CN113388873A - Flaky alumina and preparation method and application thereof - Google Patents
Flaky alumina and preparation method and application thereof Download PDFInfo
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- CN113388873A CN113388873A CN202110447904.9A CN202110447904A CN113388873A CN 113388873 A CN113388873 A CN 113388873A CN 202110447904 A CN202110447904 A CN 202110447904A CN 113388873 A CN113388873 A CN 113388873A
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 34
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 33
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 28
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000011888 foil Substances 0.000 claims abstract description 23
- 239000002245 particle Substances 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 16
- 238000009826 distribution Methods 0.000 claims abstract description 9
- 238000005520 cutting process Methods 0.000 claims abstract description 8
- 238000000576 coating method Methods 0.000 claims abstract description 7
- 239000000945 filler Substances 0.000 claims abstract description 6
- 239000011819 refractory material Substances 0.000 claims abstract description 6
- 239000012745 toughening agent Substances 0.000 claims abstract description 6
- 238000007598 dipping method Methods 0.000 claims abstract description 4
- 239000000049 pigment Substances 0.000 claims abstract description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 12
- 150000001879 copper Chemical class 0.000 claims description 10
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 10
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- 239000004094 surface-active agent Substances 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 5
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 4
- 239000004327 boric acid Substances 0.000 claims description 4
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 4
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 4
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 4
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 4
- 239000000725 suspension Substances 0.000 claims description 4
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 4
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 3
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 3
- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims 1
- 239000006185 dispersion Substances 0.000 claims 1
- 230000005611 electricity Effects 0.000 claims 1
- 239000005749 Copper compound Substances 0.000 abstract description 12
- 150000001880 copper compounds Chemical class 0.000 abstract description 12
- 230000008569 process Effects 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 2
- 239000002131 composite material Substances 0.000 abstract 2
- 239000000243 solution Substances 0.000 description 23
- -1 aluminum ions Chemical class 0.000 description 5
- 239000011259 mixed solution Substances 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 229910001431 copper ion Inorganic materials 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000001186 cumulative effect Effects 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910000619 316 stainless steel Inorganic materials 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000010297 mechanical methods and process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/04—Anodisation of aluminium or alloys based thereon
-
- 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
- C01F7/00—Compounds of aluminium
- C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
- C01F7/42—Preparation of aluminium oxide or hydroxide from metallic aluminium, e.g. by oxidation
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/66—Monolithic refractories or refractory mortars, including those whether or not containing clay
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/70—Additives characterised by shape, e.g. fibres, flakes or microspheres
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/04—Anodisation of aluminium or alloys based thereon
- C25D11/18—After-treatment, e.g. pore-sealing
- C25D11/24—Chemical after-treatment
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/20—Particle morphology extending in two dimensions, e.g. plate-like
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
Abstract
The invention discloses flaky alumina, the particle size distribution D of which10～D9010-500 μm, 50-5000 nm of median thickness, and less than or equal to 20% of thickness deviation. Sulfuric acid solution is used as electrochemical solution, and aluminum foil is used as anodeTaking the conductive electrode as a negative electrode, and electrifying between the positive electrode and the negative electrode; cutting off the edge of the aluminum foil with the surface containing the aluminum oxide film or cutting the aluminum foil into a certain size; dipping in copper compound solution, dispersing by ultrasonic wave, separating, and preparing to obtain flake alumina. The thickness of the flaky alumina prepared by the invention is uniform and controllable; the particle size is large, the composite material can be applied to functional coatings, pigments, fillers, toughening agents, refractory materials and the like, the process is simple, the reaction is simple and easy to control, the cost is low, and the composite material has a wide application prospect.
Description
Technical Field
The invention belongs to the field of flaky alumina, and relates to flaky alumina, and a preparation method and application thereof.
Background
The flaky alumina has excellent characteristics of high temperature resistance, good toughness, stable chemical property and the like, and can be used as a filler of a polymer to prolong the service life of a polymer device; the toughening agent can be used for ceramic to improve the toughness of ceramic devices; can be used for wear-resistant, corrosion-resistant and other functional coatings; can be used for preparing refractory materials, such as sintering furnaces, sintering pipes and the like. The most common methods for preparing the flaky alumina mainly comprise a molten salt method, a high-temperature sintering method, a hydrothermal (alcohol-thermal) method, a coating method, a sol-gel method, a mechanical method and the like, but the flaky alumina prepared by most methods has poor thickness uniformity and controllability, and has too small sheet diameter which can only reach several microns at most. The most mature commercialization is to prepare the flake alumina by a molten salt method, the crystal form control in the preparation process is difficult, the cost is high, and the flake diameter of the alumina is small and can only reach several microns at most, so that the requirement cannot be met.
Disclosure of Invention
It is an object of the present invention to provide a flaky alumina having a particle size distribution D which is superior to the prior art10～D9010 to 500 μm, preferably 20 to 200 μm, more preferably 50 to 100 μm; the median thickness is 50nm to 5000nm, preferably 100nm to 1000nm, more preferably 200 to 500 nm; the thickness deviation is less than or equal to 20 percent, and the thickness deviation is preferably less than or equal to 10 percent.
Preferably, the particle size distribution D of the tabular alumina10～D90The particle size is in the range of 10 to 500 μm, 300 to 400 μm, or 400 to 450 μm.
Preferably, the tabular alumina has a median thickness of any of 50nm, 110nm, 215nm, 530nm, 985nm, 5020nm, and ranges therebetween.
Preferably, the thickness deviation of the tabular alumina is 21% or less, 20.8% or less, 15.6% or less, 12.9% or less, 10.1% or less, 10% or less, 8.3% or less, 5.7% or less, and ranges therebetween.
In the present invention, the particle diameter distribution D10Diameter value representing cumulative 10% point, particle size distribution D90Representing the cumulative 90% point diameter value.
"median thickness" refers to the median of all statistical point thickness values.
"thickness variation" refers to the thickness (H) at any one statistical point and the median thickness (H)Median value) The deviation ratio between them; the calculation formula is (H-H)Median value)/HMedian value×100％。
Another object of the present invention is to provide a method for preparing flake alumina, which comprises the following steps:
s1: taking a solution containing sulfuric acid as an electrochemical solution, an electrode containing aluminum foil as a positive electrode, a conductive electrode as a negative electrode, applying current between the positive electrode and the negative electrode, and preparing an aluminum oxide film on the surface of the electrode containing aluminum foil;
s2: cutting off the edge or cutting the aluminum foil with the surface containing the aluminum oxide film prepared in the step S1 into a certain size;
s3: dipping the aluminum foil sheared in the step S2 in a solution containing copper salt, and dispersing by ultrasonic waves to prepare a suspension containing an aluminum oxide film;
s4: the suspension containing the aluminum oxide film of step S3 is separated to prepare the flaky alumina.
In the present invention, in order to make the flaky alumina undergo crystal transformation and improve the acid and alkali resistance thereof, the flaky alumina is calcined after step S4, the calcination temperature is 800 to 1200 ℃, for example, any temperature of 800 ℃, 900 ℃, 1000 ℃, 1100 ℃, 1200 ℃ and the range value between the two, preferably the calcination temperature is 900 to 1000 ℃; the calcination time is 1 to 12 hours, for example, any time of 1 to 4 hours, 6 to 8 hours, 10 to 12 hours, and a range therebetween, and preferably 2 to 4 hours.
In the invention, an aluminum oxide film is prepared on the surface of aluminum by an electrochemical method commonly called anodic oxidation, the corrosion dissolution of aluminum and the generation of the aluminum oxide film are simultaneously carried out, sulfuric acid is a strong corrosive acid, the aluminum oxide film cannot be generated when the concentration is lower than 5 wt%, the aluminum oxide film becomes brittle when the concentration is higher than 15 wt%, and the mass fraction of the sulfuric acid in the electrochemical solution is 5-15 wt%, such as 5 wt%, 7 wt%, 8 wt%, 9 wt%, 10 wt%, 11 wt%, 12 wt%, 13 wt%, 15 wt%, preferably 7-9 wt%; any mass fraction of 5 wt% to 15 wt% and the range value between the two, preferably 8 wt% to 10 wt%. In the preparation process of the aluminum oxide film, aluminum ions in the sulfuric acid solution gradually increase, when the concentration of the aluminum ions exceeds 10 wt%, the oxide film is difficult to further form, and in order to improve the compactness and thickness uniformity of the aluminum oxide film, the electrochemical solution of the step S1 further comprises an auxiliary acid consisting of at least one of citric acid, boric acid and oxalic acid; the mass fraction of the auxiliary acid is 0.5 wt% to 3 wt%, such as any mass fraction of 0.5 wt%, 1 wt%, 1.5 wt%, 2 wt%, 2.5 wt%, 3 wt% and a range value therebetween. Adding citric acid as an auxiliary acid to be complexed with aluminum ions to reduce the content of the aluminum ions in the sulfuric acid solution; or boric acid is added to prevent the alumina film from becoming loose after the temperature of the sulfuric acid solution is increased, or oxalic acid is added to improve the toughness of the alumina film, and preferably, a small amount of each of the three auxiliary acids is added.
Step S1 of the present invention includes a solution temperature of sulfuric acid of 15 to 35 ℃, more preferably, a solution temperature of 19 to 25 ℃; preferably, a current of 0.5A/dm is applied between the positive electrode and the negative electrode2～1A/dm2For example 0.5A/dm2、0.6A/dm2、0.7A/dm2、0.8A/dm2、0.9A/dm2、1.0A/dm2Preferably 0.6A/dm and the range value between the two2～0.8A/dm2(ii) a The time for applying the current between the positive electrode and the negative electrode is 120s to 3600s, preferably 600s to 1800 s.
According to the invention, copper ions and aluminum are subjected to a displacement reaction, so that the aluminum reacts into aluminum ions, and the aluminum oxide does not react with the copper ions, thereby separating the aluminum from the aluminum oxide film. In order to make the solution of the copper compound sufficiently contact with the aluminum foil, the aluminum foil having an aluminum oxide film on the surface thereof is cut to remove the edge, preferably to a certain size, so that not only the contact area between the copper compound and the aluminum foil is increased, but also the particle size of the aluminum oxide film to be peeled off is made more uniform. The solution of at least one copper compound selected from copper sulfate, copper chloride, copper nitrate and copper acetate is generally used, and copper chloride is preferred because of the small radius of chloride ion. The concentration of the copper compound influences the dissolution rate of the aluminum foil and the particle size uniformity of the flaky alumina, and the copper compound in the step S3 is selected from at least one of copper sulfate, copper chloride, copper nitrate and copper acetate, preferably copper chloride; the mass fraction of the copper compound in the copper compound solution is 0.5 wt% to 10 wt%, such as any mass fraction of 0.5 wt%, 1 wt%, 2 wt%, 4 wt%, 6 wt%, 8 wt%, 10 wt% and a value ranging therebetween, preferably 1 wt% to 8 wt%, more preferably 2 wt% to 6 wt%; the temperature of the copper compound solution is 25-60 ℃, preferably 35-50 ℃; the dipping time is 4-24 h, preferably 8-12 h; preferably, the aluminum foil is immersed in the copper compound solution while applying 50 to 100W of power for ultrasonic dispersion.
The copper compound solution of step S3 in the present invention further comprises 0.1 wt% to 1 wt% hydrochloric acid, such as any mass fraction of 0.1 wt%, 0.2 wt%, 0.4 wt%, 0.6 wt%, 0.8 wt%, 1.0 wt% and the range value therebetween, preferably 0.2 wt% to 0.6 wt%; in order to improve the adhesion and permeability of the copper compound solution on the surface of the aluminum foil, 0.01 to 0.5 weight percent of surfactant is preferably added, and 0.05 to 0.1 weight percent of surfactant is preferably included; preferably, the surfactant is at least one selected from the group consisting of alkylphenol ethoxylates, sodium dodecylbenzenesulfonate and sodium dodecylbenzenesulfonate.
In the present invention, the peeled oxide film is dispersed by ultrasonic oscillation in step S4 to reduce the particle size and improve the uniformity of the particle size, the power of the ultrasonic wave is generally 300W to 500W, preferably 200W to 400W; if the power is not too high, the alumina film is easy to shatter. The time for ultrasonic dispersion is 1 h-24 h, preferably 4 h-8 h.
According to another aspect of the invention, the flake alumina and the flake alumina prepared by the preparation method are applied to functional coatings, pigments, fillers, toughening agents and refractory materials.
The invention has the beneficial effects that:
1) the flaky alumina has uniform thickness and large particle size, and can be applied to functional coatings, fillers, toughening agents, refractory materials and the like.
2) The preparation method of the flaky alumina has the advantages of simple process, simple reaction, easy control, low cost and wide application prospect.
Detailed Description
The present application will be described in detail with reference to examples, but the present application is not limited to these examples.
According to the present invention, there is provided a flaky alumina having a median thickness of 50 to 5000nm, preferably 100 to 1000nm, more preferably 200 to 500 nm; the thickness deviation is less than or equal to 20 percent, and preferably, the thickness deviation is less than or equal to 10 percent; particle size distribution D10～D90From 10 μm to 500. mu.m, preferably from 20 μm to 200. mu.m, more preferably from 50 μm to 100. mu.m. The flaky alumina has high thickness uniformity and large particle size, and can be applied to functional coatings, fillers, toughening agents, refractory materials and the like.
The present invention will be described in further detail below with reference to examples. It is also to be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the invention, and that certain insubstantial modifications and adaptations of the invention by those skilled in the art may be made in light of the above teachings. The specific process parameters and the like of the following examples are also only one example of suitable ranges, i.e., those skilled in the art can select the appropriate ranges through the description herein, and are not limited to the specific values exemplified below.
Examples 1 to 6: using 1060 aluminum foil as a raw material, immersing an effective area of 100mm x 50mm into a sulfuric acid solution with the temperature of 21 ℃ and the weight percent of 15 mm, using 1060 aluminum foil as a positive electrode to be connected with a power supply positive electrode, using 316 stainless steel sheet as a negative electrode to be connected with a power supply negative electrode, applying constant current for a period of time, washing 1060 aluminum foil with pure water for 2 times, cutting four edges of the aluminum foil by using a cutting machine, immersing the aluminum foil into a copper chloride solution with the temperature of 25 ℃ and the weight percent of 10% for 8 hours, filtering out an aluminum oxide film by using an 80-mesh filter screen, dispersing the aluminum oxide film in pure water, placing the aluminum oxide film in an ultrasonic cleaning machine, dispersing the aluminum oxide film under 200W power of ultrasonic waves for 24 hours, testing the particle size distribution of the flaky aluminum oxide by using an optical microscope, and testing the thickness of the flaky aluminum oxide by using a scanning probe microscope. The experimental parameters and properties of examples 1-6 are shown in Table 1.
TABLE 1 Experimental parameters and Performance of examples 1-6
Example 7: unlike example 4, the 10 wt% sulfuric acid solution was replaced with 10 wt% sulfuric acid and 3 wt% boric acid, and the same operation as in example 4 was performed.
Example 8: unlike example 4, the 10 wt% sulfuric acid solution was replaced with a mixed solution of 8 wt% sulfuric acid and 2 wt% citric acid, and the same operation as in example 4 was performed.
Example 9: the same operation as in example 4 was carried out except that the 10 wt% copper chloride solution at 25 ℃ was replaced with a mixed solution of 1 wt% copper sulfate and 0.1 wt% hydrochloric acid at 35 ℃.
Example 10: unlike example 4, the same operation as in example 4 was carried out except that the 25 ℃ 10 wt% copper chloride solution was replaced with a mixed solution of 50 ℃ 2 wt% copper chloride and 0.1 wt% sodium dodecylbenzenesulfonate.
The performance of examples 7-10 was similar to that of example 4.
Although the present application has been described with reference to a few embodiments, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the application as defined by the appended claims.
Claims (10)
1. A flaky alumina characterized by having a particle size distribution D10～D9010-500 μm, 50-5000 nm of median thickness, and less than or equal to 21% of thickness deviation.
2. According to claimThe flaky alumina according to claim 1, wherein the flaky alumina has a particle size distribution D10～D9020 to 200 μm, more preferably 50 to 100 μm;
the median thickness is from 100nm to 1000nm, more preferably from 200nm to 500 nm;
the thickness deviation is less than or equal to 10 percent.
3. A preparation method of flaky alumina is characterized by comprising the following steps:
s1: taking a solution containing sulfuric acid as an electrochemical solution, taking an aluminum foil as a positive electrode, taking a conductive electrode as a negative electrode, applying current between the positive electrode and the negative electrode, and preparing an aluminum oxide film on the surface of the electrode containing the aluminum foil;
s2: cutting off the edge or cutting the aluminum foil with the surface containing the aluminum oxide film prepared in the step S1 into a certain size;
s3: dipping the aluminum foil sheared in the step S2 in a solution containing copper salt, and dispersing by ultrasonic waves to prepare a suspension containing an aluminum oxide film;
s4: the suspension containing the aluminum oxide film of step S3 is separated to prepare the flaky alumina.
4. The method for preparing the flaky alumina according to claim 3, wherein the flaky alumina is calcined after the step S4, and the calcination temperature is 800-1200 ℃, preferably 900-1000 ℃;
the calcination time is 1 to 12 hours, more preferably 2 to 4 hours.
5. The method for preparing flake alumina according to claim 3, wherein the mass fraction of sulfuric acid in the sulfuric acid-containing solution in step S1 is 5-15 wt%, preferably 8-10 wt%;
the solution containing sulfuric acid also comprises an auxiliary acid, wherein the auxiliary acid is at least one of citric acid, boric acid and oxalic acid;
the mass fraction of the auxiliary acid is 0.5 wt% -3 wt%.
6. The method for preparing the flaky alumina according to claim 3, wherein the electrochemical solution temperature of the step S1 is 15-35 ℃, more preferably, the solution temperature is 19-25 ℃;
preferably, the current for applying electricity between the positive electrode and the negative electrode is 0.5A/dm2～1A/dm2Preferably 0.6A/dm2～0.8A/dm2；
The time for electrifying between the anode and the cathode is 120 s-3600 s, and the preferable time is 600 s-1800 s.
7. The method for preparing flaky alumina according to claim 3, wherein the copper salt in the copper salt-containing solution in step S3 is at least one of copper sulfate, copper chloride, copper nitrate, and copper acetate, preferably copper chloride;
the mass fraction of the copper salt in the solution containing the copper salt is 1 to 8 weight percent, and more preferably 2 to 6 weight percent;
the temperature of the solution containing the copper salt is 25-60 ℃, preferably 35-50 ℃;
and the aluminum foil is immersed in a solution containing copper salt, and 50-100W power ultrasonic wave is applied for dispersion.
8. The method for preparing the flake alumina according to the claim 3, wherein the solution containing the copper salt in the step S3 further contains hydrochloric acid, and the mass fraction of the hydrochloric acid is 0.1-1 wt%, preferably 0.2-0.6 wt%;
the solution containing the copper salt also contains a surfactant, and the surfactant is selected from at least one of alkylphenol ethoxylates, sodium dodecyl sulfate and sodium dodecyl benzene sulfonate;
the mass fraction of the surfactant is 0.01 wt% -0.5 wt%, preferably 0.05 wt% -0.1 wt%.
9. The method for preparing flaky alumina according to claim 3, wherein the power of ultrasonic dispersion of step S4 is 300W-500W, preferably 200W-400W;
the time for ultrasonic dispersion is 1-24 h, preferably 4-8 h.
10. Use of the tabular alumina of claim 1 or 2, prepared by the preparation method of any one of claims 3 to 9, in functional coatings, pigments, fillers, toughening agents, refractories.
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