CN102584229A - Pb-based stibate niobium-Pb-based zirconate titanates piezoelectric ceramic doped with barium carbonate and preparation method thereof - Google Patents

Abstract

The invention discloses a preparation method for Pb-based stibate niobium-Pb-based zirconate titanates piezoelectric ceramics doped with barium carbonate, comprising the following steps of: (1) proportioning according to the stoichiometric ratio of Pb1-xBax(Zr0.52Ti0.48)0.98(Nb1/2Sb1/2)0.02O3 with x being equal to 4.0mol%-12.0mol%; (2) synthesizing; (3) molding and binder removing; (4) sintering at the temperature between 1260 and 1280 DEG C; (5) silver sintering; and (6) polarizing at the temperature of 120 DEG C in a polarizing electric field which is a 3.0KV/mm direct current electric field for 15 minutes. By doping Ba<2+> with different contents, comprehensive electric properties of the Pb-based stibate niobium (PSN)-Pb-based zirconate titanates (PZT) piezoelectric ceramic are greatly improved. The best comprehensive property is acquired when the doping amount is 4.0mol% and the sintering temperature is 1280 DEG C and d33 is equal to 467pC/N, kp is equal to 74.5% and tan(delta) is equal to 1.45%. The piezoelectric ceramic can be used for elements which have higher requirement on comprehensive properties of the piezoelectric ceramic, such as high-power drivers and high temperature detecting elements.

Description

Add niobium Naples yellow-lead titanate piezoelectric ceramics of barium carbonate and preparation method thereof

Technical field

The invention relates to the composition is the ceramic composition of characteristic, relates in particular to barium doping niobium Naples yellow-lead titanate piezoelectric ceramics.

Background technology

Piezoelectric ceramics is a kind of ceramic material of realizing that mechanical energy and electric energy transform each other, and it had both had the general property of ferroelectric ceramic(s), has unique piezoelectric property again.Piezoceramic material is owing to have unique piezoelectric property; Excellent electromechanical coupling performance and dielectricity and elastic performance; Therefore and characteristics such as preparation technology is simple, volume is little, do not receive EMI, cost is low have all obtained widespread use in high-technology field such as space flight, information, biology, precision instrument and industrial production.

The application of piezoelectric ceramics mainly divides two aspects: piezoelectric vibrator and transverter.In the piezoelectric vibrator application facet, mainly be vibrator, resonator, wave filter, retarding line, X-former etc.Piezoelectric ceramic transformer is a kind of novel piezoelectric device that begins to develop the 1950's; Have step-up ratio height, in light weight, advantages such as volume is little, driving voltage is low, no leakage electromagnetic field, piezoelectric transformer has been used for the required high-tension apparatuses such as polarization of robot calculator display equipment, radarscope, sem, electrostatic precipitation, ion generator and piezoelectric at present.Aspect transducer application, mainly be microphone, ultrasonic transducer, surveying instrument etc.Need become electrical quantities to detected non-electrical quantities information in all respects such as science and industrial and agricultural productions, so that amplification, computing, transmission record and demonstration, the main devices that can accomplish this conversion is to be main electronic sensor with solid component.The measurement of processing with piezoelectric ceramics and the transmitter of various physical quantitys of perception and variation thereof then are best selections, and piezoelectric transducer has also become the key part of various detecting instruments and system.Mainly contain that piezolectric gyroscope, piezoelectric accelerometer, piezoelectric ceramics under meter, piezoelectron are claimed, piezoelectricity telltale, frost sensor, surfagauge, pendulum clock comprehensive tester and Grinding Contact detector etc.

The PSN-PZT ternary system piezoelectric ceramic is with its dielectric properties preferably, more stable resonant frequency, higher electromechanical coupling factor and Tc and by broad research and application.Investigators mainly are the over-all propertieies such as dielectric of removing to regulate PSN-PZT from three aspects.The one, change Zr/Ti and (Sb _1/2Nb _1/2) amount; The 2nd, doping vario-property comprises that ion of equal value is (like Ba ²⁺Deng) and the non-equivalence ion (like Nb ⁵⁺Deng) mix etc.; The 3rd, change preparation technology's (like synthetic and sintering temperature, polarization system) etc.As everyone knows, the characteristics of PSN-PZT pottery are that electromechanical coupling factor is high, good stability, but over-all properties is general, has limited its use range.

Summary of the invention

The objective of the invention is on the basis of existing technology,, a kind of Naples yellow-Pb-based lanthanumdoped zirconate titanates (PSN-PZT) piezoelectric ceramics with better comprehensive piezoelectric property and preparation method thereof is provided through the barium titanate of the different molar content of mixing.

The present invention is achieved through following technical scheme.

A kind of niobium Naples yellow-lead titanate piezoelectric ceramics that adds barium carbonate, its feed composition and mole percent level thereof are Pb _1-xBa _x(Zr _0.52Ti _0.48) _0.98(Nb _1/2Sb _1/2) _0.02O ₃, x=4.0mol%～12.0mol% wherein.

Said piezoelectric ceramics is single calcium titanium ore structure.

A kind of preparation method who adds the niobium Naples yellow-lead titanate piezoelectric ceramics of barium carbonate has following steps:

(1) batching

Press Pb _1-xBa _x(Zr _0.52Ti _0.48) _0.98(Nb _1/2Sb _1/2) _0.02O ₃Stoichiometric ratio batching, x=0mol%～12.0mol% wherein, raw material is Pb ₃O ₄, ZrO ₂, TiO ₂, Sb ₂O ₃, Nb ₂O ₅And BaCO ₃, batch mixing in ball grinder, ball: material: the weight ratio of water is 2: 1: 0.5, and the ball milling time is 3h, then with raw material stoving;

(2) synthetic

Raw material after step (1) oven dry is put into alumina crucible, seal, in 900 ℃ of Synthetic 2 h;

(3) moulding and plastic removal

With synthetic material ball milling, the oven dry once more of step (2), the polyvinyl alcohol water solution that adds 7wt% carries out granulation, and the back of sieving is shaped to base substrate in the pressure pressed of 400Mpa; Speed with 3 ℃/min is warming up to 200 ℃ with base substrate then, rises to 400 ℃ with 1.5 ℃/min speed from 200 ℃ again, behind 400 ℃ of insulation 30min, rises to 650 ℃ and be incubated 10min with the speed of 5 ℃/min, discharges organism;

(4) sintering

Step (3) is discharged organic base substrate adopt the Pb-based lanthanumdoped zirconate titanates powder to bury burning, be warming up to 1260 ℃～1280 ℃ insulation 2h, furnace cooling with 6 ℃/min speed;

(5) silver ink firing

The piezoelectric ceramic piece that step (4) is sintered polish to thickness be 0.9～1.1mm, adopt silk-screen printing technique above that, lower surface printed silver slurry, place process furnace, be warming up to 735 ℃ and be incubated 10min, naturally cool to room temperature;

(6) polarization

Silver ink firing goods with step (5) place 120 ℃ silicone oil, apply the DC electric field of 3KV/mm, polarization 15min;

(7) test piezoelectric property

With the piezoelectric ceramic piece that step (6) polarization is handled, its piezoelectric property of test after leaving standstill 24h under the room temperature.

The ball-milling medium of said step (1) is deionized water and agate ball, and the rotating speed of ball mill is 750r/min.

The doping of the best barium titanate of said step (1) is 4.0mol%.

The optimal sintering temperature of said step (4) is 1280 ℃.

The invention has the beneficial effects as follows, through Ba ²⁺The A position replace, near the PSN-PZT piezoelectric ceramics structure that is in the accurate homotype phase boundary is changed, make unit cell volume increase, the c/a axial ratio reduces, thereby the piezoelectricity of stupalith, dielectric properties are improved, loss reduces, comprehensive electric property is improved.In doping is that 4.0mol%, sintering temperature obtain best over-all properties: d when being 1280 ℃ ₃₃=467pC/N, k _p=74.5%, Tan δ=1.45%.

Description of drawings

Fig. 1 is the variation collection of illustrative plates of all embodiment of the present invention

and tan δ;

Fig. 2 is the variation collection of illustrative plates of the electromechanical coupling factor Kp of all embodiment of the present invention;

Fig. 3 is the piezo-electric modulus coefficient d of all embodiment of the present invention ₃₃The variation collection of illustrative plates;

Fig. 4 is the XRD figure spectrum of the embodiment of the invention (2-1,2-2,2-3,2-4);

Fig. 5 is Jie's temperature collection of illustrative plates of the embodiment of the invention (2-1,2-2,2-3,2-4).

Embodiment

The present invention adopts commercially available CP raw material (purity>=99%), is Pb ₃O ₄, ZrO ₂, TiO ₂, Sb ₂O ₃, Nb ₂O ₅And BaCO ₃Preparation process is following:

(1) batching

With raw material Pb ₃O ₄, ZrO ₂, TiO ₂, Sb ₂O ₃, Nb ₂O ₅, BaCO ₃Press Pb _1-xBa _x(Zr _0.52Ti _0.48) _0.98(Nb _1/2Sb _1/2) _0.02O ₃Stoichiometric ratio batching, wherein x=4.0mol%～12.0mol%.Batch mixing in ball milling, ball: material: the weight ratio of water is 2: 1: 0.5, and the ball milling time is 3h, again with raw material stoving;

(2) synthetic

Powder after step (1) oven dry is put into alumina crucible, seal, in 900 ℃ of Synthetic 2 h;

(3) moulding and plastic removal

With synthetic material ball milling, the oven dry once more of step (2), the polyvinyl alcohol water solution that adds 7wt% carries out granulation, and the back of sieving is shaped to base substrate in the pressure pressed of 400Mpa; Speed with 3 ℃/min is warming up to 200 ℃ with base substrate then, rises to 400 ℃ with 1.5 ℃/min speed from 200 ℃ again, behind 400 ℃ of insulation 30min, rises to 650 ℃ and be incubated 10min with the speed of 5 ℃/min, discharges organism;

(4) sintering

Step (3) is discharged organic base substrate adopt the Pb-based lanthanumdoped zirconate titanates powder to bury burning, be warming up to 1260 ℃～1280 ℃ insulation 2h, furnace cooling with 6 ℃/min speed;

(5) silver ink firing

The piezoelectric ceramic piece that step (4) is sintered polish to thickness be 1mm, adopt silk-screen printing technique above that, lower surface printed silver slurry, place process furnace, be warming up to 735 ℃ and be incubated 10min, naturally cool to room temperature;

(6) polarization

Silver ink firing goods with in the step (5) place 120 ℃ silicone oil, apply the DC electric field of 3KV/mm, polarization 15min;

(7) test synthesis electric property

With the piezoelectric ceramic piece that step (6) polarization is handled, its piezoelectric property of test after leaving standstill 24h under the room temperature.

The specific embodiment of the invention sees table 1 for details.

Table 1

The concrete means of testing of the present invention:

Use the WAYNEKERR4225 type LCR automatic measuring instrument of Tianjin City, China wireless six factories; At room temperature measure the loss tangent tan δ and the capacitor C of sample; Survey frequency is 1kHz, and relative permittivity

value is drawn by computes:

$\frac{{\mathrm{\&epsiv;}}_{33}^T}{{\mathrm{\&epsiv;}}_0}=\frac{4C\&times;h}{{\mathrm{\&epsiv;}}_0\&times;{\mathrm{\&pi;D}}^2}$

In the formula: ε ₀-permittivity of vacuum, its value are 8.854 * 10 ^-12F/m; C-electric capacity, unit are the F:h-sample thickness, the m of unit; π-pi; Here get 3.1416; The D-specimen finish, the m of unit.

The present invention adopts the acoustics ZJ-3A of institute of Chinese Academy of Sciences type quasi static test appearance, the test piezoelectric coefficient d according to GB GB11309-89 ₃₃, its unit is pCN ^-1

The dynamo-electric lotus root syzygy that obtains among the present invention is counted K _PBe difference Δ f=f through resonance and anti-resonance frequency _a-f _rLook into comprehensively with PR σ that Kp table obtains, PR σ calculates through following formula:

$\mathrm{\&sigma;}=\frac{{5.332f}_r-{1.867f}_{r1}}{{0.6054f}_{r1}-{1.191f}_r}$

f _rBe resonant frequency, f _aBe anti-resonance frequency, f _R1Be first overtone resonant frequency, f _r, f _a, f _R1All adopting resonance--the antiresonance method utilizes the Shanghai XFG-7 of Ya Mei electrical apparatus factory HF signal generator to record.

Shown in Figure 1, along with Ba ²⁺The increase of replacement amount X, the relative permittivity of embodiment

Have significantly and promote.Mechanical loss tan δ is then along with Ba ²⁺The trend of increase by a small margin appears in the increase of replacement amount X.Fig. 2, Fig. 3 show along with Ba ²⁺The increase of replacement amount X, the electromechanical coupling factor Kp and the piezoelectric coefficient d of embodiment sample ₃₃All appear to increase earlier and reduce the trend that increases again again.XRD figure spectrum in conjunction with Fig. 4 can be known Ba ²⁺The replacement amount is during less than 4.0mol%, Ba ²⁺Replacement is to not very big influence of sample phase composite, and lattice just slightly expands, thus sample still near accurate homotype phase boundary, this moment, the structure reactivity of sosoloid was big.Work as Ba ²⁺The replacement amount is during greater than 4.0mol%, can find out that from XRD figure the four directions reduces mutually, and the three parts increases mutually, and this moment, accurate homotype phase boundary was to cubic phase shift, so at replacement amount X=0.04～0.08 o'clock, sample sample machine electric coupling coefficient Kp and piezoelectric coefficient d ₃₃All on a declining curve; Work as Ba ²⁺The replacement amount is during greater than 8.0mol%, along with Ba ²⁺The continuation of replacement amount X increases, and the four directions of sample is to continuing minimizing, and electricdomain becomes and turns to easily; So under same electric field action; Electricdomain turns to number to increase, and strain increases, and this moment, polarization was more prone to; So replacement amount X=0.08～0.12 o'clock, the electromechanical coupling factor Kp and the piezoelectric coefficient d of sample ₃₃All become big.Jie's temperature collection of illustrative plates by Fig. 5 can be known, works as Ba ²⁺Tc is the highest during replacement amount X=4.0mol%.Can know that in conjunction with Fig. 4 barium and niobium, antimony form a class BaTiO ₃Phase compound, Ba like this ²⁺Replace pb ²⁺Amount reduces, and makes principal crystalline phase more be Pb-based lanthanumdoped zirconate titanates, and niobium Naples yellow amount also reduces, and niobium antimony and barium carbonate reduce the reduction effect of Tc, so Tc has little rising.

The piezoceramic material of using the present invention's preparation can be applicable to the device that ultrasonic transducer, high temperature detection means etc. have higher requirements to the piezoelectric ceramics over-all properties.

Above-mentioned description to embodiment is to be convenient to the those of ordinary skill of this technical field can understand and use the present invention.The personnel of skilled obviously can easily make various modifications to these embodiment, and needn't pass through performing creative labour being applied in the General Principle of this explanation among other embodiment.Therefore, the invention is not restricted to the embodiment here, those skilled in the art should be within protection scope of the present invention for improvement and modification that the present invention makes according to announcement of the present invention.

Claims (7)

1. niobium Naples yellow-lead titanate piezoelectric ceramics that adds barium carbonate, its feed composition and mole percent level thereof are Pb _1-xBa _x(Zr _0.52Ti _0.48) _0.98(Nb _1/2Sb _1/2) _0.02O ₃, x=4.0mol%～12.0mol% wherein.

2. according to the niobium Naples yellow-lead titanate piezoelectric ceramics of the interpolation barium carbonate of claim 1, it is characterized in that said raw material is Pb ₃O ₄, ZrO ₂, TiO ₂, Sb ₂O ₃, Nb ₂O ₅And BaCO ₃

3. according to the niobium Naples yellow-lead titanate piezoelectric ceramics of the interpolation barium carbonate of claim 1, it is characterized in that said piezoelectric ceramics is single calcium titanium ore structure.

4. a kind of preparation method who adds the niobium Naples yellow-lead titanate piezoelectric ceramics of barium carbonate of claim 1, it is following to have step:

(1) batching

Press Pb _1-xBa _x(Zr _0.52Ti _0.48) _0.98(Nb _1/2Sb _1/2) 0.0 ₂O ₃Stoichiometric ratio batching, x=4.0mol%～12.0mol% wherein, raw material is Pb ₃O ₄, ZrO ₂, TiO ₂, Sb ₂O ₃, Nb ₂O ₅And BaCO ₃, batch mixing in ball grinder, ball: material: the weight ratio of water is 2: 1: 0.5, and the ball milling time is 3h, then with raw material stoving;

(2) synthetic

Raw material after step (1) oven dry is put into alumina crucible, seal, in 900 ℃ of Synthetic 2 h;

(3) moulding and plastic removal

With synthetic material ball milling, the oven dry once more of step (2), the polyvinyl alcohol water solution that adds 7wt% carries out granulation, and the back of sieving is shaped to base substrate in the pressure pressed of 400Mpa; Speed with 3 ℃/min is warming up to 200 ℃ with base substrate then, rises to 400 ℃ with 1.5 ℃/min speed from 200 ℃ again, behind 400 ℃ of insulation 30min, rises to 650 ℃ and be incubated 10min with the speed of 5 ℃/min, discharges organism;

(4) sintering

Step (3) is discharged organic base substrate adopt the Pb-based lanthanumdoped zirconate titanates powder to bury burning, be warming up to 1260 ℃～1280 ℃ insulation 2h, furnace cooling with 6 ℃/min speed;

(5) silver ink firing

The piezoelectric ceramic piece that step (4) is sintered polish to thickness be 0.9～1.1mm, adopt silk-screen printing technique above that, lower surface printed silver slurry, place process furnace, be warming up to 735 ℃ and be incubated 10min, naturally cool to room temperature;

(6) polarization

Silver ink firing goods with step (5) place 120 ℃ silicone oil, apply the DC electric field of 3KV/mm, polarization 15min;

(7) test piezoelectric property

With the piezoelectric ceramic piece that step (6) polarization is handled, its piezoelectric property of test after leaving standstill 24h under the room temperature.

5. according to the preparation method of the niobium Naples yellow-lead titanate piezoelectric ceramics of the interpolation barium carbonate of claim 2, it is characterized in that the ball-milling medium of said step (1) is deionized water and agate ball, the rotating speed of ball mill is 750r/min.

6. according to the preparation method of the niobium Naples yellow-lead titanate piezoelectric ceramics of the interpolation barium carbonate of claim 2, it is characterized in that the doping of the best barium titanate of said step (1) is 4.0mol%.

7. according to the preparation method of the niobium Naples yellow-lead titanate piezoelectric ceramics of the interpolation barium carbonate of claim 2, it is characterized in that the optimal sintering temperature of said step (4) is 1280 ℃.

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