CN1473794A - Process for preparing nano level high purity zirconium-titanium-barium-calcium poweder - Google Patents
Process for preparing nano level high purity zirconium-titanium-barium-calcium poweder Download PDFInfo
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- CN1473794A CN1473794A CNA031387446A CN03138744A CN1473794A CN 1473794 A CN1473794 A CN 1473794A CN A031387446 A CNA031387446 A CN A031387446A CN 03138744 A CN03138744 A CN 03138744A CN 1473794 A CN1473794 A CN 1473794A
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Abstract
The industrial routing of preparing nano level high purity Zr-Ti-Ba-Ca powder includes: preparing deionized water, compounding solution of titanic acid gel in pH 7-8, synthesizing solution with molar ratio of (Ba+Ca)/(Ti+Zr) higher than 1.1, washing prepared Zr-Ti-Ba-Ca powder, regulating molar precipitation among Zr, Ti, Ba and Ca, drying, grading and packing. Compared with available technology, the present invention has low material cost, simple technological process and high product performance.
Description
One. technical field: the present invention relates to a kind of preparation method of dielectric material titanate, specifically relate to a kind of preparation technology who is applied to dielectric substance hydro-thermal powder zirconium-titanium-barium-calciums such as electronic devices and components.
Two. background technology: zirconium-titanium-barium-calcium has higher dielectric constant, simultaneously because the controllability of barium and calcium, zirconium and titanium elements mol ratio makes the range of application of zirconium-titanium-barium-calcium wider.At present, still not about zirconium-titanium-barium-calcium preparation method's Invention Announce, the report of scientific and technological naturally magazine aspect does not almost have yet.The method that world industryization prepares zirconium-titanium-barium-calcium mainly contains solid phase method and add two kinds of technologies of calcium constituent in zirconium barium titanate.Solid phase method technology is to carry out high temperature sintering after titanium dioxide, carbonate (barium carbonate, lime carbonate) and zirconium white are mixed, because the zirconium-titanium-barium-calcium size-grade distribution of calcination is wayward, even the crystalline network the inside that elements such as the barium that has, calcium, titanium, zirconium can not enter into zirconium-titanium-barium-calcium goes, and causes highly purified zirconium-titanium-barium-calcium not make by this type of mode; Another kind method is to carry out calcination with add calcareous compound element in the zirconium barium titanate that makes, though this kind method is simple to operate, but because the calcium constituent that adds is difficult to be completed into the crystalline network of zirconium-titanium-barium-calcium, thereby form a large amount of free ca elements, have a strong impact on the performance and the use range of zirconium-titanium-barium-calcium product.Hydrothermal technique is state-of-the-art in the world at present powder production technology, compare with other technology, the electronic ceramics powder of hydrothermal method prepared have crystal grain grow complete, granularity is little and be evenly distributed, stoichiometry thing and crystal grain that particle agglomeration is light, can use comparatively cheap material, be easy to get suitable can be by changing the advantages such as particle properties of technological process control product.
Three. summary of the invention: the objective of the invention is to avoid solid phase method, direct a kind of technology for preparing the high-purity zirconium-titanium-barium-calcium powder of nano level of in zirconium barium titanate, adding the different shortcomings of technologies such as calcium constituent and providing.
Industrialized producing technology route provided by the invention is: preparation pure water (deionized water), and obtain solution, resulting solution, the zirconium-titanium-barium-calcium of washing preparation, the element mol ratio of adjustment barium, calcium, zirconium and titanium, the zirconium-titanium-barium-calcium that drying is prepared carries out classification, packing.
Concrete scheme is:
1. obtain solution: with the desired titanic acid gel of pure water preparation stoichiometric equation of preparation, the preparation technology of titanic acid gel joins 20-30% ammoniacal liquor to prepare in the qualified titanium tetrachloride solution to go, preparation to titanium tetrachloride solution: the percentage concentration of dichloro oxygen titanium, hydrochloric acid need be controlled at about 30%-40% and 20%, mix, make it complete reaction and generate apart from the metatitanic acid gel; Join the ammoniacal liquor that configures in the titanium tetrachloride solution for preparing with certain speed, but need prevent that the titanic acid gel for preparing from making component hydrolysis variation because of long ageing, be unfavorable for forming the positive preferably metatitanic acid network structure of quality, the pH value that reaction generates titanic acid gel afterreaction liquid should remain on 7-8, after residual chlorine ion in the titanic acid gel is washed till standard-required, must fast positive metatitanic acid be positioned in the reaction vessel.
2. resulting solution: accurate measurement barium source, zirconium source, calcium source, preferred barium source is that barium hydroxide, zirconium source are that eight water zirconium oxychlorides, calcium source are Calcium Chloride Powder Anhydrous; Then zirconium source, barium source, calcium source mixing solutions are used respectively in the pump suction reaction vessel, wherein when preparation titanic acid gel, barium source, zirconium source, calcium source mixing solutions, note the adding order and the churning time of several solns, its best solution addition sequence and churning time is: earlier the barium source is added in the gel of positive metatitanic acid, stirred 45 minutes, add the zirconium source again and stirred 30 minutes, add the calcium source at last, stirred 30 minutes; Titanic acid gel and barium source such as barium hydroxide, zirconium source are that Calcium Chloride Powder Anhydrous is when mixing as eight water zirconium oxychlorides, calcium source, at a certain temperature, water behind the titanic acid gel can be used as the dielectric object of hydro-thermal reaction, therefore, do not need the above-mentioned mixed solution of dilute with water, avoid reducing basicity, (Ba+Ca)/(Ti+Zr) mol ratio in the mixture can not be lower than 1.1, be preferably 1.1, Ti and Zr, Ba and Ca element mol ratio will meet the ratio of stoichiometric equation.PH value in this reaction solution should remain on more than 14, is preferably 14, to guarantee that zirconium-titanium-barium-calcium reacts under enough basicity, the particle diameter of zirconium-titanium-barium-calcium can be controlled between the 50-500 nanometer, and the particle size range that is easy to get most is the 100-200 nanometer; Simultaneously, guarantee that reacted basicity pH value can not be lower than 9.In the process of synthetic zirconium-titanium-barium-calcium, in order to ensure zirconium-titanium-barium-calcium crystalline nucleation rate and quality, temperature rise rate with 1.5 ℃-2 ℃ of per minutes, be preferably 1.8 ℃ of per minutes temperature of reaction is risen to 250 ℃-300 ℃ of best synthesis temperatures, the hold-time of temperature is 10-15 hour, and pressure risen to 6-9Mpa, the measure that rises to best pressure can use the method that charges into nitrogen or rare gas element to pressurize.But should be noted that all multifactor influences such as the nucleation rate of zirconium-titanium-barium-calcium and concentration that quality is subjected to solution, temperature, pressure, but these parameters change because of the variation of concrete device parameter.
3. wash the zirconium-titanium-barium-calcium of preparation: will synthesize and wash after the zirconium-titanium-barium-calcium suspension liquid that finishes is put into special container cooling; because the hydrated barta of abundant residues is still arranged in the suspension liquid; if touch carbon dioxide in air; reaction at once generates barium carbonate; the quality of zirconium-titanium-barium-calcium will greatly be influenced; in order to prevent the generation of the accident, must carry out the sfgd. that certain anti-Carbon Dioxide in Air contacts solution to the washing of zirconium-titanium-barium-calcium, as measures such as container sealing, gas shields.
4. adjustment barium, calcium, the mol ratio of zirconium and titanium elements: the zirconium-titanium-barium-calcium of the qualified no trash matter of washing that takes a morsel, use x-ray fluorescence analyzer that the element ratio is analyzed, purpose is to detect requirement that whether (Ba+Ca)/(Ti+Zr) mol ratio meet stoichiometric equation (generally, (Ba+Ca)/(Ti+Zr) element mol ratio is between 0.998-1.002), if element mol ratio (Ba+Ca)/(Ti+Zr) is lower than the requirement that the desired numerical value of stoichiometric equation maybe can not reach dielectric material, need regulate the element ratio, measure is various, can add and contain Ba, Zr, the high pure compound of Ca and Ti, institute adds Ba, Ca, the high pure compound of Zr and Ti element is a standard with dielectric material character and the application performance that does not influence electronic devices and components etc., but the adjusting of this element mol ratio is only applicable to the little situation of element mol ratio deviation of (Ba+Ca)/(Ti+Zr).Through the zirconium-titanium-barium-calcium that the element mol ratio is regulated, the performance of its product will be subjected to influence in various degree.
5. dry zirconium-titanium-barium-calcium: the suspension liquid of qualified zirconium-titanium-barium-calcium is carried out drying with drying plant, and the high pure and ultra-fine zirconium-titanium-barium-calcium powder that is obtained promptly can be used for the dielectric material of electrical condenser, other electronic devices and components etc.
Technology of the present invention is compared with other technology, and the final stoichiometry thing and the crystal grain that can use the initial material of comparatively cheap reactant, are easy to get suitable can be by changing the advantages such as particle properties of technological process control product; Prepared zirconium-titanium-barium-calcium electronic ceramics powder have crystal grain grow complete, granularity is little and be evenly distributed, particle agglomeration is lighter, especially the zirconium-titanium-barium-calcium electronic ceramics powder of this prepared does not need high-temperature calcination to handle, crystal grain-growth, the defective having avoided causing in the calcination process form and the impurity introducing, therefore, prepared powder has higher activity.
Four, description of drawings:
Figure 1A: Ba
0.97Ca
0.0.03Ti
0.8Zr
0.2O
3The zirconium-titanium-barium-calcium crystallogram;
Figure 1B: Ba
0.9Ca
0.1Ti
0.88Zr
0.12O
3The zirconium-titanium-barium-calcium crystallogram;
Fig. 2 A:Ba
0.9Ca
0.1Ti
0.88Zr
0.12O
3Zirconium-titanium-barium-calcium transmission electron microscope (TEM) figure;
Fig. 2 B:Ba
0.9Ca
0.1Ti
0.88Zr
0.12O
3Zirconium-titanium-barium-calcium transmission electron microscope (TEM) figure.
Five. embodiment:
Preparation method embodiment of the present invention is respectively described below:
Embodiment 1, with preparation Ba
0.97Ca
0.0.03Ti
0.8Zr
0.2O
3Be example, measure 1.26 liters of 3.81M titanium tetrachloride solutions and 2.46 liters of 12.30M ammonia solns react with graduated cylinder, and qualified gel is positioned in the autoclave of good seal will to react after scouring, dash with nitrogen and to sweep, environment is sealed, start agitator arm (100 rev/mins), solution stirring is even, stop to stir; Add the accurate weighing of the electronic scales eight water zirconium oxychlorides of 0.41Kg accurately then, 2.06Kg barium hydroxide, 0.023Kg Calcium Chloride Powder Anhydrous (order that reactant adds and the time of stirring are respectively: earlier the barium source is added in the gel of positive metatitanic acid, stirred 45 minutes, add the zirconium source again and stirred 30 minutes, add the calcium source at last, stirred 30 minutes), dash with nitrogen and to sweep, startup agitator arm (150 rev/mins) reacts solution and (is warming up to 120 ℃ under mechanical stirring, stop to stir), environment is sealed, be warming up to end reaction temperature (270 ℃) with 1.8 ℃/minute speed, insulation is 12 hours under 7Mpa; Suspension liquid with zirconium-titanium-barium-calcium is cooled to room temperature then, wash and in having the container of seal approach, deposit with pure water, when the solution chlorion after the flushing was lower than 10ppm, right element mol ratio was adjusted to wash qualified elder generation, adjusted and can carry out drying after qualified.
Embodiment 2, with preparation Ba
0.9Ca
0.1Ti
0.88Zr
0.12O
3Be example, measuring the titanium tetrachloride solution of 1.38 liters of 3.83M and 2.60 liters of 12.15M ammonia solns with graduated cylinder reacts and they is positioned in the autoclave of good seal, dash with nitrogen and to sweep, environment is sealed, start agitator arm (100 rev/mins), solution stirring is even, stop to stir; Add the accurate weighing of the electronic scales anhydrous zirconium oxychloride of 0.24Kg accurately then, 2.07Kg barium hydroxide, 0.076Kg Calcium Chloride Powder Anhydrous (order that reactant adds and the time of stirring are respectively: earlier the barium source is added in the gel of positive metatitanic acid, stirred 45 minutes, add the zirconium source again and stirred 30 minutes, add the calcium source at last, stirred 30 minutes), dash with nitrogen and to sweep, startup agitator arm (150 rev/mins) reacts solution and (is warming up to 120 ℃ under mechanical stirring, stop to stir), environment is sealed, be warming up to end reaction temperature (270 ℃) with 1.8 ℃/minute speed, be incubated 12 hours; Suspension liquid with zirconium-titanium-barium-calcium is cooled to room temperature then, wash and in having the container of seal approach, deposit with pure water, when the solution chlorion after the flushing was lower than 10ppm, right element mol ratio was adjusted to wash qualified elder generation, adjusted and can carry out drying after qualified.
The zirconium-titanium-barium-calcium sample that is used for X-ray diffraction (XRD) analyte preparation, need zirconium-titanium-barium-calcium powder is positioned on the clean unformed silicon oxide slide, be positioned over temperature then and be set in 100 ℃ the vacuum drying oven 1 hour, oven dry moisture content can make the powder of zirconium-titanium-barium-calcium.This powder is positioned over temperature is set in groom's stove of 1100 ℃, heat up rapidly and 1100 ℃ of insulation coolings after 1 hour down.Adopt Holland to fly sharp Pu x ' pert-MPD powder diffractometer and automatic diffraction software the phase purity XRD of this calcining back powder, under 20 ~ 60 degree, 2 θ, carry out.
With transmission electron microscope (TEM) analytical sample, can be dispersed in 20 milliliters the acetone by zirconium-titanium-barium-calcium powder and carry out detecting after the sonication about 0.04 gram vacuum-drying.
The mensuration of specific surface area can be measured by the absorption instrument BET technology of routine, and the model of absorption instrument is ASAP2010, and the specific surface area of affirmation is based on the linear regression analysis of 5 point analysiss.
Shown in Figure 1A, Figure 1B, demonstration be Ba
0.9Ca
0.1Ti
0.88Zr
0.12O
3Zirconium-titanium-barium-calcium and Ba
0.9Ca
0.1Ti
0.88Zr
0.12O
3Zirconium-titanium-barium-calcium crystallogram situation.
Fig. 2 A:Ba
0.9Ca
0.1Ti
0.88Zr
0.12O
3The electromicroscopic photograph of zirconium-titanium-barium-calcium shows different spherical polycrystalline particles and approximate single size distributes, and the particle diameter of this powder is about the 150-250 nanometer, and the range estimation particle diameter on average is approximately about 200 nanometers.
Fig. 2 B:Ba
0.9Ca
0.1Ti
0.88Zr
0.12O
3The electromicroscopic photograph of zirconium-titanium-barium-calcium shows different spherical polycrystalline particles and approximate single size distributes, and the particle diameter of this powder is about the 150-250 nanometer, and the range estimation particle diameter on average is approximately about 200 nanometers.
The specific surface area of embodiment 1 powder is 6.7 meters squared per gram, and corresponding particle size (supposition is desirable spherical) is 192 nanometers, so it is consistent with range estimation target by TEM.
The specific surface area of embodiment 2 powders is 6.8 meters squared per gram, and corresponding particle size (supposition is desirable spherical) is 189 nanometers, so it is consistent with range estimation target by TEM.
Therefore this embodiment 1,2 shows in the hydro-thermal technology of the present invention, thereby titanic acid gel, barium source, zirconium source, the mixing of calcium source are formed a kind of hydro-thermal reaction mixture and can prepare zirconium-titanium-barium-calcium under certain environment.
Though present embodiment has only illustrated Ba
0.97Ca
0.03Ti
0.8Zr
0.2O
3, Ba
0.9Ca
0.1Ti
0.88Zr
0.12O
3The preparation method of two kinds of zirconium-titanium-barium-calciums.But utilize the zirconium-titanium-barium-calcium of other different zirconium titanium elements ratios that technical scheme of the present invention can prepare equally.
Claims (6)
1, a kind of technology for preparing the high-purity zirconium-titanium-barium-calcium powder of nano level, it comprises: preparation pure water, obtain solution, resulting solution, the zirconium-titanium-barium-calcium of washing preparation, the element mol ratio of adjustment barium, calcium, zirconium and titanium, the zirconium-titanium-barium-calcium of dry preparation, classification, packing is characterized in that:
(1) obtain solution: with the desired titanic acid gel of pure water preparation stoichiometric equation of preparation, the preparation technology of titanic acid gel is to be that the ammoniacal liquor of 20-30% joins to prepare in the qualified titanium tetrachloride solution and goes with concentration range, mix, making it the gel that complete reaction generates positive metatitanic acid, is that percentage concentration with dichloro oxygen titanium, hydrochloric acid is controlled at about 30%-40% and 20% to the preparation of titanium tetrachloride solution;
(2) resulting solution: in reactor, will join in the titanic acid gel through barium source, zirconium source and the calcium source of metering and go, but will be in accordance with the addition sequence of reactant; Preferred barium source is a barium hydroxide, the zirconium source is eight water zirconium oxychlorides, the calcium source is a Calcium Chloride Powder Anhydrous, form the mixture of reaction, (Ba+Ca)/(Ti+Zr) mol ratio in the mixture can not be lower than 1.1, Ti, Zr and Ba, element mol ratio between the Ca element will meet the ratio of stoichiometric equation, pH value in the solution should remain on more than 14, the particle diameter of zirconium-titanium-barium-calcium is controlled between the 50-500 nanometer, reacted basicity pH value can not be lower than 9, in the process of synthetic zirconium-titanium-barium-calcium, temperature rise rate with 1.5 ℃-2.0 ℃ of per minutes, temperature of reaction is risen to 250 ℃-300 ℃ of best synthesis temperatures, temperature hold-time is 10-15 hour, and pressure is controlled at 6-9Mpa;
(3) zirconium-titanium-barium-calcium of washing preparation: after will synthesizing the zirconium-titanium-barium-calcium suspension liquid that finishes and putting into special container and be cooled to room temperature, wash, will take to prevent the sfgd. of Carbon Dioxide in Air contact in the water washing process with pure water;
(4) the element mol ratio of adjustment barium, calcium, zirconium and titanium: the zirconium-titanium-barium-calcium of the qualified no trash matter of washing that takes a morsel, use x-ray fluorescence analyzer that the element mol ratio is analyzed, utilize related process that the element ratio of (Ba+Ca)/(Ti+Zr) is adjusted between the 0.998-1.002.
2. the technology of the high-purity zirconium-titanium-barium-calcium powder of preparation nano level according to claim 1 is characterized in that: in the process of obtain solution, the preferred concentration of ammoniacal liquor is 28%; Best solution addition sequence is: earlier the barium source is added in the gel of positive metatitanic acid, add the zirconium source again, add the calcium source at last; In the process of resulting solution, optimum temperature rise speed is 1.8 ℃ of per minutes, 270 ℃ of best constant temperature temperature of reaction, and the best constant temperature and pressure are by force 7Mpa, the best constant fixed temperature hold-time is 12 hours.
3. the technology of the high-purity zirconium-titanium-barium-calcium powder of preparation nano level according to claim 1, it is characterized in that: the titanium source comprises high-purity barium salts such as barium hydroxide, barium chloride, the zirconium source comprises eight water zirconium oxychlorides, the zirconium hydroxide under the different states, and the calcium source is a Calcium Chloride Powder Anhydrous.
4. the technology of the high-purity zirconium-titanium-barium-calcium powder of preparation nano level according to claim 1, it is characterized in that: have adjustable between barium and calcium, zirconium and the titanium elements, the element mol ratio of Ti/ (Ti+Zr) is about 0 ~ 1.000, and the element mol ratio of Ba/ (Ba+Ca) is about 0 ~ 1.000.
5. the technology of the high-purity zirconium-titanium-barium-calcium powder of preparation nano level according to claim 1 is characterized in that the element mol ratio of (Ba+Ca)/(Ti+Zr) is adjusted, and preferably uses the compound of high-purity Ba of containing, Ca, Zr and Ti.
6. the technology of the high-purity zirconium-titanium-barium-calcium powder of preparation nano level according to claim 1, it is characterized in that: the zirconium-titanium-barium-calcium particle grain size is less than 300 nanometers.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102515753A (en) * | 2011-12-05 | 2012-06-27 | 天津师范大学 | Method for preparing zirconium barium calcium titanate lead-free piezoelectric ceramic with high piezoelectric coefficient |
| CN113702411A (en) * | 2021-09-16 | 2021-11-26 | 福建贝思科电子材料股份有限公司 | Method for measuring molar ratio of calcium to zirconium in calcium zirconate |
-
2003
- 2003-06-30 CN CN 03138744 patent/CN1222490C/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102515753A (en) * | 2011-12-05 | 2012-06-27 | 天津师范大学 | Method for preparing zirconium barium calcium titanate lead-free piezoelectric ceramic with high piezoelectric coefficient |
| CN113702411A (en) * | 2021-09-16 | 2021-11-26 | 福建贝思科电子材料股份有限公司 | Method for measuring molar ratio of calcium to zirconium in calcium zirconate |
| CN113702411B (en) * | 2021-09-16 | 2022-12-16 | 福建贝思科电子材料股份有限公司 | Method for determining molar ratio of calcium to zirconium in calcium zirconate |
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