CN115521072A - A kind of sealing glass for tantalum metal and its preparation method - Google Patents

Abstract

The invention relates to electronic component sealing glass and a preparation method thereof, in particular to sealing glass for tantalum metal and a preparation method thereof, which are used for solving the defects of the existing tantalum metal sealing glass that the melting point and the sealing temperature are too high, the acid resistance and the chemical stability are poor, or radioactive elements, heavy metals and toxic and harmful elements are contained. The sealing glass for tantalum metal comprises SiO ₂ 、B ₂ O ₃ 、Al ₂ O ₃ 、BaO、K ₂ O、Na ₂ O、Fe ₂ O ₃ 、TiO ₂ 、ZrO、LiO ₂ And a rare earth element compound LaCePrZr which does not contain radioactive elements, heavy metals and toxic harmful elementsA peptide; the sealing glass has a thermal expansion coefficient close to that of metal, can be smoothly sealed with tantalum metal, and has the advantages of excellent thermal stability, strong acid resistance, easiness in forming and the like. Meanwhile, the invention provides a preparation method of the sealing glass for tantalum metal.

Description

A kind of sealing glass for tantalum metal and its preparation method

technical field

The invention relates to a sealing glass for electronic components and a preparation method thereof, in particular to a sealing glass for tantalum metal and a preparation method thereof.

Background technique

Liquid tantalum electrolytic capacitors have large capacitance, are not easy to break down, and have low internal resistance and small size. The demand has been growing. However, it contains highly corrosive gel sulfuric acid inside, if the seal is not good, it will leak out from the inside, which will corrode the surrounding electronic components and cause adverse effects on the entire electrical appliance. Therefore, liquid electrolyte tantalum capacitors require strict hermetic sealing with glass.

The existing research on sealing glass is mainly aimed at flat solid oxide fuel cells, and few people have studied the sealing glass with low expansion coefficient for tantalum capacitors. In addition, the existing sealing glass for electronic components contains a large amount of metallic lead, for example, the lead content of the existing electronic sealing glass brand DB-435 is 34%, and the lead content of DH-704 is 77%. But the heavy metal lead is not only harmful to the human body, but also does not meet the requirements of environmental protection.

Since the thermal expansion coefficient of glass is much smaller than that of metal, a large thermal stress will be generated inside the glass sealed with metal at high temperature, which makes the glass and metal materials unable to be directly sealed. The main difficulty of tantalum metal sealing technology is to produce glass materials with a thermal expansion coefficient closer to that of tantalum metal to achieve matching sealing between glass and tantalum metal materials. However, the greater the thermal expansion coefficient of the sealing glass material, the greater its stability and heat resistance. Therefore, the sealing glass needs to have a thermal expansion coefficient similar to that of tantalum metal while ensuring its excellent stability and strength.

The composition of the sealing glass directly affects its thermal expansion performance, operability, chemical stability and mechanical strength, and also affects its tightness with metal materials. U.S. Patent US3275359A discloses a sealing glass that can be initially used for sealing tantalum metals. The sealing glass is composed of BaO 35%, Al ₂ O ₃ 25%, and B ₂ O ₃ 40% by weight. The content of Al ₂ O ₃ in the composition is about 25%, the glass has too high melting point and sealing temperature, and its acid resistance and chemical stability are poor; Chinese patent CN102452794A discloses a crystalline low melting point sealing glass and its The preparation method, the crystalline sealing glass is composed of 50-70% of _SiO2 , 10-30% of ZnO, 1-10% of B2O3, 1-8% of CaO, 1-10% of Na2O and _Li2O according to the weight percentage. 10%, Sb ₂ O ₃ 0.1-1%, in this sealing glass composition, Sb2O3 is toxic, and long-term use of this sealing glass will have adverse effects on human health; Chinese patent CN10326398A discloses a crystallization type Lead-free sealing glass and its preparation and use method, the patent uses B ₂ O ₃ , Al ₂ O ₃ , SiO ₂ , MO (one or a mixture of MgO, CaO, SrO, BaO), Bi ₂ O ₃ combination, however, because Bi element has weak radioactivity, it will still affect human health.

Based on the above-mentioned prior art, it is necessary to study a new sealing glass, which has a thermal expansion coefficient close to that of metal materials, good thermal stability, high mechanical strength, and easy to form sealing glass, and does not contain radioactive elements and heavy metals at the same time. , Toxic and harmful elements.

Contents of the invention

The purpose of the present invention is to solve the shortcomings of existing tantalum metal sealing glass, such as high melting point and sealing temperature, poor acid resistance, poor chemical stability, or containing radioactive elements, heavy metals, and toxic and harmful elements. A sealing glass for tantalum metal and a preparation method thereof are provided.

In order to solve the deficiencies in the above-mentioned prior art, the present invention provides the following technical solutions:

A sealing glass for tantalum metal, which is special in that it contains 56-60% SiO ₂ , 12-13% B ₂ O ₃ , 5-6% Al ₂ O ₃ , 5 ～6% BaO, 4～5% K ₂ O, 4～5% Na ₂ O, 0.1～0.4% Fe ₂ O ₃ , 3～4% TiO ₂ , 1～2% ZrO, 3 -4% LiO ₂ , and 1-2% rare earth element compound LaCePrZr; the molar ratio of SiO ₂ to Al ₂ O ₃ is 12-14:1.

Further, the mass percentages are 57-59% of SiO ₂ , 12-13% of B ₂ O ₃ , 5-6% of Al ₂ O ₃ , 5-6% of BaO, and 4.5-5.0% of K ₂ O, 4.0-4.5% Na ₂ O, 0.1-0.4% Fe ₂ O ₃ , 3.6-3.8% TiO ₂ , 1-2% ZrO, 3.0-3.3% LiO ₂ , and 1.0-1.5% Rare earth element compound LaCePrZr.

Further, the mass percentage is 56% of SiO ₂ , 13% of B ₂ O ₃ , 6% of Al ₂ O ₃ , 6% of BaO, 5% of K ₂ O, 4% of Na ₂ O, 0.1 % Fe ₂ O ₃ , 3.6% TiO ₂ , 2% ZrO, 3.3% LiO ₂ , and 1% rare earth compound LaCePrZr.

Further, the mass percentages are 58% SiO ₂ , 12% B ₂ O ₃ , 6% Al ₂ O ₃ , 5% BaO, 4.5% K ₂ O, 4.5% Na ₂ O, 0.4 % Fe ₂ O ₃ , 3.6% TiO ₂ , 2% ZrO, 3% LiO ₂ , and 1% rare earth compound LaCePrZr.

At the same time, the present invention also provides a method for preparing a sealing glass for tantalum metal, which is special in that, based on the above-mentioned sealing glass for tantalum metal, it includes the following steps:

Step (1), uniformly mixing all components to obtain a mixture;

Step (2), using a solvent to modulate the mixture into a slurry;

Step (3), putting the slurry into a drying oven for drying, and after drying, go through the first step of heat treatment to obtain a glass matrix;

Step (4): Carrying out the second heat treatment on the glass substrate, raising the temperature to the nucleation temperature according to the preset heating rate and keeping it warm, then raising the temperature to the crystallization temperature and keeping it warm to obtain the sealing glass.

Further, in step 3, the first heat treatment step is specifically:

(3.1) First raise the temperature to 900-950°C at the preset heating rate in the first stage, and keep it warm for more than 2 hours to obtain the pre-fired block, then raise it to 1500-1550°C at the second-stage heating rate, and keep it warm for more than 2.5 hours, so that The raw materials are completely melted and the bubbles are removed to obtain a clear glass liquid;

(3.2) Quickly pour the clarified glass liquid into the mold, remove the mold after cooling, and then put it into a muffle furnace preheated to 550°C for 3 hours and anneal to obtain a glass matrix;

(3.3) Cut the annealed glass substrate into small pieces, grind and polish it for later use.

Further, in step 4, the preset heating rate is 5-10°C/min; the nucleation temperature is 550-580°C, the holding time is 120-140min; the crystallization temperature is 1070-1150°C, The holding time is 150-180 minutes.

Further, the preset heating rate in the first stage is 10-15°C/min, and the preset heating rate in the second stage is 4-5°C/min.

Further, in step 2, the solvent is absolute ethanol, and the mass ratio of absolute ethanol to the mixture is 2.6-3:1.

Further, the step 2 also includes: ball milling the slurry, the volume of the ball mill stone is at least twice the volume of the slurry, the ball milling speed is 300-350r/min, and the ball milling time is 130-180min, which is used to make the slurry The mixing is more uniform, and the generation of bubbles and inhomogeneity in the subsequent high-temperature melting are reduced.

Compared with prior art, the beneficial effect of the present invention is:

(1) A sealing glass for tantalum metal in the present invention, including SiO ₂ , B ₂ O ₃ , Al ₂ O ₃ , BaO, K ₂ O, Na ₂ O, Fe ₂ O ₃ , TiO ₂ , ZrO, LiO ₂ , and rare earth element compound LaCePrZr, which does not contain radioactive elements, heavy metals, toxic and harmful elements; the sealing glass has a thermal expansion coefficient close to that of metal, can be successfully sealed with tantalum metal, and has excellent thermal stability and strong acid resistance Moreover, due to the similar thermal expansion coefficient, the internal stress of the sealing glass during use is reduced, thereby effectively inhibiting the formation of micro-cracks during use and prolonging the service life.

(2) A sealing glass for tantalum metal of the present invention includes 1-2% of rare earth element compound LaCePrZr, and the rare earth element compound LaCePrZr has a relatively low expansion coefficient. It can adjust the expansion coefficient of the glass without affecting the chemical properties and stability of the borosilicate glass, and as a microcrystalline structure, it can promote the borosilicate glass to become a glass-ceramic.

(3) A method for preparing a sealing glass for tantalum metal according to the present invention, which is based on the above-mentioned sealing glass for tantalum metal, through the first heat treatment and the second heat treatment, to prepare a glass that can match with tantalum metal The sealed sealing glass solves the problems of the existing tantalum metal sealing glass, such as high melting point and sealing temperature, poor acid resistance, poor chemical stability, or containing radioactive elements, heavy metals, and toxic and harmful elements. place.

Description of drawings

Fig. 1 is a thermal expansion coefficient diagram of sealing glass prepared in Examples 1 to 6 of a method for preparing sealing glass for tantalum metal according to the present invention;

Fig. 2 is a DTA diagram of sealing glasses prepared in Examples 1 to 6 of the present invention.

detailed description

The present invention will be further described below in combination with exemplary embodiments.

A sealing glass for tantalum metal, comprising 56-60% SiO ₂ , 12-13% B ₂ O ₃ , 5-6% Al ₂ O ₃ , 5-6% BaO, 4-5% K ₂ O, 4-5% Na ₂ O, 0.1-0.4% Fe ₂ O ₃ , 3-4% TiO ₂ , 1-2% ZrO, 3-4% LiO ₂ , and 1-2% of rare earth element compound LaCePrZr; the molar ratio of SiO ₂ to Al ₂ O ₃ is 12-14:1.

Among them, Al ₂ O ₃ has many advantages, not only can reduce the crystallization tendency of the glass, but also can improve the chemical stability, thermal stability, mechanical strength, hardness of the glass, and can increase the viscosity of the glass, etc. B ₂ O ₃ can reduce the thermal expansion coefficient of the glass, and a higher content of B ₂ O ₃ can effectively improve the thermal and chemical stability of the glass, improve the gloss of the glass, and improve the mechanical properties of the glass. Adding B ₂ O ₃ can also The forming temperature range of the glass can be widened. ZrO acts as a stabilizer, and its purpose is to increase the chemical stability and mechanical strength of the glass. Na ₂ O can provide free oxygen to reduce the viscosity of the glass, and is a co-solvent for the glass. The reduction of BaO addition reduces Tc and (Tc-Tg)/Tg value at the same time, that is, the crystallization of glass is easier; change the ratio of SiO ₂ /B ₂ O ₃ in glass raw materials, and increase alkali oxides to reduce The content of BaO can change the thermal expansion coefficient of the glass.

In addition, adding an appropriate amount of _TiO2 as a crystal nucleating agent is beneficial to the generation and uniform distribution of tiny crystals in the glass system, making the structure of borosilicate glass more stable and acid corrosion resistance enhanced. Zr ⁴⁺ has a large radius and acts as an exosome in the glass system. Due to the low solubility of ZrO in borosilicate glass, it can only densify the glass structure to a certain extent to enhance its acid resistance; while Ti ⁴⁺ is generally located in the In the octahedron, it acts as the network exosome, but in the case of high alkali metal content, Ti ⁴⁺ is located in the tetrahedron, so that the glass network structure is obviously denser, and the acid resistance is significantly enhanced. Borosilicate glass can have an expansion coefficient close to that of tantalum metal and good acid resistance at the same time.

The rare earth element compound LaCePrZr is a high-entropy oxide powder with a low expansion coefficient. It can adjust the expansion coefficient of the glass without affecting the chemical properties and stability of the borosilicate glass, and as a microcrystalline structure, it can promote the borosilicate glass to become a glass-ceramic.

Based on the above-mentioned sealing glass for tantalum metal, the present invention provides a method for preparing a sealing glass for tantalum metal, comprising the following steps:

Step (1), mixing all components of the sealing glass uniformly to obtain a mixture;

Step (2), using absolute ethanol to prepare the mixture into a slurry, the mass ratio of absolute ethanol to the mixture is 2.6 to 3:1; ball mill the slurry, and the volume of the ball mill stone is at least twice the volume of the slurry Above, the ball milling speed is 300~350r/min, and the ball milling time is 130~180min;

Step (3), putting the slurry into a drying oven for drying, and after drying, go through the first step of heat treatment to obtain a glass matrix;

The first heat treatment step is specifically:

(3.1) First raise the temperature to 900-950°C at the preset heating rate in the first stage, and keep it warm for more than 2 hours to obtain the pre-fired block, then raise it to 1500-1550°C at the second-stage heating rate, and keep it warm for more than 2.5 hours, so that The raw materials are completely melted and the air bubbles are removed to obtain clarified molten glass; the preset heating rate of the first stage is 10-15°C/min, and the preset heating rate of the second stage is 4-5°C/min;

(3.2) Quickly pour the clarified glass liquid into the mold, remove the mold after cooling, and then put it into a muffle furnace preheated to 550°C for 3 hours and anneal to obtain a glass matrix;

(3.3) cutting the annealed glass substrate into small pieces, grinding and polishing for later use;

Step (4), the glass substrate is subjected to the second step of heat treatment, the temperature is raised to the nucleation temperature according to the preset heating rate and kept warm, and then heated to the crystallization temperature, and kept warm to obtain the sealing glass; the preset heating rate is 5 ~10°C/min; the nucleation temperature is 550-580°C, and the holding time is 120-140min; the crystallization temperature is 1070-1150°C, and the holding time is 150-180min.

Table 1

Example 1

A method for preparing a sealing glass for tantalum metal, comprising the steps of:

Step (1), mixing all components of the sealing glass uniformly to obtain a mixture;

The sealing glass includes 57% SiO ₂ , 12.5% B ₂ O ₃ , 6% Al ₂ O ₃ , 6% BaO, 4.5% K ₂ O, 4.5% Na ₂ O, 0.2% Fe ₂ O ₃ , 3.8% TiO ₂ , 1% ZrO, 3% LiO ₂ , and 1.5% rare earth element compound LaCePrZr;

Step (2), using absolute ethanol to adjust the mixture into a slurry, the mass ratio of absolute ethanol to the mixture is 2.6:1; the slurry is ball milled, and the volume of the ball millstone is at least twice the volume of the slurry, The ball milling speed is 300r/min, and the ball milling time is 130min;

Step (3), putting the slurry into a drying oven for drying, and after drying, go through the first step of heat treatment to obtain a glass matrix;

The first step of heat treatment is specifically:

(3.1) First raise the temperature to 900°C at the preset heating rate of the first stage, and keep it warm for more than 2 hours to obtain a pre-burnt block, then raise the heating rate to 1500°C at the second stage, and keep it warm for more than 2.5 hours, so that the raw materials are completely melted and Excluding air bubbles to obtain clarified molten glass; the preset heating rate of the first stage is 10°C/min, and the preset heating rate of the second stage is 4°C/min;

(3.2) Quickly pour the clarified glass liquid into the mold, remove the mold after cooling, and then put it into a muffle furnace preheated to 550°C for 3 hours and anneal to obtain a glass matrix;

(3.3) cutting the annealed glass substrate into small pieces, grinding and polishing for later use;

Step (4), the glass substrate is subjected to the second step of heat treatment, the temperature is raised to the nucleation temperature according to the preset heating rate and kept warm, and then heated to the crystallization temperature, and kept warm to obtain the sealing glass; the preset heating rate is 5 °C/min; the nucleation temperature is 550 °C, and the holding time is 120 min; the crystallization temperature is 1070 °C, and the holding time is 150 min.

The sealing glass was processed into a plurality of cylindrical samples with a diameter of 5 mm and a height of about 25 mm for thermal expansion performance testing; thermal expansion performance testing was performed using a high-temperature horizontal dilatometer, and the thermal expansion coefficient test results are shown in Table 1 and Figure 1.

The sealing glass is processed into multiple cube samples of 10×10×10mm for acid resistance test; the acid resistance test adopts the weight loss method, and multiple cube samples are placed in 38% sulfuric acid at 85°C for 200 hours, and the glass is measured. The weight loss rate requires that the weight loss should not exceed 0.001g. The acid resistance test results are shown in Table 1 and Figure 2.

Example 2

A method for preparing a sealing glass for tantalum metal, comprising the steps of:

Step (1), mixing all components of the sealing glass uniformly to obtain a mixture;

The sealing glass includes 56% SiO ₂ , 13% B ₂ O ₃ , 6% Al ₂ O ₃ , 6% BaO, 5% K ₂ O, 1% Na ₂ O, 0.1% Fe ₂ O ₃ , 3.6% TiO ₂ , 2% ZrO, 3.3% LiO ₂ , and 1% rare earth element compound LaCePrZr;

Step (2), using absolute ethanol to adjust the mixed material into a slurry, the mass ratio of absolute ethanol to the mixed material is 2.8:1; the slurry is ball milled, and the volume of the ball millstone is at least twice the volume of the slurry, The ball milling speed is 320r/min, and the ball milling time is 140min;

Step (3), putting the slurry into a drying oven for drying, and after drying, go through the first step of heat treatment to obtain a glass matrix;

The first step of heat treatment is specifically:

(3.1) First raise the temperature to 910°C with the preset heating rate in the first stage, and keep it warm for more than 2 hours to obtain a pre-burnt block, then raise the temperature to 1510°C at the second stage, and keep it warm for more than 2.5 hours, so that the raw materials are completely melted and Remove air bubbles to obtain clarified molten glass; the preset heating rate in the first stage is 11°C/min, and the preset heating rate in the second stage is 4°C/min;

(3.2) Quickly pour the clarified glass liquid into the mold, remove the mold after cooling, and then put it into a muffle furnace preheated to 550°C for 3 hours and anneal to obtain a glass matrix;

(3.3) cutting the annealed glass substrate into small pieces, grinding and polishing for later use;

Step (4), the glass substrate is subjected to the second step of heat treatment, the temperature is raised to the nucleation temperature according to the preset heating rate, and the heat is kept, and then the temperature is raised to the crystallization temperature, and the heat is kept to obtain the sealing glass; the preset heating rate is 6 °C/min; the nucleation temperature is 560 °C, and the holding time is 120 min; the crystallization temperature is 1080 °C, and the holding time is 160 min.

The test method of this implementation is identical with embodiment 1, and test result is shown in Table 1, Fig. 1, Fig. 2.

Example 3

A method for preparing a sealing glass for tantalum metal, comprising the steps of:

Step (1), mixing all components of the sealing glass uniformly to obtain a mixture;

The sealing glass includes 59% SiO ₂ , 13% B ₂ O ₃ , 6% Al ₂ O ₃ , 6% BaO, 5% K ₂ O, 4% Na ₂ O, 0.2% Fe ₂ O ₃ , 3.8% TiO ₂ , 1% ZrO, 3% LiO ₂ , and 1% rare earth element compound LaCePrZr;

Step (2), using absolute ethanol to adjust the mixed material into a slurry, the mass ratio of absolute ethanol to the mixed material is 3:1; the slurry is ball milled, and the volume of the ball millstone is at least twice the volume of the slurry, The ball milling speed is 310r/min, and the ball milling time is 150min;

Step (3), putting the slurry into a drying oven for drying, and after drying, go through the first step of heat treatment to obtain a glass matrix;

The first step of heat treatment is specifically:

(3.1) First raise the temperature to 920°C with the preset heating rate in the first stage, and keep it warm for more than 2 hours to obtain a pre-burnt block, then raise the temperature to 1520°C at the second stage, and keep it warm for more than 2.5 hours, so that the raw materials are completely melted and Excluding air bubbles to obtain clarified molten glass; the preset heating rate of the first stage is 12°C/min, and the preset heating rate of the second stage is 4°C/min;

(3.2) Quickly pour the clarified glass liquid into the mold, remove the mold after cooling, and then put it into a muffle furnace preheated to 550°C for 3 hours and anneal to obtain a glass matrix;

(3.3) cutting the annealed glass substrate into small pieces, grinding and polishing for later use;

Step (4), the glass substrate is subjected to the second step of heat treatment, the temperature is raised to the nucleation temperature according to the preset heating rate, and the heat is kept, and then the temperature is raised to the crystallization temperature, and the heat is kept to obtain the sealing glass; the preset heating rate is 7 °C/min; the nucleation temperature is 570 °C, and the holding time is 140 min; the crystallization temperature is 1090 °C, and the holding time is 170 min.

The test method of this implementation is identical with embodiment 1, and test result is shown in Table 1, Fig. 1, Fig. 2.

Example 4

A method for preparing a sealing glass for tantalum metal, comprising the steps of:

Step (1), mixing all components of the sealing glass uniformly to obtain a mixture;

The sealing glass includes 58% SiO ₂ , 12% B ₂ O ₃ , 6% Al ₂ O ₃ , 5% BaO, 4.5% K ₂ O, 4.5% Na ₂ O, 0.4% Fe ₂ O ₃ , 3.6% TiO ₂ , 2% ZrO, 3% LiO ₂ , and 1% rare earth element compound LaCePrZr;

Step (2), using absolute ethanol to adjust the mixture into a slurry, the mass ratio of absolute ethanol to the mixture is 2.6:1; the slurry is ball milled, and the volume of the ball millstone is at least twice the volume of the slurry, The ball milling speed is 320r/min, and the ball milling time is 160min;

Step (3), putting the slurry into a drying oven for drying, and after drying, go through the first step of heat treatment to obtain a glass matrix;

The first step of heat treatment is specifically:

(3.1) First raise the temperature to 930°C at the preset heating rate in the first stage, and keep it warm for more than 2 hours to obtain a pre-burnt block, then raise the heating rate to 1530°C at the second stage, and keep it warm for more than 2.5 hours, so that the raw materials are completely melted and Excluding air bubbles to obtain clarified molten glass; the preset heating rate of the first stage is 13°C/min, and the preset heating rate of the second stage is 2°C/min;

(3.2) Quickly pour the clarified glass liquid into the mold, remove the mold after cooling, and then put it into a muffle furnace preheated to 550°C for 3 hours and anneal to obtain a glass matrix;

(3.3) cutting the annealed glass substrate into small pieces, grinding and polishing for later use;

Step (4), the glass substrate is subjected to the second step of heat treatment, the temperature is raised to the nucleation temperature according to the preset heating rate, and the heat is kept, and then the temperature is raised to the crystallization temperature, and the heat is kept to obtain the sealing glass; the preset heating rate is 8 °C/min; the nucleation temperature is 580 °C, and the holding time is 140 min; the crystallization temperature is 1120 °C, and the holding time is 180 min.

The test method of this implementation is identical with embodiment 1, and test result is shown in Table 1, Fig. 1, Fig. 2.

Example 5

A method for preparing a sealing glass for tantalum metal, comprising the steps of:

Step (1), mixing all components of the sealing glass uniformly to obtain a mixture;

The sealing glass includes 59% SiO ₂ , 12% B ₂ O ₃ , 5% Al ₂ O ₃ , 6% BaO, 4.7% K ₂ O, 4.5% Na ₂ O, 0.2% Fe ₂ O ₃ , 3.6% TiO ₂ , 1% ZrO, 3% LiO ₂ , and 1% rare earth element compound LaCePrZr;

Step (2), using absolute ethanol to adjust the mixture into a slurry, the mass ratio of absolute ethanol to the mixture is 2.6:1; the slurry is ball milled, and the volume of the ball millstone is at least twice the volume of the slurry, The ball milling speed is 330r/min, and the ball milling time is 180min;

Step (3), putting the slurry into a drying oven for drying, and after drying, go through the first step of heat treatment to obtain a glass matrix;

The first step of heat treatment is specifically:

(3.1) First raise the temperature to 940°C with the preset heating rate in the first stage, and keep it warm for more than 2 hours to obtain a pre-burnt block, then raise the heating rate to 1530°C at the second stage, and keep it warm for more than 2.5 hours, so that the raw materials are completely melted and Excluding air bubbles to obtain clarified molten glass; the preset heating rate of the first stage is 14°C/min, and the preset heating rate of the second stage is 5°C/min;

(3.2) Quickly pour the clarified glass liquid into the mold, remove the mold after cooling, and then put it into a muffle furnace preheated to 550°C for 3 hours and anneal to obtain a glass matrix;

(3.3) cutting the annealed glass substrate into small pieces, grinding and polishing for later use;

Step (4), the glass substrate is subjected to the second step of heat treatment, the temperature is raised to the nucleation temperature according to the preset heating rate, and the heat is kept, and then the temperature is raised to the crystallization temperature, and the heat is kept to obtain the sealing glass; the preset heating rate is 8 °C/min; the nucleation temperature is 570 °C, and the holding time is 130 min; the crystallization temperature is 1130 °C, and the holding time is 170 min.

The test method of this implementation is identical with embodiment 1, and test result is shown in Table 1, Fig. 1, Fig. 2.

Example 6

A method for preparing a sealing glass for tantalum metal, comprising the steps of:

Step (1), mixing all components of the sealing glass uniformly to obtain a mixture;

The sealing glass includes 58% SiO ₂ , 12.9% B ₂ O ₃ , 6% Al ₂ O ₃ , 5% BaO, 4% K ₂ O, 4% Na ₂ O, 0.1% Fe ₂ O ₃ , 3% TiO ₂ , 2% ZrO, 4% LiO ₂ , and 1% rare earth element compound LaCePrZr;

Step (2), using absolute ethanol to adjust the mixed material into a slurry, the mass ratio of absolute ethanol to the mixed material is 3:1; the slurry is ball milled, and the volume of the ball millstone is at least twice the volume of the slurry, The ball milling speed is 350r/min, and the ball milling time is 180min;

Step (3), putting the slurry into a drying oven for drying, and after drying, go through the first step of heat treatment to obtain a glass matrix;

The first step of heat treatment is specifically:

(3.1) First raise the temperature to 950°C at the preset heating rate of the first stage, and keep it warm for more than 2 hours to obtain a pre-burnt block, then raise the heating rate to 1550°C at the second stage, and keep it warm for more than 2.5 hours, so that the raw materials are completely melted and Excluding air bubbles to obtain clarified molten glass; the preset heating rate of the first stage is 15°C/min, and the preset heating rate of the second stage is 4°C/min;

(3.2) Pour the clarified glass liquid into the mold quickly, demould it after cooling, take it out, put it into a muffle furnace preheated to 550°C and keep it warm for 3 hours for annealing to obtain a glass matrix;

(3.3) cutting the annealed glass substrate into small pieces, grinding and polishing for later use;

Step (4), the glass substrate is subjected to the second step of heat treatment, the temperature is raised to the nucleation temperature according to the preset heating rate, and the heat is kept, and then the temperature is raised to the crystallization temperature, and the heat is kept to obtain the sealing glass; the preset heating rate is 10 °C/min; the nucleation temperature is 580 °C, and the holding time is 140 min; the crystallization temperature is 1150 °C, and the holding time is 180 min.

The test method of this implementation is identical with embodiment 1, and test result is shown in Table 1, Fig. 1, Fig. 2.

The above embodiments are only used to illustrate the technical solutions of the present invention, but not to limit them. For those of ordinary skill in the art, the specific technical solutions described in the foregoing embodiments can be modified, or part of the technical solutions can be modified. Features are equivalently replaced, and these modifications or replacements do not make the essence of the corresponding technical solution depart from the scope of the technical solution protected by the present invention.

Claims (10)

1. A sealing glass for tantalum metal, characterized in that it comprises 56-60% SiO ₂ , 12-13% B ₂ O ₃ , 5-6% Al ₂ O ₃ , 5 ～6% BaO, 4～5% K ₂ O, 4～5% Na ₂ O, 0.1～0.4% Fe ₂ O ₃ , 3～4% TiO ₂ , 1～2% ZrO, 3 -4% LiO ₂ , and 1-2% rare earth element compound LaCePrZr; the molar ratio of SiO ₂ to Al ₂ O ₃ is 12-14:1. 2. A sealing glass for tantalum metal according to claim 1, characterized in that: the mass percentages are 57-59% SiO ₂ , 12-13% B ₂ O ₃ , 5-6 % Al ₂ O ₃ , 5-6% BaO, 4.5-5.0% K ₂ O, 4.0-4.5% Na ₂ O, 0.1-0.4% Fe ₂ O ₃ , 3.6-3.8% TiO ₂ , 1-2% ZrO, 3.0-3.3% LiO ₂ , and 1.0-1.5% rare earth element compound LaCePrZr. 3. A sealing glass for tantalum metal according to claim 2, characterized in that: the mass percentages are 56% SiO ₂ , 13% B ₂ O ₃ , and 6% Al ₂ O ₃ , 6% BaO, 5% K ₂ O, 4% Na ₂ O, 0.1% Fe ₂ O ₃ , 3.6% TiO ₂ , 2% ZrO, 3.3% LiO ₂ , and 1% rare earth Elemental compound LaCePrZr. 4. A sealing glass for tantalum metal according to claim 2, characterized in that: the mass percentages are 58% SiO ₂ , 12% B ₂ O ₃ , and 6% Al ₂ O ₃ , 5% BaO, 4.5% K ₂ O, 4.5% Na ₂ O, 0.4% Fe ₂ O ₃ , 3.6% TiO ₂ , 2% ZrO, 3% LiO ₂ , and 1% rare earth Elemental compound LaCePrZr. 5. A preparation method for a sealing glass for tantalum metal, characterized in that, based on a kind of sealing glass for tantalum metal according to claim 1, comprising the steps of: Step (1), uniformly mixing all components to obtain a mixture; Step (2), using a solvent to modulate the mixture into a slurry; Step (3), putting the slurry into a drying oven for drying, and after drying, go through the first step of heat treatment to obtain a glass matrix; Step (4): Carrying out the second heat treatment on the glass substrate, raising the temperature to the nucleation temperature according to the preset heating rate and keeping it warm, then raising the temperature to the crystallization temperature and keeping it warm to obtain the sealing glass. 6. A method for preparing a sealing glass for tantalum metal according to claim 5, characterized in that: in step 3, the first heat treatment step is specifically: (3.1) First raise the temperature to 900-950°C at the preset heating rate in the first stage, and keep it warm for more than 2 hours to obtain the pre-fired block, then raise it to 1500-1550°C at the second-stage heating rate, and keep it warm for more than 2.5 hours, so that The raw materials are completely melted and the bubbles are removed to obtain a clear glass liquid; (3.2) Pour the clarified glass liquid into the mold quickly, demould it after cooling, take it out, put it into a muffle furnace preheated to 550°C and keep it warm for 3 hours for annealing to obtain a glass matrix; (3.3) Cut the annealed glass substrate into small pieces, grind and polish it for later use. 7. A method for preparing a sealing glass for tantalum metal according to claim 6, characterized in that: in step 4, the preset heating rate is 5-10°C/min; the nucleation temperature The temperature is 550-580°C, and the holding time is 120-140min; the crystallization temperature is 1070-1150°C, and the holding time is 150-180min. 8. A method for preparing a sealing glass for tantalum metal according to claim 7, characterized in that: the preset heating rate in the first stage is 10-15°C/min, and the preset heating rate in the second stage is Set the heating rate at 4-5°C/min. 9. A method for preparing a sealing glass for tantalum metal according to any one of claims 5 to 8, characterized in that: in step 2, the solvent is dehydrated alcohol, and the mixture of dehydrated alcohol and the mixture The mass ratio is 2.6～3:1. 10. A method for preparing a sealing glass for tantalum metal according to claim 9, characterized in that: said step 2 further comprises: ball milling the slurry, the volume of the ball mill stone being at least two times the volume of the slurry times, the ball milling speed is 300~350r/min, and the ball milling time is 130~180min.

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