CN1277781C - Method for preparing BaTiO3 base PTCR ceramic micropowder - Google Patents
Method for preparing BaTiO3 base PTCR ceramic micropowder Download PDFInfo
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- CN1277781C CN1277781C CN 200410061153 CN200410061153A CN1277781C CN 1277781 C CN1277781 C CN 1277781C CN 200410061153 CN200410061153 CN 200410061153 CN 200410061153 A CN200410061153 A CN 200410061153A CN 1277781 C CN1277781 C CN 1277781C
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Abstract
The present invention discloses a method for preparing BaTiO3 base PTCR ceramic miropowder, which comprises: an organic monomer and a cross link agent are induced in a transparent solution containing Ba<2+>, Sr<2+>, Ti<4+>and Y<3+>, and under the action of an initiator and a catalyst, a monomer in the solution and the cross link agent are polymerized in the mode of crosslink to obtain gelatin; accordingly, ions in the solution are solidified on original positions and are calcined at the temperature of 700 to 900 DEG C to obtain powder mixed with BaTiO3; a mixed solution of acceptor impurity Mn<2+> and a comburent agent Si<2+> is evenly mixed with the obtained powder in an ultrasonic way so that the acceptor impurity and the comburent agent are evenly wrapped on the surface of the powder mixed with the BaTiO3, and BaTiO3 base PTCR ceramic miropowder is obtained. The miropowder made by the method has the characteristics of high purity, small homogeneous composition, small granularity, high chemical activity, simple process, low cost, convenient operation and control of a preparation process.
Description
Technical field
The invention belongs to the powder preparing technical field, be specifically related to a kind of BaTiO
3The preparation method of base PTCR ceramic.
Background technology
In recent years, along with the development of mechanics of communication and surface mounting technique, various electronic components constantly develop to miniaturization, chip type, integrated, high reliability, low power consumption direction.For BaTiO
3Base PTCR electronic ceramics requires it to have characteristics such as high temperature coefficient of resistance and high lift-drag ratio, and the purity of this accuracy of just the PTCR materials chemistry being formed, powder, particle size, chemical uniformity, sintering activity etc. are had higher requirement.Because the PTCR ceramic composition is more, and the PTCR effect in order to obtain, require part to form (sintering aid and acceptor impurity) and be distributed in crystal boundary, this just makes preparation PTCR powder have certain singularity.Traditional solid reaction process prepares the PTCR ceramic powder and was divided into for two steps: at first mix each component by ball milling, solid state reaction synthesizing blender BaTiO is finished in calcining at high temperature
3Powder adds sintering aid and acceptor impurity by secondary ball milling and then, and this method can be with sintering aid and acceptor impurity basic controlling in crystal boundary.Because solid reaction process is based on the solid state reaction principle, the chemical uniformity of powder is difficult to guarantee, simultaneously owing to need twice ball milling and solid state reaction at high temperature to finish, prepared powder purity is not high, and the powder granule of generation is bigger, the particle size distribution broad, and there is hard aggregation in powder, be difficult for grinding, make sintering aid and acceptor impurity be difficult to add evenly, therefore utilize traditional technology to be difficult to obtain high quality P TCR powder high-purity, ultra-fine, narrow diameter distribution.
At present, the preparation method of high-quality ceramic powder focuses mostly on the methods such as coprecipitation method, hydrothermal method and sol-gel method that with the liquid phase reaction are principal character.Coprecipitation method is by add the presoma precipitation of precipitation agent acquisition barium titanate, the acquisition of the temperature lower calcination about 1000 ℃ superfine powder then in mixing solutions.Because will pass through repetitive scrubbing and high-temperature calcination and active low, environmental pollution is serious, and production cost is higher.Hydrothermal method is constructed and crystal growth by the particulate of the realization of the chemical reaction under the suitable hydrothermal condition in sealed pressure vessel atom and molecule level, prepared powder has crystal grain and grows complete, particle diameter is little and be evenly distributed, the reunion degree is little, active advantages of higher in sintering process.But temperature of reaction that the preparation process of hydrothermal method is had relatively high expectations (200-500 ℃) and higher pressure (30-50MPa), energy consumption is big, and the developing direction of current hydrothermal method is to reduce temperature of reaction and reaction pressure.Sol-gel method is a raw material with the metal alkoxide, and hydrolysis in organic medium, condensation make alkoxide solution obtain gel through the sol-gel process, and drying and calcination processing obtain superfine powder again.The characteristics that powder has the purity height, forms evenly, granularity is little, chemically reactive is high, but raw-materially cost an arm and a leg, be difficult in industry, to realize scale operation.
Xue the army and the people etc. have reported a kind of citrate solution-liquid phase pack (silicate journal 25 (1) (1997) 72-77), utilize citric acid by ammoniacal liquor and Ba
2+, Ca
2+, Sr
2+, Y
3+, Ti
4+Complexing action prepare the stabilizing solution of five components, after solution is spray-dried, obtain unbodied presoma, presoma obtains the BaTiO that mixes through thermal treatment
3Base PTCR powder.But this method needs spraying drying, the not easy to operate and control of preparation process, and sneak into impurity easily.
Summary of the invention
The objective of the invention is to overcome above-mentioned the deficiencies in the prior art part a kind of preparation BaTiO is provided
3The method of base PTCR ceramic, the ceramic that this method makes not only has the purity height, forms the characteristics even, that granularity is little, chemically reactive is high, and technology is simple, cost is low, and preparation process is convenient to operation and control.
For achieving the above object, the technical solution used in the present invention is a kind of preparation BaTiO
3The method of base PTCR ceramic comprises
(1) preparation contains Ba
2+, Sr
2+, Ti
4+And Y
3+Solution, its mol ratio is Ba
2+: Sr
2+: Ti
4+: Y
3+=(0.744～0.7985): (0.2～0.25): (1.01～1.02): (0.0015～0.006);
(2) in above-mentioned solution: organic monomer: coupling agent=100ml: (6～20) g: the ratio of (0.5～8) g, in solution, add organic monomer and coupling agent, be stirred to the dissolving of organic monomer and coupling agent, add initiator and catalyzer again, under the effect of initiator and catalyzer, organic monomer in the solution and coupling agent crosslinking polymerization obtain gel;
(3) with the gained gel 700 ℃～900 ℃ calcinings, obtain the BaTiO that mixes
3Powder;
(4) preparation contains Si
4+Solution;
(5) will more than obtain powder, contain Si
4+Solution and manganous nitrate Mn (NO
3)
2Solution is pressed powder: Si
4+: Mn
2+=1: (0.02～0.024): the mixed in molar ratio of (0.0002～0.001) makes steady suspension by ultra-sonic dispersion;
(6) suspension forms powder after drying, 600 ℃～700 ℃ calcinings, removes organism wherein, obtains BaTiO
3Base PTCR ceramic.
Described preparation contains Ba
2+, Sr
2+, Ti
4+And Y
3+The method of solution can be: press barium carbonate BaCO
3: the mol ratio of citric acid=1: 3～1: 6, weighing barium carbonate BaCO
3With citric acid, in citric acid, add deionized water, be mixed with citric acid solution, with citric acid solution and barium carbonate BaCO
3Mix, after reaction is finished, obtain containing Ba
2+Solution, and add ammoniacal liquor to pH be 7～8; Press Strontium carbonate powder SrCO
3: the mol ratio of citric acid=1: 3～1: 6, weighing Strontium carbonate powder SrCO
3With citric acid, or press Strontium carbonate powder SrCO
3: the mol ratio of nitric acid=1: 2～1: 3, weighing Strontium carbonate powder SrCO
3With nitric acid, in citric acid or nitric acid, add deionized water, be mixed with citric acid solution or salpeter solution, again with the solution and the Strontium carbonate powder SrCO that are mixed with
3Mix, after reaction is finished, obtain containing Sr
2+Solution, and add ammoniacal liquor to pH be 7～8; Press butyl (tetra) titanate Ti (OC
4H
9)
4: the weight ratio of citric acid=1: 1～1: 1.2, weighing butyl (tetra) titanate Ti (OC
4H
9)
4With citric acid, in citric acid, add deionized water, be mixed with citric acid solution, and to regulate the pH value with ammoniacal liquor be 6～7, with gained solution and butyl (tetra) titanate Ti (OC
4H
9)
4Mix, be heated to 80 ℃～85 ℃, leave standstill after the stirring, solution is divided into two-layer up and down, and lower floor's solution separating is gone out, and obtains containing Ti
4+Solution, and add ammoniacal liquor to pH be 7～8; Press yttrium oxide Y
2O
3: the mol ratio of nitric acid=1: 6～1: 8, weighing yttrium oxide Y
2O
3With nitric acid, in nitric acid, add the deionized water dilution, solution and yttrium oxide Y after will diluting again
2O
3Mix, be heated to 80 ℃～85 ℃, stir, after reaction is finished, obtain containing Y
3+Solution, and add ammoniacal liquor to pH be 7～8; Above four kinds of solution are mixed.
Described obtain after adding ammoniacal liquor contain Y
3+Solution in, can add edta edta again, and to regulate pH be 5～6, form stable Y-EDTA complex solution.
Described organic monomer can be acrylamide.Coupling agent can be N, N '-methylene-bisacrylamide.Initiator can be ammonium persulphate.Catalyzer can be N, N, N ', N '-Tetramethyl Ethylene Diamine.
Described initiator and catalyzer can be in solution: initiator: catalyzer=100ml: (60～80) mg: the ratio of (1～2) ml adds.
Described preparation contains Si
4+Solution, its method can be, and presses tetraethoxy Si (OC
2H
5)
4: the mol ratio of citric acid=1: 1.2～1: 2, weighing tetraethoxy Si (OC
2H
5)
4With citric acid, in citric acid, add deionized water, be mixed with citric acid solution, again with citric acid solution and tetraethoxy Si (OC
2H
5)
4Mix, stir, after reaction is finished, obtain containing Si
4+Solution.
In described (3), calcination time can be 2～3 hours.In described (6), calcination time can be 1～2 hour.
The present invention has following advantage:
(1) Ba
2+, Sr
2+, Ti
4+, Y
3+All with solution form uniform mixing in proportion on the atom/molecule level, prepared doping BaTiO
3The composition of powder can accurately be controlled by the ratio of regulating four metal ion species;
(2) organic monomer, coupling agent, initiator and the catalyzer of being introduced in the preparation process is organism, will be decomposed into H in calcination process
2O, CO, CO
2, NO
2, SO
2Vapor away, do not influence the component of material, can not introduce tramp material, thus synthetic powder purity height;
(3) the Gel Treatment temperature is low, has avoided grain growth and reunion, has kept high reactivity, when calcining temperature is 700 ℃, can obtain diffraction peak intensity obviously, the doping BaTiO of crystalline cubic perovskite structure fully
3Powder;
(4) the ceramic median size that makes of the present invention is a nano level, and particle size distribution is narrower, and is spherical in shape substantially, has the weakly agglomerated of loose shape between the particle, and powder sintering is active big;
(5) sintering agent Si
4+With acceptor impurity Mn
2+Add with liquid form in the doping BaTiO3 powder of preparation, make that the interpolation of sintering aid and acceptor impurity is more even.
Embodiment
Among 1～5 embodiment below the present invention, raw materials used is barium carbonate BaCO
3, Strontium carbonate powder SrCO
3, butyl (tetra) titanate Ti (OC
4H
9)
4, yttrium oxide Y
2O
3, tetraethoxy Si (OC
2H
5)
4, manganous nitrate Mn (NO
3)
2, citric acid, nitric acid, ammoniacal liquor.Organic monomer is an acrylamide, and coupling agent is N, and N '-methylene-bisacrylamide, initiator are ammonium persulphate or superoxol, and catalyzer is N, N, N ', N '-Tetramethyl Ethylene Diamine.
Embodiment 1
(1) preparation contains Ba
2+: Sr
2+: Ti
4+And Y
3+Solution, its mol ratio is Ba
2+: Sr
2+: Ti
4+: Y
3+=0.744: 0.25: 1.02: 0.006, the method for preparing this solution can be:
Press barium carbonate BaCO
3: the mol ratio of citric acid=1: 3, weighing 14.760g barium carbonate BaCO
3With the 47.110g citric acid, in citric acid, add deionized water, be mixed with citric acid solution, again with barium carbonate BaCO
3Slowly add, after reaction is finished, obtain containing Ba
2+Clear solution, and add ammoniacal liquor to pH be 8;
Press Strontium carbonate powder SrCO
3: the mol ratio of citric acid=1: 3, weighing 3.728g Strontium carbonate powder SrCO
3With the 15.829g citric acid, in citric acid, add deionized water, be mixed with citric acid solution, again with Strontium carbonate powder SrCO
3Slowly add, after reaction is finished, obtain containing Sr
2+Clear solution, and add ammoniacal liquor to pH be 7; Or press Strontium carbonate powder SrCO
3: the mol ratio of nitric acid=1: 2.5, weighing 3.728g Strontium carbonate powder SrCO
3With nitric acid, in nitric acid, add deionized water, be mixed with dilute nitric acid solution, again with Strontium carbonate powder SrCO
3Slowly add, after reaction is finished, obtain containing Sr
2+Clear solution, and add ammoniacal liquor to pH be 7;
Press butyl (tetra) titanate Ti (OC
4H
9)
4: the weight ratio of citric acid=1: 1, weighing 35.426g butyl (tetra) titanate Ti (OC
4H
9)
4With the 35.426g citric acid, in citric acid, add deionized water, be mixed with citric acid solution, and to regulate the pH value with ammoniacal liquor be 6, with butyl (tetra) titanate Ti (OC
4H
9)
4Add in the citric acid solution, be heated to 80 ℃, can stir 20 minutes, leave standstill, solution is divided into two-layer up and down, with separating funnel lower floor's solution separating is gone out, and obtains containing Ti
4+Clear solution, and add ammoniacal liquor to pH be 7;
Press yttrium oxide Y
2O
3: the mol ratio of nitric acid=1: 6, weighing 68mg yttrium oxide Y
2O
3With nitric acid, in nitric acid, add the deionized water dilution, again with yttrium oxide Y
2O
3Add, be heated to 80 ℃, can stir 30 minutes, after reaction is finished, obtain containing Y
3+Clear solution, and add ammoniacal liquor to pH be 7;
Above four kinds of solution are mixed, stir;
(2) in above-mentioned solution: the ratio of organic monomer: coupling agent=100ml: 6g: 0.5g, in solution, add organic monomer and coupling agent, be stirred to the dissolving of organic monomer and coupling agent, again by this solution: initiator: catalyzer=100ml: 60mg: 1ml, in this solution, add ammonium persulfate solution and catalyzer, under the effect of ammonium persulphate and catalyzer, organic monomer in the solution and coupling agent crosslinking polymerization obtain gel;
(3) the gained gel was calcined 3 hours at 700 ℃, obtained the BaTiO that mixes
3Powder;
(4) preparation contains Si
4+Solution, its method can be: press tetraethoxy: the mol ratio of citric acid=1: 1.2, weighing 508mg tetraethoxy Si (OC
2H
5)
4With the 608mg citric acid, in citric acid, add deionized water, be mixed with citric acid solution, again with tetraethoxy Si (OC
2H
5)
4Add and stirring, after reaction is finished, obtain containing Si
4+Clear solution;
(5) will more than obtain powder, contain Si
4+Solution and Mn (NO
3)
2Solution is pressed powder: Si
4+: Mn
2+=1: 0.024: 0.001 mixed in molar ratio makes steady suspension by ultra-sonic dispersion;
(6) suspension forms powder after drying, 600 ℃ of calcinings 2 hours, removes organism wherein, obtains BaTiO
3Base PTCR ceramic.
Gained BaTiO
3The median size of base PTCR ceramic is 70nm, and the powder specific surface area is 14.1710m
2/ g.
Embodiment 2
(1) preparation contains Ba
2+, Sr
2+, Ti
4+And Y
3+Solution, its mol ratio is Ba
2+: Sr
2+: Ti
4+: Y
3+=0.7985: 0.2: 1.01: 0.0015, the method for preparing this solution can be:
Press barium carbonate BaCO
3: the mol ratio of citric acid=1: 6, weighing 15.841g barium carbonate BaCO
3With the 101.117g citric acid, in citric acid, add deionized water, be mixed with citric acid solution, again with barium carbonate BaCO
3Slowly add, after reaction is finished, obtain containing Ba
2+Clear solution, and add ammoniacal liquor to pH be 7;
Press Strontium carbonate powder SrCO
3: the mol ratio of nitric acid=1: 2, weighing 2.982g Strontium carbonate powder SrCO
3With nitric acid, in nitric acid, add deionized water, be mixed with dilute nitric acid solution, again with Strontium carbonate powder SrCO
3Slowly add, after reaction is finished, obtain containing Sr
2+Clear solution, and add ammoniacal liquor to pH be 8; Or press Strontium carbonate powder SrCO
3: the mol ratio of citric acid=1: 4, weighing 2.982g Strontium carbonate powder SrCO
3With the 16.884g citric acid, in citric acid, add deionized water, be mixed with citric acid solution, again with Strontium carbonate powder SrCO
3Slowly add, after reaction is finished, obtain containing Sr
2+Clear solution, and add ammoniacal liquor to pH be 8;
Press butyl (tetra) titanate Ti (OC
4H
9)
4: the weight ratio of citric acid=1: 1.2, weighing 35.079g butyl (tetra) titanate Ti (OC
4H
9)
4With the 42.095g citric acid, in citric acid, add deionized water, be mixed with citric acid solution, and to regulate the pH value with ammoniacal liquor be 7, with butyl (tetra) titanate Ti (OC
4H
9)
4Add in the citric acid solution, be heated to 85 ℃, can stir 23 minutes, leave standstill, solution is divided into two-layer up and down, with separating funnel lower floor's solution separating is gone out, and obtains containing Ti
4+Clear solution, and add ammoniacal liquor to pH be 8;
Press yttrium oxide Y
2O
3: the mol ratio of nitric acid=1: 7, weighing 17mg yttrium oxide Y
2O
3With nitric acid, in nitric acid, add deionized water, again with yttrium oxide Y
2O
3Add, be heated to 85 ℃, can stir 40 minutes, after reaction is finished, obtain containing Y
3+Clear solution, and add ammoniacal liquor to pH be 8;
Above four kinds of solution are mixed, stir;
(2) in above-mentioned solution: the ratio of organic monomer: coupling agent=100ml: 20g: 8g, in solution, add organic monomer and coupling agent, be stirred to the dissolving of organic monomer and coupling agent, again by this solution: initiator: catalyzer=100ml: 80mg: 2ml, in this solution, add superoxol and catalyzer, under the effect of hydrogen peroxide and catalyzer, organic monomer in the solution and coupling agent crosslinking polymerization obtain gel;
(3) the gained gel was calcined 2 hours at 900 ℃, obtained the BaTiO that mixes
3Powder;
(4) preparation contains Si
4+Solution, its method can be: press tetraethoxy: the mol ratio of citric acid=1: 2, weighing 423mg tetraethoxy Si (OC
2H
5)
4With the 844mg citric acid, in citric acid, add deionized water, be mixed with citric acid solution, again with tetraethoxy Si (OC
2H
5)
4Add and stirring, after reaction is finished, obtain containing Si
4+Clear solution;
(5) will more than obtain powder, contain Si
4+Solution and Mn (NO
3)
2Solution is pressed powder: Si
4+: Mn
2+=1: 0.02: 0.0002 mixed in molar ratio makes steady suspension by ultra-sonic dispersion;
(6) suspension forms powder after drying, 700 ℃ of calcinings 1 hour, removes organism wherein, obtains BaTiO
3Base PTCR ceramic.
Gained BaTiO
3The median size of base PTCR ceramic is 60nm, and the powder specific surface area is 14.2250m
2/ g.
Embodiment 3
(1) preparation contains Si
4+Solution, its method can be: press tetraethoxy: the mol ratio of citric acid=1: 1.5, weighing 465mg tetraethoxy Si (OC
2H
5)
4With the 735mg citric acid, in citric acid, add deionized water, be mixed with citric acid solution, again with tetraethoxy Si (OC
2H
5)
4Add and stirring, after reaction is finished, obtain containing Si
4+Clear solution;
(2) preparation contains Ba
2+, Sr
2+, Ti
4+And Y
3+Solution, its mol ratio is Ba
2+: Sr
2+: Ti
4+: Y
3+=0.767: 0.23: 1.015: 0.003, the method for preparing this solution can be:
Press barium carbonate BaCO
3: the mol ratio of citric acid=1: 4, weighing 15.216g barium carbonate BaCO
3With the 64.752g citric acid, in citric acid, add deionized water, be mixed with citric acid solution, again with barium carbonate BaCO
3Slowly add, after reaction is finished, obtain containing Ba
2+Clear solution, and add ammoniacal liquor to pH be 7.5;
Press Strontium carbonate powder SrCO
3: the mol ratio of nitric acid=1: 3, weighing 3.429g Strontium carbonate powder SrCO
3With nitric acid, in nitric acid, add deionized water, be mixed with dilute nitric acid solution, again with Strontium carbonate powder SrCO
3Slowly add, after reaction is finished, obtain containing Sr
2+Clear solution, and add ammoniacal liquor to pH be 7.5; Or press Strontium carbonate powder SrCO
3: the mol ratio of citric acid=1: 6, weighing 3.429g Strontium carbonate powder SrCO
3With the 29.126g citric acid, in citric acid, add deionized water, be mixed with citric acid solution, again with Strontium carbonate powder SrCO
3Slowly add, after reaction is finished, obtain containing Sr
2+Clear solution, and add ammoniacal liquor to pH be 7.5;
Press butyl (tetra) titanate Ti (OC
4H
9)
4: the weight ratio of citric acid=1: 1.1, weighing 35.253g butyl (tetra) titanate Ti (OC
4H
9)
4With the 38.778g citric acid, in citric acid, add deionized water, be mixed with citric acid solution, and to regulate the pH value with ammoniacal liquor be 6.5, with butyl (tetra) titanate Ti (OC
4H
9)
4Add in the citric acid solution, be heated to 83 ℃, can stir 30 minutes, leave standstill, solution is divided into two-layer up and down, with separating funnel lower floor's solution separating is gone out, and obtains containing Ti
4+Clear solution, and add ammoniacal liquor to pH be 7.5;
Press yttrium oxide Y
2O
3: the mol ratio of nitric acid=1: 8, weighing 34mg yttrium oxide Y
2O
3With nitric acid, in nitric acid, add deionized water, again with yttrium oxide Y
2O
3Add, be heated to 80 ℃, can stir 35 minutes, after reaction is finished, obtain containing Y
3+Clear solution, and add ammoniacal liquor to pH be 7.5;
Above four kinds of solution are mixed, stir;
(3) in above-mentioned mixing solutions: the ratio of organic monomer: coupling agent=100ml: 15g: 3g, in solution, add organic monomer and coupling agent, be stirred to the dissolving of organic monomer and coupling agent, again in this solution: the ratio of initiator: catalyzer=100ml: 70mg: 1.5ml, in this solution, add ammonium persulfate solution and catalyzer, under the effect of ammonium persulphate and catalyzer, organic monomer in the solution and coupling agent crosslinking polymerization obtain gel;
(4) the gained gel was calcined 2.5 hours at 800 ℃, obtained the BaTiO that mixes
3Powder;
(5) will more than obtain powder, contain Si
4+Solution and Mn (NO
3)
2Solution is pressed powder: Si
4+: Mn
2+=1: 0.022: 0.0006 mixed in molar ratio makes steady suspension by ultra-sonic dispersion;
(6) suspension forms powder after drying, 650 ℃ of calcinings 1.5 hours, removes organism wherein, obtains BaTiO
3Base PTCR ceramic.
Gained BaTiO
3The median size of base PTCR ceramic is 90nm, and the powder specific surface area is 13.7450m
2/ g.
Embodiment 4
Be with the difference of embodiment 1: described obtain after adding ammoniacal liquor contain Y
3+Clear solution in, add edta edta again, and to regulate pH be 5, forms stable Y-EDTA complex compound clear solution, make the gelation process shortening, all the other are with embodiment 1.
Gained BaTiO
3The median size of base PTCR ceramic is 80nm, and the powder specific surface area is 14.1630m
2/ g.
Embodiment 5
Be with the difference of embodiment 2: described obtain after adding ammoniacal liquor contain Y
3+Clear solution in, add edta edta again, and to regulate pH be 6, forms stable Y-EDTA complex compound clear solution, make the gelation process shortening, all the other are with embodiment 2.
Gained BaTiO
3The median size of base PTCR ceramic is 70nm, and the powder specific surface area is 14.1750m
2/ g.
Claims (10)
1. one kind prepares BaTiO
3The method of base PTCR ceramic is characterized in that: comprise
(1) preparation contains Ba
2+, Sr
2+, Ti
4+And Y
3+Solution, its mol ratio is Ba
2+: Sr
2+: Ti
4+: Y
3+=(0.744～0.7985): (0.2～0.25): (1.01～1.02): (0.0015～0.006);
(2) in above-mentioned solution: organic monomer: coupling agent=100ml: (6～20) g: the ratio of (0.5～8) g, in solution, add organic monomer and coupling agent, be stirred to the dissolving of organic monomer and coupling agent, add initiator and catalyzer again, under the effect of initiator and catalyzer, organic monomer in the solution and coupling agent crosslinking polymerization obtain gel;
(3) with the gained gel 700 ℃～900 ℃ calcinings, obtain the BaTiO that mixes
3Powder;
(4) preparation contains Si
4+Solution;
(5) will more than obtain powder, contain Si
4+Solution and manganous nitrate Mn (NO
3)
2Solution is pressed powder: Si
4+: Mn
2+=1: (0.02～0.024): the mixed in molar ratio of (0.0002～0.001) makes steady suspension by ultra-sonic dispersion;
(6) suspension forms powder after drying, 600 ℃～700 ℃ calcinings, removes organism wherein, obtains BaTiO
3Base PTCR ceramic.
2. the method for preparing ceramic according to claim 1 is characterized in that: described preparation contains Ba
2+, Sr
2+, Ti
4+And Y
3+The method of solution is,
Press barium carbonate BaCO
3: the mol ratio of citric acid=1: 3～1: 6, weighing barium carbonate BaCO
3With citric acid, in citric acid, add deionized water, be mixed with citric acid solution, with citric acid solution and barium carbonate BaCO
3Mix, after reaction is finished, obtain containing Ba
2+Solution, and add ammoniacal liquor to pH be 7～8;
Press Strontium carbonate powder SrCO
3: the mol ratio of citric acid=1: 3～1: 6, weighing Strontium carbonate powder SrCO
3With citric acid, or press Strontium carbonate powder SrCO
3: the mol ratio of nitric acid=1: 2～1: 3, weighing Strontium carbonate powder SrCO
3With nitric acid, in citric acid or nitric acid, add deionized water, be mixed with citric acid solution or salpeter solution, again with the solution and the Strontium carbonate powder SrCO that are mixed with
3Mix, after reaction is finished, obtain containing Sr
2+Solution, and add ammoniacal liquor to pH be 7～8;
Press butyl (tetra) titanate Ti (OC
4H
9)
4: the weight ratio of citric acid=1: 1～1: 1.2, weighing butyl (tetra) titanate Ti (OC
4H
9)
4With citric acid, in citric acid, add deionized water, be mixed with citric acid solution, and to regulate the pH value with ammoniacal liquor be 6～7, with gained solution and butyl (tetra) titanate Ti (OC
4H
9)
4Mix, be heated to 80 ℃～85 ℃, leave standstill after the stirring, solution is divided into two-layer up and down, and lower floor's solution separating is gone out, and obtains containing Ti
4+Solution, and add ammoniacal liquor to pH be 7～8;
Press yttrium oxide Y
2O
3: the mol ratio of nitric acid=1: 6～1: 8, weighing yttrium oxide Y
2O
3With nitric acid, in nitric acid, add the deionized water dilution, solution and yttrium oxide Y after will diluting again
2O
3Mix, be heated to 80 ℃～85 ℃, stir, after reaction is finished, obtain containing Y
3+Solution, and add ammoniacal liquor to pH be 7～8;
Above four kinds of solution are mixed.
3. the method for preparing ceramic according to claim 2 is characterized in that: described obtain after adding ammoniacal liquor contain Y
3+Solution in, add edta edta again, and to regulate pH be 5～6, form stable Y-EDTA complex solution.
4. the method for preparing ceramic according to claim 1 is characterized in that: described organic monomer is an acrylamide.
5. the method for preparing ceramic according to claim 1 is characterized in that: described coupling agent is N, N '-methylene-bisacrylamide.
6. the method for preparing ceramic according to claim 1 is characterized in that: described initiator is an ammonium persulphate.
7. the method for preparing ceramic according to claim 1 is characterized in that: described catalyzer is N, N, N ', N '-Tetramethyl Ethylene Diamine.
8. the method for preparing ceramic according to claim 1 is characterized in that: described initiator and catalyzer are in solution: initiator: catalyzer=100ml: (60～80) mg: the ratio of (1～2) ml adds.
9. the method for preparing ceramic according to claim 1 is characterized in that: described preparation contains Si
4+Solution, its method is to press tetraethoxy Si (OC
2H
5)
4: the mol ratio of citric acid=1: 1.2～1: 2, weighing tetraethoxy Si (OC
2H
5)
4With citric acid, in citric acid, add deionized water, be mixed with citric acid solution, again with citric acid solution and tetraethoxy Si (OC
2H
5)
4Mix, stir, after reaction is finished, obtain containing Si
4+Solution.
10. the method for preparing ceramic according to claim 1 is characterized in that: in described (3), calcination time is 2～3 hours, and in described (6), calcination time is 1～2 hour.
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|---|---|---|---|
| CN 200410061153 CN1277781C (en) | 2004-11-19 | 2004-11-19 | Method for preparing BaTiO3 base PTCR ceramic micropowder |
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|---|---|---|---|
| CN 200410061153 CN1277781C (en) | 2004-11-19 | 2004-11-19 | Method for preparing BaTiO3 base PTCR ceramic micropowder |
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| CN1277781C true CN1277781C (en) | 2006-10-04 |
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