WO1996002479A1

WO1996002479A1 - Method for agglomerating a powdered or particulate material to form a solid composite material

Info

Publication number: WO1996002479A1
Application number: PCT/FR1995/000938
Authority: WO
Inventors: Christian Perrin; Hervé Farge
Original assignee: Gti Process
Priority date: 1994-07-13
Filing date: 1995-07-12
Publication date: 1996-02-01
Also published as: FR2722504B1; FR2722504A1

Abstract

A method wherein a feedstock consisting of a powdered and/or particulate material with a variable particle size is impregnated with a solution of a polyelectrolyte that is capable of being chemically combined with at least one of the components of the feedstock. The polyelectrolyte may be an ionic polymer having covalent bonds between long-chain molecule components and the available ionic bonds. The method is particularly suitable for producing readily mouldable solid bodies or consolidating loose earth in situ.

Description

PROCESS FOR THE AGGREGATION OF A PULVERULENT MATERIAL OR

PARTICULAR. WITH A VIEW TO THE CONSTITUTION OF A MATERIAL

SOLID COMPOSITE.

The subject of the invention is a method for the aggregation of a pulverulent or particulate material, of variable particle size with a view to constituting a composite solid material.

It aims more particularly, but not exclusively, the realization of easily moldable solid bodies or even the consolidation "in situ" of moving soils such as, for example, sandy soils in which one wishes to put in place foundation piles or anchor.

In general, it is known that composite materials often result from the combination of organic resins and mineral solids to obtain materials with new properties in which the mineral solids are embedded in the resin.

Their production therefore involves an operation of mixing the two products, taking into account their chemical compatibility and the rheological properties of the resin (viscosity). In practice, it can be seen that the coating limits are quickly reached, which are a function of the specific surface and therefore of the particle size of the charge. In addition, there is often a physico-chemical incompatibility between the different elements of the composite which affects the cohesion of the product.

With a view to obtaining composite materials, attempts have also been made to make chemical junctions between the mineral filler and organic compounds by taking advantage in particular of hydroxyl groups (OH sites) or else of the metal oxides present in the filler even in the case where they are considered as impurities.

Other solutions proposed exploit a phenomenon of grafting a reactive organic solvent to the charge, in particular a reactive solvent having a double bond allowing polymerization.

However, in many cases and, in particular, in the case where we want to carry out aggregation in a natural external medium, on the surface, or even in immersion, the presence of these solvents and the energy involved during the reaction. (temperature) pose insurmountable problems: physical, chemical, economic, pollution, ...

Furthermore, it is notably known that the polymerization of the monomers requires fairly precise temperature and humidity conditions which can only be obtained in controlled environments, for example in an oven.

These polymerizations are incomplete when they are not carried out under good conditions, with a level of free residual monomer which varies from one operation to another, this rate possibly being relatively high (for example of the order of 10%). It is clear that this monomer will diffuse in the ambient environment, in particular in the ground and, if it is toxic, could pollute the water tables. This is the case of the resins commonly injected into soils today (polyester acrylamine).

These injected monomers, as well as the cement slurries, have the drawback of setting after a limited period of time. As a result, the setting may take place in the injection tools or even before reaching the desired area.

The invention therefore more particularly aims to eliminate all these drawbacks while solving the problems mentioned above.

It proposes to use, no longer a monomer, as above, but a polymer produced under good industrial conditions, for example in a reactor, this polymer being a polyelectrolyte polymerizable in water or in polar solvents and suitably chosen so as to be able to chemically combine with one of the constituents of the filler (which therefore becomes complementary), and / or with a monomer soluble in water and in the polymer and capable of both homopolymerizing and of reacting on the polymer of so as to obtain a branched network.

Optionally, the above-mentioned monomer may replace water to constitute the polar organic solvent.

Advantageously, the polymer used may consist of an ionic polymer (ionomer or polyal enoate), that is to say polymers having covalent bonds between constituents of long chain molecules and available ionic bonds. This ionic polymer, soluble and having a high affinity for water, can therefore be used in a humid environment and, therefore, is suitable for the abovementioned applications. It has a correct setting time and hardening, that is to say not too short to allow a good impregnation and not too long to avoid too great a dispersion of the product. In addition, the reaction temperature of this polymer remains within the limits of ambient temperature.

The reaction between the ionic polymer and the charge is of the acid-base type generating reaction residues essentially composed of carbon dioxide CO 2 and water, (as regards a reaction with carbonates).

It is therefore important that the filler behaves like a base and is decomposable by acid. This charge may in particular comprise oxides, carbonates, mineral silicates and / or glass ionomers.

To obtain a coherent material, the polymer must be macromolecular and contain at least two reactive acid sites per chain. The basic mineral + polyelectrolyte (macromolecule) assembly must form, after reaction, crosslinked ionic polymers therefore insoluble in water. Typically, with an acrylic polyacid, it will be a metallic polyacrylate.

This polymer (polyelectrolyte polymerized in water or in polar solvents) may be obtained from monomers which may consist of acids having at least one double bond, and also, more generally, from soluble co onomers in water, the respective homopolymers of which are also soluble in the proportion used. The combination of these different monomers then makes it possible to act appreciably on the characteristics of the final material. Thus, for example, the following monomers can be used, separately or in combination:

Acids: - acrylic acid,

- methacrylic acid,

- formic acid,

- itaconic acid.

Comonomers: (non-acidic)

- hydroxylated acrylates,

- hydroxylated methacrylates,

- ethyl acrylate diglycol,

- ethyl acrylate, - methyl methacrylate (in small proportions).

The viscosity of the polymer is linked to its molar mass and to the level of dry extract used. This viscosity will be chosen only according to the use and the impregnation faculty and will result from a compromise, in fact:

- the consistency of the final material is all the more important as the dry extract used is high, - the diffusion of the polymer in the load is all the less high as the rate of dry extracts used in the solution is important.

Furthermore, the reactivity of the polymer-filler mixture, therefore its setting time, depends on the crystalline or vitreous nature of the solid: Thus, for carbonate sands (sea sands), the setting is of the order of 15 minutes but the average strength is obtained from 24 hours. Cohesion improves with time, the maximum being obtained after 7 to 8 days.

As previously mentioned, the invention applies in a particularly advantageous manner to the treatment of soils or sub-soils, and in particular sandy underwater bottoms, for example with a view to placing foundation or anchor piles.

Indeed, this solution proves to be chemically compatible with the ambient medium and, in particular, with:

a) Seawater: the polymer-filler reaction only takes place in the presence of water. It is found that this reaction also takes place in seawater, the sodium chloride content of which is approximately 35 grams per liter.

The nature of the filler: these are compressible carbonate formations which may include:

b) The coarse-grained carbonate sands with high compressibility, of Ca C O3 content greater than 10%, whether they are: - not cemented,

- modular case-hardening,

- case hardening distributed in thin layers alternating with non-cemented levels,

- fine-grained carbonate materials, - cemented carbonate formations.

In all these cases, the polymer reacts with the carbonate compounds which are present and forms a network which traps the non-reactive elements which are present in the charge, such as, for example, silica aggregates.

On the physical level, it can be seen that the impregnation of the charge with an ionic polymer solution having a percentage of dry extracts sufficient to obtain good aggregation, is carried out satisfactorily, and over a large volume thanks to a simple punctual injection of this solution. In fact, the coulis of The ionic polymers used have a viscosity of less than 2m Pa.s and can penetrate the soil without modifying its structure. This viscosity is much lower than that of resinous grouts which is much higher than 2.5 and that of sodium silicate grouts.

Grouting in the form of three-dimensional molecular structures takes place thanks to the chemical reaction of the ionic polymer with the carbonate grains, forming a multiplicity of intergranular bonds.

A rearrangement of the granular structure is thus obtained at the same time as the reduction of the pore volume by the product (of lower modulus than that of the grains), with bridging between grains at the level of the contact zones.

Of course, as long as the chemical reaction continues, the number of bonds as well as the resistance increases. The duration of this reaction is of the order of 24 hours, at the end of which the resistance is seen to stabilize around an average value, for example 3.5 MPa.

Experience shows that the best resistances obtained are those concerning a filler containing the highest percentages of carbonates, and having the finest carbonate grains, so as to drown the non-carbonate grains within a structure stiffened by the injection.

Tests have shown that it is possible to envisage injecting ionic polymers into sands, with a view to consolidating them, even if the latter are not strongly carbonated. It is also possible to treat non-carbonate sands at all provided that carbonates are added beforehand. The stress-strain curves, as a function of the percentage of carbonate, which have been obtained reveal two contradictory trends: the increase in this percentage leads not only to an increase in the resistance to simple compression and to the tangent modulus, but also to the deformation at the breakup. This is due to the fact that an increase in the percentage of carbonates results in a deficit in fine elements, deficit made up by the polymer product which, less stiff than the grains of sand, gives the sample a less fragile behavior.

The resistance tests as a function of the particle size reveal a behavior of the fragile type for the fine samples and a somewhat plastic behavior for the samples of coarser particle size. This is because:

- the intergranular space in fine samples is small, the number of intergranular contacts due, on the one hand, to the fineness of the grains and, on the other hand, to the larger number of chemical bonds, is responsible for it,

- when the grains are larger, the intergranular space is filled with product which does not react chemically and gives rise to the formation, within the sample, of a plastic structure.

The resistance of the filler after treatment can be assessed at the time of injection by measuring the carbon dioxide released during the polymer-calcium carbonate reaction.

To this end, the release of CO 2 produced by the injection should be measured, which is representative of the intensity of the reaction and therefore of the importance of the formation of intergranular bonds. This determination of the CO 2 as well as the measurement of the temperature variation within the load also makes it possible to determine the setting time.

As previously mentioned, in the case where it is desired to treat an inert filler with respect to the ionic polymer, the method according to the invention comprises a prior step of injecting carbonated material (cement).

The principle implemented by the method according to the invention will be described in more detail below, with reference to the appended drawings, given by way of nonlimiting example, in which:

FIG. 1 is a schematic representation illustrating the principle of grafting with crosslinking in the case of a reaction between a polyacid and the OH radicals available in a material;

Figure 2 illustrates the principle of crosslinking resulting from a reaction between a water-soluble monomer and a polyacid (capable of reacting with a material as shown in Figure 1);

FIG. 3 is a photo obtained with an electron microscope illustrating the coating of the grains and the filling of the voids in a charge composed of natural carbonates with a diameter of the order of 130 μm;

FIG. 4 is a photo obtained with an electron microscope illustrating the smooth and microgrenuous appearance of the injected ionic polymer, in the case where the carbonates have a diameter of the order of 0.6 to 1.6 mm; FIG. 5 illustrates the grain-polymer border for carbonates with a diameter of the order of 130 μm;

Figure 6 is a view similar to that of Figure 5 but with a higher magnification;

Figures 7 to 9 illustrate with increasing magnifications a grain breaking process.

As previously mentioned, the basic principle of the present invention consists in reacting the free carboxylic groups on the polyacid chains with metal oxides or, more generally, inorganic oxides having hydroxyl groups (OH sites) which are available on or in most materials.

In the example shown in FIG. 1, the polyacid chains are indicated by solid lines having ramifications, formed by free carboxylic groups COOH, which are grafted onto the OH sites present on the grains G of a mineral solid by returning water H20.

The acid-base type reaction can be demonstrated by infrared spectrometry; the COOH-acid groups are gradually converted into COO- groups: the band at 1700 cm ^-1 (COOH acid group) decreases in favor of two massifs at 1540-1600 cm-1 and 1400-1410 cm- (COO group "), the nature of the bond varying according to the mineral solid used:

- sodium, calcium, magnesium and zinc forming simple ionic salts, - aluminum, iron and copper forming partially covalent salts.

Furthermore, there is the formation of complexes or chelates. The essential role of the ions is to crosslink the polymer chains so as to obtain an ionic polymer matrix which binds the unreacted mineral particles.

FIG. 2 illustrates the principle of crosslinking obtained by reinforcing a network of the type of that of FIG. 1 with a monomer soluble in water and in the polyacid, typically Poly N Methylol Metacrylamide.

In this case, in addition to the polyacid / material bonds, homopolymerization of the monomer is obtained as well as a reaction of the latter on the polyacid of the type:

Ri COOH + R2 CH2 OH - Ri COO - CH2 R2 + H2θ

Tests carried out using a hydroxylated acrylic monomer such as Ethylene Glycol Mono Methacrylate, have made it possible to obtain similar results.

In these different examples, the change in rigidity after injection comes from the creation of an interpenetrating network resulting from the reaction of the ionic polymer with carbonate elements and, possibly, a monomer, this network thus trapping in a sort of cage the non-reactive elements, grains of silica or even clay.

Figures 3 to 9 show photos taken with an electron microscope during a study which made it possible to identify qualitative results concerning the quality of the attachment of the polymer (binder) to a carbonate sand and to obtain information on the mode of rupture of a sample of carbonate sand having undergone an injection of polyacid.

To be observed, the samples represented in FIGS. 3 to 9 were previously dried, metallized with gold and then placed under vacuum for a period greater than 24 hours.

The low physical cohesion of the injected samples, due to their large porosity, often caused very troublesome loading phenomena for observation, which led, in many cases, to limit the magnification of the microscope.

More specifically, the sample shown in Figure 3 was taken from the interior surface (obtained by sawing) of an injected sample. This photo shows a correct coating of the grains and a good filling of the voids. In Figure 4 appear the two aspects of the product: the smooth appearance of the amorphous polymer located between the grains, and the micrograined and finely cellular appearance resulting from the chemical reaction. This photo also shows the porous nature of the sample.

Figures 5 and 6 for example, show the boundary of a grain on which the polymer was fixed. There is a certain continuity where the distinction between the grain and the polymer product is not clear, which shows the good adhesion of the polymer on the grain. The chemical reaction produced a grain / polymer interpenetration.

FIGS. 7 to 9 show, at the rupture surface of a sample of natural carbonates with a particle size of 0.6 to 1.6 mm, a rupture in the mass of the grain. The stresses due to the crushing of the sample during the simple compression test caused, not the separation of the polymer from the surface of the grain, but a breakage of the latter in an area close to its periphery.

General observation of the sample reveals a combination of the following three types of rupture:

- separation of the polymer from the surface of the grain,

- break in the mass of the polymer,

- breaking of carbonate grains.

However, there is a preponderance of one type of failure compared to the others depending on the grain size of the sand and the average grain dimensions.

For a fine particle size for which the grains are closer together and the intergranular contacts are more abundant, a crack originating in the product then hardly spreads within the sample. In this case, because the specific surface is large, the intergranular contacts are reinforced and the cohesion of the sample is improved. Under these conditions, the generalized rupture of the sample must probably be due to the rupture of the grains, which implies a high resistance to simple compression.

However, for coarser samples (0 = 2 to 4 mm), observations show larger pores and more visible separation of the binder. Cracks arising in the product matrix, due to dislocations caused by the sample, have no difficulty in propagating within the latter. Total rupture of the sample is then obtained by separation of the grains.

Of course, the invention is not limited to underwater treatment for the subsequent driving in of anchor piles or even to similar treatments such as stabilizing dunes by the sea or even vases in estuaries.

It applies in fact, more generally, to the transformation, by injection or spraying, of the mechanical characteristics of a more or less heavy material into a rigid or semi-rigid conglomerate, it being understood that this process is limit to media of which at least one component is basic and is capable of reacting with an ionic polymer or even a medium in which a carbonate has previously been added.

By way of example, this process could be used in particular for the repair and reinforcement of structures usable in the building.

In this technical field, a particularly advantageous application of the method according to the invention relates to the production of partition panels, or even of walls, having a sandwich structure comprising a central core made of insulating and economical material disposed between two rigid walls. In this case, the production of the walls can be obtained simply by impregnating the lateral faces of the insulating core with a polyacid optionally copolymerized with a compatible monomer. In the case where the production of the panel or of the wall is carried out in situ, the impregnation may be carried out by spraying, for example with a spray gun, the polyacid and the monomer. On the other hand, in the case of prefabricated panels, these can be produced in molds with pouring or injection of the polyacid and any monomer, in order to obtain perfectly smooth walls.

The simultaneous projection of the filler and the polyacid onto a mold or a support can also be envisaged. The invention also applies to the surface reinforcement of a structure made of a material including carbonates such as hydraulic concrete. In this case, the ionic polymer can be spread by brush or by spraying on the surface of the structure. Thanks to its fluidity, the polymer not only permeates the powdery surface layer of the concrete but penetrates deep into the latter, due to its porosity. The suppression of the pulverence is therefore obtained by blocking the sulphates and the residual carbonates and their anchoring in the depth of the impregnation.

The concrete thus treated can receive a coating product such as paint or panel glue.

The results obtained during the tests carried out on hydraulic concretes result in particular from the fact that the latter have in their mass and on the surface many free metal oxides and carbonates which, by definition, favor the phenomenon of crosslinking so as to obtain the advantages following:

- blocking of carbonates, - blocking of powdery particles on the surface,

- improved adhesion of paints and other coatings and cements on the sites of the copolymer remaining available.

These results were confirmed by attachment tests of a fresh cement during which six concrete test pieces of 200 x 200 x 40 mm were tested, half of which were treated with a brush by impregnating the copolymer and dried for 24 hours. . A 20 mm thick layer of standard hydraulic cement was applied to both parts and left to dry for four weeks. Chisel peeling tests were then carried out: in all cases, the cement board was torn off but it left no trace on the untreated part. On the other hand, there remains a light layer, of the order of 0.5 mm thick on the treated part.

As previously mentioned, the method according to the invention is particularly suitable for solving the problem of the degradation of stones of monuments or works of art due in large part to the surface transformation of the stones into water-soluble sulfates.

In this type of application, two solutions can be envisaged depending on whether it is a surface treatment or a core treatment:

- The surface treatment can consist of an in situ spraying of very liquid products compatible with ambient humidity. Solidification of the surface of the stone which has become powdery is obtained: this treatment is particularly suitable for sculpted parts of works for which any mechanical action liable to deteriorate the sculptures is prohibited.

- The deep treatment of stones, by impregnation for a longer period of time: this treatment makes it possible in particular to avoid the problems of freezing and thawing which tend to cleave the stone.

The invention also applies to the production of solid bodies possibly obtained by molding from different aggregates, for example powders or metallic pellets, oxidized at the surface and chosen according to the properties which it is desired to obtain, for example thermal, sound, electrical, etc. insulation properties Thus, it is possible to produce very simply by molding refractory mittens in aluminum foam, by agglomeration of aluminum grains: the reaction takes place on the surface oxides of aluminum (in particular the trihydrates A1 (0H) 3 The foaming then comes from the creation of carbon dioxide and / or hydrogen.

The molding operation can be obtained by filling the mold with aluminum powder and then spraying the upper face of the mold with the ionic polymer solution, until a total impregnation of the powder is obtained.

Furthermore, numerous tests which have been carried out on loads of very different types have made it possible to arrive at materials which can be used in many other applications. Thus, the cold agglomeration process of metal powders or shot can consist of the first phase of sintering. Likewise, this process can also lead to the production of a coating layer on a surface that one wants to protect, or even decorate.

More specifically, tests have been carried out with a view to producing an adhesive for ceramic tiles, by cold agglomeration of aluminum shot by the action of a polyacid alone and of a polyacid with relay of a hydroxylated monomer. . It is known that the surface composition of the grains here comprises an inner layer of oxide AI2O3 followed by a monohydrate (ALOOH), and an outer layer formed by a trihydrate (A1 (0H) 3) which reacts normally with the polyacid .

In the case of a thin layer (approximately 0.5 mm), a layer of "aluminum" is obtained which is hard at room temperature after 12 hours, but whose insolubility in Water only appears after several weeks. Cross-linking is very slow.

With the hydroxylated monomer (20% by weight) catalyzed, the layer is hard after 6 hours and insoluble after 48 hours. Adhesion to ceramic, which is quite variable, remains to be studied.

In the case where a thick mass of shot (about 20 mm) is treated and the polyacid alone is used, during mixing, immediate foaming occurs due to the evolution of hydrogen. After 10 hours in a mold, the mass is demouldable but brittle. It has heterogeneous cells between 0.5 mm and 8 mm; the mass is expanded. The water absorption is around 10%.

In the case where a hydroxylated acrylic monomer (33) is also used, the expansion is much more limited with pores of the order of one millimeter and the presence of bubbles. (Typically a central bubble). Immersed after 10 hours, the test tube appears to be on the verge of solubility. After 48 hours, it is insoluble.

Tests carried out with different aluminas have led to very different results (due in particular to the variable degree of hydration of the oxide AI2O3. With an alumina trihydrate (A1 (0H) 3), it was possible to obtain a wafer slightly expanded, hard, insoluble after 48 hours but plasticized by water (possibility of deformation), the stiffness returning after drying.The product obtained is particularly important, because of its low cost and its refractory properties.

Other tests carried out with powders of electrically conductive metals, such as copper powders and nickel powders, have made it possible to demonstrate the feasibility of electrically conductive surface layers usable as shielding for example. for the protection of circuits against electromagnetic radiation. Such a layer can be obtained by the method according to the invention by impregnating the powders with a polyacid optionally associated with a monomer and by applying these powders thus impregnated on the surface to be treated.

Another particularly interesting application of the method according to the invention consists in the production of technical ceramics: This involves agglomerating mixtures of oxides having very high specific surfaces (100 to 200 m ² per gram). The binders are then removed by heating to 400 ° C. and then crystallization is then carried out between 800 ^β C and 1200 ^β C. Because the amount of copolymer (20% by weight, dry value) of the test piece before removal of the binders is much lower than that of the organic binders (resins) usually used (50% to 60%), the shrinkage phenomena are considerably reduced, which therefore constitutes an important advantage of the invention.

The behavior of the process according to the invention on a material of vegetable origin has been studied using as filler, defibrated wood: it is shredded wood whose separate fibers are used for the manufacture of certain agglomerates.

The tests consisted in intimately mixing the copolymer and the fiber, then compressing the paste obtained to obtain a substantially homogeneous "pancake", then eliminating the residual liquid.

It is found that after three weeks, the samples have acquired a certain spongy stiffness.

The same tests were repeated but followed by baking at 160 ° C-180 ° C: after 45 minutes, the test pieces were hard, only on the surface: after 60 minutes, the test pieces were hard, very light, consistent but not very solid. Immersed in water, no decohesion appeared after 2 hours.

The tests were repeated by complicating the network by the introduction of N methylol metacrylamide catalyzed 4-4 for 8 parts of wood by weight and then placing the test pieces in an oven at 150 ° C.

After 30 minutes, the test tubes are still flexible, but there is a sparkle in the ear. After 40 minutes, the test pieces are hard. The immersion tests for 3 days show that the network is well constituted.

Examples of preparation of an ionic polymer which can be used for the abovementioned applications will be described below by way of nonlimiting example.

EXAMPLE I

1000 cc of water are introduced into a reactor, which is brought to 60 ° C.

Little by little 300 cc of a mixture of acrylic acid and itaconic acid (60/40) catalyzed with 1% benzoyl peroxide to which 2% of Lauryl Mercaptan is added as transfer agent.

The reaction is complete in 5 hours and an acidic polymer of molecular weight close to 50,000 by weight is obtained.

EXAMPLE II _

300 cc of ethyl alcohol and 700 cc of water are introduced into a reactor which is brought to 60 ^β C. Then gradually introduced 1000 cc of an acrylic acid-ethyl acrylate mixture (75/25) catalyzed with 1% benzoyl peroxide to which 0.5 cc of Lauryl Mercaptan is added as a transfer agent.

The reaction is complete in 6 hours.

A copolymer with a mass close to 100,000 by weight is obtained.

In both cases, the result of the polymerization is soluble in water.

EXAMPLE III

1530 g of distilled water and 20 g of ammonium peroxodisulfate are introduced into a 10 l glass reactor equipped with a ball condenser.

This solution is heated and maintained at 80 ° C and stirred continuously.

Using dosing pumps, the following two solutions are regularly incorporated over a period of between 90 and 105 minutes:

Solution 1: 765 g of distilled water with 152 g of isopropanol and 423 g of acrylic acid. Solution 2: 460 g of distilled water with 20 g of ammonium peroxodisulfate.

38.1 g of itaconic acid are incorporated every five minutes ten times in total.

The temperature does not exceed 85 ^e C.

When everything has been incorporated, the temperature is pushed to 94 ^β C and then allowed to cool. A copolymer of dry extract 21.4% is obtained which will give, after ionic reaction with the mineral filler, a relatively rigid product.

Claims

claims

1. A method for the aggregation of a charge of pulverulent and / or particulate material, of variable particle size, for the production of a composite solid material, this method comprising the impregnation of said material with an ionic polymer (ionomer or polyalkenoate) having covalent bonds between constituents of long chain molecules having at least two reactive acid sites per chain, characterized in that the polymer is obtained from monomers consisting of acids having at least one double bond and from non-acidic water-soluble comonomers, the respective homopolymers of which are also soluble in the proportion used, the combination of these monomers making it possible to act on the characteristics of the final material.

2. Method according to claim 1, characterized in that the reaction between the ionic polymer and the charge is of the acid-base type generating reaction residues essentially composed of water, carbon dioxide for carbonates or hydrogen.

3. Method according to claim 1, characterized in that the above monomers consist of acrylic acid, methacrylic acid or formic acid or itaconic acid, and in that the comonomers consist of hydroxylated acrylates, hydroxylated methacrylates, ethyl acrylate diglycol, ethyl acrylate or methyl methacrylate.

4. Method according to one of the preceding claims, characterized in that the above charge consists of carbonate sand.

5. Method according to one of the preceding claims, characterized in that the said charge and the above polyelectrolyte are sprayed simultaneously on a mold or a support.

6. Method according to one of claims 1 to 4, characterized in that it comprises the molding of the above charge impregnated with the above polyelectrolyte.

7. A method for the in situ treatment of soils, subsoils and or seabed including carbonate formations, characterized in that it comprises injection into this soil, this subsoil or this bottom d 'A grout consisting of an aqueous polyelectrolyte solution capable of combining chemically with said carbonate formations.

8. Method according to claim 7, characterized in that it comprises an injection of carbonate material, prior to the injection of polyelectrolyte in the case where the soil, the subsoil or the bottom is initially devoid of carbonate material.

9. Method according to one of the preceding claims, characterized in that it comprises measuring the quantity of carbon dioxide released during the reaction between the charge and the ionic polymer, in order to determine the mechanical properties of the final material .

10. A method for the surface reinforcement of a structure made of a material including carbonates, characterized in that it comprises the application to the surface of the structure of an aqueous solution of ionic polymer, so as to obtain the removal pulverence by blocking sulfates and residual carbonates and their anchoring in the depth of the structure.

11. Method according to claim 10, characterized in that the above material including carbonates consists of hydraulic concrete.

12. Method according to claim 10, characterized in that the aforesaid material including carbonates consists of stones or bricks of monuments or works of art whose surface is degraded in part as a result of the surface transformation of the stones into sulfates soluble in water.

13. Method for producing panels, partitions, or even walls having a sandwich structure comprising a central core made of a filling material and two rigid side walls, this method being in accordance with claim 1, characterized in that said side walls are obtained by impregnating the side faces of the filling core with a polyacid optionally copolymerized with a compatible monomer.

14. Method for producing, by molding, solid bodies from aggregates such as powders and / or metallic pellets, surface oxidized, in accordance with the method according to claim 1, characterized in that it comprises filling the mold using said aggregates then injecting or spraying the upper face of the mold with the ionic polymer solution, until a total impregnation of the aggregates is obtained, the reaction of the ionic polymer taking place on the surface oxides.

15. The method of claim 14, characterized in that the process of obtaining the solid body by molding consists of the first phase of a sintering.

16. Method according to claim 1 for the production of an adhesive for ceramic tiles, characterized in that said adhesive is obtained by cold agglomeration of aluminum shot with a polyacid alone or of a polyacid with relay of a hydroxylated monomer.

17. The method of claim 1 for producing electrically conductive surface layers usable as shielding in particular for the protection of circuits against electromagnetic radiation, characterized in that it comprises the impregnation of electrically conductive metal powders with a polyacid and applying the impregnated powder to the surface to be treated.

18. The method of claim 1, characterized in that the above material is a material of plant origin such as wood.

19. A method for producing a refractory product according to claim 1, characterized in that the said filler comprises a metal, an oxide, or even a metal hydrate so as to obtain foaming due to the evolution of hydrogen, so as to obtain an expanded product.

20. The method of claim 19, characterized in that the said charge comprises alumina (AI2O3) or alumina trihydrate (A1 (0H) 3).