CN107954604B - High-strength transparent germanate microcrystalline glass and preparation method thereof - Google Patents
High-strength transparent germanate microcrystalline glass and preparation method thereof Download PDFInfo
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- CN107954604B CN107954604B CN201711411332.9A CN201711411332A CN107954604B CN 107954604 B CN107954604 B CN 107954604B CN 201711411332 A CN201711411332 A CN 201711411332A CN 107954604 B CN107954604 B CN 107954604B
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- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
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Abstract
The invention relates to a high-strength transparent germanate microcrystalline glass and a preparation method thereof, wherein the microcrystalline glass comprises the following components in percentage by weight: GeO251～65%，Ga2O310～20%，SiO20～18%，BaO 5～12%，Y2O33～12%，ZrO22～8%，Na20.5-2% of O. Firstly, uniformly mixing raw materials according to the formula requirement, preparing germanate base glass by using a traditional melt cooling method, processing the annealed base glass into a proper specification, then carrying out heat treatment, forming a high-frequency electric field between the upper surface and the lower surface of a glass sample while carrying out high-temperature heat treatment, adjusting the heat treatment temperature and time and the field intensity, frequency and application time of the high-frequency electric field, and cooling the sample to obtain the high-strength transparent germanate microcrystalline glass containing nano-crystals in uniform distribution. The optical transmittance of the product is more than 78% within the range of 0.3-5.0 μm, and the bending strength can reach 106-125 MPa.
Description
Technical Field
The invention relates to the technical field of new materials, in particular to high-strength transparent germanate microcrystalline glass and a preparation method thereof, which can be applied to the fields of infrared optical windows and other infrared optical elements.
Background
The infrared detection technology is one of the important ways for obtaining information in the modern society, and the requirements on the infrared detection technology are more and more strict along with the rapid development of modern electronic information. In order to obtain high-definition infrared imaging, an infrared window material is required to have a wide infrared wave transmission range and a high infrared transmittance, and particularly, in the fields of infrared guidance, infrared countermeasure and the like, the window material is required to have a high transmittance within a range of 0.3-5.0 μm, and the window material is required to have the characteristics of high temperature resistance, wind and sand erosion resistance, excellent mechanical properties and the like. At present, a few materials can meet the condition, and commonly used materials comprise MgF2、ZnS、AlON、MgAl2O4Diamond, sapphire, etc., wherein MgF2Become opaque and develop surface cracks at temperatures above 500 ℃ in a humid environment; ZnS has low mechanical strength and poor wear resistance, can generate oxidation phenomenon when the use temperature is more than 300 ℃, and can soften when the use temperature is more than 500 ℃; AlON and MgAl2O4The preparation process is immature, and the optical transmittance of the material is difficult to meet the requirement; sapphire is difficult to process and high in cost, and the mechanical property is obviously reduced when the use temperature exceeds 700 ℃; diamond is not only expensive, but also cannot prepare large-size elements, and the phenomenon of high-temperature oxidation is severe. Thus, strictly speaking, there is still no ideal oneThe infrared optical window is made of wave-transmitting material.
The germanate glass is a novel infrared wave-transmitting material, has high optical transmittance within the range of 0.3-5.0 mu m, and good chemical stability and high temperature resistance, but the mechanical property of the germanate glass still cannot meet the actual use requirement, the bending strength of the common germanate glass is only about 60MPa, and the use of industrial application requires more than 100MPa, so that the premise of realizing the industrial application is to improve the mechanical strength of the germanate glass material. The mechanical strength of germanate glass can be obviously improved by performing heat treatment on the germanate glass to convert the germanate glass into microcrystalline glass, however, fine crystal grains formed in the heat treatment process are easy to aggregate and grow, and when the size of the microcrystalline is more than 50 nanometers, the transmittance of the microcrystalline glass to visible light is obviously reduced, so that the practical use performance of the microcrystalline glass is influenced. The key to promoting the practicability of the germanate glass is how to ensure that the formed microcrystals are uniformly and dispersedly distributed in the glass matrix without agglomeration in the heat treatment process, so that the mechanical strength of the germanate glass is obviously improved on the basis of not influencing the optical performance of the germanate glass.
Disclosure of Invention
The invention aims to solve the technical problem of providing high-strength transparent germanate microcrystalline glass and a preparation method thereof, wherein the problem of agglomeration of microcrystals in the microcrystalline heat treatment process of germanate glass is solved, and the mechanical strength of the high-strength transparent germanate microcrystalline glass can be obviously improved.
In order to solve the technical problems, the technical scheme of the invention is as follows: the high-strength transparent germanate microcrystalline glass is characterized by comprising the following components in percentage by weight: GeO251～65%，Ga2O310～20%，SiO20～18%，BaO 5～12%，Y2O33～12%，ZrO22～8%，Na2O 0.5～2%。
The preparation method of the high-strength transparent germanate microcrystalline glass is characterized by comprising the following steps: the method comprises the steps of weighing and uniformly mixing the microcrystalline glass raw materials according to the weight percentage, and then carrying out melting, annealing and microcrystallization treatment to obtain the germanate microcrystalline glass.
The technological parameters of the melting process are that the melting temperature is 1300-1550 ℃, and the melting heat preservation time is 1.0-3.0 hours.
The annealing process has the technological parameters that the annealing temperature is 500-650 ℃, and the annealing time is 1.0-2.0 hours.
The technical parameters of the micro crystallization treatment process are that the nucleation temperature is 650-800 ℃, and the nucleation time is 1.0-2.0 hours; the crystallization temperature is 900-1100 ℃, and the crystallization time is 1.0-2.0 hours; a variable-frequency high-voltage electric field is applied to a glass sample in the crystallization process, the electric field intensity is 2000-8000V/cm, the frequency is 50 Hz, and no electric field is applied in the temperature rising and reducing process.
The electric furnace used in the microcrystallization treatment process is externally connected with a high-voltage variable-frequency power supply, the upper surface and the lower surface of a glass sample are respectively provided with a high-temperature-resistant positive electrode plate and a high-temperature-resistant negative electrode plate outside 1cm, the electrode plates are respectively connected with a high-voltage power supply input circuit, the power supply output voltage is adjustable from 0V to 50000V and can be set to 50 Hz power frequency output or DC output, and the electric field auxiliary heat treatment experiment cavity is provided with a vacuumizing device so as to prevent ions in the air from transferring electricity under the condition of a high-.
The invention properly adjusts the composition of the germanate glass on the basis of the existing formula of the germanate glass, simultaneously changes the heat treatment process conditions, and innovatively adopts an electric field auxiliary heat treatment mode to realize the microcrystallization of the germanate glass, so that the energy source of the germanate glass for overcoming the crystallization activation energy in the high-temperature heat treatment process not only provides heat energy for high temperature, but also comes from the electric field energy of a high-voltage electric field. Because ions in the structure can diffuse and migrate in a certain range during the high-temperature heat treatment process of the glass, the migrated ions are charged, and the charges inevitably form directional movement under the action of an electric field. When the applied electric field is an electrostatic field, positive ions in the glass structure are directionally transferred towards the negative electrode direction. If the applied electric field is a high-frequency alternating electric field, the movement direction of the ions is influenced by the direction of the electric field and may be the same as or opposite to the diffusion direction of the ions, so that the diffusion and migration rate of the ions can be promoted or inhibited, and the actual control of the microcrystalline growth process is realized. Because of strong repulsive force between two positively charged ions under the action of an electric field, the two positively charged ions are difficult to advance and retreat together under the condition of a high-temperature electric field, the agglomeration of crystal nuclei in the forming process can be inhibited, the dispersed growth of crystals is realized, the problem of the agglomeration of microcrystals in the microcrystallization heat treatment process of the germanate glass is solved, and the mechanical strength of the germanate glass is obviously improved on the premise of not obviously influencing the optical performance of the germanate glass.
The invention has the following beneficial effects:
(1) the germanate microcrystalline glass prepared by the method has good optical transmittance in a visible light region, a near infrared region and a middle infrared region, and the optical transmittance is more than 78% in a range of 0.3-5.0 mu m;
(2) the bending strength of the germanate microcrystalline glass prepared by the method can reach 106-125 MPa;
(3) the crystallite dimension of the high-strength transparent germanate microcrystalline glass prepared by the method is less than 50nm, and the crystalline grains are well dispersed in the parent glass, so that the scattering effect on incident light is small, and the optical transmittance of the material is improved.
Detailed Description
To further illustrate the technical means and effects of the present invention for achieving the predetermined objects, the following detailed description of the embodiments, methods, steps, features and effects of the high strength transparent germanate microcrystalline glass and the preparation method thereof according to the present invention with reference to the preferred embodiments is as follows:
the first embodiment is as follows:
the embodiment is a high-strength transparent germanate microcrystalline glass and a preparation method thereof, and the method comprises the following steps:
(1) the germanate base glass in the process comprises the following components in parts by weight: GeO252%，Ga2O315%，SiO215%，BaO 6%，Y2O38%，ZrO23%，Na2O 1%。
(2) The raw materials of the germanate base glass with the components are accurately weighed and uniformly mixed, and then are melted in an electric furnace, wherein the melting temperature is 1450 ℃, and the melting and heat preservation time is 1.5 hours; the annealing temperature was 550 ℃ and the annealing time was 2.0 hours.
(3) The process conditions of the electric field assisted heat treatment are as follows: the nucleation temperature is 720 ℃, and the nucleation time is 1.0 hour; the crystallization temperature is 950 ℃, and the crystallization time is 1.0 hour; applying high-voltage alternating electric fields on the upper surface and the lower surface of the glass sample at 950 ℃, wherein the frequency is 50 Hz, the electric field intensity is 5000V/cm, and after 1 hour of heat treatment, stopping heating and simultaneously stopping applying the electric fields.
(4) The optical transmittance of the prepared germanate microcrystalline glass is 79% (no hydroxyl absorption region) within the range of 0.3-5.0 mu m, and the bending strength is 112 MPa.
Example two:
the embodiment is a high-strength transparent germanate microcrystalline glass and a preparation method thereof, and the method comprises the following steps:
(1) the germanate base glass in the process comprises the following components in parts by weight: GeO260.5%，Ga2O312%，SiO28%，BaO 7%，Y2O35%，ZrO26%，Na2O 1.5%。
(2) The raw materials of the germanate base glass with the components are accurately weighed and uniformly mixed, and then are melted in an electric furnace, wherein the melting temperature is 1520 ℃, and the melting and heat preservation time is 1.0 hour; the annealing temperature was 570 ℃ and the annealing time was 1.5 hours.
(3) The process conditions of the electric field assisted heat treatment are as follows: the nucleation temperature is 750 ℃, and the nucleation time is 1.5 hours; the crystallization temperature is 990 ℃, and the crystallization time is 1.5 hours; applying high-voltage alternating electric fields on the upper surface and the lower surface of the glass sample at 990 ℃, wherein the frequency is 50 Hz, the electric field intensity is 6500V/cm, and stopping heating and simultaneously stopping applying the electric fields after 1.5 hours of heat treatment.
(4) The optical transmittance of the prepared germanate microcrystalline glass is 81.5% (no hydroxyl absorption region) within the range of 0.3-5.0 mu m, and the bending strength is 124 MPa.
Example three:
the embodiment is a high-strength transparent germanate microcrystalline glass and a preparation method thereof, and the method comprises the following steps:
(1) germanium in the processThe acid salt base glass comprises the following components in parts by weight: GeO265%，Ga2O318.5%，SiO23%，BaO 8%，Y2O33%，ZrO22%，Na2O 0.5%。
(2) The raw materials of the germanate base glass with the components are accurately weighed and uniformly mixed, and then are melted in an electric furnace, wherein the melting temperature is 1350 ℃, and the melting and heat preservation time is 2.0 hours; the annealing temperature was 600 ℃ and the annealing time was 1.5 hours.
(3) The process conditions of the electric field assisted heat treatment are as follows: the nucleation temperature is 820 ℃, and the nucleation time is 2.0 hours; the crystallization temperature is 990 ℃, and the crystallization time is 1.5 hours; applying high-voltage alternating electric fields on the upper surface and the lower surface of the glass sample at 910 ℃, wherein the frequency is 50 Hz, the electric field intensity is 7500V/cm, and after 2.0 hours of heat treatment, stopping heating and simultaneously stopping applying the electric fields.
(4) The optical transmittance of the prepared germanate microcrystalline glass is 83% (no hydroxyl absorption region) within the range of 0.3-5.0 mu m, and the bending strength is 120 MPa.
Claims (3)
1. The high-strength transparent germanate microcrystalline glass is characterized by comprising the following components in percentage by weight: GeO251～65%，Ga2O310～20%，SiO20～18%，BaO 5～12%，Y2O33～12%，ZrO22～8%，Na2O0.5～2%；
The bending strength of the germanate microcrystalline glass is 106-125 MPa, and the size of a microcrystal in the germanate microcrystalline glass is less than 50 nm;
the preparation method of the high-strength transparent germanate microcrystalline glass comprises the steps of weighing and uniformly mixing microcrystalline glass raw materials according to weight percentage, and then carrying out melting, annealing and microcrystallization treatment to obtain germanate microcrystalline glass;
the technical parameters of the micro crystallization treatment are that the nucleation temperature is 650-800 ℃, and the nucleation time is 1.0-2.0 hours; the crystallization temperature is 900-1100 ℃, and the crystallization time is 1.0-2.0 hours; a variable-frequency high-voltage electric field is applied to a glass sample in the crystallization process, the electric field intensity is 2000-8000V/cm, the frequency is 50 Hz, and no electric field is applied in the temperature rising and reducing process.
2. The high strength transparent germanate microcrystalline glass according to claim 1, characterized in that: the melting process parameters are that the melting temperature is 1300-1550 ℃, and the melting heat preservation time is 1.0-3.0 hours.
3. The high strength transparent germanate microcrystalline glass according to claim 1, characterized in that: the annealing process parameters are that the annealing temperature is 500-650 ℃, and the annealing time is 1.0-2.0 hours.
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