CN109704761A - A kind of Nb Cr/Mo codope bismuth niobate calcium high temperature piezoceramics and preparation method thereof - Google Patents
A kind of Nb Cr/Mo codope bismuth niobate calcium high temperature piezoceramics and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of Nb Cr/Mo codope bismuth niobate calcium high temperature piezoceramics and preparation method thereof, the general formula of the piezoceramic material is CaBi2Nb2‑x(Mo2/3Cr1/3)xO9, wherein 0.03≤x≤0.075.The invention also discloses the preparation methods of the piezoceramic material, using CaBi2Nb2O9Based on system piezoelectric material, a certain proportion of Cr, Mo are mixed in the Nb molar ratios according to 1:2, such novel laminated structure bismuth piezoelectric ceramic material is prepared using traditional solid phase synthesis process.Compared with prior art, the piezoceramic material that the present invention obtains, Specifeca tion speeification d33=15pC/N, TC=939 DEG C, at 600 DEG C, ρ=3.3 × 105Ω cm, furthermore stable preparation process is reliable, and production cost is low, it is easy to accomplish industrialized production has a good application prospect in high-temperature field.Using ceramic component made from this material, various piezoelectric transducers are assembled into, can be used under the special hot environment such as space flight and aviation, petrochemical industry.
Description
Technical field
The present invention relates to a kind of preparation methods of bismuth laminated bismuth niobate calcium high temperature piezoceramics, and in particular to one
The bismuth laminated bismuth niobate calcium (CaBi of kind Cr/Mo codope2Nb2O9) piezoceramic material preparation, belong to piezoelectric ceramics material
Material field.
Background technique
Currently, most widely used piezoelectric material is mainly the PZT base piezoelectric ceramic of perovskite structure, but this kind of piezoelectricity is made pottery
The Curie temperature of porcelain generally at 390 DEG C hereinafter, due to piezoelectric material depolarization phenomenon presence, piezoelectric material Curie temperature with
Under can not work normally.With the rapid development of the industry such as aerospace, geological prospecting and the need of human social
It asks, it is therefore necessary to seek a kind of Curie temperature height, the excellent environmentally friendly piezoelectric material of piezoelectric property.
Since Curie temperature is high, fatigue performance is good, bismuth laminated ceramics are considered as the reason of high-temperature piezoelectric material
Want to select.Bismuth laminated ceramic material is by (Bi2O2)2+The lattice layer of layer and perovskite structure, which alternates, to be formed by stacking
, chemical general formula is (Bi2O2)2+(Am-1BmO3m+1)2-, A is the ion for being suitble to dodecahedron coordination, such as Na in above formula+, Ca2+,
La3+It is the ion for being suitble to octahedral coordination, such as Ti Deng, B4+, Nb5+, Ta5+Deng, m is integer, value be 1 to 6.Bismuth niobate calcium
(CaBi2Nb2O9) be m=2 bismuth layer structure, Curie temperature is up to 940 DEG C, piezoelectric constant d33About 5pC/N, with
Practical application is compared, although Curie temperature meets the requirement under high temperature, application requirement (d is not achieved in its piezoelectric property33
≥15pC/N).Therefore, how piezoelectric property is improved while not reducing Curie temperature stablize use in high temperature range to obtain
Bismuth laminated piezoelectric ceramic material become piezoceramic material area research an important topic.
Currently, there is not yet improving bismuth laminated bismuth niobate calcium (CaBi with Cr/Mo codope2Nb2O9) piezoelectric ceramics material
Expect the relevant report of performance.
Summary of the invention
Insufficient for the above-mentioned prior art, the object of the present invention is to provide a kind of bismuth laminated bismuth niobate calcium high-temperature piezoelectrics
The preparation method of ceramic material, using Cr, Mo element to bismuth laminated bismuth niobate calcium (CaBi2Nb2O9) piezoceramic material into
Row is codoping modified, while not reducing Curie temperature temperature, improves its piezoelectric property, prepares a kind of novel, environment
The piezoceramic material of friendly.
In order to overcome the shortcomings of the prior art, the present invention the following technical schemes are provided:
A kind of Nb Cr/Mo codope bismuth niobate calcium high temperature piezoceramics, the general formula of the piezoceramic material are
CaBi2Nb2-x(Mo2/3Cr1/3)xO9, wherein 0.03≤x≤0.075；
In general formula, the molar ratio of index number representative element；
Preferred x=0.03,0.04,0.05,0.06,0.07 or 0.075；
It is further preferred that x=0.07；
The invention also discloses a kind of preparation method of Nb Cr/Mo codope bismuth niobate calcium high temperature piezoceramics,
Steps are as follows:
Ingredient: with CaCO3Powder, Bi2O3Powder, Nb2O5Powder, Cr2O3Powder and MoO3Powder is raw material, by general formula
CaBi2Nb2-x(Mo2/3Cr1/3)xO9The stoichiometry of middle Ca, Bi, Nb, Cr and Mo carry out ingredient, wherein 0.03≤x≤0.075；
Ball milling: the dehydrated alcohol with mixture equivalent being added into said mixture, continues ball milling 12~24 hours,
It is uniformly mixed powder and forms slurry, it is possible thereby to further improve the comprehensive of bismuth niobate calcium high temperature piezoceramics
Energy；
Drying: above-mentioned slurry being placed in constant temperature oven and is toasted, and is removed dehydrated alcohol, and grind in mortar, is obtained powder
Material；
Tabletting pre-burning: powder being placed in grinding tool and is pressed into material block in advance, will expect block pre-burning, and calcined temperature is 675~750 DEG C,
Soaking time 2~4 hours；
Secondary ball milling: by the material block after pre-burning in mortar, primary powder is obtained after being pulverized grinding, to obtained primary
The dehydrated alcohol with primary powder equivalent is added in powder, continues ball milling 12~24 hours, is uniformly mixed powder and forms slurry；
Drying: above-mentioned slurry being placed in constant temperature oven and is toasted, and removes dehydrated alcohol, and powder is ground into mortar；
Granulating and forming: the poly-vinyl alcohol solution (PVA) that distilled water and concentration are 8% is mixed into powder as adhesive
In, the quality of the distilled water of incorporation is the 2.5% of powder quality, and the quality of the adhesive of incorporation is the 5% of powder quality, is being ground
It is uniformly mixed in alms bowl；Mixed powder is placed in grinding tool, green compact are pressed into；Green compact are milled to powder in mortar, are led to
The sieve for crossing 60 mesh and 120 mesh takes the powder of 60 mesh and 120 mesh sieve middle layers, has obtained the suitable powder of granular size
Material；Powder is placed in grinding tool, is pressed into green compact under the pressure of 200MPa；
Dumping: green compact dumping was excluded the PVA in green compact, obtains porcelain billet temperature lower calcination 3 hours of 650 DEG C；
Sintering: porcelain billet is sintered, and sintering temperature is 1000~1100 DEG C, soaking time 2~4 hours, obtains ceramics
Piece；
It applies electrode: potsherd cleaning, drying, screen printing being brushed into silver electrode, silver ink firing, 500~600 DEG C of silver ink firing temperature, protected
1~2 hour warm time；
Polarization: the potsherd for having plated silver electrode is placed in 120~160 DEG C of silicone oil, polarizing voltage be 12kV/mm~
15kV/mm, polarization time are 20min~40min.
Preferably, during a ball milling and secondary ball milling, the Ball-milling Time is 12 hours.
Preferably, in the burn-in process, the calcined temperature is 725 DEG C, and the soaking time is 2 hours.
Preferably, in the sintering process, the sintering temperature is 1150 DEG C, and the soaking time is 3 hours.
Compared with prior art, technical solution of the present invention, B Nb are replaced by Cr and Mo, and control doping member
The additional amount of element, effectively increases the piezoelectric property of bismuth niobate calcium high temperature piezoceramics.It should be noted that the prior art
There are many about the report for carrying out element doping to piezoceramic material in although, it is different doped chemical, doped chemical
Different additional amounts can all produce bigger effect the overall performance of piezoceramic material, then need during the test constantly
Grope, repetition test can just obtain, and inventor has also attempted a variety of different elements to bismuth niobate calcium high-temperature high-pressure in early-stage study
The doping of electroceramics material, but the doping for other elements are prepared using Cr and Mo element codope of the invention
Bismuth laminated bismuth niobate calcium high-temperature piezoelectric material shows more excellent piezoelectric property.
It is excellent that experimental data shows that the present invention has the effect of:
The codoping modified bismuth stratiform bismuth niobate calcium (CaBi of Cr, Mo element of the present invention2Nb2O9) piezoceramic material, Curie
Temperature is 939 DEG C, piezoelectric constant d33Up to 15pC/N, and there is good high-temperature stability, at 600 DEG C, electricalresistivityρ=
3.3×105Ω cm has a good application prospect in high-temperature field.
In addition, the invention is made by conventional piezoelectric ceramic industry, preparation cost is low, and industry is simple and is suitable for high-volume
The piezoelectric property of industrialized production, the ceramic material after doping vario-property improves three times or more than before, advances high-temperature piezoelectric
The progress of material.
Detailed description of the invention
Fig. 1 is the CaBi prepared in embodiment 12Nb1.97(Mo2/3Cr1/3)0.03O9, the XRD diffraction pattern of x=0.03 ceramics,
The curve that the curve and resistivity of dielectric constant with temperature variation vary with temperature；
Fig. 2 is the CaBi prepared in embodiment 22Nb1.96(Mo2/3Cr1/3)0.04O9, the XRD diffraction pattern of x=0.04 ceramics,
The curve that the curve and resistivity of dielectric constant with temperature variation vary with temperature；
Fig. 3 is the CaBi prepared in embodiment 32Nb1.95(Mo2/3Cr1/3)0.05O9, the XRD diffraction pattern of x=0.05 ceramics,
The curve that the curve and resistivity of dielectric constant with temperature variation vary with temperature；
Fig. 4 is the CaBi prepared in embodiment 42Nb1.94(Mo2/3Cr1/3)0.06O9, the XRD diffraction pattern of x=0.06 ceramics,
The curve that the curve and resistivity of dielectric constant with temperature variation vary with temperature；
Fig. 5 is the CaBi prepared in embodiment 52Nb1.93(Mo2/3Cr1/3)0.07O9, the XRD diffraction pattern of x=0.07 ceramics,
The curve that the curve and resistivity of dielectric constant with temperature variation vary with temperature；
Fig. 6 is the CaBi prepared in embodiment 62Nb1.925(Mo2/3Cr1/3)0.075O9, the XRD diffraction of x=0.075 ceramics
The curve that figure, the curve of dielectric constant with temperature variation and resistivity vary with temperature；
Fig. 7 is different amounts of Cr/Mo doping CaBi2Nb2-x(Mo2/3Cr1/3)xO9The Curie temperature variation diagram of ceramics；
Fig. 8 is different amounts of Cr/Mo doping CaBi2Nb2-x(Mo2/3Cr1/3)xO9The room temperature piezoelectric modulus variation diagram of ceramics；
Fig. 9 is different amounts of Cr/Mo doping CaBi2Nb2-x(Mo2/3Cr1/3)xO9Ceramics 600 DEG C when change in resistance figure.
Specific embodiment
The present invention will be further explained with reference to the examples below.
Embodiment 1
Preparation meets chemical composition CaBi2Nb2-x(Mo2/3Cr1/3)xO9, the Cr/Mo of x=0.03 codoping modified niobic acid
Bismuth calcium (CaBi2Nb2O9) leadless piezoelectric ceramics, including the following steps:
(1) ingredient: with CaCO3Powder, Bi2O3Powder, Nb2O5Powder, Cr2O3Powder and MoO3Powder is raw material, by general formula
The stoichiometry of middle Ca, Bi, Nb, Cr and Mo carry out ingredient；
(2) ball millings: the dehydrated alcohol with mixture equivalent being added into said mixture, continues ball milling 12 hours,
It is uniformly mixed powder and forms slurry, it is possible thereby to further improve the comprehensive of bismuth niobate calcium high temperature piezoceramics
Energy；
(3) it dries: above-mentioned slurry being placed in constant temperature oven and is toasted, remove dehydrated alcohol, and grind in mortar, obtain
Powder；
(4) tabletting pre-burning: powder being placed in grinding tool and is pressed into material block in advance, will expect block pre-burning, and calcined temperature is 725 DEG C, is protected
Warm time 2 h；
(5) secondary ball milling: by the material block after pre-burning in mortar, primary powder is obtained after being pulverized grinding, to what is obtained
The dehydrated alcohol with primary powder equivalent is added in primary powder, continues ball milling 12 hours, is uniformly mixed powder and forms slurry；
(6) it dries: above-mentioned slurry being placed in constant temperature oven and is toasted, remove dehydrated alcohol, and pulverize in mortar
Material；
(7) poly-vinyl alcohol solution (PVA) that distilled water and concentration are 8% granulating and forming: is mixed into powder as adhesive
In material, the quality of the distilled water of incorporation is the 2.5% of powder quality, and the quality of the adhesive of incorporation is the 5% of powder quality,
It is uniformly mixed in mortar；Mixed powder is placed in grinding tool, green compact are pressed into；Green compact are milled to powder in mortar,
By the sieve of 60 mesh and 120 mesh, the powder of 60 mesh and 120 mesh sieve middle layers is taken, it is suitable to have obtained granular size
Powder；Powder is placed in grinding tool, is pressed into green compact under the pressure of 200MPa；
(8) dumping: green compact dumping was excluded the PVA in green compact, obtain porcelain billet temperature lower calcination 3 hours of 650 DEG C；
(9) it is sintered: porcelain billet is sintered, sintering temperature is 1150 DEG C, soaking time 3 hours, obtains potsherd；
(10) it applies electrode: potsherd cleaning, drying, screen printing is brushed into silver electrode, silver ink firing, silver ink firing temperature 500~600
DEG C, soaking time 1~2 hour；
(11) it polarizes: the potsherd for having plated silver electrode being placed in 120~160 DEG C of silicone oil, polarizing voltage 12kV/mm
~15kV/mm, polarization time are 20min~40min.
CaBi to be prepared in embodiment 1 as shown in fig. 12Nb2-x(Mo2/3Cr1/3)xO9, the XRD of x=0.03 ceramics spreads out
Penetrate the curve that figure, the curve of dielectric constant with temperature variation and resistivity vary with temperature；Fig. 7 is that different amounts of Cr/Mo mixes
Miscellaneous CaBi2Nb2-x(Mo2/3Cr1/3)xO9The Curie temperature variation diagram of ceramics；Fig. 8 is different amounts of Cr/Mo doping CaBi2Nb2-x
(Mo2/3Cr1/3)xO9The room temperature piezoelectric modulus variation diagram of ceramics；Fig. 9 is different amounts of Cr/Mo doping CaBi2Nb2-x(Mo2/ 3Cr1/3)xO9Ceramics 600 DEG C when change in resistance figure.
As seen from Figure 1, Cr/Mo manufactured in the present embodiment codoping modified bismuth niobate calcium leadless piezoelectric ceramics with it is pure
The XRD spectrum of the bismuth niobate calcium piezoelectric ceramics of phase is almost the same.
Test result is as follows: d33=9.5pC/N, TCElectricalresistivityρ=6.3 × 10 at=934 DEG C, 600 DEG C5Ω·cm。
Embodiment 2
Preparation meets chemical composition CaBi2Nb2-x(Mo2/3Cr1/3)xO9, the Cr/Mo of x=0.04 codoping modified niobic acid
Bismuth calcium (CaBi2Nb2O9) leadless piezoelectric ceramics, including the following steps:
(1) ingredient: with CaCO3Powder, Bi2O3Powder, Nb2O5Powder, Cr2O3Powder and MoO3Powder is raw material, by general formula
The stoichiometry of middle Ca, Bi, Nb, Cr and Mo carry out ingredient；
(2) ball millings: the dehydrated alcohol with mixture equivalent being added into said mixture, continues ball milling 12 hours,
It is uniformly mixed powder and forms slurry, it is possible thereby to further improve the comprehensive of bismuth niobate calcium high temperature piezoceramics
Energy；
(3) it dries: above-mentioned slurry being placed in constant temperature oven and is toasted, remove dehydrated alcohol, and grind in mortar, obtain
Powder；
(4) tabletting pre-burning: powder being placed in grinding tool and is pressed into material block in advance, will expect block pre-burning, and calcined temperature is 725 DEG C, is protected
Warm time 2 h；
(5) secondary ball milling: by the material block after pre-burning in mortar, primary powder is obtained after being pulverized grinding, to what is obtained
The dehydrated alcohol with primary powder equivalent is added in primary powder, continues ball milling 12 hours, is uniformly mixed powder and forms slurry；
(6) it dries: above-mentioned slurry being placed in constant temperature oven and is toasted, remove dehydrated alcohol, and pulverize in mortar
Material；
(7) poly-vinyl alcohol solution (PVA) that distilled water and concentration are 8% granulating and forming: is mixed into powder as adhesive
In material, the quality of the distilled water of incorporation is the 2.5% of powder quality, and the quality of the adhesive of incorporation is the 5% of powder quality,
It is uniformly mixed in mortar；Mixed powder is placed in grinding tool, green compact are pressed into；Green compact are milled to powder in mortar,
By the sieve of 60 mesh and 120 mesh, the powder of 60 mesh and 120 mesh sieve middle layers is taken, it is suitable to have obtained granular size
Powder；Powder is placed in grinding tool, is pressed into green compact under the pressure of 200MPa；
(8) dumping: green compact dumping was excluded the PVA in green compact, obtain porcelain billet temperature lower calcination 3 hours of 650 DEG C；
(9) it is sintered: porcelain billet is sintered, sintering temperature is 1150 DEG C, soaking time 3 hours, obtains potsherd；
(10) it applies electrode: potsherd cleaning, drying, screen printing is brushed into silver electrode, silver ink firing, silver ink firing temperature 500~600
DEG C, soaking time 1~2 hour；
(11) it polarizes: the potsherd for having plated silver electrode being placed in 120~160 DEG C of silicone oil, polarizing voltage 12kV/mm
~15kV/mm, polarization time are 20min~40min.
CaBi to be prepared in embodiment 2 as shown in Figure 22Nb2-x(Mo2/3Cr1/3)xO9, the XRD of x=0.04 ceramics spreads out
Penetrate the curve that figure, the curve of dielectric constant with temperature variation and resistivity vary with temperature；Fig. 7 is that different amounts of Cr/Mo mixes
Miscellaneous CaBi2Nb2-x(Mo2/3Cr1/3)xO9The Curie temperature variation diagram of ceramics；Fig. 8 is different amounts of Cr/Mo doping CaBi2Nb2-x
(Mo2/3Cr1/3)xO9The room temperature piezoelectric modulus variation diagram of ceramics；Fig. 9 is different amounts of Cr/Mo doping CaBi2Nb2-x(Mo2/ 3Cr1/3)xO9Ceramics 600 DEG C when change in resistance figure.
As seen from Figure 2, Cr/Mo manufactured in the present embodiment codoping modified bismuth niobate calcium leadless piezoelectric ceramics with it is pure
The XRD spectrum of the bismuth niobate calcium piezoelectric ceramics of phase is almost the same.
Test result is as follows: d33=10pC/N, TCElectricalresistivityρ=5.8 × 10 at=935 DEG C, 600 DEG C5Ω·cm。
Embodiment 3
Preparation meets chemical composition CaBi2Nb2-x(Mo2/3Cr1/3)xO9, the Cr/Mo of x=0.05 codoping modified niobic acid
Bismuth calcium (CaBi2Nb2O9) leadless piezoelectric ceramics, including the following steps:
(1) ingredient: with CaCO3Powder, Bi2O3Powder, Nb2O5Powder, Cr2O3Powder and MoO3Powder is raw material, by general formula
The stoichiometry of middle Ca, Bi, Nb, Cr and Mo carry out ingredient；
(2) ball millings: the dehydrated alcohol with mixture equivalent being added into said mixture, continues ball milling 12 hours,
It is uniformly mixed powder and forms slurry, it is possible thereby to further improve the comprehensive of bismuth niobate calcium high temperature piezoceramics
Energy；
(3) it dries: above-mentioned slurry being placed in constant temperature oven and is toasted, remove dehydrated alcohol, and grind in mortar, obtain
Powder；
(4) tabletting pre-burning: powder being placed in grinding tool and is pressed into material block in advance, will expect block pre-burning, and calcined temperature is 725 DEG C, is protected
Warm time 2 h；
(5) secondary ball milling: by the material block after pre-burning in mortar, primary powder is obtained after being pulverized grinding, to what is obtained
The dehydrated alcohol with primary powder equivalent is added in primary powder, continues ball milling 12 hours, is uniformly mixed powder and forms slurry；
(6) it dries: above-mentioned slurry being placed in constant temperature oven and is toasted, remove dehydrated alcohol, and pulverize in mortar
Material；
(7) poly-vinyl alcohol solution (PVA) that distilled water and concentration are 8% granulating and forming: is mixed into powder as adhesive
In material, the quality of the distilled water of incorporation is the 2.5% of powder quality, and the quality of the adhesive of incorporation is the 5% of powder quality,
It is uniformly mixed in mortar；Mixed powder is placed in grinding tool, green compact are pressed into；Green compact are milled to powder in mortar,
By the sieve of 60 mesh and 120 mesh, the powder of 60 mesh and 120 mesh sieve middle layers is taken, it is suitable to have obtained granular size
Powder；Powder is placed in grinding tool, is pressed into green compact under the pressure of 200MPa；
(8) dumping: green compact dumping was excluded the PVA in green compact, obtain porcelain billet temperature lower calcination 3 hours of 650 DEG C；
(9) it is sintered: porcelain billet is sintered, sintering temperature is 1150 DEG C, soaking time 3 hours, obtains potsherd；
(10) it applies electrode: potsherd cleaning, drying, screen printing is brushed into silver electrode, silver ink firing, silver ink firing temperature 500~600
DEG C, soaking time 1~2 hour；
(11) it polarizes: the potsherd for having plated silver electrode being placed in 120~160 DEG C of silicone oil, polarizing voltage 12kV/mm
~15kV/mm, polarization time are 20min~40min.
CaBi to be prepared in embodiment 3 as shown in Figure 32Nb2-x(Mo2/3Cr1/3)xO9, the XRD of x=0.05 ceramics spreads out
Penetrate the curve that figure, the curve of dielectric constant with temperature variation and resistivity vary with temperature；Fig. 7 is that different amounts of Cr/Mo mixes
Miscellaneous CaBi2Nb2-x(Mo2/3Cr1/3)xO9The Curie temperature variation diagram of ceramics；Fig. 8 is different amounts of Cr/Mo doping CaBi2Nb2-x
(Mo2/3Cr1/3)xO9The room temperature piezoelectric modulus variation diagram of ceramics；Fig. 9 is different amounts of Cr/Mo doping CaBi2Nb2-x(Mo2/ 3Cr1/3)xO9Ceramics 600 DEG C when change in resistance figure.
As seen from Figure 3, Cr/Mo manufactured in the present embodiment codoping modified bismuth niobate calcium leadless piezoelectric ceramics with it is pure
The XRD spectrum of the bismuth niobate calcium piezoelectric ceramics of phase is almost the same.
Test result is as follows: d33=12pC/N, TCElectricalresistivityρ=4.0 × 10 at=938 DEG C, 600 DEG C5Ω·cm。
Embodiment 4
Preparation meets chemical composition CaBi2Nb2-x(Mo2/3Cr1/3)xO9, the Cr/Mo of x=0.06 codoping modified niobic acid
Bismuth calcium (CaBi2Nb2O9) leadless piezoelectric ceramics, including the following steps:
(1) ingredient: with CaCO3Powder, Bi2O3Powder, Nb2O5Powder, Cr2O3Powder and MoO3Powder is raw material, by general formula
The stoichiometry of middle Ca, Bi, Nb, Cr and Mo carry out ingredient；
(2) ball millings: the dehydrated alcohol with mixture equivalent being added into said mixture, continues ball milling 12 hours,
It is uniformly mixed powder and forms slurry, it is possible thereby to further improve the comprehensive of bismuth niobate calcium high temperature piezoceramics
Energy；
(3) it dries: above-mentioned slurry being placed in constant temperature oven and is toasted, remove dehydrated alcohol, and grind in mortar, obtain
Powder；
(4) tabletting pre-burning: powder being placed in grinding tool and is pressed into material block in advance, will expect block pre-burning, and calcined temperature is 725 DEG C, is protected
Warm time 2 h；
(5) secondary ball milling: by the material block after pre-burning in mortar, primary powder is obtained after being pulverized grinding, to what is obtained
The dehydrated alcohol with primary powder equivalent is added in primary powder, continues ball milling 12 hours, is uniformly mixed powder and forms slurry；
(6) it dries: above-mentioned slurry being placed in constant temperature oven and is toasted, remove dehydrated alcohol, and pulverize in mortar
Material；
(7) poly-vinyl alcohol solution (PVA) that distilled water and concentration are 8% granulating and forming: is mixed into powder as adhesive
In material, the quality of the distilled water of incorporation is the 2.5% of powder quality, and the quality of the adhesive of incorporation is the 5% of powder quality,
It is uniformly mixed in mortar；Mixed powder is placed in grinding tool, green compact are pressed into；Green compact are milled to powder in mortar,
By the sieve of 60 mesh and 120 mesh, the powder of 60 mesh and 120 mesh sieve middle layers is taken, it is suitable to have obtained granular size
Powder；Powder is placed in grinding tool, is pressed into green compact under the pressure of 200MPa；
(8) dumping: green compact dumping was excluded the PVA in green compact, obtain porcelain billet temperature lower calcination 3 hours of 650 DEG C；
(9) it is sintered: porcelain billet is sintered, sintering temperature is 1150 DEG C, soaking time 3 hours, obtains potsherd；
(10) it applies electrode: potsherd cleaning, drying, screen printing is brushed into silver electrode, silver ink firing, silver ink firing temperature 500~600
DEG C, soaking time 1~2 hour；
(11) it polarizes: the potsherd for having plated silver electrode being placed in 120~160 DEG C of silicone oil, polarizing voltage 12kV/mm
~15kV/mm, polarization time are 20min~40min.
CaBi to be prepared in embodiment 4 as shown in Figure 42Nb2-x(Mo2/3Cr1/3)xO9, the XRD of x=0.06 ceramics spreads out
Penetrate the curve that figure, the curve of dielectric constant with temperature variation and resistivity vary with temperature；Fig. 7 is that different amounts of Cr/Mo mixes
Miscellaneous CaBi2Nb2-x(Mo2/3Cr1/3)xO9The Curie temperature variation diagram of ceramics；Fig. 8 is different amounts of Cr/Mo doping CaBi2Nb2-x
(Mo2/3Cr1/3)xO9The room temperature piezoelectric modulus variation diagram of ceramics；Fig. 9 is different amounts of Cr/Mo doping CaBi2Nb2-x(Mo2/ 3Cr1/3)xO9Ceramics 600 DEG C when change in resistance figure.
As seen from Figure 4, Cr/Mo manufactured in the present embodiment codoping modified bismuth niobate calcium leadless piezoelectric ceramics with it is pure
The XRD spectrum of the bismuth niobate calcium piezoelectric ceramics of phase is almost the same.
Test result is as follows: d33=13pC/N, TCElectricalresistivityρ=3.4 × 10 at=939 DEG C, 600 DEG C5Ω·cm。
Embodiment 5
Preparation meets chemical composition CaBi2Nb2-x(Mo2/3Cr1/3)xO9, the Cr/Mo of x=0.07 codoping modified niobic acid
Bismuth calcium (CaBi2Nb2O9) leadless piezoelectric ceramics, including the following steps:
(1) ingredient: with CaCO3Powder, Bi2O3Powder, Nb2O5Powder, Cr2O3Powder and MoO3Powder is raw material, by general formula
The stoichiometry of middle Ca, Bi, Nb, Cr and Mo carry out ingredient；
(2) ball millings: the dehydrated alcohol with mixture equivalent being added into said mixture, continues ball milling 12 hours,
It is uniformly mixed powder and forms slurry, it is possible thereby to further improve the comprehensive of bismuth niobate calcium high temperature piezoceramics
Energy；
(3) it dries: above-mentioned slurry being placed in constant temperature oven and is toasted, remove dehydrated alcohol, and grind in mortar, obtain
Powder；
(4) tabletting pre-burning: powder being placed in grinding tool and is pressed into material block in advance, will expect block pre-burning, and calcined temperature is 725 DEG C, is protected
Warm time 2 h；
(5) secondary ball milling: by the material block after pre-burning in mortar, primary powder is obtained after being pulverized grinding, to what is obtained
The dehydrated alcohol with primary powder equivalent is added in primary powder, continues ball milling 12 hours, is uniformly mixed powder and forms slurry；
(6) it dries: above-mentioned slurry being placed in constant temperature oven and is toasted, remove dehydrated alcohol, and pulverize in mortar
Material；
(7) poly-vinyl alcohol solution (PVA) that distilled water and concentration are 8% granulating and forming: is mixed into powder as adhesive
In material, the quality of the distilled water of incorporation is the 2.5% of powder quality, and the quality of the adhesive of incorporation is the 5% of powder quality,
It is uniformly mixed in mortar；Mixed powder is placed in grinding tool, green compact are pressed into；Green compact are milled to powder in mortar,
By the sieve of 60 mesh and 120 mesh, the powder of 60 mesh and 120 mesh sieve middle layers is taken, it is suitable to have obtained granular size
Powder；Powder is placed in grinding tool, is pressed into green compact under the pressure of 200MPa；
(8) dumping: green compact dumping was excluded the PVA in green compact, obtain porcelain billet temperature lower calcination 3 hours of 650 DEG C；
(9) it is sintered: porcelain billet is sintered, sintering temperature is 1150 DEG C, soaking time 3 hours, obtains potsherd；
(10) it applies electrode: potsherd cleaning, drying, screen printing is brushed into silver electrode, silver ink firing, silver ink firing temperature 500~600
DEG C, soaking time 1~2 hour；
(11) it polarizes: the potsherd for having plated silver electrode being placed in 120~160 DEG C of silicone oil, polarizing voltage 12kV/mm
~15kV/mm, polarization time are 20min~40min.
CaBi to be prepared in embodiment 5 as shown in Figure 52Nb2-x(Mo2/3Cr1/3)xO9, the XRD of x=0.07 ceramics spreads out
Penetrate the curve that figure, the curve of dielectric constant with temperature variation and resistivity vary with temperature；Fig. 7 is that different amounts of Cr/Mo mixes
Miscellaneous CaBi2Nb2-x(Mo2/3Cr1/3)xO9The Curie temperature variation diagram of ceramics；Fig. 8 is different amounts of Cr/Mo doping CaBi2Nb2-x
(Mo2/3Cr1/3)xO9The room temperature piezoelectric modulus variation diagram of ceramics；Fig. 9 is different amounts of Cr/Mo doping CaBi2Nb2-x(Mo2/ 3Cr1/3)xO9Ceramics 600 DEG C when change in resistance figure.
As seen from Figure 5, Cr/Mo manufactured in the present embodiment codoping modified bismuth niobate calcium leadless piezoelectric ceramics with it is pure
The XRD spectrum of the bismuth niobate calcium piezoelectric ceramics of phase is almost the same.
Test result is as follows: d33=15pC/N, TCElectricalresistivityρ=3.3 × 10 at=939 DEG C, 600 DEG C5Ω·cm。
Embodiment 6
Preparation meets chemical composition CaBi2Nb2-x(Mo2/3Cr1/3)xO9, the Cr/Mo of x=0.075 codoping modified niobic acid
Bismuth calcium (CaBi2Nb2O9) leadless piezoelectric ceramics, including the following steps:
(1) ingredient: with CaCO3Powder, Bi2O3Powder, Nb2O5Powder, Cr2O3Powder and MoO3Powder is raw material, by general formula
The stoichiometry of middle Ca, Bi, Nb, Cr and Mo carry out ingredient；
(2) ball millings: the dehydrated alcohol with mixture equivalent being added into said mixture, continues ball milling 12 hours,
It is uniformly mixed powder and forms slurry, it is possible thereby to further improve the comprehensive of bismuth niobate calcium high temperature piezoceramics
Energy；
(3) it dries: above-mentioned slurry being placed in constant temperature oven and is toasted, remove dehydrated alcohol, and grind in mortar, obtain
Powder；
(4) tabletting pre-burning: powder being placed in grinding tool and is pressed into material block in advance, will expect block pre-burning, and calcined temperature is 725 DEG C, is protected
Warm time 2 h；
(5) secondary ball milling: by the material block after pre-burning in mortar, primary powder is obtained after being pulverized grinding, to what is obtained
The dehydrated alcohol with primary powder equivalent is added in primary powder, continues ball milling 12 hours, is uniformly mixed powder and forms slurry；
(6) it dries: above-mentioned slurry being placed in constant temperature oven and is toasted, remove dehydrated alcohol, and pulverize in mortar
Material；
(7) poly-vinyl alcohol solution (PVA) that distilled water and concentration are 8% granulating and forming: is mixed into powder as adhesive
In material, the quality of the distilled water of incorporation is the 2.5% of powder quality, and the quality of the adhesive of incorporation is the 5% of powder quality,
It is uniformly mixed in mortar；Mixed powder is placed in grinding tool, green compact are pressed into；Green compact are milled to powder in mortar,
By the sieve of 60 mesh and 120 mesh, the powder of 60 mesh and 120 mesh sieve middle layers is taken, it is suitable to have obtained granular size
Powder；Powder is placed in grinding tool, is pressed into green compact under the pressure of 200MPa；
(8) dumping: green compact dumping was excluded the PVA in green compact, obtain porcelain billet temperature lower calcination 3 hours of 650 DEG C；
(9) it is sintered: porcelain billet is sintered, sintering temperature is 1150 DEG C, soaking time 3 hours, obtains potsherd；
(10) it applies electrode: potsherd cleaning, drying, screen printing is brushed into silver electrode, silver ink firing, silver ink firing temperature 500~600
DEG C, soaking time 1~2 hour；
(11) it polarizes: the potsherd for having plated silver electrode being placed in 120~160 DEG C of silicone oil, polarizing voltage 12kV/mm
~15kV/mm, polarization time are 20min~40min.
CaBi to be prepared in embodiment 6 as shown in Figure 62Nb2-x(Mo2/3Cr1/3)xO9, the XRD of x=0.075 ceramics spreads out
Penetrate the curve that figure, the curve of dielectric constant with temperature variation and resistivity vary with temperature；Fig. 7 is that different amounts of Cr/Mo mixes
Miscellaneous CaBi2Nb2-x(Mo2/3Cr1/3)xO9The Curie temperature variation diagram of ceramics；Fig. 8 is different amounts of Cr/Mo doping CaBi2Nb2-x
(Mo2/3Cr1/3)xO9The room temperature piezoelectric modulus variation diagram of ceramics；Fig. 9 is different amounts of Cr/Mo doping CaBi2Nb2-x(Mo2/ 3Cr1/3)xO9Ceramics 600 DEG C when change in resistance figure.
As seen from Figure 6, Cr/Mo manufactured in the present embodiment codoping modified bismuth niobate calcium leadless piezoelectric ceramics with it is pure
The XRD spectrum of the bismuth niobate calcium piezoelectric ceramics of phase is almost the same.
Test result is as follows: d33=13.5pC/N, TCElectricalresistivityρ=3.3 × 10 at=940 DEG C, 600 DEG C5Ω·cm。
The above description of the embodiment is only used to help understand the method for the present invention and its core ideas.It should be pointed out that pair
For those skilled in the art, without departing from the principle of the present invention, the present invention can also be carried out
Some improvements and modifications, these improvements and modifications also fall within the scope of protection of the claims of the present invention.To these embodiments
A variety of modifications are it will be apparent that General Principle defined herein can be for those skilled in the art
It is realized in other embodiments in the case where not departing from the spirit or scope of the present invention.Therefore, the present invention is not intended to be limited to
These embodiments shown in the application, and be to fit to consistent with principle disclosed in the present application and features of novelty widest
Range.
Claims (6)
1. a kind of Nb Cr/Mo codope bismuth niobate calcium high temperature piezoceramics, which is characterized in that the piezoceramic material
General formula is CaBi2Nb2-x(Mo2/3Cr1/3)xO9, wherein 0.03≤x≤0.075.
2. Nb Cr/Mo codope bismuth niobate calcium high temperature piezoceramics according to claim 1, which is characterized in that x
=0.03,0.04,0.05,0.06,0.07 or 0.075.
3. a kind of preparation method of Nb Cr/Mo codope bismuth niobate calcium high temperature piezoceramics, which is characterized in that including such as
Lower step:
Ingredient: with CaCO3Powder, Bi2O3Powder, Nb2O5Powder, Cr2O3Powder and MoO3Powder is raw material, by general formula
CaBi2Nb2-x(Mo2/3Cr1/3)xO9The stoichiometry of middle Ca, Bi, Nb, Cr and Mo carry out ingredient, wherein 0.03≤x≤0.075；
Ball milling: the dehydrated alcohol with mixture equivalent being added into said mixture, continues ball milling 12~24 hours, makes powder
Body is uniformly mixed and forms slurry, it is possible thereby to further improve the comprehensive performance of bismuth niobate calcium high temperature piezoceramics；
Drying: above-mentioned slurry being placed in constant temperature oven and is toasted, and is removed dehydrated alcohol, and grind in mortar, is obtained powder；
Tabletting pre-burning: powder being placed in grinding tool and is pressed into material block in advance, will expect block pre-burning, and calcined temperature is 675~750 DEG C, heat preservation
Time 2~4 hours；
Secondary ball milling: by the material block after pre-burning in mortar, primary powder is obtained after being pulverized grinding, to obtained primary powder
The dehydrated alcohol of middle addition and primary powder equivalent continues ball milling 12~24 hours, is uniformly mixed powder and forms slurry；
Drying: above-mentioned slurry being placed in constant temperature oven and is toasted, and removes dehydrated alcohol, and powder is ground into mortar；
Granulating and forming: the poly-vinyl alcohol solution (PVA) that distilled water and concentration are 8% is mixed in powder as adhesive, is mixed
The quality of the distilled water entered is the 2.5% of powder quality, and the quality of the adhesive of incorporation is the 5% of powder quality, in mortar
It is uniformly mixed；Mixed powder is placed in grinding tool, green compact are pressed into；Green compact are milled to powder in mortar, pass through 60
The sieve of mesh and 120 mesh takes the powder of 60 mesh and 120 mesh sieve middle layers, has obtained the suitable powder of granular size；It will
Powder is placed in grinding tool, is pressed into green compact under the pressure of 200MPa；
Dumping: green compact dumping was excluded the PVA in green compact, obtains porcelain billet temperature lower calcination 3 hours of 650 DEG C；
Sintering: porcelain billet is sintered, and sintering temperature is 1000~1100 DEG C, soaking time 2~4 hours, obtains potsherd；
It applies electrode: potsherd cleaning, drying, screen printing is brushed into silver electrode, silver ink firing, 500~600 DEG C of silver ink firing temperature, when heat preservation
Between 1~2 hour；
Polarization: the potsherd for having plated silver electrode being placed in 120~160 DEG C of silicone oil, and polarizing voltage is 12kV/mm~15kV/
Mm, polarization time are 20min~40min.
4. the preparation method of Nb Cr/Mo codope bismuth niobate calcium high temperature piezoceramics according to claim 3,
It is characterized in that, during a ball milling and secondary ball milling, the Ball-milling Time is 12 hours.
5. the preparation method of Nb Cr/Mo codope bismuth niobate calcium high temperature piezoceramics according to claim 3,
It is characterized in that, in the burn-in process, the calcined temperature is 725 DEG C, and the soaking time is 2 hours.
6. the preparation method of Nb Cr/Mo codope bismuth niobate calcium high temperature piezoceramics according to claim 3,
It is characterized in that, in the sintering process, the sintering temperature is 1150 DEG C, and the soaking time is 3 hours.
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| CN115028450A (en) * | 2022-06-09 | 2022-09-09 | 清华大学 | Sodium niobate-based ceramic material and preparation method thereof |
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| CN115433008A (en) * | 2021-06-04 | 2022-12-06 | 中国科学院上海硅酸盐研究所 | Bismuth calcium niobate piezoelectric ceramic with high piezoelectric property and high-temperature resistivity regulated and controlled by components and preparation method thereof |
| CN117263679A (en) * | 2023-09-14 | 2023-12-22 | 景德镇陶瓷大学 | Ce, ga and Mo co-doped CaBi 4 Ti 4 O 15 High-temperature piezoelectric ceramic material and preparation method thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115433008A (en) * | 2021-06-04 | 2022-12-06 | 中国科学院上海硅酸盐研究所 | Bismuth calcium niobate piezoelectric ceramic with high piezoelectric property and high-temperature resistivity regulated and controlled by components and preparation method thereof |
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| CN115290153A (en) * | 2022-08-02 | 2022-11-04 | 浙江元集新材料有限公司 | Venturi nozzle of disc type air flow mill for processing copper-clad plate powder and manufacturing method thereof |
| CN117263679A (en) * | 2023-09-14 | 2023-12-22 | 景德镇陶瓷大学 | Ce, ga and Mo co-doped CaBi 4 Ti 4 O 15 High-temperature piezoelectric ceramic material and preparation method thereof |
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