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  • B01J23/32—Manganese, technetium or rhenium
  • B01J23/34—Manganese
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  • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
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  • B82—NANOTECHNOLOGY
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  • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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  • C01—INORGANIC CHEMISTRY
  • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
  • C01F17/00—Compounds of rare earth metals
  • C01F17/30—Compounds containing rare earth metals and at least one element other than a rare earth metal, oxygen or hydrogen, e.g. La4S3Br6
  • C01F17/32—Compounds containing rare earth metals and at least one element other than a rare earth metal, oxygen or hydrogen, e.g. La4S3Br6 oxide or hydroxide being the only anion, e.g. NaCeO2 or MgxCayEuO
  • C01F17/34—Aluminates, e.g. YAlO3 or Y3-xGdxAl5O12
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  • C01G45/1221—Manganates or manganites with trivalent manganese, tetravalent manganese or mixtures thereof
  • C01G45/125—Manganates or manganites with trivalent manganese, tetravalent manganese or mixtures thereof of the type (MnO3)n-, e.g. CaMnO3
  • C01G45/1264—Manganates or manganites with trivalent manganese, tetravalent manganese or mixtures thereof of the type (MnO3)n-, e.g. CaMnO3 containing rare earths, e.g. (La1-xCax)MnO3 or LaMnO3
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  • C01G51/66—Complex oxides containing cobalt and at least one other metal element containing alkaline earth metals, e.g. SrCoO3
  • C01G51/68—Complex oxides containing cobalt and at least one other metal element containing alkaline earth metals, e.g. SrCoO3 containing rare earths, e.g. (La0.3Sr0.7)CoO3
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  • C01G53/68—Complex oxides containing nickel and at least one other metal element containing alkaline earth metals, e.g. SrNiO3 or SrNiO2 containing rare earths, e.g. (La1.62 Sr0.38)NiO4
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Definitions

• the present invention relates to a colloidal dispersion of a rare earth perovskite and its preparation process.
• colloidal soils or dispersions of rare earth compounds in particular rare earth oxides, are known which can be of great interest, for example for applications in catalysis.
• colloidal dispersions of rare earth compounds in the perovskite form there are currently no colloidal dispersions of rare earth compounds in the perovskite form. Such dispersions could have an interest in various applications for example in catalysis, in magnetism or in electrode materials of fuel cells.
• the object of the invention is to provide such a type of product.
• the colloidal dispersion of a rare earth compound according to the invention is characterized in that the rare earth compound is in the form of colloids of perovskite structure and of formula
• Ln is at least one rare earth other than cerium alone;
• B is at least one element chosen from the group comprising elements with an atomic number from 22 to 31, from 40 to 51, from 73 to 83 and aluminum.
• the invention also relates to a process for preparing a dispersion as defined above, which is characterized in that it comprises the following steps: - a perovskite of formula (1) and having elementary crystallites is brought into contact of size at most 500 nm with a monovalent acid having a pka of between 2.5 and 5.0;
• perovskites in a colloidal form offers various advantages: they are indeed nanometric-sized products with a specific surface advantageous for catalysis, raw materials which can be used for the preparation of films or ion-exchange membranes O 2 " and these dispersions can constitute electro-rheological or magneto-rheological fluids. Other characteristics, details and advantages of the invention will appear even more completely on reading the description which follows, as well as various concrete but nonlimiting examples intended to illustrate it.
• perovskite must be taken in the broad sense to designate any compound of chemical formula (1) given above and having a crystallographic structure of the perovskite type.
• colloidal dispersion or sol of a rare earth compound designates any system made up of fine solid particles of colloidal dimensions based on a rare earth, with the perovskite structure, in suspension in a liquid phase, said particles possibly also , optionally, contain residual amounts of bound or adsorbed ions such as for example acetates, citrates, nitrates, chlorides or ammonium or sodium ions.
• the percentage of these bound or adsorbed ions X, expressed in molar ratio X / Ln can vary between 0.01 and 1.5, more particularly between 0.01 and 0.6, it being understood that these values are given as example only.
• the dispersion may also contain residual amounts of compounds of the Ln 2 O 3 , Ln (OH) 3 , LnCO 5 , Ln (acetate) 3l SrCO 3 , BaCO 3 , CaCO 3 , MgCO 3 , B v O W ⁇ type, possibly under colloidal shape.
• the rare earth can be found either completely in the form of colloids of perovskites, or simultaneously in the form of colloids of perovskites, and other various dissolved forms of the Ln 3+ type or of poly- Ln x OH y t + ions.
• rare earth is meant the elements of the group constituted by yttrium and the elements of the periodic classification of atomic number included inclusively between 57 and 71.
• the first object of the invention is the colloidal dispersion based on a rare earth, with the perovskite structure described above and corresponding to formula (1).
• Ln denotes one or more rare earths in combination, the case of cerium present as a single rare earth being excluded.
• the rare earth may more particularly be lanthanum or even lanthanum in combination with cerium.
• the La / (La + Ce) atomic ratio is preferably at least 0.5 and more particularly at least 0.7.
• Element B which is chosen from elements with an atomic number from 22 to 31, from 40 to 51, from 73 to 83 and aluminum, can be more particularly iron, manganese, cobalt, nickel, ruthenium , chromium, palladium, platinum and copper.
• the invention applies very particularly to the case where B is iron, manganese or cobalt.
• B can be a combination of the elements supra. In the case of a combination, the combined elements are preferably of different valences. Mention may more particularly be made of the iron / cobalt combination.
• the perovskite of formula (1) can be doped.
• the rare earth Ln can be partly substituted by a monovalent or divalent cation.
• This cation can be chosen from alkalis and alkaline earths. More particularly, the cation can be sodium, potassium, lithium, calcium, magnesium, strontium and barium. Strontium is a preferred dopant.
• the products thus doped can have improved catalytic properties.
• the quantity of substituent cation is generally at most 50% and it can vary for example between approximately 1% and approximately 50%, this quantity being expressed by the cation / cation ratio (cation + Ln).
• the well-crystallized perovskite structure of the colloids of the dispersions of the invention can be observed by X-ray diffraction.
• This crystallized perovskite structure can for example be demonstrated by X-ray diffraction on the solid colloids recovered either by drying at low temperature (T ⁇ 60 ° C) colloidal dispersions, either by ultracentrifugation thereof.
• the sizes of the colloidal particles which constitute the soils of the invention are liable to vary over a wide range.
• the particles can have an average diameter of at most 500 nm, more particularly at most 200 nm and in particular between 5 and 200 nm, more particularly between 5 and 30 nm and even more particularly between 5 and 20 nm.
• This diameter is determined by photometric counting from an analysis by METHR (High Resolution Transmission Electron Microscopy) and by cryo-MET technique. This technique makes it possible to observe the samples kept frozen in their natural environment which is either water or an organic solvent. Freezing is carried out on thin films approximately 50 to 100 nm thick, either in liquid ethane for the aqueous samples or in liquid nitrogen for the others.
• the morphology can be of the anisotropic type, that is to say that the colloids have a ratio m greater than 5, more particularly greater than 10 and even more particularly greater than 25.
• Anisotropic morphologies can be presented by colloids in the form of platelets or fiber. It will be noted here and for the rest of the description that it is in the case of colloids with anisotropic morphology that the colloids can generally have the highest size, that is to say in a range between 200 nm and 500 nm.
• the dispersions of the invention have a pH value which can vary within a certain range. They may for example have a pH value of between 4 and 8.5, preferably between 4 and 6.5.
• the dispersions of the invention can have a concentration in a wide range, for example of at least 5 g / l, preferably of at least 100 g / l, this concentration being expressed by mass of perovskite.
• the dispersions according to the invention can be aqueous dispersions, the continuous phase being water, or dispersions in a continuous phase which can be constituted by a water / organic solvent mixture miscible with water or alternatively dispersions in an organic solvent miscible with water.
• solvents examples include alcohols such as methanol or ethanol, glycols such as ethylene glycol, acetate derivatives of glycols such as ethylene glycol monoacetate, glycol ethers, polyols or ketones.
• the dispersions are stable dispersions with respect to decantation over periods greater than 6 months.
• the process for preparing the dispersion of the invention will now be described.
• this process comprises a first step in which a perovskite of formula (1) is brought into contact with a specific acid.
• perovskite it is possible to use any crystallized perovskite corresponding to formula (1).
• the size of the elementary crystallites or of the organized domains of this perovskite must be at most 500 nm, in particular at most 200 nm. This size should preferably be at most 100 nm, advantageously at most 40 nm and even more advantageously at most 30 nm.
• a crystallite size of at most 500 nm or 200 nm is necessary in order to be able to obtain a colloidal dispersion and the size of the colloids will be all the smaller the smaller the size of the crystallites of the starting perovskite.
• the size of the crystallites is then calculated in a known manner by the Scherrer equation which takes into account the width of the peak at half height.
• perovskite can be prepared by any means known to those skilled in the art. Mention may be made of perovskites prepared by low temperature processes involving wet precipitation followed by calcinations, or at high temperature using flame combustion type processes, gas phase reactions.
• a perovskite with anisotropic morphology In the particular case of the preparation of colloid dispersions with anisotropic morphology, one starts from a perovskite with anisotropic morphology.
• a perovskite can be obtained by using, for example for its preparation, an anisotropic oxide, in particular MnO 2 with anisotropic morphology or also an oxy-hydroxide of Fe of the ⁇ FeOOH type with anisotropic morphology.
• an MnO 2 oxide with anisotropic morphology can be used, as described in the article by Xun Wang and Yadong Li, Chem.
• the acid with which perovskite is brought into contact is a monovalent acid which has a pka of between 2.5 and 5.0.
• This acid is preferably a water-soluble acid.
• acids which are well suited in the context of the invention there may be mentioned acetic acid, formic acid, propionic acid, monochloroacetic acid.
• Acetic acid can be very particularly used.
• the presence is usually carried out in an aqueous medium with a solution of the acid to obtain a suspension.
• the concentration of the acid in the solution is not critical and can vary widely. However, this concentration is, from preferably chosen so that the suspension obtained can also constitute a sufficiently large liquid phase to allow an attack to be carried out under good stirring conditions during the next step of heating the process. Thus, this concentration can be between 0.05 M and 5 M.
• the amount of acid used is generally such that the molar ratio H " 7 perovskite is between 0.05 and 20, more particularly between 0.05 and 5. In fact, this amount must be chosen so that the attack, which takes place during the process, perovskite by acid is a mild attack. Too little acid may not make it possible to obtain a colloidal dispersion while too much risk may lead to formation of too many ionic species.
• the contact with the acid is usually done at room temperature, that is to say between 15 ° C. and 25 ° C. It can be done by adding perovskite to a solution acid or alternatively by suspending perovskite in water and then adding the acid in an adequate amount.
• the perovskite can be ground before it is brought into contact with the acid.
• Various types of grinding can be used for example dry grinding of the air jet type or preferably wet grinding for example using a ball mill or BALL MILL mill.
• the grinder balls can be made of AI 2 O 3 or zircon, of average size centered on approximately 0.2 to 1.0 min, preferably from 0.2 to 0.8 min.
• the grinding time can vary from 2 min to 45 min.
• the second stage of the process consists in subjecting the mixture obtained at the end of the first stage to a heat treatment.
• This heat treatment allows the attack of perovskite by the acid and it is done by heating to a temperature between 50 ° C and 200 ° C.
• This treatment can be carried out in a closed enclosure, for example in a closed reactor of the autoclave type.
• the temperature of the heat treatment is a function of the solubility of the starting perovskite. This temperature could also be adapted as a function of the acid concentration and of the H + / perovskite ratio of the solution used in the first step.
• the duration of the treatment is variable and is shorter the higher the temperature.
• the next possible step in the process is a purification step. It is in fact aimed at eliminating the ionic or / and colloidal parasitic species present in the suspension obtained at the end of the heat treatment. This step can be carried out in different ways depending on the type of suspension resulting from the heat treatment.
• An anionic resin is preferably used in combination with a cationic resin.
• the resin treatment is carried out in any suitable manner.
• the resins can be brought into direct contact with the colloidal dispersion.
• the solid product is separated from the reaction medium. This separation can be done by any known technique, for example by filtration, decantation or centrifugation.
• the solid thus obtained can then be resuspended in a liquid medium, for example water, so as to give the dispersion of the invention.
• a liquid medium for example water
• These separation / redispersion operations can possibly be repeated if necessary.
• the dispersion obtained after resuspension in water can also be purified and / or concentrated by ultrafiltration or by treatment with a resin.
• this dispersion can be prepared from an aqueous dispersion as obtained by the process which has just been described and by addition of the organic solvent of the type mentioned above to this aqueous dispersion then distillation to remove the water.
• aqueous dispersion as obtained by the process which has just been described and by addition of the organic solvent of the type mentioned above to this aqueous dispersion then distillation to remove the water.
• Different variants of the process of the invention will be described below. These variants relate to different stages of the process and they can be used alone or in combination. They have in common to allow to obtain dispersions whose colloids have small average diameters, included in the range of 5 and 30 nm and more particularly from 5 to 20 nm.
• the first variant relates to the starting perovskite used in the first step of the process.
• This perovskite can be prepared according to a specific process. This process uses as starting materials salts of the elements Ln and B and, in the case of the preparation of a product based on a doped perovskite, of the mono or divalent cations.
• the salts can be salts of inorganic or organic acids, for example of the sulfate, nitrate, chloride or acetate type. Note that nitrate and acetate are particularly suitable.
• cerium salts it is possible to use more particularly cerium III acetate, cerium III chloride or cerium III or cerium IV nitrate as well as mixtures of these salts such as acetate / chloride mixtures. These salts are mixed in aqueous media to preferably form a solution.
• the mixture is then reacted with a base in basic condition so as to obtain a precipitate.
• products of the hydroxide type can be used in particular. Mention may be made of alkali or alkaline-earth hydroxides and ammonia. It is also possible to use secondary, tertiary or quaternary amines. However, amines and ammonia may be preferred insofar as they reduce the risks of pollution by alkaline or alkaline-earth cations. Mention may also be made of urea.
• the base is generally used in the form of a solution.
• the precipitation reaction takes place in basic condition, that is to say greater than 7, preferably greater than 9.
• this pH can be higher, for example by at least 12.
• the precipitate obtained at the end of the reaction is separated from the reaction medium. This separation can be done by any known technique, for example by filtration, decantation or centrifugation.
• the separated product can be washed for example by being resuspended in water and then separated again.
• the product obtained is then calcined at a temperature of at least 450 ° C. This temperature can thus be between 450 ° C and 1200 ° C, more particularly between 500 ° C and 900 ° C. This calcination is generally done in air.
• the duration of the calcination may for example be between 1 and 10 hours. This duration is usually the lower the higher the calcination temperature.
• the temperature and the calcination time are fixed to allow a product having a perovskite structure to be obtained in which the size of the elementary crystallites is small, that is to say at most 60 nm preferably, this size of the elementary crystallites being determined by X-ray diffraction as previously indicated.
• the calcination can be of the flash type. By flash calcination means the direct introduction of a product to be calcined in an oven previously warmed up.
• the rate of climb is instantaneous.
• An example of industrial flash calcination is a calcination in an oven of the tunnel oven type.
• the calcination temperature is higher than that given above. It can thus be between 800 ° C and 1200 ° C over a short period of the order of only a few minutes, for example between 1 and 15 minutes.
• the perovskite thus obtained can then be ground as indicated above.
• an aqueous starting mixture is formed of salts of the elements Ln and B with an Ln / B ratio in super-stoichiometry.
• this over-stoichiometry is fixed so that the atomic ratio Ln / B verifies the relation 1 ⁇ Ln / B ⁇ 1.25.
• organic compound chosen from carboxylic acids, amino acids, polyacrylic acids and their salts and alkylamines.
• the organic compound can be introduced either in the basic solution or in the solution of salts of the elements Ln and B. In the case of the use of two or more organic compounds, these can be added together or separately at different times.
• carboxylic acids it is possible in particular to use the aliphatic mono- or dicarboxylic acids and, among these, more particularly the saturated acids. It is also possible to use fatty acids and more particularly saturated fatty acids. Mention may thus be made in particular of lauric acid.
• dicarboxylic acids there may be mentioned oxalic and succinic acids.
• carboxylic acids phenol acids such as salicylic acid can also be used. It is also possible to use acid-alcohols such as citric acid.
• the salts of the above acids can also be used.
• the amino acid may more particularly be an aliphatic amino acid such as aminocaproic acid. It can also be a natural amino acid such as lysine, arginine, alanine, aspartic acid, glutamic acid. Again, the salts of these acids can also be used.
• polyacrylic acids and their salts such as sodium polyacrylate, and more particularly those whose molecular weight by weight is between 2000 and 5000.
• the amount of organic compound is preferably chosen so that the molar ratio of organic compound / perovskite is between 0.1 and 1 when this compound is added during the reaction between the salts Ln and B and the base.
• the quantity of organic compound is preferably chosen so that the mass ratio of organic compound / perovskite is between 1 and 60%.
• the medium to which the organic compound has been added can optionally be subjected to grinding.
• a first way consists in carrying out a high energy grinding of the wet grinding type. Such grinding takes place on the wet precipitate obtained at the end of the reaction step with the base and which has been separated from the reaction medium. Wet grinding can be done in a ball mill for example.
• a second way consists in carrying out a medium energy grinding by subjecting a suspension of the precipitate to shearing, for example using a colloid mill or a stirring turbine. This suspension may be an aqueous suspension which has been obtained after re-dispersion in water of the precipitate obtained at the end of the reaction step with the base and then separation. It can also be the reaction medium directly obtained at the end of this same step after the addition of the organic compound without there having been a separation of the precipitate from the liquid medium.
• the dispersion can be subjected to evaporation, centrifugation, lyophilization, ultrafiltration or osmotic compression for example.
• Osmotic compression is a known method, the principle of which is to balance the chemical potential of water through a membrane. This is done by placing the colloidal dispersion in a dialysis bag, for example made of cellulosic material, this bag being placed in an aqueous solution whose chemical potential of water is different from that of the aqueous phase of the dispersion. This can be done for example by using an aqueous solution of polyethylene glycol (PEG) or dextran. The PEG or dextran concentration fixes the osmotic pressure and therefore the final concentration of the colloidal dispersion. Evaporation, centrifugation and ultrafiltration can be done using any suitable device. Preferably, the dispersion is dried by stoving at low temperature, preferably at a temperature below 50 ° C, or by using a rotavapor.
• PEG polyethylene glycol
• dextran dextran
• This powder is redispersible, that is to say that it can be resuspended in water and thus lead to a colloidal dispersion according to the invention, with the characteristics described above.
• Colloids can be used as elementary constituents for the preparation of materials for catalysis, in particular for automotive post combustion or for the oxidation of volatile organic compounds. Colloids can also be used as elementary constituents for the preparation of materials for solid electrolytes (membranes with controlled diffusion of O 2 " ions, of H + ions) or for electrodes of fuel cells.
• perovskite colloids can also be used as a functional nanometric filler in polymer-based coatings to give these polymers various catalysis properties, electrical properties or magnetic properties.
• the composite coatings thus formed then develop antistatic or electromagnetic compatibility properties.
• the dispersions can also be used for the manufacture of films. These colloidal dispersions can also be used as raw materials for the preparation of electro-rheological fluids or as magneto-rheological fluids.
• This example relates to the preparation of a colloidal dispersion of LaMnO 3 .
• a lanthanum nitrate solution is obtained by diluting 146.5 g of a lanthanum solution with a density of 1.686 and 2.88 M in La with demineralized water so as to obtain 500 cm 3 of solution (i.e. 250 millimoles).
• the manganese nitrate solution is mixed with the lanthanum nitrate solution.
• the solution of manganese nitrate and lanthanum nitrate thus obtained is added instantaneously to 650 cm 3 of 3M ammonia solution with stirring. A precipitate is formed instantly.
• the pH of the suspension obtained is 9.5.
• the suspension is centrifuged at 4500 rpm for 15 min.
• the pellet obtained is taken up in 1000 cm 3 of demineralized water and stirred for 30 min. It is again centrifuged for 15 min and the solid obtained is allowed to dry at room temperature for 16 hours. The solid is again dried at 60 ° C for 10 hours.
• the product is calcined for 6 hours at 800 ° C.
• the mixture is transferred to a Teflon container inserted in a hydrothermal treatment cell (Parr bomb).
• the hydrothermal treatment is carried out at 160 ° C for 16 hours.
• the supernatant phase is drawn off.
• the pellet is redispersed with stirring in 25 cm 3 of demineralized water.
• a colloidal phase and a solid are obtained.
• colloids of average size of 35 nm are observed.
• colloids are collected in the form of a solid powder.
• the diffractogram shows the presence of a LaMnO 3 phase.
• This example relates to the preparation of a colloidal dispersion of LaMnO 3 of small size of colloids with the use of aminocaproic acid.
• a lanthanum nitrate solution is obtained by diluting 146.5 g of a lanthanum solution with a density of 1.686 and 2.88 M in La with demineralized water so as to obtain 500 cm 3 of solution (i.e. 250 millimoles).
• the manganese nitrate solution is mixed with the lanthanum nitrate solution.
• the solution of manganese nitrate and lanthanum nitrate thus obtained is added instantaneously to 650 cm 3 of 3M ammonia solution with stirring. A precipitate is formed instantly.
• the pH of the suspension obtained is 9.0.
• the suspension is centrifuged at 4500 rpm for 15 min.
• the pellet obtained is taken up in 1000 cm 3 of demineralized water and stirred for 30 min. It is again centrifuged for 15 min and the solid obtained is allowed to dry at room temperature for 16 hours. The solid is again dried at 60 ° C for 10 hours.
• the product is calcined on a level of 6 h at 550 ° C.
• the reaction is exothermic and produces a slight flight of the product.
• the mixture is transferred to a Teflon container inserted in a hydrothermal treatment cell (Parr bomb).
• the hydrothermal treatment is carried out at 160 ° C for 16 hours. .
• the pH of the dispersion is 5.1.
• the colloids are collected in the form of a solid powder.
• the diffractogram shows the presence of a LaMnO 3 phase.
• This example relates to the preparation of a colloidal dispersion of La 0.66 Sro , 33 MnO 3 with the use of lauric acid.
• a manganese nitrate solution is obtained by dissolving
• a lanthanum nitrate solution is obtained by diluting 57.6 cm 3 of a lanthanum solution of density 1, 686 and 2.88 M in La with demineralized water so as to obtain 200 cm 3 of solution ( or 166 millimoles of La).
• the manganese nitrate solution and the strontium nitrate solution are mixed with the lanthanum nitrate solution.
• the nitrate solution thus obtained is added at room temperature and at a controlled rate to 650 cm 3 of tetraethylammonium hydroxide
• the suspension is centrifuged at 4500 rpm for 15 min.
• the pellet obtained is taken up in 1000 cm 3 of demineralized water and stirred for 30 min. Centrifuge again.
• 27.9 g of lauric acid in demineralized water are added and the volume is adjusted to 225 cm 3 after adjusting the pH to 9.
• the lauric acid / Lao ratio, 66Sr 0 ⁇ 33 Mn ⁇ 3 is 0, 50 by weight.
• the mixture is left stirring for 16 hours.
• the lauric acid solution is added to the pellet previously obtained.
• the mixture obtained is ground with an ultraturax mill for 15 min.
• the product is calcined for 6 hours at 550 ° C.
• a second calcination of the product is carried out in the following manner: the product is instantaneously introduced into an oven previously brought to 900 ° C. for 10 minutes. At the end of this time, it is removed instantly.
• the mixture is transferred to a Teflon container inserted in a hydrothermal treatment cell (Parr bomb).
• the hydrothermal treatment is carried out at 160 ° C for 16 hours.
• the supernatant phase is drawn off.
• the pellet is redispersed with stirring in 25 cm 3 of demineralized water.
• a colloidal phase and a solid are obtained.
• colloids of average size of 20 nm are observed.
• colloids are collected in the form of a solid powder.
• the diffractogram shows the presence of a Lao, 66 Sro , 33 MnO 3 .
• This example relates to the preparation of a colloidal dispersion of LaFeO 3 .
• the solution of iron nitrate and lanthanum thus obtained is added instantly at room temperature to 550 cm 3 of 3M ammonia solution with stirring. A precipitate is formed instantly.
• the pH of the suspension obtained is 9.0.
• the suspension is centrifuged at 4500 rpm for 15 min.
• the pellet obtained is taken up in 1000 cm 3 of demineralized water and stirred for 30 min. It is again centrifuged for 15 min and the solid obtained is allowed to dry at room temperature for 16 hours. The solid is again dried at 60 ° C for 10 hours.
• the product is calcined for 6 hours at 650 ° C.
• the supernatant phase is drawn off.
• the pellet is redispersed with stirring in 25 cm 3 of demineralized water.
• a colloidal phase and a solid are obtained.
• colloids of average size of 35 nm are observed.
• colloids are collected in the form of a solid powder.
• the diffractogram shows the presence of a LaFe ⁇ 3 phase.
• This example concerns the preparation of a colloidal dispersion of LaCoO 3 .
• the solution of cobalt nitrate and lanthanum thus obtained is added instantaneously to ambient temperature to 630 cm 3 of 2M sodium hydroxide solution with stirring. A precipitate is formed instantly.
• the pH of the suspension obtained is 11.6.
• the suspension is centrifuged at 4500 rpm for 15 min.
• the pellet obtained is taken up in 1000 cm 3 of demineralized water and stirred for 30 min. It is again centrifuged for 15 min and the solid obtained is allowed to dry at room temperature for 16 hours.
• the solid is again dried at 60 ° C for 10 hours.
• the product is calcined by direct introduction into an oven previously maintained at 1000 ° C.
• the calcination time is 1 min 30 sec. and the product is then instantly removed from the oven.
• the supernatant phase is drawn off.
• the pellet is redispersed with stirring in 25 cm 3 of demineralized water.
• a colloidal phase and a solid are obtained.
• medium-sized colloids of 25 nm are observed.
• the colloids are collected in the form of a solid powder.
• the diffractogram shows the presence of a LaCoO 3 phase.
• This example relates to the preparation of a colloidal dispersion of LaMnO 3 in which the colloids are anisotropic.
• an anisotropic perovskite is prepared in the following manner.
• the solution is poured into a teflon container of an autoclave (Bombe de Parr). The whole is then brought to 140 ° C. for 16 hours.
• a dispersion according to the invention is then prepared in the following manner.

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