flame on the product to be treated, ovens with salt bath or with fluidized bed . In a second family of techniques, calories are generated within the semi-finished product during processing, according to techniques known as "direct heating" such as heating by Joule effect or by induction.
Ce sont ces dernières méthodes qui permettent d'obtenir les plus grandes vitesses de montée en température.
Un exemple de recuit flash dans le cas où le demi-produit est sous forme de fil est donné par les brevets français n° 2288152 et 2519025.It is these latter methods which make it possible to obtain the highest temperature rise rates.
An example of flash annealing in the case where the semi-finished product is in the form of wire is given by French patents No. 2288152 and 2519025.
Le recuit est toujours suivi d'une trempe rapide, réalisée selon les moyens connus ; en effet, si la vitesse de refroidissement était trop faible, il pourrait se produire un début de durcissement par décomposition spinodale, indésirable à ce stade.Annealing is always followed by rapid quenching, carried out according to known means; in fact, if the cooling rate were too low, it could start to harden by spinodal decomposition, undesirable at this stage.
Après la mise en forme finale qui peut être différente des méthodes de déformation mentionnées précédemment, le produit obtenu est soumis à un traitement thermique de revenu, à température moyenne entre 200 et 400° C, qui assure le durcissement par décomposition spinodale.After the final shaping which can be different from the deformation methods mentioned above, the product obtained is subjected to a heat treatment of tempering, at an average temperature between 200 and 400 ° C, which ensures hardening by spinodal decomposition.
Comme déjà mentionné, la décomposition spinodale est influencée par la teneur locale en étain de sorte qu'il est essentiel pour obtenir des produits finis de dureté et plus généralement de caractéristiques mécaniques homogènes, de conserver, jusqu'à la phase finale de revenu, une répartition de l'étain homogène. Les moyens mis en oeuvre dans l'invention permettent de conserver à l'état finement dispersé à la fois l'étain et le plomb. Ainsi, l'invention permet d'obtenir, à l'échelle industrielle et de manière économique, des produits usinables à base de Cu Ni Sn de dureté élevée et homogène.As already mentioned, the spinodal decomposition is influenced by the local tin content so that it is essential to obtain finished products of hardness and more generally of homogeneous mechanical characteristics, to maintain, until the final tempering phase, a homogeneous tin distribution. The means used in the invention make it possible to keep both the tin and the lead in the finely dispersed state. Thus, the invention makes it possible to obtain, on an industrial scale and economically, machinable products based on Cu Ni Sn of hardness high and homogeneous.
Le procédé mis au point par la demanderesse peut également s'appliquer à d'autres alliages de cuivre. Il est d'un grand intérêt pour obtenir des alliages de cuivre exempts de ségrégation, en particulier dans le cas d'alliages présentant un large intervalle de solidification, tels que les bronzes et particulièrement ceux à base de Cu et Sn.The process developed by the applicant can also be applied to other copper alloys. It is of great interest to obtain copper alloys free of segregation, in particular in the case of alloys having a wide solidification interval, such as bronzes and particularly those based on Cu and Sn.
Les exemples qui suivent illustrent l'invention sans la limiter.The examples which follow illustrate the invention without limiting it.
Dans un creuset froid on a mis 158 kg de cuivre électrolytique et 31 kg de nickel électrolytique, puis on les a fondus sous couverte de charbon de bois jusqu'à 1295° C ; puis, avec la cloche en graphite, on a introduit 16,5 kg d'étain ; après avoir attendu 20 minutes et atteint la température de 1190° C, on a désoxydé le bain avec 2,850 kg d'alliage-mère CuTi et attendu 10 minutes avant la première analyse du bain. Celle-ci ayant donné 0,35 % de titane, il n'a pas été fait d'ajout supplémentaire et on a procédé à la pulvérisation-dépôt du bain fondu après avoir remonté la température à 1385° C pour avoir une bonne fluidité.158 kg of electrolytic copper and 31 kg of electrolytic nickel were placed in a cold crucible, then they were melted under cover of charcoal up to 1295 ° C; then, with the graphite bell, 16.5 kg of tin were introduced; after having waited 20 minutes and reaching the temperature of 1190 ° C., the bath was deoxidized with 2.850 kg of CuTi mother alloy and waited 10 minutes before the first analysis of the bath. Since this gave 0.35% of titanium, no additional addition was made and spraying-deposition of the molten bath was carried out after having raised the temperature to 1385 ° C. to have good fluidity.
En faisant la pulvérisation-dépôt sur une plaque d'acier circulaire de diamètre 160 mm, on a obtenu, après séparation d'avec la plaque d'acier, une billette de 137 kg, de diamètre moyen 150 mm, longueur 855 mm.By spraying and depositing on a circular steel plate of diameter 160 mm, there was obtained, after separation from the steel plate, a billet of 137 kg, of average diameter 150 mm, length 855 mm.
Cette billette, coupée en deux tronçons, a été régularisée en diamètre par tournage au diamètre 145 mm, réchauffée dans un four à induction pendant 10,5 minutes jusqu'à 990° C et filée sur une presse de 1850 tonnes de poussée, dans un conteneur chauffé à 500° C, à une vitesse de 32 m/minute, suivant une barre de diamètre 18 mm, avec un rapport de filage de 87, trempée à l'eau dès la sortie de filière.This billet, cut into two sections, was regularized in diameter by turning to a diameter of 145 mm, heated in an induction furnace for 10.5 minutes to 990 ° C and spun on a press of 1850 tonnes of thrust, in a container heated to 500 ° C, at a speed of 32 m / minute, following an 18 mm diameter bar, with a spinning ratio of 87, quenched with water as soon as it leaves the die.
La composition de cette billette était :The composition of this billet was:
Cu = 76,89 % Ni = 14,90 % Sn = 8,2 % en poidsCu = 76.89% Ni = 14.90% Sn = 8.2% by weight
Une barre de diamètre 18 mm a été étirée sur banc droit de 20 tonnes jusqu'au diamètre 8 mm.An 18 mm diameter bar was stretched on a 20-ton straight bench up to a diameter of 8 mm.
Elle a été recuite à 825° C pendant 15 minutes et trempée en sortie de four dans l'eau à 20° C.It was annealed at 825 ° C for 15 minutes and quenched at the outlet of the oven in water at 20 ° C.
Elle a été ensuite étirée à nouveau jusqu'au diamètre final 3,81 mm.It was then stretched again to the final 3.81 mm diameter.
Après un recuit final à 825° C pendant 15 minutes suivi de trempe à l'eau et de décapage double : d'abord en bain chlorure ferrique acide, ensuite en bain sulfochromique, on a mesuré ses caractéristiques à l'état recuit et après un revenu de décomposition spinodale sur cet état recuit. Les résultats obtenus sont donnés dans le tableau suivant :
La barre est ainsi qualifiée pour la fabrication de connecteurs.The bar is thus qualified for the manufacture of connectors.
A partir d'un autre bain de métal liquide préparé dans les mêmes conditions que celui de l'exemple 1, on a fait la pulvérisation-dépôt sur une plaque de cuivre de surface 300 x 600 mm, épaisseur 25 mm, jusqu'à obtenir une épaisseur de 30 mm d'alliage à base de Cu Ni Sn. Le bloc ainsi obtenu a été fraisé sur sa face alliage pour ramener l'épaisseur de celui-ci à 25 mm.From another bath of liquid metal prepared under the same conditions as that of Example 1, the spray-deposition was carried out on a copper plate with a surface of 300 × 600 mm, thickness 25 mm, until obtaining a thickness of 30 mm of alloy based on Cu Ni Sn. The block thus obtained was milled on its alloy side to reduce the thickness of the latter to 25 mm.
Ce composite cuivre pur - alliage Cu15Ni8Sn où la liaison entre les deux matérieux est très forte, a été réchauffé à 945° C dans un four statique et laminé en 6 passes successives de 50 à 15 mm. La température à la dernière passe étant encore de 450° C, la plaque obtenue a été arrosée violemment à l'eau pour la tremper et éviter son durcissement structural.This pure copper - Cu15Ni8Sn alloy where the bond between the two materials is very strong, was reheated to 945 ° C in a static oven and rolled in 6 successive passes of 50 to 15 mm. The temperature at the last pass being still 450 ° C., the plate obtained was watered violently with water to quench it and avoid its structural hardening.
On a ensuite laminé à froid cette plaque jusqu'à 1 mm d'épaisseur. Le produit obtenu est donc un composite de 0,5 mm de cuivre intimement lié à 0,5 mm de Cu15Ni8Sn.This plate was then cold rolled to 1 mm thick. The product obtained is therefore a composite of 0.5 mm of copper intimately bound to 0.5 mm of Cu15Ni8Sn.
Après découpe en bandes de largeur 25,4 mm, le produit a servi à fabriquer des connecteurs, dans lesquels le courant électrique est conduit par le cuivre tandis que l'élasticité et la tenue à la relaxation des contraintes est assurée par l'alliage Cu15Ni8Sn.After cutting into strips 25.4 mm wide, the product was used to manufacture connectors, in which the electric current is conducted by copper while the elasticity and resistance to stress relaxation is ensured by the Cu15Ni8Sn alloy. .
Une telle association de propriétés en connectique est nouvelle et présente un grand intérêt pratique.Such an association of properties in connectors is new and is of great practical interest.
Claims (14)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR9006489 | 1990-05-11 | ||
| FR9006489A FR2661922B1 (en) | 1990-05-11 | 1990-05-11 | COPPER ALLOYS WITH SPINODAL DECOMPOSITION AND PROCESS FOR OBTAINING SAME. |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| EP0456591A1 true EP0456591A1 (en) | 1991-11-13 |
Family
ID=9396917
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP91420149A Withdrawn EP0456591A1 (en) | 1990-05-11 | 1991-05-06 | Copper-based spinodal alloys and process for their preparation |
Country Status (3)
| Country | Link |
|---|---|
| US (1) | US5196074A (en) |
| EP (1) | EP0456591A1 (en) |
| FR (1) | FR2661922B1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0545145A1 (en) * | 1991-11-28 | 1993-06-09 | Wieland-Werke Ag | Manufacture of a porous copper-based material as a preform for a machining process |
| EP0552479A1 (en) * | 1992-01-17 | 1993-07-28 | Wieland-Werke Ag | Process for improving the flexibility of cuprous semi-finished products |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2281078B (en) * | 1993-08-16 | 1997-08-13 | Smith International | Rock bit bearing material |
| US6716292B2 (en) | 1995-06-07 | 2004-04-06 | Castech, Inc. | Unwrought continuous cast copper-nickel-tin spinodal alloy |
| FR2838454B1 (en) * | 2002-04-10 | 2005-04-15 | Clal Msx | CURABLE COPPER ALLOYS WITHOUT BERYLLIUM WITH HIGH MECHANICAL CHARACTERISTICS FOR DECOLLETING |
| AU2004319350B2 (en) * | 2004-04-05 | 2010-07-08 | Swissmetal-Ums Usines Metallurgiques Suisses Sa | Free-cutting, lead-containing Cu-Ni-Sn alloy and production method thereof |
| CN105247093B (en) * | 2013-03-15 | 2017-07-21 | 美题隆公司 | Method for preparing hot-workable metastable alloys with uniform grain size |
| US9631157B2 (en) * | 2013-10-18 | 2017-04-25 | Weatherford Technology Holdings, Llc | Cu—Ni—Sn alloy overlay for bearing surfaces on oilfield equipment |
| CN119346852B (en) * | 2024-07-30 | 2025-10-10 | 松山湖材料实验室 | Copper alloy current collector for aqueous zinc ion battery, production method and application |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2282315A1 (en) * | 1974-08-21 | 1976-03-19 | Osprey Metals Ltd | METHOD AND APPARATUS FOR MANUFACTURING METAL BLANKETS BY SPRAYING |
| US4142918A (en) * | 1978-01-23 | 1979-03-06 | Bell Telephone Laboratories, Incorporated | Method for making fine-grained Cu-Ni-Sn alloys |
| US4406712A (en) * | 1980-03-24 | 1983-09-27 | Bell Telephone Laboratories, Incorporated | Cu-Ni-Sn Alloy processing |
| DE3629395A1 (en) * | 1985-08-29 | 1987-06-11 | Furukawa Electric Co Ltd | COPPER ALLOY FOR ELECTRONIC COMPONENTS AND METHOD FOR THEIR PRODUCTION |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4373970A (en) * | 1981-11-13 | 1983-02-15 | Pfizer Inc. | Copper base spinodal alloy strip and process for its preparation |
| US4525325A (en) * | 1984-07-26 | 1985-06-25 | Pfizer Inc. | Copper-nickel-tin-cobalt spinodal alloy |
-
1990
- 1990-05-11 FR FR9006489A patent/FR2661922B1/en not_active Expired - Fee Related
-
1991
- 1991-05-06 EP EP91420149A patent/EP0456591A1/en not_active Withdrawn
- 1991-05-06 US US07/696,127 patent/US5196074A/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2282315A1 (en) * | 1974-08-21 | 1976-03-19 | Osprey Metals Ltd | METHOD AND APPARATUS FOR MANUFACTURING METAL BLANKETS BY SPRAYING |
| US4142918A (en) * | 1978-01-23 | 1979-03-06 | Bell Telephone Laboratories, Incorporated | Method for making fine-grained Cu-Ni-Sn alloys |
| US4406712A (en) * | 1980-03-24 | 1983-09-27 | Bell Telephone Laboratories, Incorporated | Cu-Ni-Sn Alloy processing |
| DE3629395A1 (en) * | 1985-08-29 | 1987-06-11 | Furukawa Electric Co Ltd | COPPER ALLOY FOR ELECTRONIC COMPONENTS AND METHOD FOR THEIR PRODUCTION |
Non-Patent Citations (1)
| Title |
|---|
| POWER METALLURGY, vol. 28, no. 1, 1985, pages 13-20; R.W. EVANS et al.: "The osprey preform process" * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0545145A1 (en) * | 1991-11-28 | 1993-06-09 | Wieland-Werke Ag | Manufacture of a porous copper-based material as a preform for a machining process |
| EP0552479A1 (en) * | 1992-01-17 | 1993-07-28 | Wieland-Werke Ag | Process for improving the flexibility of cuprous semi-finished products |
Also Published As
| Publication number | Publication date |
|---|---|
| US5196074A (en) | 1993-03-23 |
| FR2661922B1 (en) | 1992-07-10 |
| FR2661922A1 (en) | 1991-11-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP0287486B1 (en) | Process for making a titanium alloy component, and component obtained | |
| EP1067203B1 (en) | Process of manufacturing iron-carbon-manganese alloy strips and strips obtained thereby | |
| EP0357743B1 (en) | Magnesium alloys with high-mecanical resistance and process for obtaining them by rapid solidification | |
| JP3786452B2 (en) | Method for thermomechanically treating a product formed of an approximate gamma titanium aluminide alloy | |
| US4238248A (en) | Process for preparing low earing aluminum alloy strip on strip casting machine | |
| EP2491155B1 (en) | Method for production of titanium welding wire | |
| FR2704869A1 (en) | Improved Ti-6Al-4V alloy, with ballistic behavior, preparation process and application. | |
| EP0414620A1 (en) | Method for making magnesium alloys by spray coating | |
| EP0362086B1 (en) | Process for producing items made from an aluminium alloy retaining a good fatigue resistance after a prolonged stay at a high temperature | |
| CN102337462B (en) | Production method for GCr15 bearing steel pipe | |
| EP0983129A1 (en) | Method for making aluminium alloy strips by continuous thin gauge twin-roll casting | |
| EP0456591A1 (en) | Copper-based spinodal alloys and process for their preparation | |
| CN114231802A (en) | Rare earth aluminum alloy bar for forging aluminum alloy wheel hub and preparation method thereof | |
| EP0460234B1 (en) | Sheet of titanium-aluminum intermetallic compound and process for producing the same | |
| FR2623818A1 (en) | NICKEL ALLOY WITH HIGH MOLYBDEN CONTENT | |
| FR2883785A1 (en) | PROCESS FOR PRODUCING CONSUMABLE DELIVERY METAL FOR WELDING OPERATION | |
| EP1287171B1 (en) | Hardened fe-ni alloy for making integrated circuit grids and method for making same | |
| AU2006218029B2 (en) | Method for casting titanium alloy | |
| JPH0635624B2 (en) | Manufacturing method of high strength aluminum alloy extruded material | |
| RU2763371C2 (en) | Brass for synchroniser rings and method for manufacturing preforms | |
| CN115287497A (en) | Tin-silver-copper target material and preparation method thereof | |
| RU2719051C1 (en) | Method of semi-finished products production from heat-resistant alloy h25n45v30 | |
| FR2669844A1 (en) | ALUMINUM ALLOY POWDER, GREEN COMPACT PRODUCT AND SINTERED COMPACT PRODUCT FOR POWDER METALLURGY. | |
| WO2026017946A1 (en) | 7xxx aluminum alloy for recycling and manufacturing method | |
| CA1193524A (en) | Process for preparing low earing aluminum alloy strip on strip casting machine |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
| AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): CH DE GB LI |
|
| 17P | Request for examination filed |
Effective date: 19911125 |
|
| 17Q | First examination report despatched |
Effective date: 19941111 |
|
| STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE APPLICATION HAS BEEN WITHDRAWN |
|
| 18W | Application withdrawn |
Withdrawal date: 19950506 |