CN101928139A - Bismuth calcium titanate-based luminous piezoelectric ceramic material and preparation method - Google Patents

Bismuth calcium titanate-based luminous piezoelectric ceramic material and preparation method Download PDF

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CN101928139A
CN101928139A CN 201010271544 CN201010271544A CN101928139A CN 101928139 A CN101928139 A CN 101928139A CN 201010271544 CN201010271544 CN 201010271544 CN 201010271544 A CN201010271544 A CN 201010271544A CN 101928139 A CN101928139 A CN 101928139A
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piezoelectric ceramic
ceramic material
calcium titanate
bismuth calcium
based luminous
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CN101928139B (en
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王旭升
彭登峰
李艳霞
张君诚
唐棉棉
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Tongji University
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Abstract

The invention relates to the field of electronic functional material, in particular to a bismuth calcium titanate-based luminous piezoelectric ceramic material and a preparation method thereof. The chemical components of the bismuth calcium titanate-based luminous piezoelectric ceramic material accord with a chemical general formula CaxBi4-yRyTi3+xO12+3x, wherein x is more than or equal to 1 and less than or equal to 2, y is more than or equal to 0.0001 and less than or equal to 0.5, and R is selected from one or more of Pr, Gd, Er, Dy, Tm, Ho, Eu, Yb and Tb. The ceramic material has ferroelectric, piezoelectric and dielectric properties and photoluminescence property at the same time, and belongs to a novel multifunctional material. The bismuth calcium titanate-based luminous piezoelectric ceramic material has excellent photoelectric property, and has wide application prospect in the fields of photoelectric integration, micro electro-mechanics, photoelectric sensing, LED technology and the like.

Description

A kind of bismuth calcium titanate-based luminous piezoelectric ceramic material and preparation method
Technical field
The present invention relates to the electronic functional material field, be specifically related to a kind of bismuth calcium titanate-based luminous piezoelectric ceramic material and preparation method thereof.
Background technology
Along with the continuous development of new and high technology, new material technology has become the countries in the world scholars and has fallen over each other the hot fields exploring and study.Piezoelectric is a class important electron functional materials, has a wide range of applications at high-technology fields such as information, laser, navigation and biologies.In order to adapt to current development of high-tech, satisfy functionalization, miniaturization and the intelligentized requirement of piezoelectric, existing both at home and abroad scholar also tries to explore and expands its new function in further investigation with when constantly improving the original performance of piezoelectric.Studies show that, by composition of raw materials choose and the control of experimental technique can make piezoelectric have multifunction.As the group at the applicant place light-machine of in having the barium titanate calcium based leadless piezoelectric ceramics system of perovskite structure, the having realized-electricity conversion multifunction that takes the lead in.Behind a spot of rare earth element praseodymium that in the lattice of barium titanate calcium two-phase composite ceramics, mixes, not only improve this stupalith ferroelectricity, also make this material have photoluminescence, electroluminescent and stress irradiance multifrequency nature simultaneously, referring to magazine " Advanced Materials ", 2005, the 17th phase, the 1254-1258 page or leaf.The adulterated barium titanate calcium multi-functional pressure of the research middle-weight rare earths praseodymium electric material has good photoelectric characteristic, has a wide range of applications at aspects such as photoelectricity, micro electronmechanical and artificial intelligence.The group at applicant place is also carrying out correlated performance research aspect the made device of this barium titanate calcium two-phase composite ceramic material system, referring to magazine " Applied Physics Express ", and 2010, the 3rd phase, article numbering: 022601.At present, domestic and international research about the rear-earth-doped multi-functional pressure electroceramics material characteristics of luminescence mainly concentrates on the barium titanate calcium system.
As an important class lead-free piezoceramic material, " bismuth stratiform " the bismuth calcium titanate base ceramic material with laminated perovskite structure has high-curie temperature, high dielectric breakdown strength, low conductivity, low-dielectric loss and good characteristics such as antifatigue.Because these characteristics, bismuth calcium titanate-based pottery has a wide range of applications in fields such as high temperature, high frequency, piezoelectric effect device and non-volatile random access memory.And at present be only limited to thin-film material at present about the report of bismuth calcium titanate-based piezoelectric optical Properties, and referring to magazine " Journal of Physics D:Applied Physics ", 2009 years, the 42nd phase, article numbering: 105411.The present invention mixes a certain amount of rare earth element for adapting to the requirement of new high-tech material technical development in the single-phase leadless piezoelectric ceramics substrate material of " bismuth stratiform " bismuth calcium titanate, by technology controlling and process to realize its photoluminescence property.This material has good photoelectric characteristic, and integrated, micro electronmechanical and fields such as photoelectric sensing, LED lighting engineering have a wide range of applications at photoelectricity.
Summary of the invention
The object of the present invention is to provide a kind of bismuth calcium titanate-based luminous piezoelectric ceramic material and preparation method thereof, to overcome the deficiencies in the prior art with ferroelectric, piezoelectricity, dielectric and photoluminescence performance.
A kind of bismuth calcium titanate-based luminous piezoelectric ceramic material, its chemical ingredients meets chemical general formula Ca xBi 4-yR yTi 3+xO 12+3x, 1≤x≤2,0.0001≤y≤0.5 wherein, described R is selected from one or more among rare earth element Pr, Gd, Er, Dy, Tm, Ho, Eu, Yb and the Tb.
Preferable, the span of y is 0.005≤y≤0.02.
The preparation method of described bismuth calcium titanate-based luminous piezoelectric ceramic material is a solid reaction process, in bismuth calcium titanate leadless piezoelectric ceramics substrate material, mix a certain amount of rare earth element,, promptly excite down and the performance of red-emitting to realize the photoluminescence property of its powder and ceramic block material by technology controlling and process at UV-light, blue light and green glow multiband light.
The preparation method of described bismuth calcium titanate-based luminous piezoelectric ceramic material specifically may further comprise the steps:
(1), according to chemical general formula Ca xBi 4-yR yTi 3+xO 12+3xThe stoichiometric ratio of middle Ca, Bi, Ti and R takes by weighing raw material: CaCO 3, Bi 2O 3, TiO 2, R oxide compound or nitrate, 1≤x≤2,0.0001≤y≤0.5 wherein.
(2), raw material that step (1) is taken by weighing mixes, add dehydrated alcohol or deionized water through grind or ball milling after, the discharging oven dry obtains powder A.
The mass ratio of described dehydrated alcohol or deionized water and raw material is 1~3: 1; The mass ratio of described ball milling material zirconia ball and raw material is 1~1.5: 1.
(3), place the alumina crucible pre-burning to obtain preburning powdered material B powder A.
Described calcined temperature is 750~950 ℃, and soaking time is 1~6h.
Preferably, described calcined temperature is 850~950 ℃, and soaking time is 2h.
(4), preburning powdered material B ground or ball milling after, adopting the quality percentage composition is that 8~10% binding agent carries out granulation to powder material B, is pressed into ceramic green sheet C then under 10~100MPa pressure.
Described binding agent is a PVAC polyvinylalcohol.
The quality percentage composition of described binding agent is the quality percentage composition of binding agent with respect to preburning powdered material.
(5), obtain described bismuth calcium titanate-based luminous piezoelectric ceramic material behind ceramic green sheet C row is sticking, the sintering.
The sticking temperature of described row is 550~600 ℃, and the sticking soaking time of row is 2~4h;
Described sintering temperature is 1000~1250 ℃, and the sintered heat insulating time is 2~6h;
Preferably, described sintering temperature is 1180~1200 ℃, and the sintered heat insulating time is 4h.
Rare earth doped bismuth calcium titanate-based luminous piezoelectric ceramic material of the present invention, the single-phase lead-free piezoceramic material of " bismuth stratiform " bismuth calcium titanate for laminated perovskite structure, by technology controlling and process, make the bismuth calcium titanate that itself does not have the characteristics of luminescence have photoluminescence property; And the bismuth calcium titanate-based multifunctional ceramic material of luminous piezoelectricity of the present invention can be excited and red-emitting by the wavelength of UV-light, blue light, three wave bands of green glow, and the strongest exciting at blue wave band, belongs to environmentally friendly luminescent material; And praseodymium barium titanate doping calcium diphase ceramic material of the prior art is a perovskite structure, and its photoluminescence can only be by ultraviolet excitation.
Bismuth calcium titanate-based luminous piezoelectric ceramic material of the present invention also has photoluminescence property when having original ferroelectric, piezoelectricity and dielectric properties, belong to the novel multifunctional material.This stupalith has good photoelectric properties, and field such as, photoelectric sensing integrated, micro electronmechanical at photoelectricity, LED technology has a wide range of applications.
Description of drawings
Fig. 1 CaBi 4-yR yTi 4O 15, x=1, the XRD figure spectrum of y=0.005,0.01,0.015,0.02 sample.
Fig. 2 CaBi 4-yR yTi 4O 15, x=1, the exciting light collection of illustrative plates of y=0.005,0.01,0.015,0.02 sample.
Fig. 3 CaBi 4-yR yTi 4O 15, x=1, the emission light collection of illustrative plates of y=0.005,0.01,0.015,0.02 sample.
Embodiment
Further set forth the present invention below in conjunction with specific embodiment, should be understood that these embodiment only are used to the present invention is described and are not used in restriction protection scope of the present invention.
Embodiment 1
With preparation CaBi 4-0.005Pr 0.005Ti 4O 15, CaBi 4-0.01Pr 0.01Ti 4O 15, CaBi 4-0.015Pr 0.015Ti 4O 15, CaBi 4-0.02Pr 0.02Ti 4O 15Be example, raw material is chosen CaCO 3, Bi 2O 3, TiO 2, Pr 6O 11, press chemical general formula CaBi 4-0.005Pr 0.005Ti 4O 15, CaBi 4-0.01Pr 0.01Ti 4O 15, CaBi 4-0.015Pr 0.015Ti 4O 15, CaBi 4-0.02Pr 0.02Ti 4O 15In the stoichiometric ratio of Ca, Bi, Ti and R take by weighing raw material, take by weighing add that dehydrated alcohol or deionized water grind and mixes behind the raw material in mortar must powder A after abundant 1, A 2, A 3, A 4, the mass ratio of wherein said dehydrated alcohol or deionized water and raw mix is 1~3: 1; The mass ratio of described ball milling material zirconia ball and raw mix is 1~1.5: 1.With powder A 1, A 2, A 3, A 4Place the alumina crucible pre-burning respectively, described calcined temperature is 850 ℃, and temperature rise rate is 3 ℃/min, is incubated after 2 hours, and naturally cooling obtains preburning powdered material B 1, B 2, B 3, B 4With preburning powdered material B 1, B 2, B 3, B 4After grinding respectively, adopt 10% PVAC polyvinylalcohol preburning powdered material B to be carried out granulation again, under 100MPa pressure, be pressed into ceramic green sheet C as binding agent 1, C 2, C 3, C 4With ceramic green sheet C 1, C 2, C 3, C 4After 550 ℃ 2 hours rows of insulation glue processing down, obtained described luminous piezoelectric ceramic material CaBi in 4 hours at 1180 ℃ of following sintered heat insulatings more respectively 4-0.005Pr 0.005Ti 4O 15, CaBi 4-0.01Pr 0.01Ti 4O 15, CaBi 4-0.015Pr 0.015Ti 4O 15And CaBi 4-0.02Pr 0.02Ti 4O 15
Luminous piezoelectric ceramic material CaBi with gained among the embodiment 1 4-0.005Pr 0.005Ti 4O 15, CaBi 4-0.01Pr 0.01Ti 4O 15, CaBi 4-0.015Pr 0.015Ti 4O 15And CaBi 4-0.02Pr 0.02Ti 4O 15Detect, obtain following Fig. 1, Fig. 2 and Fig. 3:
Fig. 1 is CaBi 4-yR yTi 4O 15, x=1, the XRD figure spectrum of y=0.005,0.01,0.015,0.02 sample.
Fig. 2 is CaBi 4-yR yTi 4O 15, x=1, the exciting light collection of illustrative plates of y=0.005,0.01,0.015,0.02 sample.
Fig. 3 is CaBi 4-yR yTi 4O 15, x=1, the emission light collection of illustrative plates of y=0.005,0.01,0.015,0.02 sample.
The luminous piezoelectric ceramic material of composing the embodiment 1 as can be known from the XRD figure of Fig. 1 is single pure phase " bismuth stratiform " bismuth calcium titanate structure, and shows not have other dephasign in the XRD figure spectrum; The exciting light collection of illustrative plates of Fig. 2 sample as can be seen, the luminous piezoelectric ceramic material in the present embodiment all can be excited by the ripple of UV-light (300nm-430nm), blue light (440nm-510nm) or three wave bands of green glow (550nm-570nm); The emission light collection of illustrative plates of Fig. 3 sample as can be seen, the equal red-emitting of the luminous piezoelectric ceramic material in the present embodiment, and the emission peak position be 614nm.
Embodiment 2
With preparation Ca 1.5Bi 4-0.01Pr 0.01Ti 4.5O 16.5Be example, raw material is chosen CaCO 3, Bi 2O 3, TiO 2, Pr 6O 11, by prescription Ca 1.5Bi 4-0.01Pr 0.01Ti 4O 16.5The element proportioning takes by weighing selected raw material, and calcined temperature is 900 ℃, and the sticking holding temperature of handling back ceramic green sheet of row is 1200 ℃, and all the other experiment conditions are consistent with embodiment 1.
After testing as can be known, the gained final sample is the luminous piezoelectric ceramic material Ca among the present invention among this embodiment 1.5Bi 4-0.01Pr 0.01Ti 4.5O 16.5
Luminous piezoelectric ceramic material in the present embodiment all can be excited by the ripple of UV-light (300nm-430nm), blue light (440nm-510nm) or three wave bands of green glow (550nm-570nm).
Embodiment 3
With preparation Ca 2Bi 4-0.02Pr 0.02Ti 5O 18Be example, raw material is chosen CaCO 3, Bi 2O 3, TiO 2, Pr 6O 11, by prescription Ca 2Bi 4-0.02Pr 0.02Ti 5O 18The element proportioning takes by weighing selected raw material, and calcined temperature is 950 ℃, and the sticking holding temperature of handling back ceramic green sheet of row is 1200 ℃, and all the other experiment conditions are consistent with embodiment 1.
After testing as can be known, after testing as can be known, the gained final sample is the luminous piezoelectric ceramic material Ca among the present invention among this embodiment 2Bi 4-0.02Pr 0.02Ti 5O 18
Luminous piezoelectric ceramic material in the present embodiment all can be excited by the ripple of UV-light (300nm-430nm), blue light (440nm-510nm) or three wave bands of green glow (550nm-570nm).
Embodiment 4
With preparation CaBi 4-0.01Eu 0.01Ti 4O 15Be example, raw material is chosen CaCO 3, Bi 2O 3, TiO 2, Eu 2O 3, by prescription Ca 2Bi 4-0.01Eu 0.01Ti 5O 18The element proportioning takes by weighing selected raw material, and calcined temperature is 850 ℃, and soaking time is 2h, and the sticking holding temperature of handling back ceramic green sheet of row is 1150 ℃, and soaking time is 6h, and all the other experiment conditions are consistent with embodiment 1.
After testing as can be known, the gained final sample is the luminous piezoelectric ceramic material CaBi among the present invention among this embodiment 4-0.01Eu 0.01Ti 4O 15
Luminous piezoelectric ceramic material in the present embodiment all can be excited by the ripple of UV-light (300nm-430nm), blue light (440nm-510nm) or three wave bands of green glow (550nm-570nm).
Embodiment 5
With preparation Ca 2Bi 4-0.02Eu 0.02Ti 5O 18Be example, raw material is chosen CaCO 3, Bi 2O 3, TiO 2, Eu 2O 3, by prescription Ca 2Bi 4-0.02Pr 0.02Ti 5O 18The element proportioning takes by weighing selected raw material, and calcined temperature is 950 ℃, and the sticking holding temperature of handling back ceramic green sheet of row is 1200 ℃, and all the other experiment conditions are consistent with embodiment 1.
After testing as can be known, the gained final sample is the luminous piezoelectric ceramic material Ca among the present invention among this embodiment 2Bi 4-0.02Eu 0.02Ti 5O 18
Luminous piezoelectric ceramic material in the present embodiment all can be excited by the ripple of UV-light (300nm-430nm), blue light (440nm-510nm) or three wave bands of green glow (550nm-570nm).
Embodiment 6
With preparation CaBi 4-0.01Eu 0.01Gd 0.01Ti 4O 15, raw material is chosen CaCO 3, Bi 2O 3, TiO 2, Eu 2O 3, Gd 2O 3, by prescription CaBi 4-0.01Eu 0.01Gd 0.01Ti 4O 15The element proportioning takes by weighing selected raw material, and calcined temperature is 850 ℃, and the sticking holding temperature of handling back ceramic green sheet of row is 1220 ℃ ℃, and all the other experiment conditions are consistent with embodiment 1.
After testing as can be known, the gained final sample is the luminous piezoelectric ceramic material CaBi among the present invention among this embodiment 4-0.01Eu 0.01Gd 0.01Ti 4O 15
Luminous piezoelectric ceramic material in the present embodiment all can be excited by the ripple of UV-light (300nm-430nm), blue light (440nm-510nm) or three wave bands of green glow (550nm-570nm).

Claims (6)

1. bismuth calcium titanate-based luminous piezoelectric ceramic material, its chemical ingredients meets chemical general formula Ca xBi 4-yR yTi 3+xO 12+3x, 1≤x≤2,0.0001≤y≤0.5 wherein, described R is selected from one or more among Pr, Gd, Er, Dy, Tm, Ho, Eu, Yb and the Tb.
2. bismuth calcium titanate-based luminous piezoelectric ceramic material as claimed in claim 1 is characterized in that, the span of y is 0.005≤y≤0.02.
3. bismuth calcium titanate-based luminous piezoelectric ceramic material as claimed in claim 1 or 2 is characterized in that, described bismuth calcium titanate-based luminous piezoelectric ceramic material makes for adopting solid reaction process.
4. as the preparation method of the arbitrary described bismuth calcium titanate-based luminous piezoelectric ceramic material of claim 1-3, it is characterized in that, comprise the steps:
(1), according to chemical general formula Ca xBi 4-yR yTi 3+xO 12+3xThe stoichiometric ratio of middle Ca, Bi, Ti and R takes by weighing raw material: CaCO 3, Bi 2O 3And TiO 2, and the oxide compound of R or nitrate, wherein 1≤x≤2,0.0001≤y≤0.5;
(2), raw material that step (1) is taken by weighing mixes, add dehydrated alcohol or deionized water through grind or ball milling after, the discharging oven dry obtains powder A;
(3), place the alumina crucible pre-burning to obtain preburning powdered material B powder A, wherein, described calcined temperature is 750~950 ℃, and soaking time is 1~6h;
(4), preburning powdered material B ground or ball milling after, adopting the quality percentage composition is that 8~10% binding agent polyvinyl alcohol carries out granulation to preburning powdered material B, is pressed into ceramic green sheet C then under 10~100MPa pressure;
(5), obtain described bismuth calcium titanate-based luminous piezoelectric ceramic material behind ceramic green sheet C row is sticking, the sintering, wherein, the sticking temperature of described row is 550~600 ℃, and the sticking soaking time of row is 2~4h; Described sintering temperature is 1000~1250 ℃, and the sintered heat insulating time is 2~6h.
5. preparation method as claimed in claim 4 is characterized in that, the mass ratio of described dehydrated alcohol or deionized water and raw material is 1~3: 1; The mass ratio of described ball milling material zirconia ball and raw material is 1~1.5: 1.
6., photoelectric sensing integrated, micro electronmechanical at photoelectricity and LED Application for Field as the arbitrary described bismuth calcium titanate-based luminous piezoelectric ceramic material of claim 1-3.
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Cited By (6)

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Publication number Priority date Publication date Assignee Title
CN102276248A (en) * 2011-04-22 2011-12-14 同济大学 Oxide up-conversion luminescence piezoelectric material of bismuth lamellar perovskite structure and preparation method thereof
CN103214241A (en) * 2013-05-03 2013-07-24 聊城大学 Barium titanate-based lead-free piezoelectric luminous material and preparation method thereof
CN104710173A (en) * 2015-03-10 2015-06-17 宁波大学 Lead-free ferroelectric upconversion fluorescent ceramic material as well as preparation method and application thereof
CN106910838A (en) * 2017-03-31 2017-06-30 华南理工大学 A kind of perovskite luminescent device based on piezoelectric film and preparation method thereof
CN110066173A (en) * 2019-04-08 2019-07-30 昆明理工大学 A kind of BaMgSiO4: Yb, Tb up-conversion luminescence Anti-false ceramic material, preparation method and applications
CN116120054A (en) * 2023-02-10 2023-05-16 厦门乃尔电子有限公司 Bismuth calcium titanate-based piezoelectric ceramic material and preparation method thereof

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Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102276248A (en) * 2011-04-22 2011-12-14 同济大学 Oxide up-conversion luminescence piezoelectric material of bismuth lamellar perovskite structure and preparation method thereof
CN102276248B (en) * 2011-04-22 2014-07-16 同济大学 Oxide up-conversion luminescence piezoelectric material of bismuth lamellar perovskite structure and preparation method thereof
CN103214241A (en) * 2013-05-03 2013-07-24 聊城大学 Barium titanate-based lead-free piezoelectric luminous material and preparation method thereof
CN104710173A (en) * 2015-03-10 2015-06-17 宁波大学 Lead-free ferroelectric upconversion fluorescent ceramic material as well as preparation method and application thereof
CN106910838A (en) * 2017-03-31 2017-06-30 华南理工大学 A kind of perovskite luminescent device based on piezoelectric film and preparation method thereof
CN106910838B (en) * 2017-03-31 2018-10-09 华南理工大学 A kind of perovskite luminescent device and preparation method thereof based on piezoelectric film
CN110066173A (en) * 2019-04-08 2019-07-30 昆明理工大学 A kind of BaMgSiO4: Yb, Tb up-conversion luminescence Anti-false ceramic material, preparation method and applications
CN110066173B (en) * 2019-04-08 2021-09-21 昆明理工大学 BaMgSiO4Yb, Tb up-conversion luminescence anti-counterfeiting ceramic material, preparation method and application thereof
CN116120054A (en) * 2023-02-10 2023-05-16 厦门乃尔电子有限公司 Bismuth calcium titanate-based piezoelectric ceramic material and preparation method thereof
CN116120054B (en) * 2023-02-10 2024-03-12 厦门乃尔电子有限公司 Bismuth calcium titanate-based piezoelectric ceramic material and preparation method thereof

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