CN115521072A - Sealing glass for tantalum metal and preparation method thereof - Google Patents
Sealing glass for tantalum metal and preparation method thereof Download PDFInfo
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- 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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- C03B19/00—Other methods of shaping glass
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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
Technical Field
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.
Background
The liquid tantalum electrolytic capacitor has large capacitance, is not easy to break down, has low internal resistance and small volume, and the demand is in a growing trend all the time. However, the inside of the electric appliance contains gel sulfuric acid with extremely strong corrosiveness, and if the sealing is not good, the gel sulfuric acid leaks out from the inside, so that electronic components around the gel sulfuric acid are corroded, and the whole electric appliance is adversely affected. Therefore, liquid electrolyte tantalum capacitors require a strict hermetic seal with glass.
The existing sealing glass research mainly aims at a flat solid oxygen hundred million fuel cell, and few researches are carried out on the sealing glass with low expansion coefficient for a tantalum capacitor. In addition, the conventional electronic component sealing glass contains a large amount of metallic lead, for example, the conventional electronic sealing glass brand DB-435 has a lead content of 34% and DH-704 has a lead content of 77%. However, heavy metal lead is not only harmful to human body, but also not in line with the requirement of environmental protection.
Because the thermal expansion coefficient of glass is far smaller than that of metal, a large thermal stress is generated inside the glass sealed with the metal at high temperature, so that the glass and the metal material cannot be directly sealed. The main difficulty of the tantalum metal sealing technology is to produce a glass material with a thermal expansion coefficient more similar to that of tantalum metal to realize matching sealing between the glass and the tantalum metal material, but the larger the thermal expansion coefficient of the sealing glass material is, the lower the stability and thermal shock resistance of the sealing glass material is, so that the sealing glass needs to have a thermal expansion coefficient similar to that of tantalum metal and simultaneously needs to ensure excellent stability and strength of the sealing glass.
The composition of the sealing glass directly influences the thermal expansion performance, operability, chemical stability and mechanical strength of the sealing glass and also influences the sealing tightness of the sealing glass and a metal material. U.S. Pat. No. 3,32753,59A discloses a sealing glass which can be used primarily for tantalum metal sealing, the sealing glass comprises, by weight, 35% BaO and Al 2 O 3 25％，B 2 O 3 40% of Al in the glass composition 2 O 3 At a content of about 25%, the glass is too highMelting point and sealing temperature, and the acid resistance and the chemical stability are poor; chinese patent CN102452794A discloses a crystal type low-melting-point sealing glass and a preparation method thereof, wherein the crystal type sealing glass comprises, by weight, 50-70% of SiO2, 10-30% of ZnO, 1-10% of B2O3, 1-8% of CaO and Na 2 O 1～10％，Li 2 O 10％，Sb 2 O 3 0.1-1%, sb2O3 in the components of the sealing glass has toxicity, and the long-term use of the sealing glass can generate adverse effects on human health; chinese patent No. 10326398A discloses a crystallization type lead-free sealing glass and a preparation method and a use method thereof, wherein B is adopted in the patent 2 O 3 、Al 2 O 3 、SiO 2 MO (one or a mixture of more of MgO, caO, srO and BaO), bi 2 O 3 However, since Bi element has weak radioactivity, it still affects human health.
Based on the above prior art, there is a need to develop a new sealing glass, which has a thermal expansion coefficient close to that of metal materials, good thermal stability, high mechanical strength, and is easy to mold, and which does not contain radioactive elements, heavy metals, and toxic and harmful elements.
Disclosure of Invention
The invention aims to solve the defects of over high melting point and sealing temperature, poor acid resistance and chemical stability, or containing radioactive elements, heavy metals and toxic and harmful elements in the existing tantalum metal sealing glass, and provides the sealing glass for tantalum metal and the preparation method thereof.
In order to solve the defects of the prior art, the invention provides the following technical solutions:
a sealing glass for tantalum metal is characterized in that: comprises 56 to 60 mass percent of SiO 2 12-13% of B 2 O 3 5 to 6% of Al 2 O 3 5 to 6 percent of BaO and 4 to 5 percent of K 2 O, 4-5% of Na 2 O, 0.1-0.4% Fe 2 O 3 3 to 4 percent of TiO 2 1-2% ofZrO, 3-4% LiO 2 And 1-2% of rare earth element compound LaCePrZr; the SiO 2 With Al 2 O 3 The molar ratio of (1) to (12) is from 12 to 14.
Further, the SiO accounts for 57-59% by mass 2 12 to 13 percent of B 2 O 3 5 to 6% of Al 2 O 3 5 to 6 percent of BaO and 4.5 to 5.0 percent of K 2 O, 4.0-4.5% of Na 2 O, 0.1-0.4% Fe 2 O 3 3.6 to 3.8 percent of TiO 2 1 to 2 percent of ZrO, 3.0 to 3.3 percent of LiO 2 And 1.0-1.5% of a rare earth element compound LaCePrZr.
Further, the SiO accounts for 56 mass percent 2 13% of B 2 O 3 6% of Al 2 O 3 6% of BaO and 5% of K 2 O, 4% of Na 2 O, 0.1% Fe 2 O 3 3.6% of TiO 2 2% ZrO, 3.3% LiO 2 And 1% of a rare earth element compound LaCePrZr.
Further, the SiO accounts for 58 percent by mass 2 12% of B 2 O 3 6% of Al 2 O 3 5% of BaO and 4.5% of K 2 O, 4.5% of Na 2 O, 0.4% Fe 2 O 3 3.6% of TiO 2 2% ZrO, 3% LiO 2 And 1% of a rare earth element compound LaCePrZr.
Meanwhile, the invention also provides a preparation method of the sealing glass for tantalum metal, which is characterized in that the sealing glass for tantalum metal comprises the following steps:
step (1), uniformly mixing all components to obtain a mixture;
step (2), preparing the mixture into slurry by adopting a solvent;
step (3), drying the slurry in a drying oven, and performing first-step heat treatment to obtain a glass matrix after drying;
and (4) carrying out second-step heat treatment on the glass substrate, heating to a nucleation temperature according to a preset heating rate, carrying out heat preservation, heating to a crystallization temperature, and carrying out heat preservation to obtain the sealing glass.
Further, in step 3, the first heat treatment step specifically includes:
(3.1) firstly increasing the temperature to 900-950 ℃ at the first-stage preset heating rate, preserving the heat for more than 2 hours to obtain a pre-sintered block, increasing the temperature to 1500-1550 ℃ at the second-stage heating rate, preserving the heat for more than 2.5 hours to completely melt the raw materials and remove bubbles to obtain clear glass liquid;
(3.2) quickly pouring the clear glass liquid into a mold, cooling, demolding, taking out, and then putting into a muffle furnace preheated to 550 ℃ for heat preservation for 3h for annealing to obtain a glass substrate;
and (3.3) cutting the annealed glass substrate into small pieces, and grinding and polishing the small pieces for later use.
Further, in the step 4, the preset heating rate is 5-10 ℃/min; the nucleation temperature is 550-580 ℃, and the heat preservation time is 120-140 min; the crystallization temperature is 1070 to 1150 ℃, and the heat preservation time is 150 to 180min.
Further, the preset heating rate of the first stage is 10-15 ℃/min, and the preset heating rate of the second stage is 4-5 ℃/min.
Further, in the step 2, the solvent is absolute ethyl alcohol, and the mass ratio of the absolute ethyl alcohol to the mixture is 2.6-3.
Further, the step 2 further comprises: ball milling is carried out on the slurry, the volume of ball milling stones is at least two times of the volume of the slurry, the ball milling rotating speed is 300-350 r/min, the ball milling time is 130-180 min, the slurry is mixed more uniformly, and the generation of bubbles and the non-uniformity phenomenon in high-temperature melting are reduced.
Compared with the prior art, the invention has the beneficial effects that:
(1) The invention relates to a sealing glass for tantalum metal, which 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 containRadioactive elements, heavy metals, toxic and harmful elements; the sealing glass has a thermal expansion coefficient close to that of metal, can be smoothly sealed with tantalum metal, has the advantages of excellent thermal stability, strong acid resistance, easiness in forming and the like, and because the thermal expansion coefficients are close, the internal stress of the sealing glass in use is reduced, so that the formation of microcracks in the use process is effectively inhibited, and the purpose of prolonging the service life is achieved.
(2) The sealing glass for tantalum metal comprises 1-2% of a rare earth element compound LaCePrZr, wherein the rare earth element compound LaCePrZr has a low expansion coefficient. The borosilicate glass can be adjusted in expansion coefficient on the premise of not influencing the chemical property and stability of the borosilicate glass, and can be used as a microcrystalline structure to promote the borosilicate glass to become microcrystalline glass.
(3) The invention relates to a preparation method of sealing glass for tantalum metal, which is based on the sealing glass for tantalum metal, and the sealing glass which can be matched and sealed with the tantalum metal is prepared through the first heat treatment step and the second heat treatment step, so that the defects that the existing tantalum metal sealing glass is too high in melting point and sealing temperature, poor in acid resistance and chemical stability, or contains radioactive elements, heavy metals and toxic and harmful elements are overcome.
Drawings
FIG. 1 is a diagram showing the thermal expansion coefficients of sealing glasses obtained in examples 1 to 6 of a method for producing a sealing glass for tantalum metal according to the present invention;
FIG. 2 is a DTA chart of sealing glasses obtained in examples 1 to 6 of the present invention.
Detailed Description
The invention will be further described with reference to exemplary embodiments.
The sealing glass for tantalum metal comprises 56-60% of SiO by mass 2 12 to 13 percent of B 2 O 3 5 to 6% of Al 2 O 3 5 to 6 percent of BaO and 4 to 5 percent of K 2 O, 4-5% of Na 2 O, 0.1-0.4% of Fe 2 O 3 3 to 4 percent of TiO 2 、1～2％ZrO, 3 to 4% LiO 2 And 1-2% of rare earth element compound LaCePrZr; the SiO 2 With Al 2 O 3 The molar ratio of (a) to (b) is 12 to 14.
Wherein, al 2 O 3 The glass has multiple advantages, can reduce the crystallization tendency of the glass, can improve the chemical stability, the thermal stability, the mechanical strength and the hardness of the glass, and can improve the viscosity of the glass and the like. B is 2 O 3 Can reduce the thermal expansion coefficient of the glass, and has higher content of B 2 O 3 Can effectively improve the thermal stability and chemical stability of glass, improve the gloss of glass and improve the mechanical property of glass, and B is added 2 O 3 The glass forming temperature range can be made wide. ZrO acts as a stabilizer, the purpose of which is to increase the chemical stability and mechanical strength of the glass. Na (Na) 2 O, which provides free oxygen and thus lowers the viscosity of the glass, is a co-solvent for the glass. The decrease of the addition amount of BaO reduces Tc and simultaneously reduces the value of (Tc-Tg)/Tg, namely the crystallization of the glass is easier; changing SiO in glass raw material 2 /B 2 O 3 The ratio, and the addition of the alkali oxide to reduce the content of BaO, can change the thermal expansion coefficient of the glass.
In addition, an appropriate amount of TiO is added 2 The boron silicate glass is used as a crystal nucleating agent, so that tiny crystals in a glass system can be generated and uniformly distributed, the structure of the boron silicate glass is more stable, and the acid corrosion resistance is enhanced. Zr 4+ The radius is large, the glass serves as a network outer body in a glass system, and because ZrO has low solubility in borosilicate glass, the structure of the glass can be densified to a certain extent only so as to enhance the acid resistance of the glass; and Ti 4+ Generally located in octahedra, acting as extranet, but with higher alkali metal content Ti 4+ Located in tetrahedrons, thereby significantly densifying the glass network structure and significantly increasing the acid resistance. The borosilicate glass can simultaneously have the expansion coefficient close to that of tantalum metal and good acid resistance.
The rare earth element compound LaCePrZr is high-entropy oxide powder and has a low expansion coefficient. The borosilicate glass can be adjusted in expansion coefficient on the premise of not influencing the chemical property and stability of the borosilicate glass, and can be used as a microcrystalline structure to promote the borosilicate glass to become microcrystalline glass.
Based on the sealing glass for tantalum metal, the invention provides a preparation method of the sealing glass for tantalum metal, which comprises the following steps:
step (1), uniformly mixing all components of the sealing glass to obtain a mixture;
step (2), preparing the mixture into slurry by using absolute ethyl alcohol, wherein the mass ratio of the absolute ethyl alcohol to the mixture is 2.6-3; ball milling is carried out on the slurry, the volume of ball milling stones is at least two times of the volume of the slurry, the ball milling rotating speed is 300-350 r/min, and the ball milling time is 130-180 min;
step (3), drying the slurry in a drying oven, and performing first-step heat treatment to obtain a glass matrix after drying;
the first heat treatment step specifically comprises the following steps:
(3.1) firstly increasing the temperature to 900-950 ℃ at the first-stage preset heating rate, preserving the heat for more than 2 hours to obtain a pre-sintered block, increasing the temperature to 1500-1550 ℃ at the second-stage heating rate, preserving the heat for more than 2.5 hours to completely melt the raw materials and remove bubbles to obtain clear glass liquid; the preset heating rate of the first stage is 10-15 ℃/min, and the preset heating rate of the second stage is 4-5 ℃/min;
(3.2) quickly pouring the clear glass liquid into a mold, cooling, demolding, taking out, and then putting into a muffle furnace preheated to 550 ℃ for heat preservation for 3h for annealing to obtain a glass substrate;
(3.3) cutting the annealed glass substrate into small pieces, and grinding and polishing the small pieces for later use;
step (4), carrying out second-step heat treatment on the glass substrate, heating to a nucleation temperature according to a preset heating rate, carrying out heat preservation, heating to a crystallization temperature, and carrying out heat preservation to obtain the sealing glass; the preset heating rate is 5-10 ℃/min; the nucleation temperature is 550-580 ℃, and the heat preservation time is 120-140 min; the crystallization temperature is 1070 to 1150 ℃, and the heat preservation time is 150 to 180min.
TABLE 1
Example 1
A preparation method of sealing glass for tantalum metal comprises the following steps:
step (1), uniformly mixing all components of the sealing glass to obtain a mixture;
the sealing glass comprises 57 mass percent of SiO 2 12.5% of B 2 O 3 6% of Al 2 O 3 6% of BaO and 4.5% of K 2 O, 4.5% of Na 2 O, 0.2% Fe 2 O 3 3.8% of TiO 2 1% of ZrO, 3% of LiO 2 And 1.5% of a rare earth element compound LaCePrZr;
step (2), preparing the mixture into slurry by using absolute ethyl alcohol, wherein the mass ratio of the absolute ethyl alcohol to the mixture is 2.6; ball milling is carried out on the slurry, the volume of ball milling stones is at least two times of the volume of the slurry, the ball milling rotating speed is 300r/min, and the ball milling time is 130min;
step (3), putting the slurry into a drying oven for drying, and performing first-step heat treatment after drying to obtain a glass matrix;
the first heat treatment step specifically comprises the following steps:
(3.1) heating to 900 ℃ at a first-stage preset heating rate, and preserving heat for more than 2 hours to obtain a pre-sintered block, and then heating to 1500 ℃ at a second-stage heating rate, and preserving heat for more than 2.5 hours to completely melt the raw materials and remove bubbles to obtain clear glass liquid; the preset heating rate of the first stage is 10 ℃/min, and the preset heating rate of the second stage is 4 ℃/min;
(3.2) quickly pouring the clear glass liquid into a mold, cooling, demolding, taking out, and then putting into a muffle furnace preheated to 550 ℃ for heat preservation for 3h for annealing to obtain a glass substrate;
(3.3) cutting the annealed glass substrate into small pieces, and grinding and polishing the small pieces for later use;
step (4), carrying out second-step heat treatment on the glass substrate, heating to a nucleation temperature according to a preset heating rate, carrying out heat preservation, heating to a crystallization temperature, and carrying out heat preservation to obtain the sealing glass; the preset heating rate is 5 ℃/min; the nucleation temperature is 550 ℃, and the heat preservation time is 120min; the crystallization temperature is 1070 ℃, and the heat preservation time is 150min.
Processing the sealing glass into a plurality of cylindrical samples with the diameter of 5mm and the height of about 25mm for detecting the thermal expansion performance; the thermal expansion performance is detected by a high-temperature horizontal expansion instrument, and the test result of the thermal expansion coefficient is shown in table 1 and figure 1.
Processing the sealing glass into a plurality of cubic samples of 10 multiplied by 10mm for acid resistance detection; the acid resistance test adopts a weight loss method, a plurality of cubic samples are placed in sulfuric acid with the concentration of 38 percent at the temperature of 85 ℃ for 200 hours, the weight loss rate of the glass is measured, the weight reduction is required to be not more than 0.001g, and the acid resistance test result is shown in table 1 and figure 2.
Example 2
A preparation method of sealing glass for tantalum metal comprises the following steps:
step (1), uniformly mixing all components of the sealing glass to obtain a mixture;
the sealing glass comprises 56 mass percent of SiO 2 13% of B 2 O 3 6% of Al 2 O 3 6% of BaO and 5% of K 2 O, 1% of Na 2 O, 0.1% Fe 2 O 3 3.6% of TiO 2 2% ZrO, 3.3% LiO 2 And 1% of a rare earth element compound LaCePrZr;
step (2), preparing the mixture into slurry by using absolute ethyl alcohol, wherein the mass ratio of the absolute ethyl alcohol to the mixture is 2.8; ball milling is carried out on the slurry, the volume of ball milling stones is at least two times of the volume of the slurry, the ball milling rotating speed is 320r/min, and the ball milling time is 140min;
step (3), drying the slurry in a drying oven, and performing first-step heat treatment to obtain a glass matrix after drying;
the first heat treatment step specifically comprises the following steps:
(3.1) firstly increasing the temperature to 910 ℃ at the preset heating rate of the first stage, and preserving the heat for more than 2h to obtain a pre-sintered block, and then increasing the temperature to 1510 ℃ at the preset heating rate of the second stage, and preserving the heat for more than 2.5h to completely melt the raw materials and remove bubbles to obtain clear glass liquid; the preset heating rate of the first stage is 11 ℃/min, and the preset heating rate of the second stage is 4 ℃/min;
(3.2) quickly pouring the clear glass liquid into a mold, cooling, demolding, taking out, and then putting into a muffle furnace preheated to 550 ℃ for heat preservation for 3h for annealing to obtain a glass substrate;
(3.3) cutting the annealed glass substrate into small pieces, and grinding and polishing the small pieces for later use;
step (4), carrying out second-step heat treatment on the glass substrate, heating to a nucleation temperature according to a preset heating rate, carrying out heat preservation, heating to a crystallization temperature, and carrying out heat preservation to obtain the sealing glass; the preset heating rate is 6 ℃/min; the nucleation temperature is 560 ℃, and the heat preservation time is 120min; the crystallization temperature is 1080 ℃ and the heat preservation time is 160min.
The test method of this embodiment is the same as that of example 1, and the test results are shown in table 1, fig. 1, and fig. 2.
Example 3
A preparation method of sealing glass for tantalum metal comprises the following steps:
step (1), uniformly mixing all components of the sealing glass to obtain a mixture;
the sealing glass comprises SiO with the mass percent of 59 percent 2 13% of B 2 O 3 6% of Al 2 O 3 6% of BaO and 5% of K 2 O, 4% of Na 2 O, 0.2% Fe 2 O 3 3.8% of TiO 2 1% of ZrO, 3% of LiO 2 And 1% of a rare earth element compound LaCePrZr;
step (2), preparing the mixture into slurry by using absolute ethyl alcohol, wherein the mass ratio of the absolute ethyl alcohol to the mixture is 3; ball milling is carried out on the slurry, the volume of ball milling stones is at least two times of the volume of the slurry, the ball milling rotating speed is 310r/min, and the ball milling time is 150min;
step (3), drying the slurry in a drying oven, and performing first-step heat treatment to obtain a glass matrix after drying;
the first-step heat treatment specifically comprises the following steps:
(3.1) heating to 920 ℃ at a first-stage preset heating rate, preserving heat for more than 2 hours to obtain a pre-sintered block, heating to 1520 ℃ at a second-stage heating rate, preserving heat for more than 2.5 hours to completely melt the raw materials and remove bubbles to obtain clear glass liquid; the preset heating rate of the first stage is 12 ℃/min, and the preset heating rate of the second stage is 4 ℃/min;
(3.2) quickly pouring the clear glass liquid into a mold, cooling, demolding, taking out, and then putting into a muffle furnace preheated to 550 ℃ for heat preservation for 3h for annealing to obtain a glass substrate;
(3.3) cutting the annealed glass substrate into small pieces, and grinding and polishing the small pieces for later use;
step (4), carrying out second-step heat treatment on the glass substrate, heating to a nucleation temperature according to a preset heating rate, carrying out heat preservation, heating to a crystallization temperature, and carrying out heat preservation to obtain the sealing glass; the preset heating rate is 7 ℃/min; the nucleation temperature is 570 ℃, and the heat preservation time is 140min; the crystallization temperature is 1090 ℃ and the heat preservation time is 170min.
The test method of this embodiment is the same as in example 1, and the test results are shown in table 1, fig. 1, and fig. 2.
Example 4
A preparation method of sealing glass for tantalum metal comprises the following steps:
step (1), uniformly mixing all components of the sealing glass to obtain a mixture;
the sealing glass comprises 58 mass percent of SiO 2 12% of B 2 O 3 6% of Al 2 O 3 5% of BaO and 4.5% of K 2 O, 4.5% of Na 2 O, 0.4% Fe 2 O 3 3.6% of TiO 2 2% of ZrO, 3% of LiO 2 And 1% of a rare earth element compound LaCePrZr;
step (2), preparing the mixture into slurry by using absolute ethyl alcohol, wherein the mass ratio of the absolute ethyl alcohol to the mixture is 2.6; ball milling is carried out on the slurry, the volume of ball milling stones is at least two times of the volume of the slurry, the ball milling rotating speed is 320r/min, and the ball milling time is 160min;
step (3), putting the slurry into a drying oven for drying, and performing first-step heat treatment after drying to obtain a glass matrix;
the first-step heat treatment specifically comprises the following steps:
(3.1) firstly raising the temperature to 930 ℃ at the preset heating rate in the first stage, and preserving the heat for more than 2 hours to obtain a pre-sintered block, and then raising the temperature to 1530 ℃ at the preset heating rate in the second stage, and preserving the heat for more than 2.5 hours to completely melt the raw materials and remove bubbles to obtain clear glass liquid; the preset heating rate of the first stage is 13 ℃/min, and the preset heating rate of the second stage is 2 ℃/min;
(3.2) quickly pouring the clear glass liquid into a mold, cooling, demolding, taking out, and then putting into a muffle furnace preheated to 550 ℃ for heat preservation for 3h for annealing to obtain a glass substrate;
(3.3) cutting the annealed glass substrate into small pieces, and grinding and polishing the small pieces for later use;
step (4), carrying out second-step heat treatment on the glass substrate, heating to a nucleation temperature according to a preset heating rate, carrying out heat preservation, heating to a crystallization temperature, and carrying out heat preservation to obtain the sealing glass; the preset heating rate is 8 ℃/min; the nucleation temperature is 580 ℃, and the heat preservation time is 140min; the crystallization temperature is 1120 ℃, and the heat preservation time is 180min.
The test method of this embodiment is the same as that of example 1, and the test results are shown in table 1, fig. 1, and fig. 2.
Example 5
A preparation method of sealing glass for tantalum metal comprises the following steps:
step (1), uniformly mixing all components of the sealing glass to obtain a mixture;
the sealing glass comprises 59 mass percent of SiO 2 12% of B 2 O 3 5% of Al 2 O 3 6% of BaO and 4.7% of K 2 O, 4.5% of Na 2 O, 0.2% Fe 2 O 3 3.6% of TiO 2 1% ZrO, 3% LiO 2 And 1% of a rare earth element compound LaCePrZr;
step (2), preparing the mixture into slurry by using absolute ethyl alcohol, wherein the mass ratio of the absolute ethyl alcohol to the mixture is 2.6; ball milling is carried out on the slurry, the volume of ball milling stones is at least two times of the volume of the slurry, the ball milling rotating speed is 330r/min, and the ball milling time is 180min;
step (3), drying the slurry in a drying oven, and performing first-step heat treatment to obtain a glass matrix after drying;
the first heat treatment step specifically comprises the following steps:
(3.1) heating to 940 ℃ at a first-stage preset heating rate, and preserving heat for more than 2h to obtain a pre-sintered block, and heating to 1530 ℃ at a second-stage heating rate, and preserving heat for more than 2.5h to completely melt the raw materials and remove bubbles to obtain clear glass liquid; the preset heating rate of the first stage is 14 ℃/min, and the preset heating rate of the second stage is 5 ℃/min;
(3.2) quickly pouring the clear glass liquid into a mold, cooling, demolding, taking out, and then putting into a muffle furnace preheated to 550 ℃ for heat preservation for 3h for annealing to obtain a glass substrate;
(3.3) cutting the annealed glass substrate into small pieces, and grinding and polishing the small pieces for later use;
step (4), carrying out second-step heat treatment on the glass substrate, heating to a nucleation temperature according to a preset heating rate, carrying out heat preservation, heating to a crystallization temperature, and carrying out heat preservation to obtain the sealing glass; the preset heating rate is 8 ℃/min; the nucleation temperature is 570 ℃, and the heat preservation time is 130min; the crystallization temperature is 1130 ℃, and the heat preservation time is 170min.
The test method of this embodiment is the same as in example 1, and the test results are shown in table 1, fig. 1, and fig. 2.
Example 6
A preparation method of sealing glass for tantalum metal comprises the following steps:
step (1), uniformly mixing all components of the sealing glass to obtain a mixture;
the sealing glass comprises 58 mass percent of SiO 2 12.9% of B 2 O 3 6% of Al 2 O 3 5% of BaO and 4% of K 2 O, 4% of Na 2 O, 0.1% Fe 2 O 3 3% of TiO 2 2% ZrO, 4% LiO 2 And 1% of a rare earth element compound LaCePrZr;
step (2), preparing the mixture into slurry by using absolute ethyl alcohol, wherein the mass ratio of the absolute ethyl alcohol to the mixture is 3; ball milling is carried out on the slurry, the volume of ball milling stones is at least two times of the volume of the slurry, the ball milling rotating speed is 350r/min, and the ball milling time is 180min;
step (3), drying the slurry in a drying oven, and performing first-step heat treatment to obtain a glass matrix after drying;
the first-step heat treatment specifically comprises the following steps:
(3.1) firstly increasing the temperature to 950 ℃ at the first-stage preset heating rate, and preserving the heat for more than 2 hours to obtain a pre-sintered block, and then increasing the temperature to 1550 ℃ at the second-stage heating rate, and preserving the heat for more than 2.5 hours to completely melt the raw materials and remove bubbles to obtain clarified glass liquid; the preset heating rate of the first stage is 15 ℃/min, and the preset heating rate of the second stage is 4 ℃/min;
(3.2) quickly pouring the clear glass liquid into a mold, cooling, demolding, taking out, and then putting into a muffle furnace preheated to 550 ℃ for heat preservation for 3h for annealing to obtain a glass substrate;
(3.3) cutting the annealed glass substrate into small pieces, and grinding and polishing the small pieces for later use;
step (4), carrying out second-step heat treatment on the glass substrate, heating to a nucleation temperature according to a preset heating rate, carrying out heat preservation, heating to a crystallization temperature, and carrying out heat preservation to obtain the sealing glass; the preset heating rate is 10 ℃/min; the nucleation temperature is 580 ℃, and the heat preservation time is 140min; the crystallization temperature is 1150 ℃, and the heat preservation time is 180min.
The test method of this embodiment is the same as that of example 1, and the test results are shown in table 1, fig. 1, and fig. 2.
The above embodiments are only used for illustrating the technical solutions of the present invention, and not for limiting the same, and it is obvious for a person skilled in the art to modify the specific technical solutions described in the foregoing embodiments or to substitute part of the technical features, and these modifications or substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions protected by the present invention.
Claims (10)
1. A sealing glass for tantalum metal, characterized in that: comprises 56 to 60 mass percent of SiO 2 12 to 13 percent of B 2 O 3 5 to 6% of Al 2 O 3 5 to 6 percent of BaO and 4 to 5 percent of K 2 O, 4-5% of Na 2 O, 0.1-0.4% of Fe 2 O 3 3 to 4 percent of TiO 2 1 to 2 percent of ZrO, 3 to 4 percent of LiO 2 And 1-2% of rare earth element compound LaCePrZr; the SiO 2 With Al 2 O 3 The molar ratio of (1) to (12) is from 12 to 14.
2. A sealing glass for tantalum metal according to claim 1, wherein: the SiO accounts for 57 to 59 mass percent 2 12 to 13 percent of B 2 O 3 5 to 6% of Al 2 O 3 5 to 6 percent of BaO and 4.5 to 5.0 percent of K 2 O, 4.0-4.5% of Na 2 O, 0.1-0.4% of Fe 2 O 3 3.6 to 3.8 percent of TiO 2 1 to 2 percent of ZrO, 3.0 to 3.3 percent of LiO 2 And 1.0-1.5% of rare earth element compound LaCePrZr.
3. A sealing glass for tantalum metal according to claim 2, wherein: the SiO accounts for 56 percent by mass 2 13% of B 2 O 3 6% of Al 2 O 3 6% of BaO and 5% of K 2 O, 4% of Na 2 O, 0.1% Fe 2 O 3 3.6% of TiO 2 2% ZrO, 3.3% LiO 2 And 1% of rare earth element compound LaCePrZr.
4. A sealing glass for tantalum metal according to claim 2, wherein: the SiO accounts for 58 mass percent 2 12% of B 2 O 3 6% of Al 2 O 3 5% of BaO and 4.5% of K 2 O, 4.5% of Na 2 O, 0.4% Fe 2 O 3 3.6% of TiO 2 2% ZrO, 3% LiO 2 And 1% of a rare earth element compound LaCePrZr.
5. A method for producing a sealing glass for tantalum metal, which is based on the sealing glass for tantalum metal of claim 1, comprising the steps of:
step (1), uniformly mixing all components to obtain a mixture;
step (2), preparing the mixture into slurry by adopting a solvent;
step (3), drying the slurry in a drying oven, and performing first-step heat treatment to obtain a glass matrix after drying;
and (4) carrying out second-step heat treatment on the glass substrate, heating to a nucleation temperature according to a preset heating rate, carrying out heat preservation, heating to a crystallization temperature, and carrying out heat preservation to obtain the sealing glass.
6. A method for producing a sealing glass for tantalum metal according to claim 5, wherein: in step 3, the first heat treatment step specifically comprises:
(3.1) firstly increasing the temperature to 900-950 ℃ at the first-stage preset heating rate, preserving the heat for more than 2 hours to obtain a pre-sintered block, increasing the temperature to 1500-1550 ℃ at the second-stage heating rate, preserving the heat for more than 2.5 hours to completely melt the raw materials and remove bubbles to obtain clear glass liquid;
(3.2) quickly pouring the clear glass liquid into a mold, cooling, demolding, taking out, and then putting into a muffle furnace preheated to 550 ℃ for heat preservation for 3h for annealing to obtain a glass substrate;
and (3.3) cutting the annealed glass substrate into small pieces, and grinding and polishing the small pieces for later use.
7. A method for producing a sealing glass for tantalum metal according to claim 6, wherein: in the step 4, the preset heating rate is 5-10 ℃/min; the nucleation temperature is 550-580 ℃, and the heat preservation time is 120-140 min; the crystallization temperature is 1070-1150 ℃, and the heat preservation time is 150-180 min.
8. A method for producing a sealing glass for tantalum metal according to claim 7, wherein: the first-stage preset heating rate is 10-15 ℃/min, and the second-stage preset heating rate is 4-5 ℃/min.
9. A method for producing a sealing glass for tantalum metal according to any one of claims 5 to 8, wherein: in the step 2, the solvent is absolute ethyl alcohol, and the mass ratio of the absolute ethyl alcohol to the mixture is 2.6-3.
10. A method for producing a sealing glass for tantalum metal according to claim 9, wherein: the step 2 further comprises: ball milling is carried out on the slurry, the volume of ball milling stones is at least two times of the volume of the slurry, the ball milling rotating speed is 300-350 r/min, and the ball milling time is 130-180 min.
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