CN113716606A - PLZT micron seed crystal, preparation method thereof and application thereof in inducing ceramic growth - Google Patents
PLZT micron seed crystal, preparation method thereof and application thereof in inducing ceramic growth Download PDFInfo
- Publication number
- CN113716606A CN113716606A CN202110983888.5A CN202110983888A CN113716606A CN 113716606 A CN113716606 A CN 113716606A CN 202110983888 A CN202110983888 A CN 202110983888A CN 113716606 A CN113716606 A CN 113716606A
- Authority
- CN
- China
- Prior art keywords
- seed crystal
- plzt
- lead
- ceramic
- zirconate titanate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/003—Titanates
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/48—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on zirconium or hafnium oxides, zirconates, zircon or hafnates
- C04B35/49—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on zirconium or hafnium oxides, zirconates, zircon or hafnates containing also titanium oxides or titanates
- C04B35/491—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on zirconium or hafnium oxides, zirconates, zircon or hafnates containing also titanium oxides or titanates based on lead zirconates and lead titanates, e.g. PZT
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3224—Rare earth oxide or oxide forming salts thereof, e.g. scandium oxide
- C04B2235/3227—Lanthanum oxide or oxide-forming salts thereof
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/74—Physical characteristics
- C04B2235/76—Crystal structural characteristics, e.g. symmetry
- C04B2235/768—Perovskite structure ABO3
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/74—Physical characteristics
- C04B2235/78—Grain sizes and shapes, product microstructures, e.g. acicular grains, equiaxed grains, platelet-structures
- C04B2235/786—Micrometer sized grains, i.e. from 1 to 100 micron
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Ceramic Engineering (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Composite Materials (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Environmental & Geological Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Compositions Of Oxide Ceramics (AREA)
- Crystals, And After-Treatments Of Crystals (AREA)
Abstract
The invention relates to a PLZT micron seed crystal, a preparation method thereof and application thereof in inducing ceramic growth. Wherein the component general formula of the lead lanthanum zirconate titanate micron seed crystal is Pb1‑xLax(ZryTi1‑y)1‑x/ 4O3Wherein x is more than or equal to 0.040 and less than or equal to 0.100, and y is more than 0.65 and less than or equal to 0.75; the grain size of the lead lanthanum zirconate titanate micron seed crystal is micron-sized.
Description
Technical Field
The invention relates to a lead lanthanum zirconate titanate micron seed crystal and a preparation method thereof, and a method for preparing electrically controlled light scattering PLZT ceramic by inducing the lead lanthanum zirconate titanate micron seed crystal, belonging to the field of seed crystal powder preparation and ceramic modification.
Background
With the continuous development of optical communication and laser technology, various opticsThe system has increasingly urgent requirements on optical modulation devices such as optical switches, optical attenuators, optical isolators and the like, and particularly is a high-speed dynamic electro-optical modulation device based on an electro-optical effect. In an electro-optical modulator, an electro-optical ceramic represented by PLZT or PLMNT has good light transmittance, has the advantage of high response speed (nanosecond level) compared with a liquid crystal material, and is LiNbO3Compared with a crystal (a symbolic electro-optical material in the communication field), the crystal has the advantage of low driving voltage due to large electro-optical coefficient.
Aiming at the application of the electro-optic ceramic-based optical modulator, at present, the electro-optic ceramic with the electrically controlled birefringence effect is mostly used for researching and comparing systems and practical application, but the electro-optic modulator requires the modulated light to be polarized light, is more complex in device design and has application limitation. The PLZT electro-optic ceramic also has another electro-optic effect, namely an electric control light scattering effect, and is characterized in that no requirement is made on the polarization state of incident light, namely the polarization is irrelevant, and the material is suitable for being designed into a high-speed polarization-irrelevant light modulation device and meets the continuously developed laser technology.
The inventor introduces that specific component PLZT has forward and backward electrically controlled light scattering properties in earlier working chinese patent No. 201210181261.9 and chinese patent No. 202110049241.5, respectively, forward light scattering is characterized in that the ceramic is in an on-state in a normal state (when no voltage is applied), when an external electric field of a specific electric field strength is applied, the ceramic changes from the on-state to an off-state (incident light is attenuated by large-scale scattering), and after the electric field is withdrawn, the ceramic returns to the on-state. The characteristic of the reverse light scattering is that the normal state is off state (light scattering state), when a reverse electric field with specific electric field intensity is applied, the reverse light scattering ceramic in the off state is changed into an on state, and the ceramic is in the off state again after the electric field is removed. The two types of electric control light scattering ceramics are suitable for optical modulators such as high-speed optical switches, optical isolators and the like, and have important application prospects in high-speed polarization-independent laser systems.
According to the direction of an applied electric field, the working modes of the electric control light scattering ceramic are divided into two types: a transverse electric field mode and a longitudinal electric field mode. The electric field direction of the transverse electric field mode is vertical to the light passing direction, and the electric field direction of the longitudinal electric field mode is parallel to the light passing direction. Compared with the two modes, the transverse electric field mode has the advantages of higher optical switching ratio and faster response speed, and the transverse electric field mode has the defects of high threshold electric field, and the higher threshold electric field marks that the material has higher energy consumption in application, so that the application range of the material is limited. Therefore, a preparation method for reducing the threshold electric field of the electrically-controlled light scattering ceramic is urgently needed in the field.
Disclosure of Invention
Aiming at the defects that the existing electrically-controlled light scattering ceramic has higher threshold electric field and limits the practical application, the invention aims to provide PLZT micron seed crystal powder for electrically-controlled light scattering ceramic of lead lanthanum zirconate titanate (PLZT), a preparation method thereof and a method for preparing the electrically-controlled light scattering PLZT ceramic with low threshold electric field by using the micron seed crystal for induced growth.
During the previous research, the inventor finds that the intrinsic mechanism of the electric control light scattering effect is as follows: under the condition of no applied electric field, the wavelength of incident light is far larger than the size of the ferroelectric domain in the material, so that the PLZT ceramic does not scatter the incident light, and the ceramic is transparent. Under the action of an external electric field, ferroelectric domains in the material are orderly arranged, when the ferroelectric domains are increased to a certain size, incident light is refracted and reflected at domain walls, the domain walls become scattering centers, the incident light is scattered, the ceramic becomes opaque, the intensity of the electric field with the mutation from transparent to opaque is called as a threshold electric field (on-off electric field intensity of the device), and the size of the threshold electric field directly determines the working voltage of the device. From the intrinsic mechanism of the electrically controlled light scattering effect, the electrically controlled light scattering performance of the PLZT ceramic is closely related to the ferroelectric domains, and if the degree of orientation of the crystal grains in the PLZT ceramic is increased, the ferroelectric domains in the ceramic are more easily arranged in order under the action of an electric field, and then a large-scale domain wall, namely a scattering center, is more easily formed under the action of the electric field. That is, the degree of ordered arrangement of ferroelectric domains in the material can significantly affect the magnitude of the threshold electric field of the PLZT ceramic for electrically controlling the light scattering effect, so increasing the degree of orientation of crystal grains in the light scattering ceramic is an effective method for reducing the threshold electric field.
The inventor further prepares PLZT seed crystal by sol-gel chemical method, and presets the seed crystal in ceramic powder to improve the electric control light scattering property. However, the prepared PLZT seed crystal is nano powder, the grain diameter is small, even if the seed crystal addition amount is up to 15 wt%, the ceramic regulation effect is not obvious. Furthermore, the inventor finds that the composition, the shape and the grain size of the lead lanthanum zirconate titanate seed phase have great influence on the induced growth of the electrically-controlled light scattering PLZT ceramic. Based on the consideration of the structural conformity and the uniform dispersion distribution of the ceramic phase of the electrically-controlled light scattering PLZT optimized component (8/68/32 and 7.43/70/30), the inventor selects lead lanthanum zirconate titanate powder which has a main phase of a rhombohedral pure perovskite phase, a cubic structure in appearance, micron-sized particle size, good dispersibility and uniform size as a crystal seed. However, how to prepare the lead lanthanum zirconate titanate seed crystal with the phase composition and appearance is the first technical difficulty faced by the inventor. In Chinese patent 3 (publication No. CN110845235A) and Chinese patent 4 (publication No. CN1818150A), PLZT nano powder of 200nm-800nm and PLZT nano rod of 80nm-400nm are prepared by a hydrothermal method respectively, and the obtained hydrothermal method is a feasible method for preparing PLZT seed crystal. However, the PLZT crystal powder prepared by the prior art has small scale and basically belongs to nanometer level. The sintering process of the PLZT ceramic is solid phase reaction sintering with participation of liquid phase, and the crystal grain nucleation and growth comprise the dissolution-precipitation process of the multicomponent oxide, namely lead oxide forms liquid phase at about 880 ℃, lead in liquid phase can dissolve multicomponent oxide powder particles, the PLZT crystal nucleus is formed and gradually grows at the temperature of 1150 ℃. Therefore, if the seed crystal size is too small, the seed crystal is dissolved by the liquid phase lead during the formation of a large amount of liquid phase lead at the initial stage of sintering, and cannot perform a seed crystal inducing effect during the grain nucleation period. Therefore, it is required that the diameter of the seed crystal powder is large, and even if the surface portion of the seed crystal is dissolved by the liquid phase lead, the remaining seed crystal core portion can still play a role in seed crystal induced growth. Therefore, the required PLZT seed crystal needs to satisfy the requirements of large particle size (micron order) and good dispersibility, and the optimization of the existing hydrothermal method for preparing PLZT powder technology is urgently needed to obtain the pure-phase PLZT seed crystal with good micron order dispersibility (the technical problem to be solved by the first step of the invention). On the basis, the PLZT ceramic with high orientation degree is obtained by seed crystal induced growth, and the electric control light scattering performance of the PLZT ceramic is improved.
In one aspect, the invention provides a method for preparing a large-size (micron-sized) lead lanthanum zirconate titanate micron seed crystal by a gel-hydrothermal method, which comprises the following steps:
(1) weighing a lead source, a lanthanum source, a zirconium source and a titanium source according to a stoichiometric ratio, dissolving the lead source, the lanthanum source, the zirconium source and the titanium source in an organic solution, and adding an alkali liquor to obtain a white colloid;
(2) washing and filtering the obtained white colloid with deionized water to obtain gel;
(2) and adding the obtained gel and a mineralizer into deionized water to obtain a suspension, performing hydrothermal treatment at 180-230 ℃ for 4-48 hours, and washing and drying to obtain the lead lanthanum zirconate titanate micron seed crystal.
According to the invention, a gel-hydrothermal method is adopted to prepare the high-purity PLZT micron seed crystal with micron-sized particle size, and then the micron seed crystal is used for inducing growth to obtain the PLZT ceramic with high orientation degree, so that the threshold electric field of the switch is reduced. The electrically-controlled light scattering PLZT ceramic has the characteristics of polarization independence, high response speed (nanosecond level) and large on-off ratio, and has important application prospect in modern laser systems. The invention can effectively reduce the threshold electric field of the electrically-controlled light scattering PLZT ceramic, promotes the practical application of the electrically-controlled light scattering ceramic, and has important practical value.
Preferably, the lead source comprises at least one of lead nitrate, lead acetate, lead oxalate; the lanthanum source comprises at least one of lanthanum nitrate, lanthanum isopropoxide and lanthanum acetate; the zirconium source comprises at least one of zirconium oxychloride, zirconium nitrate, zirconium n-propoxide and zirconium isopropoxide; the titanium source comprises at least one of titanium ethoxide, ethyl titanate and tetrabutyl titanate.
Preferably, the organic solvent is at least one (e.g., one or two mixed solutions) of ethanol, acetone, acetylacetone, and ethylene glycol monomethyl ether; the alkali liquor comprises 13-15M of ammonia water, 0.5-2M of sodium hydroxide solution and 0.5-2M of potassium hydroxide solution, and the addition amount of the alkali liquor is 80-160 vol% of the volume of the organic solvent.
Preferably, the mineralizer is at least one of NaOH and KOH; the concentration of the mineralizer in the suspension is 1-8M, preferably 1-3M, and more preferably 2M.
Preferably, the hydrothermal temperature is 200-230 ℃ and the hydrothermal time is 16-28 hours.
In a second aspect, the present invention provides a lead lanthanum zirconate titanate micron seed crystal prepared according to the above method, the component formula of the lead lanthanum zirconate titanate micron seed crystal is Pb1-xLax(ZryTi1-y)1-x/4O3Wherein x is more than or equal to 0.040 and less than or equal to 0.100, and y is more than 0.65 and less than or equal to 0.75; the phase structure is a perovskite phase, and the appearance of the phase structure is a cubic structure; preferably, the particle size of the lead lanthanum zirconate titanate micron seed crystal is micron-sized, and is preferably 2-10 μm. Wherein, when x is more than or equal to 0.073 and less than or equal to 0.075 and y is more than or equal to 0.69 and less than or equal to 0.71, the light-scattering effect is realized.
In a third aspect, the invention provides a method for preparing electrically-controlled light scattering PLZT ceramic by inducing lead lanthanum zirconate titanate micron seed crystal, wherein the general formula of the electrically-controlled light scattering PLZT ceramic is Pb1-xLax(ZryTi1-y)1-x/4O3Wherein x is more than or equal to 0.040 and less than or equal to 0.100, and y is more than 0.65 and less than or equal to 0.75; the method comprises the following steps:
(1) weighing PbO and La according to the stoichiometric ratio of the electrically-controlled light scattering PLZT ceramic2O3、ZrO2、TiO2Mixing to obtain raw material powder;
(2) adding the lead lanthanum zirconate titanate micron seed crystal into raw material powder and mixing to obtain mixed powder; preferably, the addition amount of the lead lanthanum zirconate titanate micron seed crystal is not more than 4wt%, preferably not more than 3 wt%, and more preferably not more than 2 wt% of the total mass of the raw material powder;
(3) and pressing and molding the mixed powder, and sintering in an oxygen-containing atmosphere by hot pressing to obtain the electrically-controlled light scattering PLZT ceramic.
Preferably, a binder is also added into the mixed powder; the binder is selected from at least one of polyvinyl alcohol PVA, ammonium polyacrylate and carboxymethyl cellulose; the addition amount of the binder is 5-10 wt% of the total mass of the mixed powder.
Preferably, the hot-pressing sintering temperature is 1200-1280 ℃, the time is 10-24 hours, and the pressure is 20-60 MPa; and introducing oxygen to realize oxygen-containing atmosphere, wherein the flow of the oxygen is 3-10L/min.
In a fourth aspect, the invention provides the electrically-controlled light-scattering PLZT ceramic prepared by the method, and compared with the electrically-controlled light-scattering PLZT ceramic without adding the lead lanthanum zirconate titanate micron seed crystal, the threshold electric field is obviously reduced by 15-18%.
Has the advantages that:
(1) the gel-hydrothermal method provided by the invention can be used for preparing PLZT micron seed crystal with high activity and a pure perovskite structure, and the generated micron seed crystal is a pure perovskite phase, is cubic in appearance, has the particle size of 2-10 mu m, is flat and uniform and has good dispersibility by adjusting parameters such as the concentration of a mineralizer, the hydrothermal treatment temperature, the hydrothermal treatment time and the like. The method is also suitable for preparing PLZT crystal powder with other component ranges;
(2) by adopting the preparation method of the PLZT micron seed crystal induced growth ceramic, the obtained electrically-controlled light scattering ceramic has the advantages that the on-off ratio and the transmittance are basically kept unchanged, the threshold electric field is obviously reduced (about 15-18 percent), and the material performance is superior to that of the electrically-controlled light scattering ceramic material without the micron seed crystal.
Drawings
FIG. 1 is a flow chart of the gel-hydrothermal method for preparing PLZT micron seed crystal according to the present invention;
fig. 2 is a schematic diagram of a system for testing the light scattering performance of the electrically-controlled light-scattering transparent ceramic, wherein the laser wavelength λ: 632.8nm, on-off ratio R ═ PE/P 01, wherein PE、P0The maximum optical power value in an on state and the minimum optical power value in an off state are respectively;
FIG. 3 is an SEM picture and XRD phase structure of PLZT (8/68/32) micron seed crystal prepared at 230 deg.C, hydrothermal treatment for 16h, 2M KOH concentration, the obtained seed crystal is pure perovskite structure, and has cubic particle size of about 4-8 μ M;
FIG. 4 is an SEM picture and XRD phase structure of PLZT (8/68/32) micron seed crystal prepared at 230 deg.C, hydrothermal treatment for 24h, 2M KOH concentration, the obtained seed crystal is pure perovskite structure, and has cubic particle size of about 6-10 μ M;
FIG. 5 is an SEM picture and XRD phase structure of PLZT (8/68/32) micron seed crystal prepared at 230 deg.C, hydrothermal treatment for 24h, and 5M NaOH concentration, the obtained seed crystal is pure perovskite structure, and has round particle size of about 10-15 μ M;
FIG. 6 is a SEM picture and XRD phase structure of PLZT (8/68/32) micron seed crystal prepared at 230 deg.C, hydrothermal treatment for 28h, 2M KOH concentration, the obtained seed crystal is pure perovskite structure, and has cubic particle size of about 4-6 μ M;
FIG. 7 is a SEM picture and XRD phase structure of PLZT (7.43/70/30) micron seed crystal prepared at 220 deg.C, hydrothermal treatment for 24h and 2M NaOH concentration, the obtained seed crystal is pure perovskite structure, and has cubic particle size of about 3-6 μ M;
FIG. 8 is an XRD spectrum of the electrically controlled light scattering PLZT ceramics prepared in comparative example 1 and examples 6-8, and it can be known that the ceramics all have a pure perovskite phase structure without a second phase, which shows that the introduction of the micron seed crystal does not change the phase structure of the material;
FIG. 9 is a ferroelectric loop of the electrically controlled light scattering PLZT ceramics prepared in comparative example 1 and examples 6-8, from which it can be seen that E is increased with the increase of the content of the micron seed crystalcAnd Pr，PmaxRemain substantially unchanged;
FIG. 10 is a graph of transmittance curves and plots for electrically controlled light scattering PLZT ceramics of comparative example 1, examples 6-8, from which it can be seen that the transmittance of the ceramic sample is slightly decreased, but the overall transmittance remains high at greater than 63%;
FIG. 11 is an electrically controlled light scattering characteristic curve of the electrically controlled light scattering PLZT ceramics prepared in comparative example 1 and examples 6-8, from which it can be seen that the threshold electric field of the ceramics decreases with increasing micrometer seed content, about 16%;
FIG. 12 is a ferroelectric loop of the electrically controlled light scattering PLZT ceramics prepared in comparative examples 2-3 and examples 9-10, from which it can be seen that E is increased with the content of micron seed crystalcAnd Pr，PmaxRemain substantially unchanged;
fig. 13 is an electrically controlled light scattering characteristic curve of the electrically controlled light scattering PLZT ceramics prepared in comparative examples 2 to 3 and examples 9 to 10, and it can be seen that the threshold electric field of the ceramics is reduced by about 18% as the content of the micron seed crystal is increased.
Detailed Description
The present invention is further illustrated by the following examples, which are to be understood as merely illustrative and not restrictive.
In the disclosure, the PLZT micron seed crystal is prepared by a gel-hydrothermal method. And PLZT ceramic with high orientation degree is obtained by induced growth of PLZT micron seed crystal, so that threshold electric field of switch is reduced.
In the invention, the general formula of the component of the lead lanthanum zirconate titanate electric control light scattering transparent ceramic material is Pb1-xLax(ZryTi1-y)1-x/4O3(PLZT for short), wherein x is more than or equal to 0.040 and less than or equal to 0.100, y is more than 0.65 and less than or equal to 0.75, the ceramic is mainly characterized by forward light scattering, and when x is more than or equal to 0.073 and less than or equal to 0.075 and y is more than or equal to 0.69 and less than or equal to 0.71 in the composition range, the ceramic is characterized by backward light scattering.
In the invention, the preparation method of the PLZT micron seed crystal is a gel-hydrothermal method, which mainly comprises the following steps: the preparation of the precursor, the hydrothermal reaction and the post-treatment. The generated PLZT micron seed crystal is pure perovskite phase, has cubic particle appearance, is flat and uniform and has good dispersibility. The purity of the powder obtained after multiple times of separation and filtration is about 100 percent.
The preparation method of the micron seed crystal induced growth electric control light scattering ceramic can comprise the following steps: weighing, ball-milling and mixing, drying, sieving, granulating, molding and oxygen-introducing hot-pressing sintering. Wherein PLZT micron seed crystal is added in the ball milling mixing stage.
After cutting and polishing the electrically-controlled light scattering ceramic prepared by micron seed crystal induction, electrodes are manufactured at two ends of a sample vertical to a light passing surface, and after testing, the threshold electric field is reduced by 15-20% (preferably 15-18%).
The present invention will be described in detail by way of examples. It is also to be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the invention, and that certain insubstantial modifications and adaptations of the invention by those skilled in the art may be made in light of the above teachings. The specific process parameters and the like of the following examples are also only one example of suitable ranges, i.e., those skilled in the art can select the appropriate ranges through the description herein, and are not limited to the specific values exemplified below.
In the invention, PLZT micron seed crystal is prepared by adopting the flow chart shown in figure 1; testing the optical transmittance of the electrically-controlled light-scattering transparent ceramic in the range of 350nm to 1100nm by using a HitachiU-2800 type spectrophotometer; testing the ferroelectric loop of the material by adopting a RadiantPrecision LC II ferroelectric analyzer; the testing system shown in FIG. 2 is used for detecting the material optical switching ratio R, and the testing system comprises a laser light source, a sample fixing frame, a stabilized voltage power supply, an OPM1000-ICH precision optical power meter and the like. Optical switching ratio R ═ PE/P 01, wherein PEFor maximum optical power value in the on state, P0Is an off state minimum optical power value; all performance tests were performed at room temperature, except where otherwise indicated.
Example 1 of PLZT micron seed powder
According to Pb1-xLax(ZryTi1-y)1-x/4O3Wherein x is 0.08 and y is 0.68 (abbreviated as PLZT (8/68/32)), lead glycolate, lanthanum isopropoxide, zirconium n-propoxide and tetrabutyl titanate are weighed according to stoichiometric proportion (solute) and dissolved in 2 parts (1 part means that 100g of solute is added into 100mL of solution, and the rest is analogized) of glycol monomethyl ether solution, and the solution is stirred until the solution is clear and transparent. Then 3 parts of ammonia (ca. 14M) was added to form a white colloid. Washing the gel obtained by filtering with deionized water to obtain the crystal seed precursor. Then adding 2M mineralizer KOH into the precursor, and carrying out hydrothermal treatment at 230 ℃ for 16 h; after hydrothermal synthesis, repeatedly washing and filtering the obtained product by using deionized water, and drying at 90 ℃ for 24 hours to obtain PLZT micron seed crystal powder. Fig. 3 shows the morphology and XRD phase structure for preparing hydrothermal micron seed crystal.
Preparation example 2 of PLZT micron seed powder
According to Pb1-xLax(ZryTi1-y)1-x/4O3Mixing lead acetate, lanthanum isopropoxide and n-lead acetate, where x is 0.08 and y is 0.68 (abbreviated as PLZT (8/68/32))Zirconium propanol and tetrabutyl titanate are weighed according to the stoichiometric ratio (solute), dissolved in 2 parts of ethylene glycol monomethyl ether solution, and stirred until the solution is clear and transparent. Then 3 parts of ammonia (ca. 14M) was added to form a white colloid. Washing the gel obtained by filtering with deionized water to obtain the crystal seed precursor. Then adding 2M mineralizer KOH into the precursor, and carrying out hydrothermal treatment at 230 ℃ for 24 h; after hydrothermal synthesis, repeatedly washing and filtering the obtained product by using deionized water, and drying at 90 ℃ for 24 hours to obtain PLZT micron seed crystal powder. Fig. 4 shows the morphology and XRD phase structure for preparing hydrothermal micron seed crystal.
Preparation example 3 of PLZT micron seed powder
According to Pb1-xLax(ZryTi1-y)1-x/4O3Wherein x is 0.08 and y is 0.68 (abbreviated as PLZT (8/68/32)), lead acetate, lanthanum ethoxide, zirconium isopropoxide and tetrabutyl titanate are weighed according to stoichiometric ratio (solute) and dissolved in 2 parts of mixed solution of ethylene glycol monomethyl ether and acetylacetone (acetylacetone accounts for 10wt% of the mixed solution), and the mixture is stirred until the solution is clear and transparent. Then 2 parts of sodium hydroxide solution (about 2M) is added to form white colloid, gel obtained by washing and filtering with deionized water is used as a crystal seed precursor, 5M of mineralizer NaOH is added into the precursor, hydrothermal treatment is carried out at 230 ℃ for 24h, after hydrothermal synthesis, the obtained product is repeatedly washed and filtered with deionized water, and drying is carried out at 90 ℃ for 24h, thus obtaining PLZT micron crystal seed powder, and figure 5 shows the appearance and XRD phase structure for preparing hydrothermal micron crystal seed.
Preparation example 4 of PLZT micron seed powder
According to Pb1-xLax(ZryTi1-y)1-x/4O3Wherein x is 0.08 and y is 0.68 (PLZT (8/68/32)) by proportioning, dissolving lead glycolate, lanthanum isopropoxide, zirconium n-propoxide and tetrabutyl titanate (solute) in 2 parts of ethylene glycol monomethyl ether solution according to stoichiometric ratio, and stirring until the solution is clear and transparent. Then 3 parts of ammonia (ca. 14M) was added to form a white colloid. Washing the gel obtained by filtering with deionized water to obtain the crystal seed precursor. Then adding 2M mineralizer KOH into the precursor, and carrying out hydrothermal treatment at 230 ℃ for 28 h; after hydrothermal synthesis, theAnd repeatedly washing and filtering the obtained product by using deionized water, and drying at 90 ℃ for 24 hours to obtain PLZT micron seed crystal powder. Fig. 6 shows the morphology and XRD phase structure for preparing hydrothermal micron seed crystal.
Preparation example 5 of PLZT micron seed powder
According to Pb1-xLax(ZryTi1-y)1-x/4O3Wherein x is 0.0743, y is 0.70 (PLZT (7.43/70/30)) and the materials are dissolved in 2 parts of glycol methyl ether solution by weighing the materials (solute) according to stoichiometric ratio and stirring until the solution is clear and transparent. Then 2 parts of sodium hydroxide solution (2M) were added to form a white colloid. Washing the gel obtained by filtering with deionized water to obtain the crystal seed precursor. Then 2M of mineralizer NaOH is added into the precursor, and hydrothermal treatment is carried out at 220 ℃ for 24 h; after hydrothermal synthesis, repeatedly washing and filtering the obtained product by using deionized water, and drying at 90 ℃ for 24 hours to obtain PLZT micron seed crystal powder. Figure 7 is a graph of morphology and XRD phase structure for preparing hydrothermal micron seed crystals.
PLZT micron seed induced ceramics example 6
According to Pb1-xLax(ZryTi1-y)1-x/4O3Wherein x is 0.08 and y is 0.68 (PLZT (8/68/32)) by proportioning, dissolving lead glycolate, lanthanum isopropoxide, zirconium n-propoxide and tetrabutyl titanate (solute) in 2 parts of ethylene glycol monomethyl ether solution according to stoichiometric ratio, and stirring until the solution is clear and transparent. Then 3 parts of ammonia (ca. 14M) was added to form a white colloid. Washing the gel obtained by filtering with deionized water to obtain the crystal seed precursor. Then adding 2M mineralizer KOH, and carrying out hydrothermal treatment at 230 ℃ for 24 h; after hydrothermal synthesis, repeatedly washing and filtering the obtained product by using deionized water, and drying at 90 ℃ for 24 hours to obtain PLZT micron seed crystal powder.
Ceramic powder is prepared according to PLZT (8/68/32), lead oxide, lanthanum oxide, zirconium dioxide and titanium dioxide are weighed according to stoichiometric ratio, 0.5 wt% of PLZT micron seed crystal powder is added, 0.7 part of absolute ethyl alcohol (namely 70mL of 100g of powder) is added, after 5 hours of ball milling, drying is carried out, and 200 meshes of sieving is carried out. Adding 6% PVA for granulation, pressing into a cylindrical biscuit with the diameter of 35mmx20mm, and adopting oxygen introduction hot pressing sintering. The sintering temperature is 1280 ℃/10h, the pressure is 40MP, and the oxygen flow of 5 liters/minute is kept during the sintering process. Through the procedures of cutting, grinding, polishing and the like, the ceramic block is respectively processed into phi 35mm multiplied by 1mm and 5mm multiplied by 2mm ceramic plates, optical transmittance and reverse light scattering performance tests are respectively carried out after double-side polishing, in addition, the ceramic block is also processed into 5mm multiplied by 1mm ceramic plates, ferroelectric tests are carried out after double-side fine grinding, and the main performance parameters are shown in table 1.
PLZT micron seed induced ceramics example 7
According to Pb1-xLax(ZryTi1-y)1-x/4O3Wherein x is 0.08 and y is 0.68 (PLZT (8/68/32)) by proportioning, dissolving lead glycolate, lanthanum isopropoxide, zirconium n-propoxide and tetrabutyl titanate (solute) in 2 parts of ethylene glycol monomethyl ether solution according to stoichiometric ratio, and stirring until the solution is clear and transparent. Then 3 parts of ammonia (ca. 14M) was added to form a white colloid. Washing the gel obtained by filtering with deionized water to obtain the crystal seed precursor. Then adding 2M mineralizer KOH, and carrying out hydrothermal treatment at 230 ℃ for 24 h; after hydrothermal synthesis, repeatedly washing and filtering the obtained product by using deionized water, and drying at 90 ℃ for 24 hours to obtain PLZT micron seed crystal powder.
Ceramic powder is prepared according to PLZT (8/68/32), lead oxide, lanthanum oxide, zirconium dioxide and titanium dioxide are weighed according to stoichiometric ratio, 1.0 wt% of PLZT micron seed crystal powder is added, 0.7 part of absolute ethyl alcohol (namely 70mL of 100g of powder) is added, after 5 hours of ball milling, drying is carried out, and 200 meshes of sieving is carried out. Adding 6% PVA for granulation, pressing into a cylindrical biscuit with the diameter of 35mmx20mm, and adopting oxygen introduction hot pressing sintering. The sintering temperature is 1280 ℃/10h, the pressure is 40MP, and the oxygen flow of 5 liters/minute is kept during the sintering process. Through the procedures of cutting, grinding, polishing and the like, the ceramic block is respectively processed into phi 35mm multiplied by 1mm and 5mm multiplied by 2mm ceramic plates, optical transmittance and reverse light scattering performance tests are respectively carried out after double-side polishing, in addition, the ceramic block is also processed into 5mm multiplied by 1mm ceramic plates, ferroelectric tests are carried out after double-side fine grinding, and the main performance parameters are shown in table 1.
PLZT micron seed induced ceramics example 8
According to Pb1-xLax(ZryTi1-y)1-x/4O3Wherein x is 0.08 and y is 0.68 (PLZT (8/68/32)) by proportioning, dissolving lead glycolate, lanthanum isopropoxide, zirconium n-propoxide and tetrabutyl titanate (solute) in 2 parts of ethylene glycol monomethyl ether solution according to stoichiometric ratio, and stirring until the solution is clear and transparent. Then 3 parts of ammonia (ca. 14M) was added to form a white colloid. Washing the gel obtained by filtering with deionized water to obtain the crystal seed precursor. Then adding 2M mineralizer KOH, and carrying out hydrothermal treatment at 230 ℃ for 24 h; after hydrothermal synthesis, repeatedly washing and filtering the obtained product by using deionized water, and drying at 90 ℃ for 24 hours to obtain PLZT micron seed crystal powder.
Ceramic powder is prepared according to PLZT (8/68/32), lead oxide, lanthanum oxide, zirconium dioxide and titanium dioxide are weighed according to stoichiometric ratio, 1.5 wt% of PLZT micron seed crystal powder is added, 0.7 part of absolute ethyl alcohol (namely 70mL of 100g of powder) is added, after 5 hours of ball milling, drying is carried out, and 200 meshes of sieving is carried out. Adding 6% PVA for granulation, pressing into a cylindrical biscuit with the diameter of 35mmx20mm, and adopting oxygen introduction hot pressing sintering. The sintering temperature is 1280 ℃/10h, the pressure is 40MP, and the oxygen flow of 5 liters/minute is kept during the sintering process. Through the procedures of cutting, grinding, polishing and the like, the ceramic block is respectively processed into phi 35mm multiplied by 1mm and 5mm multiplied by 2mm ceramic plates, optical transmittance and reverse light scattering performance tests are respectively carried out after double-side polishing, in addition, the ceramic block is also processed into 5mm multiplied by 1mm ceramic plates, ferroelectric tests are carried out after double-side fine grinding, and the main performance parameters are shown in table 1.
PLZT micron seed induced ceramics example 9
According to Pb1-xLax(ZryTi1-y)1-x/4O3Wherein x is 0.0743, y is 0.70 (PLZT (7.43/70/30)) and the materials are dissolved in 2 parts of glycol methyl ether solution by weighing the materials (solute) according to stoichiometric ratio and stirring until the solution is clear and transparent. Then 3 parts of ammonia (ca. 14M) was added to form a white colloid. Washing the gel obtained by filtering with deionized water to obtain the crystal seed precursor. Then adding 2M mineralizer NaOH, and carrying out hydrothermal treatment at 220 ℃ for 24 h; after hydrothermal synthesis, the product obtained is repeatedly washed with deionized water and filtered, and dried at 90 DEG CAnd obtaining PLZT micron seed crystal powder after 24 h.
Ceramic powder is prepared according to PLZT (7.43/70/30), lead oxide, lanthanum oxide, zirconium dioxide and titanium dioxide are weighed according to stoichiometric ratio, 1.0 wt% of PLZT micron seed crystal powder is added, 0.7 part of absolute ethyl alcohol (70 mL is added in 100g of powder) is added, and after 5 hours of ball milling, drying is carried out, and the mixture is sieved by a 200-mesh sieve. Adding 6% PVA for granulation, pressing into a cylindrical biscuit with the diameter of 35mmx20mm, and adopting oxygen introduction hot pressing sintering. The sintering temperature is 1280 ℃/10h, the pressure is 40MP, and the oxygen flow of 5 liters/minute is kept during the sintering process. Through the procedures of cutting, grinding, polishing and the like, the ceramic block is respectively processed into phi 35mm multiplied by 1mm and 5mm multiplied by 2mm ceramic plates, optical transmittance and reverse light scattering performance tests are respectively carried out after double-side polishing, in addition, the ceramic block is also processed into 5mm multiplied by 1mm ceramic plates, ferroelectric tests are carried out after double-side fine grinding, and the main performance parameters are shown in table 1.
PLZT micron seed induced ceramics example 10
According to Pb1-xLax(ZryTi1-y)1-x/4O3Wherein x is 0.0743, y is 0.70 (PLZT (7.43/70/30)) and the materials are dissolved in 2 parts of glycol methyl ether solution by weighing the materials (solute) according to stoichiometric ratio and stirring until the solution is clear and transparent. Then 3 parts of ammonia (ca. 14M) was added to form a white colloid. Washing the gel obtained by filtering with deionized water to obtain the crystal seed precursor. Then adding 2M mineralizer NaOH, and carrying out hydrothermal treatment at 220 ℃ for 24 h; after hydrothermal synthesis, repeatedly washing and filtering the obtained product by using deionized water, and drying at 90 ℃ for 24 hours to obtain PLZT micron seed crystal powder.
Ceramic powder is prepared according to PLZT (7.43/70/30), lead oxide, lanthanum oxide, zirconium dioxide and titanium dioxide are weighed according to stoichiometric ratio, 2.0 wt% of PLZT micron seed crystal powder is added, 0.7 part of absolute ethyl alcohol (70 mL is added in 100g of powder) is added, and after 5 hours of ball milling, drying is carried out, and the mixture is sieved by a 200-mesh sieve. Adding 6% PVA for granulation, pressing into a cylindrical biscuit with the diameter of 35mmx20mm, and adopting oxygen introduction hot pressing sintering. The sintering temperature is 1280 ℃/10h, the pressure is 40MP, and the oxygen flow of 5 liters/minute is kept during the sintering process. Through the procedures of cutting, grinding, polishing and the like, the ceramic block is respectively processed into phi 35mm multiplied by 1mm and 5mm multiplied by 2mm ceramic plates, optical transmittance and reverse light scattering performance tests are respectively carried out after double-side polishing, in addition, the ceramic block is also processed into 5mm multiplied by 1mm ceramic plates, ferroelectric tests are carried out after double-side fine grinding, and the main performance parameters are shown in table 1.
PLZT pure ceramic comparative example 1
According to Pb1-xLax(ZryTi1-y)1-x/4O3Mixing ceramic powder with x being 0.08 and y being 0.68, weighing lead oxide, lanthanum oxide, zirconium dioxide and titanium dioxide according to stoichiometric ratio, adding 0.7 part of absolute ethyl alcohol (namely adding 70mL of 100g of powder), ball-milling for 5 hours, drying, sieving by a 200-mesh sieve, and screening. Adding 6% PVA for granulation, pressing into a cylindrical biscuit with the diameter of 35mmx20mm, and adopting oxygen introduction hot pressing sintering. The sintering temperature is 1280 ℃/10h, the pressure is 40MP, and the oxygen flow of 5 liters/minute is kept during the sintering process. Through the procedures of cutting, grinding, polishing and the like, the ceramic block is respectively processed into phi 35mm multiplied by 1mm and 5mm multiplied by 2mm ceramic plates, optical transmittance and reverse light scattering performance tests are respectively carried out after double-side polishing, in addition, the ceramic block is also processed into 5mm multiplied by 1mm ceramic plates, ferroelectric tests are carried out after double-side fine grinding, and the main performance parameters are shown in table 1.
Comparative PLZT pure ceramic example 2
According to Pb1-xLax(ZryTi1-y)1-x/4O3Mixing the ceramic powder with x being 0.0743 and y being 0.70, weighing lead oxide, lanthanum oxide, zirconium dioxide and titanium dioxide according to the stoichiometric ratio, adding 0.7 part of absolute ethyl alcohol (namely adding 70mL of 100g of powder), drying after ball milling for 5 hours, sieving by a 200-mesh sieve. Adding 6% PVA for granulation, pressing into a cylindrical biscuit with the diameter of 35mmx20mm, and adopting oxygen introduction hot pressing sintering. The sintering temperature is 1280 ℃/10h, the pressure is 40MP, and the oxygen flow of 5 liters/minute is kept during the sintering process. Through the procedures of cutting, grinding, polishing and the like, the ceramic block is respectively processed into phi 35mm multiplied by 1mm and 5mm multiplied by 2mm ceramic plates, optical transmittance and reverse light scattering performance tests are respectively carried out after double-side polishing, in addition, the ceramic block is also processed into 5mm multiplied by 1mm ceramic plates, ferroelectric tests are carried out after double-side fine grinding, and the main performance parameters are shown in table 1.
Comparative example PLZT micron seed induced ceramics 3
According to Pb1-xLax(ZryTi1-y)1-x/4O3Wherein x is 0.0743, y is 0.70 (PLZT (7.43/70/30)) and the materials are dissolved in 2 parts of glycol methyl ether solution by weighing the materials (solute) according to stoichiometric ratio and stirring until the solution is clear and transparent. Then, 3 parts of ammonia (14M) was added to form a white colloid. Washing the gel obtained by filtering with deionized water to obtain the crystal seed precursor. Then adding 2M mineralizer NaOH, and carrying out hydrothermal treatment at 220 ℃ for 24 h; after hydrothermal synthesis, repeatedly washing and filtering the obtained product by using deionized water, and drying at 90 ℃ for 24 hours to obtain PLZT micron seed crystal powder.
Ceramic powder is prepared according to PLZT (7.43/70/30), lead oxide, lanthanum oxide, zirconium dioxide and titanium dioxide are weighed according to stoichiometric ratio, PLZT micron seed crystal powder with 4.0 wt% is added, 0.7 part of absolute ethyl alcohol (70 mL is added in 100g powder) is added, and after 5 hours of ball milling, drying is carried out, and sieving is carried out by a 200-mesh sieve. Adding 6% PVA for granulation, pressing into a cylindrical biscuit with the diameter of 35mmx20mm, and adopting oxygen introduction hot pressing sintering. The sintering temperature is 1280 ℃/10h, the pressure is 40MP, and the oxygen flow of 5 liters/minute is kept during the sintering process. Through the procedures of cutting, grinding, polishing and the like, the ceramic block is respectively processed into phi 35mm multiplied by 1mm and 5mm multiplied by 2mm ceramic plates, optical transmittance and reverse light scattering performance tests are respectively carried out after double-side polishing, in addition, the ceramic block is also processed into 5mm multiplied by 1mm ceramic plates, ferroelectric tests are carried out after double-side fine grinding, and the main performance parameters are shown in table 1.
Table 1 shows the performance parameters of examples 6 to 10 and comparative examples 1 to 3:
from table 1, it can be seen that, as the content of the micron seed crystal increases, the phase transition field EA-F of the forward electrically controlled light scattering PLZT ceramic gradually decreases, the threshold electric field of the light scattering performance is significantly reduced, and the ferroelectric performance of the reverse electrically controlled light scattering PLZT ceramic is not significantly changed, but the threshold electric field is also significantly reduced. However, considering that the transmittance of the electrically controlled light scattering PLZT ceramic gradually decreases with the increase of the content of the micron seed, and the on-state transmittance is affected, the value of the content x of the micron seed is preferably not more than 3, and most preferably not more than 2 wt%.
Claims (10)
1. The lead lanthanum zirconate titanate micron seed crystal is characterized in that the component general formula of the lead lanthanum zirconate titanate micron seed crystal is Pb1-xLax(ZryTi1-y)1-x/4O3Wherein x is more than or equal to 0.040 and less than or equal to 0.100, and y is more than 0.65 and less than or equal to 0.75; the grain size of the lead lanthanum zirconate titanate micron seed crystal is micron-sized.
2. The lead lanthanum zirconate titanate micron seed of claim 1, wherein the phase structure of the lead lanthanum zirconate titanate micron seed is a pure perovskite phase, with a cubic structure in appearance; the particle size of the lead lanthanum zirconate titanate micron seed crystal is 2-10 mu m.
3. A method of preparing a lead lanthanum zirconate titanate micron seed crystal of claim 1 or 2, comprising:
(1) weighing a lead source, a lanthanum source, a zirconium source and a titanium source according to a stoichiometric ratio, dissolving the lead source, the lanthanum source, the zirconium source and the titanium source in an organic solution, and adding an alkali liquor to obtain a white colloid;
(2) washing and filtering the obtained white colloid with deionized water to obtain gel;
(2) and adding the obtained gel and a mineralizer into deionized water to obtain a suspension, performing hydrothermal treatment at 180-230 ℃ for 4-48 hours, and washing and drying to obtain the lead lanthanum zirconate titanate micron seed crystal.
4. The method according to claim 3, wherein the lead source comprises at least one of lead nitrate, lead acetate, lead oxalate; the lanthanum source comprises at least one of lanthanum nitrate, lanthanum isopropoxide and lanthanum acetate; the zirconium source comprises at least one of zirconium oxychloride, zirconium nitrate, zirconium n-propoxide and zirconium isopropoxide; the titanium source comprises at least one of titanium ethoxide, ethyl titanate and tetrabutyl titanate.
5. The production method according to claim 3, wherein the organic solvent is at least one of ethanol, acetone, acetylacetone, and ethylene glycol methyl ether; the alkali liquor comprises concentrated ammonia water, a sodium hydroxide solution or a potassium hydroxide solution; the concentration of the alkali liquor is 1-15M, and the adding amount is 80-160 vol% of the volume of the organic solvent.
6. The method of any one of claims 3-5, wherein the mineralizer is at least one of NaOH and KOH; the concentration of the mineralizer in the suspension is 1-8M, and preferably 1-3M.
7. The method for preparing the electrically-controlled light scattering PLZT ceramic by inducing the lead lanthanum zirconate titanate micron seed crystal is characterized in that the general formula of the electrically-controlled light scattering PLZT ceramic is Pb1-xLax(ZryTi1-y)1-x/4O3Wherein x is more than or equal to 0.040 and less than or equal to 0.100, and y is more than 0.65 and less than or equal to 0.75; the method comprises the following steps:
(1) weighing PbO and La according to the stoichiometric ratio of the electrically-controlled light scattering PLZT ceramic2O3、ZrO2、TiO2Mixing to obtain raw material powder;
(2) adding the lead lanthanum zirconate titanate micron seed crystal of claim 1 or 2 into the raw material powder and mixing to obtain mixed powder; preferably, the adding amount of the lead lanthanum zirconate titanate micron seed crystal is not more than 4wt% of the total mass of the raw material powder;
(3) and pressing and molding the mixed powder, and sintering in an oxygen-containing atmosphere by hot pressing to obtain the electrically-controlled light scattering PLZT ceramic.
8. The method according to claim 7, wherein a binder is further added to the mixed powder; the binder is selected from at least one of polyvinyl alcohol PVA, ammonium polyacrylate and carboxymethyl cellulose; the addition amount of the binder is 5-10 wt% of the total mass of the mixed powder.
9. The method according to claim 7 or 8, wherein the temperature of the hot-press sintering is 1200-1280 ℃, the time is 10-24 hours, and the pressure is 20-60 MPa; and introducing oxygen to realize oxygen-containing atmosphere, wherein the flow of the oxygen is 3-10L/min.
10. An electrically controlled light scattering PLZT ceramic prepared according to the method of any one of claims 7-9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110983888.5A CN113716606B (en) | 2021-08-25 | 2021-08-25 | PLZT micron seed crystal, preparation method thereof and application thereof in inducing ceramic growth |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110983888.5A CN113716606B (en) | 2021-08-25 | 2021-08-25 | PLZT micron seed crystal, preparation method thereof and application thereof in inducing ceramic growth |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113716606A true CN113716606A (en) | 2021-11-30 |
| CN113716606B CN113716606B (en) | 2022-09-06 |
Family
ID=78677920
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110983888.5A Active CN113716606B (en) | 2021-08-25 | 2021-08-25 | PLZT micron seed crystal, preparation method thereof and application thereof in inducing ceramic growth |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113716606B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116947536A (en) * | 2023-09-18 | 2023-10-27 | 新明珠集团股份有限公司 | Zirconium-free ground glaze, titanium raw material opacified glazed tile and preparation method thereof |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB8705883D0 (en) * | 1986-07-30 | 1987-04-15 | Mitsubishi Mining & Cement Co | Producing ceramic composition |
| JP2007217250A (en) * | 2006-02-20 | 2007-08-30 | Nara Institute Of Science & Technology | Method for producing thin oxide film |
| US20090211515A1 (en) * | 2002-10-11 | 2009-08-27 | Ceracomp Co., Ltd. | Method for solid-state single crystal growth |
| CN103449813A (en) * | 2012-06-04 | 2013-12-18 | 中国科学院上海硅酸盐研究所 | Lanthanum-doped lead zirconate titanate electro-optic scattering transparent ceramic and preparation method thereof |
| CN106518069A (en) * | 2016-09-29 | 2017-03-22 | 广东工业大学 | Lanthanum-zirconium-doped lead titanate ferroelectric thick film ceramic material and preparation method thereof |
| CN108751990A (en) * | 2018-06-29 | 2018-11-06 | 广东工业大学 | A kind of PLZT ceramics and the preparation method and application thereof |
| CN109665839A (en) * | 2018-12-20 | 2019-04-23 | 中国科学院上海硅酸盐研究所 | A kind of high energy storage density PLZT based antiferroelectric ceramic material and its preparation method and application |
| CN110845235A (en) * | 2019-10-15 | 2020-02-28 | 广东工业大学 | Lead lanthanum zirconate titanate ceramic powder and preparation method and application thereof |
-
2021
- 2021-08-25 CN CN202110983888.5A patent/CN113716606B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB8705883D0 (en) * | 1986-07-30 | 1987-04-15 | Mitsubishi Mining & Cement Co | Producing ceramic composition |
| US20090211515A1 (en) * | 2002-10-11 | 2009-08-27 | Ceracomp Co., Ltd. | Method for solid-state single crystal growth |
| JP2007217250A (en) * | 2006-02-20 | 2007-08-30 | Nara Institute Of Science & Technology | Method for producing thin oxide film |
| CN103449813A (en) * | 2012-06-04 | 2013-12-18 | 中国科学院上海硅酸盐研究所 | Lanthanum-doped lead zirconate titanate electro-optic scattering transparent ceramic and preparation method thereof |
| CN106518069A (en) * | 2016-09-29 | 2017-03-22 | 广东工业大学 | Lanthanum-zirconium-doped lead titanate ferroelectric thick film ceramic material and preparation method thereof |
| CN108751990A (en) * | 2018-06-29 | 2018-11-06 | 广东工业大学 | A kind of PLZT ceramics and the preparation method and application thereof |
| CN109665839A (en) * | 2018-12-20 | 2019-04-23 | 中国科学院上海硅酸盐研究所 | A kind of high energy storage density PLZT based antiferroelectric ceramic material and its preparation method and application |
| CN110845235A (en) * | 2019-10-15 | 2020-02-28 | 广东工业大学 | Lead lanthanum zirconate titanate ceramic powder and preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| XINGSHENG ZONG ET AL.: "Crystallization and Morphology of Pb0.92La0.08(Zr0.68Ti0.32)0.98O3 Powders Synthesized Using the Gel-Hydrothermal Process", 《CRYSTAL RESEARCH AND TECHNOLOGY》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116947536A (en) * | 2023-09-18 | 2023-10-27 | 新明珠集团股份有限公司 | Zirconium-free ground glaze, titanium raw material opacified glazed tile and preparation method thereof |
| CN116947536B (en) * | 2023-09-18 | 2024-02-23 | 新明珠集团股份有限公司 | Zirconium-free ground glaze, titanium raw material opacified glazed tile and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113716606B (en) | 2022-09-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5019826B2 (en) | Zirconia sol and method for producing the same | |
| Zhou et al. | Cs x WO 3 nanoparticle-based organic polymer transparent foils: low haze, high near infrared-shielding ability and excellent photochromic stability | |
| Li et al. | Fabrication of transparent electro-optic (K0. 5Na0. 5) 1− xLixNb1− xBixO3 lead-free ceramics | |
| CN113716606B (en) | PLZT micron seed crystal, preparation method thereof and application thereof in inducing ceramic growth | |
| CN103930386B (en) | A kind of CaF2 class light transparent ceramic and manufacture method thereof | |
| CN101429348B (en) | Process for producing nano-titanium dioxide-zinc oxide composite powder | |
| Jalalian et al. | Biocompatible ferroelectric (Na, K) NbO3 nanofibers | |
| CN102432062B (en) | Preparation method of perovskite-like varistor ceramic material CaCu3Ti4O12 with high dielectric constant | |
| TW201609605A (en) | Method for producing transparent ceramic, transparent ceramic, magneto-optical device and rare earth oxide powder for sintering | |
| Supriya | Synthesis mechanisms and effects of BaTiO3 doping on the optical properties of Bi0. 5Na0. 5TiO3 lead-free ceramics | |
| JP5464840B2 (en) | Method for producing zirconia fine particles | |
| CN106986381A (en) | A kind of loose preparation method containing zirconium hydroxide or nm-class powder of zirconium oxide | |
| Yang et al. | Modified hydrothermal treatment route for high-yield preparation of nanosized ZrO2 | |
| CN103626492A (en) | Scandia-stabilized zirconia powder for solid oxide fuel battery | |
| CN101279719A (en) | Preparation for nano-oxide powder | |
| JP2007238422A (en) | Organic solvent-dispersed zirconia sol and its production method | |
| CN103754935B (en) | Method for synthesizing lead molybdate tower crystal at room temperature | |
| CN103449520B (en) | Rod-like niobium pentoxide template grain and preparation method thereof | |
| CN112110485A (en) | Yttrium-stabilized zirconia ceramic nano powder and preparation method and application thereof | |
| CN114133240A (en) | Method for preparing scandium-cerium-ytterbium-doped zirconia superfine powder by hydrolysis-hydrothermal method | |
| CN1477059A (en) | Preparation method of nano alumina material | |
| CN109534812B (en) | Preparation method of strontium potassium niobate microcrystalline powder with micron tube | |
| JP2014201495A (en) | Rare earth phosphate powder and production method of the same, and fluid dispersion including the powder | |
| CN1301933C (en) | Ammonium hydrogen coprecipitation method for preparing nano powder of yttrium aluminum garnet and transparent ceramics | |
| CN1187284C (en) | Lead niobate zincate-lead lanthanum zirconate titanate function ceramic and preparing method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |