WO2011070524A1

WO2011070524A1 - Boron-doped refractory material having a siaion matrix

Info

Publication number: WO2011070524A1
Application number: PCT/IB2010/055681
Authority: WO
Inventors: Najih Boumahdi; Frédéric ROULET; Eric Jorge
Original assignee: Saint-Gobain Centre De Recherches Et D'etudes Europeen
Priority date: 2009-12-09
Filing date: 2010-12-09
Publication date: 2011-06-16
Also published as: EP2509929B1; CN102656129A; FR2953512A1; CN102656129B; BR112012013867A2; BR112012013867B1; EP2509929A1; FR2953512B1; HUE039790T2

Abstract

The invention relates to a fritted refractory material comprising a refractory aggregate bonded by a matrix, the matrix being at least 5 and less than 60 wt% of the material, said matrix comprising, in the weight thereof, a crystallized SiAION phase having the formula Si_xAI_yO_uN_v, where: x is greater than or equal to 0 and less than or equal to 1; y is greater than 0 and less than or equal to 1; u is greater than or equal to 0 and less than or equal to 1; v is greater than 0 and less than or equal to 1; and at least one of the stoichiometric indices x, y, u, or v is equal to 1. Said material comprises: content greater than 5 wt% in said SiAION phase; boron content that is not in the form of a hexagonal BN phase and is greater than 0.05 wt% and less than 3.0 wt%; content less than 10 wt% in the BN hexagonal phase; and content less than 5 wt% in the Si₃N₄ phase, the weight percentages being on the basis of said material.

Description

Bore doped SiAiON matrix refractory product

The invention relates to a refractory sintered product, in particular in the form of a block. The invention also relates to the use of these products and blocks for producing metallurgical furnace coatings, and in particular coatings for crucibles or nozzles for blast furnaces, or even other refractory furnace coatings, refractory coatings. heat exchangers or cooking supports, more particularly ceramic product baking racks.

In particular for constituting the coating furnace crucibles, it is known to use carbon blocks. These blocks are conventionally obtained by shaping a paste bonded with resin or pitch, and then baking at a temperature above 1200 ° C. The product is thus calcined and the organic binders pyroized. The carbon blocks, however, have a low resistance to oxidation and corrosion by melting.

In addition, composite refractory products are known that comprise a refractory granulate bonded with a SiAION type binder matrix. Such products are in particular known from US Pat. No. 4,533,646, US Pat. No. 3,991,166, US Pat. No. 4,243,621 or EP 0 153 000. These products are resistant to oxidation by water vapor and attack by alkalis but do not withstand corrosion.

Also known are products with a binder matrix of the Si ₃ N type with boron-based addition, for example of FR 0 412 627 deposited by the Applicant. These products, however, do not have good resistance to corrosion attack by alkalis.

EP 0 482 984 discloses a refractory product comprising a refractory aggregate bonded by a matrix consisting predominantly of SiAION of formula Si ₆ . _z Al _z O _z N ₈ . _z , with 0.5 <z <4.0. Particles of hexagonal boron nitride (BN) and / or flakes of graphite are dispersed in the matrix. Such a product has a low resistance to oxidation with water vapor.

FR2892720 discloses a refractory product comprising a granulate bound by a nitrogenous matrix, whose surface layer comprises an anti-dust agent selected from calcium and boron.

W096 / 15999 is also known a refractory product comprising a refractory aggregate bonded by a matrix consisting mainly of SiAION, AIN (or one of its polymers) and titanium nitride particles, and optionally hexagonal boron nitride, amorphous carbon and / or graphite flakes. Such a product also has a low resistance to oxidation by water vapor.

There is therefore a need for a refractory product having good resistance to corrosion in cast iron, slag and alkali, and oxidation to water vapor.

An object of the invention is to satisfy this need.

The invention proposes a sintered refractory product comprising a matrix-bonded refractory granulate, said matrix comprising, in its mass, a crystallized SiAION phase of formula Si _x Al _y O _u N _v , in which

x is greater than or equal to 0, greater than 0.05, greater than 0.1 or greater than 0.2, and less than or equal to 1, less than or equal to 0.8 or less than or equal to 0.4;

-. y is greater than 0, or greater than 0.1, greater than 0.3 or greater than 0.5, and less than or equal to 1;

u is greater than or equal to 0, greater than 0.1 or greater than 0.2, and less than or equal to 1 or less than or equal to 0.7;

v is greater than 0, greater than 0.1, greater than 0.2 or greater than 0.5, or greater than 0.7, and less than or equal to 1;

at least one of the static indices x, y, u and v being equal to 1, said product comprising,

a content greater than 5% in said SiAION phase; and

a boron content other than in the form of a hexagonal phase of BN greater than 0.05% and less than 3.0%,

a phase content Si ₃ N ₄ less than 5%, preferably less than 2%, preferably substantially zero,

in percentages by weight based on said product.

As will be more clearly apparent in the remainder of the description, the inventors have discovered that the presence of boron in another form than in the form of a hexagonal phase of BN makes it possible, surprisingly, to obtain an excellent compromise between the resistance to oxidation by water vapor and resistance to corrosion by melting, slag and alkali.

The indices x, y, u and v are stoichiometric and normalized with respect to the one which is the highest, made equal to 1. This definition of the SiAlON phase excludes in particular S13. and Si ₂ ON ₂ . However, Si ₃ N ₄ and Si ₂ ON ₂ may be present in the product, especially in the granulate.

In various embodiments, a sintered product according to the invention may still have one or more of the following optional features:

The matrix represents at least 5%, at least 10%, at least 13%, or even at least 15% of the mass of the product and / or less than 60%, less than 40%, less than 30%, or even less than 25%. % of the mass of the product. By definition, the complement is constituted by the granulate;

The content of said SiAlON phase in the product is greater than 7%, greater than 10%, and / or less than 50%, preferably less than 40%, preferably less than 30%, preferably less than 25%, preferably less than 20%, in percentages by weight based on said product;

The boron content other than in the form of a hexagonal phase of BN in the product is greater than 0, 1%, greater than 0.2%, greater than 0.4%, greater than 0.5%, and less 2.7%, less than 2.5%, less than 2.0%, less than 1.5%, in percentages by weight based on said product;

The content of BN crystallized phases, and preferably the hexagonal phase content of BN, in the product is less than 10%, less than 5%, less than 3%, less than 2% of the mass of the product. This content is preferably substantially zero;

Boron, especially in the matrix, is not in TiB ₂ form;

The content of phases AIN and / or one of its polytypes, in particular 2H, 8H, 12H, 15R, 21R, and 27R, of formula Si _x AlyCVN _V ', in which the stoichiometric indices x \ y', u ' and ', normalized to the highest index, are such that 0 <x'<0.37 and 0.60 <y '<1 and 0≤ u'≤ 0.71 and 0.76≤ V≤ 1 is greater than 1%, greater than 1, 5%, greater than 2%, and / or less than or equal to 6%, in percentage by weight based on said product;

The AIN15R phase content in the product is greater than 1.0%, greater than 1.5%, greater than 1.9%, and / or less than 6%, in percentages by weight based on said product. . The AIN15R type phase is defined by the formula Si _x -ASyO _u N _V ', in which the stoichiometric indices, normalized with respect to the highest index, are such that 0.12 <x'≤ 0.33 and 0.78 <y'≤ 1 and 0.33≤u'≤0.55 and 0.80≤v ^, <1; The phase content of the formula Si _X "A n y" 0 _U "N _v -, in which the stoichiometric indices, normalized to the highest index, are such that 0.43 <x" ≤ 0.75 and 0 ≤ y "<1 and 0 <u" ≤ 1 and 0.9 <v "≤ 1, in the product, called"β'8ίΑΙΟΝ", is greater than 3%, greater than 5%, and / or less than 20 %, less than 7%, in percentages by weight based on said product;

The crystallized phase "β'βίΑΙΟΝ" can still be expressed with the formula Si ₆ - _Z AI _Z 0 _Z N ₈ . _Z , in which the index z is a stoichiometric index such that 0 <z <4.2. The "β'βιΑΙΟΝ" phase content in the product is preferably greater than 3%, greater than 5%, and / or less than 20%, less than 17%, in percentages by weight based on said product. . Preferably, z is greater than 1, or even greater than 2 and / or less than 4, or even less than 3.5.

The mass ratio of the phase quantity of the type AIN15R on the amount of phase β'εϊΑΙΟΝ in the product is greater than 0.1, greater than 0.15, or even greater than 0.2, greater than 0.3, and or less than 1, 0, preferably less than

The content of Si ₂ ON ₂ phase in the product is less than 5%, less than 3%, less than 1%, less than 0.5%, or even substantially zero, in percentages by weight based on said product;

The AlN phase content in the product is less than 5%, less than 3%, less than 1%, less than 0.5%, or even substantially zero, in percentages by weight based on said product;

The content of the Si ₃ N phase in the product is less than 5%, less than 3%, less than 1%, less than 0.5%, or even substantially zero, in percentages by weight based on said product;

In one embodiment, the product has a phosphorus content of less than 0.04%, by weight percent based on the product;

The content of residual metals, in particular of silicon, in the product is less than 1, 8%, or even 1.5%, or even less than 1%, or even less than 0.5%, in percentages by weight on a base basis. of the product ;

In one embodiment, the product has a total content of alkaline earth oxides, in particular CaO and / or MgO, of less than 2%, preferably less than 1.5% and / or greater than 0.2%. even greater than 0,4%, in mass percentages on the basis of the product;

The product has a total content of alkali metal oxides, especially Na ₂ 0 and K ₂ 0, of less than 1%, as a weight percentage based on the product; The product has a total content of alkali metal oxides of greater than 0.4% as a weight percent on the product basis;

The nitrogen content in the product is greater than 3.1%, greater than 3.5%, or even greater than or equal to 4%, as a percentage by weight on the basis of the product;

The product has a boron content such that the ratio of boron to nitrogen B / NI is greater than 0.01, greater than 0.03, greater than 0.10, and / or less than 0.4, less than 0.35, less than 0.3;

The open porosity of the sintered product is greater than 5%, greater than 10% and / or less than 25%, less than 20% and / or less than 17%

Preferably, the closed porosity of the sintered product is less than 2%, preferably less than 1%;

The sintered product is obtained by sintering a preform made by pressing, pounding, extruding, casting, vibrating or resulting from the combination of these different shaping techniques. In particular the product may be of a material selected from a concrete or a rammed earth, shaped or unformed.

In different embodiments, the granulate of a sintered product according to the invention can still have one or more of the following optional features:

Preferably, the granulate has a melting and dissociation temperature. thermal above 700 ° C;

The granulate is composed for more than 70%, or even more than 80% or even more than 90%, or even substantially 100%, by weight, of grains made of a material chosen from alumina, and in particular corundum, which is white or white. black, or tabular alumina, spinels, especially alumina-magnesia spineils, mulite, mulite precursors, chromium oxide, zirconia, zircon, nitrides, silicon nitride Si ₃ N, carbides, and in particular silicon carbide SiC, amorphous carbon or in at least partially crystallized form, and mixtures of these materials, and / or is composed of a mixture of the aforementioned grains;

In one embodiment, the granulate is non-nitrogenous;

In one embodiment, the granulate does not contain boron;

In one embodiment, the granulate has no phase

SiAION crystallized according to the preceding formula Si _x Al _y O _u N _v , In one embodiment, the granulate does not have an Si ₃ N phase and / or a Si ₂ ON ₂ phase.

In various embodiments, the matrix of a sintered product according to the invention may still have one or more of the following optional features:

The matrix comprises more than 0.2%, more than 0.5%, preferably more than 1%, preferably more than 1.5%, more preferably 1.8%, preferably more than 2%, preferably more than 2.5%, preferably more than 3%, preferably more than 3.5% boron, as a percentage by weight based on the matrix. Preferably, the matrix comprises less than 30%, less than 20%, or less than 15%, or even less than 12%, less than 10%, or even less than 9%, less than 7%, less than 5%, and even less than 4% boron, as a percentage by weight based on the matrix;

The matrix is preferably obtained by reactive sintering;

At least 90%, or even 95%, or even 99% or even 100% by weight of the crystalline nitrogen portion of the product is part of the matrix;

The portion of its matrix complementary to the nitrogenous crystalline portion of said matrix comprises, or even consist of, a hydraulic binder, a resin, in particular a thermosetting resin, or a mixture of these constituents;

The crystallized nitrogenous portion represents at least 50%, or at least 80%, or even at least 90%, or even at least 95%, or even substantially 100% of the mass of the matrix, the 100% complement being for example constituted by residual metals and oxides, in particular alumina;

Alumina, metallic silicon, and said crystallized SiAION phase of formula SixAlyOuNu, as defined above, together represent more than 80% of the mass of the matrix;

Said matrix preferably comprises a phase of the type AIN15R as defined above;

The type AIN15R phase represents more than 18% or more than 20% of the mass of the matrix;

- The matrix comprises a phase "β'είΑΙΟΝ" as defined above;

The β'3ιΑΙΟΝ phase represents more than 60%, or more than 70%, or even more than 75% of the mass of the matrix; The mass ratio of the phase quantity of the type AIN15R to the amount of SiAION phase in the matrix is between 0.3 and 1.0, preferably less than 0.7;

Said matrix consists, for more than 80% by weight, of phase SiAiON and, if appropriate, phase of the type AIN15R, in percentage by mass on the basis of the matrix;

The p'SiAION phase and the AI 15R type phase together represent more than 80%, even more than 90% or even more than 95%, or more than 99%, or even substantially 100% of the mass of the matrix, the complement 100% being preferably constituted by other nitrogen phases, in particular 8N, TiM, S13N4, ZrN, SiO ₂ ON ₂ , O'SiAION of formula Si ₂ . ₂ Al _z O -iN ₂ - ₂ with z> 0 or X SiALON (see US Pat. No. 5,521,129), possibly traces of alumina, or even of silica, and impurities and possible traces of aluminum and / or silicon metallic ; The Si ₂ ON ₂ and / or Al phase and / or Si ₃ N ₄ and / or hexagonal phase content of BN in the matrix is less than 20%, less than 10%, less than 5% less than 1%, less than 0.5%, or substantially zero, in percentages by weight on the base of said matrix;

In one embodiment, the matrix has a phosphorus content of less than 0.2% by weight percent based on the product matrix; In a preferred embodiment, the matrix comprises SiC silicon carbide particles dispersed in the matrix. Preferably, the SiC particles have a median size of between 0.1 and 100 microns, preferably less than 30 microns, even more preferably less than 10 microns;

In one embodiment, the product according to the invention comprises more than 0.5%, preferably more than 1%, preferably more than 2%, preferably more than 3%, or even more than 4% and / or, preferably, less than 10%, preferably less than 7% SiC fine particles, in percentages by weight based on the product; The weight ratio B / SiC in the product is preferably greater than or equal to 0.025, greater than 0.05, greater than 0.1 and / or less than or equal to 5, less than 3, less than 2, less than 1, less than 0.5, or even less than 0.4. Preferably the weight ratio B / SiC in the product is greater than or equal to 0.025, greater than 0.05, greater than 0.1 and / or less than 1, less than 0.5, or even less than 0.4 in Whereas fine particles of SiC. In one embodiment, all the phases containing Si, Al, O, and N, in particular all the phases of the matrix containing Si, Al, O, and N, are crystalline phases.

In one embodiment, the invention relates to a sintered block of which at least a part, or all, is constituted by a product.fritté according to the invention. A sintered block according to the invention may also have one or more of the following optional features:

The block according to the invention may have different shapes, including parts or bricks, large blocks or thin plates;

The sintered bioc has a thickness "e" of less than 100 mm, 50 mm or even 25 mm. It may in particular be in the form of a plate, as for example represented in FIG. 6, of which at least a part, preferably all, is constituted by a sintered product according to the invention;

The bioc has an outer surface of generally convex shape, for example a parallelepiped shape, or an outer surface of general shape having concavities. In other words, the outer surface of the block has concavities modifying its general shape. For example, the block may be of cross-section in the form of "U", "+", or "X". The block may have, locally, one or more holes, through or not through, for example in the form of cell or tubular hole, rectilinear or not, for example provided to facilitate the possible passage of a fluid (liquid or gas) or increase the heat exchange surfaces;

The block is a "large" block that has at least one dimension (thickness, length, or width) of at least 120 mm, preferably at least 150 mm, even 200 mm, or even 300 mm, or even 400 mm, even 600 mm or even 800 mm, or even 1000 mm. In particular, the thickness, the length and the width of the large block are at least 120 mm, even 150 mm, even 300 mm, even 400 mm, 600 mm or even 800 mm, or even 1000 mm. The use of large blocks advantageously reduces the number of joints compared to an assembly of refractory bricks. Corrosive attacks through joints are thus limited. The use of large blocks also allows rapid installation of the refractory lining. Finally, the manufacture of large blocks makes it possible, without modifying the environment around the preform, to manufacture blocks heterogeneous high performance. In such heterogeneous blocks, only the central region is in a sintered product according to the invention, as described above;

In particular for the manufacture of large blocks, the median grain size of granules is greater than 2 mm, or even greater than 4 mm and / or less than 15 mm, less than 10 mm, or less than 6 mm;

In particular for the manufacture of thin products such as plates, the median grain size of the aggregate is greater than 5 m, or even greater than 10 μηι, greater than 30 μιη or greater than 50 μm and / or less than 3 mm, less than 2 μm. mm, less than 1 mm, less than 500 mm, or even less than 100 mm;

A central region of the sintered block is a sintered product according to the invention; A peripheral region of the sintered block is not a sintered product according to the invention;

The peripheral region is a sintered product according to the invention;

In one embodiment, the entire sintered block, except the "skin", that is to say except the superficial layer extending, from the surface, to a thickness greater than 1 mm, preferably greater than 5 mm, even more preferably greater than 20 mm, is a sintered product according to the invention.

The invention also relates to a process for manufacturing a sintered product, in particular a sintered block, according to the invention, said process comprising the following successive steps:

a) preparing a starting load comprising

a refractory granulate,

precursors of SiASON, and

boron metal and / or one or more boron compounds and / or boron precursors or a boron compound,

b) pouring said starting charge into a mold;

c) forming the starting charge inside the mold, by compaction, so as to form a preform;

d) demolding said preform;

e) optionally, - drying the preform, preferably so that the residual moisture is between 0 and 0.5%;

f) baking the preform under a nitrogen reducing atmosphere or in a non-oxidizing atmosphere if nitrogen is supplied by the feedstock, preferably at a temperature between 1300 and 1600 ° C, so as to obtain a block.

According to the invention, the starting charge is determined so that, after step f), the block is according to the invention or so that the starting charge is a particular mixture. according to the invention.

Preferably, the organometallic compound is selected from the group consisting of B ₄ C, CaB ₆ , and mixtures thereof. Preferably, the organometallic compound is B ₄ C. More preferably, Ea feedstock does not contain any other boron compound that ^■. said organometallic compound.

The invention also relates to a feedstock adapted to lead by reactive sintering to a product according to the invention.

The invention finally relates to a device comprising, or even consisting of, a product according to the invention or manufactured or capable of being manufactured according to a process according to the invention, said part being chosen from:

a refractory lining of an oven, in particular a metallurgical furnace, in particular a blast furnace and, in particular, a lining of a display or belt of a nozzle or crucible;

a coating of an anode baking oven, in particular for electrotysis, for example aluminum, or a cupola for remelting metals or for melting rocks;

a coating of a heat exchanger;

a coating of a household garbage incinerator;

an anti-abrasion coating;

a ceramic part involved in a device for protecting or regulating the cast iron or steel jets, for example a slide shutter plate, a jet protective tube, a submerged nozzle or a stopper;

a ceramic part involved in a stirring device, either mechanical or by blowing gas, into the molten metal;

a seat brick serving as a housing and support for a gas insufflation device or a metal jet regulating insufflation device, as well as a pocket or distributor impact plate;

a display, a belt of a nozzle, a crucible, a belly, a vat of a blast furnace; an accessory for the foundry of cast iron, steel and special steels such as a nozzle, a buffer or a spillway;

a support for baking ceramic products, preferably in the form of a thin product.

The invention also relates to a device chosen from an oven, a heat exchanger and a support for baking ceramic products, remarkable in that it comprises sintered refractory product according to the invention. The furnace may be in particular an incinerator furnace, a metallurgical furnace, especially a blast furnace or anode baking furnace. The heat exchanger can in particular be that of a household waste incinerator.

Definitions

The term "unshaped product" means a product, wet or dry, not having intrinsic rigidity, such as a powder or a wet feedstock suitable for pouring into a mold.

On the contrary, a "shaped product" is a structured material, that is to say, retaining its shape when it is handled, such as a demolded preform or a sintered product.

"Unshaped concrete" is a dry or wet particulate mixture comprising at least one hydraulic setting agent and capable of being set in mass so as to constitute a dry and solid material whose microstructure is constituted by a granular material whose grains are secured to way of a matrix. An unshaped concrete is able to be applied by casting, associated with a vibration operation or not, or by projection.

The term "unshaped rammed earth" means a dry or wet particulate mixture which does not comprise a hydraulic setting agent and is capable of being solid so as to constitute a dry and solid material whose microstructure consists of a granular material whose grains are joined together. by means of a matrix, called "adobe". An unshaped rammed earth is able to be applied by tamping and / or pressing, associated or not with a vibration operation. In this definition, it includes in particular the rams commonly called "dry mud", in English "dry vîbrating cements", and the masses to groom, in English "ramming mixes". The shape of a concrete or adobe shaped can be any. Concrete or rammed earth may in particular be in the form of a sintered block or a layer, for example when it results from the setting of a coating mass. Conventionally, the concrete or the rammed earth is obtained by caking of a particulate mixture which has undergone an activation step ,. for example by humidification with water.

Sintering is a heat treatment by which the product forms a microstructure consisting of a granulate whose grains are joined together by means of a matrix. A sintered product according to the invention comprises a matrix containing at least one SiAION phase, of formula Si _x Al _y O _u N _v as defined above, obtained by sintering under a non-oxidizing atmosphere if nitrogen is supplied by at least one of the constituents of the feedstock or by sintering under nitrogen, preferably at a temperature between 1300 and 1600 ° C, the latter type of process, allowing a reactive sintering under nitrogen, being well known to those skilled in the art .

"Sintering under nitrogen" means sintering in a gaseous environment comprising more than 90%, preferably more than 95% or, more preferably, substantially 100% nitrogen, as a percentage by volume. A te! gaseous environment is called "nitrogenous environment".

The term "residual" refers to a constituent present in the feedstock and still present in the sintered product obtained from this feedstock.

In a sintered product according to the invention, the term "granulate" refers to all the refractory grains bonded by the matrix and which, during sintering, have substantially retained the shape and the chemical nature that they exhibited in its initial charge. Thus, depending on the size of its particles for example, a powder, for example alumina, could be considered as a granulate or as a precursor of the matrix. In particular, unlike the particles at the origin of the matrix, or "precursors of the matrix", the grains of the granulate are not completely melted or transformed during sintering.

By extension, also called "granulate" all of these grains as they appeared in the starting charge. The nature of the granulate in a sintered product according to the invention is not limiting, provided that its granules of granulate are made of a refractory material, that is to say having a melting point or dissociation greater than 1000 ° C. In one embodiment of the invention, the granulate is a material different from the constituents of the matrix.

In another embodiment of the invention, the granulate is in a material identical to some of the constituents of the matrix. For example, the granulate may incorporate a crystalline nitrogen phase comprising a SiAION phase. An observation in section, however, makes it possible to distinguish the matrix of the granulate without knowing the manufacturing process, the granulate generally having a median size much greater than that of the particles of the matrix, typically at least twice, at least 5 times, or at least 10 times higher.

By "matrix" is meant a crystallized phase or not, ensuring a continuous structure between the grains of the granulate and obtained, during sintering, from the constituents of the feedstock and possibly constituents of the gaseous environment of this feedstock. departure. A matrix substantially surrounds the grains of the granulate, that is to say the coats.

The "matrix" refers to the binder phase resulting from the sintering and must be distinguished from the binder phase that may be present before sintering, for example because of the activation of a hydraulic binder or polymerization of a resin. Sintering a SiAION granulate does not lead to a SiAiON "matrix". For example, the methods of manufacture described in EP 0 242 849, JP 07126072,. US 4,871,698, or JP 07069744 do not lead to a SiAION matrix.

A matrix obtained by reactive sintering has particularities. In particular, during the reactive sintering, nitriding of the precursor metals of the nitrogen-containing crystalline phases occurs. The resulting increase in volume, typically from 1 to 30%, advantageously makes it possible to fill the pores of the matrix and / or to compensate for the shrinkage caused by the sintering of the grains. Reactive sintering thus makes it possible to improve the mechanical strength of the sintered product. The sintered products reactively and have an open porosity and / or closed significantly lower than that (s) other sintered products under similar temperature and pressure conditions. During cooking, the sintered products reactively have substantially no shrinkage.

A "precursor of the matrix" is a constituent of the starting charge which is found in the matrix of the sintered product manufactured or which, during this manufacture, is converted into a constituent of said matrix. A matrix may comprise particles added to the feedstock and unreacted during sintering. For example, a scanning-microscope observation and EDS or EDX-type or X-ray microdiffraction techniques show that the matrix of a product comprising a corundum granule generally comprises particles of alumina. Similarly, the matrix of a product comprising a refractory granulate oxide, for example crystallized alumina, and in particular corundum and / or tabular alumina may comprise particles of silicon carbide.

The "crystallized nitrogenous part" of a product comprises all the crystallized phases of a product. The study of the composition of a product by X-ray diffraction leads to percentages on the basis of all the crystallized phases. X-ray diffraction also makes it possible to determine the nature of the crystallized phases, and therefore to establish compositions on the basis of the crystallized nitrogenous part.

By "boron content" is meant a quantity of boron, without limitation as to the form of boron (boron compounds, boron metal, etc.).

By "in the mass" of a product is meant "distributed throughout the product". In particular the constituent considered is not only present in a surface layer of this product. For boron for example, such a distribution may result in particular from a mixture of boron or boron precursor with the other constituents of the sintered product at the time of preparation of the feedstock. Preferably, the variation of the boron content measured locally in the matrix of the sintered product is less than 10%, preferably less than 5%, preferably less than 2%, or even substantially zero, between any two measurement points.

By "impurities" is meant the inevitable constituents, necessarily introduced with the raw materials or resulting from reactions with these constituents. Impurities are not necessary constituents, but only tolerated.

In a shaped material, the "size" of a particle or grain is the average between its largest dimension and its smallest dimension, these dimensions being measured on a section of said material.

In an unshaped material, the "size" of a particle or grain is its largest dimension measured on an image of that particle. Measuring the size of the grains or particles of an assembly is conventionally performed from an image of this set poured on a self-adhesive marker. We call "median size" of a set of particles or grains, generally denoted D _50l, the size dividing the grains or the particles of this set into first and second populations equal in mass, these first and second populations containing only grains. having a size greater or smaller, respectively, than the median size.

Fine particles are particles having a size of less than 100 microns and greater than 0.1 microns. Preferably, the median size of the optional SiC fine particles of a product according to the invention is less than 30 microns, preferably less than 10 microns.

The term "compaction" refers to any method of shaping, in particular by pressing, extrusion, casting, vibration, shelling or by a technology combining these different techniques.

Hereinafter called "large block" a block having a shape such that the largest sphere inscribed in the volume of material of said block has a diameter of at least 150 mm. In other words, it is possible to extract from a large block a sphere full of material and having a diameter of at least 150 mm.

The part of the feedstock consisting of the refractory components, with the exception of constituents containing boron, is referred to as "base load".

Unless otherwise stated, all percentages relating to the composition of the product, whether sintered or not, relative to the matrix or relative to the initial charge, are mass percentages.

By "comprising", it is necessary to include "comprising at least", unless otherwise indicated. For example, the matrix of a product according to the invention may comprise several SiASON phases.

Brief description of the figures

Other features and advantages of the invention will become apparent on reading the following detailed description and on examining the appended drawing in which FIGS. 1 to 5, and 7 represent, in perspective, different block shapes. sintered according to the invention and Figure 6 shows, in perspective, an example of thin plate according to the invention. detailed description

In order to manufacture a refractory product which is friable according to the invention, it is possible to proceed according to the steps described above.

In step a), the particulate materials are conventionally mixed until a homogeneous mixture is obtained.

The nature and the quantities of raw materials are determined so that the bioc of refractory product obtained at the end of step f) is in accordance with the invention.

The manner of determining the proportions of the constituents of the feedstock is well known to those skilled in the art. For example, one skilled in the art knows that the silicon carbide present in the feedstock is found in the sintered product. He also knows which constituents will be transformed to form the matrix.

Some oxides may be provided by the additives conventionally used to make products, for example, fritters, dispersants such as alkali metal polyphosphates or methacrylate derivatives. The composition of the feedstock may therefore vary, in particular as a function of the quantities and nature of the additives present, as well as the degree of purity of the raw materials used.

The nature of the granulate is not limiting.

Preferably, the aggregate is composed, for more than 70%, or even more than 80% or even more than 90%, or even substantially 100%, by weight, of alumina grains, and in particular corundum, white or black , or tubular alumina, and / or mullite or mullite precursors, and / or chromium oxide, and / or zirconia, and / or zircon and / or nitrides, and in particular silicon nitride If ₃ N ₄ , and / or carbides, and especially silicon carbide SiC. It can also be formed by grains consisting of a mixture of the preceding constituents.

In one embodiment, the granulate comprises grains of corundum and / or silicon carbide SiC, or even consists of such grains.

In one embodiment, and especially when high thermal conductivity or is sought, for example to manufacture a wall of an anode manufacturing furnace for the electrolysis of aluminum or an incinerator coating of household waste or that of a heat exchanger, the granulate contains SiC silicon carbide grains, or even consists of such grains. The product can then comprise more than 5% SiC, in percent by weight based on the product.

In one embodiment, at least 90% by weight of the grains of the granular material have a range of between 150 μm and 15 mm.

In particular for the manufacture of parts or bricks, or even large blocks, it is preferable that at least 50%, or even at least 60% or at least 70% by weight, granular grains have a size larger than 0.2 mm and / or at least 15%, or even at least 20%, or even at least 25% of the grains have a size greater than 2 mm, or even greater than 3 mm or greater than 5 mm, and / or at least 90%, or even at least 95% by weight of granular grains have a size less than 20 mm, or even less than 15 mm, or even less than 10 mm or less than 5 mm. In particular, for the production of large blocks, it is also preferable for the median diameter D ₅₀ of the grains of the granular material to be greater than 2 mm, or even greater than 4 mm and / or less than 15 mm, less than 10 mm, or less than 6 mm. mm.

In particular, for the manufacture of thin products, it is preferable that the median size D _n o of the grains of the granular material is greater than 5 μηπ, or even greater than 10 μm, greater than 30 μm or greater than 50 μm and / or less than 3 mm, less than 2 mm, less than 1 mm, less than 500 pm, or even less than 100 μιη.

In addition to the granular material, the starting charge may comprise calcined alumina, preferably having a median size of less than 10 microns, preferably greater than 5% and / or less than 20%, preferably less than 15%. preferably less than 12%, preferably less than 10%, by mass percentage on the basis of the dry mineral matter of the feedstock,

The feedstock may also comprise metallic silicon, preferably having a median size less than 100 microns and / or greater than 20 microns, or even greater than 50 microns, preferably in an amount greater than 5%, preferably greater than 6 %, preferably greater than 6.5%, preferably greater than 7%, and / or less than 20%, preferably less than 15%, preferably less than 10%, preferably less than 9%, by mass percentage on the basis of the dry mineral matter of the feedstock,

The feedstock can also comprise metallic aluminum, preferably having a median temperature less than 100 microns and / or greater than 20 microns, or even greater than 50 microns, preferably in an amount greater than 0.5%, preferably greater than 1.0%, preferably greater than 1.5%, preferably greater than 2.0%, and / or less than 10%, preferably less than 7.0%, of preferably less than 5.0%, preferably less than 4.5%, preferably less than 4.0%, preferably less than 3.5%, preferably less than 3.0%, in weight percent on the basis of the dry mineral matter of the feedstock.

Preferably, the mass ratio between the amounts of silicon metal and aluminum metal in the feedstock is greater than 1.0, preferably greater than 1.5, preferably greater than 2.0, preferably greater than 2.5, or even greater at 3.0, and / or less than 6.0, preferably less than 5.0, preferably less than 4.5, preferably less than 4.0. even less than 3.5.

These amounts of calcined alumina, metallic silicon and metallic aluminum have proved particularly suitable for improving the resistance to severe thermal shocks.

Boron is preferably added to the feedstock as a powder. Boron may in particular be provided in the form of a boron compound chosen from the group formed by boron metal and its alloys in the amorphous or crystalline state, oxides, carbides, nitrides, fluorides, alloys metals, and organometallic compounds containing boron.

The form in which boron is introduced into the feedstock can, however, lead, during nitriding, to the formation of a substantial amount of hexagonal BN phase.

Preferably, the boron is introduced into the feedstock in a form limiting the hexagonal phase formation of BN during nitriding. Preferably, the hexagonal phase content of BN in the matrix is in fact less than 20%, less than 15%, less than 12%, less than 10%, less than 5%, less than 3%, less than 2%. %, less than 1%, less than 0.5%, as a percentage by weight based on said matrix. Preferably, the matrix does not comprise a hexagonal phase of BN.

Simple tests make it possible to determine the amount of BN hexagonal phase generated as a function of the form in which the boron is introduced into the feedstock, in order to limit the amount of hexagonal phase of BN in the sintered product. Boron is preferably provided in the starting feedstock, at least in part, or even exclusively, in the form of an organometallic compound selected from B ₄ C, CaB ₆ , TiB ₂ or H ₃ BO ₃ and mixtures thereof, preferably selected from the group consisting of B ₄ C, CaB _s , and mixtures thereof. More preferably, the boron is provided in the starting batch in the B form. As shown in the examples below, the BC does not substantially generate a hexagonal phase of BN during nitriding.

Several of the boron compounds described above may be present in the feedstock.

Preferably, the starting charge comprises more than 0.1%, more than 0.5%, more than 1%, more than 1.5%, more than 2.0% and / or less than 6%, less than 5%, less than 4%, elemental boron, as a weight percentage based on the dry mineral matter of the feedstock.

Preferably, the feedstock comprises more than 0.1%, more than 0.5%, more than 1%, more than 1.5%, more than 2.0% and / or less than 6%, less of 5%, less than 4%, B ₄ C, as a weight percentage based on the dry mineral content of the feedstock, preferably in the form of fine particles (having a thickness of less than 100 microns and greater than 0.1 micron).

In one embodiment, the feedstock comprises more than 0.2%, more than 0.4%, and / or less than 5%, less than 4%, less than 2% CaB ₆ , preferably fine particulate form, in weight percent based on the dry mineral matter of the feedstock.

In particular, shaping additives may be used. These additives include plasticizers, for example modified starches or polyethylene glycols and lubricants, for example self-lubricating oils or stearate derivatives. The additives also comprise, conventionally, one or more binders whose function is to form with the raw materials of the load a sufficiently rigid mass to maintain its shape until the end of step c). The choice of binder is dependent on the desired shape. Any known binder or mixture of known binders can be used. The binders are preferably "temporary", i.e. they are removed in whole or in part during the drying and cooking steps of the workpiece. More preferably, at least one of the temporary binders is a solution of modified starch derivatives, an aqueous solution of dextrin or lignin derivatives, in particular an aqueous solution of carboxymethylcellulose or calcium lignosulfate, a solution of a synthetic agent such as polyvinyl alcohol, a resin phenolic or other epoxy resin, a furfuryl alcohol, or a mixture thereof.

More preferably, the amount of binder, especially temporary binder, and / or plasticizer is between 0.5 and 7%, preferably less than 4%, as a percentage by weight on the basis of the dry mineral matter of the starting charge.

A lime cement type hydraulic binder, for example a refractory cement, may be advantageous for curing the products in the form of large blocks after shaping and imparting good mechanical strength to the sintered product. The total content of alkaline earth oxides, and in particular CaO, in the feedstock may be greater than 0.2%, as a percentage by weight relative to the dry mineral mass of the feedstock.

Optionally, phosphorus may be provided in the feedstock, in liquid form or in the form of a powder. It may in particular be provided in the form of phosphate, and especially hydrogen phosphate, or in the form of a polyphosphate, and in particular of alkali metal aluminophosphate or polyphosphate, for example sodium hexametaphosphate. Organophosphorus compounds or organophosphorus polymers may also be suitable. Preferably, in particular for the manufacture of large blocks, the amount of phosphorus is such that the sintered product comprises more than 0.3%, preferably more than 0.4%, and / or less than 2.5%, or less than 2%, or even less than 1, 5% or even less than 1%, of phosphorus, in percentages by weight on the basis of the matrix.

In particular, the silicon of the matrix may be provided, at least in part, by a silicon metal powder. Advantageously, the use of metallic aluminum makes it possible, after sintering, to obtain a stable matrix and well surrounding the grains of the granulate. Mixed alloys containing the silicon and / or aluminum elements can also be used.

The dry starting batch is dry blended sufficiently to obtain a homogeneous mixture. It can be packaged and delivered in this form.

Then, water is conventionally added to the feedstock. In one embodiment, at least 2%, preferably at least 2.5%, and / or less than 10%, or less than 8%, or even less than 5%, of water, in percentages by weight, are added. relative to the mineral mass of the dry feedstock. The water is gradually added to the mixer in operation. Mixing of the feedstock is continued until a substantially homogeneous wet mixture is obtained. In step b), the wet mixture is poured into a mold shaped for the production of a block of the desired dimensions,

In the next compaction step c), the mixture in the mold is compacted, preferably by pressing. In the case of large blocks, a well-adapted technique is the shaping by vibration or "vibro-casting", especially using conventionally a vibrating needle like those used in engineering here.

The preform is then demolded (step d)) and then dried (step e)). Drying can be carried out at a moderately high temperature. Preferably, it is carried out at a temperature between 110 and 200 ° C, preferably under air or humidity controlled atmosphere. It typically lasts between 10 hours and one week depending on the format of the preform, preferably until the residual moisture of the preform is less than 0.5%.

The demolded preform advantageously has sufficient mechanical strength to be handled, transported and possibly assembled.

In a step f), the preform obtained at the end of step e) is placed in an oven. The duration of cooking, usually between 3 and 15 days cold cold, varies depending on the materials, but also the size and shape of the block. The cooking is preferably carried out under pure dinitrogen gas, commonly called "nitrogen". The firing cycle is preferably carried out under an absolute nitrogen pressure of about 1 bar, but a higher or lower pressure could also be suitable, and at a temperature between 1300 ° C and 160ÛX.

The peripheral region of the preform is in contact with the nitrogenous environment. During cooking, the nitrogen of this environment reacts ("reactive sintering") with some of the constituents of the preform, in particular with the calcined alumina, the silica in micron form and the metal powders, to form a matrix and thus bind the grains of the granulate. This reaction is called "nitriding".

At the end of the cooking stage, a sintered block according to the invention is obtained.

Alternatively, and although this may be difficult in practice, the preform obtained at the end of step e) can be put into place in its service position without being friitée. Sintering, carried out in situ, then leads to a sintered product according to the invention consisting of a matrix-bound granulate. At the end of the sintering, a sintered block according to the invention is obtained having a reduced open porosity and outstanding cold crushing and cold bending resistances. More specifically, the sintered product may have a cold crushing strength greater than or equal to 50 MPa, or even greater than 100 Pa, or even greater than 150 MPa. The shape of a sintered block according to the invention is not limiting.

The sintered block may thus have at least one dimension (thickness, length, overall transverse length or width) of at least 120 mm, preferably at least 150 mm, even 200 mm, or even 300 mm, or even 400 mm, even 600 mm or even 800 mm, or even 1000 mm. The thickness, the length and the width of the sintered block can be at least 120 mm, even 150 mm, even 300 mm, even 400 mm, 600 mm or even 800 mm, or even 1000 mm.

A block 10 may in particular comprise a convex outer surface 13, for example a paraplegia (FIG. 1 for example), or comprise an outer surface 13 having concavities modifying its general shape. A block 10 may thus have recesses 14 or passage channels 16 (FIG. 4) for gases. For example, blocks 10 may be in the form of "X", "U", cylinder, or "+", as shown, for example, in Figures 2, 3, 4 and 5, respectively.

The block may also have any form called "self-locking", as shown in Figure 7. The shapes and proportions of Figure 7 are not limiting.

Whatever its general shape, the outer surface 13 of the block may be smooth (FIGS. 1, 3 to 5) or may bear one or more embossings, or "corrugations" 17 (FIG. 2), and / or one or more through-holes or non-through, for example in the form of cavities or tubular holes, rectiîignes or not. This conformation can facilitate the possible passage of a fluid (liquid or gas) or increase the heat exchange surfaces.

A product according to the invention can also be used to produce thin products 20, as shown in FIG. 6.

In FIGS. 1, 6 and 7, the thickness, the length and the width of the blocks and of the thin product have been referenced "e", "L" and "I", respectively. The overall transverse length has been referenced "L" in FIGS. 2 to 5.

Examples The following examples, manufactured according to steps a) to f) previously described, are provided for illustrative purposes and in no way limit the invention.

Blocks were manufactured according to steps a) to f) of the previously described process. A feedstock was made by dry blending the various components added as powders. The water was then gradually added to the mixer in operation to obtain a mixture of a consistency suitable for shaping.

The following materials were used:

A1 97% aluminum oxide corundum alumina Al ₂ 0 ₃ , all particles having a size of less than 5 mm, having substantially the following particle size distribution, in percentages by weight:

2 - 5 mm: 25%

0.2 - 2 mm: 45%

0 - 0.2 mm: 7%;

- A2 brown corundum granulate 97% alumina Al ₂ 0 ₃ , all particles have a size less than 5 mm, having substantially the following particle size distribution, in percentages by mass:

2 - 5 mm; 25%

0.2 - 2 mm: 45%

0 - 0.2 mm: 10%;

Silicon carbide granulate, having substantially the following particle size distribution, in percentages by weight:

2 - 5 mm: 20%

0.2 - 2 mm: 40%

0 - 0.2 mm: 20%;

calcined alumina having a median size of about 6 microns,

aluminum metal powder having a median size of less than 75 microns;

silicon metal powder of median size less than 75 microns;

silicon carbide powder of median size less than 1 micron supplied by Saint-Gobain Materials;

shaping agents: dextrin binder and hydroxyethyl cellulose plasticizer provided by Aqualon;

Zirconium boride powder (ZrB ₂ ) for refractories provided by ESK and having a median size of less than 75 microns; anhydrous boric acid powder less than 200 microns in size provided by UNIVAR;

B ₄ C powder of median size less than 75 microns, manufactured by DENKA.

The starting charge formulations for the various reference examples and according to the invention are presented in the tables below.

A uniaxial hydraulic pressing step with a stress of 700 kgf / cm ² was applied to the feedstock in the mold to compact it. The size of the blocks made is 120 * 100 * 400 mm.

All the blocks were then demolded and then subjected to drying at 110 ° C. in air so that the residual moisture decreased to below 0.2%. Finally, the dried blocks were fired under nitrogen at 1470 ° C for at least 10 hours.

Various analyzes were carried out on the blocks thus produced, the results of which are presented in the following tables.

Open porosity was measured according to ISO 5017.

Elemental nitrogen (N) contents in the sintered products were measured using LECO analyzers (LECO TC 436DR; LECO CS 300). Values are given in mass percentages

The residual silicon is measured according to the method known to those skilled in the art and reference under ANSI B74-151992 (R2000).

The boron mass content is measured by induced plasma emission spectrometry (ICP).

The crystallized phases, in particular the crystalline nitrogen phases and SiCa, were measured by X-ray diffraction and quantified according to the Rietveld method. Specimens taken from these blocks were also subjected to corrosion and oxidation tests:

In these tests, the reference product is "Ref. 1 "in Tables 1 and 2," Ref. 2 "in Table 3, and" Ref. 3 in Table 4.

The "A" dynamic corrosion test, of the "plunging finger" type, was carried out by placing specimens of dimensions 25 × 25 × 180 mm ³ in rotation at a linear speed of 2 cm per second, in a liquid containing slag. blast furnace and cast iron liquid, at 1550 ° C, for 4 hours under Argon. The degree of attack is evaluated by measuring the thickness loss of a specimen as a percentage of the initial thickness (25 mm). The measurement is performed at the sliding caliper at the melting-milk interface. The more the loss of thickness is close to zero, and the more the product is deemed stable, and better in application. The following tables provide the ratio between this percentage and the percentage obtained, for this test, with the reference product, this ratio being multiplied by 100:

100 ^* test result A of the tested example

test result A of the reference product

The test result A is therefore 100 for the reference product. A result less than 100 indicates better resistance to dynamic corrosion than the reference product.

The "B" oxidation test was carried out on 25 x 25 x 70 mm ³ specimens, under steam, at a temperature of 1100 ° C, for 72 hours, according to the AST C863 standard. The oxidation stability is evaluated by measuring the variation in the length of the bars between before and after the oxidation test, expressed as a percentage of the initial length. The longer the variation in length is close to zero, the more stable the product is, and the better in application. The following tables provide the ratio between this percentage and the percentage obtained for this test with the reference example, this ratio being multiplied by 100. The result in test B is therefore 100 for the reference product. A result less than 100 indicates better oxidation resistance than the reference product.

Corrosion test "C", called "Betheieem Steel test", is an application test developed by the American steel company Betheieem Steel to characterize the stability of refractory materials subjected to alkaline corrosion such as that encountered in the blast furnace lining. This test consists of subjecting a set of refractory bars of 25 * 25 * 150 mm ³ to corrosion of K ₂ CO ₃ (potassium carbonate) under a coke bed, in a confined environment. Inside a refractory steel gasket, the bars are buried under a layer of K ₂ CO ₃ , then this layer is covered with coke having a median size of about 1 mm. The gazette is sealed by a refractory lid to maintain a reducing atmosphere throughout the corroding cooking phase. The baking lasts 6 hours at 925 ° C. At the end of the cooking, the corroded bars are recovered, washed, dried, then measure their lengths. The variations in length are expressed as a percentage of the initial lengths, that is to say measured before cooking. The longer the variation in length is close to zero, the more stable the product is, and the better in application. The following tables provide the ratio between this percentage and the percentage obtained, for this test, with the reference example, this ratio being multiplied by 100. The result on test C is therefore 100 for the reference product. A result less than 100 indicates a better resistance to alkaline corrosion than the reference product.

The "D" test is a test of resistance to severe thermal cycling .. !! consists of placing 10 refractory rods of 25 ^* 25 ^* 150 mm ³ previously dried at 0 ° C for half an hour in an oven at 1100 ° C for half an hour. These bars are then dipped in a tray d ^? water at room temperature for about 5 minutes. The bars are replaced directly in the oven without prior drying so as to restart a second quenching cycle with water. The operation continues until 30 cycles. Each bar is then observed and the eye can easily identify the appearance of external cracks.

The detection thresholds "SD" depend on the measuring devices used. These thresholds are as follows:

for X-ray diffraction, Rietveld method: 0.5%, - for chemical analysis by X-ray fluorescence: 0.05%, for LECO (nitrogen, carbon): 0.05%,

for boron and residual silicon: <0.01%.

The matrix corresponds to everything that does not appear as corundum by a phase analysis in XRD.

The following tables summarize the tests performed and the results obtained.

Table 2

"Fis": presence of cracks

Table 3

Table 4

Reference product 1, Ref. 1, is a product not doped with boron. Surprisingly, the addition of boron (product according to Examples 1 to 6) in a defined range leads to improved results.

The best performances in terms of resistance to corrosion and oxidation are obtained for Examples 8, 9, 4 and 5 with boron contents ranging from 0.68% to 1.27%, as a percentage on the basis of product. .

Furthermore, the addition of boron in form CaB ₆ (Example 7) provides, in comparison with Example 1 according to the invention (addition of boron in form B ₄ C), an improvement in terms of resistance to oxidation but leads to a reduction in resistance to corrosion by alkalis.

Example 8 (5% fine particles of added SiC, 1% B ₄ C) and Example 9 (3% fine SiC added, 2% B ₄ C) show the best performance in terms of the sum of the test results. In particular, this performance is much higher than that of the reference example Ref. 2, which does not contain boron and for which fine particles of SiC have also been added. This performance is also greater than that of Examples 5 and especially 3, which do not contain fine particles of SiC, mats for which an addition of boron in an equivalent amount has been achieved. These results reflect a synergistic effect associated with the concomitant presence of fine particles of SiC and boron in the matrix of a product according to the invention.

Moreover, without this being explained by the inventors, unacceptable color heterogeneity between the core and the periphery of the blocks begins to be noticeable from a boron content of about 3.0% on the basis of the product. about 30% based on the matrix.

Examples 11 and 12 show that the ZrB ₂ form of boron in the feedstock leads to poor oxidation resistance (test B) or even poor alkali resistance (test C) for example 12. a preferred embodiment of the invention, the feedstock comprises less than 3.0%, less than 2.0%, less than 1.0%, less than 0.5%, or substantially no boron under the ZrB ₂ form, in percentages by weight based on the dry mineral mass of the feedstock.

Examples 14 to 16 show that the B ₂ 0 _{3 form} of boron in the feedstock can lead to cracks after drying and before baking. These cracks affect the cohesion of the pieces. Example 13 shows that a limited amount of B ₂ 0 ₃ in the feedstock does not lead to the appearance of cracks but leads to poor resistance to oxidation (test B).

In a preferred embodiment of the invention, the starting charge comprises less than 3.0%, less than 2.0%, less than 1.0%, less than 0.5%, or substantially no boron under the B ₂ 0 _{3 form} , in percentages by weight based on the dry mineral matter of the feedstock.

Examples 17 to 22 show, at a level of B ₄ C equivalent, an AB and C test performance comparable to that of Examples 1 to 5. These examples, however, have improved thermal cycling behavior.

Examples 23 to 26 show that the invention also provides good results with SiC granulate (sum of tests A B and C), particularly when boron is added as B C in the feedstock.

Of course, the invention is not limited to the embodiments described, provided by way of illustration and not limitation.

In particular, a sintered product according to the invention can be used in other applications than blast furnaces, for example as a coating of a furnace for melting metals, as an anti-abrasion coating or in a heat exchanger.

Claims

1. A refracted refractory product comprising a refractory aggregate bound by a matrix, the matrix representing at least 5% and less than 60% of the mass of the product, said matrix comprising, in its mass, a crystallized SiAION phase of formula Si _x A) _y O _n N _v , in which

x is greater than or equal to 0 and less than or equal to 1; y is greater than 0 and less than or equal to 1;

u is greater than or equal to 0 and less than or equal to 1; v is greater than 0 and less than or equal to 1;

at least one of the stoichiometric indices x, y, u and v being equal to 1, said product comprising,

a content greater than 5% in said SiAION phase;

a boron content other than in the form of a hexagonal phase of BN greater than 0.05% and less than 3.0%, and

a hexagonal phase content of BN less than 10%,

a content of Si ₃ N phase of less than 5%,

in percentages by weight based on said product.

2. Product according to the preceding claim, wherein

x is greater than 0.05; and or

y is greater than 0.1; and or

u is greater than 0, 1; ei or

v is greater than 0, 1.

3. A product according to any one of the preceding claims, having greater than 0.5% and less than 2.0% boron other than as a hexagonal phase of BN, as a weight percentage based on the product.

4. The product according to any of the preceding claims, wherein the hexagonal phase content of BN is less than 2% of the mass of the product.

5. Product according to the preceding claim, wherein the hexagonal phase content of BN is substantially zero.

6. A product according to any one of the preceding claims, wherein the phase content AIN and / or one of its polytypes, in particular 2H, 8H, 12H, 15R, 21R, and 27R, of formula Si _x A! _y O _U 'N _V ', in which the stoichiometric indices x ', y', u 'and v', normalized, are such that 0≤ x'≤ 0.37 and 0.60≤ y'≤1 and 0 < u '≤ 0.71 and 0.76≤v'≤1, is greater than 1%, as a percentage by weight based on said product.

7. A product according to any one of the preceding claims, wherein the phase content of the formula Si _x AlyO _U 'N _v ., In which the stoichiometric indices, normalized to the highest index, are such that 0 , 12 <x'≤ 0.33 and -0.78 <y'≤ 1 and 0.33 <u '<0.55 and 0.80≤ v'≤ 1, known as the type

"AIN15R" is greater than 1.0% as a weight percent based on the product.

8. A product according to any one of the preceding claims, comprising a phase of formula Si _x -Al _y Ο _α -Ν _ν -, in which the stoichiometric indices, normalized with respect to the highest index, are such that

0.43 ≤ x "<0.75 and 0 <y"<1 and 0 <u " _. ≤ 1 and 0.9 ≤ v"<1, so-called "β'εΐΑΙΟΝ", the SiAION phase content in the product being greater than 3%, as a percentage by mass on the basis of the product.

9. A product according to any one of the preceding claims, comprising a phase of formula Si _x Al _y O _u Nv, in which the stoichiometric indices are such that 0.12 x x '0,3 0.33 and 0.78 y y' ≤ 1 and 0.33≤ u '<0.55 and 0.80≤' ≤ 1, called the type "AIN15R", and a phase of formula Si _X "A! _Y " 0 _U "N _v <, in which the stoichiometric indices, normalized to the highest index, are such that 0.43 <x "<0.75 and 0 <y" ≤ 1 and 0 <u "<1 and 0,9≤ v" ≤ 1, called "p'SiAION", the stoichiometric indices being normalized with respect to the highest index, the weight ratio A1 15R / p'SiAION being between 0.3 and 1, 0.

A product according to any one of the preceding claims, comprising less than 3% of Si ₃ N ₄ and / or less than 3% of AlN phase and / or less than 3% of Si ₂ ON ₂ phase in weight percent on the product base.

11. A product according to any one of the preceding claims, wherein the matrix comprises more than 0.5% of silicon carbide particles, in mass percentage on its base of the product, all of said silicon carbide particles having a median size of between 0.1 and 100 microns.

12. Product according to the preceding claim, wherein the mass ratio between the boron content and the SiC content in the product, B / SiC, is between 0.05 and 3, considering only the SiC particles having a size less than 100 microns and greater than 0.1 micron.

13. Product according to the preceding claim, wherein the mass ratio between the boron content and the SiC content in the product, B / SiC, is between 0.025 and 3, considering only the SIC particles having a size. less than 100 microns and greater than 0.1 micron,

A product according to any one of the preceding claims, wherein the alumina, the metallic silicon, and the said crystallized SiAlON phase of the formula Si _x AlO + _u N _v , together represent more than 80% of the mass of the matrix.

15. A product according to any one of the preceding claims, wherein the mass ratio of boron to nitrogen B / N in the product is greater than 0.01 and less than 0.4.

16. A product according to any one of the preceding claims, wherein the matrix is obtained by reactive sintering.

17. Product according to any one of the preceding claims, wherein the aggregate comprises more than 70% by weight of corundum and / or silicon carbide and / or alumina-magnesia spinelies.

18. A product according to any one of the preceding claims, wherein at least 90% by weight of the crystalline nitrogen portion of the product is part of the matrix.

19. Device comprising a product according to any one of the preceding claims, and chosen from:

a refractory lining of an oven;

a cupola for remelting metals or for melting rocks;

a coating of a heat exchanger; a coating of a household garbage incinerator;

an anti-abrasion coating;

a ceramic part involved in a device for protecting or regulating cast iron or steel jets;

a seat brick serving as a housing and support for a gas insufflation device or a metal jet regulating insufflation device,

a pocket impactor or splitter;

a display, a belt of a nozzle, a crucible, a belly, a vat of a blast furnace;

a nozzle, a plug or a spillway for the foundry of cast iron, steel and special steels;

a support for the baking of ceramic products.

20. Device according to the preceding claim, selected from a refractory lining of a blast furnace.

21. A method of manufacturing a sintered product according to any one of claims 1 to 18, comprising the following successive steps:

a) preparing a starting load comprising

a refractory granulate,

precursors of SiAION, and

an organometallic compound selected from B ₄ C, CaB _e , TiB ₂ , H ₃ B0 ₃ and mixtures thereof,

b) pouring said starting charge into a mold;

d) demolding said preform;

e) optionally drying the preform, preferably so that the residual moisture is between 0 and 0.5%;

f) firing the preform under a nitrogen reducing atmosphere or in a non-oxidizing atmosphere if nitrogen is supplied by the feedstock, preferably at a temperature between 1300 and 1600 ° C, so as to obtain a block,

22. Method according to the preceding claim, wherein the organometallic compound is selected from the group consisting of B ₄ C, CaB _s , and mixtures thereof.

23. A process according to any one of the two immediately preceding claims, wherein the organometallic compound is B ₄ C.

24. A process according to any one of the three immediately preceding claims, wherein the feedstock does not comprise any other boron compound than said organometallic compound.