CN102584228A - Cerium-oxide-doped niobium-stibium lead-zirconate-titanate piezoelectric ceramic - Google Patents

Abstract

The invention discloses a cerium-oxide-doped niobium-stibium lead-zirconate-titanate piezoelectric ceramic material, which is made of Pb0.93Ba0.07 (Nb1/2 Sb1/2) 0.06 (Zr0.52Ti0.48) 0.94O3 and x percent of cerium oxide by weight, wherein x is equal to 0.1-5.0. Sintering temperature is 1220 DEG C to 1280 DEG C and heat is preserved for 2 hours. By adopting the traditional solid-phase synthesis preparation method, the cerium-oxide-doped niobium-stibium lead-zirconate-titanate piezoelectric ceramic with good comprehensive electrical properties is provided, the compositions and the steps are simple, the operation is easy, the repeatability is good and the rate of finished products is high. The piezoelectric ceramic obtained by adopting the method is very suitable for preparing devices such as high-power drivers and high-temperature detectors which have high requirements on the comprehensive properties of the piezoelectric ceramic.

Description

Niobium antimony-the lead titanate piezoelectric ceramics of doping cerium dioxide

Technical field

The invention relates to the composition is the ceramic composition of characteristic, relates in particular to a kind of cerium dioxide (CeO that adds ₂) ferroelectric niobium antimony-lead lanthanum zirconate titanate (PLZT) electrooptical ceramics material.

Background technology

Piezoelectric ceramics is a kind of function ceramics that can mechanical energy and electric energy be transformed each other, belongs to the ceramic category.Piezoceramic material is owing to have excellent dielectricity and piezoelectric property, and preparation technology is simple, cost is low, therefore in high-technology field such as information, space flight, laser and biology and industrial production, has all obtained widespread use.

Because the fusing point of PbO is lower, saturated vapor pressure is high in the time of pure PZT (Pb-based lanthanumdoped zirconate titanates) ceramic high temperature agglomerating, is prone to produce plumbous volatilization, and the stability of the wayward performance of component is relatively poor with repeatability, and this has just limited the application of PZT.Doping PZT piezoelectric ceramics has appearred in nineteen sixties, not only reduced synthesis temperature and reduced plumbous volatilization, and some performance also is improved.But the PZT of even now binary can not satisfy the demand of society far away; This has just promoted the novel piezoelectric investigation of materials; People's broad research three, four-component-system piezoelectric ceramics; Like PMN-PZT, PMN-PZT-PT, PSN-PZN-PZT, PLN-PMN-PZT etc., these novel piezoelectric ceramics have higher development prospect.

In actual components and parts, different application requires difference to the performance perameter of piezoceramic material, and this just forces people that piezoceramic material is carried out corresponding improvement in performance.At present, two kinds of methods of main both at home and abroad employing: a kind of is doping vario-property, certain foreign ion that promptly mixes, and through A position or B position ion are replaced on a small quantity, the performance perameter of adjustment material is to satisfy the requirement of piezo component; Another kind is to improve preparation technology, as confirming best calcining temperature, binder removal system, polarization condition etc., makes some performance of piezoelectric ceramics improve, to satisfy the requirement of piezo component.

Niobium antimony-Pb-based lanthanumdoped zirconate titanates series piezoelectric ceramic is the good stupalith of a kind of piezoelectric property; It has higher piezo-electric modulus and electromechanical coupling factor; Frequency stability and time stability are fine, can be applied to make wave filter, the oscillator underwater acoustic transducer; Great Power Driver, the automatic readout device of vehicle designation, wave filter oscillator, high temperature detect high temperature flaw detection thickness measuring etc.But the niobium antimony-Pb-based lanthanumdoped zirconate titanates series piezoelectric ceramic electromechanical coupling factor that does not add the modification hotchpotch is less; It is that object is studied that the present invention selects niobium antimony-Pb-based lanthanumdoped zirconate titanates series piezoelectric ceramic for use; And native system carried out the cerium oxide doping vario-property, obtain comparatively ideal piezoceramic material.Cerium (Ce) ion is the ion that typically appraises at the current rate, how with CeO ₂Form introduce.Consider from the ionic radius size; The Ce ionic radius that appraises at the current rate is between Zr, Ti ionic radius and Pb ionic radius; Therefore Ce both can replace the Pb of A position; Zr, the Ti that also can replace the B position, an amount of doping both can have been played " soft " doping characteristics, can improve electromechanical coupling factor and piezo-electric modulus effectively; Can play " rigid " doping characteristics again, promptly can improve the mechanical quality factor of material, reduce the dielectric loss of material, improve the temperature stability of piezoelectric ceramics.

Summary of the invention

The present invention adopts the preparation method of traditional solid phase synthesis, provides a kind of and is matrix, doping cerium dioxide, obtains the better piezoelectric ceramics of comprehensive electric property with niobium antimony-Pb-based lanthanumdoped zirconate titanates (PSN-PZT).

The present invention is achieved through following technical scheme:

Niobium antimony-the lead titanate piezoelectric ceramics of doping cerium dioxide, its feed composition and mass percentage content thereof are: with Pb _0.93Ba _0.07(Nb _1/2Sb _1/2) _0.06(Zr _0.52Ti _0.48) _0.94O ₃For foundation stone goes out, add 0.1～5.0wt.%CeO ₂

Said piezoelectric ceramics is single calcium titanium ore structure.

Said raw material is Pb ₃O ₄, BaCO ₃, ZrO ₂, TiO ₂, Nb ₂O ₅, Sb ₂O ₃And CeO ₂

Said piezoelectric ceramics adopts the preparation method of traditional solid phase synthesis, in 1220 ℃～1280 ℃ sintering, and insulation 2h.

The invention has the beneficial effects as follows, the niobium antimony-lead titanate piezoelectric ceramics of the good doping cerium dioxide of a kind of comprehensive electric property is provided, its composition and process step are simple, easy handling, good reproducibility, yield rate are high.

Description of drawings

Fig. 1: the present invention is at 1260 ℃, 1280 ℃ sintered heat insulating 2h, CeO ₂Doping is to the PSN-PZT piezoelectric coefficient d ₃₃Influence.

Fig. 2: the present invention is at 1260 ℃, 1280 ℃ sintered heat insulating 2h, CeO ₂Doping is to the influence of PSN-PZT electromechanical coupling factor Kp.

Fig. 3: the present invention is at 1260 ℃, 1280 ℃ sintered heat insulating 2h, CeO ₂Doping is to the PSN-PZT specific inductivity

Influence.

Fig. 4: the present invention is at 1260 ℃, 1280 ℃ sintered heat insulating 2h, CeO ₂Doping is to the influence of PSN-PZT dielectric loss tan δ.

Embodiment

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

The concrete preparation method of the niobium antimony-lead titanate piezoelectric ceramics of doping cerium dioxide of the present invention is following:

(1) batching

With Pb _0.93Ba _0.07(Nb _1/2Sb _1/2) _0.06(Zr _0.52Ti _0.48) _0.94O ₃Be the basis, add xwt.%CeO ₂, wherein x=1.0,2.0,3.0,4.0,5.0 by above-mentioned prescription, is got in x=0.1～5.0, takes by weighing raw material Pb ₃O ₄, BaCO ₃, ZrO ₂, TiO ₂, Nb ₂O ₅, Sb ₂O ₃And CeO ₂, mixing, in the nylon jar of packing into, ball-milling medium is water and agate ball, ball: material: the weight ratio of water is 2: 1: 0.5, and ball milling 4h, rotating speed are 750 rev/mins, and compound is put into 90 ℃ of oven dry of baking oven, puts into mortar again and grinds, and crosses 60 mesh sieves.

(2) pre-burning

The powder that step (1) is ground after sieving is put into crucible, with the compacting of agate rod, add a cover, sealing is warmed up to 900 ℃ of insulation 2h with 7 ℃/min speed in retort furnace, naturally cool to room temperature and come out of the stove.

(3) secondary ball milling

The powder of step (2) oven dry is ground in mortar, cross 60 mesh sieves, the ball grinder of packing into adds an amount of water, and ball milling 4h, rotating speed are 750 rev/mins, then powder are put into 90 ℃ of oven dry of baking oven.

(4) granulation

Powder porphyrize in mortar with step (3) oven dry sieves, and the adding weight concentration is 5%～10% PVA (Z 150PH); Fully stir; Sieve, powder is put into the stainless steel mould that diameter is 35mm, depress to cylindric blank at 100～120Mpa pressure.

(5) moulding

Cylindric blank after step (4) granulation is left standstill 24h, grind, cross the 60m sieve, again powder is put into the stainless steel mould that diameter is 12mm, depress to cylindric blank at 400Mpa pressure.

(6) binder removal

Step (5) blank is put into retort furnace; Speed with 3 ℃/min is warming up to 200 ℃ with base substrate, rises to 400 ℃ with 1.5 ℃/min speed from 200 ℃ again, behind 400 ℃ of insulation 30min; Rise to 650 ℃ and be incubated 10min with the speed of 5 ℃/min, discharge organism.

(7) sintering

Step (6) binder removal is gone out the organism blank put into crucible, seal, do to bury with the PSN-PZT powder and expect to bury burning, heat-up rate is 7 ℃/min, at 1260 ℃, 1280 ℃ insulation 2h, naturally cools to room temperature with stove respectively.

(8) burn electrode

The ceramic plate that step (7) is sintered is polished thick to 1mm, dries naturally, adopts silk-screen printing technique lower surface coated silver slurry above that, places 7 ℃/min of retort furnace to be warmed up to 735 ℃ of insulation 10min, naturally cools to room temperature.

(9) test dielectric properties.

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, relative permittivity ε _rValue is drawn by computes: $\frac{{\mathrm{\&epsiv;}}_{33}^T}{{\mathrm{\&epsiv;}}_0}=\frac{4C\&times;h}{{\mathrm{\&epsiv;}}_0\&times;{\mathrm{\&pi;\; <figure-callout\; id="2"\; label="D"\; filenames="HDA0000130962020000022.png"\; state="\{\{state\}\}">D</figure-callout>}}^2}$

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:

$\mathrm{\&sigma;}=\frac{{5.332f}_r-{1.867\mathrm{<figure-callout\; id="1"\; label="f\; r"\; filenames="HDA0000130962020000022.png"\; state="\{\{state\}\}">f</figure-callout>}}_r}{{0.6054f}_{r1}-{1.191f}_r}$

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.

Can find out with Fig. 2 by accompanying drawing 1.: the d of sample ₃₃With Kp along with various ce O ₂The variation tendency of doping is very similar, all occurs increasing the trend that afterwards reduces earlier, and all obtains peak during for 3wt.% in doping.Can find out by accompanying drawing 3: the sample specific inductivity With CeO ₂The increase of doping shows to increase earlier and afterwards reduces the trend that increases again.Can be found out by accompanying drawing 4: the sample loss is with CeO ₂The increase of doping shows and reduces earlier the trend that afterwards increases.Optimum performance parameters is at CeO ₂1280 ℃ of calcinings obtain during doping 3wt.%, are d ₃₃=600pC/N, kp=68%,

Tan δ=1.55%, Tc=255 ℃.

The piezoceramic material of using the present invention's preparation can be applicable to prepare the device that underwater acoustic 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 (4)

1. the niobium antimony-lead titanate piezoelectric ceramics of a doping cerium dioxide, its feed composition and mass percentage content thereof are: with Pb _0.93Ba _0.07(Nb _1/2Sb _1/2) _0.06(Zr _0.52Ti _0.48) _0.94O ₃For foundation stone goes out, add xwt.%CeO ₂, x=0.1～5.0 wherein.

2. according to the niobium antimony-lead titanate piezoelectric ceramics of the doping cerium dioxide of claim 1, it is characterized in that said piezoelectric ceramics is single calcium titanium ore structure.

3. according to the niobium antimony-lead titanate piezoelectric ceramics of the doping cerium dioxide of claim 1, it is characterized in that said raw material is Pb ₃O ₄, BaCO ₃, ZrO ₂, TiO ₂, Nb ₂O ₅, Sb ₂O ₃And CeO ₂

4. according to the niobium antimony-lead titanate piezoelectric ceramics of the doping cerium dioxide of claim 1, it is characterized in that said piezoelectric ceramics adopts the preparation method of traditional solid phase synthesis, in 1220 ℃～1280 ℃ sintering, insulation 2h.

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