Yttrium fluosilicate crystalline phase yttrium aluminum silicate oxyfluoride glass ceramic and preparation method thereof
阅读说明：本技术 一种氟硅酸钇晶相钇铝硅酸盐氧氟玻璃陶瓷及其制备方法 (Yttrium fluosilicate crystalline phase yttrium aluminum silicate oxyfluoride glass ceramic and preparation method thereof ) 是由 王觅堂 郑庆双 张晓伟 张栋梁 于 2020-12-30 设计创作，主要内容包括：本发明公开了一种氟硅酸钇晶相钇铝硅酸盐氧氟玻璃陶瓷及其制备方法,包括以下步骤：S1：将各原料组分按比例混合均匀,之后加热至熔融态并恒温,将熔融液体固化成型,保温预设时间后降温处理或直接水淬,得到钇铝硅酸盐玻璃；S2：将钇铝硅酸盐玻璃经第一升温并保温处理后成核,之后经第二升温并保温处理后晶化,冷却,得到钇铝硅酸盐氧氟玻璃陶瓷。根据本发明将Y-2O-3、Al-2O-3、SiO-2和YF-3按照一定的比例熔制成玻璃后,再对玻璃进行析晶热处理,能够短时间内析出大量的Y-3Si-3O-(10)F晶相,而且制备过程简单,生产成本低。(The invention discloses yttrium fluosilicate crystalline phase yttrium aluminum silicate oxyfluoride glass ceramic and a preparation method thereof, wherein the preparation method comprises the following steps: s1: uniformly mixing the raw material components in proportion, heating to a molten state, keeping the temperature constant, solidifying and molding the molten liquid, and cooling or directly quenching with water after keeping the temperature for a preset time to obtain yttrium aluminum silicate glass; s2: carrying out first temperature rise and heat preservation treatment on the yttrium aluminum silicate glass, nucleating, then carrying out second temperature rise and heat preservation treatment, crystallizing, and cooling to obtain the yttrium aluminum silicate oxyfluoride glass ceramic. According to the invention Y 2 O 3 、Al 2 O 3 、SiO 2 And YF 3 After being melted into glass according to a certain proportion, the glass is subjected to crystallization heat treatment, so that a large amount of Y can be precipitated in a short time 3 Si 3 O 10 F crystal phase, simple preparation process and low production cost.)
1. Y3Si3O10An yttrium alumino silicate oxyfluoride glass ceramic of crystal phase F, characterized in that it comprises:
Y2O325 to 45 parts by mass of Al2O38 to 28 parts by mass of SiO225-40 parts by mass and YF310-30 parts by mass of a glass ceramic which is a main crystal phase or a single crystal phase and is Y3Si3O10F。
2. The yttrium fluosilicate crystalline phase yttrium alumino-silicate oxyfluoride glass-ceramic and process for its preparation according to claim 1, wherein Y is2O325 to 30 parts by mass of Al2O38 to 15 parts by mass of SiO225-31 parts by mass and YF310 to 24 parts by mass.
3. The yttrium fluosilicate crystalline phase yttrium alumino-silicate oxyfluoride glass-ceramic and process for its preparation according to claim 1, wherein Y is2O325 to 28 parts by mass of Al2O38 to 13 parts by mass of SiO225-37 parts by mass and YF310 to 22 parts by mass.
4. A Y as claimed in claim 13Si3O10The preparation method of the F crystal phase yttrium aluminum silicate oxyfluoride glass ceramic is characterized by comprising the following steps:
S1uniformly mixing the raw material components in proportion;
S2heating to a molten state and keeping the temperature for a preset time;
S3solidifying and molding the molten liquid, preserving the heat for a preset time, and then cooling or directly quenching and cooling the molten liquid to obtain the yttrium aluminum silicate oxyfluoride glass;
S4subjecting the yttrium aluminum silicate oxyfluoride glass to a first literPerforming temperature and heat preservation treatment and nucleating;
S5crystallizing after the second temperature rise and heat preservation, and cooling to obtain the yttrium aluminum silicate oxyfluoride glass ceramic.
5. A Y as claimed in claim 43Si3O10The preparation method of the F crystal phase yttrium aluminum silicate oxyfluoride glass ceramic is characterized in that the step S2The mixed raw material components are heated to 1400-1700 ℃ to melt the raw materials into liquid, and the temperature is kept at 1400-1700 ℃ for 1-4 h.
6. A Y as claimed in claim 43Si3O10The preparation method of the F crystal phase yttrium aluminum silicate oxyfluoride glass ceramic is characterized in that the step S3Pouring the molten liquid onto a preheated graphite grinding tool for solidification and molding, then preserving the heat at 700-900 ℃ for 1-2 h, and then cooling to room temperature to obtain the yttrium aluminum silicate oxyfluoride glass.
7. A Y as claimed in claim 43Si3O10The preparation method of the F crystal phase yttrium aluminum silicate oxyfluoride glass ceramic is characterized in that the step S4The first temperature raising and maintaining step includes: heating to 750-900 ℃ at a heating rate of 1-8 ℃/min, and then preserving heat for 1-8 h.
8. A Y as claimed in claim 43Si3O10The preparation method of the F crystal phase yttrium aluminum silicate oxyfluoride glass ceramic is characterized in that the step S5The second temperature raising and maintaining step includes: heating to 950-1200 ℃ at a heating rate of 1-8 ℃/min, and then preserving heat for 1-10 h.
Technical Field
The invention relates to the technical field of glass ceramics, in particular to yttrium fluosilicate crystalline phase yttrium aluminum silicate oxyfluoride glass ceramics and a preparation method thereof.
Background
Oxide-based fluorescent materials are scientifically worked outExtensive research has been carried out, for example phosphates, borates, silicates doped with rare earth ions. Among the three, silicate-based fluorescent materials have recently attracted much attention because of their excellent thermal properties, chemical resistance, low cost and high luminous efficiency. Yttrium silicate phosphors have been studied by several researchers, among which Lu et al [ Journal of Nanoscience and Nanotechnology, 2010,10(3),2152]For Y2Si2O7：Eu3+ the structural and spectral characteristics were studied. For other yttrium silicates doped with optically active rare earth ions, especially fluorine-containing yttrium silicate Y3Si3O10The study of the spectral properties of F is a promising direction for the development of new luminescent materials. Kyoung Hyuk Jang et al Journal of Alloys and Compounds 2012,536,47]Yttrium fluosilicate (Y) was treated in 20123Si3O10F) Middle doped optical active rare earth ion (Er)3The fluorescent property and crystal structure after (+) were investigated.
However, the preparation of Y is now publicly reported3Si3O10The method for F crystal is only hydrothermal synthesis method, and Y crystal3Si3O10The preparation of the F crystal needs to be heated for 120 hours at the temperature of 250 ℃ (the F crystal is filled in a reaction kettle and is under certain pressure), and the preparation method is complex and takes longer time.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide yttrium fluosilicate crystalline phase yttrium aluminum silicate oxyfluoride glass ceramic and a preparation method thereof, and Y is prepared by2O3、Al2O3、SiO2And YF3After being melted into glass according to a certain proportion, the glass is subjected to crystallization heat treatment, so that a large amount of Y can be precipitated in a short time3Si3O10F crystal phase, simple preparation process and low production cost. To achieve the above objects and other advantages in accordance with the present invention, there is provided a Y3Si3O10An yttrium alumino silicate oxyfluoride glass ceramic of crystal phase F comprising:
Y2O325 to 45 parts by mass of、Al2O38 to 28 parts by mass of SiO225-40 parts by mass and YF310-30 parts by mass of a glass ceramic which is a main crystal phase or a single crystal phase and is Y3Si3O10F。
Preferably, Y is2O325 to 30 parts by mass of Al2O38 to 15 parts by mass of SiO225-31 parts by mass and YF310 to 24 parts by mass.
Preferably, Y is2O325 to 28 parts by mass of Al2O38 to 13 parts by mass of SiO225-37 parts by mass and YF310 to 22 parts by mass.
Y3Si3O1The preparation method of the 0F crystal phase yttrium aluminum silicate oxyfluoride glass ceramic comprises the following steps:
S1uniformly mixing the raw material components in proportion;
S2heating to a molten state and keeping the temperature for a preset time;
S3solidifying and molding the molten liquid, preserving the heat for a preset time, and then cooling or directly quenching and cooling the molten liquid to obtain the yttrium aluminum silicate oxyfluoride glass;
S4carrying out first temperature rise and heat preservation treatment on the yttrium aluminum silicate oxyfluoride glass to form core;
S5crystallizing after the second temperature rise and heat preservation, and cooling to obtain the yttrium aluminum silicate oxyfluoride glass ceramic.
Preferably, said step S2The mixed raw material components are heated to 1400-1700 ℃ to melt the raw materials into liquid, and the temperature is kept at 1400-1700 ℃ for 1-4 h.
Preferably, said step S3Pouring the molten liquid onto a preheated graphite grinding tool for solidification and molding, then preserving the heat at 700-900 ℃ for 1-2 h, and then cooling to room temperature to obtain the yttrium aluminum silicate oxyfluoride glass.
Preferably, said step S4Wherein the first temperature raising and maintaining step comprises: heating to 750-900 ℃ at a heating rate of 1-8 ℃/min, and then preserving heat for 1-8 h.
Preferably, said step S5The second temperature raising and maintaining step includes: heating to 950-1200 ℃ at a heating rate of 1-8 ℃/min, and then preserving heat for 1-10 h.
Compared with the prior art, the invention has the beneficial effects that:
(1) through a large number of experiments, the following results are found: by the method provided by the invention, Y is2O3、Al2O3、SiO2And YF3After being melted into glass according to a certain proportion, the glass is subjected to crystallization heat treatment, and a large amount of main crystal phase or single crystal phase Y can be prepared3Si3O10An yttrium aluminum silicate oxyfluoride glass ceramic of F.
(2) The invention not only can realize the preparation of a large amount of Y in a short time3Si3O10F crystal, simple preparation process, simple and convenient operation, low production cost and wide application value.
Drawings
FIG. 1 is a differential scanning calorimetry trace of yttrium aluminosilicate oxyfluoride glass in an embodiment of a yttrium fluorosilicate crystalline phase yttrium aluminosilicate oxyfluoride glass ceramic and method of making the same according to the present invention;
FIG. 2 is an X-ray diffraction analysis spectrum of yttrium aluminosilicate oxyfluoride glass ceramics in example one, comparative example one and comparative example two of yttrium fluorosilicate crystalline phase yttrium aluminosilicate oxyfluoride glass ceramics according to the present invention and a method of preparing the same;
FIG. 3 is a drawing of a first embodiment of a yttrium fluosilicate crystalline yttrium aluminum silicate oxyfluoride glass ceramic and method of making same according to the present invention3Si3O10The scanning electron micrograph of the F crystal phase yttrium aluminum silicate oxyfluoride glass ceramic.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Referring to fig. 1-3, a yttrium fluosilicate crystalline phase yttrium aluminum silicate oxyfluoride glass ceramic and a preparation method thereof comprises the following steps: y is2O325 to 45 parts by mass of Al2O38 to 28 parts by mass of SiO225-40 parts by mass and YF310-30 parts by mass of a glass ceramic which is a main crystal phase or a single crystal phase and is Y3Si3O10F。
Further, Y2O325 to 30 parts by mass of Al2O38 to 15 parts by mass of SiO225-31 parts by mass and YF310 to 24 parts by mass.
Further, Y2O325 to 28 parts by mass of Al2O38 to 13 parts by mass of SiO225-37 parts by mass and YF310 to 22 parts by mass.
Y3Si3O1The preparation method of the 0F crystal phase yttrium aluminum silicate oxyfluoride glass ceramic comprises the following steps:
S1uniformly mixing the raw material components in proportion;
S2heating to a molten state and keeping the temperature for a preset time;
S3solidifying and molding the molten liquid, preserving the heat for a preset time, and then cooling or directly quenching and cooling the molten liquid to obtain the yttrium aluminum silicate oxyfluoride glass;
S4carrying out first temperature rise and heat preservation treatment on the yttrium aluminum silicate oxyfluoride glass to form core;
S5crystallizing after the second temperature rise and heat preservation, and cooling to obtain the yttrium aluminum silicate oxyfluoride glass ceramic.
Mixing the raw material components uniformly according to a proportion, then placing the mixture into a quartz crucible or a corundum crucible, placing the mixture into a silicon-molybdenum furnace, heating the mixture to 1400-1700 ℃ to melt the raw materials into a liquid state, and heating the liquid state to 1Keeping the temperature of 400-1700 ℃ for 1-4 h; and then pouring the molten liquid in the crucible onto a preheated graphite grinding tool for solidification and molding, quickly putting the crucible into a box-type furnace at 700-900 ℃, preserving the heat for 1-2 h, cooling the crucible to room temperature along with the furnace, or directly quenching the molten liquid with water to prepare the transparent yttrium aluminum silicate oxyfluoride glass. Wherein, the raw material components are mixed according to the following proportion: y is2O325 to 45 parts by mass of Al2O38 to 28 parts by mass of SiO225-40 parts by mass and YF310 to 30 parts by mass.
The glass transition temperature and crystallization peak temperature of the glass were obtained by differential scanning calorimetry, and the following crystallization heat treatment system was prepared. Putting a transparent yttrium aluminum silicate oxyfluoride glass sample into a box-type resistance furnace, heating to 750-900 ℃ at a heating rate of 1-8 ℃/min, and preserving heat for 1-8 h for nucleation; and continuously heating to 950-1200 ℃ at the heating rate of 1-8 ℃/min, preserving the heat for 1-10 h for crystallization, and cooling the sample along with the furnace to obtain the yttrium aluminum silicate oxyfluoride glass ceramic.
Then adopting X-ray diffraction analysis to determine that the main crystal phase or single crystal phase of the yttrium aluminum silicate oxyfluoride glass ceramic is Y3Si3O10F; observing the main crystal phase or single crystal phase as Y by using a scanning electron microscope3Si3O1The micro-morphology of the 0F yttrium aluminum silicate oxyfluoride glass ceramic.
Further, the step S2The mixed raw material components are heated to 1400-1700 ℃ to melt the raw materials into liquid, and the temperature is kept at 1400-1700 ℃ for 1-4 h.
Further, the step S3Pouring the molten liquid onto a preheated graphite grinding tool for solidification and molding, then preserving the heat at 700-900 ℃ for 1-2 h, and then cooling to room temperature to obtain the yttrium aluminum silicate oxyfluoride glass.
Further, the step S4The first temperature raising and maintaining step includes: heating to 750-900 ℃ at a heating rate of 1-8 ℃/min, and then preserving heat for 1-8 h.
Further, the step S5The second temperature raising and maintaining step includes: heating at a rate of 1-8 deg.C/min toAnd keeping the temperature for 1-10 h at 950-1200 ℃.
Example one
This embodiment provides a Y3Si3O10The preparation method of the F crystal phase yttrium aluminum silicate oxyfluoride glass ceramic comprises the following steps:
S1: according to the mass percent of 30 percent Y2O3、15％Al2O3、31％SiO2And 24% YF3Weighing the components, fully and uniformly mixing the components, placing the mixture into a corundum crucible, placing the corundum crucible into a silicon-molybdenum furnace, heating the mixture to 1550 ℃, melting the raw materials into a liquid state, preserving heat for 2 hours at the temperature of 1550 ℃, pouring the liquid in the crucible onto a preheated graphite mold, curing and forming, quickly placing the crucible into a 780 ℃ box-type furnace, preserving heat for 2 hours, and cooling the crucible to room temperature to obtain the transparent yttrium aluminum silicate oxyfluoride glass.
S2: obtaining the glass transition temperature and the crystallization peak temperature of the glass by a differential scanning calorimetry analyzer, and making the following crystallization heat treatment system as shown in figure 1; putting a transparent yttrium aluminum silicate oxyfluoride glass sample into a box-type resistance furnace, heating to 820 ℃ at the heating rate of 5 ℃/min, and preserving heat for 2h for nucleation; continuously heating to 1052 ℃ at the heating rate of 5 ℃/min, and carrying out heat preservation for 3 hours for crystallization to obtain the yttrium aluminum silicate oxyfluoride glass ceramic.
The crystal phase of the yttrium aluminum silicate oxyfluoride glass ceramic of the embodiment is determined to be Y by X-ray diffraction analysis3Si3O10F, as shown in FIG. 2; y-containing observation of this example with a scanning Electron microscope3Si3O10The microstructure of the F crystal phase yttrium aluminum silicate oxyfluoride glass ceramic is shown in figure 3.
Example two
The embodiment provides a preparation method of yttrium aluminum silicate oxyfluoride glass ceramic, which comprises the following steps:
S1: 28% by mass of Y2O3、13％Al2O3、37％SiO2And 22% YF3Weighing the components, mixing the components uniformly, placing the mixture in a corundum crucible, placing the corundum crucible in a silicon-molybdenum furnace, and raising the temperatureAnd (3) heating to 1500 ℃, melting the raw materials into liquid, preserving heat for 2 hours at 1500 ℃, pouring the liquid in the crucible onto a preheated graphite grinding tool for solidification and molding, quickly putting the crucible into a 750 ℃ box-type furnace, preserving heat for 2 hours, and cooling to room temperature along with the furnace to obtain the transparent yttrium aluminum silicate oxyfluoride glass.
S2: obtaining the glass transition temperature and the crystallization peak temperature of the glass by a differential scanning calorimetry analyzer, and making the following crystallization heat treatment system; putting a transparent yttrium aluminum silicate oxyfluoride glass sample into a box-type resistance furnace, heating to 800 ℃ at the heating rate of 5 ℃/min, and preserving heat for 2h for nucleation; and continuously heating to 1032 ℃ at the heating rate of 5 ℃/min, and preserving the heat for 3 hours for crystallization to obtain the yttrium aluminum silicate oxyfluoride glass ceramic.
EXAMPLE III
The embodiment provides a preparation method of yttrium aluminum silicate oxyfluoride glass ceramic, which comprises the following steps:
S1: according to the mass percent of 34 percent Y2O3、16％Al2O3、36％SiO2And 14% YF3Weighing the components, fully and uniformly mixing the components, placing the mixture into a corundum crucible, placing the corundum crucible into a silicon-molybdenum furnace, heating the mixture to 1550 ℃, melting the raw materials into a liquid state, preserving heat for 2 hours at the temperature of 1550 ℃, pouring the liquid in the crucible onto a preheated graphite grinding tool for curing and forming, quickly placing the crucible into a 800 ℃ box-type furnace, preserving heat for 2 hours, and cooling the crucible to room temperature to obtain the transparent yttrium aluminum silicate oxyfluoride glass.
S2: obtaining the glass transition temperature and the crystallization peak temperature of the glass by a differential scanning calorimetry analyzer, and making the following crystallization heat treatment system; putting a transparent yttrium aluminum silicate oxyfluoride glass sample into a box-type resistance furnace, heating to 820 ℃ at the heating rate of 5 ℃/min, and preserving heat for 2h for nucleation; and continuously heating to 1060 ℃ at the heating rate of 5 ℃/min, and preserving the heat for 3 hours for crystallization to obtain the yttrium aluminum silicate oxyfluoride glass ceramic.
In addition, in order to further highlight the advantages of the technical solution of the present invention, the following comparative examples were provided. The following comparative examples were all set on the basis of example one.
Comparative example 1
This comparative example compares with example one, step S1The proportions of the raw material components are different. Specifically, the method comprises the following steps:
the comparative example provides a method of making an yttrium aluminosilicate glass ceramic comprising the steps of:
S1: according to the mass percent of 45 percent of Y2O3、15％Al2O3、35％SiO2And 5% YF3Weighing the components, fully and uniformly mixing the components, placing the mixture into a corundum crucible, placing the corundum crucible into a silicon-molybdenum furnace, heating the mixture to 1550 ℃, melting the raw materials into a liquid state, preserving heat for 2 hours at the temperature of 1550 ℃, pouring the liquid in the crucible onto a preheated graphite mold, curing and forming, quickly placing the crucible into a 780 ℃ box-type furnace, preserving heat for 2 hours, and cooling the crucible to room temperature to obtain the transparent yttrium aluminum silicate oxyfluoride glass.
S2: obtaining the glass transition temperature and the crystallization peak temperature of the glass by a differential scanning calorimetry analyzer, and making the following crystallization heat treatment system; putting a transparent yttrium aluminum silicate oxyfluoride glass sample into a box-type resistance furnace, heating to 820 ℃ at the heating rate of 5 ℃/min, and preserving heat for 2h for nucleation; continuously heating to 1052 ℃ at the heating rate of 5 ℃/min, and carrying out heat preservation for 3 hours for crystallization to obtain the yttrium aluminum silicate oxyfluoride glass ceramic.
The main crystal phase of the yttrium aluminum silicate oxyfluoride glass ceramic of the embodiment is determined to be Y by X-ray diffraction analysis2Si2O7Containing only small amounts of Y3Si3O10F, as shown in FIG. 2.
Comparative example No. two
This comparative example compares with example one, step S2The temperature system of the crystallization heat treatment is different. Specifically, the method comprises the following steps:
the comparative example provides a method of making an yttrium aluminosilicate glass ceramic comprising the steps of:
S1: according to the mass percent of 30 percent Y2O3、15％Al2O3、31％SiO2And 24% YF3Weighing the components, mixing the components uniformly, placing the mixture in a corundum crucible, and putting the corundum crucible into the corundum crucibleHeating to 1550 deg.c in a Si-Mo furnace to melt the material into liquid, maintaining at 1550 deg.c for 2 hr, pouring the liquid in the crucible onto preheated graphite mold for curing and forming, fast setting in 780 deg.c box furnace, maintaining for 2 hr, and cooling to room temperature to obtain the transparent yttrium aluminum silicate oxyfluoride glass.
S2: obtaining the glass transition temperature and the crystallization peak temperature of the glass by a differential scanning calorimetry analyzer, and making the following crystallization heat treatment system; putting a transparent yttrium aluminum silicate oxyfluoride glass sample into a box-type resistance furnace, heating to 820 ℃ at the heating rate of 5 ℃/min, and preserving heat for 2h for nucleation; continuously heating to 950 ℃ at the heating rate of 5 ℃/min, and preserving heat for 3h for crystallization.
The yttrium aluminosilicate glass of the comparative example was determined to have no precipitated crystals by X-ray diffraction analysis, as shown in FIG. 2.
Of course, other parameters and conditions in the preparation process are possible in addition to those exemplified in examples one to three.
By the method provided by the invention, Y is2O3、Al2O3、SiO2And YF3After being melted into glass according to a certain proportion, the glass is subjected to crystallization heat treatment, and not only can a large amount of main crystal phase or single crystal phase Y be prepared3Si3O10The yttrium aluminum silicate oxyfluoride glass ceramic of F has simple preparation process, simple and convenient operation and low production cost, and can realize the preparation of a large amount of Y in short time3Si3O10F, crystals.
The number of devices and the scale of the processes described herein are intended to simplify the description of the invention, and applications, modifications and variations of the invention will be apparent to those skilled in the art.
While embodiments of the invention have been described above, it is not limited to the applications set forth in the description and the embodiments, which are fully applicable in various fields of endeavor to which the invention pertains, and further modifications may readily be made by those skilled in the art, it being understood that the invention is not limited to the details shown and described herein without departing from the general concept defined by the appended claims and their equivalents.
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