CN108560052B - Preparation method and application of monocrystal hexagonal alumina - Google Patents
Preparation method and application of monocrystal hexagonal alumina Download PDFInfo
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- CN108560052B CN108560052B CN201810385666.1A CN201810385666A CN108560052B CN 108560052 B CN108560052 B CN 108560052B CN 201810385666 A CN201810385666 A CN 201810385666A CN 108560052 B CN108560052 B CN 108560052B
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/10—Inorganic compounds or compositions
- C30B29/16—Oxides
- C30B29/20—Aluminium oxides
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B7/00—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions
- C30B7/14—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions the crystallising materials being formed by chemical reactions in the solution
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Abstract
The invention relates to a preparation method of single crystal hexagonal alumina, which comprises the following steps: (1) adding a crystallization agent into an aluminum salt solution; (2) dropwise adding the precipitant solution into the solution obtained in the step (1) under the stirring condition, continuously stirring, controlling the pH value to be 9-10, then adding molten salt, and uniformly mixing to prepare a gel mixture; (3) drying the gel mixture and then calcining at a high temperature; (4) and cooling and washing the calcined mixture, filtering and drying to obtain the single crystal hexagonal alumina particles. The invention also relates to the single crystal hexagonal alumina prepared by the method and application of the single crystal hexagonal alumina as a lacquer painting mosaic material. The aluminum salt is used as a raw material, a crystal forming agent is added, regular growth of alumina can be promoted, single crystal hexagonal alumina particles with the particle size of 40-60um and the thickness of 1-4um are prepared by a molten salt method, and the single crystal hexagonal alumina particles are inlaid in a lacquer painting and are starlight, so that the special artistic effect of the smart crystal is achieved.
Description
Technical Field
The invention relates to a preparation method and application of single crystal hexagonal alumina, in particular to a preparation method of single crystal hexagonal alumina, single crystal hexagonal alumina prepared by the method and application of the single crystal hexagonal alumina as a lacquer painting mosaic material.
Background
The Chinese lacquer painting is a new painting on the current painting altar, is created by painting with natural lacquer as a main material, has double attributes of painting and technology, and is based on the unique aesthetic quality lattice of the painting altar. This unique aesthetic quality is dependent on the inlay material in addition to the characteristics from the lacquer. The inlay material used on the lacquer painting needs to have certain hardness, wear resistance, good chemical stability and other characteristics, and commonly used precious metal materials such as gold, silver and the like, shell materials such as noctilucent snails, abalone shells and the like, thin eggshells, selected inorganic nonmetal materials such as jades and the like. The materials are pasted on the positions needed by the picture by using the lacquer, and the materials are ground by combining with other decoration processes through the lacquer, so that unique effects of different material textures, colors and the like can be generated.
The phase of the flaky alumina is α -Al2O3Also called corundum, has a mohs hardness of 9, is a high-hardness substance with hardness second to that of diamond, and has good wear resistance, high temperature resistance and stable chemical properties. However, the currently disclosed flaky alumina is mainly applied to the polishing industry and the pearly luster industry, and the prepared flaky alumina has a small particle size (about 10um), is difficult to apply to a lacquer painting mosaic material and presents artistic effects.
Disclosure of Invention
The invention aims to provide the single crystal hexagonal alumina which has larger particles, certain thickness, smooth surface, good dispersibility and regular shape.
The invention also aims to provide a preparation method of the single-crystal hexagonal alumina.
The invention further aims to provide application of the single-crystal hexagonal alumina as a lacquer painting mosaic material.
The invention firstly provides a preparation method of single crystal hexagonal alumina, which comprises the following steps:
(1) adding a crystal forming agent into an aluminum salt solution, and uniformly stirring;
(2) dropwise adding the precipitant solution into the solution obtained in the step (1) under the stirring condition, continuously stirring, controlling the pH value to be 9-10, and finally adding molten salt to uniformly mix to prepare a gel mixture;
(3) drying the gel mixture, and then calcining at high temperature of 1150-1350 ℃ for 2-8 h;
(4) and cooling the calcined mixture to room temperature, washing with water, removing molten salt, filtering and drying to obtain the single-crystal hexagonal alumina particles.
Further:
the aluminum salt solution includes an aluminum sulfate solution. The mass concentration of the aluminum salt is 20-60%.
The precipitant solution comprises a sodium hydroxide solution or a sodium carbonate solution. The mass concentration of the precipitant is 15-40%.
The crystallization agent is one or a mixture of two of zirconium salt and molybdate; the addition amount of the crystallization agent is calculated according to the amount of finally obtained alumina, and the weight proportion is 0.05-5%, and preferably 0.1-3%. By selecting the dosage of the crystal forming agent, the particle morphology of the flaky alumina can be improved, so that the flaky alumina has relatively complete hexagonal characteristics.
The zirconium salt comprises zirconium fluoride, zirconium chloride and zirconium nitrate.
The molybdate comprises sodium molybdate, potassium molybdate and ammonium phosphomolybdate.
The molten salt is one or a mixture of two of potassium salt and sodium salt. More preferably, the potassium salt is potassium sulfate and the sodium salt is sodium sulfate.
The invention also provides the single crystal hexagonal alumina prepared by the preparation method, the grain diameter is 40-60um, and the thickness is 1-4 um.
The invention finally provides the application of the single crystal hexagonal aluminum oxide as a lacquer painting mosaic material.
The invention has the following advantages: the aluminum salt is used as a raw material, a crystal forming agent is added, regular growth of alumina can be promoted, single crystal hexagonal alumina particles with the particle size of 40-60um and the thickness of 1-4um are prepared by a molten salt method, and the single crystal hexagonal alumina particles are inlaid in a lacquer painting and are starlight, so that the special artistic effect of the smart crystal is achieved.
Drawings
The invention will be further described with reference to the following examples with reference to the accompanying drawings.
FIG. 1 is an electron micrograph of the crystal grain shape of the single crystal alumina of example 1.
FIG. 2 is an X-ray diffraction pattern of the crystalline single crystal alumina of example 1.
FIG. 3 is a photograph of a single crystal spot from selected areas of the single crystal alumina crystal of example 1 by electron diffraction.
FIG. 4 is an electron micrograph of the crystal grain shape of the single crystal alumina of example 3.
FIG. 5 is an electron micrograph of the crystal thickness of the single crystal alumina of example 3.
FIG. 6 is an electron micrograph of the crystal thickness of the single crystal alumina of example 4.
FIG. 7 is an electron micrograph of the shape of the alumina crystal particles of comparative example 1.
FIG. 8 is an electron micrograph of the crystal thickness of alumina of comparative example 1.
Detailed Description
Example 1
1) Dissolving 100g of aluminum sulfate octadecahydrate in 200mL of deionized water, and adding 10mL of zirconium fluoride solution with the mass percentage of 1% to prepare solution A; 37.8g of sodium hydroxide was dissolved in 100mL of deionized water to prepare solution B.
2) Slowly adding the solution B into the solution A under the stirring condition (the stirring speed is 550r/min), continuously stirring for 25min after the solution B is added, controlling the pH value to be 9, adding 40g of potassium sulfate and 40g of sodium sulfate, and uniformly mixing to prepare a gel mixture.
3) And drying the gel mixture, and then putting the gel mixture into a high-temperature resistor to crystallize through high-temperature molten salt, wherein the temperature is 1200 ℃, and the heat preservation time is 3 h.
4) And cooling the calcined mixture, washing with water, removing molten salt, filtering, and drying to obtain single crystal hexagonal alumina particles with the average particle size of 50um and the thickness of 1-4 um. As shown in fig. 1-3.
Example 2
1) 200g of aluminum sulfate octadecahydrate is dissolved in 400mL of deionized water, 18mL of sodium molybdate dihydrate solution with the mass percentage of 5% is added to prepare solution A; 75.6g of sodium hydroxide was dissolved in 200mL of deionized water to prepare a solution B.
2) Slowly adding the solution B into the solution A under the stirring condition (the stirring speed is 550r/min), continuously stirring for 25min after the solution B is added, controlling the pH value to be 9.3, adding 80g of potassium sulfate and 80g of sodium sulfate, and uniformly mixing to prepare a gel mixture.
3) And drying the gel mixture, and then putting the gel mixture into a high-temperature resistor to crystallize through high-temperature molten salt, wherein the temperature is 1250 ℃, and the heat preservation time is 2 h.
4) Cooling the calcined mixture with water, washing to remove molten salt, filtering, and drying to obtain single crystal hexagonal oxide with average particle diameter of 48umThe aluminum oxide particles with the thickness of 1-4 um. are shown in figures 1-3. the XRD spectrum of figure 2 shows that the phase corresponding to pdf card number 46-1212 is corundum alpha aluminum oxide, namely α -Al2O3。
Example 3
1) Dissolving 100g of aluminum sulfate octadecahydrate in 200mL of deionized water, and adding 8mL of zirconium fluoride solution with the mass percent of 1% and 8mL of sodium molybdate dihydrate solution with the mass percent of 5% to prepare solution A; 37.8g of sodium hydroxide was dissolved in 100mL of deionized water to prepare solution B.
2) Slowly adding the solution B into the solution A under the stirring condition (the stirring speed is 550r/min), continuously stirring for 25min after the solution B is added, controlling the pH value to be 9.5, adding 40g of potassium sulfate and 40g of sodium sulfate, and uniformly mixing to prepare a gel mixture.
3) And drying the gel mixture, and then putting the gel mixture into a high-temperature resistor to crystallize through high-temperature molten salt, wherein the temperature is 1300 ℃, and the heat preservation time is 4 h.
4) And cooling the calcined mixture, washing with water, removing molten salt, filtering, and drying to obtain the single crystal hexagonal alumina particles with the average particle size of 52um and the thickness of 1-4 um. As shown in fig. 4-5.
Example 4
1) 200g of aluminum sulfate octadecahydrate is dissolved in 400mL of deionized water, 10mL of zirconium chloride solution with the mass percentage of 5% and 12mL of sodium molybdate dihydrate solution with the mass percentage of 10% are added to prepare solution A; 100.2g of sodium carbonate was dissolved in 300mL of deionized water to prepare solution B.
2) Slowly adding the solution B into the solution A under the stirring condition (the stirring speed is 550r/min), continuously stirring for 25min after the solution B is added, controlling the pH value to be 9.8, adding 80g of potassium sulfate and 80g of sodium sulfate, and uniformly mixing to prepare a gel mixture.
3) And drying the gel mixture, putting the dried gel mixture into a high-temperature resistor, and crystallizing the gel mixture by using high-temperature molten salt at 1280 ℃ for 8 hours.
4) And cooling the calcined mixture, washing with water, removing molten salt, filtering, and drying to obtain the single crystal hexagonal alumina particles with the average particle size of 56um and the thickness of 1-4 um. As shown in fig. 6.
Example 5
1) Dissolving 100g of aluminum sulfate octadecahydrate in 200mL of deionized water, and adding 10mL of ammonium phosphomolybdate with the mass percentage of 3% to prepare solution A; 50.1g of sodium carbonate was dissolved in 150mL of deionized water to prepare solution B.
2) Slowly adding the solution B into the solution A under the stirring condition (the stirring speed is 550r/min), continuously stirring for 25min after the solution B is added, controlling the pH value to be 9, adding 40g of potassium sulfate and 40g of sodium sulfate, and uniformly mixing to prepare a gel mixture.
3) And drying the gel mixture, and then putting the gel mixture into a high-temperature resistor to crystallize through high-temperature molten salt, wherein the temperature is 1240 ℃, and the heat preservation time is 4 h.
4) And cooling the calcined mixture, washing with water, removing molten salt, filtering, and drying to obtain the single crystal hexagonal alumina particles with the average particle size of 53um and the thickness of 1-4 um.
TABLE 1 thickness and average particle diameter of single crystal flaky alumina prepared in examples 1 to 5
| Crystal-type agent% | Thickness um | Average particle diameter um | |
| Example 1 | 0.2 | 1-4 | 50 |
| Example 2 | 1.5 | 1-4 | 48 |
| Example 3 | 1.8 | 1-4 | 52 |
| Example 4 | 2.9 | 1-4 | 56 |
| Example 5 | 1.6 | 1-4 | 53 |
As shown in Table 1, the single-crystal hexagonal alumina of the present invention prepared in examples 1 to 5 had a thickness of 1 to 4um and an average particle diameter of 40 to 60 um.
Comparative example 1
Alumina crystals were prepared in the same manner as in example 5, except that 10mL of titanium sulfate 8% by mass was used instead of 10mL of ammonium phosphomolybdate solution 3% by mass, and as seen in the electron micrographs of fig. 7 and 8, alumina crystals having a thickness of 0.2 to 0.4um and an average particle diameter of 12um were obtained. It was concluded that the crystal particles were irregular in shape and too thin, having a smaller average particle size, than the crystals of examples 1-5, and that inlaying them in lacquer paintings did not have the unique artistic effect of a crystal of agility.
Although specific embodiments of the invention have been described above, it will be understood by those skilled in the art that the specific embodiments described are illustrative only and are not limiting upon the scope of the invention, and that equivalent modifications and variations can be made by those skilled in the art without departing from the spirit of the invention, which is to be limited only by the appended claims.
Claims (8)
1. A preparation method of monocrystal hexagonal alumina is characterized in that: the method comprises the following steps:
(1) adding a crystal forming agent into an aluminum salt solution, and uniformly stirring; the crystallization agent is one or a mixture of two of zirconium salt and molybdate; the addition amount of the crystal forming agent is calculated according to the amount of finally obtained alumina, and the weight proportion is 0.1-3%; the zirconium salt is zirconium fluoride, zirconium chloride or zirconium nitrate;
(2) dropwise adding the precipitant solution into the solution obtained in the step (1) under the stirring condition, continuously stirring, controlling the pH value to be 9-10, and finally adding molten salt to uniformly mix to prepare a gel mixture;
(3) drying the gel mixture, and then calcining at high temperature of 1150-1350 ℃ for 2-8 h;
(4) and cooling the calcined mixture to room temperature, washing with water to remove molten salt, filtering and drying to obtain single crystal hexagonal alumina particles with the particle size of 40-60um and the thickness of 1-4 um.
2. The method of preparing single crystal hexagonal alumina of claim 1, characterized in that: the aluminum salt solution is an aluminum sulfate solution.
3. The method of preparing single crystal hexagonal alumina of claim 1, characterized in that: the precipitant solution is sodium hydroxide solution or sodium carbonate solution.
4. The method of preparing single crystal hexagonal alumina of claim 1, characterized in that: the molybdate is sodium molybdate, potassium molybdate or ammonium phosphomolybdate.
5. The method of preparing single crystal hexagonal alumina of claim 1, characterized in that: the molten salt is one or a mixture of two of potassium salt and sodium salt.
6. The method of preparing hexagonal single crystal alumina of claim 5, wherein: the potassium salt is potassium sulfate, and the sodium salt is sodium sulfate.
7. A single-crystal hexagonal alumina obtained by the production method according to any one of claims 1 to 6.
8. Use of the hexagonal single crystal alumina of claim 7 as a lacquer setting material.
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| DE2850064B1 (en) * | 1978-11-18 | 1980-05-08 | Giulini Chemie | Hexagonal tabular alpha alumina single crystals and process for their manufacture |
| FR2652075B1 (en) * | 1989-09-21 | 1991-12-06 | Atochem | ALPHA ALUMINA MACROCRYSTALS IN THE FORM OF PLATES AND PROCESS FOR OBTAINING SAME. |
| JP3242561B2 (en) * | 1995-09-14 | 2001-12-25 | メルク・ジヤパン株式会社 | Flaky aluminum oxide, pearlescent pigment and method for producing the same |
| CN100390330C (en) * | 2006-09-21 | 2008-05-28 | 中国铝业股份有限公司 | Method for preparing flake alpha Al2O3 monocrystal grains at low temperature |
| CN101607726A (en) * | 2008-06-20 | 2009-12-23 | 大连交通大学 | Former grade particles is the manufacture method of the alpha-alumina powder of nearly hexagonal plate sheet or drum type |
| CN101660204A (en) * | 2009-09-09 | 2010-03-03 | 中国科学院青海盐湖研究所 | Preparation method of hexagonal piece aluminum oxide whisker material |
| CN101691302B (en) * | 2009-09-27 | 2012-05-02 | 上海大学 | Method for preparing sheet-shaped alpha-alumina particles |
| CN102924092A (en) * | 2012-10-24 | 2013-02-13 | 江苏大学 | Low-cost and pollution-free preparation method for highly dispersed flaky alumina |
| EP2799398B1 (en) * | 2013-04-30 | 2018-05-23 | Merck Patent GmbH | alpha-Alumina flakes |
| CN104986786B (en) * | 2015-07-31 | 2018-02-27 | 华南理工大学 | A kind of controllable sheet α Al of particle size2O3Powder and preparation method thereof |
| CN105731509B (en) * | 2016-05-18 | 2018-01-16 | 湖北大学 | A kind of sheet α Al2O3Powder and preparation method thereof |
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