CN116283288A - Transparent photoelectric ceramic material with ultrahigh electro-optic coefficient and piezoelectric property and preparation method thereof - Google Patents
Transparent photoelectric ceramic material with ultrahigh electro-optic coefficient and piezoelectric property and preparation method thereof Download PDFInfo
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- CN116283288A CN116283288A CN202211537131.4A CN202211537131A CN116283288A CN 116283288 A CN116283288 A CN 116283288A CN 202211537131 A CN202211537131 A CN 202211537131A CN 116283288 A CN116283288 A CN 116283288A
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- 229910010293 ceramic material Inorganic materials 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- 239000000843 powder Substances 0.000 claims abstract description 95
- 239000000919 ceramic Substances 0.000 claims abstract description 43
- 238000000137 annealing Methods 0.000 claims abstract description 9
- 238000000498 ball milling Methods 0.000 claims description 120
- 238000001035 drying Methods 0.000 claims description 69
- 238000001354 calcination Methods 0.000 claims description 63
- 239000002243 precursor Substances 0.000 claims description 35
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 25
- 238000005245 sintering Methods 0.000 claims description 25
- 238000000034 method Methods 0.000 claims description 22
- 210000002381 plasma Anatomy 0.000 claims description 22
- 238000002156 mixing Methods 0.000 claims description 21
- 239000011777 magnesium Substances 0.000 claims description 20
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 19
- 239000000203 mixture Substances 0.000 claims description 16
- 229940046892 lead acetate Drugs 0.000 claims description 14
- 239000000395 magnesium oxide Substances 0.000 claims description 14
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 13
- 229910052760 oxygen Inorganic materials 0.000 claims description 13
- 239000001301 oxygen Substances 0.000 claims description 13
- 239000000463 material Substances 0.000 claims description 12
- 230000008569 process Effects 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 11
- 238000002490 spark plasma sintering Methods 0.000 claims description 11
- 230000005684 electric field Effects 0.000 claims description 10
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 9
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Inorganic materials O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 claims description 9
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 claims description 9
- 239000012700 ceramic precursor Substances 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 8
- 230000010287 polarization Effects 0.000 claims description 7
- 239000010936 titanium Substances 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- 230000004888 barrier function Effects 0.000 claims description 6
- 239000011888 foil Substances 0.000 claims description 6
- 229910002804 graphite Inorganic materials 0.000 claims description 6
- 239000010439 graphite Substances 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- 125000003158 alcohol group Chemical group 0.000 claims description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 4
- 229910052693 Europium Inorganic materials 0.000 claims description 3
- 229910052746 lanthanum Inorganic materials 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 239000011733 molybdenum Substances 0.000 claims description 2
- 230000005693 optoelectronics Effects 0.000 claims 1
- 230000009021 linear effect Effects 0.000 abstract description 13
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 32
- 238000000227 grinding Methods 0.000 description 31
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 28
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 21
- 238000007664 blowing Methods 0.000 description 16
- -1 polytetrafluoroethylene Polymers 0.000 description 16
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 16
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- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 12
- 229910052749 magnesium Inorganic materials 0.000 description 12
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- 239000004570 mortar (masonry) Substances 0.000 description 11
- 239000013078 crystal Substances 0.000 description 10
- 230000000694 effects Effects 0.000 description 8
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- 238000002834 transmittance Methods 0.000 description 8
- 239000007791 liquid phase Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
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- 229910021193 La 2 O 3 Inorganic materials 0.000 description 4
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- 239000012071 phase Substances 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000000382 optic material Substances 0.000 description 2
- 239000005304 optical glass Substances 0.000 description 2
- 239000004482 other powder Substances 0.000 description 2
- 238000000643 oven drying Methods 0.000 description 2
- 230000005374 Kerr effect Effects 0.000 description 1
- 229910013641 LiNbO 3 Inorganic materials 0.000 description 1
- 230000005697 Pockels effect Effects 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
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- 238000010586 diagram Methods 0.000 description 1
- 239000011363 dried mixture Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- CPBQJMYROZQQJC-UHFFFAOYSA-N helium neon Chemical compound [He].[Ne] CPBQJMYROZQQJC-UHFFFAOYSA-N 0.000 description 1
- 230000010365 information processing Effects 0.000 description 1
- GQYHUHYESMUTHG-UHFFFAOYSA-N lithium niobate Chemical compound [Li+].[O-][Nb](=O)=O GQYHUHYESMUTHG-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
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- 238000010298 pulverizing process Methods 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
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Abstract
The invention relates to the field of functional ceramic materials, in particular to a transparent photoelectric ceramic material with ultrahigh electro-optic coefficient and piezoelectric property and a preparation method thereof. The invention provides a preparation method of a transparent photoelectric ceramic material with an ultrahigh electro-optic coefficient and piezoelectric property, which comprises the following steps: a is that x (Pb y Pb) 1‑x [(Mg (1+z)1/3 Nb 2/3 ) 1‑t Ti t ]O 3 The preparation method comprises the following steps: preparing transparent photoelectric ceramic powder; the obtained transparent photoelectric ceramic powder is sintered by discharge plasma,And annealing and polarizing to obtain the transparent photoelectric ceramic material with ultrahigh electro-optic coefficient and piezoelectric property. The transparent photoelectric ceramic material obtained by the preparation method provided by the invention has high transparency, ultrahigh linear electro-optic coefficient and ultrahigh piezoelectric property.
Description
Technical Field
The invention relates to the field of functional ceramic materials, in particular to a transparent photoelectric ceramic material with ultrahigh electro-optic coefficient and piezoelectric property and a preparation method thereof.
Background
The integrated optics is used as a technical platform with wide application prospect in data communication and quantum information processing, and has important application value. The electro-optic effect is generally defined as the dependence of the refractive index on the applied electric field, the magnitude of which can be fitted to the electro-optic coefficient. Electro-optic effects are critical in nonlinear optics, laser technology, quantum optics, and optical communications. In a compound with a centrosymmetric structure, the electro-optic coefficient is very weak and can be fitted to the quadratic effect or kerr effect. In compounds with non-centrosymmetric structure, the electro-optic effect becomes larger and can be fitted to a linear or pockels effect. In electro-optic modulation, linear electro-optic effects are receiving a great deal of attention because of the urgent need for lower operating voltages or electric fields. One of the major challenges in integration and miniaturization is the higher electro-optic coefficient, which can achieve high integration density, high frequency modulation, low driving voltage and power consumption.
Currently high linear electro-optic effects exist only in ferroelectric materials. Lithium niobate single crystals are commercially available electro-optic materials in electro-optic devices having a moderate electro-optic coefficient (about 21 pm/V). The current limitation is high cost of single crystal preparation and poor temperature stability of electro-optic coefficient, and along with the requirements of device integration and miniaturization, the existing electro-optic performance is difficult to meet the future optical communication and other laser technology application, and the novel electro-optic material with better performance is urgently needed to replace commercial LiNbO 3 And (3) single crystals.
Lead magnesium niobate-lead titanate (1-x%) Pb (Mg 1/3 Nb 2/3 )O 3 -x％PbTiO 3 (PMN-PT) is a commercial piezoelectric single crystal with perovskite structure having an electro-optic effect (currently commercially available LiNbO) of up to 100-200 pm/V when its composition approaches the so-called "quasi-crystalline phase boundary" (x.apprxeq.33, x is mole percent) 3 10 times that of single crystals) makes it more competitive in high power and high speed optical communication devices with low drive voltages.
At present, lead magnesium niobate-lead titanate can be prepared by a mode of single crystal growth, but during the crystal growth process, solute redistribution and related concentration segregation make fine regulation and control of components of the lead magnesium niobate-lead titanate single crystal difficult to realize, so that the linear photoelectric coefficient and piezoelectric property of the lead magnesium niobate-lead titanate single crystal are low, and the commercial application of the lead magnesium niobate-lead titanate single crystal is hindered.
The lead magnesium niobate-lead titanate transparent ferroelectric ceramic has better component and performance stability due to lower cost and energy consumption, thus being used as a selection of lead magnesium niobate-lead titanate material application. However, the residual pores and birefringence of the lead magnesium niobate-lead titanate material during sintering cause scattering to scatter light more, thereby affecting the linear photoelectric coefficient and piezoelectric properties of the lead magnesium niobate-lead titanate material. At present, the sintering method of the lead magnesium niobate-lead titanate transparent ceramic comprises pressureless sintering and hot-pressed sintering, and the lead magnesium niobate-lead titanate transparent ferroelectric ceramic related in the prior art cannot have high linear photoelectric coefficient and piezoelectric property while being transparent.
Disclosure of Invention
Therefore, the technical problem to be solved by the invention is to overcome the defect that the lead magnesium niobate-lead titanate transparent ferroelectric ceramic in the prior art cannot have high linear photoelectric coefficient and piezoelectric property while being transparent, thereby providing a transparent photoelectric ceramic material with ultrahigh photoelectric coefficient and piezoelectric property and a preparation method thereof.
The invention provides a preparation method of a transparent photoelectric ceramic material with an ultrahigh electro-optic coefficient and piezoelectric property, which comprises the following steps: a is that x (Pb y Pb) 1-x [(Mg (1+z)1/3 Nb 2/3 ) 1-t Ti t ]O 3 Wherein A is at least one of La, sm and Eu, x is more than or equal to 0.02 and less than or equal to 0.04,0.03, y is more than or equal to 0.10,0.002 and z is more than or equal to 0.03,0.30 and t is more than or equal to 0.34; the preparation method comprises the following steps:
1) Preparation of MgNb by using magnesium oxide and niobium pentoxide as raw materials 2 O 6 Precursor powder;
2) MgNb obtained in step 1) 2 O 6 Preparing transparent photoelectric ceramic powder by using precursor powder, lead-containing compound, titanium oxide and oxide of A as raw materials;
3) Sintering, annealing and polarizing the transparent photoelectric ceramic powder obtained in the step 2) through discharge plasmas to obtain the transparent photoelectric ceramic material with the ultrahigh electro-optic coefficient and the piezoelectric property;
wherein the lead-containing compound comprises PbO and/or lead acetate.
Optionally, the ball milling tank used in the step 1) is a polytetrafluoroethylene ball milling tank, and the milling balls are agate balls; further, the diameter of the grinding balls used in ball milling of magnesium oxide and niobium pentoxide is 4-10mm.
Optionally, the particle size of the magnesium oxide is 40-100nm, and the purity is more than or equal to 99.9%.
Optionally, the purity of the niobium pentoxide is more than or equal to 99.9%.
Preferably, in step 1), the molar ratio of magnesium oxide to niobium pentoxide is (1.002-1.03): 1, a step of;
preferably, the specific process for preparing the transparent photoelectric ceramic powder in the step 2) comprises the following steps:
s1, mgNb obtained in the step 1) 2 O 6 Precursor powder, pbO and TiO 2 Ball-milling and mixing with the oxide of the A, drying, calcining, ball-milling and crushing, and drying to obtain transparent photoelectric ceramic precursor base powder;
s2, ball-milling and mixing the transparent photoelectric ceramic precursor base powder obtained in the step S1 with a lead acetate solution, drying and calcining to obtain transparent photoelectric ceramic powder;
in step S1, mgNb 2 O 6 Precursor powder, pbO and TiO 2 The mole ratio of the element A in the oxide of A is (0.22-0.23): (0.97-0.99): (0.3-0.34): (0.02-0.04); in step S2, the molar ratio of lead acetate in the lead acetate solution to PbO in step S1 is (0.01-0.1): 1.
optionally, in step S1, the ball milling tank used for ball milling and mixing is a polytetrafluoroethylene ball milling tank, the grinding balls are agate balls, and the diameter of the grinding balls is 4-10mm; the ball milling tank used for ball milling and crushing is a zirconia ball milling tank, the grinding balls are zirconia grinding balls, and the diameter of the grinding balls is 1-4mm.
Optionally, in step S2, the ball milling tank used for ball milling and mixing is a polytetrafluoroethylene ball milling tank, the grinding balls are agate balls, and the diameter of the grinding balls is 4-10mm.
Preferably, the specific process for preparing the transparent photoelectric ceramic powder in the step 2) comprises the following steps:
MgNb obtained in the step 1) 2 O 6 Precursor powder, pbO and TiO 2 And (3) ball-milling and mixing the mixed oxide of the A, drying, calcining, ball-milling and crushing, and drying to obtain transparent photoelectric ceramic powder.
In step 2), mgNb 2 O 6 Precursor powder, pbO and TiO 2 The molar amount ratio of element A in the oxide of A is (0.22-0.23): (0.98-1.09): (0.3-0.34): (0.02-0.04).
Optionally, in the step 2), the ball milling tank used for ball milling and mixing is a polytetrafluoroethylene ball milling tank, the grinding balls are agate balls, and the diameter of the grinding balls is 4-10mm; the ball milling tank used for ball milling and crushing is a zirconia ball milling tank, the grinding balls are zirconia grinding balls, and the diameter of the grinding balls is 1-4mm.
Preferably, mgNb is prepared in step 1) 2 O 6 The precursor powder is prepared through ball milling magnesia and niobium pentoxide with alcohol as ball milling medium at 120-200 r/min for 0.5-2 hr, stoving at 80-100 deg.c for 5-10 hr, calcining at 900-1100 deg.c for 2-15 hr, ball milling with alcohol as ball milling medium at 120-200 r/min for 0.5-2 hr, stoving at 80-100 deg.c for 5-10 hr, and calcining at 1000-1200 deg.c for 2-6 hr 2 O 6 Precursor powder.
Optionally, obtaining the MgNb 2 O 6 The MgNb is manually smashed through a mortar after precursor powder 2 O 6 Precursor powder is manually ground for 5-10min.
Preferably, in the step S1, the ball milling medium for ball milling and mixing is alcohol, the ball milling speed is 120-200 r/min, and the ball milling time is 1-2 h; the drying temperature is 80-100 ℃ and the drying time is 5-10h; the calcination process comprises first calcination and second calcination, wherein the temperature of the first calcination is 700-850 ℃ and the time is 5-15h; the temperature of the second calcination is 870-950 ℃ and the time is 1-3h; the ball milling and crushing medium is alcohol, the ball milling speed is 200-1000 r/min, and the ball milling time is 0.5-10 h; the drying temperature is 80-100 ℃ and the drying time is 5-10h;
in the step S2, the concentration of the lead acetate solution is 2-20g/L; the rotation speed of ball milling and mixing is 120-200 r/min, and the time of ball milling and mixing is 0.5-2 h; the drying temperature is 80-100 ℃ and the drying time is 5-10h; the calcination temperature is 300-500 ℃ and the calcination time is 2-10h.
Optionally, in step S1, after the second calcination, before ball milling and pulverizing, the product obtained after the second calcination is further placed in an agate mortar for manual grinding for 5-15min.
Preferably, the ball milling medium for ball milling and mixing is alcohol, the ball milling speed is 120-200 r/min, and the ball milling time is 1-2 h; the drying temperature is 80-100 ℃ and the drying time is 5-10h; the calcination process comprises first calcination and second calcination, wherein the temperature of the first calcination is 700-850 ℃ and the time is 5-15h; the temperature of the second calcination is 870-950 ℃ and the time is 1-3h; the ball milling and crushing medium is alcohol, the ball milling speed is 200-1000 r/min, and the ball milling time is 0.5-10 h; the drying temperature is 80-100 ℃ and the drying time is 5-10h.
Optionally, after the second calcination, before ball milling and crushing, the product obtained after the second calcination is manually ground for 5-15min in an agate mortar.
Preferably, the spark plasma sintered barrier layer in step 3) is selected from at least one of graphite paper and molybdenum foil; the pressure of the spark plasma sintering is 50-200MPa, the temperature is 850-1000 ℃ and the time is 3-60min.
Preferably, after the spark plasma sintering in the step 3), the method further comprises the step of burying the spark plasma sintering product by using the transparent photoelectric ceramic powder obtained in the step 2) before annealing;
preferably, the annealing process of step 3) comprises heating to 90-120 ℃, then heating to 1000-1300 ℃ at a heating rate of 0.25-0.5 ℃/min under an oxygen atmosphere, and preserving the heat for 2-20h under the oxygen atmosphere.
Optionally, the pressure in the oxygen atmosphere is 0.01-0.05MPa.
Optionally, the burying process comprises placing the discharge plasma sintering product in a first alumina crucible, and burying the discharge plasma sintering product with the transparent photoelectric ceramic powder obtained in the step 3); and then placing the first alumina crucible into a second alumina crucible, burying the first alumina crucible by using the transparent photoelectric ceramic powder obtained in the step 3), covering the second alumina crucible with an alumina crucible cover, and sealing the second alumina crucible by using refractory cement.
Preferably, the polarization is direct current electric field polarization, the voltage intensity of the direct current electric field is 3-10kV/cm, and the polarization time is 10-30 min.
The invention also provides a transparent photoelectric ceramic material with ultrahigh electro-optic coefficient and piezoelectric property, which is prepared by the preparation method.
The technical scheme of the invention has the following advantages:
(1) The invention provides a preparation method of a transparent photoelectric ceramic material with an ultrahigh electro-optic coefficient and piezoelectric property, which comprises the following steps: a is that x Pb y Pb[(Mg (1+z)1/3 Nb 2/3 ) 1-t Ti t ]O 3 Wherein A comprises at least one of La, sm and Eu, x is more than or equal to 0.02 and less than or equal to 0.04,0.03, y is more than or equal to 0.10,0.002 and z is more than or equal to 0.03,0.30 and t is more than or equal to 0.34; the preparation method comprises the following steps: 1) Preparation of MgNb by using magnesium oxide and niobium pentoxide as raw materials 2 O 6 Precursor powder; 2) MgNb obtained in step 1) 2 O 6 Preparing transparent photoelectric ceramic powder by using precursor powder, lead-containing compound, titanium oxide and oxide of A as raw materials; 3) Sintering, annealing and polarizing the transparent photoelectric ceramic powder obtained in the step 2) through discharge plasmas to obtain the transparent photoelectric ceramic material with the ultrahigh electro-optic coefficient and the piezoelectric property; wherein the lead-containing compound comprises PbO and/or lead acetate.
1) On the basis of limiting each component element, the invention takes magnesium oxide and niobium pentoxide as raw materials to prepare MgNb 2 O 6 Precursor powder and MgNb 2 O 6 Preparing transparent photoelectric ceramic powder by using precursor powder, lead-containing compound, titanium oxide and oxide of A as raw materials, and then sintering the powder by discharge plasma, wherein the lead-containing compound is generated in the discharge plasma sintering processThe content design enables the PbO to be coated with other powder in a liquid phase, thereby realizing liquid phase sintering auxiliary spark plasma sintering, and the liquid phase sintering auxiliary spark plasma sintering can enable the material to be densified rapidly, and micro-pores in the material sintering process can be removed effectively, so that scattering of the micro-pores to light is reduced, and the prepared material has high transparency; meanwhile, the component design of the invention combines with liquid phase sintering to assist in spark plasma sintering to lead a large number of active nanometer micro-areas to be introduced into the material, and the interface of the active nanometer micro-areas and the nanometer micro-areas can lead to abnormal distortion of electron cloud, thereby leading the material to have ultrahigh linear electro-optic coefficient (up to 1400 pm/V) and piezoelectric property (d) after subsequent annealing and polarization 33 Up to 1500).
Therefore, the transparent photoelectric ceramic material obtained by the preparation method provided by the invention has high transparency, ultrahigh linear electro-optic coefficient and ultrahigh piezoelectric property.
2) The preparation method of the transparent photoelectric ceramic material provided by the invention further comprises the specific process of preparing the transparent photoelectric ceramic powder in the step 2): s1, mgNb obtained in the step 1) 2 O 6 Precursor powder, pbO and TiO 2 Ball-milling and mixing with the oxide of the A, drying, calcining, ball-milling and crushing, and drying to obtain transparent photoelectric ceramic precursor base powder; s2, ball-milling and mixing the transparent photoelectric ceramic precursor base powder obtained in the step S1 with a lead acetate solution, drying and calcining to obtain transparent photoelectric ceramic powder; according to the invention, by adding part of the lead-containing compound in the form of lead acetate solution, the liquid phase cladding of other powder of PbO can be further promoted, so that the migration of an interface during sintering is promoted, the liquid phase sintering auxiliary spark plasma sintering is better realized, and the transparency and the linear photoelectric coefficient of the finally obtained material are further improved.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are needed in the description of the embodiments or the prior art will be briefly described, and it is obvious that the drawings in the description below are some embodiments of the present invention, and other drawings can be obtained according to the drawings without inventive effort for a person skilled in the art.
FIG. 1 is a microstructure scanning electron microscope topography of a transparent photoelectric ceramic material prepared in example 1;
FIG. 2 is a graph showing the transmittance versus wavelength of the transparent electro-optic ceramic material of example 1 of the present invention at a test wavelength of 300nm-2550 nm;
FIG. 3 shows the electro-optic coefficients of the transparent electro-optic ceramic material of example 1 of the present invention at different temperatures.
Detailed Description
The following examples are provided for a better understanding of the present invention and are not limited to the preferred embodiments described herein, but are not intended to limit the scope of the invention, any product which is the same or similar to the present invention, whether in light of the present teachings or in combination with other prior art features, falls within the scope of the present invention.
The specific experimental procedures or conditions are not noted in the examples and may be followed by the operations or conditions of conventional experimental procedures described in the literature in this field. The reagents or apparatus used were conventional reagent products commercially available without the manufacturer's knowledge.
The refractory cement used in the examples was purchased from Zhengzhou volitation specialty cement plant under the model CA50.
Example 1
The embodiment provides a preparation method of a transparent photoelectric ceramic material with an ultrahigh electro-optic coefficient and piezoelectric performance, wherein the composition general formula of the transparent photoelectric ceramic material with the ultrahigh electro-optic coefficient and the piezoelectric performance is as follows: la (La) 0.03 (Pb 0.04 Pb) 0.97 [(Mg (1.002/3 Nb 2/3 ) 0.67 Ti 0.33 ]O 3 The preparation method comprises the following steps:
(1) 1.002mol of MgO powder (particle size 50nm, purity 99.9%) and 1mol of Nb 2 O 5 Placing the powder (purity 99.99%) into a polytetrafluoroethylene ball milling tank, and selecting agateBall (diameter 4 mm) is ball-milled with alcohol as ball-milling medium, ball-milled for 0.5h at 150r/min, then put into electrothermal blowing dry box, dried for 8h at 90 ℃, calcined for 12h at 1000 ℃, put into polytetrafluoroethylene ball-milling pot again after calcining, agate ball is selected as ball-milled medium, ball-milled for 1.5h at 200r/min with alcohol, then put into electrothermal blowing dry box, dried for 8h at 90 ℃, calcined for 6h at 1100 ℃ to obtain MgNb 2 O 6 Precursor powder (MgNb to be obtained) 2 O 6 Manually breaking a precursor powder mortar, manually grinding for 5min, and preparing for subsequent use;
(2) 0.015mol of La 2 O 3 1.0088mol of PbO and 0.2233333mol of MgNb obtained in the step (1) 2 O 6 Precursor powder, 0.33mol of TiO 2 Placing the mixture into a polytetrafluoroethylene ball milling tank, selecting agate balls as grinding balls (with the diameter of 4 mm), taking alcohol as a ball milling medium, performing ball milling for 1h at the rotating speed of 150r/min, placing the mixture into an electrothermal blowing drying oven, drying for 8h at the temperature of 90 ℃, placing the mixed powder into an alumina crucible after drying, calcining for 12h at the temperature of 800 ℃ and calcining for 2h at the temperature of 900 ℃; after calcination, manually grinding for 10min by using an agate mortar, putting into a zirconia ball milling tank, selecting zirconia balls (with the diameter of 1 mm), ball milling for 2h by taking alcohol as a ball milling medium at the rotating speed of 1000r/min, and drying in an electrothermal blowing drying oven for 8h at the temperature of 90 ℃ to obtain transparent photoelectric ceramic powder;
(3) Placing 15g of transparent photoelectric ceramic powder obtained in the step (2) in a graphite mold with the diameter of 20mm, taking Mo foil as a barrier layer between a sleeve, a pressure head and the powder, sintering discharge plasma for 60min at 900 ℃ and 200MPa in a discharge plasma sintering furnace, placing the sintered product in an alumina crucible with the inner diameter of 22mm, burying the discharge plasma sintered product by adopting the transparent photoelectric ceramic powder obtained in the step (2), placing the crucible in an alumina crucible with the inner diameter of 35mm, burying an alumina crucible with the inner diameter of 22mm by adopting the transparent photoelectric ceramic powder obtained in the step (2), covering an alumina crucible cover on the alumina crucible with the inner diameter of 35mm, and sealing the alumina crucible with the inner diameter of 35mm by adopting refractory cement; and then the crucible is insulated at 90 ℃ for 1h to solidify cement, and then is placed in a tubular atmosphere furnace, the temperature is raised to 1250 ℃ at the temperature rising rate of 0.5 ℃/min under the oxygen atmosphere (0.02 MPa), and the crucible is annealed for 2h under the oxygen atmosphere at 1250 ℃, and then polarized for 10min under a 3kV/cm direct current electric field, so that the transparent photoelectric ceramic material with the ultrahigh electro-optic coefficient and the piezoelectric property is obtained.
Example 2
The embodiment provides a preparation method of a transparent photoelectric ceramic material with an ultrahigh electro-optic coefficient and piezoelectric performance, wherein the composition general formula of the transparent photoelectric ceramic material with the ultrahigh electro-optic coefficient and the piezoelectric performance is as follows: la (La) 0.03 (Pb 0.03 Pb) 0.97 [(Mg 1.005/3 Nb 2/3 ) 0.67 Ti 0.33 ]O 3 The preparation method comprises the following steps:
(1) 1.005mol of MgO powder (particle size 50nm, purity 99.9%) and 1mol of Nb 2 O 5 Placing the powder (purity 99.99%) into a polytetrafluoroethylene ball milling tank, selecting agate balls (diameter 4 mm) as grinding balls, using alcohol as a ball milling medium, ball milling for 0.5h at a rotating speed of 150r/min, then placing into an electrothermal blowing drying oven, drying for 8h at 90 ℃, calcining for 12h at 1000 ℃, placing into the polytetrafluoroethylene ball milling tank again after calcining, selecting agate balls as grinding balls, using alcohol as a ball milling medium, ball milling for 1h at 200r/min, placing into an electrothermal blowing drying oven, drying for 8h at 90 ℃, calcining for 6h at 1100 ℃ after drying, and obtaining the MgNb 2 O 6 Precursor powder (MgNb to be obtained) 2 O 6 Manually breaking a precursor powder mortar, manually grinding for 5min, and preparing for subsequent use;
(2) 0.015mol of La 2 O 3 0.9991mol of PbO and 0.2233333mol of MgNb obtained in the step (1) 2 O 6 Precursor powder, 0.33mol of TiO 2 Putting into polytetrafluoroethylene ball milling tank, selecting agate balls as grinding balls (diameter is 4 mm), ball milling with alcohol as ball milling medium at 150r/min for 1 hr, oven drying in electrothermal blast drying oven at 90deg.C for 8 hr, oven drying, placing the mixed powder into alumina crucible, calcining at 800deg.C for 12 hr, and calcining at 900deg.C for 2 hrThe method comprises the steps of carrying out a first treatment on the surface of the After calcination, manually grinding for 10min by using an agate mortar, putting into a zirconia ball milling tank, selecting zirconia balls (with the diameter of 1 mm), ball milling for 0.5h by taking alcohol as a ball milling medium at the rotating speed of 1000r/min, and drying in an electrothermal blowing drying oven for 8h at the temperature of 90 ℃ to obtain transparent photoelectric ceramic powder;
(3) Placing 15g of transparent photoelectric ceramic powder obtained in the step (2) in a graphite mold with the diameter of 20mm, taking Mo foil as a barrier layer between a sleeve, a pressure head and the powder, sintering discharge plasma for 60min at 900 ℃ and 200MPa in a discharge plasma sintering furnace, placing the sintered product in an alumina crucible with the inner diameter of 22mm, burying the discharge plasma sintered product by adopting the transparent photoelectric ceramic powder obtained in the step (2), placing the crucible in an alumina crucible with the inner diameter of 35mm, burying the crucible with the transparent photoelectric ceramic powder obtained in the step (2), covering the alumina crucible with the inner diameter of 22mm, covering the alumina crucible with the inner diameter of 35mm, and sealing the alumina crucible with the inner diameter of 35mm by using refractory cement; and then the crucible is insulated at 90 ℃ for 1h to solidify cement, and then is placed in a tubular atmosphere furnace, the temperature is raised to 1250 ℃ at the temperature rising rate of 0.5 ℃/min under the oxygen atmosphere (0.02 MPa), and the crucible is annealed for 2h under the oxygen atmosphere at 1250 ℃, and then polarized for 10min under a 3kV/cm direct current electric field, so that the transparent photoelectric ceramic material with the ultrahigh electro-optic coefficient and the piezoelectric property is obtained.
Example 3
The embodiment provides a preparation method of a transparent photoelectric ceramic material with an ultrahigh electro-optic coefficient and piezoelectric performance, wherein the composition general formula of the transparent photoelectric ceramic material with the ultrahigh electro-optic coefficient and the piezoelectric performance is as follows: la (La) 0.03 (Pb 0.04 Pb) 0.97 [(Mg 1.002/3 Nb 2/3 ) 0.67 Ti 0.33 ]O 3 The preparation method comprises the following steps:
(1) 1.002mol of MgO powder (particle size 50nm, purity 99.9%) and 1mol of Nb 2 O 5 Placing the powder (optical glass grade, purity 99.99%) into polytetrafluoroethylene ball milling tank, selecting agate balls (diameter 4 mm) as grinding balls, and alcohol as ball milling medium, ball milling for 0.5 hr at 150r/minDrying in an electrothermal blowing drying oven at 90 ℃ for 8 hours, calcining at 1000 ℃ for 12 hours, putting into a polytetrafluoroethylene ball milling tank again after calcining, selecting agate balls as milling balls and alcohol as milling medium, ball milling for 1.5 hours under the condition of 200r/min, putting into an electrothermal blowing drying oven, drying at 90 ℃ for 8 hours, calcining at 1100 ℃ for 6 hours, and obtaining the MgNb 2 O 6 Precursor powder (MgNb to be obtained) 2 O 6 Manually breaking a precursor powder mortar, manually grinding for 5min, and preparing for subsequent use;
(2) 0.015mol of La 2 O 3 0.9894mol of PbO and 0.2233333mol of MgNb obtained in the step (1) 2 O 6 Precursor powder, 0.33mol of TiO 2 Placing the mixture into a polytetrafluoroethylene ball milling tank, selecting agate balls as grinding balls (with the diameter of 4 mm), taking alcohol as a ball milling medium, performing ball milling for 1h at the rotating speed of 150r/min, placing the mixture into an electrothermal blowing drying oven, drying for 8h at the temperature of 90 ℃, placing the mixed powder into an alumina crucible after drying, calcining for 12h at the temperature of 800 ℃ and calcining for 2h at the temperature of 900 ℃; after calcination, manually grinding for 10min by using an agate mortar, putting into a zirconia ball milling tank, selecting zirconia balls (with the diameter of 1 mm), ball milling for 2h by taking alcohol as a ball milling medium at the rotating speed of 1000r/min, and drying in an electrothermal blowing drying oven for 8h at the temperature of 90 ℃ to obtain transparent photoelectric ceramic precursor base powder;
(3) Mixing the transparent photoelectric ceramic precursor base powder prepared in the step (2) with 15.77mL of lead acetate solution with the concentration of 400g/L, putting the mixture into a zirconia ball milling tank, selecting zirconia balls (with the diameter of 1 mm), ball milling the mixture for 0.5h at the rotating speed of 1000r/min by taking alcohol as a ball milling medium, putting the mixture into an electrothermal blowing drying box, drying the mixture at the temperature of 90 ℃ for 8h, and calcining the dried mixture at the temperature of 400 ℃ for 2h to obtain transparent photoelectric ceramic powder;
(4) Placing 15g of transparent photoelectric ceramic powder obtained in the step (3) in a graphite mold with the diameter of 20mm, taking Mo foil as a barrier layer between a sleeve, a pressure head and the powder, sintering discharge plasma for 60min at 900 ℃ and 200MPa in a discharge plasma sintering furnace, placing the sintered product in an alumina crucible with the inner diameter of 22mm, burying the discharge plasma sintered product by adopting the transparent photoelectric ceramic powder obtained in the step (3), placing the crucible in an alumina crucible with the inner diameter of 35mm, burying the crucible with the transparent photoelectric ceramic powder obtained in the step (3), covering the alumina crucible with the inner diameter of 22mm, covering the alumina crucible with the inner diameter of 35mm, and sealing the alumina crucible with the inner diameter of 35mm by using refractory cement; and then the crucible is insulated at 90 ℃ for 1h to solidify cement, and then is placed in a tubular atmosphere furnace, the temperature is raised to 1250 ℃ at the temperature rising rate of 0.5 ℃/min under the oxygen atmosphere (0.02 MPa), and the crucible is annealed for 2h under the oxygen atmosphere at 1250 ℃, and then polarized for 10min under a 3kV/cm direct current electric field, so that the transparent photoelectric ceramic material with the ultrahigh electro-optic coefficient and the piezoelectric property is obtained.
Example 4
The embodiment provides a preparation method of a transparent photoelectric ceramic material with an ultrahigh electro-optic coefficient and piezoelectric performance, wherein the composition general formula of the transparent photoelectric ceramic material with the ultrahigh electro-optic coefficient and the piezoelectric performance is as follows: la (La) 0.01 Sm 0.02 (Pb 0.03 Pb) 0.97 [(Mg 1.002/3 Nb 2/3 ) 0.67 Ti 0.33 ]O 3 The preparation method comprises the following steps:
(1) 1.002mol of MgO powder (particle size 50nm, purity 99.9%) and 1mol of Nb 2 O 5 Placing the powder (optical glass grade, purity 99.99%) into a polytetrafluoroethylene ball milling tank, selecting agate balls (diameter 4 mm) as grinding balls, using alcohol as a ball milling medium, ball milling for 0.5h at a rotating speed of 150r/min, then placing into an electrothermal blowing drying oven, drying for 8h at 90 ℃, calcining for 12h at 1000 ℃ after drying, placing into the polytetrafluoroethylene ball milling tank again after calcining, selecting agate balls as grinding balls, using alcohol as a ball milling medium, ball milling for 1.5h at 200r/min, placing into an electrothermal blowing drying oven, drying for 8h at 90 ℃, calcining for 6h at 1100 ℃ after drying, and obtaining the MgNb 2 O 6 Precursor powder (MgNb to be obtained) 2 O 6 Manually breaking a precursor powder mortar, manually grinding for 5min, and preparing for subsequent use;
(2) 0.005mol of La 2 O 3 0.01mol of Sm 2 O 3 0.9991mol of PbO, 0.2233333molMgNb obtained in step (1) 2 O 6 Precursor powder, 0.33mol of TiO 2 Placing the mixture into a polytetrafluoroethylene ball milling tank, selecting agate balls as grinding balls (with the diameter of 4 mm), taking alcohol as a ball milling medium, performing ball milling for 1h at the rotating speed of 150r/min, placing the mixture into an electrothermal blowing drying oven, drying for 8h at the temperature of 90 ℃, placing the mixed powder into an alumina crucible after drying, calcining for 12h at the temperature of 800 ℃ and calcining for 2h at the temperature of 900 ℃; after calcination, manually grinding for 10min by using an agate mortar, putting into a zirconia ball milling tank, selecting zirconia balls (with the diameter of 1 mm), ball milling for 0.5h by taking alcohol as a ball milling medium at the rotating speed of 1000r/min, and drying in an electrothermal blowing drying oven for 8h at the temperature of 90 ℃ to obtain transparent photoelectric ceramic powder;
(3) Placing 15g of transparent photoelectric ceramic powder obtained in the step (2) in a graphite mold with the diameter of 20mm, taking Mo foil as a barrier layer between a sleeve, a pressure head and the powder, sintering discharge plasma for 60min at 900 ℃ and 200MPa in a discharge plasma sintering furnace, placing the sintered product in an alumina crucible with the inner diameter of 22mm, burying the discharge plasma sintered product by adopting the transparent photoelectric ceramic powder obtained in the step (2), placing the crucible in an alumina crucible with the inner diameter of 35mm, burying the crucible with the transparent photoelectric ceramic powder obtained in the step (2), covering the alumina crucible with the inner diameter of 22mm, covering the alumina crucible with the inner diameter of 35mm, and sealing the alumina crucible with the inner diameter of 35mm by using refractory cement; and then the crucible is insulated at 90 ℃ for 1h to solidify cement, and then is placed in a tubular atmosphere furnace, the temperature is raised to 1250 ℃ at the temperature rising rate of 0.5 ℃/min under the oxygen atmosphere (0.02 MPa), and the crucible is annealed for 2h under the oxygen atmosphere at 1250 ℃, and then polarized for 10min under a 3kV/cm direct current electric field, so that the transparent photoelectric ceramic material with the ultrahigh electro-optic coefficient and the piezoelectric property is obtained.
Comparative example 1
The present comparative example is different from example 3 in that the spark plasma sintering at 900 c in step 4) of example 3 was replaced with sintering at 900 c under 200MPa pressure (under non-spark plasma sintering conditions) for 60min.
Test case
The transparent photoelectric ceramic materials obtained in examples 1 to 4 and comparative example 1 were cut into blocks having a thickness of 0.16mm, a length of 4mm and a width of 4mm for testing.
1. Scanning electron microscope analysis
The microstructure of the transparent photoelectric ceramic material prepared in example 1 was analyzed by scanning electron microscopy. Fig. 1 is a microstructure scanning electron microscope morphology diagram of the transparent photoelectric ceramic material prepared in example 1.
2. Transmittance test
The transmittance of the transparent electro-optic ceramic material is tested by adopting an ultraviolet-visible-infrared spectrophotometer, and when the surface reflection loss is not considered, the linear transmittance of the transparent electro-optic ceramic material in the embodiment can reach more than 65-70% in the wavelength range of 900-3000 nm. FIG. 2 is a graph showing the relationship between the transmittance and the wavelength of the transparent electro-optic ceramic material in example 1 at a test light wavelength of 300nm to 2550 nm. The transmittance of the transparent optoceramic material at 633nm is shown in Table 1.
TABLE 1
| Examples | 1 | 2 | 3 | 4 | Comparative example | 1 |
| Transmittance of light | 64％ | 63％ | 67％ | 62％ | Transmittance of light | 30% (translucence) |
3. Electro-optic coefficient testing
The electro-optic coefficient is tested by adopting a Corcontent compensation method (Senarmont compensator method), the principle is that a 633nm helium-neon laser is used as a light source, and a phase compensation method is adopted for measurement, wherein the phase of the polarized light delayed by the electro-optic effect of the sample is as follows:
wherein Δn is the refractive index change value at the applied dc voltage; lambda laser wavelength, taken as 633X 10 -9 m; l thickness of sample in the direction of light path.
The electro-optic coefficient fitting formula is:
wherein, d electrode spacing; l the thickness of the sample in the direction of the light path; lambda laser wavelength, taken as 633X 10 -9 m; n is the refractive index of the standard sample, and 2.59 is taken; u is the externally applied DC voltage.
FIG. 3 shows the electro-optic coefficients of the transparent electro-optic ceramic material of example 1 at different temperatures, wherein the electro-optic coefficients are linear electro-optic coefficients in the range of 7-57 ℃ and the electro-optic coefficients are 1350-1500pm/V.
The coefficients of the transparent electro-optic ceramic materials of examples 1-4 and comparative example 1 at 30℃are shown in Table 2.
TABLE 2
4. Piezoelectric constant d 33 Testing
D using ZJ-3 type piezoelectric coefficient tester 33 The test results are shown in Table 3.
TABLE 3 Table 3
It is apparent that the above examples are given by way of illustration only and are not limiting of the embodiments. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. While still being apparent from variations or modifications that may be made by those skilled in the art are within the scope of the invention.
Claims (10)
1. The preparation method of the transparent photoelectric ceramic material with the ultrahigh electro-optic coefficient and the piezoelectric property is characterized in that the transparent photoelectric ceramic material with the ultrahigh electro-optic coefficient and the piezoelectric property has the following composition general formula: a is that x (Pb y Pb) 1-x [(Mg (1+z)1/3 Nb 2/3 ) 1-t Ti t ]O 3 Wherein A is at least one of La, sm and Eu, x is more than or equal to 0.02 and less than or equal to 0.04,0.03, y is more than or equal to 0.10,0.002 and z is more than or equal to 0.03,0.30 and t is more than or equal to 0.34; the preparation method comprises the following steps:
1) Preparation of MgNb by using magnesium oxide and niobium pentoxide as raw materials 2 O 6 Precursor powder;
2) MgNb obtained in step 1) 2 O 6 Preparing transparent photoelectric ceramic powder by using precursor powder, lead-containing compound, titanium oxide and oxide of A as raw materials;
3) Sintering, annealing and polarizing the transparent photoelectric ceramic powder obtained in the step 2) through discharge plasmas to obtain the transparent photoelectric ceramic material with the ultrahigh electro-optic coefficient and the piezoelectric property;
wherein the lead-containing compound comprises PbO and/or lead acetate.
2. The process according to claim 1, wherein in step 1), the molar ratio of magnesium oxide to niobium pentoxide is (1.002-1.03): 1, a step of;
preferably, the specific process for preparing the transparent photoelectric ceramic powder in the step 2) comprises the following steps:
s1, mgNb obtained in the step 1) 2 O 6 Precursor powder, pbO and TiO 2 Ball-milling and mixing with the oxide of the A, drying, calcining, ball-milling and crushing, and drying to obtain transparent photoelectric ceramic precursor base powder;
s2, ball-milling and mixing the transparent photoelectric ceramic precursor base powder obtained in the step S1 with a lead acetate solution, drying and calcining to obtain transparent photoelectric ceramic powder;
in step S1, mgNb 2 O 6 Precursor powder, pbO and TiO 2 The mole ratio of the element A in the oxide of A is (0.22-0.23): (0.97-0.99): (0.3-0.34): (0.02-0.04); in step S2, the molar ratio of lead acetate in the lead acetate solution to PbO in step S1 is (0.01-0.1): 1.
3. the preparation method according to claim 1, wherein the specific process of preparing the transparent optoelectronic ceramic powder in step 2) comprises:
MgNb obtained in the step 1) 2 O 6 Precursor powder, pbO and TiO 2 Ball-milling and mixing with the oxide of A, drying, calcining, ball-milling and crushing, and drying to obtain transparent photoelectric ceramic powder;
in step 2), mgNb 2 O 6 Precursor powder, pbO and TiO 2 The mole ratio of the element A in the oxide of A is (0.22-0.23): (0.98-1.09): (0.3-0.34): (0.02-0.04).
4. The method according to claim 1, wherein MgNb is prepared in step 1) 2 O 6 The precursor powder comprises the steps of mixing magnesium oxide and pentoxideThe MgNb is obtained by taking alcohol as a ball milling medium, ball milling for 0.5-2h at the rotating speed of 120-200 r/min, drying for 5-10h at the temperature of 80-100 ℃, calcining for 2-15h at the temperature of 900-1100 ℃, ball milling for 0.5-2h at the rotating speed of 120-200 r/min, drying for 5-10h at the temperature of 80-100 ℃ and calcining for 2-6h at the temperature of 1000-1200 ℃ after taking alcohol as the ball milling medium 2 O 6 Precursor powder.
5. The preparation method according to claim 2, wherein in the step S1, the ball milling medium for ball milling and mixing is alcohol, the ball milling speed is 120-200 r/min, and the ball milling time is 1-2 h; the drying temperature is 80-100 ℃ and the drying time is 5-10h; the calcination process comprises first calcination and second calcination, wherein the temperature of the first calcination is 700-850 ℃ and the time is 5-15h; the temperature of the second calcination is 870-950 ℃ and the time is 1-3h; the ball milling and crushing medium is alcohol, the ball milling speed is 200-1000 r/min, and the ball milling time is 0.5-10 h; the drying temperature is 80-100 ℃ and the drying time is 5-10h;
in the step S2, the concentration of the lead acetate solution is 2-20g/L; the rotation speed of ball milling and mixing is 120-200 r/min, and the time of ball milling and mixing is 0.5-2 h; the drying temperature is 80-100 ℃ and the drying time is 5-10h; the calcination temperature is 300-500 ℃ and the calcination time is 2-10h.
6. The preparation method according to claim 3, wherein the ball milling medium for ball milling and mixing is alcohol, the ball milling speed is 120-200 r/min, and the ball milling time is 1-2 h; the drying temperature is 80-100 ℃ and the drying time is 5-10h; the calcination process comprises first calcination and second calcination, wherein the temperature of the first calcination is 700-850 ℃ and the time is 5-15h; the temperature of the second calcination is 870-950 ℃ and the time is 1-3h; the ball milling and crushing medium is alcohol, the ball milling speed is 200-1000 r/min, and the ball milling time is 0.5-10 h; the drying temperature is 80-100 ℃ and the drying time is 5-10h.
7. The method of any one of claims 1-6, wherein the spark plasma sintered barrier layer in step 3) is selected from at least one of graphite paper and molybdenum foil; the pressure of the spark plasma sintering is 50-200MPa, the temperature is 850-1000 ℃ and the time is 3-60min.
8. The method according to any one of claims 1 to 7, further comprising, after the spark plasma sintering of step 3), a step of burying the spark plasma sintered product with the transparent photoelectric ceramic powder obtained in step 2) before annealing;
preferably, the annealing process of step 3) comprises heating to 90-120 ℃, then heating to 1000-1300 ℃ at a heating rate of 0.25-0.5 ℃/min under an oxygen atmosphere, and preserving the heat for 2-20h under the oxygen atmosphere.
9. The method according to any one of claims 1 to 8, wherein the polarization is a direct current electric field polarization, the voltage strength of the direct current electric field is 3 to 10kV/cm, and the polarization time is 10 to 30min.
10. A transparent optoceramic material having an ultra-high electro-optic coefficient and piezoelectric properties, characterized by being prepared by the preparation method of any one of claims 1 to 9.
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| CN1721366A (en) * | 2004-07-15 | 2006-01-18 | 中国科学院电工研究所 | The preparation method of superfine powder of lead magnesium niobate-lead titanate solid solution |
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| CN1721366A (en) * | 2004-07-15 | 2006-01-18 | 中国科学院电工研究所 | The preparation method of superfine powder of lead magnesium niobate-lead titanate solid solution |
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