CN112663143B - Preparation method of high-purity lead germanate crystal with cubic perovskite structure - Google Patents
Preparation method of high-purity lead germanate crystal with cubic perovskite structure Download PDFInfo
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- CN112663143B CN112663143B CN202011414554.8A CN202011414554A CN112663143B CN 112663143 B CN112663143 B CN 112663143B CN 202011414554 A CN202011414554 A CN 202011414554A CN 112663143 B CN112663143 B CN 112663143B
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Abstract
The invention discloses a preparation method of a high-purity lead germanate crystal sample with a cubic perovskite structure. Firstly, germanic acid with monoclinic structureLead crystal (PbGeO) 3 ) Or lead oxide (PbO) and germanium dioxide (GeO) 2 ) The mixture is used as a raw material, high-temperature rapid quenching is carried out under the normal pressure condition to synthesize the lead germanate glass, and then high-temperature high-pressure treatment is carried out on the glassy lead germanate, so that the high-purity cubic perovskite structure lead germanate crystal is obtained. The high temperature and high pressure synthesis process of high purity cubic lead germanate crystal is not only for preparing perovskite structure alkali earth metal germanate (such as CaGeO) 3 、SrGeO 3 And BaGeO 3 ) The high-purity sample provides a technical example and is beneficial to rapidly promoting the structure research, physical property detection and device preparation of various high-purity germanate functional materials.
Description
Technical Field
The invention belongs to the technical field of luminescent materials, and relates to a high-temperature high-pressure synthesis method of a perovskite structure germanate high-purity crystal, in particular to a technical method for preparing a high-purity cubic perovskite structure lead germanate crystal from glassy lead germanate under the condition of high temperature and high pressure.
Background
The germanate crystal has various structural polytypes such as monoclinic, tetragonal, trigonal, hexagonal and cubic under different temperature and pressure conditions, a wide band gap and high electron mobility. The rare earth doped perovskite structure germanate has good long afterglow luminescence, and is widely applied to the fields of high-power and medium-long wave laser preparation, military detection, laser medical treatment and the like. In order to accurately obtain the lattice parameters of the germanate with the perovskite structure and deeply research the structural phase change nature and the physical characteristics of various phases, the high-purity germanate crystal is strongly expected to be prepared in the scientific field. The application avoids the conventional technical method for synthesizing the crystal by using the high-temperature sintering of the crystal, is beneficial to synthesizing a high-purity crystal material by using a laser heating method of an amorphous material under a high-pressure condition on the basis of the structural characteristics of long-range order and short-range order of the crystal, and provides a new technical method for synthesizing a high-purity germanate crystal sample under a high pressure.
Disclosure of Invention
In view of the problems of the prior art, the present invention aims to provide a technical method for transforming the amorphous phase of the material into the high-purity crystalline phase.Firstly, synthesizing glassy lead germanate by normal pressure high temperature rapid quenching, and then preparing high purity cubic perovskite structure lead germanate (PbGeO) by laser heating under high pressure condition 3 )。
In order to achieve the technical purpose, the invention is specifically realized by the following technical scheme:
the invention provides a method for preparing lead germanate glass by normal-pressure high-temperature rapid quenching; on the other hand, the method for synthesizing the high-purity cubic perovskite PbGeO by applying the glassy lead germanate under the conditions of high temperature and high pressure 3 A method for producing crystals.
The lead germanate glass and the high-purity lead germanate (PbGeO) with a cubic perovskite structure 3 ) The crystals were prepared by the following method:
1) lead germanate crystal (PbGeO) with monoclinic structure 3 ) Or lead oxide (PbO) and germanium dioxide (GeO) 2 ) The mixture is used as a raw material, and the lead germanate glass is synthesized by high-temperature rapid quenching under the normal pressure condition;
2) PbGeO in glass state 3 Pressing the powder into a round cake, placing the round cake and ruby particles in a solid argon environment, and pressurizing to 35-40 GPa;
3) heating to 1200-1500 ℃ by using a laser double-sided heating system, keeping the temperature for 20-30 min, and quenching to room temperature to obtain the high-purity cubic perovskite PbGeO 3 And (4) crystals.
The solid argon is obtained by condensing argon through liquid nitrogen.
Preferably, the laser double-sided heating system provided by the invention is heated to 1200 ℃.
The invention has the beneficial effects that:
the invention utilizes PbGeO with normal pressure and high temperature 3 The melt flows out of the vertical muffle furnace (separated from the high-temperature container), and the melt is rapidly cooled and synthesized into PbGeO when meeting liquid nitrogen or fluid water stored at the bottom end of the furnace 3 And (3) glass. Glassy state of PbGeO 3 Crystallizing under high temperature and high pressure to obtain high purity cubic perovskite structure polycrystal. This is a process for preparing alkaline earth germanates of perovskite structure (e.g. CaGeO) 3 、SrGeO 3 And BaGeO 3 ) Is provided withThe technical example provides technical support for structural research, physical property detection and device preparation of various high-purity germanate functional materials.
Drawings
FIG. 1 shows the fast quenching preparation of glassy PbGeO in example 1 of the present invention 3 Raman signatures at normal and high pressures;
FIG. 2 shows a glass state of PbGeO in example 1 of the present invention 3 High-purity cubic perovskite structure PbGeO synthesized by laser heating under high pressure condition 3 Diffraction spectra.
FIG. 3 shows a PbGeO glass state in example 2 of the present invention 3 Diffraction spectra at 10GPa with laser heating.
FIG. 4 shows crystalline PbGeO in example 3 of the present invention 3 Diffraction spectra at 10GPa with laser heating.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to specific embodiments of the present invention, and it should be understood 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.
Example 1 preparation of PbGeO from a glassy state 3 Synthesizing high-purity cubic perovskite structure PbGeO by using raw materials 3 。
Lead germanate crystal (PbGeO) with monoclinic structure 3 ) Or the molar ratio is 1.005: 1 lead oxide (PbO) and germanium dioxide (GeO) 2 ) The mixture is used as raw material. After thorough mixing and grinding, the mixture is pressed into a round cake and then is put into a platinum crucible with a sample capable of being poured. After the sample was transferred to a vertical muffle furnace, the sample was heated to 660 ℃ at a rate of 10 ℃ per minute and held at that temperature for 4 hours. And opening a heat insulation plug at the bottom end of the vertical muffle furnace and placing a liquid nitrogen container below the heat insulation plug. And quickly pouring the lead germanate melt into liquid nitrogen to obtain a quenching sample. Characterization of the sample by Raman and X-ray diffraction as glassy PbGeO 3 。
PbGeO in glass state 3 Powder compactionA small round cake with a thickness of about 25 μm and a diameter of about 120 μm was prepared and filled into a metal cavity with a thickness of about 40 μm and a diameter of about 150 μm (the metal cavity was made of T301 stainless steel or rhenium plate and was formed by pressing a pair of diamond pairs with an anvil surface diameter of 400 μm). The method of condensing argon by using liquid nitrogen is characterized by that the argon gas is fed into PbGeO filled with glass state by means of condensing device 3 Powder and ruby particles (press marks), and solid argon is a pressure transmission medium and a heat insulation material. The method comprises the steps of applying the built laser double-sided heating system, carrying out high-pressure high-temperature treatment on a sample in a diamond pressure cavity in an environment with the pressure of 35-40 GPa, the temperature of 1200-1500 ℃ and the time of 20-30 min, and quenching to room temperature to synthesize the high-purity cubic perovskite structure PbGeO 3 。
FIG. 1 shows a glass state PbGeO prepared by rapid quenching in an embodiment of the invention 3 Raman signatures at normal and high pressures;
FIG. 2 shows a glass state of PbGeO in an example of the present invention 3 High-purity cubic perovskite structure PbGeO synthesized by laser heating under high pressure condition 3 A diffraction spectrum.
Example 2 comparative example
The glassy PbGeO obtained in example 1 3 The powder was pressed into small round cakes with a thickness of about 25 μm and a diameter of about 120 μm and loaded into metal cavities with a thickness of about 40 μm and a diameter of about 150 μm (the metal cavities were made of T301 stainless steel or rhenium plates pressed from a pair of diamond pairs with anvil faces of 400 μm diameter). The method of condensing argon by using liquid nitrogen is characterized by that the argon gas is fed into PbGeO filled with glass state by means of condensing device 3 Powder and ruby particles (press marks), and solid argon is a pressure transmission medium and a heat insulation material. Applying the constructed laser double-sided heating system, carrying out high-pressure high-temperature treatment on a sample in a diamond pressure cavity in an environment with the pressure of 10GPa, the temperature of 1200-1500 ℃ and the time of 20-30 min, and quenching to room temperature to synthesize PbGeO 3 The product, which was subjected to x-ray diffraction characterization, gave the results shown in FIG. 3, the disordered multimodal spectrum indicating that no cubic perovskite PbGeO structure was obtained 3 。
Example 3 comparative example
Crystalline PbGeO 3 (SG:P2/n,a＝11.460,b＝7.237,
β＝113.29°,
) Pressed into small round cakes having a thickness of about 25 μm and a diameter of about 120 μm and loaded into metal cavities having a thickness of about 40 μm and a diameter of about 150 μm (the metal cavities are made of T301 stainless steel or rhenium plates and are formed by pressing a pair of diamond pairs having anvil faces with a diameter of 400 μm). The method for condensing argon by using liquid nitrogen fills argon into PbGeO filled with glass state through a condensing device 3 Powder and ruby particles (press marks), and solid argon is a pressure transmission medium and a heat insulation material. The method comprises the steps of applying the built laser double-sided heating system, carrying out high-pressure high-temperature treatment on a sample in a diamond pressure cavity in an environment with the pressure of 10GPa, the temperature of 1200-1500 ℃ and the time of 20-30 min, and quenching to room temperature to synthesize PbGeO 3 The product, which was subjected to x-ray diffraction characterization, gave the results shown in FIG. 4, the disordered multimodal spectrum indicating that no cubic perovskite PbGeO structure was obtained 3 。
While the present invention has been described in detail by way of the foregoing embodiments, it should be understood that the above description should not be construed as limiting the invention. Various modifications and alterations to this invention will become apparent to those skilled in the art upon reading the foregoing description. Accordingly, the scope of the invention should be determined from the following claims.
Claims (5)
1. The preparation method of the high-purity lead germanate crystal with the cubic perovskite structure is characterized by comprising the following steps of: pressurizing and heating glassy lead germanate in an inert atmosphere environment, and then quenching to obtain high-purity lead germanate crystals with cubic perovskite structures; the pressurizing pressure is 35-40 GPa; the heating temperature is 1200-1500 ℃; the heating and pressurizing time is 20-30 min.
2. The method of claim 1, wherein: the preparation of the glassy lead germanate comprises the following steps: and (3) carrying out high-temperature quenching on the raw material containing the germanium element, the oxygen element and the lead element under the normal pressure condition to obtain the glassy germanate.
3. The method of claim 2, wherein: when the glassy lead germanate is quenched at high temperature under normal pressure, the raw material melt obtained at high temperature is separated from the container thereof and then is cooled by rapid liquid nitrogen or water.
4. The production method according to claim 2, characterized in that: the raw material is a mixture of lead oxide and germanium dioxide.
5. The method of claim 4, wherein: the molar ratio of the lead oxide to the germanium dioxide is 1.005: 1.
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| RU2381201C1 (en) * | 2008-11-06 | 2010-02-10 | Федеральное государственное образовательное учреждение высшего профессионального образования "Сибирский федеральный университет" | Method for production of piezoceramics based on lead germanate |
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