Preparation method of trivalent chromium ion doped magnesium aluminate spinel transparent ceramic
阅读说明：本技术 一种三价铬离子掺杂镁铝尖晶石透明陶瓷的制备方法 (Preparation method of trivalent chromium ion doped magnesium aluminate spinel transparent ceramic ) 是由 郝艳 王申 张艺博 于 2021-07-27 设计创作，主要内容包括：本发明公开了一种三价铬离子掺杂镁铝尖晶石透明陶瓷的制备方法,包括如下步骤：(1)原料称量；(2)球磨混合；(3)干压成型；(4)预烧结；(5)热压烧结；(6)退火处理；(7)后处理。本发明属于透明陶瓷制备技术领域,具体是指一种三价铬离子掺杂镁铝尖晶石透明陶瓷的制备方法。(The invention discloses a preparation method of trivalent chromium ion doped magnesium aluminate spinel transparent ceramic, which comprises the following steps: (1) weighing raw materials; (2) ball milling and mixing; (3) dry pressing and forming; (4) pre-sintering; (5) hot pressing and sintering; (6) annealing treatment; (7) and (5) post-treatment. The invention belongs to the technical field of transparent ceramic preparation, and particularly relates to a preparation method of trivalent chromium ion doped magnesium aluminate spinel transparent ceramic.)
1. A preparation method of trivalent chromium ion doped magnesium aluminate spinel transparent ceramic is characterized by comprising the following steps:
(1) raw material weighing, Y2O3And LiF, which comprises the following raw materials in parts by mole: 10 parts of MgO and Al2O39.98-9.995 parts of Cr2O30.005-0.02 parts of a sintering aid, wherein the sintering aid is MgO and Al2O3And Cr2O30-4 wt% of the mixing weight;
(2) ball-milling mixes, adopts the ball mill to mix for 2 ~ 20h, and the ball mill rotational speed is 200 ~ 600rpm, chooses agate jar or polyurethane jar for use, and the ball-milling chooses agate ball or zirconium ball for use, and the ball-milling medium comprises liquid medium and ball-milling, and the liquid medium is deionized water or alcohols, raw materials: ball: the mass ratio of the liquid medium is 1: 5-20: 1-20;
(3) performing dry pressing forming, namely drying the mixed slurry obtained in the step (2) at 80-120 ℃, and performing dry pressing forming by using a tablet press, wherein a shaft one-way pressurizing mode is adopted in the dry pressing forming process, the pressure is 2-10 Mpa, and the pressure maintaining time is 1-10 min, so as to prepare a biscuit;
(4) pre-sintering, placing the formed blank in a corundum crucible, placing the corundum crucible and a sample in a muffle furnace, heating to 1000-1400 ℃ at a heating rate of 1-10 ℃/min, and keeping the temperature for 1-4 hours;
(5) hot-pressing sintering, namely putting the blank pre-sintered in the step (4) into a hot-pressing sintering furnace for hot-pressing sintering, wherein the sintering temperature is 1500-1700 ℃, the sintering time is 1-20 h, and the sintering pressure value is 20-60 Mpa;
(6) annealing, demolding after hot-pressing sintering is finished, and putting a sample into a corundum crucible to perform annealing treatment in an oxidizing environment, wherein the annealing temperature is 800-1200 ℃, and the annealing time is 1-10 hours;
(7) and (4) post-treatment, namely performing plane grinding and polishing treatment on the product obtained by the step (6) to obtain the trivalent chromium ion doped magnesium aluminate spinel transparent ceramic.
2. The method for preparing trivalent chromium ion doped magnesia-alumina spinel transparent ceramic according to claim 1, wherein the sintering aid in the step (1) is Y2O3And one or both of LiF.
3. The method for preparing trivalent chromium ion doped magnesia-alumina spinel transparent ceramic according to claim 1, wherein the drying temperature of the mixed slurry in the step (3) is 100 ℃.
4. The preparation method of the trivalent chromium ion doped magnesium aluminate spinel transparent ceramic according to claim 1, wherein the heat preservation time in the step (5) is 5-10 hours.
5. The method for preparing the trivalent chromium ion doped magnesium aluminate spinel transparent ceramic according to claim 1, wherein the thickness of the trivalent chromium ion doped magnesium aluminate spinel transparent ceramic after the plane grinding and polishing treatment in the step (7) is 1 mm.
Technical Field
The invention belongs to the technical field of transparent ceramic preparation, and particularly relates to a preparation method of trivalent chromium ion doped magnesium aluminate spinel transparent ceramic.
Background
Magnesium aluminate spinel (MgAl)2O4) The transparent ceramic has the advantages that the transparent wave band covers the ultraviolet region to the infrared region, has excellent optical performance, has physicochemical characteristics of abrasion resistance, corrosion resistance, high temperature resistance, irradiation resistance, high hardness, high bending strength, proper thermal expansion coefficient and the like, has good chemical stability and mechanical stability in the temperature range below 1250 ℃, is an ideal functional material, and can be widely applied to various fields of laser, illumination, transparent armored vehicles, military, national defense and the like.
The research on magnesium aluminate spinel transparent ceramics began in the 70's of the 20 th century. In 1974, the U.S. scientist Batton prepared magnesia-alumina spinel transparent ceramics by a high-temperature sintering method, but due to the limitations of the method and the process, the transmittance of the material is low, and severe light scattering exists. Subsequently, many scholars respectively adopt a melting casting method, a vacuum hot pressing method, a spark plasma sintering technology and other methods to obtain the magnesia-alumina spinel transparent ceramics with excellent optical properties. The research of MAS transparent ceramics in China starts from 90 years in the 20 th century, and MAS transparent ceramics with high transmittance from ultraviolet to infrared regions are developed in 1996, the light transmission range of the MAS transparent ceramics almost covers the ultraviolet to infrared regions (190nm < lambda < 6000nm), the transmittance is close to the theoretical value from 1000-. Meanwhile, the magnesia-alumina spinel transparent ceramic also has corrosion resistance, high dielectric property, good electrical insulation property and mechanical processing property, the hardness of the magnesia-alumina spinel transparent ceramic changes less obviously with temperature, and the magnesia-alumina spinel transparent ceramic is transparent ceramic with excellent comprehensive performance.
Transition metal ion Cr3+Is an important luminescence center ion, which is at about 470nm (4A2→4T1) And 570nm (4A2→4T2) The wave band has stronger two absorption bands. At MgAl2O4Middle, Cr3+Ion outer layer 3d3Electron generation 686nm (2E)g→4A2g) Red light emission of Cr3+MgAl prepared by introducing magnesium aluminate spinel2O4Transparent ceramic with Cr3+Strong red light emission and excellent optical characteristics of magnesium aluminate spinel.
Disclosure of Invention
In order to solve the problems, the invention provides a preparation method of trivalent chromium ion doped magnesia-alumina spinel transparent ceramic.
In order to realize the functions, the technical scheme adopted by the invention is as follows: a preparation method of trivalent chromium ion doped magnesium aluminate spinel transparent ceramic comprises the following steps:
(1) raw material weighing, Y2O3And LiF, which comprises the following raw materials in parts by mole: 10 parts of MgO and Al2O39.98-9.995 parts of Cr2O30.005-0.02 parts of a sintering aid, wherein the sintering aid is MgO and Al2O3And Cr2O30-4 wt% of the mixing weight;
(2) ball-milling mixes, adopts the ball mill to mix for 2 ~ 20h, and the ball mill rotational speed is 200 ~ 600rpm, chooses agate jar or polyurethane jar for use, and the ball-milling chooses agate ball or zirconium ball for use, and the ball-milling medium comprises liquid medium and ball-milling, and the liquid medium is deionized water or alcohols, raw materials: ball: the mass ratio of the liquid medium is 1: 5-20: 1-20;
(3) performing dry pressing forming, namely drying the mixed slurry obtained in the step (2) at 80-120 ℃, and performing dry pressing forming by using a tablet press, wherein a shaft one-way pressurizing mode is adopted in the dry pressing forming process, the pressure is 2-10 Mpa, and the pressure maintaining time is 1-10 min, so as to prepare a biscuit;
(4) pre-sintering, placing the formed blank in a corundum crucible, placing the corundum crucible and a sample in a muffle furnace, heating to 1000-1400 ℃ at a heating rate of 1-10 ℃/min, and keeping the temperature for 1-4 hours;
(5) hot-pressing sintering, namely putting the blank pre-sintered in the step (4) into a hot-pressing sintering furnace for hot-pressing sintering, wherein the sintering temperature is 1500-1700 ℃, the sintering time is 1-20 h, and the sintering pressure value is 20-60 Mpa;
(6) annealing treatment, namely demolding after hot-pressing sintering is finished, putting a sample into a corundum crucible, and annealing treatment is carried out in an oxidizing environment at the annealing temperature of 800-1200 ℃ for 1-10 h, wherein the oxidizing environment is utilized for annealing, so that carbon pollution and oxygen defects are mainly reduced;
(7) and (4) post-treatment, namely performing plane grinding and polishing treatment on the product obtained by the step (6) to obtain the trivalent chromium ion doped magnesium aluminate spinel transparent ceramic.
Preferably, the sintering aid in the step (1) is Y2O3And one or both of LiF.
Preferably, the drying temperature of the mixed slurry in the step (3) is 100 ℃.
Preferably, the heat preservation time in the step (5) is 5-10 h.
The invention adopts the scheme to obtain the following beneficial effects: according to the preparation method of the trivalent chromium ion doped magnesium aluminate spinel transparent ceramic, provided by the invention, the light transmittance of the trivalent chromium ion doped magnesium aluminate spinel transparent ceramic obtained by doping the trivalent chromium ion into the magnesium aluminate spinel is better than 65% at the wavelength band of 600-6000 nm, and reaches 67% at the emission wavelength, so that the trivalent chromium ion doped magnesium aluminate spinel transparent ceramic is very suitable for being used as a working substance of a red laser and a fluorescent temperature sensitive material.
Drawings
FIG. 1 is a process flow diagram of a method for preparing a trivalent chromium ion doped magnesia-alumina spinel transparent ceramic according to the invention;
FIG. 2 is a SEM comparison of transparent ceramics prepared in example 1 and example 3 in a method for preparing trivalent chromium ion doped magnesium aluminate spinel transparent ceramics according to the invention;
FIG. 3 is a transmittance curve of a transparent ceramic prepared in example 3 of a method for preparing a trivalent chromium ion-doped magnesium aluminate spinel transparent ceramic according to the invention;
fig. 4 is a fluorescence spectrum of a transparent ceramic prepared in example 3 of a method for preparing a trivalent chromium ion-doped magnesium aluminate spinel transparent ceramic according to the present invention.
Detailed Description
The technical solutions of the present invention will be described in further detail with reference to specific embodiments, and all the portions of the present invention not described in detail are the prior art.
The present invention will be described in further detail with reference to examples.
Example 1 (reference group)
A preparation method of trivalent chromium ion doped magnesium aluminate spinel transparent ceramic comprises the following steps:
(1) weighing 3.3996g (0.08435mol) of MgO powder and 8.668g (0.08345mol) of gamma-Al2O3Powder, 0.2856g of Y2O3Powder and 0.12g LiF powder;
(2) ball-milling and mixing, namely putting the powder weighed in the step (1) into an agate ball-milling tank, adding 72g of agate balls and 36g of absolute ethyl alcohol, and then grinding for 3 hours to obtain slurry;
(3) dry pressing, drying the slurry at 100 ℃ after ball milling, performing dry pressing by using a tablet press, axially and unidirectionally pressurizing by using 8MPa pressure, maintaining the pressure for 8min, and pressing into wafers with the diameter of 24mm to obtain biscuit blanks;
(4) pre-sintering, namely placing the corundum crucible obtained in the step (3) into a muffle furnace, heating to 1400 ℃ at the heating rate of 4 ℃/min, and preserving heat for 3 hours;
(5) hot-pressing sintering, namely putting the pre-sintered precast slab into a hot-pressing sintering furnace for sintering, heating to 1000 ℃ at the heating rate of 17 ℃/min, then heating to 1700 ℃ at the heating rate of 7 ℃/min, keeping the temperature for 6h, and keeping the sintering pressure at 50 Mpa;
(6) annealing treatment, namely demolding after hot-pressing sintering is finished, and putting a sample into a corundum crucible to perform annealing treatment in an oxidizing environment, wherein the annealing temperature is 1000 ℃, and the annealing time is 8 hours;
(7) and (4) post-treatment, namely performing plane grinding and polishing treatment on the product obtained by the step (6), and grinding and polishing the ceramic to the thickness of 1mm by adopting a polishing machine to obtain trivalent chromium ion doped magnesia-alumina spinel transparent ceramic, wherein Cr is3+The atomic percentage of (A) is 0.37%
Example 2
A preparation method of trivalent chromium ion doped magnesium aluminate spinel transparent ceramic comprises the following steps:
(1) weighing 3.3996g (0.08435mol) of MgO powder and 8.5952g (0.08430mol) of gamma-Al2O3Powder, 0.0077g (0.00005mol) Cr2O3Powder, 0.2856g of Y2O3Powder and 0.12g LiF powder;
(2) ball-milling and mixing, namely putting the powder weighed in the step (1) into an agate ball-milling tank, adding 72g of agate balls and 36g of absolute ethyl alcohol, and then grinding for 3 hours to obtain slurry;
(3) dry pressing, drying the slurry at 100 ℃ after ball milling, performing dry pressing by using a tablet press, axially and unidirectionally pressurizing by using 4MPa pressure, maintaining the pressure for 10min, and pressing into wafers with the diameter of 24mm to obtain biscuit blanks;
(4) pre-sintering, namely putting the corundum crucible obtained in the step (3) into a muffle furnace, heating to 1300 ℃ at the heating rate of 4 ℃/min, and keeping the temperature for 2 hours;
(5) hot-pressing sintering, namely putting the pre-sintered precast slab into a hot-pressing sintering furnace for sintering, heating to 1000 ℃ at the heating rate of 17 ℃/min, then heating to 1700 ℃ at the heating rate of 7 ℃/min, keeping the temperature for 7.5h, and keeping the sintering pressure at 30 Mpa;
(6) annealing treatment, namely demolding after hot-pressing sintering is finished, and putting a sample into a corundum crucible to perform annealing treatment in an oxidizing environment, wherein the annealing temperature is 800 ℃, and the annealing time is 6 hours;
(7) and (4) post-processing, namely performing plane grinding and polishing treatment on the product obtained by the step (6), and grinding and polishing the ceramic to the thickness of 1mm by adopting a polishing machine.
Example 3
A preparation method of trivalent chromium ion doped magnesium aluminate spinel transparent ceramic comprises the following steps:
(1) raw material weighing, 3.3996g (0.08435mol) of MgO powder and 8.5844g (0.084mol) of gamma-Al2O3Powder, 0.0237g (0.000156mol) Cr2O3Powder, 0.2856g of Y2O3Powder and 0.12g LiF powder;
(2) ball-milling and mixing, namely putting the powder weighed in the step (1) into an agate ball-milling tank, adding 72g of agate balls and 36g of absolute ethyl alcohol, and then grinding for 3 hours to obtain slurry;
(3) dry pressing, drying the slurry at 100 ℃ after ball milling, performing dry pressing by using a tablet press, axially and unidirectionally pressurizing by using 8MPa pressure, maintaining the pressure for 8min, and pressing into wafers with the diameter of 24mm to obtain biscuit blanks;
(4) pre-sintering, namely placing the corundum crucible obtained in the step (3) into a muffle furnace, heating to 1400 ℃ at the heating rate of 4 ℃/min, and preserving heat for 3 hours;
(5) hot-pressing sintering, namely putting the pre-sintered precast slab into a hot-pressing sintering furnace for sintering, heating to 1000 ℃ at the heating rate of 17 ℃/min, then heating to 1700 ℃ at the heating rate of 7 ℃/min, keeping the temperature for 6h, and keeping the sintering pressure at 50 Mpa;
(6) annealing treatment, namely demolding after hot-pressing sintering is finished, and putting a sample into a corundum crucible to perform annealing treatment in an oxidizing environment, wherein the annealing temperature is 1000 ℃, and the annealing time is 8 hours;
(7) and (4) post-treatment, namely performing plane grinding and polishing treatment on the product obtained by the step (6), and grinding and polishing the ceramic to the thickness of 1mm by adopting a polishing machine to obtain trivalent chromium ion doped magnesia-alumina spinel transparent ceramic, wherein Cr is3+The atomic percentage of (B) was 0.37%.
The prepared transparent ceramics are characterized, fig. 2(a) and (b) are respectively the cross-sectional scanning electron micrographs of the transparent ceramics prepared in the examples 1 and 3, and it is seen that the transparent ceramics of the examples 1 and 3 are all relatively dense, have no obvious pores and have the grain size of about 30 μm to 100 μm; FIG. 3 is a graph showing transmittance curves of the transparent ceramics obtained in examples 1 and 3 in the UV-visible-IR region, in which the transparent ceramics have a wide range of transmittance, and the transparent ceramics obtained in example 3 have a transmittance of more than 60% in the wavelength range of 600nm to 6000nm, in which the transparent ceramics obtained in example 1 have a transmittance of more than 70%; the transparent ceramic prepared in example 3 was subjected to fluorescence spectrum detection, as shown in fig. 4, it can be seen that the ceramic can be effectively excited in the range of 350nm to 600nm to generate deep red emission light, the strongest emission peak is located at 686nm, and the optimal excitation wavelength is 552 nm.
The present invention and its embodiments have been described above, but the description is not limited thereto, and the embodiments shown in the examples are only one embodiment of the present invention, but are not limited thereto. In conclusion, those skilled in the art should appreciate that they can readily use the disclosed conception and specific embodiments as a basis for designing or modifying other structures for carrying out the same purposes of the present invention without departing from the spirit and scope of the invention as defined by the appended claims.