CN1187284C - Lead niobate zincate-lead lanthanum zirconate titanate function ceramic and preparing method thereof - Google Patents

Lead niobate zincate-lead lanthanum zirconate titanate function ceramic and preparing method thereof Download PDF

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CN1187284C
CN1187284C CNB021511136A CN02151113A CN1187284C CN 1187284 C CN1187284 C CN 1187284C CN B021511136 A CNB021511136 A CN B021511136A CN 02151113 A CN02151113 A CN 02151113A CN 1187284 C CN1187284 C CN 1187284C
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pzn
ceramics
plzt
lead
zirconate titanate
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CN1420106A (en
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殷庆瑞
郑鑫森
仇萍荪
丁爱丽
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Shanghai Institute of Ceramics of CAS
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Shanghai Institute of Ceramics of CAS
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Abstract

The present invention relates to transparent plumbum zincate niobium-plumbum lanthanum zirconate titanate functional ceramics and a preparing method thereof, which belongs to the field of transparent ceramics. The present invention is characterized in that the transparent ceramics comprise (Pb<1-x>La<x>)(Zn<1/3>, Nb<2/3>)<1-y>(Zr<1-z>Ti<z>)yO3, wherein x is more than 0 and less than or equal to 0.10, y is from 0.5 to 0.8, and z is from 0.4 to 0.70; the transparent ceramics are prepared by an oxygen introducing technology and a hot-pressing technology, and the flow quantity of oxygen is 3 liter/minute in the whole sintering process; the sintering temperature is 1200 to 1250 DEG C, and the pressure intensity is 480 Kg/cm<2>. the prepared PZN-PLZT ceramics are in a pure perovskite structure, the curie temperature is 240 DEG C, and the piezoelectric constant is from 500 to 700 PC/N; the PZN-PLZT ceramics have a diffusion transformation characteristic, and have high transmissivity in a range of 190 to 11000 nm, and the transmissivity of the PZN-PLZT ceramics is the sum of the transmissivity of PZN single crystal and PLZT ceramics.

Description

Lead zinc niobate-lead lanthanum zirconate titanate transparent functional pottery and preparation method thereof
Technical field
The present invention relates to lead zinc niobate-lead lanthanum zirconate titanate transparent functional pottery and preparation method thereof.Or rather, be to come the new transparent functional stupalith of processability near monocrystalline with improved ceramic process, this novel material has large size that the high-performance of monocrystalline, optically transparent advantage have stupalith to possess again, easily processing, characteristics that cost is low concurrently, belongs to the transparent ceramic material field.
Background technology
The PZN monocrystalline of uhligite phase structure has the dielectric properties of excellence, big electrostrictive effect and tangible electrooptic effect, is the optimal candidate material of driving mechanism, transmitter, photomodulator, has application prospect.But in general, complicated process of preparation, the size of monocrystalline is little, homogeneity range is limited, cost is high, very difficult realization on a large scale, practical cheaply; And the valence link that forms between each constituent element of PZN pottery and the oxygen a little less than, so the uhligite phase structure in the PZN pottery can't stable existence, must coming in addition with other the component of perovskite structure, modification could form the PZN pottery with high performance perovskite structure, yet, owing to adopt traditional ceramic process, even modification the PZN pottery in have pore and a large amount of crystal boundaries, so optically be opaque, can not be implemented in optic application.
Ceramic process-----hot pressing that utilization has improved, logical oxygen agglomerant artistic skill are eliminated pore, intergranule in the pottery effectively and can closely be contacted and make crystal boundary become very thin, can become pottery transparent on the optics by such prepared for the pottery of some component, as the PZLT crystalline ceramics.The infra-red range of this crystalline ceramics from the visible light of 380nm to 11 μ m all has very high transmitance, presents fairly obvious electrooptic effect, can be used as optics such as electrooptical shutter, light rate subtract, optical storage, light demonstration.But compare with PZN monocrystalline performance, no matter be that optical property or dielectric properties still have tangible gap, transmitance is low than the PZN monocrystalline, the little magnitude of electro-optic coefficient, ultraviolet band is light tight is the problem that transmission region is wide not enough, also have big insertion loss in optical communication, has influenced its practical application in optical communication.
Though the PZN monocrystalline has especially excellent dielectric, piezoelectricity and optical property, the growth technique complexity of monocrystalline, cost height, evenly area is very limited, therefore also is difficult to realize real application.
Can prepare functional materials--the PZN-PLZT of a kind of new transparent performance with the technology of pottery near monocrystalline, the advantage of PZN monocrystalline and PLZT pottery superposition in addition, and complementary original shortcoming, this just draws purpose of the present invention.
Summary of the invention
The objective of the invention is to adopt logical oxygen, a kind of transparent lead zinc niobate of ceramics injection prepared-Pb-based lanthanumdoped zirconate titanates crystalline ceramics.
The PZN-PLZT crystalline ceramics of the present invention's preparation, its general formula can be expressed as:
(Pb 1-xLa x)(Zn 1/3，Nb 2/3) 1-y(Zr 1-zTi z) yO 3
In the formula: 0＜x≤0.10; 0.5≤y≤0.8; 0.4≤z≤0.70
This crystalline ceramics has excellent piezoelectric effect, and dielectric properties realize optical clear in wide wavelength region, and best group becomes: (Pb 0.97La 0.03) (Zn 1/3, Nb 2/3) 0.3(Zr 0.53Ti 0.47) 0.70O 3
PZN-PLZT pottery provided by the invention be with general ceramic process through the batching, in ball grinding cylinder, use ZrO 2The ball uniform mixing, dry, be milled into uniformed powder, dry-pressing becomes right cylinder again, sintering after the logical then oxygen hot pressing.Sintering process is characterised in that:
(1) in sintering process, keeps 3 liters/minute oxygen flow;
(2) the hot pressed sintering condition is to be warmed up to 950 ℃ with 200 ℃/speed at one hour rating, is incubated 30 minutes; Pressurize gradually when heating up then, with same speed temperature is raised to 1200 ℃, pressure is raised to 480Kg/cm 2, be incubated 6 hours; Release and temperature still is raised to 1250 ℃ with 200 ℃ of/hour speed is incubated 10 hours, and crystal grain is grown enough energy, then drops to 950 ℃ with 140 ℃ of/hour speed, furnace cooling.Also can be raised to 1200 ℃, pressure is raised to 480Kg/cm 2, be incubated after 6 hours release and drop to 950 ℃, furnace cooling with 140 ℃ of/hour speed.
Phase structure of the present invention is by X diffractometer (D/MAX 2550V Raguku, Japan) determine, use Perkin UV/VIS (190nm-1100nm) and Perkin2000 (1100nm-12000nm) segmentation to measure with scanning electron microscope (SEM JSM-6700 field emission scanning electron microscope) test sample microstructure, from ultraviolet to infrared light transmission features, HP4284LRC is used for the dielectric properties of research material, piezoelectric constant Berlincour apparatus measures.Measure the volume density of PZN-PLZT pottery according to the Archimedian theorem.
Technology with hot pressing, logical oxygen successfully is prepared into the PZN-PLZT crystalline ceramics (Fig. 1) of the pure perovskite with excellent properties first.Not having in the pottery can detected pore, intercrystalline is in conjunction with close, crystal boundary very thin (Fig. 2), density reaches 8.04 gram/cubic centimetres, far above conventional ceramic (7.6 gram/cubic centimetre), realize in from ultraviolet to infrared wide region transparent (Fig. 3) that up to the present this be, Shang Weijian has report.Electrical property research is pointed out: the same with the PLZT pottery with the PZN monocrystalline, the dielectric constant with temperature of PZN-PLZT and the variation of frequency also present the feature that spreads phase transformation, and Curie temperature is 240 ℃, and than PZN and PLZT height (Fig. 4), promptly compare the temperature range of work with PLZT wideer with PZN.The diameter of sample can reach 5 centimetres (Fig. 5).
PZN-PLZT crystalline ceramics characteristics provided by the invention are:
1, do not have in the PZN-PLZT crystalline ceramics that the detected pore of available SEM and TEM, intergranule closely contact, crystal boundary is very thin.
2, the transmitance of PZN-PLZT crystalline ceramics is the superposition of PZN monocrystalline and PLZT crystalline ceramics transmitance, in infrared 11000nm scope high transmitance is arranged from ultraviolet 190nm.
3.PZN-PLZT present the structure of pure perovskite, piezoelectric property improves than the PLZT crystalline ceramics, piezoelectric constant is relevant with component, in the 500-700pc/N scope; Present the disperse transformation behavior; Curie temperature is 240 ℃, than the height of PZN and PLZT.
4. compare with the PZN monocrystalline, low, the even area of cost is big, and specimen finish can reach 5 centimetres.
Description of drawings
Fig. 1 is a PZN-PLZT pottery X diffraction spectra, presents the structure of pure perovskite.
Fig. 2 is the SEM photo of PZN-PLZT pottery section.
Fig. 3 is that the PZN-PLZT pottery is at ultraviolet and infrared transmittance curve.
Fig. 4 is the relation of PZN-PLZT specific inductivity and frequency and temperature.
Fig. 5 is that diameter is 5 centimetres a PZN-PLZT crystalline ceramics.
Embodiment
Further illustrate substantial characteristics of the present invention and obvious improvement below by embodiment, yet the present invention absolutely not only is confined to described embodiment.
Embodiment 1
Purity reaches the 99.4-99.8% high purity, granularity is ferric oxide (PbO), zinc oxide (ZnO), the niobium oxides (Nb of micron dimension 2O 5), zirconium white (ZrO 2), titanium oxide (TiO 2) and lanthanum trioxide (La 2O 3) as starting materials, press formula weight (Pb 1-0.03La 0.03) (Zn 1/3Nb 2/3) 1-0.7(Zr 1-0.47Ti 0.47) 0.7O 3Be mixed with the blended powder, powder is put into the plastic tank that fills alcohol, mix, dry, be milled into uniform powder then with zirconia ball.Under 100 kilograms pressure powder being pressed into diameter again is that 60 millimeters, height are 70 millimeters right cylinders.Right cylinder is put into the hot pressing furnace sintering, in sintering process, keep flow and be 3 liters/minute Oxygen Flow and pass through stove.Sintering condition is as follows: be incubated half an hour when being raised to 950 ℃ with 200 ℃/hour heat-up rates, when heating up, add upward pressure gradually then, when temperature rises to 1200 ℃, pressure is raised to 480 kilograms, insulation is 6 hours under such condition, pressure is removed thereupon, and temperature continues to be raised to 1250 ℃ and be incubated 10 hours with 200 ℃/speed at one hour rating.Then cooling to 950 ℃ with 140 ℃/hour speed naturally cools to then and takes out sample when being lower than 100 ℃.Ceramics sample behind the sintering is cut, polishes, makes electrode to satisfy the requirement of measuring electricity and optical property.
Embodiment 2
Press formula weight (Pb 1-0.028La 0.028) (Zn 1/3Nb 2/3) 0.3(Zr 1-0.47Ti 0.47) 0.7O 3Preparation PZN-PLZT crystalline ceramics, other technological process is identical with embodiment 1.
Embodiment 3
Press formula weight (Pb 1-0.032La 0.032) (Zn 1/3Nb 2/3) 0.3(Zr 1-0.47Ti 0.47) 0.7O 3Preparation PZN-PLZT crystalline ceramics, other technological process is identical with embodiment 1.
Embodiment 4
Press formula weight (Pb 1-0.06La 0.06) (Zn 1/3Nb 2/3) 0.3(Zr 1-0.47Ti 0.47) 0.7O 3Preparation PZN-PLZT crystalline ceramics, different with embodiment 1 just is warmed up to 1200 ℃, pressure 480Kg/cm 2, being incubated after 6 hours is that release is lowered the temperature and no longer intensification.
Embodiment 5
Press formula weight (Pb 1-0.09La 0.09) (Zn 1/3Nb 2/3) 0.3(Zr 1-0.47Ti 0.47) 0.7O 3Preparation PZN-PLZT crystalline ceramics, other technological process is identical with embodiment 1.
Embodiment 6
Press formula weight (Pb 1-0.03La 0.03) (Zn 1/3Nb 2/3) 0.3(Zr 1-0.60Ti 0.60) 0.7O 3Preparation PZN-PLZT crystalline ceramics, other technological process embodiment 1 is identical.
Embodiment 7
Press formula weight (Pb 1-0.03La 0.03) (Zn 1/3Nb 2/3) 0.5(Zr 1-0.47Ti 0.47) 0.5O 3Preparation PZN-PLZT crystalline ceramics, other technological process is identical with embodiment 1.
Table 1 embodiment performance provided by the invention gathers
Embodiment X Y Z Component Transmitance d 33
1 0.030 0.070 0.47 (Pb 0.97La 0.03)(Zn 1/3Nb 2/3) 0.3(Zr 0.53Ti 0.47) 0.7O 3 As clear as crystal 620
2 0.028 0.070 0.47 (Pb 0.972La 0.028)(Zn 1/3Nb 2/3) 0.3(Zr 0.53Ti 0.47) 0.7O 3 As clear as crystal 570
3 0.032 0.070 0.47 (Pb 0.968La 0.032)(Zn 1/3Nb 2/3) 0.3(Zr 0.53Ti 0.47) 0.7O 3 As clear as crystal 470
4 0.060 0.070 0.47 (Pb 0.94La 0.60)(Zn 1/3Nb 2/3) 0.3(Zr 0.53Ti 0.47) 0.7O 3 Transparent 300
5 0.090 0.070 0.47 (Pb 0.91La 0.90)(Zn 1/3Nb 2/3) 0.3(Zr 0.53Ti 0.47) 0.7O 3 Transparent 320
6 0.030 0.070 0.60 (Pb 0.97La 0.03)(Zn 1/3Nb 2/3) 0.3(Zr 0.40Ti 0.60) 0.7O 3 Transparent 290
7 0.030 0.050 0.47 (Pb 0.97La 0.03)(Zn 1/3Nb 2/3) 0.5(Zr 0.53Ti 0.47) 0.5O 3 Transparent 150

Claims (4)

1, a kind of lead zinc niobate-lead lanthanum zirconate titanate transparent functional pottery is characterized in that the composition expression formula of described transparent functional pottery is:
(Pb 1-xLa x)(Zn 1/3，Nb 2/3) 1-y(Zr 1-zTi z) yO 3
In the formula: 0＜x≤0.10; 0.5≤y≤0.8; 0.4≤z≤0.70.
2. by the described lead zinc niobate of claim 1-lead lanthanum zirconate titanate transparent functional pottery, it is characterized in that consisting of of described transparent functional pottery:
(Pb 0.97La 0.03)(Zn 1/3，Nb 2/3) 0.3(Zr 0.53Ti 0.47) 0.70O 3。
3, by the preparation method of the described lead zinc niobate of claim 1-lead lanthanum zirconate titanate transparent functional pottery, comprise batching, uniform mixing, drying forming and hot pressed sintering, it is characterized in that:
(1) in the whole process of hot pressed sintering, keeps 3 liters/minute oxygen flow;
(2) the hot pressed sintering condition is to be warmed up to 950 ℃ with 200 ℃/speed at one hour rating, is incubated 30 minutes; Pressurization when heating up with same speed then, when temperature is raised to 1200 ℃, pressure is raised to 480Kg/cm 2, be incubated 6 hours; Release temperature then still is raised to 1250 ℃ with 200 ℃ of/hour speed, is incubated 10 hours, drops to 950 ℃ with 140 ℃ of/hour speed at last, furnace cooling.
4, by the preparation method of the described lead zinc niobate of claim 1-lead lanthanum zirconate titanate transparent functional pottery, comprise batching, uniform mixing, drying forming and hot pressed sintering, it is characterized in that:
(1) in the whole process of hot pressed sintering, keeps 3 liters/minute oxygen flow;
(2) the hot pressed sintering condition is to be warmed up to 950 ℃ with 200 ℃/speed at one hour rating, is incubated 30 minutes; Pressurization when heating up then with same speed; When temperature is raised to 1200 ℃, pressure is raised to 480Kg/cm 2, be incubated 6 hours; Release and drop to 950 ℃, furnace cooling then with 140 ℃ of/hour speed.
CNB021511136A 2002-12-06 2002-12-06 Lead niobate zincate-lead lanthanum zirconate titanate function ceramic and preparing method thereof Expired - Fee Related CN1187284C (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
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CN100344576C (en) * 2005-09-09 2007-10-24 中国科学院上海硅酸盐研究所 Lanthanum-doped lead niobate zincate zirconate titanate piezo-electric ceramic material and its preparation method

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CN101863660A (en) * 2010-06-11 2010-10-20 天津大学 La2O3-doped lead zinc niobate-lead zirconate titanate piezoelectric ceramic
CN102295456B (en) * 2011-06-15 2013-11-20 中国科学院上海硅酸盐研究所 PMN-PZT-based transparent electro-optic ceramic material and preparation method thereof
CN102383189B (en) * 2011-11-02 2013-12-18 南京航空航天大学 Preparation method for lead zinc niobate-lead titanate monocrystal
CN107540373B (en) * 2017-08-25 2021-03-02 昆明理工大学 La ion doped PZT-based piezoelectric ceramic material and preparation method thereof
EP3846231B1 (en) * 2018-08-30 2024-09-11 FUJIFILM Corporation Piezoelectric device and method of manufacturing piezoelectric device
CN112759390A (en) * 2019-11-04 2021-05-07 中国科学院上海硅酸盐研究所 Has high kpPSN-PZT piezoelectric ceramic and preparation method thereof

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100344576C (en) * 2005-09-09 2007-10-24 中国科学院上海硅酸盐研究所 Lanthanum-doped lead niobate zincate zirconate titanate piezo-electric ceramic material and its preparation method

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