FR2538370A1 - Vitreous ceramic materials, process for the manufacture of such materials and application of the latter to adhesive bonding of ceramic articles - Google Patents

Vitreous ceramic materials, process for the manufacture of such materials and application of the latter to adhesive bonding of ceramic articles Download PDF

Info

Publication number
FR2538370A1
FR2538370A1 FR8221915A FR8221915A FR2538370A1 FR 2538370 A1 FR2538370 A1 FR 2538370A1 FR 8221915 A FR8221915 A FR 8221915A FR 8221915 A FR8221915 A FR 8221915A FR 2538370 A1 FR2538370 A1 FR 2538370A1
Authority
FR
France
Prior art keywords
materials
alumina
bonding
parts
binder
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
Application number
FR8221915A
Other languages
French (fr)
Other versions
FR2538370B1 (en
Inventor
Claudette Drouet
Louis Minjolle
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Ceraver SA
Original Assignee
Ceraver SA
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Ceraver SA filed Critical Ceraver SA
Priority to FR8221915A priority Critical patent/FR2538370B1/en
Publication of FR2538370A1 publication Critical patent/FR2538370A1/en
Application granted granted Critical
Publication of FR2538370B1 publication Critical patent/FR2538370B1/en
Expired legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C03C8/24—Fusion seal compositions being frit compositions having non-frit additions, i.e. for use as seals between dissimilar materials, e.g. glass and metal; Glass solders
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
    • C03C10/0036—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing SiO2, Al2O3 and a divalent metal oxide as main constituents
    • C03C10/0045—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing SiO2, Al2O3 and a divalent metal oxide as main constituents containing SiO2, Al2O3 and MgO as main constituents
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B37/00—Joining burned ceramic articles with other burned ceramic articles or other articles by heating
    • C04B37/003—Joining burned ceramic articles with other burned ceramic articles or other articles by heating by means of an interlayer consisting of a combination of materials selected from glass, or ceramic material with metals, metal oxides or metal salts
    • C04B37/005—Joining burned ceramic articles with other burned ceramic articles or other articles by heating by means of an interlayer consisting of a combination of materials selected from glass, or ceramic material with metals, metal oxides or metal salts consisting of glass or ceramic material
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2237/00—Aspects relating to ceramic laminates or to joining of ceramic articles with other articles by heating
    • C04B2237/02—Aspects relating to interlayers, e.g. used to join ceramic articles with other articles by heating
    • C04B2237/04—Ceramic interlayers
    • C04B2237/09—Ceramic interlayers wherein the active component for bonding is not the largest fraction of the interlayer
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2237/00—Aspects relating to ceramic laminates or to joining of ceramic articles with other articles by heating
    • C04B2237/02—Aspects relating to interlayers, e.g. used to join ceramic articles with other articles by heating
    • C04B2237/10—Glass interlayers, e.g. frit or flux
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2237/00—Aspects relating to ceramic laminates or to joining of ceramic articles with other articles by heating
    • C04B2237/30—Composition of layers of ceramic laminates or of ceramic or metallic articles to be joined by heating, e.g. Si substrates
    • C04B2237/32—Ceramic
    • C04B2237/36—Non-oxidic
    • C04B2237/365—Silicon carbide
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2237/00—Aspects relating to ceramic laminates or to joining of ceramic articles with other articles by heating
    • C04B2237/30—Composition of layers of ceramic laminates or of ceramic or metallic articles to be joined by heating, e.g. Si substrates
    • C04B2237/32—Ceramic
    • C04B2237/36—Non-oxidic
    • C04B2237/368—Silicon nitride
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2237/00—Aspects relating to ceramic laminates or to joining of ceramic articles with other articles by heating
    • C04B2237/50—Processing aspects relating to ceramic laminates or to the joining of ceramic articles with other articles by heating
    • C04B2237/76—Forming laminates or joined articles comprising at least one member in the form other than a sheet or disc, e.g. two tubes or a tube and a sheet or disc
    • C04B2237/765—Forming laminates or joined articles comprising at least one member in the form other than a sheet or disc, e.g. two tubes or a tube and a sheet or disc at least one member being a tube
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2237/00—Aspects relating to ceramic laminates or to joining of ceramic articles with other articles by heating
    • C04B2237/50—Processing aspects relating to ceramic laminates or to the joining of ceramic articles with other articles by heating
    • C04B2237/84—Joining of a first substrate with a second substrate at least partially inside the first substrate, where the bonding area is at the inside of the first substrate, e.g. one tube inside another tube

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Dispersion Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Structural Engineering (AREA)
  • Ceramic Products (AREA)

Abstract

Vitreous ceramic materials comprising silica, alumina, magnesia and yttrium oxide. Their respective quantities by weight correspond to the inequalities: 32.5 % SiO2 + MgO 77.5 %; 17.5 % Al2O3 62.5 %; 5 % Y2O3 50 %. Application of these materials to adhesive bonding of articles of the same kind made of silicon carbide, silicon nitride or Si Al ON, the yttrium oxide facilitating the wetting of an adhesive bonding slip on the surface of these articles.

Description

Matériaux céramiques vitreux, procédé de fabrication de tels matériaux et application de ces derniers
La présente invention concerne de nouveaux matériaux céramiques vitreux à base de silice, d'alumine, de magnésie et d'oxyde d'yttrium.Vitreous ceramic materials, process for making such materials, and application of the latter
The present invention relates to new vitreous ceramic materials based on silica, alumina, magnesia and yttrium oxide.

On utilise de plus en plus fréquemment de nouveaux matériaux céramiques cristallins, tels que le carbure de silicium, le nitrure de silicium, les nitrures de silicium modifies par addition d'oxygène et~d'alu- minium dans leur réseau cristallin, pour la fabrication de pièces et d'appareils destinés à être soumis à des contraintes mécaniques importantes à température élevée. New crystalline ceramic materials are used more and more frequently, such as silicon carbide, silicon nitride, silicon nitrides modified by addition of oxygen and ~ aluminum in their crystal lattice, for the manufacture of parts and appliances intended to be subjected to significant mechanical stresses at high temperature.

Il est toutefois difficile d'assembler des pièces en ces matériaux par collage, car cela nécessiterait des adhésifs résistant aux températures élevées et aux contraintes entraînées par les dilatations thermiques, présentant un coefficient de dilatation assez peu différent de ceux des matériaux à assembler, et mouillant bien ceux-ci. It is however difficult to assemble parts of these materials by gluing, as this would require adhesives resistant to high temperatures and to the stresses caused by thermal expansion, having a coefficient of expansion quite little different from that of the materials to be assembled, and wetting well these.

La présente invention vise à procurer des matériaux utilisables comme adhésifs pour le collage des matériaux céramiques cristallins mentionnés ci-dessus. The present invention aims to provide materials which can be used as adhesives for bonding the crystalline ceramic materials mentioned above.

Ces matériaux sont constitués par les mélanges de silice, dsalu- mine, de magnésie et d'oxyde d'yttrium répondant aux proportions pondérales
32,5 % 4 Silice et magnésie X 77,5 %
17,5 % 6 alumine 4 62,5 %
5% < Y203 \ < 50 %
De tels matériaux correspondent à l'aire du triangle ICB du diagramme ternaire silice + magnésie-alumine-oxyde d'yttrium de la figure 1 du dessin annexé.Parmi ces matériaux, ceux correspondant à l'aire du triangle ABC peuvent être fabriqués en-partant de cordiérite, d'alumine et d'oxyde d'yttrium et sont représentés par l'aire ABC du diagramme ternaire eordiérite-alumine-oxyde d'yttrium de la figure 2, dont les cotés correspondent aux limites de composition (en poids)
50% 4 cordiérite 4 95%
0% 6 alumine 4 45%
5% 4 oxyde d'yttrium #50% ou. exprimées en oxyde magnésie : 6,9% à 13,1% silice : 25,6% à 48,6%

Figure img00020001

silice + magnésie = 32,5% à 61,7% alumine : 17,5% à 6275% oxyde d'yttrium : 5% à 50%
Les matériaux ci-dessus peuvent hêtre additionnes d'au moins un oxyde métallique favorisant leur dévitrification, tels que le bioxyde de titane, la zircone, l'oxyde de zinc, en proportion allant jusqu'à 5% en poids, ee qui améliore leur résistance mécanique à chaud entre 10000 et 13500C. These materials consist of mixtures of silica, dsalumin, magnesia and yttrium oxide corresponding to the weight proportions
32.5% 4 Silica and magnesia X 77.5%
17.5% 6 alumina 4 62.5%
5% <Y203 \ <50%
Such materials correspond to the area of the triangle ICB of the ternary diagram silica + magnesia-alumina-yttrium oxide of FIG. 1 of the appended drawing. Among these materials, those corresponding to the area of the triangle ABC can be manufactured in- starting from cordierite, alumina and yttrium oxide and are represented by the area ABC of the ternary diagram eordierite-alumina-yttrium oxide of FIG. 2, the dimensions of which correspond to the limits of composition (by weight)
50% 4 cordierite 4 95%
0% 6 alumina 4 45%
5% 4 yttrium oxide # 50% or. expressed as oxide of magnesia: 6.9% to 13.1% silica: 25.6% to 48.6%
Figure img00020001

silica + magnesia = 32.5% to 61.7% alumina: 17.5% to 6275% yttrium oxide: 5% to 50%
The above materials may be added with at least one metal oxide promoting their devitrification, such as titanium dioxide, zirconia, zinc oxide, in a proportion of up to 5% by weight, which improves their mechanical resistance when hot between 10000 and 13500C.

Ces matériaux vitreux mouillent bien les matériaux céramiques cristallins, tels que le carbure de silicium, les nitrures de silicium et les nitrures de silicium modifiés (Si Al ON), grace à la présence de l'oxyde d'yttrium qui joue le rôle de mouillant. Ils permettent de former des joints très adhérents de faible épaisseur
Comme ils sont à base d'oxydes et présentent une température de transition vitreuse élevée (entre 9000 et 1000C), ils conviennent parfaitement dans l'appareillage fonctionnant à chaud, éventuellement en atmosphère oxydante, notamment dans les échangeurs thermiques fonctionnant vers 8000C. These vitreous materials wet crystalline ceramic materials well, such as silicon carbide, silicon nitrides and modified silicon nitrides (Si Al ON), thanks to the presence of yttrium oxide which acts as a wetting agent. . They make it possible to form very adherent joints of small thickness
As they are based on oxides and have a high glass transition temperature (between 9000 and 1000C), they are perfectly suited for apparatus operating hot, possibly in an oxidizing atmosphere, in particular in heat exchangers operating around 8000C.

Ces verres peuvent être dévitrifiés, soit par addition des oxydes métalliques mentionnés ci-dessus, soit par un ou plusieurs cycles de refroidissement lent. These glasses can be devitrified, either by adding the metal oxides mentioned above, or by one or more slow cooling cycles.

Le procédé de fabrication le plus général des matériaux vitreux ci-dessus consiste à mélanger des poudres de silice, de magnésie, d'alumine et d'oxyde d'yttrium par broyage en jarre, à fondre le mélange pulvérulent obtenu à une température supérieure à 1500 C sous atmosphère oxydante, notamment à 11 air, puis à laisser refroidir le verre formé. The most general manufacturing process for the above vitreous materials consists in mixing silica, magnesia, alumina and yttrium oxide powders by grinding in jars, melting the powder mixture obtained at a temperature above 1500 C under an oxidizing atmosphere, in particular with 11 air, then allowing the formed glass to cool.

Pour les matériaux dont le rapport des quantités de silice et d'alumine correspond à celui de la cordiérite, ou mélange des poudres de cordiérite naturelle ou synthétique, d'alumine et d'oxyde d'yttrium par broyage en jarre, puis fond également le mélange pulvérulent obtenu à une température supérieure à 15000 sous atmosphère oxydante et lalsse refroidir le verre formé. For materials whose ratio of the quantities of silica and alumina corresponds to that of cordierite, or mixture of natural or synthetic cordierite powders, alumina and yttrium oxide by grinding in jar, then also melts the powder mixture obtained at a temperature above 15000 under an oxidizing atmosphere and then cool the glass formed.

L'invention s'étend enfin à un procédé de collage de pièces de même nature en carbure de silicium, nitrure de silicium ou nitrure de silicium modifié (Si Al ON), dans lequel on concasse un matériau céramique vitreux tel que défini ci-dessus, le broie en jarre en milieu liquide, le sèche, l'additionne d'un liant et d'un solvant de façon à former une pite, applique cette pâte entre les pièces à coller, sèche lten emble en étuve, puis le porte à une température voisine de 14000C sous atmosphère neutre. De préférence, après ce chauffage vers 14000C, on soumet les pièces collées à un ou plusieurs refroidissements lents assurant la dévitrification du matériau de collage. The invention finally extends to a method of bonding parts of the same kind made of silicon carbide, silicon nitride or modified silicon nitride (Si Al ON), in which a vitreous ceramic material is crushed as defined above. , grinds it in a jar in a liquid medium, dries it, adds a binder and a solvent so as to form a pite, applies this paste between the parts to be bonded, dries lten emble in an oven, then takes it to a temperature close to 14000C in a neutral atmosphere. Preferably, after this heating around 14000C, the bonded parts are subjected to one or more slow coolings ensuring devitrification of the bonding material.

Il est décrit ci-après, à titre d'exemples, une opération de synthèse d'un matériau céramique vitreux, une opération de dépose de ce matériau sur des pièces-à assembler et de cuisson de l'assemblage, ainsi qu'un échangeur de chaleur, représenté en figure 3 du dessin, assemblé à l'aide d'un tel matériau céramique. It is described below, by way of examples, an operation for synthesizing a vitreous ceramic material, an operation for depositing this material on parts to be assembled and firing the assembly, as well as an exchanger heat, shown in Figure 3 of the drawing, assembled using such a ceramic material.

EXEMPLE 1 - Synthèse d'un matériau céramique vitreux
Après mélange intime des matières premières (silice et magnésie, alumine et oxyde d'yttrium, ou cordiérite, alumine et oxyde d'yttrium) par broyage en jarre, on améne à la fusion les poudres au voisinage de 15500C en présence d'air, en prolongeant le traitement 2 heures.EXAMPLE 1 - Synthesis of a vitreous ceramic material
After intimate mixing of the raw materials (silica and magnesia, alumina and yttrium oxide, or cordierite, alumina and yttrium oxide) by grinding in a jar, the powders are brought to fusion in the vicinity of 15500C in the presence of air, extending the treatment for 2 hours.

Après refroidissement, le verre est- concassé et broyé en jarre, en milieu aqueux, jusqu'à ce que la dimension moyenne des grains soit inférieure à 80 microns. On obtient ainsi un matériau vitreux bien homogène.After cooling, the glass is crushed and ground in a jar, in an aqueous medium, until the average grain size is less than 80 microns. A very homogeneous glassy material is thus obtained.

EXEMPLE 2 - Dépose du verre et cuisson d'assemblage
On ajoute à la poudre de verre broyée.un liant et un solvant. On peut utiliser différents couples liant-solvant.EXAMPLE 2 - Glass removal and assembly cooking
A binder and a solvent are added to the ground glass powder. Different binder-solvent pairs can be used.

Selon une première variante, le liant peut être un éther cellulosique que l'on disperse dans. l'eau. On peut ainsi préparer un gel de l'éther cellulosique commercialisé sous la désignation "Bermocoll E 600l' dans l'eau à 4%, et mélange la poudre broyée du matériau vitreux à ce gel dans la proportion de 60 à 80% en poids de poudre pour 40 à 20% de gel. According to a first variant, the binder can be a cellulose ether which is dispersed in. the water. It is thus possible to prepare a gel of cellulosic ether sold under the designation "Bermocoll E 600l 'in water at 4%, and the ground powder of the vitreous material is mixed with this gel in the proportion of 60 to 80% by weight of powder for 40 to 20% gel.

Le liant peut être également un polystyrène plastifié à l'aide de phtalate de butyle, que l'on dissout dans un solvant tel que le tri- chioréthylène. On prépare par exemple une solution contenant an poids 5% de polystyrène, 5% de phtalate de butyle et 90% de trichlororéthylène. On mélange eette solution à la poudre du matériau vitreux dans les proportions de 60 à 80% en poids de poudre pour 40 à 20% de solution
Il est également possible d'utilises comme liant un polysaccharide dissous dans l'eau à raison de 10% an poids.On mélange 70 à 80% de poudre broyée du matériau vitreux à 30 à 20% de solution
On constitue ainsi à l'aide du liant et du solvant une patte susceptible d'etre déposée au pinceau sur les pièces à coller. Le choix du liant a été effectué de façon que la patte soit suffisamment fluide pour s'écouler dans des interstices minces (de quelques dizièmes de mm), mais présente assez de rigidité pour rester an place sans s'écouler dans le cas de joints verticaux.The binder can also be a polystyrene plasticized with butyl phthalate, which is dissolved in a solvent such as trichiorethylene. For example, a solution is prepared containing 5% by weight of polystyrene, 5% of butyl phthalate and 90% of trichlorethylene. This solution is mixed with the powder of the vitreous material in the proportions of 60 to 80% by weight of powder for 40 to 20% of solution
It is also possible to use as a binder a polysaccharide dissolved in water at a rate of 10% by weight. 70 to 80% of ground powder of the vitreous material is mixed with 30 to 20% of solution
Using the binder and the solvent, a tab is thus able to be deposited with a brush on the parts to be bonded. The choice of binder was made so that the tab was fluid enough to flow through thin gaps (a few tenths of a mm), but had enough rigidity to remain in place without flowing in the case of vertical joints. .

Après séchage en étuve, l'assemblage est progressivement porté au voisinage de 14000C sous atmosphère neutre (argon)
On peut soumettre le matériau céramique vitreux formant adhésif entre les pièces à des cycles de refroidissement lent assurant sa dévi trification si on le juge nécessaire
Il a été préparé en particulier les matériaux vitreux présentant les compositions pondérales suivantes (points D, E, F, G, des figures 1 et 2).After drying in an oven, the assembly is gradually brought to around 14000C under a neutral atmosphere (argon)
The glassy ceramic adhesive material between the parts can be subjected to slow cooling cycles ensuring its deflection if it is deemed necessary.
In particular, the vitreous materials having the following weight compositions were prepared (points D, E, F, G, of Figures 1 and 2).

D E F G
Cordiérite 60 60 60 70
Oxyde d'yttrium 40 30 20 20
Alumine 0 10 20 10
ou en pourcentages pondéraux en oxydes
D E F G
Silice + magnésie 39 39 39 45,5
Oxyde d'yttrium 40 30 20 20
Alumine 2i 31 41 34,5
Il a été préparé également une composition à base de silice + magnésie, oxyde d'yttrium et alumine, dans laquelle le rapport des quantités de silice et d'alumine ne correspondait pas à la cordiérite (point H de la figure 1)
Silice + magnésie 71,75 %
Oxyde d'yttrium 20,75 %
Alumine 17,50 %
Les coefficients de dilatation des matériaux de composition correspondant à l'aire du triangle ABI de la figure 1 varient dans de larges proportions, et l'on peut donc choisir parmi ceux-ci un matériau de coefficient de dilatation voisin de celui de nombreux matériaux céramiques cristallins.DEFG
Cordierite 60 60 60 70
Yttrium oxide 40 30 20 20
Alumina 0 10 20 10
or as percentages by weight of oxides
DEFG
Silica + magnesia 39 39 39 45.5
Yttrium oxide 40 30 20 20
Alumina 2i 31 41 34.5
A composition based on silica + magnesia, yttrium oxide and alumina was also prepared, in which the ratio of the quantities of silica and alumina did not correspond to cordierite (point H in FIG. 1)
Silica + magnesia 71.75%
Yttrium oxide 20.75%
Alumina 17.50%
The expansion coefficients of the materials of composition corresponding to the area of the triangle ABI in FIG. 1 vary within wide proportions, and one can therefore choose from these a material with a coefficient of expansion close to that of many ceramic materials. crystalline.

On a utilisé des matériaux céramiques vitreux selon l'invention en particulier pour l'assemblage d'éléments d'échangeurs de chaleur en carbure de silicium fritté, destinés à fonctionner dans des turbomachines. Vitreous ceramic materials according to the invention have been used in particular for the assembly of elements of heat exchangers made of sintered silicon carbide, intended to operate in turbomachinery.

Ces échangeurs, dont un schéma de principe est représenté en figure 3, sont constitués de plus de 200 tubes tels que les tubes 1 de la figure, assemblés sur des flasques d'extrémité 2. Les viroles externe 3, interne 4 et disques de fermeture d'extrémité 5 sont scellés les uns aux autres avec le même matériau vitreux. Tous ces collages assurent ainsi l'étanchéité entre le flux froid (par exemple air froid) qui circule dans les tubes et le flux chaud (air chaud) qui circule à contre-courant autour des tubes. Les joints tels que 6, 7, 8 en matériau céramique vitreux ont supporté des températures en^"1!dbéet F'el' des gaz chauds portés à 8270C sans altération.These exchangers, a schematic diagram of which is shown in FIG. 3, consist of more than 200 tubes such as the tubes 1 in the figure, assembled on end flanges 2. The outer ferrules 3, internal 4 and closing discs end 5 are sealed to each other with the same glassy material. All these bondings thus ensure the seal between the cold flow (for example cold air) which circulates in the tubes and the hot flow (hot air) which circulates against the current around the tubes. The seals such as 6, 7, 8 of vitreous ceramic material withstood temperatures in ^ "1! Dbeet F'el 'of hot gases brought to 8270C without alteration.

Bien que le procédé de fabrication des matériaux céramiques vitreux décrit ci-dessus paraisse la forme d'exécution de l'invention préférable, on comprendra que diverses modifications peuvent lui être apportées sans sortir de son cadre, les liants et solvants mentionnés pouvant pouvant être remplacés par d'autres qui joueraient le meme role technique.  Although the process for manufacturing vitreous ceramic materials described above appears to be the preferred embodiment of the invention, it will be understood that various modifications can be made to it without departing from its scope, the binders and solvents mentioned being able to be replaced. by others who would play the same technical role.

Claims (12)

REVENDICATIONS 1/ Matériaux céramique vitreux, comprenant de la silice, de l'alumine, de la magnésie et de l'oxyde d'yttrium, caractérisés en ce que leurs quantités pondérales respectives répondent aux inégalités 32,5 %\ < Si02 + MgO 4 77s5 % 1 / Vitreous ceramic materials, comprising silica, alumina, magnesia and yttrium oxide, characterized in that their respective weight quantities respond to inequalities 32.5% \ <Si02 + MgO 4 77s5 % 17,5 % 4 Al203 4 62,5 % 17.5% 4 Al203 4 62.5% 58 4 Y203 4 50 % 2/ Matériaux selon la revendication 1, caractérisés en ce que le rapport de leurs quantités de silice et de magnésie correspond à celui de la cordiérite. 58 4 Y203 4 50% 2 / Materials according to claim 1, characterized in that the ratio of their quantities of silica and magnesia corresponds to that of cordierite. 3/ Matériaux selon les revendications 4. ou 2, caractérisés ea ce- qu'ils comportent en outre jusqu'a 5% en poids dgau moins un oxyde métallique favorisant leur dévitrification.3 / Materials according to claims 4 or 2, characterized ea that they further comprise up to 5% by weight of at least one metal oxide promoting their devitrification. 4/ Matériaux selon la revendication 3, caractérisés en ce que l'oxyde métallique dévitrifiant est choisi dans le groupe constitué par le bioxyde de titane, la zircone et l'oxyde de zinc.4 / Materials according to claim 3, characterized in that the devitrifying metal oxide is chosen from the group consisting of titanium dioxide, zirconia and zinc oxide. 5/ Procédé de fabrication d'un matériau selon la revendication 1, caractérisé en ce que lton mélange des poudres de silice, de magnésie d'alumine et d'oxyde d'yttrium par broyage en jarre, fond le mélange pulvérulent obtenu à une température supérieure à 150O0C sous atmosphère oxydante, puis laisse refroidir le verre forme.5 / A method of manufacturing a material according to claim 1, characterized in that lton mixture of silica powders, alumina magnesia and yttrium oxide by grinding in jar, melts the powder mixture obtained at a temperature higher than 150O0C under an oxidizing atmosphere, then allows the glass to cool. 6/ Procédé de fabrication d'un matériau selon la revendication 2, caractérisé en ce que l'on mélange des poudres de cordiérite, d'alumine et d'oxyde d'yttrium par broyage en jarre, fond le mélange pulvérulent obtenu à une température supérieure à 15000C sous atmosphère oxydante, puis laisse refroidir le verre formé.6 / A method of manufacturing a material according to claim 2, characterized in that one mixes cordierite, alumina and yttrium oxide powders by grinding in a jar, melts the pulverulent mixture obtained at a temperature above 15000C in an oxidizing atmosphere, then allows the formed glass to cool. 7/ Application des matériaux selon l'une des revendications 1 à 4 au collage de pièces de même nature en carbure de silicium, nitrure de silicium ou nitrure de silicium modifié par addition d'aluminium et d'oxygène.7 / Application of the materials according to one of claims 1 to 4 for bonding parts of the same kind made of silicon carbide, silicon nitride or silicon nitride modified by addition of aluminum and oxygen. 8/ Procédé de collage entre elles de pièces de même nature en carbure de silicium, nitrure de silicium ou nitrure de silicium modifié par addition d'aluminium et d'oxygène, caractérisé an ce que-l9Qn concasse un matériau selon l'une des revendications 1 à 4, le bote en jarre en milieu liquide, le sèche, l'additionne d'un liant et d'un solvant de façon à former une pâte mouillant bien les pièces à coller, applique cette pâte entre ces pièces sèche l'ensemble en étuve, puis le porte à une température voisine de 14000C sous atmosphère neutre.8 / A method of bonding together parts of the same kind in silicon carbide, silicon nitride or silicon nitride modified by addition of aluminum and oxygen, characterized in that -19Qn crushes a material according to one of claims 1 to 4, the jar in a jar in a liquid medium, dries it, adds a binder and a solvent so as to form a paste wetting the parts to be bonded well, apply this paste between these parts dries the whole in an oven, then bring it to a temperature close to 14000C in a neutral atmosphere. 9/ Procédé de collage selon la revendication 8, caractérisé en ce que l'on utilise comme liant un éther cellulosique et comme solvant de l'eau. 9 / bonding method according to claim 8, characterized in that one uses as a binder a cellulose ether and as water solvent. 10/ Procédé de collage selon la revendication 8, caractérisé en ce que l'on utilise comme liant du polystyrène plastifié et comme solvant le trichloréthylène.10 / A bonding method according to claim 8, characterized in that one uses as binder plasticized polystyrene and as solvent trichlorethylene. 11/ Procédé de collage selon la revendication 8, caractérisé en ce que l'on utilise comme liant un polysaccharide et comme solvant de l'eau. 11 / A bonding method according to claim 8, characterized in that one uses as a binder a polysaccharide and as water solvent. 12/ Procédé de collage selon l'une des revendications 8 à 11, caractérisé en ce que l'on utilise un matériau céramique vitreux additionné d'un oxyde métallique dévitrifiant.12 / A bonding method according to one of claims 8 to 11, characterized in that one uses a vitreous ceramic material added with a devitrifying metal oxide. 13/ Procédé de collage selon l'une des revendications 8 à 12, caractérisé en ce qu'après chauffage à 14000C sous atmosphère neutre on soumet les pièces collées à au moins un cycle de refroidissement lent assurant la dévitrification du matériau de collage. 13 / A bonding method according to one of claims 8 to 12, characterized in that after heating to 14000C in a neutral atmosphere, the bonded parts are subjected to at least one slow cooling cycle ensuring devitrification of the bonding material.
FR8221915A 1982-12-28 1982-12-28 VITREOUS CERAMIC MATERIALS, PROCESS FOR MANUFACTURING SUCH MATERIALS AND APPLICATION THEREOF FOR BONDING CERAMIC PARTS Expired FR2538370B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
FR8221915A FR2538370B1 (en) 1982-12-28 1982-12-28 VITREOUS CERAMIC MATERIALS, PROCESS FOR MANUFACTURING SUCH MATERIALS AND APPLICATION THEREOF FOR BONDING CERAMIC PARTS

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
FR8221915A FR2538370B1 (en) 1982-12-28 1982-12-28 VITREOUS CERAMIC MATERIALS, PROCESS FOR MANUFACTURING SUCH MATERIALS AND APPLICATION THEREOF FOR BONDING CERAMIC PARTS

Publications (2)

Publication Number Publication Date
FR2538370A1 true FR2538370A1 (en) 1984-06-29
FR2538370B1 FR2538370B1 (en) 1986-01-24

Family

ID=9280586

Family Applications (1)

Application Number Title Priority Date Filing Date
FR8221915A Expired FR2538370B1 (en) 1982-12-28 1982-12-28 VITREOUS CERAMIC MATERIALS, PROCESS FOR MANUFACTURING SUCH MATERIALS AND APPLICATION THEREOF FOR BONDING CERAMIC PARTS

Country Status (1)

Country Link
FR (1) FR2538370B1 (en)

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0404632A1 (en) * 1989-06-21 1990-12-27 AEROSPATIALE Société Nationale Industrielle Composite material with reinforced glass-ceramic matrix and process for the preparation thereof
US5384293A (en) * 1991-09-26 1995-01-24 Omori; Mamoru Rare earth oxide-alumina-silica sintered body and method of producing the same
WO2004063110A2 (en) * 2003-01-03 2004-07-29 Battelle Memorial Institute Glass-ceramic material and method of making
WO2004071990A2 (en) * 2003-02-05 2004-08-26 3M Innovative Properties Company Al2o3-la2o3-y2o3-mgo ceramics, and methods of making the same
EP1544565A3 (en) * 2003-12-16 2009-02-18 Deutsches Zentrum für Luft- und Raumfahrt e.V. Plate heat exchanger, process for manufacturing a plate heat exchanger, and ceramic fibre reinforced composite material, more particularly for plate heat exchanger
US20100055498A1 (en) * 2008-09-01 2010-03-04 COMMISSARIAT A L'ENERGIE ATOMIQUE and INSTITUT NATIONAL POLYTECHNIQUE DE GRENOBLE Process for the Moderately Refractory Assembling of Articles Made of SiC-Based Materials by Non-Reactive Brazing in an Oxidizing Atmosphere, Brazing Compositions, and Joint and Assembly Obtained by this Process
WO2013092931A1 (en) 2011-12-22 2013-06-27 Commissariat à l'énergie atomique et aux énergies alternatives Method for assembling parts made of sic materials by means of non-reactive brazing in an oxidizing atmosphere, brazing compositions, and gasket and assembly obtained by said method
JP2015067472A (en) * 2013-09-27 2015-04-13 京セラ株式会社 Jointed ceramic
JP2018027890A (en) * 2017-09-07 2018-02-22 京セラ株式会社 Ceramic conjugate
CN110903102A (en) * 2019-11-25 2020-03-24 西北工业大学 SiCfCaO-Y at port of/SiC nuclear cladding tube2O3-Al2O3-SiO2Glass packaging method

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA2454068A1 (en) 2001-08-02 2003-02-13 3M Innovative Properties Company Al2o3-rare earth oxide-zro2/hfo2 materials, and methods of making and using the same
KR20080086542A (en) 2001-08-02 2008-09-25 쓰리엠 이노베이티브 프로퍼티즈 캄파니 Method of making articles from glass and glass ceramic articles so produced
US8056370B2 (en) 2002-08-02 2011-11-15 3M Innovative Properties Company Method of making amorphous and ceramics via melt spinning
US7811496B2 (en) 2003-02-05 2010-10-12 3M Innovative Properties Company Methods of making ceramic particles

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5742580A (en) * 1980-08-27 1982-03-10 Asahi Glass Co Ltd Ceramic bonding composition and bonding method therefor
EP0055049A1 (en) * 1980-12-20 1982-06-30 Thorn Emi Plc Discharge lamp arc tubes

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5742580A (en) * 1980-08-27 1982-03-10 Asahi Glass Co Ltd Ceramic bonding composition and bonding method therefor
EP0055049A1 (en) * 1980-12-20 1982-06-30 Thorn Emi Plc Discharge lamp arc tubes

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
CHEMICAL ABSTRACTS, vol. 97, 1982, page 300, résumé no. 187018e, COLUMBUS, Ohio (US) & CS - A - 193 878 (J. BANYR et al.) (1er janvier 1982) *
CHEMICAL ABSTRACTS, vol. 97, no. 10, septembre 1982, page 326, résumé no. 77477w, COLUMBUS, Ohio (US) & JP - A - 82 42 580 (ASAHI GLASS CO., LTD.) (10 mars 1982) *

Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0404632A1 (en) * 1989-06-21 1990-12-27 AEROSPATIALE Société Nationale Industrielle Composite material with reinforced glass-ceramic matrix and process for the preparation thereof
FR2648806A1 (en) * 1989-06-21 1990-12-28 Ceramiques Composites COMPOSITE MATERIAL WITH A REINFORCED VITROCERAMIC MATRIX AND PROCESS FOR PREPARING THE SAME
US5104830A (en) * 1989-06-21 1992-04-14 Ceramiques Et Composites Composite shaped articles comprising reinforced glass-ceramic matrices
US5384293A (en) * 1991-09-26 1995-01-24 Omori; Mamoru Rare earth oxide-alumina-silica sintered body and method of producing the same
WO2004063110A2 (en) * 2003-01-03 2004-07-29 Battelle Memorial Institute Glass-ceramic material and method of making
WO2004063110A3 (en) * 2003-01-03 2004-10-21 Battelle Memorial Institute Glass-ceramic material and method of making
WO2004071990A2 (en) * 2003-02-05 2004-08-26 3M Innovative Properties Company Al2o3-la2o3-y2o3-mgo ceramics, and methods of making the same
WO2004071990A3 (en) * 2003-02-05 2005-02-03 3M Innovative Properties Co Al2o3-la2o3-y2o3-mgo ceramics, and methods of making the same
EP1544565A3 (en) * 2003-12-16 2009-02-18 Deutsches Zentrum für Luft- und Raumfahrt e.V. Plate heat exchanger, process for manufacturing a plate heat exchanger, and ceramic fibre reinforced composite material, more particularly for plate heat exchanger
US20100055498A1 (en) * 2008-09-01 2010-03-04 COMMISSARIAT A L'ENERGIE ATOMIQUE and INSTITUT NATIONAL POLYTECHNIQUE DE GRENOBLE Process for the Moderately Refractory Assembling of Articles Made of SiC-Based Materials by Non-Reactive Brazing in an Oxidizing Atmosphere, Brazing Compositions, and Joint and Assembly Obtained by this Process
FR2935376A1 (en) * 2008-09-01 2010-03-05 Commissariat Energie Atomique METHOD OF REFRACTORALLY MEDIUM ASSEMBLY OF SIC - BASED MATERIAL PARTS BY NON - REACTIVE BRAZING IN OXIDIZING ATMOSPHERE, BRAZING COMPOSITIONS, AND JOINT AND ASSEMBLY OBTAINED BY THIS METHOD.
EP2192097A1 (en) 2008-09-01 2010-06-02 Commissariat à l'énergie atomique et aux énergies alternatives Method for assembly by refractory means of parts made from SiC-based materials by non-reactive brazing in an oxidising atmosphere, brazing suspension and seal and assembly obtained by this method.
US10093582B2 (en) 2008-09-01 2018-10-09 Commissariat A L'energie Atomique Et Aux Energies Alternatives Process for the moderately refractory assembling of articles made of SiC-based materials by non-reactive brazing in an oxidizing atmosphere, brazing compositions, and joint and assembly obtained by this process
WO2013092931A1 (en) 2011-12-22 2013-06-27 Commissariat à l'énergie atomique et aux énergies alternatives Method for assembling parts made of sic materials by means of non-reactive brazing in an oxidizing atmosphere, brazing compositions, and gasket and assembly obtained by said method
US9776929B2 (en) 2011-12-22 2017-10-03 Commissariat A L'energie Atomique Et Aux Energies Alternatives Method for assembling parts made of SiC materials by means of non-reactive brazing in an oxidizing atmosphere, brazing compositions, and gasket and assembly obtained by said method
JP2015067472A (en) * 2013-09-27 2015-04-13 京セラ株式会社 Jointed ceramic
JP2018027890A (en) * 2017-09-07 2018-02-22 京セラ株式会社 Ceramic conjugate
CN110903102A (en) * 2019-11-25 2020-03-24 西北工业大学 SiCfCaO-Y at port of/SiC nuclear cladding tube2O3-Al2O3-SiO2Glass packaging method

Also Published As

Publication number Publication date
FR2538370B1 (en) 1986-01-24

Similar Documents

Publication Publication Date Title
FR2538370A1 (en) Vitreous ceramic materials, process for the manufacture of such materials and application of the latter to adhesive bonding of ceramic articles
US3993844A (en) Composite ceramic articles and method of making
US6221499B1 (en) Method using a thick joint for joining parts in SiC-based materials by refractory brazing and refractory thick joint thus obtained
US4735866A (en) Copper-silver-titanium-tin filler metal for direct brazing of structural ceramics
FR2806405A1 (en) PROCESS FOR ASSEMBLING PIECES OF SIC-BASED MATERIALS BY NON-REACTIVE REFRACTORY BRAZING, BRAZING COMPOSITION, AND REFRACTORY SEALING AND ASSEMBLY OBTAINED BY THIS PROCESS
EP1167320B1 (en) Reduced cost fusion-cast alumina-zirconia-silica products and their use
US4698271A (en) Copper-silver-titanium filler metal for direct brazing of structural ceramics
EP0301492B1 (en) Method for bonding cubic boron nitride sintered compact
US3403043A (en) Ceramic-metal seals
JPS6311574A (en) Thermocouple protection tube and manufacture
US4384909A (en) Bonding Si3 N4 ceramics
Wang et al. Joining of AlON ceramics by using β-SiAlON/Y-Si-Al-ON glass-ceramic as interlayer
FR2698092A1 (en) Sintered composite body of ceramic material bonded by glass.
EP2192097B1 (en) Moderately refractory method for assembling parts made from SiC-based materials by non-reactive brazing in an oxidising atmosphere, brazing suspension and seal and assembly obtained by this method.
FR2831533A1 (en) PROCESS FOR METALLIZING AND / OR SELECTIVELY BRAZING BY A METALLIZATION COMPOSITION OF NON-WETTING OXIDE CERAMIC PIECES BY SAID COMPOSITION
US3489627A (en) Sio2,-cao-bao composition and method for bonding therewith
JPH07315964A (en) Single-layer high-temperature coating provided on ceramic base material and its formation
FR2524462A1 (en) MATERIAL TO BE PROJECTED IN FLAME WITH LOW DILATION BASED ON SIO2 AND CAD
EP1212264B1 (en) Glass compositions
FR2624851A1 (en) REFRACTORY COMPOSITION OF ALUMINA-ZIRCONIUM-SILICA GRAINS FOR THE MANUFACTURE OF REFRACTORY ARTICLES, IN PARTICULAR TILES, REFRACTORY COATING OF OVENS OR THE LIKE
JPS61136605A (en) Joining method of sintered hard material and metallic material
JPS596277B2 (en) Sealing composition
JP3154770B2 (en) Silicon nitride ceramics joints
EP0718253B1 (en) Brazing composition and process for an alumina containing ceramic
EP1462430A1 (en) Method for passivating the surface of contact of a refractory container mainly of mullite and coating produced by this process

Legal Events

Date Code Title Description
ST Notification of lapse