CN1088147A - Method for preparing thermal-reaction electronic ceramic micropowder in liquid phase - Google Patents
Method for preparing thermal-reaction electronic ceramic micropowder in liquid phase Download PDFInfo
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- CN1088147A CN1088147A CN 92108647 CN92108647A CN1088147A CN 1088147 A CN1088147 A CN 1088147A CN 92108647 CN92108647 CN 92108647 CN 92108647 A CN92108647 A CN 92108647A CN 1088147 A CN1088147 A CN 1088147A
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Abstract
A kind of liquid phase parcel-thermal-reaction electronic ceramic micro mist preparation method, adopt a part of component to be prepared into the aqueous solution, use drying process with atomizing then, make on the surface of its solid phase midbody particle that is wrapping to another part component equably, make various multi-component electronic ceramics micro mists through thermal response again.This powder has high coking property, chemical uniformity is good, and particle size is trickle, homogeneous, and shape is like sphere and be in good characteristics such as dispersion state.Do not need expensive equipment and raw material, be convenient to suitability for industrialized production.Solved in the electronic ceramics micro mist chemical preparation, the indissoluble component is difficult to be prepared into solution or strength of solution is low, preparation cost is high and problem such as powder characteristic difference.Be used for the preparation of silver-colored partially hydrochlorate, niobate, titanate, zirconium titanate and PTC ceramic powder.
Description
That the present invention relates to is the ceramic powder preparation method, particularly relates to electronic ceramics, as lead meta-columbute PbNb
2O
6(PN), O lead magnoniobate Pb(Mg1/3Nb2/3)
3(PMN), barium titanate BaTiO
3(BT) and Pb-based lanthanumdoped zirconate titanates system's stupalith powder preparing methods such as (PZT).
Electronic ceramics is that a class is used the important widely stupalith of the utmost point, and in the world, the share that the output value of electron ceramic material is occupied in the ceramic gross output value is up to more than 70%.Along with developing rapidly and the continuous expansion of industrialized scale of science and technology, all quality and the quantity to the electron ceramic material powder proposes higher requirement.Powder is the basis of stupalith, is the fundamental factor of decision stupalith quality, also is to promote new material industryization and improve one of important factor of industrial economy benefit.Current basic demand to the electron ceramic material powder is:
(1) high chemical uniformity and higher degree;
(2) has single particle size;
(3) granule-morphology is sphere or torispherical;
(4) cost is lower.
The preparation method commonly used of electronic ceramics powder has traditional solid phase method, liquid phase method, chemical preparation method (as coprecipitation method), vapor phase process and sol-gel method etc. at present.But these methods still can not satisfy the growing requirement of research, production and application of electron ceramic material fully.
Though traditional solid phase method is for a long time in the research of stupalith, be employed in producing, and the low advantage of cost is arranged.But, limited the development of electron ceramic material more and more significantly because chemical constitution lack of homogeneity, particle size are big and shortcoming such as wider distribution.Coprecipitation method reaches its maturity, and in scale production, be used, but coprecipitation method has a fatal shortcoming, that is,, caused precipitation to have successively because each is formed sedimentary solubility product and differs bigger, make many components stupalith (most electron ceramic materials belong to the form more) powder that makes be not easy to obtain the ideal chemical uniformity, therefore, this method only is applicable to the stupalith powder of preparation single-component or two components, as Al
2O
3, ZrO
2Or contain the stable ZrO of yttrium
2, and BaTiO
3, SrTiO
3Deng, can make that the chemical group poling is even, particle size is little and single, good dispersity and shape such as globular powder with vapor phase process and sol-gel method, but these methods needing expensive specific installation and raw materials, cost is very high, so be difficult to industrialization.Still be in the laboratory applications stage at present.[Adv Powder Technol，Pap ASM Mater Sci Semin.1981（Pub.1928），23-27，Jpn J.Appl Phys，Part 1 1987，26（suppl.26-2），145-8 Adv Ceram Mater 1988，315），485-90].
The object of the present invention is to provide a kind of employing liquid phase parcel-thermal-reaction electronic ceramic micropowder preparing process,, reach in order to solve the defective of existing technology of preparing:
(1) simplify micro mist preparation technology, be convenient to produce in enormous quantities;
(2) some are difficult to be prepared into the difficulty that component caused of solution in the solution chemical preparation;
(3) reduce cost;
(4) improve powder chemical constitution homogeneity.
Main technical schemes of the present invention is as follows:
1. the selection of solid phase matrix is with definite:
For some be difficult to be prepared into solution component (as niobium), be difficult to be prepared into component (as titanium and zirconium) of the little and solution that toxic is little of corrodibility etc., then select the intermediate (as Nb(OH) of their oxyhydroxide not soluble in water (or hydrate) and salt for use
5, Zr(OH)
4, metatitanic acid etc.) as the solid phase matrix.
2. the preparation of parcel liquid phase:
The component of being convenient to be prepared into solution during electron ceramic material formed is determined it as liquid phase part, and it is prepared into more stable Citrate trianion, acetate or formate and nitrate aqueous solution; It is deionized water that used raw material all requires to analyze pure water, and the solution after the preparation is measured in its concentration and the plastic tank of packing into standby respectively after filtering.Citrate trianion series strength of solution is that 25-200mg/ml(calculates with metal oxide, and is as follows), the serial strength of solution of acetate (or formate) is that 20-200mg/ml, nitrate series strength of solution are 10-300mg/ml.
3. liquid phase technique for packing: in advance each soluble salt is mixed with the aqueous solution separately, analyze in its concentration (mg/ml) and the plastic tank of packing into standby after filtering, the requirement of forming by dosage and batching then, according to the purity of solid phase matrix and the concentration of each solution, calculate the consumption (g) and the required volume (ml) of each solution of solid phase matrix.Weigh up the weight of required solid phase matrix earlier, place in the corresponding Glass Containers, measure the required volume of each solution subsequently more one by one, and under continuous condition of stirring, each solution is poured into one by one, after stirring, through piezoelectric supersonic dispersion treatment 4-8 hour, can carry out spraying drying, make the presoma of electronic ceramics powder.
4. thermal rection condition:
Thermal response is carried out in air, and heat-up rate is 60-150 ℃/hr; Temperature of reaction is 300-1050 ℃, and soaking time is 2-6 hour, and rate of temperature fall is 40-120 ℃/hr.
Effect of the present invention is as follows:
1. chemical constitution is convenient to accurate control.Owing to adopted spraying drying, each component is difficult for running off, and is convenient to control so form; Precision then is decided by the precision of chemico-analytic precision and weighing and cubic measure.The deviation of general chemical constitution can be controlled in the 0.015ml, and good reproducibility.
2. the chemical uniformity of powder is good:
Because chemically reactive of respectively forming in thermal process reactor is high, reaction can be carried out relatively fully with complete, so chemical uniformity is good, the sign amount is≤8 * 10
-4And solid phase method powder chemical uniformity sign amount is 〉=1.6 * 10 (g),
-2(g).
3. the thermal response temperature is low:
The thermal response temperature reduces 100-300 ℃ than solid phase method.
4. powder sintering is good:
Can reduce sintering temperature 100-200 ℃, and improve the volume density of porcelain base.
5. less, even, the good dispersity of powder granule size, particle shape is bordering on sphere.
6. technology is easy flexibly, and adaptability is strong, be convenient to apply on industrial production, and cost is lower.
The present invention is realized by following examples:
Embodiment 1: preparation PMN system ferroelectric ceramic material powder 100 grams
With PbO, MgCO
3Be starting raw material, use citric acid, formic acid, deionized water, ammoniacal liquor etc. respectively with PbO, MgCO
3Molten Jie filters, and is prepared into the aqueous solution.With each strength of solution of chemical titration, PbO content is 112.45mg/ml in the lead citrate solution again, and MgO content is 23.88mg/ml in the magnesium formiate solution.Take by weighing 31.88 gram Nb(OH)
5Raw material, put into the 1000ml beaker, add 200ml deionized water and an amount of dispersion agent, disperseed 2 hours through piezoelectric supersonic, the lead citrate solution and the 190.5ml magnesium formiate solution mechanically mixing that move into 611.5ml again stirred 0.5 hour, disperseed 1 hour through piezoelectric supersonic again, and (condition is last spraying drying: spray velocity: 30ml/min, air flow quantity: the 450l/min drying temperature advances 150 ℃, goes out 100 ℃; Blower fan aperture 75%) after, promptly gets the presoma of PMN ceramic powder.Presoma is contained in the pure alumina crucible, sends to and carries out thermal response in the electric furnace.Thermal response is carried out in air, and heat-up rate is 100-120 ℃/hr, and temperature of reaction is 700 ℃, is incubated 2 hours, and rate of temperature fall is 100 ℃/hr, gained PMN powder D
50=0.51 μ m(settling process, as follows); D
S=0.17 μ m(BET specific surface method, as follows).The chemical constitution good uniformity, its sign amount is 4.5 * 10
-4Gram, the deviation of chemical constitution is less than 0.015ml.The χ ray structure analysis is the result show, no pyrrhite phase in the powder.
Embodiment 2: preparation PMN system ferroelectric ceramic material powder 100 grams
The preparation of presoma is with embodiment 1, the gained presoma is contained in carries out thermal response in the pure alumina crucible, and its temperature changes 550 ℃ into, is incubated 3 hours, and all the other are with embodiment 1.Gained PMN powder D
50=0.36 μ m, D
S=0.13 μ m.The χ ray structure analysis is the result show, exists pyrrhite phase and free lead and niobium in the powder.
Embodiment 3: preparation PMN system ferroelectric ceramic material powder 100 grams
The preparation of presoma is with embodiment 1, and the thermal response temperature changes 800 ℃ into, is incubated 4 hours, and all the other are with embodiment 1, gained PMN powder D
50=0.69 μ m, D
S=0.3 μ m.The χ ray structure analysis is the result show, no pyrrhite exists with other impurity mutually.
Embodiment 4: preparation PN system high-temperature piezoelectric stupalith powder 100 grams
With lead nitrate, nitrate of baryta is starting raw material, they are molten in deionized water, be prepared into lead nitrate and barium nitrate aqueous solution, filter the concentration of back with chemical titration solution, the content of PbO is 213.23mg/ml in the lead nitrate solution, and BaO content is 15.08mg/ml in the nitrate of baryta solution.Take by weighing 71.28 gram Nb(OH)
5Raw material, put into the beaker of 1000ml, add 300ml deionized water and an amount of dispersion agent,, move into 201.38ml lead nitrate solution and 147.21ml nitrate of baryta solution again through piezoelectric supersonic dispersion treatment 2 hours, mechanically mixing stirred 0.5 hour, used the piezoelectric supersonic dispersion treatment again 1 hour, spraying drying then, condition is: spray velocity 45ml/min, air flow quantity 500l/min drying temperature advances 150 ℃, goes out 100 ℃; Blower fan aperture 80% promptly gets the presoma of PN ceramic powder.Thermal response is carried out in oxygen-rich air, and dress crucible and shove charge situation are with embodiment 1, and temperature rise rate is 100-120 ℃/hr, and temperature of reaction is 700 ℃, is incubated 1 hour, and rate of temperature fall is 100 ℃/hr, gained powder D
50=0.55 μ m D
S=0.21 μ m.The chemical constitution good uniformity, its sign amount is 8 * 10
-4Gram, the component deviation is less than 0.015mg.The χ ray structure analysis is the result show, the thing that exists in the powder is three parts-PbNb mutually
2O
6With quadrature-PbNb
2O
6, and do not have free PbO and Nb
2O
5Exist.
Embodiment 5: preparation PN system high-temperature piezoelectric stupalith powder 100 grams
The presoma preparation is contained in the presoma that is obtained in the pure alumina crucible with embodiment 4, sends into electric furnace and carries out thermal response.The thermal response temperature changes 500 ℃ into.The χ ray structure analysis result of gained powder shows and remains in the powder at free PbO and Nb
2O
5
Embodiment 6: preparation PN system high-temperature piezoelectric stupalith powder 100 grams
The preparation of presoma is with embodiment 4, and the thermal response temperature of presoma changes 800 ℃ into, and all the other are with embodiment 4.The χ ray structure analysis is the result show, do not had free PbO and Nb
2O
5Dephasign exists.The D of powder
50=0.75 μ m, D
S=0.34 μ m.The chemical constitution good uniformity, the deviation value of chemical constitution is less than 0.015mg.Its sign amount is 6.7 * 10
-4Gram.
Embodiment 7: preparation BaTiO
3System's stupalith powder 100 grams
With BaCO
3Be starting raw material, it dissolved, be prepared into the barium formate aqueous solution, filter back its strength of solution of chemical titration with formic acid, deionized water.BaO content is 74.10mg/ml in its solution.Take by weighing 45.61 gram metatitanic acid raw materials, put into the 1000ml beaker, add 200ml deionized water and an amount of dispersion agent, after 2 hours, move into 887.18ml barium formate solution through the piezoelectric supersonic dispersion treatment, mechanically mixing stirred 0.5 hour, again through piezoelectric supersonic dispersion treatment 1 hour, spraying drying then, condition is: spray velocity: 50ml/min, air flow quantity: 500l/min; Drying temperature advances 150 ℃, goes out 100 ℃, vacuum fan aperture 90%.Promptly get BT system ceramic powder presoma.Carry out thermal response with embodiment 1, temperature changes 1000 ℃ into, is incubated 3 hours, and rate of temperature fall is 60-100 ℃/hr, gained powder D
50=0.61 μ m, D
S=0.38 μ m.The good uniformity of powder chemical constitution, its sign amount is 6 * 10
-4Gram, the chemical constitution deviation value is within the 0.00mol.χ ray structure analysis result shows that no educt exists.
Embodiment 8: preparation BT series ceramic material powder 100 grams
The preparation of presoma is with embodiment 7, and the thermal response temperature changes 1050 ℃ into, and all the other are with embodiment 7.Gained powder D
50=0.67 μ m, D
S=0.41 μ m.No educt exists, and the chemical constitution deviation value is less than 0.01mol.
Embodiment 9: preparation BaTiO
3System's stupalith powder 100 grams
Presoma preparation is with embodiment 7, and the thermal response temperature is 950 ℃, and all the other are with embodiment 7, gained powder D
50=0.54 μ m, D
S=0.35 μ m.The χ ray structure analysis is the result show, free PbO and TiO are still arranged
2Exist.
Claims (4)
1, a kind of liquid phase parcel-thermal-reaction electronic ceramic micro mist preparation method comprises and adopts oxysalt, water-fast oxyhydroxide and carbonate solid phase matrix, piezoelectric supersonic dispersion and spray drying technology, thermal rection condition etc., it is characterized in that:
(1) preparation of liquid phase-various oxysalt solution, its concentration are with metal oxide convert (mg/ml):
A. Citrate trianion series aqueous solution 25-200
B. acetate or formate series aqueous solution 20-200
C. nitrate series aqueous solution 10-300
(2) liquid phase technique for packing:
Solid-liquid phase weight ratio 1: 5-35
Disperse to use the piezoelectric supersonic dispersion treatment
Spraying drying condition spray velocity: 30-50ml/min
Air flow quantity: 450-500l/min
Drying temperature: 150 ℃ of imports export 100 ℃
(3) thermal rection condition: 500-1050 ℃/1-4 hour.
2, according to the ceramic preparation method of claim 1, it is characterized in that: described oxysalt series is: lead citrate, magnesium formiate, nitrate of baryta, barium acetate.
3, according to the ceramic preparation method of claim 1, it is characterized in that: described solid phase matrix is the oxyhydroxide (hydrate) that is insoluble in water or the intermediate of salt.
4, according to the ceramic preparation method of claim 1 or 3, it is characterized in that: described oxyhydroxide, salt intermediate are:
Nb(OH)
5, Zr(OH)
4, metatitanic acid.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 92108647 CN1088147A (en) | 1992-11-30 | 1992-11-30 | Method for preparing thermal-reaction electronic ceramic micropowder in liquid phase |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 92108647 CN1088147A (en) | 1992-11-30 | 1992-11-30 | Method for preparing thermal-reaction electronic ceramic micropowder in liquid phase |
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| CN1088147A true CN1088147A (en) | 1994-06-22 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101857436A (en) * | 2010-06-12 | 2010-10-13 | 中国地质大学（武汉） | Potassium-sodium niobate base lead-free piezoelectric ceramic powder and preparation method thereof |
| CN104761260A (en) * | 2015-03-18 | 2015-07-08 | 中国科学院福建物质结构研究所 | (Ba<x>Ca<1-x>)(Ti<y>M<1-y>)O3 system piezoelectric ceramic material and preparation method thereof |
| CN109265167A (en) * | 2018-09-05 | 2019-01-25 | 佛山市亿强电子有限公司 | A kind of method and piezoelectric ceramics of Low Temperature Sintering of PZT Piezoelectric Ceramics |
-
1992
- 1992-11-30 CN CN 92108647 patent/CN1088147A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101857436A (en) * | 2010-06-12 | 2010-10-13 | 中国地质大学（武汉） | Potassium-sodium niobate base lead-free piezoelectric ceramic powder and preparation method thereof |
| CN104761260A (en) * | 2015-03-18 | 2015-07-08 | 中国科学院福建物质结构研究所 | (Ba<x>Ca<1-x>)(Ti<y>M<1-y>)O3 system piezoelectric ceramic material and preparation method thereof |
| CN104761260B (en) * | 2015-03-18 | 2017-01-25 | 中国科学院福建物质结构研究所 | Preparation method of (Ba＜x＞Ca＜1-x＞)(Ti＜y＞M＜1-y＞)O3 system piezoelectric ceramic material |
| CN109265167A (en) * | 2018-09-05 | 2019-01-25 | 佛山市亿强电子有限公司 | A kind of method and piezoelectric ceramics of Low Temperature Sintering of PZT Piezoelectric Ceramics |
| CN109265167B (en) * | 2018-09-05 | 2021-04-20 | 佛山市亿强电子有限公司 | Method for sintering PZT piezoelectric ceramic at low temperature and piezoelectric ceramic |
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