CN104163454A - Preparing method of lithium tantalate crystal - Google Patents
Preparing method of lithium tantalate crystal Download PDFInfo
- Publication number
- CN104163454A CN104163454A CN201410312827.6A CN201410312827A CN104163454A CN 104163454 A CN104163454 A CN 104163454A CN 201410312827 A CN201410312827 A CN 201410312827A CN 104163454 A CN104163454 A CN 104163454A
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- CN
- China
- Prior art keywords
- lithium tantalate
- urea
- tantalum pentoxide
- temperature
- lithium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- WSMQKESQZFQMFW-UHFFFAOYSA-N 5-methyl-pyrazole-3-carboxylic acid Chemical compound CC1=CC(C(O)=O)=NN1 WSMQKESQZFQMFW-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 238000000034 method Methods 0.000 title abstract description 21
- 239000013078 crystal Substances 0.000 title abstract description 14
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000004202 carbamide Substances 0.000 claims abstract description 31
- PBCFLUZVCVVTBY-UHFFFAOYSA-N tantalum pentoxide Inorganic materials O=[Ta](=O)O[Ta](=O)=O PBCFLUZVCVVTBY-UHFFFAOYSA-N 0.000 claims abstract description 28
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 claims abstract description 26
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims abstract description 25
- 238000002360 preparation method Methods 0.000 claims abstract description 14
- 239000002994 raw material Substances 0.000 claims abstract description 14
- 239000002019 doping agent Substances 0.000 claims description 13
- 239000000463 material Substances 0.000 claims description 12
- 238000010792 warming Methods 0.000 claims description 8
- 239000012467 final product Substances 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 2
- 238000005096 rolling process Methods 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 16
- 238000000354 decomposition reaction Methods 0.000 abstract description 4
- 229910052808 lithium carbonate Inorganic materials 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 230000035484 reaction time Effects 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 239000007788 liquid Substances 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract 1
- 238000005245 sintering Methods 0.000 description 10
- 239000000203 mixture Substances 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 4
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 238000003746 solid phase reaction Methods 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 150000003384 small molecules Chemical class 0.000 description 3
- 238000010671 solid-state reaction Methods 0.000 description 3
- 238000010897 surface acoustic wave method Methods 0.000 description 3
- 238000010189 synthetic method Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 235000011089 carbon dioxide Nutrition 0.000 description 2
- 229910001947 lithium oxide Inorganic materials 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 238000012544 monitoring process Methods 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 238000005204 segregation Methods 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- PNEFIWYZWIQKEK-UHFFFAOYSA-N carbonic acid;lithium Chemical compound [Li].OC(O)=O PNEFIWYZWIQKEK-UHFFFAOYSA-N 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000009643 growth defect Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- GCICAPWZNUIIDV-UHFFFAOYSA-N lithium magnesium Chemical compound [Li].[Mg] GCICAPWZNUIIDV-UHFFFAOYSA-N 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000000246 remedial effect Effects 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Landscapes
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention provides an application of urea in preparation of a lithium tantalate crystal and discloses a preparing method of the lithium tantalate crystal. By utilization of low-temperature (about 120 DEG C) decomposition of the urea, lithium carbonate and tantalum pentoxide are further mixed in the urea in a liquid state, the urea is decomposed when the temperature rises continuously and releases a large amount of heat, and the temperature can instantaneously reach 1200 DEG C, thus providing energy for reactions of raw materials. During continuous decomposition of the urea, the urea releases a large amount of micromolecules, such as NH3, H2O, CO2 and NOX, and the micromolecules penetrate into the lithium carbonate and the tantalum pentoxide, thus largely reducing the reaction temperature for production of lithium tantalate. According to the method, by utilization of the urea, the reaction temperature for the lithium tantalate is largely reduced, and the reaction time for the lithium tantalate is shortened. The cycle is shortened, and the reaction temperature is reduced, so that a great advance is made for synthesis of the lithium tantalate.
Description
Technical field
The present invention relates to optical material field, more specifically, relate to a kind of preparation method of lithium tantalate.
Background technology
Lithium tantalate (Lithium Tantalate, LiTa03, LT) crystal is a kind ofly important to have that multifunction piezoelectric actuator, ferroelectric and electric light, acousto-optic, non-linear, light are sold off and the crystalline material of the feature such as laser activity, is the artificial lens that a kind of optical property is many, overall target is good.
Be accompanied by the fast development of laser technology, lithium tantalate is widely used at aspects such as electrooptic modulator, second harmonic generator, Q-switch, SAW (Surface Acoustic Wave) filter and integrated opticss.As piezoelectric, its outstanding advantages be time of lag temperature factor low, the Heat stability is good of device, it is the excellent material of making surface acoustic wave colour television set intermediate-frequency filter, be outstanding pyroelectric infrared detector material, can be used for the transmission type sensors of slim small-bore high sensor and monitoring laser energy.
Monocrystalline lithium tantalate uses Czochralski grown, and preparing polycrystal is the requisite preparation work of growing single-crystal.The polycrystal raw material of doping optical level and near-stoichiometric lithium tantalate monocrystalline is prepared multiplex solid state reaction.First after raw material Quilonum Retard (Li2C03), tantalum pentoxide (Ta205) powder and the doping agent (metal oxide solid powder) of growth lithium tantalate evenly being mixed in proportion, carry out sintering.The mol ratio of raw material determines by the crystal type of growing, and as stoichiometric ratio, near stoichiometric proportion or a certain amount of doping can affect the ratio of raw material.Sintering process is divided into two steps, within 3～5 hours, make Quilonum Retard decompose carbonic acid gas (CO2) at 650～700 DEG C of sintering, then be warming up to 1250～1300 DEG C of constant temperature 8～12 hours, make tantalum pentoxide (Ta205) and Lithium Oxide 98min (Li20) fully carry out solid state reaction and generate lithium tantalate, primitive reaction flow process is as follows:
It is inhomogeneous that this reaction process exists hotchpotch to mix, and easily forms cluster; Mixture reaction is abundant not, and product easily produces concentration gradient; The high temperature sintering time is difficult to reasonable control, as shortly in sintering time reacts insufficient, and the long Lithium Oxide 98min of sintering time (Li20) volatilization too much, causes feed composition segregation.The inhomogeneous meeting of polycrystal directly affects crystal mass and even causes crystal cleavage.The common remedial measure of this problem is in the melt process before lithium tantalate growth, locating (approximately 1700 DEG C) constant temperature higher than approximately 50 DEG C of melting temperatures more than 3 hours, even to guarantee fusant reaction, but still easily cause solute segregation, crystal produces growth defect.Although current published terms of settlement product purity is high, evenly, its technical process is very complicated and length consuming time often, consumes energy high, causes manpower and materials consumption, is unsuitable for industrial production in reaction.How to improve technique and solve solid state reaction and prepare the variety of problems of polycrystal, efficient quick prepare lithium tantalate polycrystal, be the long-term difficult problem in crystal industry.
Summary of the invention
One of object of the present invention is the highly energy-consuming problem when overcoming lithium tantalate and preparing.
First provide a kind of urea element in the application of preparing in lithium tantalate.
The quality of described urea element accounts for 20～30% of raw material.
The preparation method that a kind of lithium tantalate is provided according to demand, comprises the following steps
S1. grind urea element, Quilonum Retard, tantalum pentoxide and doping agent (conventional doping agent, mostly is metal oxide solid powder in the art),
S2. dry Quilonum Retard, tantalum pentoxide and doping agent;
S3. the urea element of step 1 gained and Quilonum Retard, tantalum pentoxide and the doping agent of step S2 gained are mixed, wherein urea element accounts for 20～30% of gross weight; The proportioning of Quilonum Retard, tantalum pentoxide and doping agent is to determine according to the producer's demand, is need to produce what crystal formation and just select existing formula.
S4. shake and expect;
S5. the compound of step S4 gained is warming up to 700 DEG C, and maintains 3～5 hours, to obtain final product.
The time of the rolling material described in S4 is 20～30 hours,
The intensification time used described in S5 is 3～4 hours.
Principle of the present invention is: the base-material mixing is in heat-processed, and first urea element decomposes (approximately 120 DEG C), and Quilonum Retard and tantalum pentoxide further mix in liquid urea element.Temperature continues to raise, and urea element decomposes the large calorimetric of release, can instantaneously reach 1200 DEG C, for base-material reaction provides energy.Urea element constantly decomposition discharges a large amount of small molecules simultaneously, as NH
3, H
2o, CO
2, NO
x.Small molecules penetrates in tantalum pentoxide and Quilonum Retard, can significantly reduce the temperature of reaction that generates lithium tantalate.The combined reaction of decomposition caused heat release constantly absorbs, and after having reacted, discharges small molecules, also can take away part heat.In thermostatic process, the lithium tantalate having reacted undergoes phase transition.
CO(NH
2)
2→(CO)
2NH(NH
2)
2+NH
3 (1)
CO(NH
2)
2→C3N
3(OH)
3+NH
3 (2)
Li
2CO
3+Ta
2O
5→LiTaO
3 (3)
The present invention has the following advantages
1. technical process is simple to operate: chemical reaction flow process operation disclosed by the invention is very simple, only has an operation " be warming up to for 3 hours 700 DEG C and constant temperature 3 hours ", all much more simple than existing disclosed preparation method, temperature control flow process, without manual monitoring, has been saved manpower.
2. the reaction times is short: compare published lithium tantalate polycrystal material preparation method, the chemical time of the open method of this patent is the shortest, and whole flow process comprises intensification, constant temperature, cooling three steps only needs 6 hours.Save preparation time and mean and shortened the production cycle, reduce production costs.
3. temperature of reaction is low: the solid phase reaction method of lithium tantalate polycrystalline need be more than 1200 DEG C constant temperature approximately 12 hours, the disclosed method of this patent only need be warming up to 700 DEG C.
4. conserve energy: the disclosed method of this patent, has the reaction times short, the feature that temperature of reaction is low.Than traditional technology, foreshortened to 6 hour from approximately 20 hours total heat-up time, and temperature of reaction is reduced to 700 DEG C from 1250 DEG C.Comprehensive above advantage, the large energy of present method saving, sintering process power consumption is about 1/16 of traditional technology.
5. save chemical reagent: in method of the present invention, except necessary reactant carbonic acid lithium, tantalum pentoxide and hotchpotch, only need the pure urea element of 3 times of raw materials quality.Than published method, without using strong acid, highly basic, without regulating pH, without water-bath, crystallization, the filtrations operation of etc.ing, product is pure and be dryly directly used in that crystal is grown or polycrystalline is studied.
Brief description of the drawings
Fig. 1 is the X ray diffracting spectrum of the lithium tantalate that makes of embodiment 1.
Embodiment
Further describe the present invention below in conjunction with the drawings and specific embodiments.Unless stated otherwise, reagent, equipment and the method that the present invention adopts is the conventional commercial reagent of the art, equipment and the conventional method using.
The preparation of embodiment 1 stoichiometric lithium tantalate crystals
The synthetic method of lithium tantalate of the present invention comprises the following steps:
S1. grind raw material: grind respectively urea element, Quilonum Retard, tantalum pentoxide
S2. drying material; By Quilonum Retard and tantalum pentoxide, be placed in loft drier respectively and fully dry and anhydrate;
S3. Quilonum Retard, the tantalum pentoxide of the urea element of step 1 gained and step S2 gained are mixed, wherein urea element accounts for 75% of gross weight; The mol ratio of Quilonum Retard, tantalum pentoxide and doping agent is 50:50.
S4. batch mixing: will claim to such an extent that raw material mixes in S3, and shake and expect approximately 24 hours;
S5. sintering: even mixture after distant is placed in aluminium sesquioxide boat, is warming up to 800 DEG C from normal temperature, is down to room temperature after constant temperature 3 with stove, to obtain final product.
Prove that by X diffraction the present invention has generated lithium tantalate, result as shown in Figure 1.
The preparation of embodiment 2 congruent lithium tantalates
The synthetic method of lithium tantalate of the present invention comprises the following steps:
S1. grind raw material: grind respectively urea element, Quilonum Retard, tantalum pentoxide;
S2. drying material; Quilonum Retard, tantalum pentoxide and hotchpotch are placed in respectively to loft drier fully dries and anhydrates;
S3. the urea element of step 1 gained and Quilonum Retard, tantalum pentoxide and the doping agent of step S2 gained are mixed, wherein urea element accounts for 75% of gross weight; The mol ratio of Quilonum Retard, tantalum pentoxide is 48.61:51.39.
S4. batch mixing: will claim to such an extent that raw material mixes in S3, and shake and expect approximately 20 hours;
S5. sintering: even mixture after distant is placed in quartz beaker, is warming up to 700 DEG C from normal temperature, is down to room temperature after constant temperature 4 with stove, to obtain final product.
The preparation of embodiment 3 magnesium lithium tantalite doping crystal
The synthetic method of lithium tantalate of the present invention comprises the following steps:
S1. grind raw material: grind respectively urea element, Quilonum Retard, tantalum pentoxide and hotchpotch, described hotchpotch is magnesium oxide;
S2. drying material; Quilonum Retard, tantalum pentoxide and hotchpotch are placed in respectively to loft drier fully dries and anhydrates;
S3. the urea element of step 1 gained and Quilonum Retard, tantalum pentoxide and the doping agent of step S2 gained are mixed, wherein urea element accounts for 20% of gross weight; The mass ratio of Quilonum Retard, tantalum pentoxide and doping agent is 48.13:50.87:1.
S4. batch mixing: will claim to such an extent that raw material mixes in S3, and shake and expect approximately 30 hours;
S5. sintering: even mixture after distant is placed in quartz beaker, is warming up to 700 DEG C from normal temperature, is down to room temperature after constant temperature 3 with stove, to obtain final product.
Claims (5)
1. a urea element is in the application of preparing in lithium tantalate.
2. application according to claim 1, is characterized in that, the quality of described urea element accounts for 20 ~ 30% of raw material gross weight.
3. a preparation method for lithium tantalate, is characterized in that, comprises the following steps
S1. grind urea element, Quilonum Retard, tantalum pentoxide and doping agent;
S2. dry Quilonum Retard, tantalum pentoxide and doping agent;
S3. the urea element of S1 gained and Quilonum Retard, tantalum pentoxide and the doping agent of S2 gained are mixed, wherein urea element accounts for 20 ~ 30% of gross weight;
S4. shake and expect;
S5. the compound of S4 gained is warming up to 700 DEG C ~ 800 DEG C, and maintains 3 ~ 5 hours, to obtain final product.
4. preparation method according to claim 3, is characterized in that, the time of the rolling material described in S4 is 20 ~ 30 hours.
5. preparation method according to claim 3, is characterized in that, the intensification time used described in S5 is 3 ~ 4 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410312827.6A CN104163454B (en) | 2014-09-01 | 2014-09-01 | A kind of preparation method of lithium tantalate |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410312827.6A CN104163454B (en) | 2014-09-01 | 2014-09-01 | A kind of preparation method of lithium tantalate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104163454A true CN104163454A (en) | 2014-11-26 |
| CN104163454B CN104163454B (en) | 2016-01-20 |
Family
ID=51907463
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|---|---|---|---|
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Country Status (1)
| Country | Link |
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| CN (1) | CN104163454B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110241456A (en) * | 2019-07-11 | 2019-09-17 | 北方民族大学 | The method that flux method grows uniform near-stoichiometric lithium tantalate crystals |
| CN113716533A (en) * | 2021-08-04 | 2021-11-30 | 杭州赛聚科技有限公司 | Preparation method of intelligent material |
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|---|---|---|---|---|
| CN1754014A (en) * | 2003-03-06 | 2006-03-29 | 信越化学工业株式会社 | Process for producing lithium tantalate crystal |
| CN103787415A (en) * | 2014-01-23 | 2014-05-14 | 上海海事大学 | Method for preparing lithium tantalate nano-powder by adopting solvothermal method |
| CN103833079A (en) * | 2014-02-14 | 2014-06-04 | 上海海事大学 | Method for preparation of lithium tantalate nano-powder by hydrothermal process |
-
2014
- 2014-09-01 CN CN201410312827.6A patent/CN104163454B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1754014A (en) * | 2003-03-06 | 2006-03-29 | 信越化学工业株式会社 | Process for producing lithium tantalate crystal |
| CN103787415A (en) * | 2014-01-23 | 2014-05-14 | 上海海事大学 | Method for preparing lithium tantalate nano-powder by adopting solvothermal method |
| CN103833079A (en) * | 2014-02-14 | 2014-06-04 | 上海海事大学 | Method for preparation of lithium tantalate nano-powder by hydrothermal process |
Non-Patent Citations (2)
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110241456A (en) * | 2019-07-11 | 2019-09-17 | 北方民族大学 | The method that flux method grows uniform near-stoichiometric lithium tantalate crystals |
| CN113716533A (en) * | 2021-08-04 | 2021-11-30 | 杭州赛聚科技有限公司 | Preparation method of intelligent material |
| CN113716533B (en) * | 2021-08-04 | 2022-11-18 | 杭州赛聚科技有限公司 | Preparation method of intelligent material |
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| CN104163454B (en) | 2016-01-20 |
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