CN104051606B - A kind of potassium-sodium niobate-based multilayer piezoelectric ceramic element and preparation method thereof - Google Patents
A kind of potassium-sodium niobate-based multilayer piezoelectric ceramic element and preparation method thereof Download PDFInfo
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Abstract
A kind of potassium-sodium niobate-based multilayer piezoelectric ceramic element of the present invention, the formula stoichiometric formula of the potassium niobate sodium-based leadless piezoelectric ceramic is：[(Na0.52K0.44)1‑xLix](Nb0.93‑ ySb0.07Tay)O3, wherein 0.02≤x≤0.06,0.02≤y≤0.06, its piezoelectric constant is 300 350pC/N even more highs, and dielectric constant is 1,700 2000, and electromechanical coupling factor is 0.40 0.45.
Description
Technical field
The present invention relates to ceramic material technical field, more particularly to a kind of lithium, antimony, tantalum codope potassium-sodium niobate Quito
Layer piezo ceramic element, the present invention is further directed to the potassium-sodium niobate-based multilayer piezoelectric ceramic element of lithium, antimony, tantalum codope
Preparation method.
Background technology
Multilayer piezoelectric ceramic element is a kind of important electric function ceramic element, compared to common single layer piezoelectric ceramics unit
Part, low with driving voltage, piezoelectric strain is big, it is easy to the advantages of minimizing, be thinned.Multilayer piezoelectric ceramic element is widely used in
Piezoelectric transformer, piezoelectric actuator, piezoelectric speaker, the floating energy device of piezoelectricity, and multilayer ceramic capacitor, wherein piezoelectric actuator
Including automobile engine injection system, ultrasonic motor, linear ultrasonic motor, the high-precision pointed collar domain such as micro positioner, and multilayer device
Part small volume, consumption are big, so the research of multilayer piezoelectric ceramic has important scientific meaning and market value.However, at present
Multilayer piezoelectric ceramic select raw material be generally lead zirconate titanate system ceramics, the poisonous lead oxide containing more than 60wt%, production,
Using with waste procedures in easily to human body health and environment cause harm.2006, European Union's issue and implementation RoHS were instructed
(instruction of some harmful components is used on being limited in electronic and electrical equipment), forbids using lead etc. harmful in electronic product
The states such as composition, subsequent Korean and Japanese of Sino-U.S. also issue or plan the similar decree of issue in succession.The subsequent world has started Study For Zirconium metatitanic acid
The upsurge of the alternative materials of lead series piezoelectric ceramic, i.e. leadless piezoelectric ceramics.Although present lead zirconate titanate series piezoelectric ceramic is still enjoyed
The prerogarive of mercy of this instruction, European Union can all be carried out to the technical merit that lead-free systems piezoelectric ceramics substitutes lead series piezoelectric ceramic every year
Assessment, once ripe, it will carry out the unleaded process of piezoelectric ceramics immediately.So with leadless piezoelectric ceramics as raw material
Multilayer piezoelectric ceramic technology of preparing have it is contemplated that and urgent application value.
Potassium-sodium niobate series piezoelectric ceramic with preferable piezoelectric and dielectric properties and Curie temperature higher under its Unit Weight,
One of always most important lead-free piezoceramic material system.2004, Japanese scholars Saito et al. was common by lithium, antimony, tantalum
Doping and texturing realize the breakthrough of potassium/sodium niobtae piezoelectric piezoelectric property, wherein solid phase method codope obtain it is optimal
Piezoelectric constant has reached more than 300pC/N first.Further studied by domestic and foreign scholars and improved, potassium/sodium niobtae no-lead
Piezoelectric ceramics has become one of material system of most potential replacement lead series piezoelectric ceramic.At present, potassium/sodium niobtae no-lead pressure
The research and preparation of electroceramics sandwich type element are in the stage of fast development, and the present invention uses electrical with dielectric high, high pressure
Lithium, antimony, the potassium sodium niobate ceramic formula of tantalum codope of energy, multilayer leadless piezoelectric ceramics is prepared by the preparation technology after improvement
Element, with important production practices meaning.
CN101456733A discloses one kind formula (Na0.52K0.44Li0.04)(Nb0.80Ta0.20)O3, the potassium niobate of expression
The preparation method of sodium base leadless piezoelectric ceramic thin sheet, by pretreatment of raw material, mixed material, pre-burning, slurrying, curtain coating, punching, row
Glue, sintering, by silver, polarization process step composition.It is of the invention compared with existing piezoelectric ceramics preparation method, employ slurrying, stream
Prolong processing step, be prepared into pure calcium ore deposit structure, density is big by the emperor himself, fine grain and crystal grain is homogeneous, good electrical property potassium-sodium niobate-based nothing
Lead piezoelectric ceramics thin slice, thickness is 0.12mm.The potassium niobate sodium base leadless piezoelectric ceramic thin sheet prepared using the inventive method, system
It is standby into leadless piezoelectric buzzer, non-environmental-pollution, when driving voltage is 3V, acoustic pressure reaches maximum 86.06dB in 4.445kHz；
When driving voltage is 6V, 9V, maximum sound pressure shows the electricity that piezoelectric buzzer has had than increasing people respectively to 91.91,95.22dB
Acoustic performance, reaches as the application requirement of microphone device.It uses the technology of preparing once calcined, due to potassium/sodium niobtae no-lead
Piezoelectric ceramics contains the alkali metals such as potassium, sodium, lithium, and high temperature sintering 4-8 hours at 1150-1170 DEG C is volatile, once forges
The technical scheme of burning easily causes powder into mutually uneven, the phenomenon of powder real composition deviation original formulation, and it has piezoelectric constant
The dielectric constant of the about piezoelectric constant of 200-250pC/N, and 500-1100.Mass produce practice in be more easy to occur and more
Seriously, the uniformity and yields of properties of product be directly affects.
The content of the invention
Therefore, to be solved by this invention is that existing potassium niobate sodium base leadless piezoelectric ceramic thin sheet is deposited in preparation process
It is easy to volatilization problems in alkali metal, causes the value of product real composition off-design, or even produce with non-stoichiometric
Component zone, generation tungsten bronze, the equal dephasign of burnt green stone, reduces the piezoelectric property of ceramics, increases dielectric loss, in turn results in
Properties of product decline, be this invention provides a kind of potassium-sodium niobate-based multilayer piezoelectric ceramic element, it has piezoelectricity higher
Performance.
The present invention has further related to the preparation method of above-mentioned potassium-sodium niobate-based multilayer piezoelectric ceramic element.
The present invention is adopted the following technical scheme that：
A kind of potassium-sodium niobate-based multilayer piezoelectric ceramic element, the formula of the potassium niobate sodium-based leadless piezoelectric ceramic original paper
Learning metering formula is：
[(Na0.52K0.44)1-xLix](Nb0.93-ySb0.07Tay)O3
Wherein 0.02≤x≤0.06,0.02≤y≤0.06.
The preparation method of above-mentioned potassium-sodium niobate-based multilayer piezoelectric ceramic element, comprises the steps
S1, pretreatment
By [(Na0.52K0.44)1-xLix](Nb0.93-ySb0.07Tay)O3Particle diameter is obtained after required raw material drying ball milling for 700-
The slurry of 1300nm；
S2, first calcining and ball mill grinding
Slurry drying prepared by step S1, is 800 DEG C -850 DEG C and calcines 2-5h after pulverizing and sieving in temperature, cools down, so
Afterwards with absolute ethyl alcohol as dispersant, with zirconia ball as ball-milling medium ball milling after obtain slurry of the particle diameter as 1500-2000nm；
S3, secondary clacining and ball mill grinding
It is 800 DEG C -850 DEG C in temperature after slurry dries pulverizing sieving prepared by step S2 and calcines 2-5h, cools down, then
With absolute ethyl alcohol as dispersant, with zirconia ball as ball-milling medium ball milling after obtain the slurry of particle diameter 700-1300nm, after drying
It is potassium/sodium niobtae ceramic powder；
S4, flow casting molding
According to potassium/sodium niobtae ceramic powder：Binding agent：The volume ratio of solvent is 1:0.25-0.35：0.35-0.5's
Ratio is added in ball grinder, and with zirconia ball as ball-milling medium, slurry after ball milling is with quiet after vavuum pump degasification deaeration 1-2h
Put, the film that thickness is 10-200 μm is cast into using casting machine；
S5, printing, lamination, hot pressing and cutting
The diaphragm that obtains of curtain coating is printed electrode pattern as needed, and new diaphragm is put after ground floor drying, is pressed follow-up
Continuous to print electrode, such circulating printing is stacked to the number of plies of design；Multilayer Film plastic packaging after lamination, connects end electricity after hot pressing
Pole, obtains final multi-layer ceramics green compact；
S6, dumping, co-sintering and polarization
After by ceramic green aluminum oxide or load bearing board of zirconia clamping, it is embedded in aluminium oxide ceramics powder, is placed in electric furnace,
The slow intensification dumping between 200-500 DEG C, programming rate is 10-12 DEG C/h；Green compact after dumping are sintered at 1050-1100 DEG C
2-4h, rear furnace cooling, polarization, you can.
The step S1 is that alkali metal source is dried into 8-12h, and and Nb at 60-80 DEG C2O5、Ta2O5、Sb2O3After mixing
With absolute ethyl alcohol as dispersant, ball milling is carried out by ball-milling medium of zirconia ball.
Described alkali metal source is Li2CO3、Na2CO3And K2CO3。
Slurry crosses 60 mesh sieves in the step S2 and step S3.
Binding agent in the step S4 is polyvinyl butyral resin, the solvent be toluene or dimethylbenzene, absolute ethyl alcohol,
One kind or wherein several mixtures in isopropanol.
Electrode material selects silver palladium alloy, nickel or copper in the step S5.
Hot pressing in the step S5 be temperature be 60-80 DEG C, pressure be 40-60MPa under the conditions of keep 10~30 points
Clock.
Ceramic green load bearing board support described in the step S6 is become with preventing from shrinking uneven in temperature-rise period
Shape.
Polarization described in the step S6 is will to sinter the multi-layer ceramics sample for obtaining to use silicone oil oil bath polarization or air
Polarization.
The process conditions of described silicone oil oil bath polarization are：Silicone oil oil bath temperature is 60-120 DEG C, and Polarization field strength is 2-
3kV/mm, the polarization time is 20-30 minutes；The condition of described air polarization is：Poling temperature is 60-120 DEG C, pole in air
Change field intensity is 1-2kV/mm, and the polarization time is 20-30 minutes.
Above-mentioned technical proposal of the invention has advantages below compared to existing technology：
(1) the formula stoichiometric formula that uses of potassium-sodium niobate-based multilayer piezoelectric ceramic element that the present invention is provided for
[(Na0.52K0.44)1-xLix](Nb0.93-ySb0.07Tay)O3, being one has the composition of higher pressure electrical property interval, this into
The potassium-sodium niobate-based multilayer piezoelectric ceramic element of lithium, antimony, tantalum codope niobium in by stages has piezoelectric property higher, and piezoelectricity is normal
Number is 300-350pC/N even more highs, and dielectric constant is 1700-2000, and electromechanical coupling factor is 0.40-0.45.Due to tradition
Alkali metal volatilization is easily caused its true component deviation design component when being sintered in potassium-sodium niobate series piezoelectric ceramic preparation process, this
The interval proposition of one composition can be effectively ensured the performance of the piezoelectric ceramics of output, and advantage is had more especially in large-scale production.
(2) the invention provides a kind of solid phase method preparation method of improved potassium/sodium niobtae ceramic powder.By secondary
Calcining ball milling, can effectively improve powder into Phase Proportion, improve the uniformity of powder distribution, obtain high activity, uniform, tiny
Potassium/sodium niobtae ceramic powder, greatly facilitates the steps such as follow-up forming and sintering.This improved method is in high-volume potassium niobate
There is efficiency and more preferable effect higher in the production of sodium system ceramic powder.
(3) system for burning till type altogether is prepared into from powder the invention provides a kind of potassium/sodium niobtae multilayer piezoelectric ceramic element
Make method, it is adaptable to the design of the unleaded multilayer piezoelectric ceramic element of the different-thickness number of plies of multiple use and manufacture.
(4) potassium-sodium niobate-based multilayer piezoelectric ceramic element of the invention employs component Sb, and the component can be significantly reduced
Orthorhombic phase-Tetragonal the phase transition temperature of potassium-sodium niobate-based ceramics, promotes the enhancing mechanism of many crystal transitions, improves the dielectric of ceramics
Constant, remanent polarization and piezoelectric constant.
(5) in the present invention in the preparation method of potassium-sodium niobate-based multilayer piezoelectric ceramic element the sintering temperature that uses for
1050-1100 DEG C, compared with 1150-1170 DEG C that prior art CN101456733A is used, at least 50 DEG C of temperature reduction, and
Sintering time was reduced to 2-4 hours by 4-8 hours, can effectively reduce the volatilization of alkali metal.
Brief description of the drawings
In order that present disclosure is more likely to be clearly understood, below according to specific embodiment of the invention and combine
Accompanying drawing, the present invention is further detailed explanation, wherein
Fig. 1 is the laser particle size point of the final powder of lead free piezoelectric ceramics of potassium sodium niobate of embodiments in accordance with the present invention 4
Butut；
Fig. 2 is the ESEM of the section polishing of the potassium/sodium niobtae multi-layer ceramic component of embodiments in accordance with the present invention 4
Photo；
Specific embodiment
In order that the object, technical solutions and advantages of the present invention are clearer, below in conjunction with accompanying drawing to reality of the invention
The mode of applying is described in further detail.
The present invention can be embodied in many different forms, and should not be construed as limited to embodiment set forth herein.
Conversely, there is provided these embodiments so that the disclosure will be thorough and complete, and will it is of the invention design be fully conveyed to
Those skilled in the art, the present invention will only be defined by the appended claims.
Embodiment 1
The formula stoichiometric formula of potassium-sodium niobate-based multilayer piezoelectric ceramic element is in the present embodiment：
(Na0.52K0.44Li0.04)(Nb0.91Sb0.07Ta0.02)O3
The preparation method of above-mentioned potassium-sodium niobate-based multilayer piezoelectric ceramic element comprises the following steps：
(1) raw material prepares and dispensing
Li2CO3、Na2CO3、K2CO3These alkali carbonates are hygroscopic to make moist, and it is standby to dry 12h at 60 DEG C before
With.According to the stoichiometric proportion of formula formula, weigh first：Li2CO3、Na2CO3、K2CO3；Then Nb is weighed2O5、Ta2O5、
Sb2O3。
(2) ball mill mixing
It is dispersant that the raw material that will be prepared adds absolute ethyl alcohol, with zirconia ball as ball-milling medium, planetary ball mill ball
Mill 4h (producer's model of planetary ball mill ball milling please be provided).
(3) first calcining and ball mill grinding
Mixed powder is obtained after the slurry drying obtained after ball mill mixing, mixed powder pulverizes and sieves, accurate by 60 targets
After sieve, it is put into the alumina crucible added a cover, 800 DEG C of calcining 5h, furnace cooling in air.The powder obtained after calcining is with anhydrous
Ethanol is dispersant, with zirconia ball as ball-milling medium, planetary ball mill ball milling 8h.
(4) secondary clacining and ball mill grinding
Mixed powder is obtained after first ball mill grinding disposed slurry drying, mixed powder pulverizes and sieves, by 60 mesh standard sieves
Afterwards, it is put into the alumina crucible added a cover, 5h, furnace cooling is calcined again for 800 DEG C in air.The powder obtained after calcining is with nothing
Water-ethanol is dispersant, with zirconia ball as ball-milling medium, planetary ball mill ball milling 8h.It is after the slurry drying that ball milling is obtained
Final potassium/sodium niobtae ceramic powder.
(5) flow casting molding
According to ceramic powder：Binding agent：The ratio of solvent is 1:0.25：0.35 ratio is added in ball grinder, wherein, glue
Knot agent is PVB (polyvinyl butyral resin), and solvent is toluene.With zirconia ball as ball-milling medium, planetary ball mill ball milling
36h.Slurry after ball milling is stood with after vavuum pump degasification deaeration 2h, is cast using casting machine, the specification regulation according to casting machine
Line speed, drying temperature etc., it is 200 μm that thickness is controlled as needed.
(6) printing, lamination, hot pressing and cutting
The diaphragm that obtains of curtain coating prints electrode pattern as needed, and electrode material can select silver palladium alloy.Ground floor is dried
New diaphragm being put afterwards, and being pressed with dry press, continue to print electrode after pressing, such circulating printing is stacked to the layer of design
Number.After Multilayer Film plastic packaging after lamination, hot pressing is carried out using hot water isostatic pressed, temperature is 80 DEG C, pressure is holding under 40MPa
10 minutes.Multilayer Film after hot pressing carries out last cutting and goes to corner according to design, connects termination electrode, obtains final many
Layer ceramic green.
(7) dumping and co-sintering
The support of ceramic green load bearing board is deformed with preventing from shrinking uneven in temperature-rise period, between 200-500 DEG C
Slow intensification dumping, programming rate is 10-12 DEG C/h.Green compact after dumping sinter 2h at 1050-1100 DEG C, after it is cold with stove
But.
(8) polarize
The multi-layer ceramics sample that sintering is obtained can be polarized using silicone oil oil bath：Silicone oil oil bath temperature is 60 DEG C, Polarization field strength
It is 3kV/mm, the polarization time is 30 minutes.
Embodiment 2
The formula stoichiometric formula of potassium-sodium niobate-based multilayer piezoelectric ceramic element is in the present embodiment：
(Na0.52K0.44Li0.04)(Nb0.87Sb0.07Ta0.06)O3
(1) raw material prepares and dispensing
Li2CO3、Na2CO3、K2CO3These alkali carbonates are hygroscopic to make moist, and it is standby to dry 8h at 80 DEG C before.
According to the stoichiometric proportion of formula formula, weigh first：Li2CO3、Na2CO3、K2CO3；Then Nb is weighed2O5、Ta2O5、Sb2O3。
(2) ball mill mixing
It is dispersant that the raw material that will be prepared adds absolute ethyl alcohol, with zirconia ball as ball-milling medium, planetary ball mill ball
Mill 4h grinds formula ball mill ball milling 24h with common tank.
(3) first calcining and ball mill grinding
Mixed powder is obtained after the slurry drying obtained after ball mill mixing, mixed powder pulverizes and sieves, accurate by 60 targets
After sieve, it is put into the alumina crucible added a cover, 850 DEG C of calcining 2h, furnace cooling in air.The powder obtained after calcining is with anhydrous
Ethanol is dispersant, with zirconia ball as ball-milling medium, planetary ball mill ball milling 4h.
(4) secondary clacining and ball mill grinding
Mixed powder is obtained after first ball mill grinding disposed slurry drying, mixed powder pulverizes and sieves, by 60 mesh standard sieves
Afterwards, it is put into the alumina crucible added a cover, 2h, furnace cooling is calcined again for 850 DEG C in air.The powder obtained after calcining is with nothing
Water-ethanol is dispersant, with zirconia ball as ball-milling medium, formula ball mill ball milling 24h is ground with common tank.The slurry that ball milling is obtained
It is final potassium/sodium niobtae ceramic powder after drying.
(5) flow casting molding
According to ceramic powder：Binding agent：The ratio of solvent is 1:0.35：0.5 ratio is added in ball grinder, wherein, glue
Knot agent is PVB (polyvinyl butyral resin), and solvent is dimethylbenzene.With zirconia ball as ball-milling medium, planetary ball mill ball milling
16h.Slurry after ball milling is stood with after vavuum pump degasification deaeration 1h, is cast using casting machine, the specification regulation according to casting machine
Line speed, drying temperature etc., it is 10 μm that thickness is controlled as needed.
(6) printing, lamination, hot pressing and cutting
The diaphragm that obtains of curtain coating prints electrode pattern as needed, and electrode material can select silver palladium alloy, nickel, copper etc..The
New diaphragm is put after one layer of drying, and is pressed with dry press, continue to print electrode after pressing, such circulating printing is stacked to and sets
The number of plies of meter.After Multilayer Film plastic packaging after lamination, hot pressing is carried out using hot water isostatic pressed, temperature is 60 DEG C, and pressure is 60MPa
It is lower to be kept for 30 minutes.Multilayer Film after hot pressing carries out last cutting and goes to corner according to design, connects termination electrode, obtains most
Whole multi-layer ceramics green compact.
(7) dumping and co-sintering
The support of ceramic green load bearing board is deformed with preventing from shrinking uneven in temperature-rise period, between 200-500 DEG C
Slow intensification dumping, programming rate is 10-12 DEG C/h.Green compact after dumping sinter 3h at 1050-1100 DEG C, after it is cold with stove
But.
(8) polarize
The multi-layer ceramics sample that sintering is obtained can use air polarization two ways：Poling temperature is 60 DEG C, pole in air
Change field intensity is 1kV/mm, and the polarization time is 20 minutes.
Embodiment 3
The formula stoichiometric formula of potassium-sodium niobate-based multilayer piezoelectric ceramic element is in the present embodiment：
(Na0.52K0.44Li0.04)(Nb0.90Sb0.07Ta0.03)O3
(1) raw material prepares and dispensing
Li2CO3、Na2CO3、K2CO3These alkali carbonates are hygroscopic to make moist, and it is standby to dry 10h at 70 DEG C before
With.According to the stoichiometric proportion of formula formula, weigh first：Li2CO3、Na2CO3、K2CO3；Then Nb is weighed2O5、Ta2O5、
Sb2O3。
(2) ball mill mixing
It is dispersant that the raw material that will be prepared adds absolute ethyl alcohol, with zirconia ball as ball-milling medium, planetary ball mill ball
Mill 4h.
(3) first calcining and ball mill grinding
Mixed powder is obtained after the slurry drying obtained after ball mill mixing, mixed powder pulverizes and sieves, accurate by 60 targets
After sieve, it is put into the alumina crucible added a cover, 830 DEG C of calcining 3h, furnace cooling in air.The powder obtained after calcining is with anhydrous
Ethanol is dispersant, with zirconia ball as ball-milling medium, planetary ball mill ball milling 6h.
(4) secondary clacining and ball mill grinding
Mixed powder is obtained after first ball mill grinding disposed slurry drying, mixed powder pulverizes and sieves, by 60 mesh standard sieves
Afterwards, it is put into the alumina crucible added a cover, 4h, furnace cooling is calcined again for 830 DEG C in air.The powder obtained after calcining is with nothing
Water-ethanol is dispersant, with zirconia ball as ball-milling medium, planetary ball mill ball milling 4h.It is after the slurry drying that ball milling is obtained
Final potassium/sodium niobtae ceramic powder.
(5) flow casting molding
According to ceramic powder：Binding agent：The ratio of solvent is 1:0.3：0.34 ratio is added in ball grinder, wherein, glue
Knot agent is PVB (polyvinyl butyral resin), and solvent is absolute ethyl alcohol.With zirconia ball as ball-milling medium, planetary ball mill ball
Mill 20h.Slurry after ball milling is stood with after vavuum pump degasification deaeration 1.5h, is cast using casting machine, according to the specification of casting machine
Regulation line speed, drying temperature etc., it is 50 μm that thickness is controlled as needed.
(6) printing, lamination, hot pressing and cutting
The diaphragm that obtains of curtain coating prints electrode pattern as needed, and electrode material can select silver palladium alloy, nickel, copper etc..The
New diaphragm is put after one layer of drying, and is pressed with dry press, continue to print electrode after pressing, such circulating printing is stacked to and sets
The number of plies of meter.After Multilayer Film plastic packaging after lamination, hot pressing is carried out using hot water isostatic pressed, temperature is 70 DEG C, and pressure is 50MPa
It is lower to be kept for 15 minutes.Multilayer Film after hot pressing carries out last cutting and goes to corner according to design, connects termination electrode, obtains most
Whole multi-layer ceramics green compact.
(7) dumping and co-sintering
The support of ceramic green load bearing board is deformed with preventing from shrinking uneven in temperature-rise period, between 200-500 DEG C
Slow intensification dumping, programming rate is 10-12 DEG C/h.Green compact after dumping sinter 3h at 1050-1100 DEG C, after it is cold with stove
But.
(8) polarize
The multi-layer ceramics sample that sintering is obtained can use air polarization two ways：Poling temperature is 80 DEG C, pole in air
Change field intensity is 1.5kV/mm, and the polarization time is 25 minutes.
Embodiment 4
The formula stoichiometric formula of potassium-sodium niobate-based multilayer piezoelectric ceramic element is in the present embodiment：
(Na0.52K0.44Li0.04)(Nb0.89Sb0.07Ta0.04)O3
(1) raw material prepares and dispensing
Li2CO3、Na2CO3、K2CO3These alkali carbonates are hygroscopic to make moist, and it is standby to dry 11h at 65 DEG C before
With.According to the stoichiometric proportion of formula formula, weigh first：Li2CO3、Na2CO3、K2CO3；Then Nb is weighed2O5、Ta2O5、
Sb2O3。
(2) ball mill mixing
It is dispersant that the raw material that will be prepared adds absolute ethyl alcohol, with zirconia ball as ball-milling medium, formula ball is ground with common tank
Grinding machine ball milling 24h.
(3) first calcining and ball mill grinding
Mixed powder is obtained after the slurry drying obtained after ball mill mixing, mixed powder pulverizes and sieves, accurate by 60 targets
After sieve, it is put into the alumina crucible added a cover, 840 DEG C of calcining 4h, furnace cooling in air.The powder obtained after calcining is with anhydrous
Ethanol is dispersant, with zirconia ball as ball-milling medium, formula ball mill ball milling 24h is ground with common tank.
(4) secondary clacining and ball mill grinding
Mixed powder is obtained after first ball mill grinding disposed slurry drying, mixed powder pulverizes and sieves, by 60 mesh standard sieves
Afterwards, it is put into the alumina crucible added a cover, 3h, furnace cooling is calcined again for 810 DEG C in air.The powder obtained after calcining is with nothing
Water-ethanol is dispersant, with zirconia ball as ball-milling medium, formula ball mill ball milling 48h is ground with common tank.The slurry that ball milling is obtained
It is final potassium/sodium niobtae ceramic powder after drying.
(5) flow casting molding
According to ceramic powder：Binding agent：The ratio of solvent is 1:0.28：0.45 ratio is added in ball grinder, wherein, glue
Knot agent is PVB (polyvinyl butyral resin), and solvent is isopropanol.With zirconia ball as ball-milling medium, planetary ball mill ball milling
30h.Slurry after ball milling is stood with after vavuum pump degasification deaeration 1-2h, is cast using casting machine, and the specification according to casting machine is adjusted
Section line speed, drying temperature etc., it is 100 μm that thickness is controlled as needed.
(6) printing, lamination, hot pressing and cutting
The diaphragm that obtains of curtain coating prints electrode pattern as needed, and electrode material can select silver palladium alloy, nickel, copper etc..The
New diaphragm is put after one layer of drying, and is pressed with dry press, continue to print electrode after pressing, such circulating printing is stacked to and sets
The number of plies of meter.After Multilayer Film plastic packaging after lamination, hot pressing is carried out using hot water isostatic pressed, temperature is 75 DEG C, and pressure is 55MPa
It is lower to be kept for 20 minutes.Multilayer Film after hot pressing carries out last cutting and goes to corner according to design, connects termination electrode, obtains most
Whole multi-layer ceramics green compact.
(7) dumping and co-sintering
The support of ceramic green load bearing board is deformed with preventing from shrinking uneven in temperature-rise period, between 200-500 DEG C
Slow intensification dumping, programming rate is 10-12 DEG C/h.Green compact after dumping sinter 2h at 1050-1100 DEG C, after it is cold with stove
But.
(8) polarize
The multi-layer ceramics sample that sintering is obtained can be polarized using silicone oil oil bath：Silicone oil oil bath temperature is 100 DEG C, Polarization field strength
It is 2.5kV/mm, the polarization time is 28 minutes.
Embodiment 5
The formula stoichiometric formula of potassium-sodium niobate-based multilayer piezoelectric ceramic element is in the present embodiment：
(Na0.52K0.44Li0.04)(Nb0.88Sb0.07Ta0.05)O3
Wherein step (1) raw material prepares and dispensing, (1) and step (2) the step of step (2) ball mill mixing is with embodiment 1；
(3) first calcining and ball mill grinding
Mixed powder is obtained after the slurry drying obtained after ball mill mixing, mixed powder pulverizes and sieves, accurate by 60 targets
After sieve, it is put into the alumina crucible added a cover, 835 DEG C of calcining 4h, furnace cooling in air.The powder obtained after calcining is with anhydrous
Ethanol is dispersant, with zirconia ball as ball-milling medium, formula ball mill ball milling 48h is ground with common tank.
(4) secondary clacining and ball mill grinding
Mixed powder is obtained after first ball mill grinding disposed slurry drying, mixed powder pulverizes and sieves, by 60 mesh standard sieves
Afterwards, it is put into the alumina crucible added a cover, 4.5h, furnace cooling is calcined again for 845 DEG C in air.The powder obtained after calcining with
Absolute ethyl alcohol is dispersant, with zirconia ball as ball-milling medium, formula ball mill ball milling 35h is ground with common tank.The slurry that ball milling is obtained
It is final potassium/sodium niobtae ceramic powder after material drying.
(5) flow casting molding
According to ceramic powder：Binding agent：The ratio of solvent is 1:0.32：0.42 ratio is added in ball grinder, wherein, glue
Knot agent is PVB (polyvinyl butyral resin), and solvent is toluene.With zirconia ball as ball-milling medium, planetary ball mill ball milling
35h.Slurry after ball milling is stood with after vavuum pump degasification deaeration 1.5h, is cast using casting machine, and the specification according to casting machine is adjusted
Section line speed, drying temperature etc., it is 150 μm that thickness is controlled as needed.
(6) printing, lamination, hot pressing and cutting
The diaphragm that obtains of curtain coating prints electrode pattern as needed, and electrode material can select silver palladium alloy, nickel, copper etc..The
New diaphragm is put after one layer of drying, and is pressed with dry press, continue to print electrode after pressing, such circulating printing is stacked to and sets
The number of plies of meter.After Multilayer Film plastic packaging after lamination, hot pressing is carried out using hot water isostatic pressed, temperature is 75 DEG C, and pressure is 55MPa
It is lower to be kept for 25 minutes.Multilayer Film after hot pressing carries out last cutting and goes to corner according to design, connects termination electrode, obtains most
Whole multi-layer ceramics green compact.
(7) dumping and co-sintering
The support of ceramic green load bearing board is deformed with preventing from shrinking uneven in temperature-rise period, between 200-500 DEG C
Slow intensification dumping, programming rate is 10-12 DEG C/h.Green compact after dumping sinter 2.5h (2) at 1050-1100 DEG C, after with
Stove is cooled down.
(8) polarize
The multi-layer ceramics sample that sintering is obtained can be polarized using silicone oil oil bath：Silicone oil oil bath temperature is 110 DEG C, Polarization field strength
It is 2kV/mm, the polarization time is 26 minutes.
The potassium-sodium niobate-based multilayer piezoelectric ceramic element function test table that the embodiment 1-6 of table 1 is prepared
| Powder granule size (nm) | Dielectric constant | Single layer piezoelectric constant (pC/N) |
| Embodiment 1719 | 1737 | 272 |
| Embodiment 3771 | 1766 | 318 |
| Embodiment 41300 | 1910 | 334 |
Certainly, above-described embodiment is only intended to clearly illustrate example, and not to the restriction of implementation method.It is right
For those of ordinary skill in the art, can also make on the basis of the above description other multi-forms change or
Change.There is no need and unable to be exhaustive to all of implementation method.And the obvious change thus extended out or
Among changing still in protection scope of the present invention.
Claims (9)
1. a kind of potassium-sodium niobate-based multilayer piezoelectric ceramic element, it is characterised in that the potassium-sodium niobate-based multilayer piezoelectric ceramic unit
The formula stoichiometric formula of part is：
(Na0.52K0.44Li0.04)(Nb0.93-ySb0.07Tay)O3, wherein 0.02≤y≤0.06；
The preparation method of the potassium-sodium niobate-based multilayer piezoelectric ceramic element, comprises the steps：
S1, pretreatment
By (Na0.52K0.44Li0.04)(Nb0.93-ySb0.07Tay)O3Required alkali metal source Li2CO3、Na2CO3And K2CO3In 60-
80 DEG C of drying 8-12h, and and Nb2O5、Ta2O5、Sb2O3With absolute ethyl alcohol as dispersant after mixing, it is situated between by ball milling of zirconia ball
Matter carries out ball milling and obtains the slurry that particle diameter is 700-1300nm；
S2, first calcining and ball mill grinding
By step S1 prepare slurry drying, after pulverizing and sieving temperature be 800 DEG C -850 DEG C calcining 2-5h, cooling, then with
Absolute ethyl alcohol is dispersant, with zirconia ball as ball-milling medium ball milling after obtain slurry of the particle diameter as 1500-2000nm；
S3, secondary clacining and ball mill grinding
It is 800 DEG C -850 DEG C in temperature after slurry dries pulverizing sieving prepared by step S2 and calcines 2-5h, cooling, then with nothing
Water-ethanol is dispersant, with zirconia ball as ball-milling medium ball milling after obtain the slurry of particle diameter 700-1300nm, be niobium after drying
Sour potassium sodium system ceramic powder；
S4, flow casting molding
According to potassium/sodium niobtae ceramic powder：Binding agent：The volume ratio of solvent is 1:0.25-0.35：The ratio of 0.35-0.5
It is added in ball grinder, with zirconia ball as ball-milling medium, the slurry after ball milling is stood with after vavuum pump degasification deaeration 1-2h, is made
The film that thickness is 10-200 μm is cast into casting machine；
S5, printing, lamination, hot pressing and cutting
The diaphragm that obtains of curtain coating is printed electrode pattern as needed, and new diaphragm is put after ground floor drying, continues to print after pressing
Brush electrode, such circulating printing is stacked to the number of plies of design；Multilayer Film plastic packaging after lamination, connects termination electrode after hot pressing,
Obtain final multi-layer ceramics green compact；
S6, dumping, co-sintering and polarization
After by ceramic green aluminum oxide or load bearing board of zirconia clamping, it is embedded in aluminium oxide ceramics powder, is placed in electric furnace,
Slow intensification dumping between 200-500 DEG C, programming rate is 10-12 DEG C/h；Green compact after dumping sinter 2- at 1050-1100 DEG C
4h, rear furnace cooling, polarization, you can.
2. potassium-sodium niobate-based multilayer piezoelectric ceramic element according to claim 1, it is characterised in that described potassium-sodium niobate-based
In the formula stoichiometric formula of multilayer piezoelectric ceramic element, y=0.04.
3. potassium-sodium niobate-based multilayer piezoelectric ceramic element according to claim 1, it is characterised in that the step S2 and step
Slurry crosses 60 mesh sieves in rapid S3.
4. potassium-sodium niobate-based multilayer piezoelectric ceramic element according to claim 1, it is characterised in that in the step S4
Binding agent is polyvinyl butyral resin, and the solvent is the one kind or wherein several in toluene or dimethylbenzene, absolute ethyl alcohol, isopropanol
The mixture planted.
5. potassium-sodium niobate-based multilayer piezoelectric ceramic element according to claim 1, it is characterised in that electricity in the step S5
Pole material selection silver palladium alloy, nickel or copper.
6. potassium-sodium niobate-based multilayer piezoelectric ceramic element according to claim 5, it is characterised in that in the step S5
Hot pressing be temperature be 60-80 DEG C, pressure be 40-60MPa under the conditions of keep 10~30 minutes.
7. potassium-sodium niobate-based multilayer piezoelectric ceramic element according to claim 1, it is characterised in that institute in the step S6
The ceramic green load bearing board support stated is deformed with preventing from shrinking uneven in temperature-rise period.
8. potassium-sodium niobate-based multilayer piezoelectric ceramic element according to claim 7, it is characterised in that institute in the step S6
It is that will sinter the multi-layer ceramics sample for obtaining to use silicone oil oil bath polarization or air polarization to state polarization.
9. potassium-sodium niobate-based multilayer piezoelectric ceramic element according to claim 8, it is characterised in that described silicone oil oil bath
The process conditions of polarization are：Silicone oil oil bath temperature is 60-120 DEG C, and Polarization field strength is 2-3kV/mm, and the polarization time is 20-30 points
Clock；The condition of described air polarization is：Poling temperature is 60-120 DEG C in air, and Polarization field strength is 1-2kV/mm, during polarization
Between be 20-30 minutes.
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| CN107512909B (en) * | 2017-10-01 | 2020-10-09 | 王干 | Preparation method of completely-crimpable piezoelectric nano composite generator |
| CN107935592B (en) * | 2017-12-05 | 2020-04-17 | 盐城工学院 | Lead-free piezoelectric ceramic and preparation method thereof |
| CN110316758A (en) * | 2019-08-12 | 2019-10-11 | 信阳学院 | It is a kind of that potassium-sodium niobate raw powder's production technology is prepared using microwave operational principle |
| CN111635229A (en) * | 2020-05-29 | 2020-09-08 | 上海甚恒生物科技有限公司 | Preparation method of lead-free piezoelectric ceramic material |
| CN113072362A (en) * | 2020-10-15 | 2021-07-06 | 中科传感技术(青岛)研究院 | Sintering method for protecting surface electrode of multilayer piezoelectric ceramic piece |
| CN115286386B (en) * | 2022-08-27 | 2023-07-18 | 四川大学 | Non-stoichiometric Nb 5+ Potassium sodium bismuth niobate tantalum zirconium iron acid ceramic and preparation method thereof |
| CN116354719B (en) * | 2023-03-28 | 2024-05-28 | 南充三环电子有限公司 | Potassium sodium niobate-based ceramic and preparation method and application thereof |
| CN116514544A (en) * | 2023-04-25 | 2023-08-01 | 陕西声科电子科技有限公司 | Preparation method of multilayer piezoelectric ceramic and ultrasonic probe |
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