CN100430336C - Process for preparing superfine powder of lead magnesium niobate-lead titanate solid solution - Google Patents
Process for preparing superfine powder of lead magnesium niobate-lead titanate solid solution Download PDFInfo
- Publication number
- CN100430336C CN100430336C CNB2004100689491A CN200410068949A CN100430336C CN 100430336 C CN100430336 C CN 100430336C CN B2004100689491 A CNB2004100689491 A CN B2004100689491A CN 200410068949 A CN200410068949 A CN 200410068949A CN 100430336 C CN100430336 C CN 100430336C
- Authority
- CN
- China
- Prior art keywords
- powder
- solution
- pmnt
- preparation
- precipitation
- 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.)
- Expired - Fee Related
Links
Images
Landscapes
- Inorganic Compounds Of Heavy Metals (AREA)
- Compositions Of Oxide Ceramics (AREA)
Abstract
The present invention relates to a method for preparing superfine powder of lead magnesium niobate-lead titanate solid solution, which is characterized in that conventional methods and processes for preparing superfine powder are changed; a means that collosol is slowly added to one kind of alkaline solution by a capillary pipe with a peristaltic pump is adopted to control a generation condition of powder, the particle diameter of particles of the powder is limited fundamentally, and the problems of long preparing period of the powder, and high sintering temperature are solved; in a powder drying stage, cleaning with organic solvent, and vacuum freeze drying are combined, and thus, the problem of poor dispersivity of the powder in the current preparing method is solved. By the test analysis of a transmission electron microscope (TEM), an energy dispersive spectroscopy (EDS) instrument, an X-ray diffraction analysis (XRD) instrument, etc., the superfine powder prepared by the present invention has the characteristics of low sintering temperature, accurate component, fine and homogeneous granularity, high dispersivity and complete perovskite phase structure.
Description
Technical field
The present invention relates to a kind of method of ferroelectric material preparation, particularly the preparation method of PMN-PT (PMNT) sosoloid superfine powder.
Background technology
Lead magnesium niobate-lead titanate solid solution (Pb (Mg
1/3Nb
2/3) O
3-PbTiO
3, be abbreviated as PMNT), be a kind of relaxation property ferroelectrics with uhligite phase structure, the specific inductivity of Yin Qigao and bigger field cause coefficient of dilatation and are widely used in preparation multilayer film electrical condenser and dynamo-electric conversion transverter and other microelectronics.PMNT also has the big characteristics of pyroelectric coefficient, is adapted at using as working medium in refrigerator, the infrared eye.
Along with development of electronic technology, thick-film material and thick film device have become the focus of domestic and international research, and thick-film material is widely used in preparation piezoelectricity, ferroelectric, pyroelectric electric device.The device that thick-film material is made not only operating voltage is low, the frequency of utilization height, can with semiconductor integrated circuit, thick film integrated circuit compatibility, and electrical property excellence (close with the ceramic body material devices of same material) is so thick-film material has important application prospects.And an important method of thick-film material preparation is exactly powder-sol method.Powder-sol method is to add powder in colloidal sol, forms the colloidal sol suspension liquid of powder, prepares a kind of method of thick film then with the means of even glue.Thick film with powder-sol method preparation has big area imporosity, flawless, uniformity coefficient high conformity and the high characteristics of resistivity.This be adopt in the past preparation method difficult the realization, demonstrate great superiority.The structure of the thick-film material of powder-sol method preparation and the performance that performance all depends critically upon powder, the performance of powder and pattern etc. then have confidential relation with preparation process.In order to obtain the thick-film material of structure and excellent performance, just need obtain high-purity superfine powder.
The preparation method of PMNT superfine powder generally has oxide compound solid sintering technology, sol-gel method, coprecipitation method etc.The oxide compound solid sintering technology is to be raw material with carbonate or oxide compound, roasting at high temperature after mixing through ball milling and the technology of producing ceramic powder material.The advantage of this method is that processing unit is simple, and shortcoming is that the uhligite phase content is generally less than 90% because in this technological process, raw material will be sneaked into some impurity unavoidably through repeatedly ball milling and pulverizing, causes product purity lower.In addition, because maturing temperature is up to more than 1000 ℃, causing has higher reunion between powder granule, and granularity is bigger and inhomogeneous, product performance are unstable, can not be used to produce high-quality components and parts.
Sol-gel method is the another kind of important method for preparing powder.It is raw material that traditional sol-gel method generally adopts the organo-metallic alkoxide, obtains the solid precursor by processes such as hydrolysis, polymerization, dryings, and then obtains powder body material through suitable thermal treatment.Because gelation process is slower, therefore general synthesis cycle is longer.The another one shortcoming of sol-gel method is that before drying, it is serious that big molecular network makes the powder reuniting that finally makes in the gelling system owing to exist gelation process, and particle can not be too thin.In order to obtain enough thin powder, need carry out in conjunction with the crushing technology of powder, increased the complicacy of technology.
Chemical coprecipitation technique is improved high temperature solid-state technology, concrete is exactly earlier metal nitrate or aqueous chloride solution to be pressed the certain mol proportion mixing, add precipitation agent then, obtain uniform coprecipitate, make ceramic powder thereby throw out carries out thermolysis again after washing, drying.Compare with the high temperature solid-state technology, chemical coprecipitation technique can be produced the electronic ceramics powder with better stoichiometric composition, the powder characteristic of being produced is better than the powder that the conventional high-temperature technology is produced, states such as Japan and the United States intend replacing the high temperature solid-state technology with chemical coprecipitation technique in the eighties, but reason owing to Technology itself, producing barium titanate with Oxalic Acid Method is example, (C
2O
4)
2-to TiO
2+ and Ba
2+ network different with degree, in the product that makes, can occur lack the barium phenomenon, cause sintering character to reduce, so this technology does not have the big area popularization.
Patent 00111682.7 has adopted colloidal sol-sedimentary method to prepare Pb-based lanthanumdoped zirconate titanates (PZT) superfine powder, this method uses acetone to be catalyzer as precipitation agent, ammoniacal liquor, colloidal sol and acetone are mixed rapidly according to certain ratio, violent stirring, add strong aqua simultaneously rapidly as catalyzer, obtain throw out.Throw out through cleaning, obtain after dry, the thermal treatment dispersed better, granularity is at the PZT of 120～180nm superfine powder.But because the difference of material system, program with this patent prepares the PMNT superfine powder, following problem can appear: 1, owing to adopted in this method colloidal sol is added method in the acetone rapidly, though carrying out the intensive stirring when adding, but owing to enter a large amount of colloidal sol the time, be difficult to avoid growing up of crystal grain, the generation and the growth process of crystal grain are separated fully, this just grows up for particulate and has created condition, can cause oarse-grained generation simultaneously, make the uniform particles variation of generation.2, employing places baking oven to carry out powder rapid drying 60 ℃～80 ℃ exsiccant methods precipitation, can cause the reunion of part powder, influences the dispersiveness of final powder.
Summary of the invention
In view of the limitation of present superfine powder technology of preparing, the present invention proposes a kind of novel method of the PMNT of preparation superfine powder.This method adopts and prepares precursor solution earlier on the basis of traditional coprecipitation method, and the method with sonic oscillation and chemical precipitation obtains the PMNT powder then.It is tiny that the powder of this method preparation has crystal grain, size evenly, good dispersity, the characteristics that sintering temperature is low.Compare with the method for front, both avoided the formation of molecular network in the long-time gelation process of sol-gel method and the gelation process, the high temperature of having avoided high temperature solid-phase sintering to need again, test-results proves, the superfine powder particle diameter that the present invention obtains is thinner, and process of the test is controlled easily.
Preparation method's of the present invention sequence of process steps is as follows:
1, preparation precursor sol liquid
With analytical pure plumbic acetate Pb (CH
3COO)
23H
2O, magnesium acetate Mg (CH
3COO)
24H
2O, metatitanic acid four fourth fat Ti (OC
4H
9)
4With ethanol niobium Nb (OC
2H
5)
5Be raw material, according to molecular formula (1-x) Pb (Mg
1/3Nb
2/3) O
3-xPbTiO
3(be called for short PMNT, 0＜x＜1) mol ratio of molecule in, and amount of substance excessive (5～10) mol% of the amount of substance that makes Mg excessive (3～6) mol%, Pb, that is: making the ratio of the amount of substance of each element in the precursor liquid during preparation is Pb: Mg: Nb: Ti=(1.1～1.05): (1.03～1.06) (1-x)/3: 2 (1-x)/3: x.With concentration be 0.2mol/l colloidal sol be formulated as example, introduce the preparation process of colloidal sol.Get plumbic acetate 1.672g and put into beaker, in temperature is 120 ℃ loft drier, be incubated 30～60 minutes, be dissolved in then in the above ethylene glycol monomethyl ether of 7ml, fully stirring and dissolving.Accurately take by weighing magnesium acetate 0.270g and put into beaker, in temperature is 120 ℃ loft drier, be incubated 30～60 minutes, then it is dissolved in the ethylene glycol monomethyl ether more than the 7ml, fully stirring and dissolving.Getting the ethanol niobium of 0.7632g and the metatitanic acid four fourth fat of 0.136g is dissolved in respectively in the ethylene glycol monomethyl ether of 3ml, and in the solution of ethanol niobium and metatitanic acid four fourth fat, add the methyl ethyl diketone of 2ml respectively, more than four kinds of solution respectively after the sufficient stirring and dissolving, admixed together, and methyl ethyl diketone, the acetic acid of 3ml and the formyl ammonium of 4ml of adding 4ml, sonic oscillation 10～20min stirred 0.5～1 hour, obtained stable PMNT precursor liquid.
2, preparation basic solution
Acetone and ammoniacal liquor is mixed with 5: 1～10: 1 ratio, and the pH value of adjusting solution with the fierce 5～10min that stirs of magnetic stirring apparatus, mixes two kinds of solution between 7～9, obtains the needed basic solution of co-precipitation;
3, precipitation
The basic solution that the preparation of the 2nd step is obtained places the electric current sonic oscillation of ultrasonic generator with 200mA, by the kapillary that has peristaltic pump the PMNT precursor liquid is joined in the basic solution then.Precursor liquid during peristaltic pump work in the compressing container makes precursor liquid enter basic solution by kapillary.The present invention is with the adding speed of peristaltic pump control colloidal sol, particle diameter with kapillary control colloidal sol, the precursor liquid that will account for basic solution volume 1/10～1/5 slowly joins in the basic solution, while adding sonic oscillation, the colloidal sol nucleation rate of adding is increased, new precipitated phase is easy to generate, but be difficult to grow up, after precursor liquid adds fully, continued sonic oscillation 10～15 minutes, for preventing that undue sonic oscillation from producing precipitation, adopted every sonic oscillation 1～2 minute, the mode that stops 1～2 minute interruption sonic oscillation is carried out, after sonic oscillation is finished, sedimentary precursor liquid is powerful to be stirred 0.5～1 hour to producing with magnetic stirring apparatus, guaranteed that the composition in the solution is precipitated out fully.
4, precipitation process
After precipitation forms, at first use supercentrifuge to produce sedimentary basic solution behind the precursor liquid and filter, obtain the precipitation of white adding in the 3rd step.To precipitate then and wash repeatedly, reduce particle owing to the hydroxyl bridging action forms hard aggregation on the one hand, and utilize acetone to have less capillary characteristics on the other hand, weaken the capillary force in the dehydration, intergranular bonding strength is reduced with acetone.Be medium with acetone at last, carry out sonic oscillation, pulverize, guarantee that particulate is tiny evenly with the particle that further utilizes hyperacoustic cavitation and mechanical shock effect to have grown up with ultrasonic generator.Utilizes vacuum freezing drying device at-50 ℃～-60 ℃ after filtering, pressure is under the situation of 13～26Pa precipitation to be dehydrated, and obtains good dispersity, than the littler ultrafine powder of the dry median size of usual way.
5, sintering
In order to obtain the PMNT ceramic powder of uhligite phase, the powder that vacuum lyophilization is obtained places heat treatment furnace to calcine, and calcining temperature is controlled at 650 ℃～750 ℃, is incubated 1～3 hour, obtains the PMNT ultrafine powder.In order to guarantee the homogeneity of powder, the PMNT ultrafine powder after the calcining is carried out settlement separate, obtain the PMNT ultrafine powder of 40～80nm.
So far, the preparation of PMN-PT superfine powder of the present invention is finished.
The present invention utilizes the principle of co-precipitation, the mode and the ultra-sonic oscillation that add by rational control colloidal sol change reaction conditions, suppress the generation of crystal grain and grow up, preparation PMNT superfine powder, complete uhligite phase, granularity have been obtained in the PMNT of 40～80nm ultrafine powder, have that sintering temperature is low, good dispersity, the tiny and uniform characteristics of granularity, for the preparation of ferroelectric thick film and ferroelectric ceramic(s) is had laid a good foundation.
Characteristics of the present invention are:
1, the preparation composition of colloidal sol of the present invention accurately, be easy to control, and it is convenient to mix, the precursor liquid good stability has guaranteed the formation of complete uhligite phase on composition.
2, the present invention makes the basic solution that colloidal sol precipitation needs earlier, adopts kapillary colloidal sol is joined in this basic solution slowly that has peristaltic pump then.Because tiny caliber has limited the contact area of colloidal sol and basic solution, therefore the crystal grain that forms is very little, simultaneously, because this precipitation is to carry out in ultrasonic generator, particle at the mouth of pipe in case form with regard to owing to sonic oscillation leaves capillary exit, no longer include the possibility of growing up, both combinations have fundamentally limited the generation size of crystal grain, suppressed growing up of crystal grain, make new precipitated phase be easy to generate, but be difficult to grow up, and the particle of having grown up is made it broken by hyperacoustic mechanical effect, guaranteed that the particle diameter of ultrafine powder is tiny.
3, the present invention has used the vacuum freezing device at the drying stage of powder, and in conjunction with the repeatedly cleaning of organic solvent (acetone) to powder, the powder reuniting of having avoided the oven dry insulation to cause makes powder that better dispersiveness be arranged.
4, the PMNT superfine powder sintering temperature of the present invention preparation is low, and good dispersity, particle diameter and have uhligite phase completely between 40～80nm.
Description of drawings
Fig. 1 .PMNT ultrafine powder is 750 ℃ in thermal treatment temp, X-ray diffraction analysis (XRD) collection of illustrative plates during insulation 1h.
The TEM photo of Fig. 2 .PMNT ultrafine powder.
Embodiment
Embodiment 1
The first step: PMNT colloidal sol synthetic.
With molecular formula 0.9Pb (Mg
1/3Nb
2/3) O
3-0.1PbO
3Each composition mol ratio of (the excessive 10mol% of amount of substance of the excessive 5mol% of the amount of substance of Mg, Pb) is a measurement standard, the PMNT precursor liquid of preparation 0.2mol/l.Take by weighing the plumbic acetate (Pb (CH of 1.672g
3COO)
23H
2O), the magnesium acetate of 0.270g (Mg (CH
3COO)
24H
2O), the ethanol niobium (Ni (OC of 0.7632g
2H
5)) and the metatitanic acid four fourth fat (Ti (OC of 0.136g
4H
9)
4).With plumbic acetate (Pb (CH
3COO)
23H
2O) and magnesium acetate (Mg (CH
3COO)
24H
2O) in 120 ℃ loft drier, be incubated 30 minutes, then it be dissolved in respectively in the ethylene glycol monomethyl ether of 7ml, stirred 1 hour, it is fully dissolved.Ethanol niobium and metatitanic acid four fourth fat are dissolved in respectively in the ethylene glycol monomethyl ether of 3ml, stirred 0.5 hour, the methyl ethyl diketone that in the solution of ethanol niobium and metatitanic acid four fourth fat, adds 2ml then respectively, more than four kinds of solution respectively after the sufficient stirring and dissolving, admixed together, and methyl ethyl diketone, the acetic acid of 3ml and the formyl ammonium of 4ml of adding 4ml, sonic oscillation 20 minutes, stirred 1 hour, and obtained stable PMNT precursor liquid.
Second step: the preparation of basic solution
30ml acetone and 6ml ammoniacal liquor is mixed with 5: 1 ratio, and the pH value that makes solution stirred 10 minutes with magnetic stirring apparatus is fierce about 8, obtained the needed basic solution of co-precipitation.
The 3rd step: precipitation
The basic solution of second step preparation is placed ultrasonic container sonic oscillation, add precursor liquid 6ml slowly with the kapillary that has peristaltic pump then, after adding fully, continued ultrasonic 10 minutes, utilize the powerful stirring of magnetic stirring apparatus 0.5 hour then, guarantee that the ultimate constituent that adds in the solution is precipitated out fully.
The 4th step: precipitation process
With whizzer the throw out in the solution is filtered out, clean repeatedly, and adopt the ultrasonic way that stopped 1 minute the ultrasonic concussion in interval in 1 minute to handle, at last with the ultrafine powder vacuum lyophilization that filters out with acetone.
The 5th step: sintering
Dry later powder places heat treatment furnace 750 ℃ of calcinings 2 hours, obtains the PMNT ultrafine powder, in order to guarantee the homogeneity of powder, carries out settlement separately, obtains the PMNT ultrafine powder of 40～80nm.
Embodiment 2
The first step: PMNT colloidal sol synthetic.
With molecular formula 0.9Pb (Mg
1/3Nb
2/3) O
3-0.1PbO
3Each composition mol ratio of (the excessive 10mol% of amount of substance of the excessive 3mol% of the amount of substance of Mg, Pb) is a measurement standard, the PMNT precursor liquid of preparation 0.2mol/l.Take by weighing the plumbic acetate (Pb (CH of 1.672g
3COO)
23H
2O), the magnesium acetate of 0.1893g (Mg (CH
3COO)
24H
2O), the ethanol niobium (Ni (OC of 0.7632g
2H
5)) and the metatitanic acid four fourth fat (Ti (OC of 0.136g
4H
9)
4).With plumbic acetate (Pb (CH
3COO)
23H
2O) and magnesium acetate (Mg (CH
3COO)
24H
2O) be insulation 60 minutes in 120 ℃ the loft drier in temperature, be dissolved in respectively then in the 7ml ethylene glycol monomethyl ether, stirred 1 hour, make its sufficient dissolving.Ethanol niobium and metatitanic acid four fourth fat are dissolved in respectively in the ethylene glycol monomethyl ether of 5ml, stirred 0.5 hour, the methyl ethyl diketone that in the solution of ethanol niobium and metatitanic acid four fourth fat, adds 1ml then respectively, more than four kinds of solution respectively after the sufficient stirring and dissolving, admixed together, and methyl ethyl diketone, the acetic acid of 3ml and the formyl ammonium of 4ml of adding 2ml, sonic oscillation 20 minutes, stirred 0.5 hour, and obtained stable PMNT precursor liquid.
Second step: the preparation of basic solution
Acetone 21ml and ammoniacal liquor 3ml is mixed, and the pH value that makes solution stirred 10 minutes with magnetic stirring apparatus is fierce about 7, obtained the needed basic solution of co-precipitation.
The 3rd step: precipitation
Place ultrasonic container ultrasonic the basic solution of second step preparation, add precursor liquid 5ml slowly with the kapillary that has peristaltic pump then, after adding fully, continued sonic oscillation 10 minutes, utilize the powerful stirring of magnetic stirring apparatus 0.5 hour then, guarantee that the ultimate constituent that adds in the solution is precipitated out fully.
The 4th step: precipitation process
With whizzer the throw out in the solution is filtered out, clean repeatedly, and adopt per way that stopped 1 minute interval sonic oscillation in 1 minute to handle, at last with the ultrafine powder vacuum lyophilization that filters out with acetone.
The 5th step: sintering
Dry later powder places heat treatment furnace 750 ℃ of calcinings 1 hour, obtains the PMNT ultrafine powder, in order to guarantee the homogeneity of powder, carries out settlement separately, obtains the PMNT ultrafine powder of 40～80nm.
Embodiment 3
The first step: PMNT colloidal sol synthetic.
With molecular formula 0.9Pb (Mg
1/3Nb
2/3) O
3Each composition mol ratio of-0.1PbO3 (the excessive 5mol% of amount of substance of the excessive 5mol% of the amount of substance of Mg, Pb) is a measurement standard, the PMNT precursor liquid of preparation 0.2mol/l.Take by weighing the plumbic acetate (Pb (CH of 1.596g
3COO)
23H
2O), the magnesium acetate of 0.2696g (Mg (CH
3COO)
24H
2O), the ethanol niobium (Ni (OC of 0.7632g
2H
5)) and the metatitanic acid four fourth fat (Ti (OC of 0.136g
4H
9)
4).With plumbic acetate (Pb (CH
3COO)
23H
2O) and magnesium acetate (Mg (CH
3COO)
24H
2O) in temperature is 120 ℃ loft drier, be incubated 40min, be dissolved in respectively then in the 7ml ethylene glycol monomethyl ether, stirred 1 hour, make its sufficient dissolving.Ethanol niobium and metatitanic acid four fourth fat are dissolved in respectively in the ethylene glycol monomethyl ether of 3ml, stirred 0.5 hour, the methyl ethyl diketone that in the solution of ethanol niobium and metatitanic acid four fourth fat, adds 1ml then respectively, more than four kinds of solution respectively after the sufficient stirring and dissolving, admixed together, and methyl ethyl diketone, the acetic acid of 3ml and the formyl ammonium of 4ml of adding 2ml, sonic oscillation 10 minutes, stirred 1 hour, and obtained stable PMNT precursor liquid.
Second step: the preparation of basic solution
Acetone 20ml and ammoniacal liquor 5ml is mixed, and the pH value that makes solution stirred 5 minutes with magnetic stirring apparatus is fierce about 9, obtained the needed basic solution of co-precipitation.
The 3rd step: precipitation
Place ultrasonic container ultrasonic the basic solution of second step preparation, add precursor liquid 5ml slowly with the kapillary that has peristaltic pump then, after adding fully, continued sonic oscillation 10 minutes, utilize the powerful stirring of magnetic stirring apparatus 0.5 hour then, guarantee that the ultimate constituent that adds in the solution is precipitated out fully.
The 4th step: precipitation process
With whizzer the throw out in the solution is filtered out, clean repeatedly, and adopt the ultransonic way in the ultrasonic interval that stopped 2 minutes in 2 minutes to handle, at last with the ultrafine powder vacuum lyophilization that filters out with acetone.
The 5th step: sintering
Dry later powder places heat treatment furnace 650 ℃ of calcinings 2 hours, obtains the PMNT ultrafine powder, in order to guarantee the homogeneity of powder, carries out settlement separately, obtains the PMNT ultrafine powder of 40～80nm.
Embodiment 4
The first step: PMNT colloidal sol synthetic.
With molecular formula 0.71Pb (Mg
1/3Nb
2/3) O
3-0.29PbO
3Each composition mol ratio of (the excessive 10mol% of amount of substance of the excessive 3mol% of the amount of substance of Mg, Pb) is a measurement standard, the PMNT precursor liquid of preparation 0.2mol/l.Take by weighing the plumbic acetate (Pb (CH of 4.18g
3COO)
23H
2O), the magnesium acetate of 0.5217g (Mg (CH
3COO)
24H
2O), the ethanol niobium (Ni (OC of 1.5052g
2H
5)) and the metatitanic acid four fourth fat (Ti (OC of 0.986g
4H
9)
4).With plumbic acetate (Pb (CH
3COO)
23H
2O) and magnesium acetate (Mg (CH
3COO)
24H
2O) be insulation 40 minutes in 120 ℃ the loft drier in temperature, be dissolved in respectively then in the 10ml ethylene glycol monomethyl ether, stirred 1 hour, make its sufficient dissolving.Ethanol niobium and metatitanic acid four fourth fat are dissolved in respectively in the ethylene glycol monomethyl ether of 8ml, stirred 0.5 hour, the methyl ethyl diketone that in the solution of ethanol niobium and metatitanic acid four fourth fat, adds 4ml then respectively, more than four kinds of solution respectively after the sufficient stirring and dissolving, admixed together, and methyl ethyl diketone, the acetic acid of 2ml and the formyl ammonium of 4ml of adding 2ml, sonic oscillation 10 minutes, stirred 1 hour, and obtained stable PMNT precursor liquid.
Second step: the preparation of basic solution
30ml acetone and 6ml ammoniacal liquor is mixed, and the pH value that makes solution stirred 10 minutes with magnetic stirring apparatus is fierce about 8, obtained the needed basic solution of co-precipitation.
The 3rd step: precipitation
The basic solution of second step preparation is placed ultrasonic container sonic oscillation, add precursor liquid 4ml slowly with the kapillary that has peristaltic pump then, after adding fully, continued ultrasonic 10 minutes, utilize the powerful 0.5h of stirring of magnetic stirring apparatus then, guarantee that the ultimate constituent that adds in the solution is precipitated out fully.
The 4th step: precipitation process
With whizzer the throw out in the solution is filtered out, clean repeatedly, and the ultransonic way in interval that adopts ultrasonic concussion to stop 1 minute in 1 minute handles, at last with the ultrafine powder vacuum lyophilization that filters out with acetone.
The 5th step: sintering
Dry later powder places heat treatment furnace 650 ℃ of calcinings 2.5 hours, obtains the PMNT ultrafine powder, in order to guarantee the homogeneity of powder, carries out settlement separately, obtains the PMNT ultrafine powder of 40～80nm.
Embodiment 5
The first step: PMNT colloidal sol synthetic.
With molecular formula 0.65Pb (Mg
1/3Nb
2/3) O
3-0.35PbO
3Each composition mol ratio of (the excessive 5mol% of amount of substance of the excessive 6mol% of the amount of substance of Mg, Pb) is a measurement standard, the PMNT precursor liquid of preparation 0.2mol/l.Take by weighing the plumbic acetate (Pb (CH of 3.99g
3COO)
23H
2O), the magnesium acetate of 0.5369g (Mg (CH
3COO)
24H
2O), the ethanol niobium (Ni (OC of 1.5052g
2H
5)) and the metatitanic acid four fourth fat (Ti (OC of 0.986g
4H
9)
4).With plumbic acetate (Pb (CH
3COO)
23H
2O) and magnesium acetate (Mg (CH
3COO)
24H
2O) in temperature is 120 ℃ loft drier, be incubated 40min, be dissolved in respectively then in the 10ml ethylene glycol monomethyl ether, stirred 1 hour, make its sufficient dissolving.Ethanol niobium and metatitanic acid four fourth fat are dissolved in respectively in the ethylene glycol monomethyl ether of 8ml, stirred 0.5 hour, the methyl ethyl diketone that in the solution of ethanol niobium and metatitanic acid four fourth fat, adds 4ml then respectively, more than four kinds of solution respectively after the sufficient stirring and dissolving, admixed together, and methyl ethyl diketone, the acetic acid of 2ml and the formyl ammonium of 4ml of adding 2ml, sonic oscillation 10 minutes, stirred 1 hour, and obtained stable PMNT precursor liquid.
Second step: the preparation of basic solution
Acetone 30ml and ammoniacal liquor 3ml is mixed, and the pH value that makes solution stirred 15 minutes with magnetic stirring apparatus is fierce about 7, obtained the needed basic solution of co-precipitation.
The 3rd step: precipitation
Place ultrasonic container ultrasonic the basic solution of second step preparation, add precursor liquid 3ml slowly with the kapillary that has peristaltic pump then, after adding fully, continued sonic oscillation 15 minutes, utilize the powerful stirring of magnetic stirring apparatus 0.5 hour then, guarantee that the ultimate constituent that adds in the solution is precipitated out fully.
The 4th step: precipitation process
With whizzer the throw out in the solution is filtered out, clean repeatedly, and adopt the way that whenever stopped 2 minutes in ultrasonic 2 minutes to handle, at last with the ultrafine powder vacuum lyophilization that filters out every sonic oscillation with acetone.
The 5th step: sintering
Dry later powder places heat treatment furnace 700 ℃ of calcinings 2 hours, obtains the PMNT ultrafine powder, in order to guarantee the homogeneity of powder, carries out settlement separately, obtains the PMNT ultrafine powder of 40～80nm.
PMNT ultrafine powder with the inventive method preparation is passed through TEM (transmission electron microscope) analysis (TEM), energy spectrum analysis (EDS), X-ray diffraction analysis microcosmic test analysis means such as (XRD), confirm that it has that composition is accurate, granularity is tiny evenly, the characteristics of good dispersity, can obtain the PMNT ultrafine powder of complete uhligite phase by regulating processing parameter.
Fig. 1. being depicted as the PMNT ultrafine powder is 750 ℃ in thermal treatment temp, X-ray diffraction analysis (XRD) collection of illustrative plates when being incubated 1 hour.The TEM photo (X50000) of PMNT ultrafine powder shown in Figure 2.
Following table is depicted as the EDAX results of ultrafine powder.
Table 1PMNT composition relatively
| Pb | Nb | Mg | Ti | O | |
| |
20 | 12 | 6 | 2 | 60 |
| The powder ratio | 19.31 | 12.03 | 5.60 | 2.13 | 60.93 |
| Deviation | -0.69 | +0.03 | -0.40 | +0.13 | +0.93 |
Claims (1)
1, a kind of preparation method of superfine powder of lead magnesium niobate-lead titanate solid solution is characterized in that this method is made up of following 5 sequence of steps:
(1) preparation PMNT precursor sol liquid
With analytical pure plumbic acetate Pb (CH
3COO)
23H
2O, magnesium acetate Mg (CH
3COO)
24H
2O, metatitanic acid four fourth fat Ti (OC
4H
9)
4With ethanol niobium Nb (OC
2H
5)
5Be raw material, according to molecular formula (1-x) Pb (Mg
1/3Nb
2/3) O
3-xPbTiO
3The mol ratio of middle molecule, and amount of substance excessive (5～10) mol% of the amount of substance that makes Mg excessive (3～6) mol%, Pb, that is: making the ratio of the amount of substance of each element in the precursor liquid during preparation is Pb: Mg: Nb: Ti=(1.1～1.05): (1.03～1.06) (1-x)/3: 2 (1-x)/3: x; Wherein, molecular formula (1-x) Pb (Mg
1/3Nb
2/3) O
3-xPbTiO
3Be called for short PMNT, and 0＜x＜1;
Get plumbic acetate 1.672g, in temperature is 120 ℃ loft drier, be incubated 30～60 minutes, be dissolved in then in the ethylene glycol monomethyl ether of 7ml, fully stirring and dissolving; Accurately take by weighing magnesium acetate 0.27g, in temperature is 120 ℃ loft drier, be incubated 30～60 minutes, then it is dissolved in the ethylene glycol monomethyl ether of 7ml, fully stirring and dissolving; Getting the ethanol niobium of 0.7632g and the metatitanic acid four fourth fat of 0.136g is dissolved in respectively in the ethylene glycol monomethyl ether of 3ml, and in the solution of ethanol niobium and metatitanic acid four fourth fat, add the methyl ethyl diketone of 2ml respectively, more than four kinds of solution respectively after the sufficient stirring and dissolving, admixed together, and methyl ethyl diketone, the acetic acid of 3ml and the formyl ammonium of 4ml of adding 4ml, sonic oscillation 10～20 minutes stirred 0.5～1 hour, obtained stable PMNT precursor liquid;
(2) preparation basic solution
Acetone and ammoniacal liquor is mixed with 5: 1～10: 1 ratio, and the pH value of adjusting solution with the fierce 5～10min that stirs of magnetic stirring apparatus, mixes two kinds of solution between 7～9, obtains the needed basic solution of co-precipitation;
(3) precursor liquid that will account for basic solution volume (1/10～1/5) with the kapillary that has peristaltic pump joins in the basic solution slowly, while adding sonic oscillation, after adding fully, continued ultrasonic 5～10 minutes, every sonic oscillation 1～3 minute, stop 1～3 minute, after sonic oscillation was finished, sedimentary precursor liquid is powerful to be stirred 0.5～1 hour to producing with magnetic stirring apparatus;
(4) filter with supercentrifuge having produced sedimentary basic solution behind the adding precursor liquid in the 3rd step, clean the precipitation that obtains repeatedly with acetone then, clean after 3～5 times, precipitation is placed acetone, carry out sonic oscillation with ultrasonic generator, precipitation after will filtering at last places the vacuum freezing case at-50 ℃～-60 ℃, and pressure is to dehydrate under the situation of 13～26Pa, obtains ultrafine powder;
(5) powder that vacuum lyophilization is obtained places heat treatment furnace 650 ℃～750 ℃ calcinings, is incubated 1～3 hour, obtains the PMNT ultrafine powder.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100689491A CN100430336C (en) | 2004-07-15 | 2004-07-15 | Process for preparing superfine powder of lead magnesium niobate-lead titanate solid solution |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100689491A CN100430336C (en) | 2004-07-15 | 2004-07-15 | Process for preparing superfine powder of lead magnesium niobate-lead titanate solid solution |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1721366A CN1721366A (en) | 2006-01-18 |
| CN100430336C true CN100430336C (en) | 2008-11-05 |
Family
ID=35912033
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2004100689491A Expired - Fee Related CN100430336C (en) | 2004-07-15 | 2004-07-15 | Process for preparing superfine powder of lead magnesium niobate-lead titanate solid solution |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100430336C (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100479214C (en) * | 2007-08-22 | 2009-04-15 | 中国科学院上海技术物理研究所 | Making method for niobium-magnesium acid lead-Ti acid lead iron electric thin film with self-polarization effect |
| CN101550014B (en) * | 2009-05-12 | 2012-08-08 | 聊城大学 | Preparation method of lead based relaxor ferroelectric ceramic powder material with pure perovskite structure |
| CN106835080B (en) * | 2017-01-22 | 2019-11-01 | 武汉理工大学 | Lead magnesium niobate-lead titanate and lead zirconate titanate heterojunction structure film and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1375843A (en) * | 2002-05-10 | 2002-10-23 | 北京科技大学 | Prepn. of nanoemter level laminated ceramic capacitor dielectric material |
-
2004
- 2004-07-15 CN CNB2004100689491A patent/CN100430336C/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1375843A (en) * | 2002-05-10 | 2002-10-23 | 北京科技大学 | Prepn. of nanoemter level laminated ceramic capacitor dielectric material |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1721366A (en) | 2006-01-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100450969C (en) | Process for preparing submicro-crystal piezoelectric ceramics | |
| CN101607823B (en) | Hydrothermal high-temperature mixed synthetic method of piezoelectric ceramic powder | |
| WO2004028971A1 (en) | The process for preparing a strontium titanate powder | |
| CN112479708A (en) | Lead-free piezoelectric ceramic for medical ultrasonic transducer and preparation method and application thereof | |
| CN101219897A (en) | Colloidal sols gelatin synthesizing method for leadless piezoelectric ceramic lithium sodium kalium niobate nano-powder | |
| CN101475376A (en) | Method for microwave-hydrothermal synthesis of potassium-sodium niobate leadless piezoelectric ceramic | |
| CN101613201B (en) | Method for synthesizing potassium-sodium niobate leadless piezoelectric ceramic powder by two hydro-thermal steps | |
| CN111269009A (en) | Bismuth zirconate manganate-bismuth scandate-lead titanate series piezoelectric ceramic material and preparation method thereof | |
| CN100430336C (en) | Process for preparing superfine powder of lead magnesium niobate-lead titanate solid solution | |
| CN101921108A (en) | Barium strontium titanate-based superfine powder and preparation method thereof | |
| JP2013510062A (en) | Method for producing barium titanate | |
| CN115353145B (en) | Sn (Ba, ca) TiO prepared by vacuum plasma field assisted sol-gel technology 3 Method for preparing powder | |
| CN105254295A (en) | Preparation method of neodymium doped barium titanate ceramic nano-powder | |
| CN110372372A (en) | The preparation method of the bismuth-sodium titanate base lead-free piezoelectric ceramic of low-dielectric loss under high temperature | |
| CN1401611A (en) | Bismuth sodium titanate series film material and preparing process thereof | |
| CN101219893A (en) | Method for producing nano-barium titanate based PTCR porcelain powder with low-temperature solid-state reaction | |
| CN104987063B (en) | A kind of method that microemulsion method prepares bismuth sodium potassium titanate Nano microsphere | |
| CN102557636B (en) | Sol-gel synthesis method for bismuth layer high-temperature piezoelectric ceramic sodium bismuth niobate nanopowder | |
| CN104761256B (en) | A kind of bismuth-sodium titanate base 03 is combined ferroelectric thick film and its preparation method and application | |
| CN101767818A (en) | Ion-doped potassium bismuth titanate nano powder and preparation method thereof | |
| CN101585704B (en) | Leadless piezoelectric ceramics material and method for preparing same | |
| CN101328058A (en) | Preparation of lead magnesio-niobate ferroelectric material | |
| CN104496463B (en) | The method that surfactant assisted in situ co-precipitation prepares core-shell structure nanopowder body | |
| CN103332734A (en) | Method for preparing CaBi4Ti4O15 nano-powder | |
| CN110451954B (en) | Sodium bismuth titanate-based low-lead piezoelectric film with high inverse piezoelectric coefficient and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20081105 Termination date: 20100715 |