FR2621580A1 - Tooling and hardware for the metallurgy and melt-processing of nonferrous metals, and process of manufacture - Google Patents

Tooling and hardware for the metallurgy and melt-processing of nonferrous metals, and process of manufacture Download PDF

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Publication number
FR2621580A1
FR2621580A1 FR8714096A FR8714096A FR2621580A1 FR 2621580 A1 FR2621580 A1 FR 2621580A1 FR 8714096 A FR8714096 A FR 8714096A FR 8714096 A FR8714096 A FR 8714096A FR 2621580 A1 FR2621580 A1 FR 2621580A1
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Prior art keywords
ceramic
sio2
small tools
geopolymeric
metallurgy
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FR8714096A
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French (fr)
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FR2621580B3 (en
Inventor
Michel Davidovics
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GEOPOLYMERE SARL
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GEOPOLYMERE SARL
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Priority to EP87906748A priority Critical patent/EP0288502B1/en
Priority to DE8787906748T priority patent/DE3771708D1/en
Priority to FR8714096A priority patent/FR2621580B3/en
Priority to AT87906748T priority patent/ATE65484T1/en
Priority to PCT/FR1987/000396 priority patent/WO1988002741A1/en
Priority to US07/218,286 priority patent/US4888311A/en
Publication of FR2621580A1 publication Critical patent/FR2621580A1/en
Application granted granted Critical
Publication of FR2621580B3 publication Critical patent/FR2621580B3/en
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    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
    • C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
    • C04B41/5076—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials with masses bonded by inorganic cements
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    • C04B14/38—Fibrous materials; Whiskers
    • C04B14/42—Glass
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    • C04B20/00—Use of materials as fillers for mortars, concrete or artificial stone according to more than one of groups C04B14/00 - C04B18/00 and characterised by shape or grain distribution; Treatment of materials according to more than one of the groups C04B14/00 - C04B18/00 specially adapted to enhance their filling properties in mortars, concrete or artificial stone; Expanding or defibrillating materials
    • C04B20/10—Coating or impregnating
    • C04B20/1055—Coating or impregnating with inorganic materials
    • C04B20/1077—Cements, e.g. waterglass
    • C04B20/1081—Mineral polymers, e.g. geopolymers
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    • C04B28/006—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing mineral polymers, e.g. geopolymers of the Davidovits type
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    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
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    • C04B35/16—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on silicates other than clay
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    • C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
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  • Structural Engineering (AREA)
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  • Manufacture Of Alloys Or Alloy Compounds (AREA)
  • Compositions Of Oxide Ceramics (AREA)

Abstract

Small tooling and hardware for the metallurgy and melt-processing of nonferrous metals, produced with the aid of ceramic-ceramic composite materials consisting of a fibrous reinforcement made of ceramic fibres and a geopolymeric ceramic matrix containing: a) a poly(sialate) Mn(-Si-O-Al-O-)n and/or poly(sialate-siloxo) Mn(-Si-O-Al-O-Si-O-)n geopolymer, M denoting at least one alkali metal cation and n the degree of polymerisation, b) siliceous and/or aluminous and/or silicoaluminous ultrafine components less than 5 microns, preferably less than 2 microns, in size, the said geopolymeric ceramic matrix being obtained by polycondensation, at a temperature of between 20 DEG C and 120 DEG C, of an alkali metal aluminosilicate reaction mixture, the composition of the main ingredients of the said geopolymeric compound, expressed in terms of the molar ratios of the oxides, being within or equal to the following values: M2O/SiO2 0.10 to 0.95 SiO2/Al2O3 2.50 to 6.00 M2O/Al2O3 0.25 to 5.70 M2O denoting either Na2O and/or K2O or the mixture of at least one alkali metal oxide with CaO.

Description

L'invention a pour objet la description et la fabrication de
petit outillages et de matériel utilisés pour la coulée des métaux non ferreux. Ils sont réalisés avec des matériaux composites à renfort
fibreux céramique, résistant à la température, dont la matrice céramique est un composé géopolymérique silico-aluminate qui est le résultat d'une
réaction de polycondensation minérale de mélanges réactionnels à base de
silico-aluminates alcalins et/ou alcalino-terreux.The subject of the invention is the description and the manufacture of
small tools and equipment used for the casting of non-ferrous metals. They are made with reinforced composite materials
ceramic fiber, temperature resistant, whose ceramic matrix is a geopolymeric silico-aluminate compound which is the result of a
mineral polycondensation reaction of reaction mixtures based on
alkali and / or alkaline earth silico-aluminates.

Ces matériaux composites sont appelés dans ce qui suit "matériaux composites céramique-céramique". Leur fabrication et leur propriétés ont eté décrites dans la demande de brevet français nr. 86.14224 déposee par l'un des demandeurs. These composite materials are called in the following "ceramic-ceramic composite materials". Their manufacture and their properties have been described in French patent application nr. 86.14224 filed by one of the applicants.

Les objets réalisés avec les materiaux composites céramique-céra- mique selon l'invention sont par nature non inflammables et resistants à la chaleur. Ils pourront donc servir de barrière thermique ou de coupe feu. Leur facilité de mise en forme permet la realisation de toute sorte d'objet, en plaque, en creux, en bosse, de tuyau. Ces objets seront utiles dans les industries de transformation nécessitant des matériaux ayant un bon comportement mecanique à chaud. Ce sera le cas par exemple des industries de transformation des matériaux thermoplastiques en général (plastiques organiques ou métaux) ou les matériaux composites céramique-cêramique selon l'invention permettent la confection de moule, de forme ou d'outil.Ils pourront également etre tres utiles dans la manipulation de métaux liquides, en métallurgie et en fonderie. The objects produced with the ceramic-ceramic composite materials according to the invention are by their nature non-flammable and heat resistant. They can therefore serve as a thermal barrier or firebreak. Their ease of shaping allows the realization of any kind of object, in plate, in hollow, in bump, of pipe. These objects will be useful in processing industries requiring materials with good mechanical behavior when hot. This will be the case, for example, in the industries of transformation of thermoplastic materials in general (organic plastics or metals) or the ceramic-ceramic composite materials according to the invention allow the making of mold, shape or tool. They can also be very useful in the handling of liquid metals, metallurgy and foundry.

Dans ces industries de la fonderie, il existe un besoin constant en objets utilisés comme petit outillage ou petit matériel qui servent à la coulée des metaux. Nous citerons par exemple, à titre purement indicatif et non limitatif, quelques objets qui peuvent être réalisés à l'aide des matériaux composites ceramique-ceramique selon l'invention: louche de coulée, godet de coulée, garnissage pour jaquette refractaire, anneau de coulée, goulotte de coule, canne de plongée, canne de protection de thermocouple, système d'attaque et de remplissage de moule, busette. Les objets utilisés jusque maintenant étaient fabriques soit avec de la fonte ou de l'acier, de la céramique ou des ciments réfractaires silico-alumineux traditionnels. Ces objets sont massifs, lourds et très fragiles dans le cas de la céramique et des ciments réfractaires.Dans le cas de la coulee de l'aluminium, et des alliages, ces objets doivent être protegés par une couche, appelée poteyage, destinée à éviter le collage de l'alluminium sur les parois de l'objet.
En outre ce poteyage a un rôle de protection chimique contre la corrosion par les bains de métaux non-ferreux fondus. Ce poteyage doit etre renouvellé très frequemment, ce qui entraine de fréquents arrêts et réduit considérablement la productivité.In these foundry industries, there is a constant need for objects used as small tools or small equipment which are used for casting metals. We will cite for example, purely by way of nonlimiting indication, some objects which can be produced using ceramic-ceramic composite materials according to the invention: ladle, pouring cup, lining for refractory jacket, casting ring , sinking chute, diving rod, thermocouple protection rod, mold attack and filling system, nozzle. The objects used until now were made either from cast iron or steel, ceramic or traditional silico-aluminous refractory cements. These objects are massive, heavy and very fragile in the case of ceramic and refractory cements. In the case of the casting of aluminum, and alloys, these objects must be protected by a layer, called poteyage, intended to avoid the bonding of the aluminum on the walls of the object.
In addition, this coating has a role of chemical protection against corrosion by baths of molten non-ferrous metals. This coating must be renewed very frequently, which leads to frequent stops and considerably reduces productivity.

Au contraire, il a été découvert que les matériaux composites céramique-céramique selon l'invention ne se mouillaient absolument pas par l'aluminium fondu. De plus ils ne sont pas attaqués par les alcalis, les chlorures et autres produits d'affinage de l'aluminium. Par conséquent, ils peuvent être utilisés sans aucun poteyage. On the contrary, it has been discovered that the ceramic-ceramic composite materials according to the invention absolutely do not get wet by molten aluminum. In addition, they are not attacked by alkalis, chlorides and other aluminum refining products. Therefore, they can be used without any poteyage.

En général on définit la mouillabilité d'une surface par un liquide, par l'angle de contact .i. entre une goutte de ce liquide et la surface solide. Lorsque cet angle de contact est inférieur à 90 degrés, il y a mouillage. C'est le cas du contact entre une goutte d'aluminium liquide et des matériaux comme la fonte et les réfractaires silico-alumineux. Au contraire lorque l'angle .f. est supérieur à 90 degrés, le liquide mouille mal. C'est le cas pour l'aluminium liquide et la céramique à base de silice vitreuse. Lorsque l'angle . . est supérieur à 130 degrés, le liquide ne mouille absolument pas. C'est le cas entre l'aluminium liquide et le graphite. Dans le cadre des matériaux composites selon l'invention, l'angle .< est superieur à 130 degres, et par conséquent le métal fondu ne mouille absolument pas sa surface. In general, the wettability of a surface is defined by a liquid, by the contact angle .i. between a drop of this liquid and the solid surface. When this contact angle is less than 90 degrees, there is wetting. This is the case of contact between a drop of liquid aluminum and materials such as cast iron and silico-aluminous refractories. On the contrary when the angle .f. is greater than 90 degrees, the liquid wets badly. This is the case for liquid aluminum and ceramic based on vitreous silica. When the angle. . is greater than 130 degrees, the liquid absolutely does not wet. This is the case between liquid aluminum and graphite. In the context of the composite materials according to the invention, the angle. <Is greater than 130 degrees, and consequently the molten metal absolutely does not wet its surface.

L'objet principal de cette invention est la description de petit outillage et materiel fabriqués à l'aide de materiaux composites céramique-céramique, dont la matrice céramique est constituee par un compose geopolymérique silico-aluminate alcalin et/ou alcalino-terreux; plus particulierement l'invention concerne la realisation d'objets, articles, petit materiel et outillage destinés à la métallurgie des métaux non-ferreux. Un autre objet de cette invention est la description des procédés de fabrication de ces articles. The main object of this invention is the description of small tools and materials manufactured using ceramic-ceramic composite materials, the ceramic matrix of which is constituted by a geopolymeric compound alkali silico-aluminate and / or alkaline earth; more particularly the invention relates to the production of objects, articles, small materials and tools intended for the metallurgy of non-ferrous metals. Another object of this invention is the description of the methods of manufacturing these articles.

La polycondensation de la matrice céramique est du type hydrothermale. Elle s'effectue à une temperature comprise entre 20"C et 1200C et est voisine de celle qui permet l'obtention de mineraux comme les zéolithes ou feldspathoides synthétiques, ou les géopolymeres de type poly(sialate) ou poly(sialate siloxo). The polycondensation of the ceramic matrix is of the hydrothermal type. It is carried out at a temperature between 20 "C and 1200C and is close to that which allows the obtaining of minerals such as zeolites or synthetic feldspathoides, or geopolymers of poly (sialate) or poly (sialate siloxo) type.

Dans le cadre de l'invention, l'appellation materiau composite designe un materiau compose de 2 ou plusieurs constituants en contact intime à l'échelle microscopique. Dans le cas des composites à matrice organique, qui sont les plus connus, les constituants sont:
1) un renfort fibreux orienté ou aléatoire qui donne ses
propriétés de resistance et de régidité mécanique au composite
final.In the context of the invention, the term composite material designates a material composed of 2 or more constituents in intimate contact on a microscopic scale. In the case of the organic matrix composites, which are the best known, the constituents are:
1) an oriented or random fibrous reinforcement which gives its
strength and mechanical stiffness properties of the composite
final.

2) une matière plastique thermodurcissable ou thermospl asti que qui
permet de figer la pièce dans la forme finale tout en assurant
la transmission des efforts aux fibres.2) a thermosetting plastic or thermospl asti que which
freeze the part in the final form while ensuring
the transmission of forces to the fibers.

Dans le cadre de l'invention, le renfort fibreux est constitué de fibres céramiques. La matiere plastique du point 2) est un geopol;mére thermodurcissable et la matrice ainsi obtenue est du type céramique. In the context of the invention, the fibrous reinforcement consists of ceramic fibers. The plastic of point 2) is a geopol; thermosetting mother and the matrix thus obtained is of the ceramic type.

La notion de composite céramique-céramique est définie dans l'ouvrage de R. Naslain, Introduction aux Matériaux Composites, Editions du CNRS, Paris, 1985. Dans le chapitre XVIII de cet ouvrage on apprend les différentes technologies utilisées par l'homme de l'art pour réaliser l'impregnation à coeur d'un matériau fibreux par la matrice céramique. On connait trois methodes d'élaboration: la voie gazeuse, liquide ou solide. Ces méthodes d'imprégnation ont toutes en commun de nécessiter des températures extremement élevées accompagnées de techniques permettant d'éviter la destruction, à ces températures, des renforts fibreux.L'imprégnation par voie liquide d'une matrice vitro-ceramique silico-alumineuse comporte en général quatre étapes:- 1) la préparation d'un préimpregné à l'aide d'une barbotine, 2) réalisation d'une préforme composite, 3) compression entre 6-10 MPa à haute température 1200-1500"C et sous atmosphère controlee, 4) ceramisation par recuit à 900-1000"C. I1 y a une analogie entre cette technique et les procédés de mise en ouvre des materiaux composites à matrice organique, avec cependant une différence essentielle se situant au niveau de la valeur de la température de mise en oeuvre, 100"-2500C pour les organiques contre 1000-1500 C pour les céramiques. The notion of ceramic-ceramic composite is defined in the book by R. Naslain, Introduction to Composite Materials, Editions du CNRS, Paris, 1985. In chapter XVIII of this book we learn the different technologies used by man of the art to achieve the impregnation at heart of a fibrous material by the ceramic matrix. Three production methods are known: the gaseous, liquid or solid route. These impregnation methods all have in common the need for extremely high temperatures accompanied by techniques which make it possible to avoid the destruction, at these temperatures, of fibrous reinforcements. The impregnation by liquid means of a silico-aluminous vitro-ceramic matrix comprises in general four stages: - 1) the preparation of a prepreg using a slip, 2) production of a composite preform, 3) compression between 6-10 MPa at high temperature 1200-1500 "C and under controlled atmosphere, 4) annealing ceramization at 900-1000 "C. There is an analogy between this technique and the methods of processing composite materials with an organic matrix, with however an essential difference being at the level of the value of the processing temperature, 100 "-2500C for the organics against 1000-1500 C for ceramics.

Tout au contraire, les composites ceramique-ceramique selon l'invention sont caracterises par la facilité de mise en oeuvre à basse température, les resistances à la température et les resistances mecaniques. Ces trois qualités étaient jusqu'alors inconciliables. La facilité de mise en oeuvre se trouvait dans les matières plastiques organiques; la résistance à la temperature etait la caracteristique des ceramiques; la résistance mécanique s'obtenait avec les composites. Les matériaux composites selon l'invention concilient ces trois propriétés.  On the contrary, the ceramic-ceramic composites according to the invention are characterized by the ease of processing at low temperatures, the temperature resistances and the mechanical resistances. These three qualities were previously irreconcilable. Ease of use was found in organic plastics; resistance to temperature was the characteristic of ceramics; mechanical resistance was obtained with composites. The composite materials according to the invention reconcile these three properties.

Ils se transforment à basse température, entre 20"C et 1200C avec les mêmes technologies que les plastiques organiques, restent stables jusque 1200"C-1400"C et la présence de fibres céramiques à haute performance leur confèrent des proprietés mécaniques elevées, dans une très large plage de température.They transform at low temperatures, between 20 "C and 1200C with the same technologies as organic plastics, remain stable until 1200" C-1400 "C and the presence of high performance ceramic fibers give them high mechanical properties, in a very wide temperature range.

La quantite de fibre ceramique est au moins egal à 30 X en poids par rapport à la masse du matériau composite. De préférence elle sera supérieure, et sera de l'ordre de 45% à 60% en poids, pour 40% à 55X en poids de matrice céramique géopolymère. The quantity of ceramic fiber is at least equal to 30% by weight relative to the mass of the composite material. Preferably it will be greater, and will be of the order of 45% to 60% by weight, for 40% to 55X by weight of geopolymer ceramic matrix.

Les exemples qui suivent illustrent les procedés de preparation et certaines propriétés non limitatives du petit outillage et matériel pour la metallurgie et la fonderie des métaux non-ferreux, réalisés à l'aide de matériaux composites ceramique-céramique constitués d'un renfort fibreux en fibres céramiques et une matrice céramique géopolymerique contenant::
a) un géopolymére poly(sialate) Mn(-Si-O-Al-O-)n et/ou poly(sialate-siloxo) Mn(-Si-O-Al-O-Si-O-)n, M representant ou moins un cation alcalin et n le degré de polycondensation,
b) des élements ultra-fins siliceux et/ou alumineux et/ou silico-alumineux, de dimension inferieure à 5 microns, de préférence inférieure à 2 microns,
la dite matrice céramique géopolymèrique etant obtenue par polycondensation à une température comprise entre 20 C et 1200C d'un mélange réactionnel alumino-silicate alcalin, la composition des principaux ingrédients du dit composé géopolymérique exprimee en terme des rapports molaires des oxydes est comprise ou égale aux valeurs suivantes::
M20/Si02 0.10 à 0.95
SiO2/A1203 2.50 à 6.00
M20/A1203 0.25 à 5.70
M20 représentant soit Na20 et/ou K20, soit le melange d'au moins un oxyde alcalin avec CaO.The following examples illustrate the preparation processes and certain non-limiting properties of small tools and equipment for the metallurgy and foundry of non-ferrous metals, produced using ceramic-ceramic composite materials consisting of a fibrous fiber reinforcement. ceramics and a geopolymer ceramic matrix containing:
a) a poly (sialate) Mn (-Si-O-Al-O-) n and / or poly (sialate-siloxo) Mn (-Si-O-Al-O-Si-O-) n, M representative geopolymer or less an alkaline cation and n the degree of polycondensation,
b) ultra-fine siliceous and / or aluminous and / or silico-aluminous elements, of dimension less than 5 microns, preferably less than 2 microns,
said geopolymeric ceramic matrix being obtained by polycondensation at a temperature between 20 ° C. and 1200 ° C. of an alkaline alumino-silicate reaction mixture, the composition of the main ingredients of said geopolymeric compound expressed in terms of molar ratios of oxides is included or equal to following values:
M20 / Si02 0.10 to 0.95
SiO2 / A1203 2.50 to 6.00
M20 / A1203 0.25 to 5.70
M20 representing either Na20 and / or K20, or the mixture of at least one alkaline oxide with CaO.

Exemple 1)
On prépare une résine géopolymere d'impregnation, à l'aide du géopolymère K-PSS, K-Poly(sialate-siloxo), GEOPOLYMITE 50 (marque dépo sée) fabriquée par la société GEOPOLYMERE S.A.R.L., en France, selon le
Brevet Européen EP 0066.571 et la demande de Brevet français 86.14224 déposee par l'un des demandeurs. La GEOPOLYMITE 50 est une résine prête à l'emploi à 2 constituants (A) et (B) qui doivent être mélangés en partie egal en poids. La partie (A) est un liquide durcisseur, la partie (B), une poudre fine de granulométrie inférieure à 5 microns. L'analyse chimique des constituants est donnee par le Tableau 1:
TABLEAU 1
Analyse chimique de GEOPOLYMITE 50 (en poids).Example 1)
A geopolymer impregnation resin is prepared, using the geopolymer K-PSS, K-Poly (sialate-siloxo), GEOPOLYMITE 50 (registered trademark) manufactured by the company GEOPOLYMERE SARL, in France, according to the
European patent EP 0066.571 and the French patent application 86.14224 filed by one of the applicants. GEOPOLYMITE 50 is a ready-to-use resin with 2 constituents (A) and (B) which must be mixed in equal parts by weight. Part (A) is a hardening liquid, part (B), a fine powder with a particle size less than 5 microns. The chemical analysis of the constituents is given in Table 1:
TABLE 1
Chemical analysis of GEOPOLYMITE 50 (by weight).

partie (A) partie (B) (A+B)
SiO2 20.95 30.22 25.60
A1203 28.30 14.15
K20 25.98 0.63 13.30
CaO - 28.00 14.00
MgO - 2.76 1.38
F - 9.94 4.87
H20 53.03 - 26.51
TOTAL 99.96 99.85 99.51
Le rapport molaire des oxydes des principaux ingrédients de la
GEOPOLYMITE 50 sont:
M20/SiO2 0.91
SiO2/A12O3 3.10
M20/A1203 2.82
Avec cette résine GEOPOLYMITE 50 on imprègne un tissus tafta de 2009 dont la fibre est du SiC de marque NICALON.Le renfort fibreux en
SiC represente 40% en poids du materiau imprégné. Le composite humide ainsi obtenu est séché à 70 C pendant 10 à 15 minutes, jusqu'à l'obtention d'une perte de poids en eau de 10%. I1 est ensuite placé dans un réfrigérateur à -17 C. Le préimprègné Fibre SiC/GEOPOLYMITE 50 se conserve au froid; on peut le laisser quelques semaines dans ces conditions. Ultérieurement, la polycondensation et le thermodurcissement pourront être activés thermiquement. part (A) part (B) (A + B)
SiO2 20.95 30.22 25.60
A1203 28.30 14.15
K20 25.98 0.63 13.30
CaO - 28.00 14.00
MgO - 2.76 1.38
F - 9.94 4.87
H20 53.03 - 26.51
TOTAL 99.96 99.85 99.51
The molar ratio of the oxides of the main ingredients of the
GEOPOLYMITE 50 are:
M20 / SiO2 0.91
SiO2 / A12O3 3.10
M20 / A1203 2.82
With this GEOPOLYMITE 50 resin we impregnate a tafta fabric from 2009 whose fiber is SiC from NICALON brand.
SiC represents 40% by weight of the impregnated material. The wet composite thus obtained is dried at 70 ° C. for 10 to 15 minutes, until a water weight loss of 10% is obtained. It is then placed in a refrigerator at -17 C. The Fiber SiC / GEOPOLYMITE 50 prepreg keeps cold; we can leave it for a few weeks under these conditions. Later, polycondensation and thermosetting can be activated thermally.

Exemple 2):
Le matériau composite préimprégné de l'exemple 4) est découpé en 8 rectangles de 20cmx10cm. Ces rectangles sont posés l'un sur l'autre et placés dans une presse chauffante à 110C pendant 7 minutes. On obtient une plaque dure que l'on met dans un sachet en plastique, le tout étant laissé dans une etuve à 70"C pendant 2 heures. La plaque est ensuite enlevée de l'étuve et du sac plastique. Elle est séchée à 700C.Example 2):
The prepreg composite material of example 4) is cut into 8 rectangles of 20 cm × 10 cm. These rectangles are placed one on top of the other and placed in a heating press at 110C for 7 minutes. A hard plate is obtained which is put in a plastic bag, the whole being left in an oven at 70 "C for 2 hours. The plate is then removed from the oven and from the plastic bag. It is dried at 700C .

La plaque composite a une résistance à la flexion égale à l9OMPa.  The composite plate has a flexural strength equal to l9OMPa.

Cette valeur se conserve jusque une température de 1000 C environ.This value can be stored up to a temperature of around 1000 C.

Cette plaque est séchée à une température de 400"C pour éliminer l'eau. Elle est ensuite trempée dand un bain d'aluminium fondu. Le ménisque au contact entre la plaque et le métal fondu est inversé. I1 n'y a absolument pas de mouillage entre l'aluminium fondu et la plaque, l'angle de contact .. est supérieur à 130 degrés. This plate is dried at a temperature of 400 "C to remove the water. It is then quenched in a bath of molten aluminum. The meniscus in contact between the plate and the molten metal is reversed. There is absolutely no wetting between the molten aluminum and the plate, the contact angle .. is greater than 130 degrees.

Les matériaux composites céramique-ceramique selon l'invention sont extrémenent intéressants du point de vue des applications industrielles. Selon la technique de façonnage employée, les objets qui seront manufacturés auront des caractéristiques bien particulieres. On pourra employer soit les préimprègnés, soit l'imprégnation par enroulement filamentaire pour la réalisation de tube, fourreau, canne, anneau, creuset, godet, objet de révolution, ou toute autre technique de façonnage couramment en usage par le spécialiste des materiaux composites à matrice organique. On citera par exemple le façonnage sous presse, en autoclave, sous vide. The ceramic-ceramic composite materials according to the invention are extremely advantageous from the point of view of industrial applications. Depending on the shaping technique used, the objects to be manufactured will have very specific characteristics. We can use either prepregs or impregnation by filament winding for the production of tube, sheath, cane, ring, crucible, bucket, object of revolution, or any other shaping technique commonly used by specialists in composite materials. organic matrix. Mention will be made, for example, of shaping in the press, in an autoclave, under vacuum.

Tout homme de l'art comprendra aisément l'intérêt des matériaux composites céramique-céramique selon l'invention, plus particulierement lorsqu'il comparera les matériaux selon l'invention avec les matériaux obtenus à l'aide des techniques céramiques traditionelles. Comme le montre le Tableau 2, le procédé selon l'invention permet d'obtenir à une température de 70"C, des matériaux composites céramique-céramique ayant les mêmes caractéristiques que ceux réalisés à des températures de l'ordre de 1400"C. I1 est évident, que ces hautes températures limitent grandement les applications technologiques de ces matériaux, alors que la très basse température de fabrication des composites selon l'invention permet la réalisation, en grande série, et facilement, de toute forme et objet. Les valeurs du Tableau 2, pour les matrices céramiques, sont reproduites de "Ceramic Source '87" publié par American Ceramic
Society, USA (1986).Anyone skilled in the art will readily understand the advantage of ceramic-ceramic composite materials according to the invention, more particularly when he will compare the materials according to the invention with the materials obtained using traditional ceramic techniques. As shown in Table 2, the process according to the invention makes it possible to obtain, at a temperature of 70 "C., ceramic-ceramic composite materials having the same characteristics as those produced at temperatures of the order of 1400" C. It is obvious that these high temperatures greatly limit the technological applications of these materials, while the very low temperature for manufacturing the composites according to the invention allows the production, in large series, and easily, of any shape and object. The values in Table 2, for ceramic matrices, are reproduced from "Ceramic Source '87" published by American Ceramic
Society, USA (1986).

TABLEAU 2
Comparaison entre composite Fibre SiC/Matrice Ceramique
et Composite Fibre SiC/Matrice K-PSS GEOPOLYMITE
Composite Fabrication Flexion MPa
(Fibre/Matrice) Temp. "C Unidirectionel
SiC/SiC2 1.400 135
SiC/Li. Alum. Silicate 1.400 860
SiC/cordierite 1.400 170
SiC/2rO2 1.400 180
SiC/mullite 1.400 80
SiC/VYCOR 1.500 440
5iC/VPS+50 ' BN 1.500 320
SiC/K-PSS GEOPOLYMITE 70 380
Le renfort fibreux permet l'obtention d'objet très résistants et très légers. Ce renfort peut etre en différentes fibres ceramiques. En particulier il pourra être à base de SiC (fibre Nicalon par exemple), d'A1203 (fibre Nextel par exemple), de silice vitreuse. I1 pourra également être constitué de mélange combinant les différentes fibres céramiques entre elles, verre, carbone, SiC, A1203, silice. On peut également incorporer des fils métalliques comme par exemple l'Inconel.TABLE 2
Comparison between SiC Fiber / Ceramic Matrix composite
and Composite Fiber SiC / Matrix K-PSS GEOPOLYMITE
Composite Fabrication Flexion MPa
(Fiber / Matrix) Temp. "C Unidirectional
SiC / SiC2 1.400 135
SiC / Li. Alum. Silicate 1,400 860
SiC / cordierite 1.400 170
SiC / 2rO2 1.400 180
SiC / mullite 1.400 80
SiC / VYCOR 1.500 440
5iC / VPS + 50 'BN 1.500 320
SiC / K-PSS GEOPOLYMITE 70 380
The fibrous reinforcement makes it possible to obtain very resistant and very light objects. This reinforcement can be made of different ceramic fibers. In particular, it may be based on SiC (Nicalon fiber for example), A1203 (Nextel fiber for example), vitreous silica. It can also consist of a mixture combining the different ceramic fibers together, glass, carbon, SiC, A1203, silica. It is also possible to incorporate metallic wires such as the Inconel.

Les exemples ont ete donnés dans un but d'expliquer les propriétés et les modes d'obtention de petit outillage et matériel pour la métallurgie et la fonderie des métaux non-ferreux, réalisés avec des materiaux composites ceramique-céramique selon l'invention. Bien entendu ils n'ont pas de caractère limitatif.  The examples were given with the aim of explaining the properties and the methods of obtaining small tools and equipment for metallurgy and the foundry of non-ferrous metals, produced with ceramic-ceramic composite materials according to the invention. Of course they are not limiting.

Claims (6)

REVENDICATIONS 1) Petit outillage et matériel pour la métallurgie et la fonderie des métaux non-ferreux caractérisés en ce qu'ils sont réalisés à l'aide de matériaux composites céramique-céramique constitués d'un renfort fibreux en fibres céramiques et une matrice céramique géopolymèrique contenant:1) Small tools and equipment for metallurgy and foundry of non-ferrous metals characterized in that they are made using ceramic-ceramic composite materials consisting of a fibrous reinforcement in ceramic fibers and a geopolymeric ceramic matrix containing : a) un géopolymere poly(sialate) Mn(-Si-O-Al-O-)n et/ou poly(sialate-siloxo) Mn(-Si-O-Al-O-Si-O-)n, M représentant au moins un cation alcalin et n le degre de polymérisation;; a) a poly (sialate) Mn (-Si-O-Al-O-) n and / or poly (sialate-siloxo) Mn (-Si-O-Al-O-Si-O-) n geopolymer, M representing at least one alkaline cation and n the degree of polymerization ;; b) des éléments ultrafins siliceux et/ou alumineux et/ou silicoalumineux, de dimension inférieure à 5 microns, de préférence inférieure à 2 microns, b) ultrafine siliceous and / or aluminous and / or silicoaluminous elements, of dimension less than 5 microns, preferably less than 2 microns, la dite matrice céramique géopolymérique étant obtenue par polycondensation, à une température comprise entre 20"C et 1200C, d'un mélange réactionnel alumino-silicate alcalin, la composition des principaux ingrédients du dit composé géopolymèrique exprimée en terme des rapports molaires des oxydes étant comprise ou égale aux valeurs suivantes: said geopolymer ceramic matrix being obtained by polycondensation, at a temperature between 20 "C and 1200C, of an alkaline alumino-silicate reaction mixture, the composition of the main ingredients of said geopolymeric compound expressed in terms of molar ratios of oxides being included or equal to the following values: M20/SiO2 0.10 à 0.95 M20 / SiO2 0.10 to 0.95 SiO2/A1203 2.50 à 6.00 SiO2 / A1203 2.50 to 6.00 M20/A1203 0.25 à 5.70 M20 / A1203 0.25 to 5.70 M20 representant soit Na2O et/ou K20, soit le mélange d'au moins un oxyde alcalin avec CaO.M20 representing either Na2O and / or K20, or the mixture of at least one alkaline oxide with CaO. 2) Petit outillage et matériel selon la revendication 1), caractérisés en ce que le dit renfort fibreux constitue au moins 30% en poids, de préférence au moins 45% en poids, du dit matériau composite céramiquecéramique.2) Small tools and material according to claim 1), characterized in that said fibrous reinforcement constitutes at least 30% by weight, preferably at least 45% by weight, of said ceramic-ceramic composite material. 3) Petit outillage et matériel selon la revendication 2) caractérises en ce que le dit renfort fibreux est constitué de fibres de Carbure de3) Small tools and equipment according to claim 2) characterized in that said fibrous reinforcement consists of Carbide fibers Silicium SiC.Silicon SiC. 4) Petit outillage et materiel selon l'une quelconque des revendications 1) ,2) et 3), caractérisés en ce que l'angle définissant la mouillabili te par un métal fondu, ou angle de contact .... entre une goutte de metal liquide et la surface du dit matériau composite ceramique-céramique est superieur à 130 degrés.4) Small tools and equipment according to any one of claims 1), 2) and 3), characterized in that the angle defining the wetting by a molten metal, or contact angle .... between a drop of liquid metal and the surface of said ceramic-ceramic composite material is greater than 130 degrees. M20 représentant soit Na20 et/ou K20, soit le mélange d'au moins un oxyde alcalin avec CaO, et à laisser durcir par polycondensation à une température comprise entre 20"C et 120"C. M20 representing either Na20 and / or K20, or the mixture of at least one alkaline oxide with CaO, and to be allowed to harden by polycondensation at a temperature between 20 "C and 120" C. M20/A1203 0.25 à 5.70 M20 / A1203 0.25 to 5.70 SiO2/A1203 2.50 à 6.00 SiO2 / A1203 2.50 to 6.00 M20/SiO2 0.10 à 0.95 M20 / SiO2 0.10 to 0.95 5) Procédé de fabrication de petit outillage et matériel pour la métallurgie et la fonderie des metaux non ferreux selon l'une quelconque des revendications 1) à 4) caractérisé en ce qu'il consiste à impregner un renfort constitue de fibres céramiques avec un melange aqueux silico-aluminate alcalin dont les rapports molaires des principaux ingredients exprimés en terme d'oxyde sont compris ou égaux aux valeurs suivantes 5) A method of manufacturing small tools and equipment for metallurgy and foundry of non-ferrous metals according to any one of claims 1) to 4) characterized in that it consists in impregnating a reinforcement consists of ceramic fibers with a mixture aqueous alkaline silico-aluminate whose molar ratios of the main ingredients expressed in terms of oxide are included or equal to the following values 6) Petit outillage et materiel pour la coulée des métaux non-ferreux tels que: louche de coulée, godet, creuset, garnissage, anneau, goulotte, canne de plongee, canne de thermocouple, système d'attaque et de remplissage, obtenus selon le procedé de la revendication 5). 6) Small tools and materials for the casting of non-ferrous metals such as: ladle, bucket, crucible, packing, ring, chute, diving rod, thermocouple rod, attack and filling system, obtained according to method of claim 5).
FR8714096A 1986-10-14 1987-10-13 TOOLS AND EQUIPMENT FOR METALLURGY AND FOUNDRY OF NON-FERROUS METALS, AND PROCESS FOR OBTAINING SAME Expired - Lifetime FR2621580B3 (en)

Priority Applications (6)

Application Number Priority Date Filing Date Title
EP87906748A EP0288502B1 (en) 1986-10-14 1987-10-13 Ceramic-ceramic composite material and production method
DE8787906748T DE3771708D1 (en) 1986-10-14 1987-10-13 CERAMIC-CERAMIC COMPOSITE AND METHOD FOR THE PRODUCTION THEREOF.
FR8714096A FR2621580B3 (en) 1987-10-13 1987-10-13 TOOLS AND EQUIPMENT FOR METALLURGY AND FOUNDRY OF NON-FERROUS METALS, AND PROCESS FOR OBTAINING SAME
AT87906748T ATE65484T1 (en) 1986-10-14 1987-10-13 CERAMIC-CERAMIC COMPOSITE AND PROCESS FOR ITS PRODUCTION.
PCT/FR1987/000396 WO1988002741A1 (en) 1986-10-14 1987-10-13 Ceramic-ceramic composite material and production method
US07/218,286 US4888311A (en) 1986-10-14 1988-06-10 Ceramic-ceramic composite material and production method

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FR8714096A FR2621580B3 (en) 1987-10-13 1987-10-13 TOOLS AND EQUIPMENT FOR METALLURGY AND FOUNDRY OF NON-FERROUS METALS, AND PROCESS FOR OBTAINING SAME

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023044551A1 (en) * 2021-09-24 2023-03-30 Instituto Hercílio Randon Inorganic composite, use, mechanical shaping tool, mould, manufacturing method

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023044551A1 (en) * 2021-09-24 2023-03-30 Instituto Hercílio Randon Inorganic composite, use, mechanical shaping tool, mould, manufacturing method

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