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• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
  • B01J13/0004—Preparation of sols
  • B01J13/0008—Sols of inorganic materials in water
  • B01J13/0013—Sols of inorganic materials in water from a precipitate
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
  • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
  • B01J13/0004—Preparation of sols
  • B01J13/0034—Additives, e.g. in view of promoting stabilisation or peptisation
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
  • B01J13/0004—Preparation of sols
  • B01J13/0047—Preparation of sols containing a metal oxide
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B82—NANOTECHNOLOGY
  • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
  • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
• • C—CHEMISTRY; METALLURGY
  • 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
  • C01F17/20—Compounds containing only rare earth metals as the metal element
  • C01F17/206—Compounds containing only rare earth metals as the metal element oxide or hydroxide being the only anion
• • C—CHEMISTRY; METALLURGY
  • 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
  • C01F17/20—Compounds containing only rare earth metals as the metal element
  • C01F17/206—Compounds containing only rare earth metals as the metal element oxide or hydroxide being the only anion
  • C01F17/224—Oxides or hydroxides of lanthanides
  • C01F17/235—Cerium oxides or hydroxides
• • C—CHEMISTRY; METALLURGY
  • 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
  • C01F17/20—Compounds containing only rare earth metals as the metal element
  • C01F17/206—Compounds containing only rare earth metals as the metal element oxide or hydroxide being the only anion
  • C01F17/241—Compounds containing only rare earth metals as the metal element oxide or hydroxide being the only anion containing two or more rare earth metals, e.g. NdPrO3 or LaNdPrO3
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
  • C01G19/00—Compounds of tin
  • C01G19/02—Oxides
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
  • C01G23/00—Compounds of titanium
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
  • C01G25/00—Compounds of zirconium
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
  • C01G25/00—Compounds of zirconium
  • C01G25/006—Compounds containing, besides zirconium, two or more other elements, with the exception of oxygen or hydrogen
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
  • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
  • C09C3/08—Treatment with low-molecular-weight non-polymer organic compounds
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
  • C01P2002/00—Crystal-structural characteristics
  • C01P2002/50—Solid solutions
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
  • C01P2002/00—Crystal-structural characteristics
  • C01P2002/50—Solid solutions
  • C01P2002/52—Solid solutions containing elements as dopants
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
  • C01P2002/00—Crystal-structural characteristics
  • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
  • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
  • C01P2002/00—Crystal-structural characteristics
  • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
  • C01P2002/77—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by unit-cell parameters, atom positions or structure diagrams
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
  • C01P2004/00—Particle morphology
  • C01P2004/60—Particles characterised by their size
  • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer

Definitions

• the present invention relates to a colloidal dispersion of a cerium compound and at least one other element M selected from zirconium, rare earths, titanium and tin, a dispersible solid based on this same compound and their process of preparation.
• cerium oxide and another element such as zirconium or a rare earth are of great interest. Because of their high oxygen storage capacity and thermal stability, they can be used in the field of catalysis. They can also be used as a protection agent against ultraviolet rays or as pigments.
• the dispersion of the invention is a colloidal dispersion, in a continuous phase, of a cerium compound and at least one other element M selected from zirconium, rare earths (Ln) other than cerium , titanium and tin and is characterized in that the compound is in the form of a mixed oxide in which the cerium and the element M are in pure solid solution and in that the compound comprises cerium in the form of cerium III in an amount expressed as a total cerium III / cerium atomic ratio of between 0.005 and 0.06.
• the invention also relates to a process for preparing the above dispersion which comprises the following steps:
• a liquid medium comprising salts of cerium and at least one element M, the cerium salts being salts of cerium IV and cerium III; the medium is brought into contact with a base so as to obtain a pH of at least 9, whereby a precipitate is obtained;
• the precipitate is peptized by treatment with an acid, whereby the dispersion is obtained; the method further comprising at least one washing step either after the precipitate separation step or after the peptization step.
• the above process comprises a relatively small number of steps and makes it possible to arrive directly by simple chemical operations with the desired dispersion and this for a wide range of dispersions with regard to the nature of the elements of the mixed oxide.
• FIG. 1 is an X-ray diagram of a compound based on cerium and titanium derived from a dispersion according to the invention
• FIG. 2 is an X-ray diagram of a compound based on cerium and zirconium derived from a dispersion according to the invention.
• colloidal dispersion or sol of a cerium compound and of another element M designates any system consisting of fine solid particles of colloidal dimensions of this compound, ie particles of which the size is generally between 1 nm and 100 nm, more particularly between 2 nm and 50 nm.
• These particles are based on a cerium oxide and the other element M, in suspension in a liquid continuous phase, said particles containing, as counter-ions, bound or adsorbed ions such as, for example, acetates, nitrates, chlorides or ammoniums.
• the cerium and the other element M may be either totally in the form of colloids, or simultaneously in the form of ions or polyions and in the form of colloids.
• the continuous liquid phase is generally in the case of the present invention, an aqueous phase, more particularly water.
• rare earth is understood to mean the elements of the group constituted by yttrium and the elements of the periodic classification of atomic number inclusive of between 57 and 71.
• trivalent rare earth we mean , unless otherwise indicated, a rare earth that can only occur in the trivalent form.
• the abovementioned compound is in the form of a mixed oxide (Ce, M) ⁇ 2 in which the cerium and the element M are in solid solution.
• Ce, M mixed oxide
• one of the elements, generally the element M, is totally incorporated in the crystal lattice of the oxide of the other matrix element, for example cerium. This incorporation can be demonstrated by the X-ray diffraction technique on colloids after washing, in particular by ultrafiltration or else by ultracentrifugation and drying at a temperature of 60 ° C.
• the X-ray diagrams reveal the presence of a crystalline structure corresponding to the oxide of the matrix element (cerium oxide generally) and whose mesh parameters are more or less offset relative to a pure oxide of this first matrix element, thus demonstrating the incorporation of the other element in the crystal lattice of the oxide of the first.
• the X-ray diagrams then reveal a crystalline structure of the fluorine type just like the crystalline CeO 2 crystalline oxide, and whose mesh parameters are more or less staggered with respect to a pure ceric oxide, thus reflecting the incorporation of the element M into the crystalline lattice of the cerium oxide.
• the solid solution is pure, that is to say that the total amount of one element is in solid solution in the other, for example, all the element M in solid solution in cerium oxide.
• the X-ray diagrams show only the presence of the solid solution and do not include lines corresponding to an oxide oxide of the element other than the matrix element, for example an oxide of the element M .
• cerium III may be present in the compound as a cation either in adsorbed form on the surface of the particles of the cerium compound or in the crystalline mesh of the compound. Of course, these two forms can coexist.
• the element M is zirconium. More particularly in the case of this variant, the compound may have the formula (1) Cei-x Zr x ⁇ 2 wherein x is less than 1 and is at least 0.01, preferably at least 0 02.
• the element M is a combination of zirconium and tin. More particularly in the case of this variant, the compound can satisfy the following formula (2) Cei- x- yZr ⁇ Sn y ⁇ 2 in which x + y ⁇ 1, x satisfies the condition 0.05 ⁇ x ⁇ 0.95 and y is at least equal to 0.01, the high value of y being chosen in such a way that a solution is obtained solid.
• x satisfies the condition 0.20 ⁇ x ⁇ 0.8 and even more preferably the condition 0.40 ⁇ x ⁇ 0.60.
• y is at least 0.05 and even more preferably y is at least 0.2.
• y is at most 0.4, and even more preferably at most 0.25.
• the element M is a combination of zirconium and at least one rare earth Ln.
• the invention is particularly applicable to the case where the rare earth is a trivalent rare earth.
• the rare earth may in particular be lanthanum, gadolinium, terbium, praseodymium or neodymium.
• the compound can satisfy the formula (3) Ce 1- x - yZr ⁇ Ln y ⁇ 2 in which x + y ⁇ 1, x satisfies the condition 0.05 ⁇ x ⁇ 0.95 and y is at least 0.01, the high value of y being chosen such that a solid solution is obtained.
• the element M is a combination of zirconium, tin and at least one rare earth Ln.
• the invention is particularly applicable to the case where the rare earth is a trivalent rare earth, and the rare earth may be in particular lanthanum, gadolinium, terbium, praseodymium or neodymium.
• the compound may have the formula (4) Cei -x -y -z Zr ⁇ Sn y Ln z ⁇ 2 wherein x + y + z ⁇ 1, x adheres to the condition 0.05 ⁇ x ⁇ 0.95, y is at least 0.01, z is at least 0.01.
• x satisfies the condition 0.20 ⁇ x ⁇ 0.8 and y is at least 0.10, and still more preferably x satisfies the condition 0.40 ⁇ x ⁇ 0.60 and y is at least equal to 0.2.
• the high values of y and z are chosen in such a way that a solid solution is obtained.
• y is at most 0.4, and even more preferably at most 0.25; moreover, preferably, z is at most equal to 0.05 and even more preferentially to not more than 0.03.
• the compound of the dispersion of the invention may also be a compound in which M is a rare earth or a combination of rare earths.
• the invention is particularly applicable to the case where the rare earth is a trivalent rare earth.
• the rare earth may be especially lanthanum, gadolinium, terbium, praseodymium or neodymium.
• the compound may then correspond more particularly to the formula (5) below Cei-x Ln x ⁇ 2 in which x is at most equal to 0.15 and is at least 0.01, preferably at least 0, 02 and even more preferably at least 0.04.
• x is at most equal to 0.10 and even more preferentially to at most 0.05.
• the rare earth may be present, at least in part, in Ln III form and, again, either in the crystalline mesh or in adsorbed form on the surface of the particles of the cerium compound.
• the latter element may be present both in the forms Pr III and Pr IV and, in this case, x is more particularly at least 0.04 and even more particularly between 0.03. and 0.08.
• the particles constituting the compound of the dispersion have a fine and narrow particle size. Indeed, they have a size, measured by their average diameter, which is preferably at most 10 nm and which may be more particularly between 2 and 8 nm. This size is determined by transmission electron microscopy (TEM), in a conventional manner, on a previously dried sample on a copper grid supported carbon membrane and on an average of 50 measurements.
• TEM transmission electron microscopy
• cryo-MET can be used to determine the aggregation state of the particles. It allows to observe by transmission electron microscopy samples kept frozen in their natural environment which may be water for example.
• the dispersion of the invention generally has a mixed oxide concentration of at least 0.1 M, preferably at least 0.25 M and advantageously greater than 1 M.
• a particular mode corresponds to dispersions whose pH is basic.
• the cerium compound and at least one other element M is in the form of particles further comprising citrate anions, these anions being adsorbed on the surface of the particles.
• the pH of the dispersions is at least 7, preferably at least 8.
• Another specific embodiment corresponds to dispersions which are functionalized.
• the cerium compound and at least one other element M is in the form of particles comprising on the surface a bifunctional compound comprising a function R 1 of amine, sulfate, phenyl, alkylethoxy or succinate type and a R 2 function of carboxylic, dicarboxylic, phosphoric, phosphonic or sulfonic type, the functions R 1 and R 2 being separated by an organic chain of the - (CH 2 ) X - type, x being preferably at most equal to 6. It may be thought that this bifunctional compound is bound at the surface by complexing type interactions between the R 2 function and the cerium or M present on the surface of the colloidal particles.
• the bifunctional compound may be chosen from amino-aliphatic acids, for example amino-caproic acid, amino-sulphonic acids such as aminoethyl-sulphonic acid or polyoxyethylenated alkyl ether phosphates.
• colloidal dispersions of the invention are particularly stable, that is to say that no decantation or phase separation is observed over a period which may be greater than 1 year.
• the process for preparing the dispersions of the invention will now be described.
• this process comprises a first step in which a liquid medium comprising cerium salts and at least one element M, the cerium salts being cerium IV and cerium III salts.
• the proportion of salts of cerium III and of cerium IV salts, expressed by the molar ratio CeI II / Ce total (CeIII + CeIV), is generally at least 2% and at most 20%, preferably between 2 % and 10%, this proportion being chosen according to the desired level of cerium III in the colloidal dispersion that is to be prepared.
• the liquid medium is usually water and the salts are usually provided as solutions.
• the salts may be salts of inorganic or organic acids, for example of the sulfate, nitrate, chloride or acetate type, it being understood that the starting medium must comprise at least one cerium IV salt.
• Ce IV it is more particularly possible to use a solution of ceric-ammoniacal nitrate to which Ce III is added in the form of cerous nitrate or Ce III acetate or cerous chloride. It is also possible to use a solution of ceric nitrate obtained by attacking CeO 2 with nitric acid supplemented with Ce III. It is advantageous to use a solution of ceric nitrate obtained by electrolysis and containing Ce III.
• the Ti IV solution may be TiOCI 2 .
• the Zr IV solution may be ZrOCI 2 or ZrO (NO 3 ) 2 .
• SnCI 4 , 5H 2 O can be used as tin salts.
• Ln rare earths are generally provided in the form of Ln NI salts, for example by nitrates.
• the second step of the method consists in bringing the previously formed medium into contact with a base.
• the products of the hydroxide type can be used in particular.
• alkali or alkaline earth hydroxides and ammonia there may be mentioned 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 in that they reduce the risk of pollution by alkaline or alkaline earth cations.
• the medium After the addition of the base, it is possible to ripen the medium for a period which may vary for example between 10 minutes and 1 hour, generally at room temperature.
• the precipitate can be separated from the liquid medium by any known method, for example by centrifugation.
• the precipitate from the reaction can then be washed. This washing can be done by returning the precipitate in water and, after stirring, separating the solid from the liquid medium by centrifugation, for example. This operation can be repeated several times if necessary. Generally, this washing is carried out so as to obtain a washing pulp, that is to say the water in which the precipitate is resuspended, with a pH of at most 8.75, preferably at most 8, advantageously of at most 7.
• the process of the invention comprises at least one washing step, this washing being able to take place under the conditions which have just been described, that is to say either on the precipitate, or on the dispersion, or still on both.
• the preparation process is of the type described above but is completed by a step of bringing it into contact with the acid.
• citric More specifically, the citric acid can be added to the dispersion obtained after peptization, for example in the form of a hydrated citric acid powder. The citric acid then dissolves with stirring.
• the molar ratio citric acid / mixed oxide is in the range of values given above, that is to say generally between 0.1 and 0.6. It is possible to let the resulting medium between 30 minutes and 24 hours at room temperature.
• a solution of a base is then gradually added, this base being of the same type as that described previously for the precipitation step, so as to obtain the desired pH of at least 7, preferably at least 8. More specifically, the addition can be carried out between 10 minutes and 2 hours at room temperature.
• the bifunctional compound is added to the dispersion obtained after peptization.
• the invention also relates to a dispersible solid, that is to say capable of leading to a colloidal dispersion according to the invention.
• This solid is in the form of a powder or a paste. It is based on a cerium compound and at least one other element M chosen from zirconium, rare earths (Ln) other than cerium, titanium and tin, this compound being in the form of a mixed oxide in which the cerium and the element M are in solid solution. All that has been said above concerning the compound in the form of mixed oxide is also applicable here.
• the particles constituting the solid comprise on the surface, in complexed form, the citrate anion or the bifunctional compound.
• the solid can be obtained by simple evaporation of the water from the dispersion, under mild conditions, that is to say at a temperature of at most 80 ° C.
• the solid has the property of being redispersible, ie of being able to give a colloidal dispersion according to the invention and as described above when it is suspended in a liquid phase, in particular in water.
• the dispersions of the invention can be used in many applications. Catalysis can be mentioned especially for automotive afterburning, in this case the dispersions are used in the preparation of catalysts.
• the dispersions can also be used for the lubrication, in ceramics, the manufacture of pigments, this is particularly the case of dispersions in which the compound is a mixed oxide of cerium and praseodymium and which have a red color.
• the dispersions can also be used for their anti-UV properties, for example in the preparation of polymer films (of the acrylic or polycarbonate type, for example) or of cosmetic compositions, especially in the preparation of anti-UV creams.
• Dispersions based on a mixed oxide of cerium and gadolinium can be used for the preparation of materials for fuels. They can finally be used on a substrate as anticorrosion agents.
• This example relates to the preparation of a colloidal dispersion of particles of formula Ce 0.78 TiO, 22 ⁇ 2 .
• the pH is 1, 3.
• the characteristics of the dispersion obtained are given below.
• the dispersion is washed by dialysis using dialysis membranes. 80 ml of the colloidal dispersion are poured into a dialysis bag and dialyzed in a 500 ml test tube filled with deionized water. It is allowed to dialyze for 24 hours and the water is renewed 5 times.
• EXAMPLE 2 This example relates to the preparation of a colloidal dispersion of particles of the formula Ce 0 ⁇ 94 Pr 0i06 O 2 .
• the precipitate is washed on frit 4 times 1 liter of deionized water.
• the pH of the pulp is 7.5. After filtration, it is resuspended with a solution containing 11.6 g of 68% nitric acid (125 mM H + ) and the volume is made up to 250 ml.
• the molar ratio H + / (Ce + Pr) is equal to 1.
• the pH is 1.1.
• the concentration of Ce + Pr is equal to 0.5 M. It is left stirring overnight.
• the colloidal dispersion is washed by dialysis as in Example 1.
• the colloidal dispersion is clear to the eye and red.
• the size of the colloids determined by MET is 4 nm.
• An X-ray diffraction analysis is carried out on dried colloids obtained by evaporation at 50 ° C. of the dialyzed colloidal dispersion.
• EXAMPLE 3 This example relates to the preparation of a colloidal dispersion of particles of formula Ce 0153 Zr 0.46 O 2 .
• the precipitate formed is filtered and washed with 1 liter of deionized water, 4 times in succession.
• the pH of the pulp is 7.5.
• This operation is repeated twice (three operations in total).
• the colloid size determined by MET on the colloidal dispersion thus washed is 4 nm.
• This example relates to the preparation of a colloidal dispersion of particles of formula Ceo, 38 Zro, 37 Sno, 24 ⁇ 2 .
• 35 ml of ceric nitrate solution obtained by electrolytic oxidation of a Ce 3+ solution having a concentration of 1.425 M in Ce 4+ (ie 50 mM Ce 4+ ), 0.11 M in Ce 3+ and 0, 7 M in HNO 3 are added to 15 ml of Zr 4+ solution of ZrO (NO 3 ) 2 at 3.32 M (50 mM Zr 4+ ).
• the volume is made up to 1000 ml.
• the pH is 1, 2.
• the concentration of Ce + Zr is equal to 0.625 M; It is stirred overnight. A clear colloidal dispersion is obtained in the eye.
• the dispersion is washed by dialysis as in Example 1.
• the colloid size determined by MET on the colloidal dispersion thus washed is 4 nm.
• This example relates to the preparation of a colloidal dispersion of particles of formula Ceo , 53 Zro , 46 ⁇ 2 at basic pH.
• Example 5 The dispersion of Example 5 at pH 8.5, obtained by addition of citrate, is evaporated at 45 ° C. A powder is obtained which is redispersible by the addition of water.
• This example relates to the preparation of a colloidal dispersion of particles of formula Ce o .g Gd 0 .iO 2 .
• Ce (NO 3 ) 4 ceric nitrate solution obtained by electrolytic oxidation of a Ce 3+ solution and having a concentration of 1.425 M in Ce 4+ (ie 200 mM Ce 4+ ), of 0, 11 M in Ce 3+ and 0.7 M in HNO 3 .
• Gd (NO 3 ) 3 at 2.35 M in Gd 3+ (50 mM Gd 3+ ) and complete the volume at 2000 ml.
• the pH is 1.2. 160 ml of NH 3 solution at 28% are added instantaneously, the pH is then 10.
• the precipitate is washed on frit 4 times 1 liter of deionized water.
• the pH of the pulp is 7.2.
• the colloidal dispersion obtained is then washed by dialysis. 80 ml of the colloidal dispersion are poured into a dialysis bag and dialyzed in a 500 ml test tube filled with deionized water. It is allowed to dialyze for 24 hours and the water is renewed 5 times. The pH is 5.
• the colloidal dispersion is clear to the eye, the size of the colloids is 4 nm and the chemical composition determined by assay is Ceo, gGdo, i ⁇ 2 .
• This example relates to the preparation of a colloidal dispersion of particles of formula Ce 0 , 15 Zro, 83 La 0 , o 2 O 2.
• 6.6 ml of ceric nitrate solution obtained by electrolytic oxidation of a Ce 3+ solution with a concentration of 1.425 M in Ce 4+ (ie 9.4 mM Ce 4+ ), 0.11 M in Ce 3 + and 0.7 M in HNO 3 are added to 15 ml of Zr 4+ solution of ZrO (NO 3 ) 2 at 3.32 M (50 mM Zr 4+ ).
• We then realize the addition of 4.5 ml of La solution (NO 3 J 3 at 2.785 M in La 3+ (12.5 mM La 3+ ) .
• the volume is made up to 500 ml with deionized water. is 1, 3.
• the dispersion is washed by dialysis as in Example 1.
• An X-ray diffraction analysis is carried out on dried colloids obtained by evaporation at 50 ° C. of the dialysed colloidal dispersion.
• the diffraction pattern exhibits the characteristic lines of a single crystalline phase of solid solution type.

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