EP0258153A1 - Master alloys for the modification of the eutectic phase of aluminium-silicon alloys - Google Patents
Master alloys for the modification of the eutectic phase of aluminium-silicon alloys Download PDFInfo
- Publication number
- EP0258153A1 EP0258153A1 EP87420186A EP87420186A EP0258153A1 EP 0258153 A1 EP0258153 A1 EP 0258153A1 EP 87420186 A EP87420186 A EP 87420186A EP 87420186 A EP87420186 A EP 87420186A EP 0258153 A1 EP0258153 A1 EP 0258153A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- sodium
- calcium
- alloys
- modification
- aluminium
- 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.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C21/00—Alloys based on aluminium
- C22C21/02—Alloys based on aluminium with silicon as the next major constituent
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C24/00—Alloys based on an alkali or an alkaline earth metal
Definitions
- the invention relates to a parent composition for modifying the eutectic phase of aluminum-silicon alloys.
- the patent recommends a new solution consisting in using strontium and / or barium as a modifier, possibly with beryllium.
- these elements allow a change in the morphology of the eutectic but do not modify the behavior of the alloy during shrinkage. It is also the same for other elements that were recommended later such as antimony and tellurium.
- This composition allows the simultaneous addition of the two elements metallic sodium and calcium so as to reach in the metallic bath a concentration by weight preferably between 20 and 100 ppm. This addition is generally made after placing the composition in a plastic or metallic packaging to protect it from the oxidizing actions of air humidity.
- This composition preferably contains between 15 and 40% by weight of calcium. It surprisingly allows sodium to keep its very good modification efficiency, to improve the behavior of shrinkage while maintaining the property of calcium to lengthen the duration of the treatment effect observed with sodium alone.
- Another advantage and not least of this composition is to improve the regularity of the yield of introducing sodium into the bath, which without the presence of calcium burns on the surface of the bath, so that one is almost sure not to have scrap for insufficient modification.
- the dispersion of calcium in sodium having a melting point close to 1000 ° C and therefore significantly higher than that of sodium which is 97 ° C, greatly slows the combustion of the mixture in the bath and thus improves the regularity of the introduction yield.
- the duration of the modification treatment being increased, it is possible to lower the amount of sodium to be introduced and correspondingly to decrease the degassing tendency of the liquid bath which is strongly influenced by the sodium content of the metal.
- Such a dispersion of calcium in sodium can be obtained during the manufacture of sodium by igneous electrolysis which, as is known, consists in subjecting a molten mixture of sodium chloride and calcium chloride, optionally in the presence of barium chloride , by the action of a direct electric current so that one obtains around 600 ° C on the cathode a sodium more or less charged with calcium.
- the calcium having a solubility in sodium which decreases when the temperature drops precipitates in a finely dispersed form at within the sodium mass. It suffices to separate this mass which is deposited, for example by decantation, at the bottom of the container in which the cooling takes place to collect a product conforming to the claimed parent composition.
- This product can then be cast in the form of cylindrical billets which are transformed into rods or wires by extrusion and which are conditioned in the absence of air in containers made of plastic or metallic materials, preferably consisting of sheets. heat-sealed aluminum.
- Such a product can contain a few% by weight of calcium oxide or sodium oxide without this presence affecting the good properties of the modifier thus obtained.
- the invention can be illustrated using the following example of application: A series No. 1 of 25 tests was carried out in each of which 500 kg of an aluminum alloy containing 13% silicon and 3% of copper were placed in an oven and brought to 725 ° C. After degassing with nitrogen, 50 g of the composition according to the invention was added, which contained 65% sodium, 30% calcium, which corresponds to an initial theoretical content of the bath of 65 ppm of Na and 30 ppm of It.
- the sodium and calcium contents present in the bath were noted during each of the tests, the mean content and the standard deviation for each of the elements in each series were calculated, as well as the yield of introduction in% based on the ratio of the present content to the initial content.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Silicon Compounds (AREA)
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
- Silicon Polymers (AREA)
Abstract
Description
L'invention est relative à une composition mère pour la modification de la phase eutectique des alliages aluminium-silicium.The invention relates to a parent composition for modifying the eutectic phase of aluminum-silicon alloys.
Il y a plus de 60 ans que les fabricants de pièces moulées en alliages d'aluminium-silicium savent qu'il est possible d'améliorer la qualité des dites pièces en introduisant dans le métal fondu et immédiatement avant la coulée des quantités relativement petites d'éléments ou de composés appelés "modificateurs" ou encore "affinants". Le brevet allemand n° 459.408 de A. PACZ énumère un certain nombre de ces modificateurs parmi lesquels on trouve, notamment, les métaux alcalins et alcalino-terreux et leurs composés.Manufacturers of aluminum-silicon alloy castings have known for over 60 years that the quality of such parts can be improved by introducing relatively small quantities into the molten metal immediately before casting. 'elements or compounds called "modifiers" or "refiners". German patent No. 459,408 to A. PACZ lists a number of these modifiers, among which are found, in particular, alkali and alkaline earth metals and their compounds.
Mais, l'expérience aidant, il s'est avéré, comme le dit le brevet français 1 507 664, qu'en 1967, parmi tous ces produits, seul le sodium ou les substances dégagement du sodium ont pu trouver une large application en fonderie. Cela s'explique en raison de deux propriétés essentielles de ce métal:
- d'une part, son aptitude, notamment dans les alliages d'aluminium contenant environ 13% de silicium et dits eutectiques, à modifier totalement la morphologie du silicium eutectique et à substituer à la structure aciculaire habituelle une structure fibreuse, ce qui confère au produit ainsi obtenu des caractéristiques d'allongement nettement améliorées.
- d'autre part, sa capacité à diminuer fortement la tendance à la retassure des alliages coulés, ce qui permet d'obtenir une plus grande homogénéité physique des pièces et par suite une meilleure tenue mécanique.However, with the help of experience, it turned out, as French patent 1 507 664 says, that in 1967, among all these products, only sodium or the sodium release substances could find wide application in foundries . This is due to two essential properties of this metal:
on the one hand, its ability, in particular in aluminum alloys containing around 13% of silicon and called eutectics, to completely modify the morphology of eutectic silicon and to replace the usual acicular structure with a fibrous structure, which gives the product thus obtained markedly improved elongation characteristics.
- Secondly, its ability to greatly reduce the tendency for shrinkage of cast alloys, which makes it possible to obtain greater physical homogeneity of the parts and consequently better mechanical strength.
Toutefois, cet élément présente quelques inconvénients comme le dit le brevet français 1 507 664 à la page 1 "une addition unique de sodium ne permet d'obtenir un affinage que pour une durée insuffi sante.Lors de la coulée en coquille, par exemple, les bains d'alliages Al-Si doivent par suite être réaffinés périodiquement d'où une gêne pour un travail continu.
L'expérience montre que le réglage du degré correct d'affinage des bains Al-Si n'est pas toujours possible avec une précision suffisante car des erreurs de dosage et de mode opératoire pour l'introduction du sodium métallique ou des substances dégageant du sodium dans des bains correspondants ne peuvent pas toujours être évitées et conduisent à de graves défauts ou au rebut de pièces coulées à partir de ces bains. La grande volatibilité et la forte réactivité du sodium imposent, en outre, des limites étroites de l'emploi d'agents de purification agissant par dégazage ou de toute autre façon dans les bains d'alliages Al-Si affinés au sodium."However, this element has some drawbacks as stated in French patent 1 507 664 on page 1 "a single addition of sodium only allows refining for an insufficient period During shell casting, for example, baths of Al-Si alloys must therefore be periodically re-refined, causing discomfort for continuous work.
Experience shows that adjusting the correct degree of refining of Al-Si baths is not always possible with sufficient precision because of dosing and operating errors for the introduction of metallic sodium or sodium-releasing substances. in corresponding baths cannot always be avoided and lead to serious defects or to the rejection of parts cast from these baths. The high volatility and the high reactivity of sodium also impose strict limits on the use of purifying agents which act by degassing or in any other way in baths of sodium-refined Al-Si alloys. "
Le même brevet fait alors allusion, pour parer à ces inconvénients, à l'utilisation de calcium "qui donne certes dans les bains d'Al-Si un affinage plus faible que celui obtenu avec le sodium mais sa durée est par contre plus longue que celle du sodium".The same patent then alludes, to avoid these drawbacks, to the use of calcium "which certainly gives in Al-Si baths a weaker refinement than that obtained with sodium but its duration is on the other hand longer than that of sodium ".
Mais, il ajoute que "le calcium présente toutefois de graves inconvénients. C'est ainsi que l'addition de calcium favorise fortement la tendance des alliages Al-Si eutectiques à l'oxydation et des alliages ainsi traités présentent un aspect désagréable par suite de leur couleur gris sale.... L'inconvénient essentiel des alliages Al-Si affinés au calcium réside toutefois dans le fait que seules les parties des pièces coulées solidifiées très rapidement, par exemple, dans les pièces coulées en coquille avec une épaisseur de 3mm, présentent une structure pseudo-affinée avec formation d'une structure lamellaire aux points de surchauffe locale. Les zones lamellaires sont d'autant plus nombreuses que la solidifiaction est plus lente, ce qui entraîne la formation de retassures caractéristiques de la structure lamellaire. Ces retassures sont extrêmement gênantes car les méthodes d'alimentation ne permettent pas de les éliminer".However, he adds that "calcium has serious drawbacks, however. The addition of calcium strongly promotes the tendency of eutectic Al-Si alloys to oxidize and the alloys thus treated have an unpleasant appearance as a result of their dirty gray color .... The main drawback of calcium-refined Al-Si alloys however lies in the fact that only the parts of the cast parts solidify very quickly, for example, in the shell molded parts with a thickness of 3 mm. , present a pseudo-refined structure with the formation of a lamellar structure at the local overheating points. The lamellar zones are more numerous as the solidification is slower, which leads to the formation of recesses characteristic of the lamellar structure. recesses are extremely annoying because the feeding methods do not make it possible to eliminate them ".
Au sujet de l'utilisation du calcium, ce brevet conclut ainsi : "l'affinage des Al-Si au calcium présente dans l'ensemble plus de conséquences défavorables faisant passer nécessairement au second plan la plus longue durée de l'effet d'affinage obtenu. Ce procédé n'a donc pas pu s'imposer en pratique en dépit d'avantages apparents. On s'efforce, au contraire, dans les usines d'aluminium d'éliminer le calcium des alliages Al-Si."Regarding the use of calcium, this patent concludes as follows: "the refining of Al-Si to calcium has on the whole more unfavorable consequences necessarily passing to the second longest shot of the refining effect obtained. This process has therefore not been able to impose itself in practice in spite of apparent advantages. On the contrary, efforts are being made in aluminum factories to remove calcium from Al-Si alloys. "
Le brevet préconise alors une nouvelle solution consistant à utiliser comme modificateur du strontium et/ou du baryum éventuellement avec du beryllium.The patent then recommends a new solution consisting in using strontium and / or barium as a modifier, possibly with beryllium.
Certes, ces éléments permettent un changement de morphologie de l'eutectique mais ne modifient pas le comportement de l'alliage à la retassure. Il en est d'ailleurs de même pour d'autres éléments qui ont été recommandés par le suite tels que l'antimoine et le tellure.Admittedly, these elements allow a change in the morphology of the eutectic but do not modify the behavior of the alloy during shrinkage. It is also the same for other elements that were recommended later such as antimony and tellurium.
Le même brevet cite encore l'utilisation simultanée de calcium et de beryllium bien que ce mélange n'apporte aucune solution au problème de la retassure et ne résolve qu'incomplètement le problème de modification de la morphologie.The same patent also cites the simultaneous use of calcium and beryllium although this mixture does not provide any solution to the problem of shrinkage and only partially solves the problem of modifying the morphology.
En conséquence, au vu de ces enseignements, l'homme de l'art se trouve réduit à utiliser soit le sodium avec le risque d'avoir à mettre au rebut des pièces insuffisamment modifiées du fait de la fugacité de l'effet de cet élément et de la difficulté d'en introduire des quantités régulières dans le bain traité, soit des éléments tels que le strontium, le baryum, l'antimoine avec l'iconvénient de la retassure; en tout cas, il n'aura guère tendance à utiliser le calcium en raison de ce qui a été dit plus haut.
C'est dans le but de disposer d'un modificateur possédant les avantages du sodium à savoir: bonne capacité de modification, aptitude à la suppression de la retassure,mais non les inconvénients tels que durée d'action limitée et teneur aléatoire,que la demanderesse a cherché et mis au point un nouveau produit. Pour cela, elle a détruit le préjugé concernant le calcium et propose dans le cadre de la modification de la phase eutectique des alliages aluminium-silicium une composition mère caractérisée par une dispersion de calcium dans du sodium.Consequently, in view of these teachings, a person skilled in the art is reduced to using either sodium with the risk of having to discard parts which have been insufficiently modified due to the fleeting effect of this element. and the difficulty of introducing regular amounts of it into the treated bath, ie elements such as strontium, barium, antimony with the drawback disadvantage; in any case, he will hardly tend to use calcium because of what has been said above.
It is for the purpose of having a modifier having the advantages of sodium, namely: good capacity for modification, ability to suppress shrinkage, but not the disadvantages such as limited duration of action and random content, that the Applicant has sought and developed a new product. For this, it has destroyed the prejudice concerning calcium and proposes in the context of the modification of the eutectic phase of aluminum-silicon alloys a mother composition characterized by a dispersion of calcium in sodium.
Cette composition permet l'addition simultanée des deux éléments métalliques sodium et calcium de manière à atteindre dans le bain métallique une concentration en poids comprise de préférence entre 20 et 100 ppm. Cette addition est généralement faite après avoir placé la composition dans un emballage plastique ou métallique pour le protéger des actions oxydantes de l'humidité de l'air.This composition allows the simultaneous addition of the two elements metallic sodium and calcium so as to reach in the metallic bath a concentration by weight preferably between 20 and 100 ppm. This addition is generally made after placing the composition in a plastic or metallic packaging to protect it from the oxidizing actions of air humidity.
Cette composition contient, de préférence, entre 15 et 40% en poids de calcium. Elle permet de façon surprenante de garder au sodium sa très bonne efficacité de modification, d'améliorer le comportement à la retassure tout en maintenant la propriété du calcium d'allonger la durée de l'effet de traitement observé avec le sodium seul.This composition preferably contains between 15 and 40% by weight of calcium. It surprisingly allows sodium to keep its very good modification efficiency, to improve the behavior of shrinkage while maintaining the property of calcium to lengthen the duration of the treatment effect observed with sodium alone.
Un autre avantage et non des moindres de cette composition est d'améliorer la régularité du rendement d'introduction du sodium dans le bain, qui sans la présence de calcium vient brûler à la surface du bain,de sorte qu'on est à peu près sûr de ne pas avoir de rebut pour insuffissance de modification. En effet, la dispersion de calcium dans le sodium,ayant un point de fusion voisin de 1000°C et donc nettement supérieur à celui du sodium qui est de 97°C, ralentit fortement la combustion du mélange dans le bain et améliore ainsi la régularité du rendement d'introduction.Another advantage and not least of this composition is to improve the regularity of the yield of introducing sodium into the bath, which without the presence of calcium burns on the surface of the bath, so that one is almost sure not to have scrap for insufficient modification. Indeed, the dispersion of calcium in sodium, having a melting point close to 1000 ° C and therefore significantly higher than that of sodium which is 97 ° C, greatly slows the combustion of the mixture in the bath and thus improves the regularity of the introduction yield.
De plus, la durée du traitement de modification étant augmentée, on peut abaisser la quantité de sodium à introduire et corrélativement diminuer la tendance au dégazage du bain liquide qui est fortement influencée par la teneur en sodium du métal.In addition, the duration of the modification treatment being increased, it is possible to lower the amount of sodium to be introduced and correspondingly to decrease the degassing tendency of the liquid bath which is strongly influenced by the sodium content of the metal.
Une telle dispersion de calcium dans le sodium peut être obtenue lors de la fabrication du sodium par électrolyse ignée qui, comme il est connu, consiste à soumettre un mélange fondu de chlorure de sodium et de chlorure de calcium,éventuellement en présence de chlorure de baryum,à l'action d'un courant électrique continu de sorte qu'on obtient vers 600°C sur la cathode un sodium plus ou moins chargé en calcium.Such a dispersion of calcium in sodium can be obtained during the manufacture of sodium by igneous electrolysis which, as is known, consists in subjecting a molten mixture of sodium chloride and calcium chloride, optionally in the presence of barium chloride , by the action of a direct electric current so that one obtains around 600 ° C on the cathode a sodium more or less charged with calcium.
Par refroidissement entre 105 et 115°C de ce mélange des deux métaux, le calcium ayant une solubilité dans le sodium qui décroit quand la température baisse, précipite sous une forme finement dispersée au sein de la masse de sodium. Il suffit de séparer cette masse qui se dépose,par exemple par décantation,au fond du récipient dans lequel s'effectue le refroidissement pour recueillir un produit conforme à la composition mère revendiquée. Ce produit peut être alors être coulé sous forme de billettes cylindriques qui sont transformées en baguettes ou en fils par extrusion et qui sont conditionnées à l'abri de l'air dans des conteneurs en matériaux plastiques ou métalliques, de préférence, constitués par des feuilles d'aluminium thermosoudées.By cooling between 105 and 115 ° C of this mixture of the two metals, the calcium having a solubility in sodium which decreases when the temperature drops, precipitates in a finely dispersed form at within the sodium mass. It suffices to separate this mass which is deposited, for example by decantation, at the bottom of the container in which the cooling takes place to collect a product conforming to the claimed parent composition. This product can then be cast in the form of cylindrical billets which are transformed into rods or wires by extrusion and which are conditioned in the absence of air in containers made of plastic or metallic materials, preferably consisting of sheets. heat-sealed aluminum.
Un tel produit peut contenir quelques % en poids d'oxyde de calcium ou d'oxyde de sodium sans que cette présence n'affecte les bonnes propriétés du modificateur ainsi obtenu.Such a product can contain a few% by weight of calcium oxide or sodium oxide without this presence affecting the good properties of the modifier thus obtained.
L'invention peut être illustrée à l'aide de l'exemple d'application suivant: On a réalisé une série n° 1 de 25 essais dans chacun desquels 500 kg d'un alliage d'aluminium contenant 13% de silicium et 3% de cuivre ont été placés dans un four et portés à 725°C. Après dégazage à l'azote, on a ajouté 50 g de la composition suivant l'invention qui contenait 65% de sodium, 30% de calcium, ce qui corespond à une teneur théorique initiale du bain de 65 ppm de Na et 30 ppm de Ca.The invention can be illustrated using the following example of application: A series No. 1 of 25 tests was carried out in each of which 500 kg of an aluminum alloy containing 13% silicon and 3% of copper were placed in an oven and brought to 725 ° C. After degassing with nitrogen, 50 g of the composition according to the invention was added, which contained 65% sodium, 30% calcium, which corresponds to an initial theoretical content of the bath of 65 ppm of Na and 30 ppm of It.
Après une attente de 10 minutes, on a prélevé un échantillon qui a été soumis à l'analyse pour déterminer la teneur en sodium et en calcium efectivement en solution dans le bain.After waiting 10 minutes, a sample was taken which was subjected to analysis to determine the sodium and calcium content efectively in solution in the bath.
Dans une série n° 2 de 20 essais, on a effectué les mêmes opérations, sauf en ce qui concerne l'agent de modificateur et qui était constitué ici de 50 g de sodium soit une teneur théorique initiale du bain de 100 ppm.In a series 2 of 20 tests, the same operations were carried out, except for the modifier, which here consisted of 50 g of sodium, ie an initial theoretical content of the bath of 100 ppm.
On a noté les teneurs en sodium et en calcium présentes dans le bain au cours de chacun des essais, calculé la teneur moyenne et l'écart type pour chacun des éléments dans chacune des séries, ainsi que le rendement d'introduction en % basé sur le rapport de la teneur présente à la teneur initiale.The sodium and calcium contents present in the bath were noted during each of the tests, the mean content and the standard deviation for each of the elements in each series were calculated, as well as the yield of introduction in% based on the ratio of the present content to the initial content.
Les résultats figurent dans le tableau suivant :
On constate que si le rendement est à peu près le même dans les deux séries, par contre, l'écart type est beaucoup plus faible pour la série N° 1, ce qui indique une meilleure régularité dans le rendement d'introduction et par suite une garantie plus grande d'avoir moins de rebuts par insuffisance de modification.We note that if the yield is roughly the same in the two series, on the other hand, the standard deviation is much lower for the series N ° 1, which indicates a better regularity in the yield of introduction and consequently a greater guarantee of having fewer rejects due to insufficient modification.
A cet avantage, doivent s'ajouter ceux procurés par le sodium sans en avoir les inconvénients tels que la fugacité de l'effet modificateur, autant de qualités qui font de la composition suivant l'invention un produit apportant un progrès important par rapport aux techniques connues.To this advantage, must be added those provided by sodium without having the disadvantages such as the transience of the modifying effect, as many qualities which make the composition according to the invention a product providing significant progress compared to the techniques known.
Claims (4)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AT87420186T ATE49022T1 (en) | 1986-07-04 | 1987-07-01 | SUMMARY ALLOYS FOR MODIFICATION OF THE EUTECTIC PHASE OF ALUMINUM-SILICON ALLOYS. |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR8610129A FR2601041A1 (en) | 1986-07-04 | 1986-07-04 | MOTHER COMPOSITION FOR THE MODIFICATION OF THE EUTECTIC PHASE OF ALUMINUM-SILICON ALLOYS |
| FR8610129 | 1986-07-04 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0258153A1 true EP0258153A1 (en) | 1988-03-02 |
| EP0258153B1 EP0258153B1 (en) | 1989-12-27 |
Family
ID=9337342
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP87420186A Expired EP0258153B1 (en) | 1986-07-04 | 1987-07-01 | Master alloys for the modification of the eutectic phase of aluminium-silicon alloys |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP0258153B1 (en) |
| AT (1) | ATE49022T1 (en) |
| DE (1) | DE3761256D1 (en) |
| ES (1) | ES2012409B3 (en) |
| FR (1) | FR2601041A1 (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR575973A (en) * | 1923-01-22 | 1924-08-08 | British Aluminium Co Ltd | Alloy enhancements |
| DE709361C (en) * | 1930-08-24 | 1941-08-14 | Silumin Ges M B H | Process for modifying silicon-containing aluminum alloys |
| DE907704C (en) * | 1943-02-26 | 1954-03-29 | Vaw Ver Aluminium Werke Ag | Process for the treatment of aluminum-silicon alloys |
| DE1198072B (en) * | 1959-04-15 | 1965-08-05 | Riedelbauch & Stoffregen Dr | Salt mixture for refining Al-Si alloys |
| FR1421855A (en) * | 1964-02-03 | 1965-12-17 | Riedelbauch & Stoffregen Dr | Refining process for aluminum-silicon alloys |
| DE1285178B (en) * | 1965-04-09 | 1968-12-12 | Riedelbauch & Stoffregen Dr | Process for maintaining the refinement state of silicon-containing aluminum alloys over a longer period of time |
-
1986
- 1986-07-04 FR FR8610129A patent/FR2601041A1/en not_active Withdrawn
-
1987
- 1987-07-01 ES ES87420186T patent/ES2012409B3/en not_active Expired - Lifetime
- 1987-07-01 AT AT87420186T patent/ATE49022T1/en not_active IP Right Cessation
- 1987-07-01 EP EP87420186A patent/EP0258153B1/en not_active Expired
- 1987-07-01 DE DE8787420186T patent/DE3761256D1/en not_active Expired - Lifetime
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR575973A (en) * | 1923-01-22 | 1924-08-08 | British Aluminium Co Ltd | Alloy enhancements |
| DE709361C (en) * | 1930-08-24 | 1941-08-14 | Silumin Ges M B H | Process for modifying silicon-containing aluminum alloys |
| DE907704C (en) * | 1943-02-26 | 1954-03-29 | Vaw Ver Aluminium Werke Ag | Process for the treatment of aluminum-silicon alloys |
| DE1198072B (en) * | 1959-04-15 | 1965-08-05 | Riedelbauch & Stoffregen Dr | Salt mixture for refining Al-Si alloys |
| FR1421855A (en) * | 1964-02-03 | 1965-12-17 | Riedelbauch & Stoffregen Dr | Refining process for aluminum-silicon alloys |
| DE1285178B (en) * | 1965-04-09 | 1968-12-12 | Riedelbauch & Stoffregen Dr | Process for maintaining the refinement state of silicon-containing aluminum alloys over a longer period of time |
Non-Patent Citations (1)
| Title |
|---|
| ZEITSCHRIFT FÜR METALLKUNDE, vol. 57, no. 5, 1966, pages 396-401; S.T. CHIU: "The effect of various elements on the modification of Al-Si alloys" * |
Also Published As
| Publication number | Publication date |
|---|---|
| DE3761256D1 (en) | 1990-02-01 |
| EP0258153B1 (en) | 1989-12-27 |
| ES2012409B3 (en) | 1990-03-16 |
| ATE49022T1 (en) | 1990-01-15 |
| FR2601041A1 (en) | 1988-01-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP0357743B1 (en) | Magnesium alloys with high-mecanical resistance and process for obtaining them by rapid solidification | |
| EP1766102B1 (en) | Method for making high-tenacity and high-fatigue strength aluminium alloy products | |
| EP0158571B1 (en) | Al-cu-li-mg alloys with a very high specific mechanical resistance | |
| JPH0816254B2 (en) | Method for producing alloy containing titanium carbide | |
| CA2052372C (en) | Process for improved microshrinkage performance of magnesium alloys | |
| CN114231802A (en) | Rare earth aluminum alloy bar for forging aluminum alloy hub and preparation method thereof | |
| EP0258153B1 (en) | Master alloys for the modification of the eutectic phase of aluminium-silicon alloys | |
| FR2604185A1 (en) | ALUMINUM-TITANIUM MASTER ALLOYS CONTAINING ADDITIONS OF A THIRD ELEMENT, USEFUL FOR THE REFINING OF ALUMINUM GRAIN | |
| EP0233872A1 (en) | Method for the treatment of metals and alloys for the refining thereof. | |
| WO2006120322A1 (en) | Grain refinement agent comprising titanium nitride and method for making same | |
| FR2514786A1 (en) | Bismuth removal from molten lead - using mixt. of calcium-magnesium alloy granules, pref. of eutectic compsn. | |
| GB2171723A (en) | Producing an alloy containing titanium carbide | |
| FR2649416A1 (en) | PROCESS FOR SEPARATING CALCIUM AND LITHIUM NITROGEN | |
| RU2742874C1 (en) | Method of obtaining a composite material based on aluminium or its alloy doped with titanium | |
| EP0069680A1 (en) | Process for grain-refining primary silicon of hypereutectic aluminium-silicon alloys | |
| FR2561665A1 (en) | PROCESS FOR THE PREPARATION OF A TITANIUM-CONTAINING HYDROGEN ALLOY | |
| EP0064468B1 (en) | Process for manufacturing foils consisting of hypoeutectic aluminium-iron alloys | |
| FR2524490A1 (en) | PROCESS FOR OBTAINING VERY HIGH PURITY ALUMINUM FROM EUTECTIC ELEMENTS | |
| CH261434A (en) | Magnesium alloy. | |
| BE437399A (en) | ||
| JPH0361752B2 (en) | ||
| FR2527637A1 (en) | Internally oxidised silver alloy prodn. for electric contact - using stage reducing surface concn. or intensity of dissolved metal including tin | |
| CH395550A (en) | Manufacturing process of an aluminum alloy | |
| FR2697030A1 (en) | Process for producing magnesium alloys of high purity and alloy thus obtained. | |
| BE472680A (en) |
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): AT BE CH DE ES GB IT LI NL SE |
|
| 17P | Request for examination filed |
Effective date: 19880314 |
|
| 17Q | First examination report despatched |
Effective date: 19890526 |
|
| GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
| AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): AT BE CH DE ES GB IT LI NL SE |
|
| REF | Corresponds to: |
Ref document number: 49022 Country of ref document: AT Date of ref document: 19900115 Kind code of ref document: T |
|
| ITF | It: translation for a ep patent filed |
Owner name: ING. A. GIAMBROCONO & C. S.R.L. |
|
| GBT | Gb: translation of ep patent filed (gb section 77(6)(a)/1977) | ||
| REF | Corresponds to: |
Ref document number: 3761256 Country of ref document: DE Date of ref document: 19900201 |
|
| PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
| STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
| 26N | No opposition filed | ||
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: GB Payment date: 19910614 Year of fee payment: 5 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 19910622 Year of fee payment: 5 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: CH Payment date: 19910624 Year of fee payment: 5 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: AT Payment date: 19910625 Year of fee payment: 5 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: SE Payment date: 19910627 Year of fee payment: 5 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: ES Payment date: 19910711 Year of fee payment: 5 |
|
| ITTA | It: last paid annual fee | ||
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: NL Payment date: 19910731 Year of fee payment: 5 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: BE Payment date: 19910802 Year of fee payment: 5 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GB Effective date: 19920701 Ref country code: AT Effective date: 19920701 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SE Effective date: 19920702 Ref country code: ES Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION Effective date: 19920702 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LI Effective date: 19920731 Ref country code: CH Effective date: 19920731 Ref country code: BE Effective date: 19920731 |
|
| BERE | Be: lapsed |
Owner name: S.A. METAUX SPECIAUX Effective date: 19920731 Owner name: FONDERIES MONTUPET Effective date: 19920731 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: NL Effective date: 19930201 |
|
| GBPC | Gb: european patent ceased through non-payment of renewal fee |
Effective date: 19920701 |
|
| NLV4 | Nl: lapsed or anulled due to non-payment of the annual fee | ||
| REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DE Effective date: 19930401 |
|
| EUG | Se: european patent has lapsed |
Ref document number: 87420186.6 Effective date: 19930204 |
|
| REG | Reference to a national code |
Ref country code: ES Ref legal event code: FD2A Effective date: 19990601 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IT Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20050701 |