A silicate glass with high zirconium oxide content and its preparation method and application

Abstract

The present invention discloses a silicate glass with a high zirconium oxide content, a preparation method and an application thereof, wherein the glass comprises the following components in percentage by weight: 39-49% SiO 2 , 0.5‑5%Al 2 O 3 , 6‑11% B 2 O 3 , 0.5‑1.9%Na 2 O, 1‑3% CaO, 15‑19% ZrO 2 , 1‑3% TiO 2 , 4‑10% Gd 2 O 3 , 11‑17% Y 2 O 3 . The present invention also provides a method for preparing silicate glass with a high zirconium oxide content, comprising the following steps: (1) glass batching: first subjecting the glass raw materials to a high-temperature burning and dehydration treatment, and then batching according to the weight percentage of each component; (2) glass melting: placing the mixture into a platinum crucible and heating and melting it; (3) material leaking molding: after the glass is evenly melted, pour it into a preheated mold for casting and molding, and after annealing and cooling, a silicate glass material with a high zirconium oxide content is obtained. The silicate glass with a high zirconium oxide content prepared by the present invention can be used to prepare optical window glass and pressure-resistant and temperature-resistant optical containers.

Description

Technical Field

[0001] The invention relates to the technical field of special glass materials and preparation thereof, and in particular to silicate glass with high zirconium oxide content and a preparation method and application thereof. Background Art

[0002] Introducing a certain amount of ZrO into silicate glass 2 , can significantly improve the chemical stability and mechanical properties of glass such as acid resistance, alkali resistance, water resistance, etc. However, the introduction of ZrO 2 While improving the above properties of glass materials, it will also bring many problems, such as the increase in glass melting temperature, the increase in glass high temperature viscosity leading to difficulty in removing bubbles, and the increase in the tendency of glass crystallization, which seriously affects the performance and quality of the glass. 2 The content of ZrO is generally controlled below 5wt.%, so that the glass 2 The use of ZrO is limited. However, with the advancement of science and technology and the improvement of industrial level, low ZrO 2 The performance of glass with high ZrO content cannot meet the requirements of high-tech development, especially in the field of optical glass with high requirements for high temperature and high pressure resistance and chemical stability, such as high temperature and high pressure window glass, sodium vapor resistant lampshade glass, etc. Therefore, it is urgent to develop high ZrO 2 Content of silicate glass.

[0003] Preparation of ZrO in the prior art 2 The method of preparing silicate glass with a content of more than 5wt.% is mainly to increase the glass melting temperature, prolong the glass clarification time or use a method with a high boron oxide or high alkali metal content. 2 In the glass with a content of more than 5wt.%, the glass melting viscosity is reduced mainly by high content of boron oxide fluxing or high content of alkali metal oxides destroying the glass network structure, and the ZrO content of the silicate glass prepared by these schemes is 2 The content is generally controlled at 5-10wt.%, but high boron oxide or high alkali metal content will significantly reduce the chemical stability of the glass and is only suitable for low viscosity glass melting. 2 Silicate glasses with a content of ≥15wt.% still have problems such as poor glass melting uniformity, easy crystallization of glass, and difficulty in engineering preparation. Summary of the invention

[0004] The purpose of the present invention is to overcome the shortcomings of the current prior art and provide a ZrO 2 A silicate glass with a high zirconium oxide content of more than 15 wt.%, excellent chemical stability, suitable thermal expansion coefficient, high glass transition temperature, excellent mechanical properties and the like, and a preparation method thereof.

[0005] The present invention also provides an application of silicate glass with a high zirconium oxide content. The silicate glass with a high zirconium oxide content has good chemical corrosion resistance and is suitable for high temperature and high pressure resistant optical windows, optical glass, window glass, pressure and temperature resistant optical containers, optoelectronic substrate glass, chemical industry observation windows, video or camera lenses, special glass fibers, etc.

[0006] In order to achieve the above object, the technical solution adopted by the present invention is:

[0007] A silicate glass with a high zirconium oxide content, comprising the following components in percentage by weight:

[0008]

[0009] Further, a silicate glass with a high zirconium oxide content is characterized in that it preferably includes the following components in percentage by weight:

[0010]

[0011]

[0012] A silicate glass with a high zirconium oxide content, characterized in that the silicate glass with a high zirconium oxide content substantially does not contain [OH] - Even if ions are present, they are brought in by impurities in the raw materials or preparation process. Strictly controlling the hydroxyl content in the glass has improved the optical and mechanical properties of the glass.

[0013] The present invention also provides a method for preparing silicate glass with a high zirconium oxide content, which is characterized by comprising the following steps:

[0014] (1) Glass batching: Before batching, the glass raw materials are subjected to high-temperature burning and dehydration treatment, and then the high-purity raw materials are proportioned according to the designed components. According to the weight percentage of each component, the corresponding raw material weight is converted, and then each raw material is weighed. Among them, ZrO 2 The components are introduced by nano-scale zirconium silicate powder, without using zirconium dioxide.

[0015] (2) Glass melting: The glass batch materials are cooled, ground and mixed to form a mixture, and the mixture is placed in a platinum crucible and then heated in a glass melting furnace at 1560°C-1600°C for 4 to 8 hours; the glass mixture is melted in an oxidizing atmosphere, and the glass melt needs to be stirred several times during the melting process to make the glass melt uniform;

[0016] (3) Leakage molding: After the glass is evenly melted, the molten glass is poured into a specified shape and then placed in an annealing furnace for annealing at a temperature of 650-670°C for 6-10 hours. The glass is then cooled to room temperature in the furnace, and a silicate glass material with a high zirconium oxide content is obtained by cooling.

[0017] Furthermore, the zirconium silicate is a nano-scale powder with an average particle size of 50 nm. The zirconium silicate powder raw material needs to be stabilized before being used in glass batching, including powder homogenization and removal of harmful impurities such as Fe 2 O 3 wait.

[0018] Furthermore, the glass raw materials are subjected to a high-temperature burning dehydration treatment at 610-700° C., the dehydration treatment time is 12-23 hours, and the moisture and hydroxyl content of the raw materials are strictly controlled.

[0019] Furthermore, the glass is melted in an oxidizing atmosphere, that is, dry oxygen is blown into the molten glass using a platinum tube, and the flow rate of the oxygen blown is 0.9-1.5 L / min.

[0020] Furthermore, the discharge temperature in the leakage molding step is 1400°C-1450°C.

[0021] Compared with the prior art, the silicate glass with high zirconium oxide content described in the present invention adopts a low-alkali formula and has the following advantages:

[0022] (1) High ZrO 2 Component content, ZrO in the silicate glass with high zirconium oxide content provided by the present invention 2 The component content is 15-19%;

[0023] (2) It has excellent chemical stability, with water resistance of Class I, acid resistance of Class II or above, and alkali resistance of Class I;

[0024] (3) It has excellent thermal properties, with a thermal expansion coefficient of (57-75)×10 at 30-300°C. －7 / ℃, glass transition temperature T g Greater than 650℃, good thermal shock resistance;

[0025] (4) It has excellent mechanical properties and its flexural strength is greater than 300MPa.

[0026] The present invention also provides an application of silicate glass with a high zirconium oxide content. The silicate glass with a high zirconium oxide content has good chemical corrosion resistance and is suitable for high temperature and high pressure resistant optical windows, optical glass, window glass, pressure and temperature resistant optical containers, optoelectronic substrate glass, chemical industry observation windows, video or camera lenses, special glass fibers, etc.

[0027] In the present invention, SiO 2 It is the main component of the glass skeleton structure and plays a major role in the glass skeleton. 2 The weight percentage (wt.%) is 39-49%. SiO 2 The content of SiO is lower than 39wt.%, which makes it difficult to obtain glass with excellent thermal stability and reduces the chemical resistance of the glass. 2 When the content is higher than 49wt.%, the high temperature viscosity of the glass will increase, resulting in the glass melting temperature being too high and the chemical resistance being reduced.

[0028] Al 2 O 3 It is an intermediate oxide of glass and its content cannot be too high. 2 O 3 It is introduced by alumina powder instead of aluminum hydroxide. The chemical bond strength of Al-O is smaller, which is beneficial to improve the transmittance performance of the glass. When there is enough oxygen in the glass, by introducing an appropriate amount of Al 2 O 3 , forming aluminum oxide tetrahedron [AlO 4 ], can repair the internal broken network structure, and form a continuous, uniform and unified network with silicon-oxygen tetrahedron, so that the broken network in the glass is reduced, which is beneficial to improve the chemical resistance and stability of the glass, and at the same time is beneficial to reduce the tendency of glass crystallization. 2 O 3 The weight percentage is 0.5-5wt.%, Al 2 O 3 When the content of Al is less than 0.5wt.%, the chemical stability and mechanical properties of the glass will be reduced. 2 O 3 The content of is higher than 5wt.%, which will increase the high-temperature viscosity of the glass and cause the glass melting temperature to be too high.

[0029] B 2 O 3 It is an oxide that forms glass and is also a component of the glass skeleton. It is also a flux that reduces the viscosity of the glass melt. In an oxidizing atmosphere, B 3+ There is a free oxygen abstraction to form a boron-oxygen tetrahedron [BO 4 ] trend, making the glass structure more compact, thereby improving the chemical resistance of the glass. 2 O3 The weight percentage is 6-11wt.%, B 2 O 3 When the content is less than 6wt.%, it cannot play a role in fluxing. 2 O 3 A content higher than 11 wt.% will reduce the chemical stability of the glass.

[0030] Na 2 O is an oxide outside the glass structure network, which can increase ZrO 2 Melting content in glass, Na 2 The weight percentage of O is 0.5-1.9wt.%, Na 2 When the content of O is greater than 1.9 wt.%, the chemical resistance of the glass may be reduced.

[0031] CaO is an external oxide of the glass structure network, and the weight percentage of CaO is 1-3wt.%. If the CaO content is lower than 1wt.%, the glass forming ability will be reduced. If the CaO content is higher than 3wt.%, the chemical resistance of the glass will be reduced and the crystallization tendency of the glass will be increased.

[0032] ZrO 2 The introduction of ZrO is to enhance the chemical resistance and mechanical properties of glass. 2 The weight percentage is 15-19wt.%ZrO 2 When the amount of ZrO introduced is less than 15wt.%, it is difficult to obtain glass with excellent chemical resistance and excellent mechanical properties. 2 When the amount of introduction is greater than 19wt.%, it will make the glass melting difficult and increase the crystallization tendency of the glass.

[0033] T i 2 It is used to lower the crystallization temperature of glass. 4+ When combined with alkaline earth metal oxides, they can capture free oxygen to form [TiO 4 ] uniform network, which reduces the number of broken networks in the glass and is beneficial to reducing crystallization; TiO 2 The weight percentage is 1-3wt.%, TiO 2 When the content is greater than 3wt.%, the mechanical properties of the glass will be reduced.

[0034] G 2 O 3 It is a rare earth oxide, Gd 3+ The large ion radius and strong electric field produce a strong aggregation effect in the glass, which can increase the mass of cations and improve the chemical stability of the glass. 2 O 3 The weight percentage is 4-10wt.%, Gd2 O 3 The content of Gd is less than 4wt.%, which will reduce the chemical resistance and mechanical properties of the glass. 2 O 3 When the content is greater than 10 wt.%, the thermal expansion coefficient of the glass will increase and the transition temperature of the glass will decrease.

[0035] Y 2 O 3 It can increase the mass of cations, reduce the number of non-bridging oxygen in the glass network structure, strengthen the glass network structure, and make the atomic arrangement in the glass structure more compact, which can significantly improve the bending strength and mechanical properties of the glass. 2 O 3 The weight percentage is 11-17wt.%, Y 2 O 3 The content of Y is less than 11wt.%, which will reduce the mechanical properties of the glass. 2 O 3 When the content is greater than 17 wt.%, the chemical resistance of the glass will be reduced.

[0036] The silicate glass with high zirconium oxide content described in the present invention substantially does not contain [OH] - Here, “substantially free of a specific component” means that it is not intentionally added, and does not exclude extremely small amounts of impurities that are inevitably mixed in from raw material impurities, etc., but the amount contained will not affect the desired properties. Even if an extremely small amount is contained, it is brought in by other glass raw materials.

[0037] The present invention successfully prepares a silicate glass material with high zirconium oxide content, which has the advantages of excellent chemical stability, suitable thermal expansion coefficient, high glass transition temperature, excellent mechanical properties and the like.

[0038] The present invention also provides an application of silicate glass with a high zirconium oxide content. The silicate glass with a high zirconium oxide content has good chemical corrosion resistance and is suitable for high temperature and high pressure resistant optical windows, optical glass, window glass, pressure and temperature resistant optical containers, optoelectronic substrate glass, chemical industry observation windows, video or camera lenses, special glass fibers, etc. DETAILED DESCRIPTION

[0039] In order to make the purpose, technical solution and advantages of the present invention clearer, the implementation mode of the present invention is further described in detail below. However, the specific embodiments given by the applicant cannot and should not be regarded as limitations on the technical solution of the present invention. Any changes to the definitions of components or technical features and / or formal but not substantial changes to the overall structure should be regarded as the scope of protection defined by the technical solution of the present invention.

[0040] Table 1 lists in detail the glass chemical composition (wt. %) and glass chemical resistance of the examples.

[0041] First, glass raw materials are selected according to the glass composition of the embodiment in Table 1 for batching, wherein the raw materials are acid-washed quartz sand (150 μm sieve oversize is less than 1%, 45 μm sieve undersize is less than 30%, Fe2O3 content is less than 0.01wt.%), aluminum oxide powder (analytical pure, average particle size 50 μm), anhydrous boric acid (analytical pure, 400 μm sieve oversize is less than 10%, 63 μm sieve undersize is less than 10%), sodium carbonate (analytical pure, average particle size 50 μm), calcium nitrate (analytical pure, average particle size 250 μm), nano zirconium silicate (analytical pure, average particle size 50 μm), titanium oxide (analytical pure, average particle size 50 μm), gadolinium oxide (5N, average particle size 50 μm), yttrium oxide (5N, average particle size 50 μm), Fe in the glass raw materials 2 O 3 Strict control is carried out and the requirement is less than 100PPm. The clarifier uses a conventional clarifier in a conventional amount, such as antimony trioxide.

[0042] Among them, the thermal expansion coefficient and glass transition temperature of the glass were tested with reference to the method of GB / T 7962.16-2010 "Test method for colorless optical glass Part 16: Linear expansion coefficient, transition temperature and sag temperature"; the flexural strength of the glass was tested with reference to GB / T 37781-2019 "Test method for flexural strength of glass materials"; the water resistance stability of silicate glass with high zirconium oxide content was tested with reference to the method of GB / T 6582-2021 "Test method and classification of water resistance of glass particles at 98°C"; the acid resistance stability of silicate glass with high zirconium oxide content was tested with reference to the method of GB / T 15728-2021 "Weight test method and classification of glass resistance to boiling hydrochloric acid corrosion"; the alkali resistance stability of silicate glass with high zirconium oxide content was tested with reference to the method of GB / T 6580-2021 "Test method and classification of glass resistance to corrosion by boiling mixed alkali aqueous solution".

[0043] Table 1 Chemical composition (wt.%) and glass properties of the examples

[0044]

[0045] Example 1

[0046] The glass raw materials were selected according to the components of Example 1 and prepared, and subjected to high-temperature calcination dehydration treatment at 610°C for 23 hours to reduce the moisture and hydroxyl content of the glass raw materials. The moisture and hydroxyl content of the raw materials were strictly controlled, and then the high-purity raw materials were proportioned according to the glass chemical composition of Table 1, and then the raw materials were weighed, ground and mixed evenly to form a mixture, and the mixture was placed in a platinum crucible, and then placed in a glass melting furnace at 1600°C and heated for 4 hours; the glass mixture was melted in an oxidizing atmosphere, and Oxygen is blown into the glass melt with a platinum tube at a flow rate of 0.9 L / min; the glass melt is stirred 2 to 3 times during the glass melting process to make it uniform; after the glass is melted uniformly, the molten glass is cooled to 1450°C and poured into a preheated heat-resistant steel mold to be cast into a specified test sample required to be formed, and then placed in an annealing furnace for annealing treatment at a temperature of 670°C for 6 hours, and a silicate glass material with a high zirconium oxide content is obtained with furnace cooling. Its test performance is shown in Table 1 Example 1.

[0047] Example 2

[0048] The actual composition of the glass is shown in Table 1 Example 2. The same raw materials and raw material requirements as those in Example 1 are used, and the raw materials are subjected to a high-temperature calcination dehydration treatment at 700°C for 12 hours, and a melting process system of melting at 1560°C for 8 hours. Oxygen is blown into the molten glass using a platinum tube, and the flow rate of oxygen blown is 1.5L / min. After the glass is evenly melted, the molten glass is cooled to 1430°C and poured into a preheated heat-resistant steel mold to be cast into the specified test sample requirements, and then placed in an annealing furnace for annealing treatment. The annealing temperature is 650°C, and the annealing time is 10 hours. A silicate glass material with a high zirconium oxide content is obtained as the furnace cools. The same test conditions as in Example 1 are used, and its test performance is shown in Table 1.

[0049] As shown in Example 2.

[0050] Example 3

[0051] The actual composition of the glass is shown in Table 1 Example 3. The same raw materials and raw material requirements as those in Example 1 are used, and the glass raw materials are subjected to high-temperature burning and dehydration treatment at 650°C for 18 hours to reduce the moisture and hydroxyl content of the glass raw materials, and the moisture and hydroxyl content of the raw materials are strictly controlled. In addition, a melting process system of melting at 1580°C for 6 hours is adopted, and oxygen is blown into the glass melt using a platinum tube, and the flow rate of oxygen blowing is 1.2L / min. After the glass is melted uniformly, the molten glass liquid is cooled to 1400°C and the material is poured into a preheated heat-resistant steel mold to be cast into the specified test sample requirements, and then placed in an annealing furnace for annealing treatment, using an annealing temperature of 660°C, an annealing time of 8 hours, and the same test conditions as those in Example 1. Its test performance is shown in Table 1 Example 3.

[0052] Example 4

[0053] The actual composition of the glass refers to Example 4 in Table 1. The same raw materials and raw material requirements as those in Example 1 are used, and the same melting process system, annealing process system and test conditions are adopted. Its test performance is shown in Example 4 in Table 1.

[0054] Example 5

[0055] The actual composition of the glass refers to Example 5 in Table 1, using the same raw materials and raw material requirements as Example 1, and adopting the same melting process system, annealing process system and test conditions. Its test performance is shown in Example 5 in Table 1.

[0056] The present invention successfully prepares a silicate glass material with high zirconium oxide content, which has the advantages of excellent chemical stability, suitable thermal expansion coefficient, high glass transition temperature, excellent mechanical properties and the like.

[0057] The present invention also provides an application of silicate glass with a high zirconium oxide content. The silicate glass with a high zirconium oxide content has good chemical corrosion resistance and is suitable for high temperature and high pressure resistant optical windows, optical glass, window glass, pressure and temperature resistant optical containers, optoelectronic substrate glass, chemical industry observation windows, video or camera lenses, special glass fibers, etc.

[0058] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims

1. A silicate glass with a high zirconium oxide content, characterized in that: The composition comprises the following weight percentages:

2. A silicate glass with a high zirconium oxide content according to claim 1, characterized in that: Contains virtually no [OH] - Even if ions are present, they are brought in by impurities from the raw materials or during the preparation process. The hydroxyl content in the glass is strictly controlled.

3. The method for preparing a silicate glass with a high zirconium oxide content according to claim 1, characterized in that: The following steps are involved: (1) Glass batching: Before batching, the glass raw materials are subjected to high-temperature burning and dehydration treatment, and then the high-purity raw materials are proportioned according to the designed components. The corresponding raw material weight is converted according to the weight percentage of each component, and then each raw material is weighed. The ZrO2 component is introduced by nano-scale zirconium silicate powder, and zirconium dioxide is not used; (2) Glass melting: The glass batch materials are cooled, ground and mixed to form a mixture, which is then placed in a platinum crucible and heated in a glass melting furnace at 1560°C-1600°C for 4 to 8 hours. The glass mixture is melted in an oxidizing atmosphere, and the molten glass needs to be stirred several times during the melting process to make the molten glass uniform. (3) Leakage molding: After the glass is evenly melted, the molten glass is poured into a specified shape and then placed in an annealing furnace for annealing at a temperature of 650-670°C for 6-10 hours. The glass is then cooled to room temperature with the furnace. A silicate glass material with a high zirconium oxide content is obtained by cooling.

4. The method for preparing silicate glass with high zirconium oxide content according to claim 3, characterized in that: The zirconium silicate is a nanometer-grade powder, and the average particle size of the powder is 50 nm.

5. The method for preparing silicate glass with high zirconium oxide content according to claim 3, characterized in that: The glass raw materials are subjected to high-temperature burning and dehydration treatment at 610-700° C. for 12-23 hours, and the moisture and hydroxyl content of the raw materials are strictly controlled.

6. The method for preparing silicate glass with high zirconium oxide content according to claim 3, characterized in that: The oxidizing atmosphere melting during the melting is to blow dry oxygen into the molten glass using a platinum tube, and the flow rate of the oxygen blown is 0.9-1.5 L / min.

7. The method for preparing silicate glass with high zirconium oxide content according to claim 3, characterized in that: The discharge temperature in the leakage molding step is 1400°C-1450°C.

8. Use of silicate glass with a high zirconium oxide content according to claim 1 or 2, characterized in that: The silicate glass with high zirconium oxide content is suitable for high temperature and high pressure resistant optical windows, optical glass, window glass, pressure and temperature resistant optical containers, optoelectronic substrate glass, chemical industry observation windows, video or camera lenses, and special glass fibers.

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