EP0162871A1

EP0162871A1 - Refractory concrete composition and metallurgical application

Info

Publication number: EP0162871A1
Application number: EP84904078A
Authority: EP
Inventors: Maurice René COLSON
Original assignee: Stephan Pasek & Cie SA; STEPHAN PASEK AND CIE SA
Current assignee: Stephan Pasek & Cie SA; STEPHAN PASEK AND CIE SA
Priority date: 1983-11-28
Filing date: 1984-11-22
Publication date: 1985-12-04
Also published as: ES8506554A1; WO1985002397A1; EP0144303A1; LU85107A1; ES537856A0

Abstract

La composition de béton refractaire est constituée à raison de 5 à 20% et de préférence à raison d'environ 10% d'un liant constitué de silice d'une granulométrie inférieure à 5 mum et de préférence comprise entre 1 et 2 mum et d'un composé alumineux à haute teneur en alumine d'une granulométrie inférieure à 20 mum et de préférence comprise entre 0 et 10 mum dans des proportions respectives d'approximativement de 3 à 7 propres à obtenir une mullitisation à haute température lors de la montée en température. Application à la réalisation de revêtements de protection ou d'objets moulés notamment destinés aux installations de coulée en continu de l'acier par injection à froid.The refractory concrete composition is made up of 5 to 20% and preferably about 10% of a binder consisting of silica with a particle size less than 5 mum and preferably between 1 and 2 mum and d '' an aluminous compound with a high alumina content of a particle size less than 20 mum and preferably between 0 and 10 mum in respective proportions of approximately 3 to 7 suitable for obtaining a mullitization at high temperature during the rise in temperature. Application to the production of protective coatings or molded objects, in particular intended for installations for the continuous casting of steel by cold injection.

Description

Composition of refractory concrete and application in metallurgy.

The present invention relates to an improved refractory concrete composition which has better physical properties, in particular with regard to resistance to high temperatures and mechanical resistance parameters. These compositions are in particular intended for metallurgical uses and other applications where high resistance of this composition to abrasion-compression is required and the invention extends to the application of said compositions for metallurgical uses, comprising a cold injection.

Refractory concrete compositions are widely used for the lining of furnaces and ladles for metallurgical use, and in particular for the production of molded parts obtained by injecting concrete into jigs and intended for the continuous casting of steel. , such as so-called "tundish" distributors. Initially, the production of a refractory concrete composition required the use of relatively large quantities (of the order of 20%) of binders in the form of refractory cement. The large quantity of binders required was due to the fact that the grains of binders formed lumps and were therefore not completely available with their entire surface for the function of binders.

However, the high lime content of the refractory cement acts on the temperature limit for the use of the refractory concrete and efforts have therefore been made to lower the cement content.

A partial solution to these difficulties has been obtained by the use of thixotropic concretes comprising deflocculating agents and, preferably, very fine binders, so that all the grains of the binder can exert their action. Because deflocculating agents destroy lumps, the content of refractory cement. composition may be somewhat lowered, which increases the temperature limit for use.

EP-A-0004509 discloses refractory compositions useful for the production of pastes with a low water content intended to be sprayed into hot masonry, comprising the following essential constituents:

(1) 30 to 60% by weight of a coarse fraction consisting of grains of which more than 50% are greater than 0.5 mm;

(2) 10 to 30% by weight of a fine fraction consisting of particles of which at least 50% are less than 75 microns;

(3) 10 to 30% by weight of a very fine fraction made up of particles of which at least 50% are less than 5 microns;

(4) 10 to 30% by weight of an ultra-fine fraction consisting of particles of which at least 80% are less than 0.1 microns; the fractions (1) to (4) being formed of mineral matter.

These compositions do not make it possible to reconcile the requirements of good resistance to high temperatures with rapid setting facilitating demolding or stripping of the template in which the product is injected cold.

By the document CHEMICAL ABSTRACTS, Vol 96, nº 8, February 1982, page 304, summary 56852d (Colombus, Ohio US) we know a mixture containing 60 to 80% of primary aggregates, 10 to 40% of other refractory aggregates, 1 to 5% of stainless steel fibers, 1 to 15% of refractory clay, 1 to 8% of calcium aluminate cement, a workability agent and aluminum powder.

This composition which is intended for plugging tap holes and therefore for hot work. The presence of clay which disturbs the behavior of the composition when it is subjected to high temperatures makes it unsuitable for the use envisaged according to the invention. The present invention aims to produce refractory concrete compositions exhibiting good behavior at high temperature which are also capable of being cold injected into templates for the production of elements used in the continuous casting of steel and which characterized by grip behaviors such that rapid release is possible.

The object of the invention is achieved by a refractory concrete composition consisting of 5 to 20%, and preferably approximately 10% of a binder consisting of silica with a particle size less than 5 microns and preferably between 0 and 2 μm and an aluminous compound with a high alumina content of a particle size less than 20 μm and preferably between 0 and 10 μm in a ratio of the order of 3 to 7 to allow mullitization at high temperature during processing, the balance of the composition to reach 100% consisting of a small proportion of refractory cement, by refractory aggregates, by conventional deflocculating agents and other possible additives.

The term “aluminous compound with a high alumina content” means an alumina or a corundum containing more than 90% of Al ₂ O ₃ . It has also appeared to be particularly advantageous for said silica to contain 0.2 to 5.0% and preferably about 2% of carbon. Advantageously, this carbon covers the grains. The silica consequently takes on a gray to blackish appearance, in particular when it is wet and it seems that the presence of carbon contributes to improving the properties of the product, in particular with a view to its use by injection.

The refractory cement present in said balance of the composition is chosen essentially as a function of the type of aggregates and is present in an amount, expressed relative to the total composition, of the order of about 0.5 to 15%, a content of the order of 12% constituting a typical example for a concrete consisting of chamotte with 44% Al ₂ O ₃ as aggregate. Since essentially the refractory cement is responsible for the lime content of the final composition, since the cement is essentially a lime aluminate, it will be understood that the refractory cement content will be chosen, towards the lowest contents compatible with the 'intended use and choice of refractory aggregates, in order to lower the final lime content. The aggregates added to the mixture are the conventional aggregates for the type of use envisaged. It can be aluminous aggregates such as chamotte, in particular chamotte with a low alumina content (for example 28 to 32%) or a higher content (for example 40 to 45% or even 55 to 60%) kerphalite, bauxite, gypsum and also aggregates from the crushing of new or used bricks, corundum, etc. The use of magnesian aggregates, chromite or zircon, also falls within the scope of the invention .

The composition will also contain conventional deflocculating agents in order to form thixotropic compositions such as silicates, phosphates, carbonates, or organic deflocculants such as humates, gluconates etc.

The composition may also contain other optional additives and, by way of example, mention may be made of the addition to the composition of ferrosilicon at a content of the order of 2%, this additive having the property of increasing the slump temperature under load as well as the addition of aluminum powder which allows easier drying of the product.

The composition of refractory concrete finds its application in all metallurgical uses.

The composition has in particular the advantage that it can be prepared with a view to its use with very low water contents and that it exhibits good behavior, in particular during the miss by operation by needle vibration. or at the table as well as during an injection processing.

The aluminous compound with a high alumina content with a particle size of less than 20 μm can advantageously be a corundum, a calcined alumina etc.

It should be noted that the use of the binder composed of silica and aggregates in particular as described has already been proposed as an additive in concrete compositions which are not refractory and which are intended essentially for construction uses. It is however particularly unexpected to use, according to the invention, for uses of refractory concretes, compositions which comprise both silica and alumina, because generally, in particular when using aluminous refractory aggregates, an attempt is made to reduce the silica content to the lowest possible value.

Without the Applicant intending to limit itself to any particular explanation, it believes that the improved results observed with the compositions of the invention, in particular with regard to the refractoriness characteristics, probably result from the mullitization which occurs during the temperature rise of the product, the compound which forms being mullite or a related compound whose properties contribute to better behavior of the concrete.

The compounds of the invention, as has been mentioned, can be used by any suitable means to form protective coatings or molded articles, in particular intended for installations for the continuous casting of steel.

The invention will be described in more detail with reference to the following examples which firstly illustrate a composition of the invention and, in the following examples, prior art compositions, in order to demonstrate the improved properties obtained by the present invention. These examples, however, have no limiting character and are intended only to illustrate one of the forms of the invention.

It should be noted that, in the present specification, the proportions indicated are, unless otherwise indicated, always percentages expressed by weight. When respective proportions are expressed in parts, they are also parts by weight. EXAMPLE 1

A mixture is prepared: Cement (lime aluminate type SECAR 70) 12% Chamotte at 44% Al ₂ O ₃ of grain size

0 to 0.08 mm 7%

0.08 to 0.2mm 5%

0.2 to 2mm 34%

2 to 4 mm 31.9%

Corundum with ganulometry 0 to 10μ 7%

Silica with grain size 0 to 2 μ containing 2% C ... 3% Deflocculant such as for example sodium hexametaphosphate 0.1%

Characteristics obtained (Abrasion / Cohesion according to Jourdain tests compared to existing products with the same cement content):

EXAMPLE 2 A mixture is prepared:

Cement (Lime aluminate: SECAR 70) 10%

Colloidal silica 3% Fine corundum (less than 20 μm) 7% Chamotte with 60% alumina

- particle size 3 to 6 μm 25%

- particle size 1 to 3 μm 22%

- particle size 0 to 1 μm 25% - particle size DIN 70 (0 to 80 μm) 8%

0.1% of deflocculant of the sodium hexametaphosphate type is added to this mixture.

This mixture is separated into two equal portions, the first being used alone (preparation A), the second receiving an addition at the rate of 2% (addition of 20 kg per ton) of ferrosilicon (preparation B).

After addition of mixing water in the necessary quantity according to the indications in Table II below, the compression was measured at ordinary temperature (CTO) after setting and after cooking for 5 hours at different temperatures. The measured values expressed in Pascal units are given in Table II.

We also measured the expansion expressed as the temperature in ºC for 0.5% of expansion (t0.5) and 1% of expansion (t ₁ ), the temperature in ºC of the greatest difference between expansion and shrinkage (t ● dip) and the corresponding withdrawal in%.

The sagging without load of 1 kg / cm ² of a standard test piece (5 cm high and 5 cm in diameter) as a function of the temperature rise to values t0.5, t ₁ , t ₂ , t ₅ expressed in ºC was also measured.

The values in Table II indicate the remarkable improvement in the behavior of preparation B (containing ferrosilicum). In both cases, however, the preparations are easily injectable into cold templates and can easily be removed from the mold.

Claims

CLAIMS 1. Composition of refractory concrete intended in particular for metallurgical uses, characterized in that it is constituted in a proportion of 5 to 20%, and preferably in an amount of approximately 10% of a binder consisting of silica of a smaller particle size at 5 μm and preferably between 0 and 2 μm and an aluminous compound with a high alumina content of a particle size less than 20 μm and preferably between 0 and 10 μm in a ratio of the order of 3 to 7 to allow mullitization at high temperature during processing, the balance of the composition to reach 100% consisting of a small proportion of refractory cement, by refractory aggregates, by conventional deflocculating agents and other possible additives.

2. Composition according to claim 1 characterized in that said silica contains 0.2 to 5.0% and preferably about 2% of carbon which covers the grains.

3. Composition according to claim 1 or 2 characterized in that the refractory cement present in said balance of the composition is chosen essentially as a function of the type of aggregates and is present in an amount, expressed relative to the total composition, of l about 0.5 to 15%.

4. Composition according to claim 3 characterized in that said refractory cement is present in an amount of the order of 12%.

5. Composition according to any one of claims 1 to 4 characterized in that the aggregates present in the mixture are aluminous aggregates such as chamotte, in particular chamotte with a low alumina content (28 to 60%), kerphalite, bauxite or corundum, sillimanite, kyanite, tabular alumina.

6. Composition according to any one of claims 1 to 4 characterized in that the aggregates present in the mixture are magnesium aggregates, chromite or zircon, magnesia silicate and composition products from the crushing of new or used bricks .

7. Composition according to any one of Claims 1 to 6, characterized in that the composition contains conventional deflocculating agents with a view to forming thixotropic compositions, in particular silicates, phosphates or carbonates or organic deflocculants.

8. Composition according to any one of claims 1 to 7 characterized in that it contains a ferrosilicon in a content of 0 to 4% and preferably of the order of 2%.

9. Composition according to any one of claims 1 to 8 characterized in that the aluminous compound with a high alumina content of a particle size less than 20 μm is a corundum.

10. Composition according to any one of claims 1 to 9 characterized in that it contains aluminum powder.

11. Application of the composition according to any one of claims 1 to 10 in metallurgy for the production of protective coatings or molded objects in particular intended for installations for the continuous casting of steel by cold injection.