CN116514548A - Method for preparing high-transmittance lanthanum gadolinium zirconate transparent ceramic by solid phase method - Google Patents
Method for preparing high-transmittance lanthanum gadolinium zirconate transparent ceramic by solid phase method Download PDFInfo
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- CN116514548A CN116514548A CN202310469465.0A CN202310469465A CN116514548A CN 116514548 A CN116514548 A CN 116514548A CN 202310469465 A CN202310469465 A CN 202310469465A CN 116514548 A CN116514548 A CN 116514548A
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- 239000000919 ceramic Substances 0.000 title claims abstract description 164
- 238000000034 method Methods 0.000 title claims abstract description 85
- SJYRPJPOXAEUIL-UHFFFAOYSA-N [La].[Gd] Chemical compound [La].[Gd] SJYRPJPOXAEUIL-UHFFFAOYSA-N 0.000 title claims abstract description 77
- 238000002834 transmittance Methods 0.000 title claims abstract description 66
- 238000010532 solid phase synthesis reaction Methods 0.000 title claims abstract description 29
- 238000005245 sintering Methods 0.000 claims abstract description 77
- 239000000843 powder Substances 0.000 claims abstract description 49
- 238000002360 preparation method Methods 0.000 claims abstract description 33
- 239000000292 calcium oxide Substances 0.000 claims abstract description 31
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims abstract description 31
- 235000015895 biscuits Nutrition 0.000 claims abstract description 29
- 230000008569 process Effects 0.000 claims abstract description 28
- 239000002994 raw material Substances 0.000 claims abstract description 27
- 239000012071 phase Substances 0.000 claims abstract description 22
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000002243 precursor Substances 0.000 claims abstract description 18
- 238000007792 addition Methods 0.000 claims abstract description 15
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000000137 annealing Methods 0.000 claims abstract description 10
- 239000011812 mixed powder Substances 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 229910010293 ceramic material Inorganic materials 0.000 claims abstract description 8
- 238000000465 moulding Methods 0.000 claims abstract description 8
- 229910001938 gadolinium oxide Inorganic materials 0.000 claims abstract description 7
- 229940075613 gadolinium oxide Drugs 0.000 claims abstract description 7
- CMIHHWBVHJVIGI-UHFFFAOYSA-N gadolinium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[Gd+3].[Gd+3] CMIHHWBVHJVIGI-UHFFFAOYSA-N 0.000 claims abstract description 7
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910001928 zirconium oxide Inorganic materials 0.000 claims abstract description 6
- 238000005498 polishing Methods 0.000 claims abstract description 4
- 238000010438 heat treatment Methods 0.000 claims description 14
- 239000002002 slurry Substances 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 10
- 238000000498 ball milling Methods 0.000 claims description 9
- 238000001354 calcination Methods 0.000 claims description 5
- 238000005266 casting Methods 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- YWYZEGXAUVWDED-UHFFFAOYSA-N triammonium citrate Chemical compound [NH4+].[NH4+].[NH4+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O YWYZEGXAUVWDED-UHFFFAOYSA-N 0.000 claims description 4
- 238000000748 compression moulding Methods 0.000 claims description 3
- 229920001577 copolymer Polymers 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 239000003292 glue Substances 0.000 claims description 3
- 230000000630 rising effect Effects 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 238000007493 shaping process Methods 0.000 claims description 2
- 238000007873 sieving Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 14
- 238000005265 energy consumption Methods 0.000 abstract description 7
- 230000000052 comparative effect Effects 0.000 description 26
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 16
- 239000000395 magnesium oxide Substances 0.000 description 11
- 230000000694 effects Effects 0.000 description 9
- 230000003287 optical effect Effects 0.000 description 7
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 6
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 3
- 238000000280 densification Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 229910001408 cation oxide Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- 238000003746 solid phase reaction Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 description 2
- XPFAJCSMHOQBQB-UHFFFAOYSA-N 2-aminoacetic acid;nitric acid Chemical compound O[N+]([O-])=O.NCC(O)=O XPFAJCSMHOQBQB-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 229910004261 CaF 2 Inorganic materials 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 206010017472 Fumbling Diseases 0.000 description 1
- 229910002617 Gd(NO3)3·6H2O Inorganic materials 0.000 description 1
- 229910002422 La(NO3)3·6H2O Inorganic materials 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 238000009694 cold isostatic pressing Methods 0.000 description 1
- 238000009841 combustion method Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- MWFSXYMZCVAQCC-UHFFFAOYSA-N gadolinium(iii) nitrate Chemical compound [Gd+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O MWFSXYMZCVAQCC-UHFFFAOYSA-N 0.000 description 1
- 230000005251 gamma ray Effects 0.000 description 1
- 230000008570 general process Effects 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 239000012780 transparent material Substances 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
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- 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
- C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
- C04B2235/3208—Calcium oxide or oxide-forming salts thereof, e.g. lime
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- 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
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- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
- C04B2235/3244—Zirconium oxides, zirconates, hafnium oxides, hafnates, or oxide-forming salts thereof
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Abstract
The invention provides a method for preparing high-transmittance lanthanum gadolinium zirconate transparent ceramic by a solid phase method, and belongs to the technical field of transparent ceramic preparation. The method comprises the following steps: (1) Preparing precursor powder by adopting a solid phase method, mixing lanthanum oxide, gadolinium oxide and zirconium oxide powder as raw materials in the preparation of the precursor powder, and adding calcium oxide into the mixed raw materials, wherein the addition amount of the calcium oxide is 0.05-0.10wt% of the total weight of the mixed powder raw materials; (2) biscuit molding: preparing the precursor powder obtained in the step (1) into a ceramic biscuit by adopting a molding process; (3) ceramic sintering: and (3) placing the ceramic biscuit prepared in the step (2) in a vacuum environment, sintering into pure-phase ceramic according to a specific sintering procedure, annealing the pure-phase ceramic, and polishing to obtain the lanthanum gadolinium zirconate transparent ceramic material. The process reduces the sintering temperature, and the obtained lanthanum gadolinium zirconate transparent ceramic material has high transmittance and greatly reduces the production cost and the energy consumption.
Description
Technical Field
The invention belongs to the technical field of preparation of transparent ceramics, and particularly relates to a method for preparing high-transmittance lanthanum gadolinium zirconate transparent ceramics by a solid phase method.
Background
The transparent ceramic (Transparent Ceramic) is a polycrystalline ceramic material with certain light transmittance, also called optical ceramic, prepared by a ceramic process. Since the end of the 50 s of the 20 th century, the American Electrical company scientist Coble successfully prepared the first translucent Al 2 O 3 The concept that the traditional ceramic cannot realize transparency is broken, and a brand new field of ceramic preparation and application is developed from the beginning of the ceramic, and transparent ceramics are generated.
The transparent ceramic has the typical characteristics of corrosion resistance, high temperature resistance, good electrical insulation and the like of the traditional ceramic, and has the optical characteristics of glass, so that the transparent ceramic has been widely applied in the fields of lighting technology, optics, special instrument manufacturing, wireless electronic technology, high temperature technology and the like in recent years. The transparent ceramics can also replace transparent materials such as single crystals, glass and the like to be applied to the fields of army and civil such as protection windows, laser electro-optics, novel light sources, medical instruments and the like.
Transparent ceramics can be classified into oxide transparent ceramics (e.g. Al 2 O 3 、MgO、Y 2 O 3 、Y 3 Al 5 O 12 ) Fluoride transparent ceramics (e.g. CaF 2 、MgF 2 ) Nitride transparent ceramics (such as AlN), sulfide transparent ceramics (such as ZnS), and the like. The transparent ceramics can be divided into transparent laser ceramics (Dy: caF) 2 And Nd: YAG), transparent scintillating ceramics (e.g. Gd 2 O 2 S: ce), transparent ferroelectric ceramics (e.g. PLZT, PZT), and infrared transparent ceramics (e.g. MgF) 2 、ZnS)。
For the preparation of transparent ceramics of various different materials, although the general process is similar to that of common ceramics, the process flow of powder preparation, compression molding and ceramic sintering is adopted, the phase change condition of the transparent ceramics is complex along with the reaction temperature and the sintering process, and the preparation process of different raw materials cannot be easily referred to. This is because the crystal form and the orientation of crystal grains of the various raw material powders are different, which affects the light transmittance of the transparent ceramic, and the manufacturing process also affects the light transmittance of the ceramic, and the different manufacturing processes, for example, although only differing in sintering temperature, also affects the preparation of the intermediate phase and the pure phase.
The transparent ceramic generally needs to adopt high-purity and superfine powder raw materials, and is doped with as few additives as possible to reduce impurity second phases, meanwhile, the processes such as forming, sintering and the like need to be strictly controlled, so that the air holes and impurities are ensured to be fully discharged, and the ceramic density is close to the theoretical density, so that the transparent ceramic with high light transmittance can be prepared.
The lanthanum gadolinium zirconate transparent ceramic is a novel ceramic material invented in recent years. With conventional transparent ceramic materials (e.g. Al 2 O 3 YAG, spinel, alON, etc.), the lanthanum gadolinium zirconate transparent ceramic has higher theoretical density and high atomic number, shows excellent characteristics of high refractive index (more than 2.10), wide infrared band transmission range (cut-off wavelength of 8.0 μm), stronger X-ray and gamma-ray stopping ability, and the like, and has potential application in the fields of high refractive index optical lenses, infrared windows, scintillator materials and comprehensive shielding windows.
Before the development of the lanthanum gadolinium zirconate transparent ceramic, although various other types of transparent ceramics have been prepared and have higher transmittance, the development of the lanthanum gadolinium zirconate transparent ceramic is still in a state of being in a lag state, because other raw material powder preparation processes have been developed, but the preparation of the lanthanum gadolinium zirconate transparent ceramic cannot form a good reference. The powder prepared by the traditional solid phase method has low sintering activity and high sintering temperature, and is difficult to prepare single-phase transparent ceramic, and the sintering temperature of the powder generally reaches 1800-1900 ℃. The preparation process of the lanthanum gadolinium zirconate transparent ceramic raw material powder still remains to be researched, and before the high-purity raw material powder is not well prepared, the preparation work of the transparent ceramic is more difficult to be carried out smoothly.
Based on the above, researchers first prepare high-purity powderThe body is used for preparing the lanthanum gadolinium zirconate transparent ceramic. Wang et al (Z.Wang, G.Zhou, X.Qin, Y.Yang, G.Zhang, Y.Menke, and S.Wang, journal of the European Ceramic SocieTY33,643, 2013.) first prepared LaGdZr by combustion 2 O 7 Pure phase powder; the LaGdZr was prepared by co-precipitation with the aid of Gui et al (D.- -Y.Gui, Z.- -K.Cao, W.Han, J.- -Q.Qi, T.- -C.Lu, Y.Zou, and C.- -H.Wang, ceramics International 44,7006,2018.) 2 O 7 Pure phase powder improves the transmittance of the lanthanum gadolinium zirconate transparent ceramic; han et al (W.Han, Z.Tang, N.Ma, S.Peng, N.Wei, Z.Huang, Y.Yang, J.Qi, and T.Lu, journal of Alloys and Compounds 771,944,2019.) and Zhao et al (W.Zhao, K.Zhang, W.Li, T.Deng, B.Luo, and H.Zhang, ceramics International 45,20078,2019.) prepared LaGdZr by solid phase method 2 O 7 The precursor powder optimizes ball milling and sintering technology, and further improves the transmittance of the lanthanum gadolinium zirconate transparent ceramic. The research explores various processes for preparing the raw materials of the lanthanum gadolinium zirconate transparent ceramic powder, and successfully prepares the lanthanum gadolinium zirconate transparent ceramic flake sample with the diameter of 10-20 mm and the visible band interval transmittance of 60-75%. However, the transmittance of the lanthanum gadolinium zirconate transparent ceramic obtained by the method is generally low, and still needs to be further improved.
In recent years, in order to improve LaGdZr 2 O 7 The transparency and density of ceramics have been studied extensively both in terms of powder preparation and sintering processes. Lanthanum gadolinium zirconate (La) was developed by Shanghai silicate institute of academy of sciences in China in 2012 2-x Gd x Zr 2 O 7 Wherein x is more than 0 and less than 2), the transparent ceramic material adopts zirconium nitrate, lanthanum nitrate and gadolinium nitrate as raw materials in the powder preparation process, the lanthanum gadolinium zirconate powder is prepared by combining glycine-nitrate combustion method, the dry pressing and cold isostatic pressing forming process are adopted in the forming process, the sintering process and the annealing process are combined, and the vacuum degree of the sintering process is 10 -2 ～10 -4 Sintering is carried out for 4-10 hours at 1800-1900 ℃ under the vacuum condition of Pa, the sintering temperature is higher, and the cost of sintering equipment is high. In addition, la is obtained 2-x Gd x Zr 2 O 7 Transparent ceramicThe linear transmittance of the porcelain 1mm sample at 1000nm is only 70.7% at maximum, and the transmittance is required to be improved.
The 2017 institute of fluid physics of China engineering institute provides a preparation method of high-purity and high-morphology uniform lanthanum gadolinium zirconate powder and transparent ceramic, which is prepared by mixing Gd (NO 3 ) 3 ·6H 2 O、La(NO 3 ) 3 ·6H 2 O、ZrOCl 2 ·8H 2 O is according to Gd 3+ 、La 3+ With Zr 4+ Preparing a mixed salt solution according to the molar ratio of 1:1:2, then titrating the mixed salt solution into ammonia water until the pH value is 10-12 to obtain a mixed solution, aging the mixed solution, and performing suction filtration and washing to obtain a colloidal precipitate, wherein the colloidal precipitate is dispersed in ethanol to obtain white slurry; then the white paste is moved into a reaction kettle for treatment, and then is filtered and washed to obtain white precipitate, the white precipitate is dried to obtain precursor blocks, the precursor blocks are ground to obtain precursor powder, and the precursor powder is calcined and ground to obtain GdLaZr 2 O 7 Ceramic powder. The process for preparing the powder is complex, and in addition, the biscuit prepared by the powder needs to be subjected to vacuum degree of less than or equal to 10 -2 Pa, sintering temperature is 1800-1900 ℃ for 6-10 h, sintering temperature is higher, sintering cost is high, and meanwhile, the transmittance of the prepared transparent ceramic is less than 60%, and the transmittance is still to be greatly improved.
Subsequently, la was prepared by aqueous phase Acrylamide (AM) gel casting technique using lanthanum oxide, gadolinium oxide and zirconium oxide as raw materials 0.4 Gd 1.6 Zr 2 O 7 The transparent ceramic can be obtained by sintering at 1700-1900 ℃ for 10-12 hours, the sintering temperature is reduced to a certain extent, and the transmittance of the transparent ceramic obtained by the method reaches 78.7% at 1100nm, but due to La in the raw materials 2 O 3 Hydrolysis to produce alkaline slurry, which is difficult to apply to La 0.4 Gd 1.6 Zr 2 O 7 The ceramic product with high transmittance cannot be prepared under a solid-phase reaction system by simple solid-phase reaction sintering of the ceramic.
Because the powder prepared by the traditional solid phase method has low sintering activity and high sintering temperature, the transparent ceramic with single phase is difficult to prepare. The existing process for preparing the lanthanum gadolinium zirconate transparent ceramic cannot generally prepare active powder by adopting a solid phase method, has the problems of complex manufacturing process, higher cost and high sintering temperature, and meanwhile, the transmittance of the lanthanum gadolinium zirconate transparent ceramic prepared by adopting the solid phase method is generally lower, and the process still needs to be improved. Therefore, the combination of a simple manufacturing process with a reduced sintering temperature of high transmittance transparent ceramics while improving optical quality would be a necessary condition to determine whether this type of ceramic would promote its industrial and commercial applications.
At present, a method for preparing high-purity active powder by a simple solid phase method and preparing high-transmittance lanthanum gadolinium zirconate transparent ceramic at a lower sintering temperature is not developed, and the problem is needed to be solved.
Disclosure of Invention
The invention aims to solve the technical problems, and provides a method for preparing high-transmittance lanthanum gadolinium zirconate transparent ceramics by a solid phase method. The technical aim of the invention is to solve the problem that the single-phase transparent ceramic is difficult to prepare due to low sintering activity and high sintering temperature of the prepared powder by the traditional solid phase method, so as to provide a simple method for preparing high-purity powder by the solid phase method to prepare high-transmittance lanthanum gadolinium zirconate transparent ceramic; on the other hand, the method solves the problems that the sintering temperature of the existing transparent ceramic is generally higher and the transmittance of the lanthanum gadolinium zirconate transparent ceramic prepared by a solid phase method is generally lower, so that the method for preparing the high-transmittance lanthanum gadolinium zirconate transparent ceramic at a lower sintering temperature is provided.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
a method for preparing high-transmittance lanthanum gadolinium zirconate transparent ceramics by a solid phase method comprises the following steps:
(1) Preparation of precursor powder: mixing lanthanum oxide, gadolinium oxide and zirconium oxide powder as raw materials, adding calcium oxide into the mixed raw materials, performing ball milling mixing, drying and sieving by adopting a solid phase method, and calcining to prepare precursor powder; the addition amount of the calcium oxide accounts for 0.05 to 0.10 weight percent of the total weight of the mixed raw materials;
(2) Shaping a biscuit: preparing the precursor powder obtained in the step (1) into a ceramic biscuit by adopting a molding process;
(3) Sintering ceramics: sintering the ceramic biscuit prepared in the step (2) into pure-phase ceramic according to a specific sintering procedure in a vacuum environment, annealing the pure-phase ceramic, and polishing to obtain a lanthanum gadolinium zirconate transparent ceramic material;
wherein, the sintering procedure is as follows: the temperature is kept at 1250 ℃ for 2 to 3 hours, the temperature is kept at 1650 ℃ for 2 to 3 hours, the temperature is kept at 1750 ℃ for 4 to 6 hours, and the temperature rising rate is less than or equal to 5 ℃/min.
Most of ceramic powder prepared by the traditional solid phase method has low sintering activity and high sintering temperature, and single-phase transparent ceramic is difficult to prepare, so that the transmittance is low. The invention provides a simple solid phase method for preparing precursor powder and realizing a method for preparing high-transmittance lanthanum gadolinium zirconate transparent ceramic by reducing sintering temperature. The inventor unexpectedly found that the technical purpose of the invention can be realized by adding calcium oxide in the solid phase method process and controlling the addition amount of the calcium oxide to be 0.05-0.10wt percent, so that the problems existing in the existing solid phase method can be well solved. Because the ionic radius is similar, the added calcium oxide is favorable for forming a substitution mechanism and increasing the concentration of oxygen vacancies in crystal lattices, thereby greatly promoting sintering, obviously reducing the temperature of subsequent sintering, well realizing the effect of preparing the high-transmittance lanthanum gadolinium zirconate transparent ceramic by adopting a solid phase method and at a lower sintering temperature, reducing energy consumption and production cost and having great significance for commercialization of the lanthanum gadolinium zirconate transparent ceramic.
In general, to achieve high transmittance, fewer pores are critical to high optical quality and densification of transparent ceramics. To achieve high optical quality and high densification of lanthanum gadolinium zirconate transparent ceramics, a high temperature vacuum sintering method with a sintering temperature of 1800 ℃ or higher and continuous sintering for at least 4 hours is generally required. However, to realize a high-temperature vacuum environment above 1800 ℃, the requirements on heating and heat preservation of equipment are high, and the energy consumption is high, so that the production cost is high. Taking a high vacuum tungsten wire sintering furnace as an example, the volume of the high vacuum tungsten wire sintering furnace is 0.12m 3 Is arranged in the furnace chamber ofThe furnace body heating system consumes about 17kW when the temperature is kept at 1850 ℃. The method reduces the sintering temperature, optimizes the existing high-temperature sintering procedure, obviously reduces the energy consumption and the production cost under the condition of ensuring the high optical quality and the high densification of the lanthanum gadolinium zirconate transparent ceramic, and compared with the volume of 0.12m 3 The energy consumption of the furnace body heating system is only about 6kW when the furnace chamber is insulated at 1750 ℃, and the energy consumption of the existing sintering process is up to more than 10 kW.
La was prepared by the above method of the present invention 0.4 Gd 1.6 Zr 2 O 7 The properties of the transparent ceramic are as follows: density: 6.64g/cm 3 The highest transmittance was 79%.
In the process of fumbling, a great number of failures are encountered, and initially, when the inventor determines that the preparation is carried out by adopting a cation-binding solid phase method with different valence states, different cation oxides have important influence on the transmittance of the lanthanum gadolinium zirconate transparent ceramic, and the consumption of the cation oxides has great influence on the transmittance of the lanthanum gadolinium zirconate transparent ceramic. As shown in the comparative example of the invention, when the addition amount of CaO is increased to 1.5 weight percent and 2.0 weight percent, the transmittance of the obtained gadolinium lanthanum zirconate transparent ceramic is obviously reduced; while when CaO is replaced by MgO and SiO in the same valence state 2 When ethyl orthosilicate is added and mainly SiO2 is used, the transmittance of the prepared gadolinium lanthanum zirconate transparent ceramic is generally low even if the addition amount is controlled to be in the range of 0.05-0.20 wt%.
Based on this, the inventor further researches and discovers that the sintering procedure has a critical influence on the transmittance of the obtained lanthanum gadolinium zirconate transparent ceramic. As shown in the comparative example of the invention, when the temperature rising rate in the sintering process is too high, the success rate of the obtained ceramic sample is greatly reduced, and the larger the sample size is, the easier the sample is to crack, and the transmittance at the moment is reduced; when the sintering process is replaced by other sintering processes, the samples are found to have a plurality of cracks, and the sample transmittance is greatly reduced. Therefore, the sintering procedure of the invention is critical to the transmittance and the product qualification rate of the obtained lanthanum gadolinium zirconate transparent ceramic.
Further, in the step (1), the molar ratio of lanthanum oxide, gadolinium oxide and zirconium oxide powder in the mixed raw material is 4:1:1.
Further, the calcination process in the step (1) is to heat the ball-milled and refined powder to 700-900 ℃ and calcine for 3-4 h.
Further, the ball milling time in the step (1) is 1-3 h.
Further, the molding process in the step (2) adopts a compression molding process or a gel injection molding process.
Further, the specific steps of the gel casting process in the step (2) are as follows:
adding the precursor powder obtained in the step (1) into a premix solution containing ammonium citrate, an isobutylene maleic anhydride copolymer and deionized water to obtain slurry, ball milling for 1-3 h, pouring out the slurry, performing bubble removal treatment on the obtained slurry, then injecting into a mold for molding, after the biscuit is completely demoulded, putting the demoulded biscuit into a drying box for drying, performing glue removal treatment on the dried biscuit, putting the dried biscuit into a cold isostatic press, and keeping the biscuit under the pressure of 200-300 MPa for 10-15 min to obtain a relatively compact ceramic biscuit.
Further, the vacuum degree of the vacuum environment in the step (3) is 10 -3 Pa。
Further, the annealing treatment in the step (3) is performed as follows: and cooling to 1200 ℃ for annealing treatment for 4 hours, wherein the cooling rate is less than or equal to 5 ℃/min.
The beneficial effects of the invention are as follows:
(1) The invention adopts the oxide combined solid phase method to prepare La 0.4 Gd 1.6 Zr 2 O 7 The transparent ceramic solves the problems that the powder prepared by the existing solid phase method has low activity and high sintering temperature, and the high-transmittance transparent ceramic cannot be prepared; compared with other oxides (such as silicon oxide or magnesium oxide), the transmittance of the prepared transparent ceramic is greatly improved;
(2) The preparation method provided by the invention can obviously reduce the sintering temperature of the conventional lanthanum gadolinium zirconate transparent ceramic, and reduce the sintering temperature of the lanthanum gadolinium zirconate transparent ceramicThe requirements of production equipment and the energy consumption reduce the production cost, and can realize high transmittance La 0.4 Gd 1.6 Zr 2 O 7 Industrial preparation of transparent ceramics;
(3) Compared with other preparation methods, the preparation method can adopt a simple solid phase method, can obtain high-transmittance lanthanum gadolinium zirconate transparent ceramic under the condition of reducing the sintering temperature, has good uniformity, no impurity and air holes and high density, almost approximates to theoretical transmittance in visible light and infrared band range, greatly reduces the production cost, can realize industrial production, and can well meet potential application requirements.
Drawings
FIG. 1 shows that the lanthanum gadolinium zirconate transparent ceramics are prepared when the addition amount of CaO is 0.05 to 0.20wt% (based on the weight percentage of the mixed powder raw materials).
FIG. 2 shows that the transparent ceramic of lanthanum gadolinium zirconate is prepared when the added amount of MgO is 0.05 to 0.20wt% (based on the weight percentage of the mixed powder raw material).
FIG. 3 is SiO 2 The addition amount of the lanthanum gadolinium zirconate transparent ceramic is 0.05 to 0.20 weight percent (calculated by weight percent of the mixed powder raw material).
FIG. 4 is an X-ray diffraction pattern of the lanthanum gadolinium zirconate transparent ceramic prepared in example 1.
FIG. 5 is a schematic diagram of CaO, mgO and SiO, respectively 2 The transmittance of the lanthanum gadolinium zirconate transparent ceramic prepared by using the additive (the dosage is 0.1 weight percent).
FIG. 6 shows a lanthanum gadolinium zirconate transparent ceramic prepared with CaO added in an amount of 0.00 to 0.20wt% (based on the weight percentage of the mixed powder raw materials).
Fig. 7 is a graph showing the comparison of lanthanum gadolinium zirconate transparent ceramics prepared in the examples and comparative examples.
Fig. 8 shows the transparent gadolinium lanthanum zirconate ceramics prepared in the examples and comparative examples.
FIG. 9 shows a transparent gadolinium lanthanum zirconate ceramic prepared in accordance with the method of comparative example.
Detailed Description
In order that the objects, technical solutions and advantages of the present invention will become more apparent, the following detailed description of the present invention will be made with reference to the examples, which are given by way of illustration and explanation only, and are not intended to limit the present invention. Some non-essential modifications and adaptations of the invention according to the foregoing summary will still fall within the scope of the invention.
Example 1
A preparation method of high-transmittance lanthanum gadolinium zirconate transparent ceramic comprises the following steps:
(1) Preparation of precursor powder: uniformly mixing zirconia, lanthanum oxide and gadolinium oxide powder according to a molar ratio of 4:1:1 to obtain a mixed powder raw material, adding 0.1wt% (calculated by weight percent of the mixed powder raw material) of calcium oxide, uniformly mixing the materials by adopting a solid phase method, and performing ball milling;
(2) Preparing a biscuit: mixing the obtained product in the step (1), isobutylene maleic anhydride copolymer (Isobam), ammonium citrate (TAC) and deionized water to prepare slurry, ball milling for 30min by using a planetary ball mill, removing bubbles in the slurry by using a vacuum bubble removing machine, pouring the ball-milled slurry into a mould for drying after 10 min, drying at room temperature until demoulding, putting into a 40 ℃ drying oven, drying at 70 ℃ for 24 h, and forming a biscuit. Performing glue discharging treatment on the dried biscuit, placing the dried biscuit in a cold isostatic press, and keeping the biscuit at the pressure of 200MPa for 10 minutes to obtain a compact biscuit;
(3) Sintering: placing the compact biscuit in a vacuum environment, and preserving heat for 2 hours at 1250 ℃ and 3 hours at 1650 ℃ at a heating rate of 4 ℃/min; preserving the temperature at 1750 ℃ for 6 hours, and sintering by a sintering program with the heating rate of 3 ℃/min to obtain pure phase ceramic; annealing the pure phase ceramic at 1200 ℃ for 4 hours, and polishing to obtain La with high transmittance 0.4 Gd 1.6 Zr 2 O 7 Transparent ceramics.
Example 2
The method of example 1 was referred to, except that the mass fraction of calcium oxide in step (1) was 0.05wt%.
Comparative examples 1 and 2 below examined the effect of the amount of calcium oxide added on the preparation of lanthanum gadolinium zirconate transparent ceramics.
Comparative example 1
Preparation of La by the method of reference example 1 0.4 Gd 1.6 Zr 2 O 7 The transparent ceramic is different in that the mass fraction of the calcium oxide in the step (1) is controlled to be 0.15wt%.
Comparative example 2
Preparation of La by the method of reference example 1 0.4 Gd 1.6 Zr 2 O 7 Transparent ceramic, except that the mass fraction of calcium oxide in step (1) was controlled to be 0.2wt%.
Comparative example 3
Preparation of La by the method of reference example 1 0.4 Gd 1.6 Zr 2 O 7 Transparent ceramics were used as comparative examples except that no calcium oxide was added.
The physical diagrams of the lanthanum gadolinium zirconate transparent ceramics prepared in the above examples 1-2 and comparative examples 1-3 are shown in fig. 1, and the transmittance test results of the lanthanum gadolinium zirconate transparent ceramics are shown in fig. 6. The X-ray diffraction pattern of the lanthanum gadolinium zirconate transparent ceramic prepared by the method of the example is shown in FIG. 4 (taking example 1 as an example, other methods result in a similar way). It can be seen that when CaO is not added (as in comparative example 3, denoted as C 0.00 ) The transmittance of the obtained lanthanum gadolinium zirconate transparent ceramic is lower, C 0.00 When CaO was added in an amount of 0.05 to 0.10wt% (examples 1 and 2), the transmittance of the lanthanum gadolinium zirconate transparent ceramics was significantly improved by C 0.05 ＝78.8％，C 0.10 =79.1%. When the addition amount of CaO is increased to 0.15 to 0.20 weight percent (as in comparative examples 1 and 2), the transmittance of the lanthanum gadolinium zirconate transparent ceramic is obviously reduced and is reduced to be lower than C 0.00 C respectively 0.15 ＝69.1％，C 0.20 =65.4%. It can be seen that when the CaO addition amount is large, the transmittance of the lanthanum gadolinium zirconate transparent ceramic is obviously reduced, and the high transmittance transparent ceramic cannot be prepared.
Example 3
The procedure of example 1 was followed except that in the sintering procedure of step (3), the temperature was maintained at 1250℃for 3 hours, 1650℃for 2 hours, and the rate of temperature increase was 4℃per minute; and (3) preserving heat for 4 hours at 1750 ℃ and sintering at a heating rate of 3 ℃/min.
Example 4
The procedure of example 1 was followed, except that in the sintering procedure of step (3), the temperature was maintained at 1250℃for 2.5 hours, 1650℃for 2.5 hours, and the rate of temperature increase was 5℃per minute; and (3) preserving the temperature at 1750 ℃ for 5 hours, and sintering at a heating rate of 4 ℃/min.
The transmittance of the lanthanum gadolinium zirconate transparent ceramics prepared in examples 3 and 4 is 78.6% and 79.0%, respectively.
Comparative examples 4-7 below examined the effect of different oxides on the preparation of lanthanum gadolinium zirconate transparent ceramics.
Comparative example 4
The preparation method of example 1 was referred to, except that magnesium oxide was used instead of calcium oxide in step (1), and the amount of magnesium oxide added was 0.1wt%, and the other methods were the same. The transmittance test result of the prepared lanthanum gadolinium zirconate transparent ceramic is shown in fig. 5 (MgO curve in the figure).
Comparative example 5
Referring to the scheme of comparative example 4, magnesium oxide was used instead of calcium oxide, but the mass fraction of magnesium oxide was controlled to be 0.05 to 0.20wt% based on the total weight of the mixed powder material. The physical diagram of the prepared lanthanum gadolinium zirconate transparent ceramic is shown in figure 2, M in figure 2 0.05 -M 0.20 Represents the lanthanum gadolinium zirconate transparent ceramics prepared with the mass fractions of added magnesium oxide of 0.05wt%, 0.10wt%, 0.15wt% and 0.20wt%, respectively. As a result, it was found that the lanthanum gadolinium zirconate transparent ceramics prepared by the methods of comparative examples 1 and 2 had many cracks on the surface, and the transmittance was not high, and tested, M 0.05 -M 0.20 The transmittance of (a) was 65.1%, 67.6%, 68.1% and 66.3%, respectively.
Comparative example 6
With reference to the preparation method of example 1, except that in step (1) ethyl orthosilicate (TEOS,wherein the main function is SiO 2 ) The addition amount of TEOS was 0.1wt% instead of calcium oxide, and the other methods were the same. The transmittance test result of the prepared lanthanum gadolinium zirconate transparent ceramic is shown in fig. 5 (TEOS curve in the figure).
Comparative example 7
Referring to the preparation method of comparative example 6, the mass fraction of TEOS was controlled to be 0.05 to 0.20wt% based on the total weight of the mixture. The physical diagram of the obtained lanthanum gadolinium zirconate transparent ceramic is shown in fig. 3. T in FIG. 3 0.05 -T 0.20 Respectively represents the lanthanum gadolinium zirconate transparent ceramics prepared by adding silicon oxide with the mass fraction of 0.05 to 0.20wt%. As a result, the transparent lanthanum gadolinium zirconate ceramic prepared by the method has low transmittance and T although no obvious crack appears 0.05 -T 0.20 The transmittance of (a) was 64.5%, 63.2%, 60.7%, 58.1%, respectively.
The following comparative examples 8 to 10 examined the effect of the sintering procedure on the prepared lanthanum gadolinium zirconate transparent ceramic.
Comparative example 8
According to the preparation method of example 1, when the heating rate of the sintering program in the step (3) was controlled to be 6 ℃/min, ceramic samples were prepared at different CaO additions, and the results are shown in FIG. 7. In fig. 7, lanthanum gadolinium zirconate transparent ceramics prepared according to the method of example 1 with different CaO addition amounts are shown in the upper row, and lanthanum gadolinium zirconate transparent ceramics prepared according to the method of comparative example with different CaO addition amounts are shown in the lower row. It can be found that the success rate of the ceramic sample is greatly reduced due to the too high heating rate in the sintering process, the surface of the sample is easily cracked, the transmittance at the moment is reduced, a compact structure cannot be formed, and the result is shown in fig. 7.
Comparative example 9
Following the procedure of example 1, the densified green body is placed in a vacuum environment in step (3) and the sintering procedure is controlled as follows: preserving heat for 4 hours at 1450 ℃ with a heating rate of 5 ℃/min; preserving heat for 6 hours at 1750 ℃ with a heating rate of 6 ℃/min; after sintering, pure phase ceramics were obtained, and the pure phase ceramics were annealed at 1200 ℃ for 4 hours, and the influence on the ceramic samples with different amounts of CaO and MgO added was examined, respectively, and as a result, it was found that many cracks occurred in the ceramic samples with or without the addition of the above oxides, and the transmittance was greatly reduced, with the result shown in fig. 8.
Comparative example 10
Following the procedure of example 1, the densified green body is placed in a vacuum environment in step (3) and the sintering procedure is controlled as follows: preserving heat for 1.5h at 1250 ℃ and 4h at 1650 ℃ with a heating rate of 5 ℃/min; preserving heat for 6 hours at 1750 ℃ with a heating rate of 6 ℃/min; and sintering to obtain pure-phase ceramic, and annealing the pure-phase ceramic at 1200 ℃ for 4 hours to prepare a ceramic sample. As a result, it was found that many cracks were generated on the surface of the obtained ceramic sample by the above sintering procedure, and the transmittance was greatly reduced, and the result was shown in FIG. 9.
Claims (8)
1. The method for preparing the high-transmittance lanthanum gadolinium zirconate transparent ceramic by a solid phase method is characterized by comprising the following steps of:
(1) Preparation of precursor powder: mixing lanthanum oxide, gadolinium oxide and zirconium oxide powder as raw materials, adding calcium oxide into the mixed raw materials, performing ball milling mixing, drying and sieving by adopting a solid phase method, and calcining to prepare precursor powder; the addition amount of the calcium oxide accounts for 0.05 to 0.10 weight percent of the total weight of the mixed powder raw materials;
(2) Shaping a biscuit: preparing the precursor powder obtained in the step (1) into a ceramic biscuit by adopting a molding process;
(3) Sintering ceramics: sintering the ceramic biscuit prepared in the step (2) into pure-phase ceramic according to a specific sintering procedure in a vacuum environment, annealing the pure-phase ceramic, and polishing to obtain a lanthanum gadolinium zirconate transparent ceramic material;
wherein, the sintering procedure is as follows: the temperature is kept at 1250 ℃ for 2 to 3 hours, the temperature is kept at 1650 ℃ for 2 to 3 hours, the temperature is kept at 1750 ℃ for 4 to 6 hours, and the temperature rising rate is less than or equal to 5 ℃/min.
2. The method of claim 1, wherein the mixed raw material in step (1) has a molar ratio of lanthanum oxide, gadolinium oxide and zirconium oxide powder of 4:1:1.
3. The method according to claim 1, wherein the calcination process in step (1) is calcination for 3 to 4 hours by heating the ball-milled powder to 700 to 900 ℃.
4. The method according to claim 1, wherein the ball milling in step (1) is performed for a time of 1 to 3 hours.
5. The method of claim 1, wherein the molding process in step (2) is a compression molding or a gel casting process.
6. The method of claim 5, wherein the step (2) of the gel casting process comprises the specific steps of:
adding the precursor powder obtained in the step (1) into a premix solution containing ammonium citrate, an isobutylene maleic anhydride copolymer and deionized water to obtain slurry, ball milling for 1-3 h, pouring out the slurry, performing bubble removal treatment on the obtained slurry, then injecting into a mold for molding, after the biscuit is completely demoulded, putting the demoulded biscuit into a drying box for drying, performing glue removal treatment on the dried biscuit, putting the dried biscuit into a cold isostatic press, and keeping the biscuit under the pressure of 200-300 MPa for 10-15 min to obtain a relatively compact ceramic biscuit.
7. The method according to claim 1, wherein the vacuum environment in step (3) has a vacuum level of 10 -3 Pa and below.
8. The method of claim 1, wherein the annealing in step (3) is performed by: and cooling to 1200 ℃ for annealing treatment for 4 hours, wherein the cooling rate is less than or equal to 5 ℃/min.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102815941A (en) * | 2012-09-13 | 2012-12-12 | 中国科学院上海硅酸盐研究所 | Rare-earth-ion-doped lanthanum gadolinium zirconate transparent ceramic material and preparation method thereof |
| US20190276367A1 (en) * | 2018-03-09 | 2019-09-12 | Shin-Etsu Chemical Co., Ltd. | Transparent ceramics, manufacturing method thereof, and magneto-optical device |
| US20190345383A1 (en) * | 2017-01-31 | 2019-11-14 | Mitsubishi Chemical Corporation | Gadolinium oxysulfide sintered body, and scintillator, scintillator array, radiation detector, and radiation inspection apparatus including gadolinium oxysulfide sintered body |
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| CN102815941A (en) * | 2012-09-13 | 2012-12-12 | 中国科学院上海硅酸盐研究所 | Rare-earth-ion-doped lanthanum gadolinium zirconate transparent ceramic material and preparation method thereof |
| US20190345383A1 (en) * | 2017-01-31 | 2019-11-14 | Mitsubishi Chemical Corporation | Gadolinium oxysulfide sintered body, and scintillator, scintillator array, radiation detector, and radiation inspection apparatus including gadolinium oxysulfide sintered body |
| US20190276367A1 (en) * | 2018-03-09 | 2019-09-12 | Shin-Etsu Chemical Co., Ltd. | Transparent ceramics, manufacturing method thereof, and magneto-optical device |
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| SHIWEI DENG等: "Effect of CaO doping on densification and microstructure control of highly transparent La0.4Gd1.6Zr2O7 ceramics", J AM CERAM SOC., 11 December 2022 (2022-12-11), pages 2252 - 2260 * |
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