CN1417128A - Method for producing tantalum or niobate compound - Google Patents
Method for producing tantalum or niobate compound Download PDFInfo
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- CN1417128A CN1417128A CN 02150089 CN02150089A CN1417128A CN 1417128 A CN1417128 A CN 1417128A CN 02150089 CN02150089 CN 02150089 CN 02150089 A CN02150089 A CN 02150089A CN 1417128 A CN1417128 A CN 1417128A
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- niobate
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- 229910052715 tantalum Inorganic materials 0.000 title claims abstract description 51
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 150000001875 compounds Chemical class 0.000 title claims abstract description 35
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 40
- 238000005406 washing Methods 0.000 claims abstract description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 24
- 238000001914 filtration Methods 0.000 claims abstract description 23
- 238000002156 mixing Methods 0.000 claims abstract description 22
- 238000005245 sintering Methods 0.000 claims abstract description 22
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims abstract description 16
- 239000010955 niobium Substances 0.000 claims abstract description 14
- 239000002253 acid Substances 0.000 claims abstract description 13
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 9
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000000463 material Substances 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 10
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Chemical compound O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 claims description 10
- 238000001556 precipitation Methods 0.000 claims description 9
- PBCFLUZVCVVTBY-UHFFFAOYSA-N tantalum pentoxide Inorganic materials O=[Ta](=O)O[Ta](=O)=O PBCFLUZVCVVTBY-UHFFFAOYSA-N 0.000 claims description 9
- 238000001354 calcination Methods 0.000 claims description 2
- 239000013078 crystal Substances 0.000 abstract description 72
- 239000000203 mixture Substances 0.000 abstract description 17
- 239000000843 powder Substances 0.000 abstract description 7
- 239000007787 solid Substances 0.000 abstract description 3
- 238000005303 weighing Methods 0.000 abstract description 3
- 230000007547 defect Effects 0.000 abstract description 2
- -1 lithium tantalate compound Chemical class 0.000 description 52
- WSMQKESQZFQMFW-UHFFFAOYSA-N 5-methyl-pyrazole-3-carboxylic acid Chemical compound CC1=CC(C(O)=O)=NN1 WSMQKESQZFQMFW-UHFFFAOYSA-N 0.000 description 30
- GQYHUHYESMUTHG-UHFFFAOYSA-N lithium niobate Chemical compound [Li+].[O-][Nb](=O)=O GQYHUHYESMUTHG-UHFFFAOYSA-N 0.000 description 26
- 238000002441 X-ray diffraction Methods 0.000 description 24
- 238000001878 scanning electron micrograph Methods 0.000 description 12
- 238000001228 spectrum Methods 0.000 description 12
- 239000012535 impurity Substances 0.000 description 9
- 229910052808 lithium carbonate Inorganic materials 0.000 description 7
- 238000010586 diagram Methods 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 5
- 238000005554 pickling Methods 0.000 description 3
- 239000010453 quartz Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 150000004679 hydroxides Chemical class 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 208000035824 paresthesia Diseases 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G33/00—Compounds of niobium
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G35/00—Compounds of tantalum
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention provides a method for producing tantalum or niobate compounds, which uses high-purity H2TaF7Or H2NbF7And/or H2NbOF5The solution is precipitated and the like to react, firstly a compound containing tantalum or niobium is produced, then the compound containing tantalum or niobium and high-purity carbonate or hydroxide are subjected to homogeneous mixing, low-temperature drying, sintering, acid washing, water washing, filtering and drying to obtain the tantalum or niobate compound, the tantalum or niobate compound can be powder or crystal, and when the tantalum or niobate compound produced by the method is used for producing tantalum or niobate crystals, the defects of unstable crystal quality and the like caused by uneven mixing and inaccurate weighing of the traditional solid powder mixture are fundamentally overcome.
Description
Technical Field
The invention provides a method for producing a tantalum or niobate compound.
Background
Lithium Tantalate (Lithium Tantalate) crystal is grown by czochralski method in 1965 by baraman et al, has good performances of electric light, pyroelectric, etc., immediately draws attention of various national scholars, and is applied to aspects of infrared deep measurement, etc. Through further research on lithium tantalate crystal materials, the lithium tantalate crystal materials are found to have good piezoelectric effect, the Q value of the lithium tantalate crystal is similar to that of a quartz crystal, the lithium tantalate crystal has zero-temperature coefficient cut type, the electromechanical coupling coefficient is as high as 60%, and the quartz crystal is only 9-10%. Therefore, the resonator made of lithium tantalate crystal material has capacitance ratio (C)0/C1) The characteristic of small frequency interval and wide frequency interval in series-parallel connection can be used for high-precision broadband filters and large-frequency bias-controlled oscillators. Theoretically, the phase noise of the oscillator is lower than that of a quartz crystal oscillator, so that the tantalum or lithium niobate crystal attracts attention at home and abroad in the aspects of frequency control and selection.
At present, the substrate materials of filters such as color displays and computer displays mainly comprise lithium tantalate, lithium niobate and other crystal materials, the market demand for lithium tantalate, lithium niobate and other crystal materials is rapidly increased, and how to improve the processing quality and the yield of the lithium tantalate and lithium niobate crystal materials becomes one of the problems which are urgently needed to be solved by crystal material manufacturers at present.
The traditional production process of tantalum or niobate crystals is as follows: with high purity Ta2O5Or Nb2O5Mixing with high-purity carbonate or hydroxide, and sintering at high temperatureBriquetting and crystal pulling to obtain the tantalum or niobate crystal. The carbonate or hydroxide may be Li2CO3Or carbonates or hydroxides of LiOH and alkali metals, alkaline earth metals and transition metals and composite carbonates or hydroxides thereof. The following problems often arise when tantalum or niobate crystals are produced by this method: 1.Ta2O5Or Nb2O5And the carbonate or the hydroxide are both solid powders, and the mixture is not uniformly mixed, so that the pulled tantalum or niobate crystals are not uniform, and the crystals are turbid or cracked in severe cases. 2. Because the weighing is inaccurate during mixing, the components are easy to deviate during mixing, and even tantalum or niobate crystals cannot be obtained. This results in a reduction in the yield of crystals and an increase in the cost.
Disclosure of Invention
The invention mainly provides a method for producing tantalum or niobate compounds by homogeneous reaction, when the tantalum or niobate compounds produced by the method are used for producing tantalum or niobate crystals, the defects of unstable crystal quality and the like caused by uneven mixing and inaccurate weighing of the traditional solid powder mixed materials are fundamentally overcome.
In order to achieve the above object, the present inventors have made intensive studies on conventional high purity Ta2O5Or Nb2O5The mixing and sintering process with high purity carbonate or hydroxide is changed into that firstly a tantalum or niobium containing compound is produced, then the tantalum or niobium containing compound and the high purity carbonate or hydroxide are subjected to homogeneous mixing, low temperature drying, sintering and reaction to obtain a tantalum or niobate compound, and the tantalum or niobate compound is subjected to acid washing, water washing, filtering and drying to obtain the pure tantalum or niobate compound which can be used for producing tantalum or niobate crystals. The acid used for pickling may be H2C2O4、H2CO2Iso-organic acids or HCl, HNO3And the like.
The technical scheme of the invention is to provide a method for producing tantalum or niobate compounds, which is characterized in that high-purity H is used2TaF7Or H2NbF7And/or H2NbOF5After a series of reactions such as precipitation, the solution firstly produces a compound containing tantalum or niobium, and then the compound containing tantalum or niobium and high-purity carbonate or hydroxide are subjected to homogeneous mixing, low-temperature drying, sintering, acid washing, water washing, filtering and drying to obtain the tantalum or niobate compound.
According to a specific scheme ofthe invention, the method comprises the following steps: to high purity H2TaF7Or H2NbF7And/or H2NbOF5Adding proper amount of H into the solution2O2Solution, then pure NH is introduced3Precipitating, and filtering to obtain (NH)4)3TaO8Or (NH)4)3NbO8(ii) a To obtain (NH)4)3TaO8Or (NH)4)3NbO8Adding a proper amount of H2O2The solution and high-purity carbonate or hydroxide are subjected to homogeneous mixing, low-temperature drying, sintering, acid washing, water washing, filtering and drying to obtain the tantalum or niobate compound. In this scheme, high purity H2TaF7Or H2NbF7And/or H2NbOF5Adding H into the solution2O2The amount of the solution is 1.05-1.15 times of the theoretical amount.
In the technical scheme of the invention, Li is used2CO3And H2C2O4The chemical reaction for example is:
according to a second embodiment of the present invention, the method comprises: to high purity H2TaF7 or H2NbF7And/or H2NbOF5Pure NH is directly introduced into the solution3Precipitating, washing with water, filtering to obtain Ta (OH)5Or Nb (OH)5(ii) a To the obtained Ta (OH)5Or Nb (OH)5Adding a proper amount of pure water and high-purity carbonate or hydroxide, uniformly mixing, drying at low temperature, sintering, acid washing, water washing, filtering and drying to obtain the tantalum or niobate compound.
In the technical scheme of the invention, Li is used2CO3And H2C2O4The chemical reaction for example is:
according to a third embodiment of the invention, the method comprises the following steps: to high purity H2TaF7Or H2NbF7And/or H2NbOF5Pure NH is directly introduced into the solution3Precipitating, washing with water, filtering, drying, and calcining to obtain Ta2O5Or Nb2O5(ii) a To the obtained Ta2O5Or Nb2O5Adding a proper amount of pure water and high-purity carbonate or hydroxide, uniformly mixing, drying at low temperature, sintering, acid washing, water washing, filtering and drying to obtain the tantalum or niobate compound.
In the technical scheme of the invention, Li is used2CO3And H2C2O4The chemical reaction for example is:
in the three specific schemes, the low-temperature drying temperature is 45-100 ℃, the sintering temperature of the tantalum-containing material is 800-.
Pure NH is introduced into the three specific schemes of the invention3When the precipitation is carried out, the pH value of the precipitation is 9-11, and the addition amount of the high-purity carbonate or hydroxide is 0.95-1.05 times of the theoretical amount.
The tantalum or niobate compound obtained by the invention has chemical uniformity, the chemical impurity content can reach the standard of producing tantalum or niobate crystals, particularly, the tantalum or niobate compound does not contain fluorine or trace fluorine, and the tantalum or niobate compound can produce the tantalum or niobate crystals with more excellent quality.
Drawings
FIG. 1 is a process flow diagram for producing tantalum or niobate compounds in accordance with the present invention.
FIG. 2-a is a scanning electron micrograph of a powdery lithium tantalate compound produced according to example 1 of the present invention.
FIG. 2-b is a scanning electron micrograph of a powdery lithium tantalate compound produced according to example 2 of the present invention.
FIG. 2-c is a scanning electron micrograph of a powdery lithium tantalate compound produced according to example 3 of the present invention.
FIG. 3 is a scanning electron micrograph of a crystalline lithium tantalate compound produced according to the present invention.
FIG. 4-a is a scanning electron micrograph of a powdery lithium niobate compound produced according to example 4 of the present invention.
FIG. 4-b is a scanning electron micrograph of a powdery lithium niobate compound produced according to example 5 of the present invention.
FIG. 4-c is a scanning electron micrograph of a powdery lithium niobate compound produced according to example 6 of the present invention.
FIG. 5 is a scanning electron micrograph of a crystalline lithium niobate compound produced according to the present invention.
FIG. 6-a is an X-ray diffraction pattern of the lithium tantalate compound produced in example 1 of the present invention.
FIG. 6-b is an X-ray diffraction pattern of the lithium tantalate compound produced in example 2 of the present invention.
FIG. 6-c is an X-ray diffraction pattern of the lithium tantalate compound produced in example 3 of the present invention.
FIG. 7-a is an X-ray diffraction pattern of the lithium niobate compound produced in example 4 of the present invention.
FIG. 7-b is an X-ray diffraction pattern of the lithium niobate compound produced in example 5 of the present invention.
FIG. 7-c is an X-ray diffraction pattern of the lithium niobate compound produced in example 6 of the present invention.
FIG. 8-a is an X-ray diffraction pattern of lithium tantalate crystals drawn from the lithium tantalate compound produced in example 1 of the present invention.
FIG. 8-b is an X-ray diffraction pattern of lithium tantalate crystals drawn from the lithium tantalate compound produced in example 2 of the present invention.
FIG. 8-c is an X-ray diffraction chart of lithium tantalate crystals drawn from the lithium tantalate compound produced in example 3 of the present invention.
FIG. 9-a is an X-ray diffraction pattern of a lithium niobate crystal pulled out of the lithium niobate compound produced in example 4 of the present invention.
FIG. 9-b is an X-ray diffraction pattern of a lithium niobate crystal pulled out from the lithium niobate compound produced in example 5 of the present invention.
FIG. 9-c is an X-ray diffraction pattern of a lithium niobate crystal pulled out from the lithium niobate compound produced in example 6 of the present invention.
FIG. 10-a is a graph showing a dielectric temperature spectrum of lithium tantalate crystals drawn from a lithium tantalate compound produced in example l of the present invention.
FIG. 10-b is a graph showing the dielectric temperature spectrum of lithium tantalate crystals drawn from the lithium tantalate compound produced in example 2 of the present invention.
FIG. 10-c is a graph showing the dielectric temperature spectrum of lithium tantalate crystals drawn from the lithium tantalate compound produced in example 3 of the present invention.
FIG. 11-a is a dielectric temperature spectrum curve of a lithium niobate crystal pulled out of a lithium niobate compound produced in example 4 of the present invention.
FIG. 11-b is a dielectric temperature spectrum curve of a lithium niobate crystal pulled out of the lithium niobate compound produced in example 5 of the present invention.
FIG. 11-c is a graph showing the dielectric temperature spectrum of a lithium niobate crystal pulled from a lithium niobate compound produced in example 6 of the present invention.
Detailed Description
Example 1
Taking high-purity H2TaF720L of solution with a concentration of 62.5gTa2O5L, adding H2O2846.84g of H2O2Solution, then pure NH is introduced3Precipitating to pH 10, and filtering to obtain (NH)4)3TaO81613.1 g. To 1613.1g (NH)4)3TaO8Adding a proper amount of H2O2Solution and 164.14g of high purity Li2CO3Drying the mixture at 55 deg.C after mixing, sintering the mixture at 1100 deg.C for 10 hr after drying, and then adding 8% H2C2O4The solution is pickled, washed, filtered and dried to obtain pure product which can be used for producing the tantalum acidA powdery lithium tantalate compound for lithium crystal. The particle size of the lithium tantalate compound is shown in Table 1, the content of impurity elements is shown in Table 2, the scanning electron micrograph thereof is shown in the attached figure 2-a of the specification, the X-ray diffraction pattern thereof is shown in the attached figure 6-a of the specification, the X-ray diffraction pattern of the lithium tantalate crystal drawn therefrom is shown in the attached figure 8-a of the specification, the dielectric temperature spectrum curve of the lithium tantalate crystal drawn therefrom is shown in the attached figure 10-a of the specification, and the process flow diagram is shown in the attached figure 1.
Example 2
Taking high-purity H2TaF720L of solution with a concentration of 62.5gTa2O5/L, direct introduction of pure NH3Precipitating until the pH value is 10, washing with water, and filtering to obtain Ta (OH)51505.3 g. To 1505.3gTa (OH)5Adding a proper amount of pure water and 209.06g of high-purity Li2CO3Drying the mixture at 75 deg.C after mixing, sintering the mixture at 1100 deg.C for 10 hr after drying, and then adding 8% H2C2O4And (3) pickling, washing, filtering and drying the solution to obtain a pure powdery lithium tantalate compound which can be used for producing lithium tantalate crystals. The particle size of the lithium tantalate compound is shown in Table 1, the content of impurity elements is shown in Table 2,the scanning electron micrograph thereof is shown in the accompanying FIG. 2-b, the X-ray diffraction pattern thereof is shown in the accompanying FIG. 6-b, and the X-ray diffraction pattern of the lithium tantalate crystal drawn therefromSee the attached figure 8-b of the specification, the dielectric temperature spectrum curve of the lithium tantalate crystal drawn by the drawing is shown in the attached figure 10-b of the specification, and the process flow chart is shown in the attached figure 1.
Example 3
Taking high-purity H2TaF720L of solution with a concentration of 62.5gTa2O5/L, direct introduction of pure NH3Precipitating until the pH value is 10, washing with water, filtering, drying, and roasting to obtain Ta2O51235.2 g. To 1235.2g Ta2O5Adding a proper amount of pure water and 206.80g of high-purity Li2CO3Drying the mixture at 75 deg.C after mixing, sintering the mixture at 1100 deg.C for 10 hr after drying, and then adding 8% H2C2O4And (3) pickling, washing, filtering and drying the solution to obtain a pure powdery lithium tantalate compound which can be used for producing lithium tantalate crystals. The particle size of the lithium tantalate compound is shown in Table l, the content of impurity elements is shown in Table 2, the scanning electron micrograph thereof is shown in the accompanying drawing 2-c of the specification, the X-ray diffraction pattern thereof is shown in the accompanying drawing 6-c of the specification, the X-ray diffraction pattern of the lithium tantalate crystal drawn therefrom is shown in the accompanying drawing 8-c of the specification, the dielectric temperature spectrum curve of the lithium tantalate crystal drawn therefrom is shown in the accompanying drawing 10-c of the specification, and the process flow diagram is shown in FIG. 1.
Pure powdery lithium tantalate compound which can be used for producing lithium tantalate crystals and is obtained in example 1 and/or example 2 and/or example 3 is sintered for 10 hours at 1300-1350 ℃, or the mixture which is dried at low temperature is directly sintered for 10 hours at 1300-1350 ℃, so that pure crystalline lithium tantalate compound which can be used for producing lithium tantalate crystals can be obtained, and scanning electron micrographs thereof are shown in figure 3 of the specification.
Example 4
Taking high-purity H2NbF7And/or H2NbOF520L of solution with a concentration of 106.3gNb2O5L, adding H2O22391.35g of H2O2Solution, then pure NH is introduced3Precipitating to pH 10, and filtering to obtain (NH)4)3NbO83733.2 g. To 3733.2g (NH)4)3NbO8Adding a proper amount of H2O2Solution and 502.29g of high purity Li2CO3Drying the mixture at 55 deg.C after mixing, sintering the mixture at 1000 deg.C for 10 hr after drying, and then adding 8% H2C2O4The solution is washed by acid, washed by water, filtered and dried to obtain pure powdery lithium niobate compound which can be used for producing lithium niobate crystals. The granularity of the lithium niobate compound is shown in table l, the content of impurity elements is shown in table 2, the scanning electron microscope photo is shown in figure 4-a of the specification, the X-ray diffraction pattern is shown in figure 7-a of the specification, the X-ray diffraction pattern of the lithium niobate crystal pulled out of the lithium niobate compound is shown in figure 9-a of the specification, the dielectric temperature spectrum curve of the lithium niobate crystal pulled out of the lithium niobate compound is shown in figure 11-a of the specification, and the process flow diagram is shown in figure 1.
Example 5
Taking high-purity H2NbF7And/or H2NbOF520L of solution with a concentration of 106.3gNb2O5/L, direct introduction of pure NH3Precipitating to pH 10, washing with water, filtering to obtain Nb (OH)52823.3 g. To 2823.3gNb (OH)5Adding a proper amount of pure water and 586.87g of high-purity Li2CO3Drying the mixture at 75 ℃ after mixing, sintering the mixture for 10 hours at 1000 ℃ after drying the mixture, and then using 8% H2C2O4The solution is washed by acid, washed by water, filtered and dried to obtain pure powdery lithium niobate compound which can be used for producing lithium niobate crystals. The granularity of the lithium niobate compound is shown in table 1, the content of impurity elements is shown in table 2, the scanning electron microscope photo is shown in figure 4-b of the specification, the X-ray diffraction pattern is shown in figure 7-b of the specification, the X-ray diffraction pattern of the lithium niobate crystal pulled out of the lithium niobate compound is shown in figure 9-b of the specification, the dielectric temperature spectrum curve of the lithium niobate crystal pulled out of the lithium niobate compound is shown in figure 11-b of the specification, and the process flow diagram is shown in figure l of the specification.
Example 6
Taking high-purity H2NbF7And/or H2NbOF520L of solution with a concentration of 106.3gNb2O5/L, direct introduction of pure NH3Precipitating to pH 10, washing with water, and filteringFiltering, drying and roasting to obtain Nb2O52118.3 g. To 2118.3gNb2O5Adding a proper amount of pure water and 589.30g of high-purity Li2CO3Drying the mixture at 75 ℃ after mixing, sintering the mixture for 10 hours at 1000 ℃ after drying the mixture, and then using 8% H2C2O4The solution is pickled, washed, filtered and dried to obtain pure lithium niobate crystalA powdery lithium niobate compound for body use. The granularity of the lithium niobate compound is shown in table 1, the content of impurity elements is shown in table 2, the scanning electron microscope photo is shown in figure 4-c of the specification, the X-ray diffraction pattern is shown in figure 7-c of the specification, the X-ray diffraction pattern of the lithium niobate crystal pulled out of the lithium niobate compound is shown in figure 9-c of the specification, the dielectric temperature spectrum curve of the lithium niobate crystal pulled out of the lithium niobate compound is shown in figure 11-c of the specification, and the process flow diagram is shown in figure 1.
Pure lithium niobate compound powder which can be used for producing lithium niobate crystals and obtained in the embodiment 4 and/or the embodiment 5 and/or the embodiment 6 can be sintered for 10 hours at the temperature of 1100-1150 ℃ or directly sintered for 10 hours at the temperature of 1100-1150 ℃ to obtain pure lithium niobate compound crystal which can be used for producing lithium niobate crystals, and the scanning electron microscope picture of the compound is shown in the attached figure 5 of the specification.
Any one or two or more of the pure lithium tantalate compounds obtained in examples 1 to 3, which can be used as powders or crystals for producing lithium tantalate crystals, were mixed and briquetted, put into a platinum crucible and charged, and then heated to 1680 ℃ to melt for 5 hours. And after the lithium tantalate compound is completely melted, seeding, neck drawing, shouldering and body drawing are carried out, and after the lithium tantalate crystal grows to a preset length, the drawing, the cooling and the discharging are stopped, so that the lithium tantalate crystal is obtained.
Any one or two or more of the pure lithium niobate compounds obtained in examples 4 to 6, which can be used as powders or crystals for producing lithium niobate crystals, were mixed and briquetted, charged into a platinum crucible and charged into a furnace, and then melted by heating to 1350 c for 5 hours. After the lithium niobate compound is completely melted, seeding, drawing neck, lifting, shouldering and pulling body, and after the lithium niobate compound is completely melted, the lithium niobate compound is placed in a potStopping pulling, cooling and discharging after the lithium crystal grows to a preset length to obtain the lithium niobate crystal. TABLE 1 particle size of tantalum or lithium niobate compounds
TABLE 2 impurity element content of tantalum or lithium niobate compounds
| Particle size (μm) | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Example 6 | |
| FLT6-2 | FLT6-3 | FLT6-4 | FLN2-2 | FLN2-3 | FLN2-4 | ||
| Granule Degree of rotation Is divided into Cloth | d10％ | 0.87 | 0.83 | 1.21 | 0.46 | 0.51 | 0.52 |
| d50％ | 4.32 | 4.19 | 5.97 | 2.43 | 2.07 | 2.47 | |
| d90％ | 13.37 | 12.57 | 15.22 | 9.31 | 6.73 | 9.01 | |
| Average particle diameter | 5.82 | 5.52 | 7.25 | 3.86 | 3.01 | 3.75 | |
| Impurities Element(s) (ppm) | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Example 6 |
| FLT6-2 | FLT6-3 | FLT6-4 | FLN2-2 | FLN2-3 | FLN2-4 | |
| Al | 0.008 | 0.85 | 1.25 | 0.007 | 0.75 | 1.05 |
| Ca | 0.12 | 0.10 | 6.0 | 0.17 | 1.45 | 0.35 |
| Co | 0.0005 | 0.0005 | 0.0025 | 0.0005 | 0.0005 | 0.0005 |
| Cr | 0.20 | 0.007 | 0.30 | 0.11 | 0.35 | 0.25 |
| Cu | 0.10 | 0.03 | 0.085 | 0.015 | 0.25 | 0.25 |
| Fe | 1.85 | 0.12 | 1.3 | 0.22 | 3.0 | 0.85 |
| Mg | 0.40 | 0.25 | 0.35 | 0.075 | 0.41 | 0.25 |
| Mn | 0.007 | 0.005 | 0.0035 | 0.01 | 0.025 | 0.01 |
| Mo | 0.20 | 0.075 | 0.001 | 0.0005 | 0.30 | 0.005 |
| Ni | 0.005 | 0.003 | 0.11 | 0.005 | 0.15 | 0.005 |
| Pb | 0.005 | 0.15 | 0.0005 | 0.007 | 0.25 | 0.05 |
| Si | 0.73 | 1.21 | 2.31 | 1.2 | 1.2 | 2.0 |
| Sn | 0.005 | 0.0005 | 0.0005 | 0.007 | 0.005 | 0.0005 |
| Ti | 0.03 | 0.0007 | 0.005 | 0.005 | 0.01 | 0.05 |
| V | 0.75 | 0.34 | 0.15 | 0.15 | 0.25 | 0.15 |
| W | 0.0005 | 0.0005 | 0.0005 | 0.0005 | 0.0005 | 0.0005 |
| Zr | 0.006 | 0.0005 | 0.0005 | 0.0005 | 0.0005 | 0.0005 |
| Pt | 0.0005 | 0.0005 | 0.0005 | 0.0005 | 0.0005 | 0.0005 |
| OH | 1.22 | 2.7 | 17.2 | 2.47 | 2.21 | 1.1 |
| F | 13.0 | 12.0 | 14.0 | 10.0 | 13.0 | 10.0 |
Claims (10)
1. A process for preparing tantalum or niobate compound features use of high-purity H2TaF7Or H2NbF7And/or H2NbOF5After a series of reactions such as precipitation, the solution firstly produces a compound containing tantalum or niobium, and then the compound containing tantalum or niobium and high-purity carbonate or hydroxide are subjected to homogeneous mixing, low-temperature drying, sintering, acid washing, water washing, filtering and drying to obtain the tantalum or niobate compound.
2. The method of claim 1, wherein the precipitation reaction comprises: to high purity H2TaF7Or H2NbF7And/or H2NbOF5Adding proper amount of H into the solution2O2Solution, then pure NH is introduced3Precipitating, and filtering to obtain (NH)4)3TaO8Or (NH)4)3NbO8(ii) a To obtain (NH)4)3TaO8Or (NH)4)3NbO8Adding a proper amount of H2O2The solution and high-purity carbonate or hydroxide are subjected to homogeneous mixing, low-temperature drying, sintering, acid washing, water washing, filtering and drying to obtain the tantalum or niobate compound.
3. The method of claim 1, wherein the precipitation reaction comprises: to high purity H2TaF7Or H2NbF7And/or H2NbOF5Pure NH is directly introduced into the solution3Precipitating, washing with water, filtering,to obtain Ta (OH)5Or Nb (OH)5(ii) a To the obtained Ta (OH)5Or Nb (OH)5Adding a proper amount of pure water and high-purity carbonate or hydroxide, uniformly mixing, drying at low temperature, sintering, acid washing, water washing, filtering and drying to obtain the tantalum or niobate compound.
4. The method of claim 1, wherein the precipitation reaction comprises: to high purity H2TaF7Or H2NbF7And/or H2NbOF5Pure NH is directly introduced into the solution3Precipitating, washing with water, filtering, drying, and calcining to obtain Ta2O5Or Nb2O5(ii) a To the obtained Ta2O5Or Nb2O5Adding a proper amount of pure water and high-purity carbonate or hydroxide, uniformly mixing, drying at low temperature, sintering, acid washing, water washing, filtering and drying to obtain the tantalum or niobate compound.
5. The method according to any one of claims 1 to 4, wherein the temperature of the low-temperature drying is 45 to 100 ℃.
6. The method as claimed in any one of claims 1 to 4, wherein the sintering temperature of the tantalum-containing material is 800-1350 ℃ and the sintering temperature of the niobium-containing material is 800-1150 ℃.
7. The method according to claim 6, characterized in that more preferably the sintering temperature of the tantalum containing material is 950-.
8. The process according to claim 1 or 2, characterized in that high purity H is fed to2TaF7Or H2NbF7And/or H2NbOF5Adding H into the solution2O2The amount of the solution is 1.05-1.15 times of the theoretical amount.
9. According to the rightA method according to any of claims 2 to 4, characterized in that pure NH is introduced3When the precipitation is carried out, the pH value of the precipitation is 9-11.
10. The method according to any one of claims 2 to 4, characterized in that the high purity carbonate or hydroxide is added in an amount of 0.95 to 1.05 times the theoretical amount.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1315733C (en) * | 2004-05-21 | 2007-05-16 | 南京大学 | Preparation method of stable water-soluble niobium and tantalum precursor and application thereof |
| CN100510203C (en) * | 2007-05-10 | 2009-07-08 | 中国科学院安徽光学精密机械研究所 | Crystal growth way of crystal pulling method for tantalate |
| CN102442700A (en) * | 2011-09-16 | 2012-05-09 | 广东致远新材料有限公司 | Method for preparing high-purity spherical niobium oxide by peroxidizing precipitation |
| CN103011291A (en) * | 2012-12-19 | 2013-04-03 | 宁夏东方钽业股份有限公司 | Preparation method of tantalum and niobium composite carbide |
| CN103084164A (en) * | 2013-02-04 | 2013-05-08 | 上海交通大学 | Preparation method of tantalum pentoxide nanoparticle/graphene composite photocatalyst |
| CN104986800A (en) * | 2015-07-14 | 2015-10-21 | 宜春金洋新材料股份有限公司 | Method for preparing niobium hydroxide precipitate by taking fluoroniobate as raw material |
| CN105883919A (en) * | 2016-04-28 | 2016-08-24 | 宁夏东方钽业股份有限公司 | Preparation method of spherical tantalum oxide or spherical niobium oxide |
| CN113526553A (en) * | 2021-08-30 | 2021-10-22 | 南京弘顺和生物科技有限公司 | Preparation method and production equipment of superfine niobium hydroxide |
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- 2002-11-26 CN CN 02150089 patent/CN1289402C/en not_active Expired - Fee Related
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1315733C (en) * | 2004-05-21 | 2007-05-16 | 南京大学 | Preparation method of stable water-soluble niobium and tantalum precursor and application thereof |
| CN100510203C (en) * | 2007-05-10 | 2009-07-08 | 中国科学院安徽光学精密机械研究所 | Crystal growth way of crystal pulling method for tantalate |
| CN102442700A (en) * | 2011-09-16 | 2012-05-09 | 广东致远新材料有限公司 | Method for preparing high-purity spherical niobium oxide by peroxidizing precipitation |
| CN103011291A (en) * | 2012-12-19 | 2013-04-03 | 宁夏东方钽业股份有限公司 | Preparation method of tantalum and niobium composite carbide |
| CN103011291B (en) * | 2012-12-19 | 2015-09-09 | 宁夏东方钽业股份有限公司 | A kind of preparation method of tantalum niobium double carbide |
| CN103084164A (en) * | 2013-02-04 | 2013-05-08 | 上海交通大学 | Preparation method of tantalum pentoxide nanoparticle/graphene composite photocatalyst |
| CN103084164B (en) * | 2013-02-04 | 2015-01-28 | 上海交通大学 | Preparation method of tantalum pentoxide nanoparticle/graphene composite photocatalyst |
| CN104986800A (en) * | 2015-07-14 | 2015-10-21 | 宜春金洋新材料股份有限公司 | Method for preparing niobium hydroxide precipitate by taking fluoroniobate as raw material |
| CN105883919A (en) * | 2016-04-28 | 2016-08-24 | 宁夏东方钽业股份有限公司 | Preparation method of spherical tantalum oxide or spherical niobium oxide |
| CN113526553A (en) * | 2021-08-30 | 2021-10-22 | 南京弘顺和生物科技有限公司 | Preparation method and production equipment of superfine niobium hydroxide |
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