EP0121529B1 - Method for manufacturing aluminium- and boron-based composite alloys and application thereof - Google Patents
Method for manufacturing aluminium- and boron-based composite alloys and application thereof Download PDFInfo
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- EP0121529B1 EP0121529B1 EP83903090A EP83903090A EP0121529B1 EP 0121529 B1 EP0121529 B1 EP 0121529B1 EP 83903090 A EP83903090 A EP 83903090A EP 83903090 A EP83903090 A EP 83903090A EP 0121529 B1 EP0121529 B1 EP 0121529B1
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- boron
- aluminum
- aluminium
- alloys
- boride
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
-
- 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
- C22C1/02—Making non-ferrous alloys by melting
- C22C1/026—Alloys based on aluminium
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- G—PHYSICS
- G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
- G21F—PROTECTION AGAINST X-RADIATION, GAMMA RADIATION, CORPUSCULAR RADIATION OR PARTICLE BOMBARDMENT; TREATING RADIOACTIVELY CONTAMINATED MATERIAL; DECONTAMINATION ARRANGEMENTS THEREFOR
- G21F1/00—Shielding characterised by the composition of the materials
- G21F1/02—Selection of uniform shielding materials
- G21F1/08—Metals; Alloys; Cermets, i.e. sintered mixtures of ceramics and metals
Definitions
- the present invention relates to a process for the production of coposite alloys based on alloyed or unalloyed aluminum and boron and to its application.
- the alloy thus produced serves as the master alloy for refining the aluminum, that is to say that it is introduced in very small quantity into the bath to be refined and consequently the problem of its homogeneity is not of paramount importance, because what counts above all is to obtain an average concentration of boron in the bath.
- French patent 2,231,764 thus claims a process for the manufacture of borated metal products intended for the nuclear industry, characterized in that the metallic material and the boron-based body are in the form of powders, these powders being mixed, pressed and sintered.
- This process is characterized in that aluminum or an aluminum alloy belonging to the 2000 to 8000 series is used in the liquid state, the metal bath is protected by a deoxidizing flow and maintained with stirring an aluminum boride chosen from diboride, dodecaborure or a mixture of the two at a speed adjusted so as to maintain said bath above its solidification temperature.
- This boride which is either diboride AIB 2 , or dodecaborure AIB, 2 , or a mixture of the two, is a well-defined compound, with great air stability, low volatility, having the advantage of not producing d noxious fumes. It can be prepared in various ways known to those skilled in the art and put in the form of particles with an average particle size of between 5 and 30 ⁇ m coated with aluminum to facilitate wetting and introduction into liquid aluminum.
- the boride introduction rate is adjusted so as to keep the aluminum or alloy bath above its solidification temperature.
- the gas is then degassed under nitrogen or under vacuum and the alloy is quickly poured either into a mold to directly obtain a piece of suitable shape, either in an ingot mold to give a product which is then subjected to at least one of the processing operations such as rolling, forging, spinning, drawing, etc.
- a composite alloy of the AS10B 3 type was prepared by the process according to the invention which was then transformed by molding into baskets intended for the transport of radioactive materials. Micrographic examination of the alloy showed an even distribution of the boride in the aluminum alloy matrix. Comparative metallurgical tests with normal A-S10, we deduce that the presence of boron does not affect the qualities of the matrix which retains a good part of its properties whether they are physical: density, thermal conductivity, coefficient of expansion, solidification interval; mechanical: resistance and elongation although the latter characteristic is slightly lowered; technological: good aptitude for forging, rolling, drawing, molding, welding, machinability and sealing.
- the process according to the invention finds its application in the manufacture of composite alloys from which good resistance to abrasion or friction is expected.
- This compasite alloy thus advantageously replaces all mechanically welded or molded products with borated material insert both from the point of view of ease of implementation and cost price in particular when we make the comparison with borated copper plates or steel racks stainless boré.
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Metallurgy (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Organic Chemistry (AREA)
- Ceramic Engineering (AREA)
- Physics & Mathematics (AREA)
- General Engineering & Computer Science (AREA)
- High Energy & Nuclear Physics (AREA)
- Manufacture Of Alloys Or Alloy Compounds (AREA)
- Powder Metallurgy (AREA)
- Extrusion Of Metal (AREA)
- Forging (AREA)
- Lubricants (AREA)
- Polyesters Or Polycarbonates (AREA)
- Diaphragms For Electromechanical Transducers (AREA)
- Metal Extraction Processes (AREA)
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- Radiation-Therapy Devices (AREA)
Abstract
Description
La présente invention est relative à un procédé de fabrication d'alliages coposites à base d'aluminium allié ou non et de bore et à son application.The present invention relates to a process for the production of coposite alloys based on alloyed or unalloyed aluminum and boron and to its application.
Il est courant chez les fondeurs d'aluminium d'ajouter du bore au métal fondu pour faire apparaître des cristaux de TiB2 qui jouent un rôle important sur la germination des cristaux d'Al à la solidification et constituent un excellent moyen d'affinage du grain à la coulée.It is common among aluminum smelters to add boron to the molten metal to reveal TiB 2 crystals which play an important role in the germination of Al crystals on solidification and constitute an excellent means of refining the grain at pouring.
Il est connu également de doper les alliages d'aluminium avec cet élément pour précipiter le titane sous forme de cristaux de TiB2 et améliorerainsi leur conductibilité électrique.It is also known to dop aluminum alloys with this element to precipitate titanium in the form of TiB 2 crystals and thus improve their electrical conductivity.
Dans ces applications, les additions de bore à l'aluminium se font suivant des concentrations relativement faibles et voisines de quelques centaines de ppm et si l'introduction de quantités aussi petites a pu poser des problemes à une certaine époque, elle a été résolue depuis par l'utilisation d'alliages mères tels que l'AT5B. Il n'en est pas de même lorsqu'il s'agit d'atteindre des concentrations en bore de l'ordre de plusieurs pour cent.In these applications, the additions of boron to aluminum take place at relatively low concentrations of around a few hundred ppm and if the introduction of such small quantities could have posed problems at one time, it has been resolved since by the use of master alloys such as AT5B. It is not the same when it comes to achieving boron concentrations of the order of several percent.
On sait, en effet, que la solubilité du bore dans l'aluminium est très faible et de l'ordre de 300 ppm au point de fusion de l'aluminium de sorte que si on cherche à fabriquer des alliages chargés en bore par la voie classique fusion-coulée en lingots, on se heurte à des difficultes dues à la fois une mise en solution incomplète, à des pertes en bore importantes et à une forte ségrégation du bore. Ce qui a pour effet de conduire à des alliages composites ne répondant pas globalement aux compositions attendues et présentant une structure hétérogène.It is known, in fact, that the solubility of boron in aluminum is very low and of the order of 300 ppm at the melting point of aluminum so that if one seeks to manufacture alloys loaded with boron by the conventional ingot-casting in ingots, we run up against difficulties due at the same time to an incomplete dissolution, to significant losses in boron and to a strong segregation of boron. This has the effect of leading to composite alloys which do not generally respond to the expected compositions and which have a heterogeneous structure.
C'est pourquoi des chercheurs et des sociétés ont cherché à remédier à ces défauts et proposé diverses solutions plus ou moins intéressantes.This is why researchers and companies have sought to remedy these shortcomings and have proposed various more or less interesting solutions.
Dans le brevet français 1 265 089 concernant un alliage d'aluminium contenant 2,5 à 10 % de bore, l'inventeur rappelle que jusqu'alors on avait été amené à préparer de tels alliages soit en ajoutant le bore à l'aluminium fondu, soit en réduisant un composé du bore tel que le borax avec l'aluminium fondu. Cependant, dans le premier cas, les alliages ne contenaient qu'une très faible quantité de bore sous forme alliée et nécessitaient des périodes de dissolution excessivement longues tandis que dans l'autre cas, l'utilisation du borax se traduisait par des occlusions d'une valeur indésirable d'oxygène et d'autres impuretés. L'inventeur préconise alors d'in corporer le bore par réduction d'un fluoborate d'un métal alcalin en contact avec l'aluminium fondu. Cependant, il faut savoir qu'un tel procédé outre l'installation onéreuse qu'il nécessite pour sa mise en oeuvre conduit à de mauvais rendements, une partie du bore étant perdue à la fois sous forme de KBf4 et de BF3 composé éminemment toxique en raison des émissions de HF auquel il donne lieu en atmosphère humide.In the French patent 1 265 089 concerning an aluminum alloy containing 2.5 to 10% of boron, the inventor recalls that until then one had been led to prepare such alloys either by adding boron to the molten aluminum , or by reducing a boron compound such as borax with molten aluminum. However, in the first case, the alloys contained only a very small amount of boron in alloyed form and required excessively long dissolution periods, while in the other case, the use of borax resulted in occlusions of an undesirable value of oxygen and other impurities. The inventor then recommends incorporating the boron by reduction of a fluoborate of an alkali metal in contact with the molten aluminum. However, it should be known that such a process, in addition to the expensive installation which it requires for its implementation, leads to poor yields, part of the boron being lost both in the form of KBf 4 and of BF 3 eminently composed toxic due to the HF emissions it gives rise to in a humid atmosphere.
Par ailleurs, l'alliage ainsi produit sert d'alliage mère pour l'affinage de l'aluminium, c'est-à-dire qu'il est introduit en quantité très faible dans le bain à affiner et par suite le problème de son homogénéité n'est pas d'une importance capitale, car ce qui compte avant tout c'est d'obtenir une concentration moyenne en bore dans le bain.Furthermore, the alloy thus produced serves as the master alloy for refining the aluminum, that is to say that it is introduced in very small quantity into the bath to be refined and consequently the problem of its homogeneity is not of paramount importance, because what counts above all is to obtain an average concentration of boron in the bath.
Le problème devient plus difficile quand les alliages riches en bore sont destinés par exemple à la confection de pièces qui doivent avoir soit une bonne résistance à l'abrasion soit une capacité convenable d'absorption de rayonnements neutroniques car il faut alors que le bore soit régulièrement distribué de façon à pouvoir exercer sa fonction uniformément dans l'ensemble de la pièce.The problem becomes more difficult when the boron-rich alloys are intended for example for the manufacture of parts which must have either a good abrasion resistance or a suitable capacity of absorption of neutron radiations because it is then necessary that the boron is regularly distributed so that it can perform its function uniformly throughout the room.
Aussi, les solutions proposées à ce jour, s'écartent-elles du procédé d'obtention des alliages mères et s'orientent plutôt vers la métallurgie des poudres. C'est ainsi que le brevet français 2 231 764 revendique un procédé de fabrication de produits métalliques borés destinés à l'industrie nucléaire, caractérisé en ce que la matière métallique et le corps à base de bore sont à l'état de poudres, ces poudres étant mélangées, pressées et frittées.Also, the solutions proposed to date deviate from the process for obtaining mother alloys and are rather oriented towards powder metallurgy. French patent 2,231,764 thus claims a process for the manufacture of borated metal products intended for the nuclear industry, characterized in that the metallic material and the boron-based body are in the form of powders, these powders being mixed, pressed and sintered.
C'est là évidemment un moyen d'atteindre l'homogénéité souhaitée, cependant, elle nécessite la mise en oeuvre de poudres dont l'obtention constitue une étape supplémentaire par rapport à la voie classique fusionmoulage et ne permet pas toujours de donner aux pièces les formes souhaitées. Une autre solution consiste à faire des alliages composites aluminium-carbure de bore (B4C), mais on éprouve de sérieuses difficultés pour couler de tels alliages sans parler des médiocres caractéristiques mécaniques et de l'inusinabilité des produits obtenus. En milieu aqueux, ces alliages doivent souvent être protégés par un placage aluminium.This is obviously a means of achieving the desired homogeneity, however, it requires the use of powders, the obtaining of which constitutes an additional step compared to the conventional fusion-molding route and does not always make it possible to give the parts the desired shapes. Another solution consists in making aluminum-boron carbide composite alloys (B4C), but there are serious difficulties in casting such alloys, not to mention the poor mechanical characteristics and the inexhaustibility of the products obtained. In aqueous media, these alloys must often be protected by aluminum plating.
C'est pourquoi la demanderesse, estimant que les solutions proposées n'étaient pas suffisantes, a cherché et mis au point un procédé de fabrication d'alliages composites à base d'aluminium allié ou non et contenant jusqu'à 30 0/0 de bore, de structure homogène, présentant des caractéristiques mécaniques convenables, procédé dans lequel les pertes en bore sont pratiquement nulles et dont la mise en oeuvre ne nécessite pas de matériel complexe et cher.This is why the applicant, believing that the solutions proposed were not sufficient, sought and developed a process for manufacturing composite alloys based on aluminum alloy or not and containing up to 30 0/0 of boron, of homogeneous structure, having suitable mechanical characteristics, process in which boron losses are practically zero and whose implementation does not require complex and expensive equipment.
Ce procédé est caractérisé en ce que l'on met en oeuvre de l'aluminium ou un alliage d'aluminium appartenant aux séries 2000 à 8 000 à l'état liquide, on introduit dans le bain de métal protégé par un flux désoxydant et maintenu sous agitation un borure d'aluminium choisi parmi le diborure, le dodécaborure ou un mélange des deux à une vitesse réglée de manière à maintenir ledit bain au-dessus de sa température de solidification.This process is characterized in that aluminum or an aluminum alloy belonging to the 2000 to 8000 series is used in the liquid state, the metal bath is protected by a deoxidizing flow and maintained with stirring an aluminum boride chosen from diboride, dodecaborure or a mixture of the two at a speed adjusted so as to maintain said bath above its solidification temperature.
On recourt donc à la méthode la plus classique d'obtention des alliages en métallurgie; toutefois, à la différence des procédés antérieurs, le bore n'est plus à l'état élémentaire ou d'oxydes ou de sels tels que le borax et les fluoborates mais à l'état de borure d'aluminium.We therefore resort to the most classic method of obtaining alloys in metallurgy; however, unlike previous processes, boron is no longer in the elementary state or of oxides or salts such as borax and fluoborates but in the form of aluminum boride.
Ce borure, qui est soit le diborure AIB2, soit le dodécaborure AIB,2, soit un mélange des deux, est un composé bien défini, de grande stabilité à l'air, peu volatil, présentant l'avantage de ne pas produire d'émanations nocives. Il peut être préparé de différentes façons connues de l'homme de l'art et mis sous forme de particules de granulométrie moyenne comprise entre 5 et 30 µm enrobées d'aluminium pour faciliter le mouillage et l'introduction dans l'aluminium liquide.This boride, which is either diboride AIB 2 , or dodecaborure AIB, 2 , or a mixture of the two, is a well-defined compound, with great air stability, low volatility, having the advantage of not producing d noxious fumes. It can be prepared in various ways known to those skilled in the art and put in the form of particles with an average particle size of between 5 and 30 μm coated with aluminum to facilitate wetting and introduction into liquid aluminum.
Il est introduit dans un bain d'aluminium ou d'un quelconque de ses alliages appartenant aux séries 2000 et 8000 ayant de préférence été soumis au préalable à un traitement d'affinage au moyen d'AI5B par exemple. Ce bain est protégé en surface par un flux désoxydant utilisé de façon classique dans la métallurgie de l'aluminium et maintenu sous agitation pendant la durée d'introduction du borure.It is introduced into a bath of aluminum or of any of its alloys belonging to the 2000 and 8000 series having preferably been subjected beforehand to a refining treatment by means of AI5B for example. This bath is protected on the surface by a deoxidizing flux conventionally used in aluminum metallurgy and kept under stirring for the duration of introduction of the boride.
La vitesse d'introduction du borure est réglée de manière à maintenir le bain d'aluminium ou d'alliage au-dessus de sa température de solidification.The boride introduction rate is adjusted so as to keep the aluminum or alloy bath above its solidification temperature.
Il peut être utile de procédér à ces cperations dans une installation maintenue sous une atmosphère de gaz inerte tel que l'azote U par exemple de façon à parer à toute contamination par l'air ou l'humidité.It may be useful to carry out these operations in an installation maintained under an atmosphere of inert gas such as nitrogen U for example so as to counter any contamination by air or humidity.
Lorsque la quantité de borure nécessaire à l'obtention de la concentration souhaitée dans l'alliage composite a été ajoutée, on procédéalors à un dégazage du bain sous azote ou sous vide et on coule rapidement l'alliage soit dans un moule pour obtenir directement une pièce de forme convenable, soit dans une lingotière pour donner un produit qui est ensuite soumis à l'une au moins des opérations de transformation telle que le laminage, le forgeage, le filage, l'étirage, etc...When the amount of boride necessary to obtain the desired concentration in the composite alloy has been added, the gas is then degassed under nitrogen or under vacuum and the alloy is quickly poured either into a mold to directly obtain a piece of suitable shape, either in an ingot mold to give a product which is then subjected to at least one of the processing operations such as rolling, forging, spinning, drawing, etc.
A titre d'exemple, on a préparé par le procède suivant l'invention un alliage composite du type AS10B3 qu'on a ensuite transformé par moulage en paniers destinés au transport de matières radioactives. Un examen micrographique de l'alliage a montré une répartition régulière du borure dans la matrice d'alliage d'aluminium. Des essais métallurgiques comparatifs avec l'A-S10 normal, on déduit que la présence du bore n'affecte pas les qualités de la matrice qui garde une bonne partie de ses propriétes qu'elles soient physiques: masse volumique, conductibilité thermique, coefficient de dilatation, intervalle de solidification; mécaniques: résistance et allongement bien que cette dernière caractéristique soit légèrement abaissée; technologique: bonne aptitude au forgeage, au laminage, à l'étirage, au moulage, au soudage, à l'usinabilite et à l'étanchéité.By way of example, a composite alloy of the AS10B 3 type was prepared by the process according to the invention which was then transformed by molding into baskets intended for the transport of radioactive materials. Micrographic examination of the alloy showed an even distribution of the boride in the aluminum alloy matrix. Comparative metallurgical tests with normal A-S10, we deduce that the presence of boron does not affect the qualities of the matrix which retains a good part of its properties whether they are physical: density, thermal conductivity, coefficient of expansion, solidification interval; mechanical: resistance and elongation although the latter characteristic is slightly lowered; technological: good aptitude for forging, rolling, drawing, molding, welding, machinability and sealing.
Par ailleurs, des essais d'hydrolyse se traduisent par une bonne stabilité de cet alliage dans l'eau déminéralisée à 40° C et l'absence detoute trace de corrosion.In addition, hydrolysis tests result in good stability of this alloy in demineralized water at 40 ° C and the absence of any trace of corrosion.
Le procédé selon l'invention trouve son application dans la fabrication d'alliages composites dont on attend une bonne résistance à l'abrasion ou au frottement.The process according to the invention finds its application in the manufacture of composite alloys from which good resistance to abrasion or friction is expected.
Il trouve également son application en raison de la présence du bore, élément capteur de neutrons et de ses autres propriétés, dans la confection de barrières neutroniques utilisées dans le domaine de l'énergie nucleaire sous forme de paniers de stockage et de transport de déchets nucléaires, que ce soit dans l'air ou en milieu aqueux.It also finds its application due to the presence of boron, a neutron sensor element and its other properties, in the making of neutron barriers used in the field of nuclear energy in the form of baskets for storage and transport of nuclear waste. , whether in air or in an aqueous medium.
Cet alliage compasite remplace ainsi avantageusament toutes les fabrications mécanosoudées ou moulées avec insert en matière borée à la fois du point de vue facilité de mise en oeuvre et prix de revient notamment quand on fait la comparaison avec les plaques de cuivre borées ou les casiers en acier inoxydable boré.This compasite alloy thus advantageously replaces all mechanically welded or molded products with borated material insert both from the point of view of ease of implementation and cost price in particular when we make the comparison with borated copper plates or steel racks stainless boré.
Claims (4)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AT83903090T ATE20606T1 (en) | 1982-10-05 | 1983-10-04 | PROCESSES FOR THE PRODUCTION OF ALUMINUM- AND BORON-BASED COMPOSITE ALLOYS, AND THEIR USE. |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR8217108 | 1982-10-05 | ||
| FR8217108A FR2533943B1 (en) | 1982-10-05 | 1982-10-05 | PROCESS FOR THE MANUFACTURE OF COMPOSITE ALLOYS BASED ON ALUMINUM AND BORON AND ITS APPLICATION |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0121529A1 EP0121529A1 (en) | 1984-10-17 |
| EP0121529B1 true EP0121529B1 (en) | 1986-07-02 |
Family
ID=9278213
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP83903090A Expired EP0121529B1 (en) | 1982-10-05 | 1983-10-04 | Method for manufacturing aluminium- and boron-based composite alloys and application thereof |
Country Status (24)
| Country | Link |
|---|---|
| US (1) | US4595559A (en) |
| EP (1) | EP0121529B1 (en) |
| JP (1) | JPS59501672A (en) |
| KR (1) | KR890002621B1 (en) |
| AT (1) | ATE20606T1 (en) |
| AU (1) | AU557011B2 (en) |
| BR (1) | BR8307559A (en) |
| CA (1) | CA1186533A (en) |
| DE (1) | DE3364385D1 (en) |
| DK (1) | DK159502C (en) |
| ES (1) | ES8501804A1 (en) |
| FI (1) | FI74047C (en) |
| FR (1) | FR2533943B1 (en) |
| GR (1) | GR78730B (en) |
| IE (1) | IE56054B1 (en) |
| IL (1) | IL69891A (en) |
| IN (1) | IN159721B (en) |
| IT (1) | IT1166980B (en) |
| MX (1) | MX7635E (en) |
| NO (1) | NO161923C (en) |
| NZ (1) | NZ205845A (en) |
| PT (1) | PT77457B (en) |
| WO (1) | WO1984001390A1 (en) |
| ZA (1) | ZA837413B (en) |
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| JP6067386B2 (en) * | 2012-05-24 | 2017-01-25 | 株式会社神戸製鋼所 | Method for producing boron-containing aluminum sheet |
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| JP5829997B2 (en) | 2012-10-17 | 2015-12-09 | 株式会社神戸製鋼所 | Boron-containing aluminum material and method for producing the same |
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| US1921998A (en) * | 1930-09-04 | 1933-08-08 | Nat Smelting Co | Method of improving aluminum and alloys thereof |
| US3037857A (en) * | 1959-06-09 | 1962-06-05 | Union Carbide Corp | Aluminum-base alloy |
| FR1261481A (en) * | 1960-06-03 | 1961-05-19 | Union Carbide Corp | Aluminum alloys with high modulus of elasticity |
| FR1265089A (en) * | 1960-08-16 | 1961-06-23 | Kawecki Chemical Company | Advanced alloy |
| GB1127211A (en) * | 1965-03-04 | 1968-09-18 | United States Borax Chem | Improvements in or relating to alloys |
| GB1122871A (en) * | 1965-03-22 | 1968-08-07 | Pilkington Brothers Ltd | Improvements in or relating to the manufacture of flat glass |
| FR1470191A (en) * | 1966-02-28 | 1967-02-17 | United States Borax Chem | Process for preparing aluminum alloys |
| US3503738A (en) * | 1967-09-15 | 1970-03-31 | Hugh S Cooper | Metallurgical process for the preparation of aluminum-boron alloys |
| GB1268812A (en) * | 1969-04-23 | 1972-03-29 | Anglo Metallurg Ltd | Improvements in or relating to alloys containing boron and aluminium |
| US3864154A (en) * | 1972-11-09 | 1975-02-04 | Us Army | Ceramic-metal systems by infiltration |
| US4248630A (en) * | 1979-09-07 | 1981-02-03 | The United States Of America As Represented By The Secretary Of The Navy | Method of adding alloy additions in melting aluminum base alloys for ingot casting |
| FR2476542B1 (en) * | 1980-02-26 | 1983-03-11 | Vallourec | |
| CS219357B1 (en) * | 1981-09-14 | 1983-03-25 | Ivan Beranek | Method of preparation of solid rafination preparation for rafination of aluminium and the alloys thereof |
-
1982
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