CN114044689B - Sealing body based on composite glass material, preparation method and application - Google Patents
Sealing body based on composite glass material, preparation method and application Download PDFInfo
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- CN114044689B CN114044689B CN202111329901.1A CN202111329901A CN114044689B CN 114044689 B CN114044689 B CN 114044689B CN 202111329901 A CN202111329901 A CN 202111329901A CN 114044689 B CN114044689 B CN 114044689B
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/083—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
- C03C3/085—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal
- C03C3/087—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal containing calcium oxide, e.g. common sheet or container glass
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B37/00—Joining burned ceramic articles with other burned ceramic articles or other articles by heating
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B37/00—Joining burned ceramic articles with other burned ceramic articles or other articles by heating
- C04B37/003—Joining burned ceramic articles with other burned ceramic articles or other articles by heating by means of an interlayer consisting of a combination of materials selected from glass, or ceramic material with metals, metal oxides or metal salts
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
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- Y02E60/50—Fuel cells
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Abstract
The invention relates to a sealing body based on a composite glass material, a preparation method and application, wherein the preparation method comprises the following steps: (1) Mixing raw materials according to the material composition of the composite glass material, melting, and quenching in cold water to obtain a glass frit; (2) Ball-milling the glass frit to obtain glass powder; (3) Mixing the glass powder with adhesive to obtain a glass sealing material; (4) And (3) coating the glass sealing material on a part to be sealed, applying extrusion force along the direction vertical to a sealing interface, heating to the glue discharging temperature for glue discharging, continuing heating for crystallization after the glue discharging is finished, and cooling to obtain a sealing body. The sealing body provided by the application is suitable for sealing glass, ceramic and metal interfaces, has a proper thermal expansion coefficient, can improve the chemical stability of the sealing body and a sealing object, has good self-healing performance, and effectively prolongs the service life of a sealing device.
Description
Technical Field
The invention belongs to the field of heterogeneous sealing of metal phases and ceramic phases, in particular relates to the field of heterogeneous sealing of metal phases and ceramic phases in fuel cells, electrolytic cells, sensors, actuators and the like, and particularly relates to a sealing body based on a composite glass material, a preparation method and application thereof.
Background
The sealing glass is an intermediate layer material for sealing glass, ceramics, metals, composite materials, and the like. Glass seals are finding increased interest in many applications, such as vacuum electronics, microelectronics, automotive, aerospace, and the like. The glass sealing material has high mechanical strength, high hardness, good wear resistance, good chemical stability and good thermal stability.
The compactness of the sealing glass and the sealing device influences the performance of the electronic device. When the sealing glass is used for sealing at a higher working temperature, the sealing material at least has a thermal expansion coefficient matched with a battery material, stable chemical properties, proper glass softening temperature (Tp) and good air tightness.
There is a need in the art to develop a sealing glass that can seal devices with higher operating temperatures, achieving good sealing properties.
Disclosure of Invention
In view of the deficiencies of the prior art, it is an object of the present invention to provide a method for producing a composite glass material-based sealing body, comprising the steps of:
(1) Mixing raw materials according to the material composition of the composite glass material, melting, and quenching in cold water to obtain a glass frit;
the composite glass material comprises the following components in terms of oxides:
58-64 wt% SiO 2 1.5 to 4.5wt% of Al 2 O 3 5 to 18 weight percent of CaO, 2 to 12 weight percent of MgO and 5 to 9 weight percent of K 2 O, 2.5-7 wt% of Na 2 O, 1.5 to 8.5 weight percent of BaO and the balance of impurities;
(2) Ball-milling the glass frit to obtain glass powder;
(3) Mixing the glass powder with adhesive to obtain a glass sealing material;
(4) And (3) coating the glass sealing material on a part to be sealed, applying extrusion force along the direction vertical to a sealing interface, heating to the glue discharging temperature for glue discharging, continuing heating for crystallization after the glue discharging is finished, and cooling to obtain a sealing body.
Preferably, the extrusion force in the step (4) is 0.14 to 0.40kg/cm 2 (e.g., 0.15 kg/cm) 2 、0.18kg/cm 2 、 0.20kg/cm 2 、0.23kg/cm 2 、0.27kg/cm 2 、0.33kg/cm 2 、0.37kg/cm 2 Etc.); said crystallizing comprisingHeating to 730-850 deg.C (such as 740 deg.C, 750 deg.C, 760 deg.C, 770 deg.C, 780 deg.C, 790 deg.C, 800 deg.C, 810 deg.C, 820 deg.C, 830 deg.C, 840 deg.C), and keeping the temperature for 2-5 h (such as 3h, 4 h); the temperature reduction is to use temperature or storage temperature.
Further preferably, the extrusion force in the step (4) is 0.14 to 0.40kg/cm 2 (ii) a The crystallization comprises heating to 800-850 ℃, and then preserving heat for 2-5 h; the temperature reduction is to reduce the temperature to the use temperature or to reduce the temperature to the storage temperature.
In the preparation method provided by the invention, the sealing body with high amorphous phase content and a monoclinic phase crystal structure diopside phase as a main crystal phase in a crystal phase can be obtained by the material composition of the composite glass material and proper crystallization conditions.
When the sealing glass is in contact with a sealing object, elements can migrate at an interface, and the sealing effect of the sealing glass is influenced. Especially for devices with higher operating temperatures, such as Solid Oxide Fuel Cells (SOFC), element migration occurs more easily, and once element migration has occurred, the sealing characteristics of the sealing glass are easily affected. For example, sealing glasses containing alkaline earth metal oxides (e.g., srO-La) 2 O 3 -Al 2 O 3 -SiO 2 Or BaO-CaO-Al 2 O 3 -SiO 2 ) Can form crystals (SrCrO) which are not beneficial to sealing after being sealed with a Cr-containing stainless steel plate 4 、BaCrO 4 ) Leading to sealing failure and seriously influencing the use and sealing effect of the SOFC. In the sealing body provided by the application, diopside crystal phase exists in the form of the diopside crystal with a monoclinic phase crystal structure, and element migration between different interfaces can be effectively blocked.
When the sealing material cracks at low temperature, the glass can be softened by raising the temperature, the cracks are healed, and sealing is realized. The sealing body provided by the application has good self-healing performance.
The melting conditions (melting temperature, melting time, melting conditions, etc.) are not particularly limited in the present application, and conditions capable of melting the raw material may be used in the present application, and may be exemplified by microwave-assisted melting, plasma heating melting, or muffle furnace melting, and the like.
Preferably, the melting temperature in step (1) is 1400-1600 ℃ (e.g. 1450 ℃, 1500 ℃, 1550 ℃ etc.), and the melting time is 2-5 h (e.g. 2.5h, 3.0h, 3.5h, 4.0h, 4.5h, etc.).
The application does not do specific limitation to the particle size of the glass powder, the type and the addition amount of the bonding glue, and the application can be used as long as the bonding glue is uniformly dispersed.
Preferably, the particle size of the glass powder is 0.070-0.090 mm (e.g., 0.072mm, 0.075mm, 0.077mm, 0.079mm, 0.082mm, 0.085mm, 0.087mm, 0.089mm, etc.).
Preferably, in step (3), the mass ratio of the glass powder to the adhesive paste is from 4.
The coating thickness of the glass sealing material at the part to be sealed is 0.5-2 mm, preferably 0.5-1.2 mm, and further preferably 0.8-1.2 mm.
The glue discharging temperature can be selected according to the selected adhesive glue, the exemplary glue discharging condition is that the heat is preserved for 1-4 h under the condition of 200-300 ℃, and the extrusion force is 0.30-0.40 kg/cm 2 。
As an alternative solution, the adhesive used in the present application may be any one of silk-screen printing glues, such as a mixture of ethyl cellulose and terpineol.
As a preferred technical scheme, the crystallization comprises the steps of heating to 730-780 ℃, and controlling the extrusion force to be 0.30-0.40 kg/cm 2 Treating for 1.5-2.5 h, then continuously heating to 820-850 ℃, and adjusting the extrusion force to 0.14-0.24 kg/cm 2 Treating for 1.5-2.5 h, and then cooling to obtain the sealing body.
In the preferred embodiment, the sealing body has better sealing effect and better self-healing property, which may be due to the more uniform distribution of diopside crystal phases and the more uniform alignment of crystal phase orientations in the direction parallel to the interface.
It is another object of the invention to provide a composite glass material-based seal prepared by the method of one of the objects.
Preferably, the encapsulant contains 50wt% or more amorphous phase; and in the crystalline phase, the main crystalline phase is a pyrochlore crystalline phase.
By primary crystalline phase is generally understood a crystalline phase which constitutes > 50% of the crystalline phase.
In the sealing body provided by the application, the content of the potassium feldspar is very low, and no diffraction peak appears in XRD detection.
Preferably, the hemispheric temperature of the encapsulant is in the range of 800 ℃ to 880 ℃ (e.g., 820 ℃, 850 ℃, 870 ℃, etc.).
Preferably, the thermal expansion coefficient of the sealing body is 8.0 x 10 -6 K -1 ～12.0×10 -6 K -1 (e.g., 8.5X 10) -6 K -1 、9.0×10 -6 K -1 、9.5×10 -6 K -1 、10.0×10 -6 K -1 、10.5×10 -6 K -1 、11.0×10 -6 K -1 、11.5 ×10 - 6 K -1 Etc.).
The sealing body provided by the invention takes the diopside crystal phase as the main crystal phase and contains more amorphous phases, so that the sealing body can be ensured to have proper thermal expansion coefficient, self-healing property and softening temperature (the hemisphere temperature is 800-880 ℃), and sealing can be carried out under the condition of 750-870 ℃.
Preferably, the sealing body contains the following components in terms of oxides according to the material composition:
58 to 64wt% of SiO 2 1.5-4.5 wt% of Al 2 O 3 5 to 18 weight percent of CaO, 2 to 12 weight percent of MgO and 5 to 9 weight percent of K 2 O, 2.5-7 wt% of Na 2 O, 1.5-8.5 wt% of BaO and the balance of impurities.
The impurity may be Y 2 O 3 、ZrO 2 、Fe 2 O 3 、P 2 O 3 、TiO 2 And the like, or a combination of at least two thereof. The impurities are derived from raw materials in the process of forming the sealing body, such as ore raw materials and the like.
It is a further object of the present invention to provide the use of a composite glass material based seal according to one of the objects as any one or a combination of at least two of a solid fuel cell seal, an electrolytic cell seal, a sensor seal, an actuator seal, a display screen seal, a microelectronic seal.
Compared with the prior art, the method has the following beneficial effects:
the sealing body provided by the application is suitable for sealing glass, ceramic and metal interfaces, especially for sealing interfaces with higher working temperature, has a proper thermal expansion coefficient, can effectively block element migration between different interfaces, improves the chemical stability of the sealing body and a sealing object, has good self-healing performance, and effectively prolongs the service life of a sealing device in an environment with higher working temperature.
Drawings
FIG. 1 is an XRD spectrum of the seal of example 1;
FIG. 2 is an electron micrograph of a cross-sectional profile of the seal and stainless SUS430 of example 1;
FIG. 3 is a diagram of element migration at the circled portion of FIG. 2;
fig. 4 is a graph showing the measurement of the thermal expansion coefficient of the sealing body of example 1.
Detailed Description
The technical solution of the present invention is further explained with reference to the following embodiments, but it should be noted that the embodiments are only an embodiment and explanation of the spirit of the technical solution of the present invention, and should not be construed as a limitation to the scope of the present invention.
The reagents and instruments used in the examples are commercially available and the detection methods are conventional methods well known in the art.
Example 1
The 8YSZ ceramic and stainless steel SUS430 are used as sealing objects to carry out face-to-face sealing, and the following sealing operations are carried out:
(1) Mixing raw materials according to the material composition of the composite glass material, melting at 1400-1600 ℃, wherein the melting time is 2-5 h, and quenching in cold water to obtain a glass frit;
the material composition of the composite glass material is calculated by oxides and prepared according to the following components:
62wt% SiO 2 3wt% of Al 2 O 3 9wt% CaO, 4.5wt% MgO, 8.5wt% K 2 O, 6wt% of Na 2 O, 7wt% BaO, and the balance impurities;
(2) Ball-milling the glass frit to obtain glass powder with the particle size of 0.070-0.090 mm;
the glass powder is heated from room temperature to 700 ℃ at the speed of 5 ℃/min by ZRPY-1000 equipment, and the thermal expansion coefficient of the glass powder is measured; a muffle furnace is selected, the temperature is increased from room temperature to 900 ℃ at the speed of 5 ℃/min, and the hemispherical temperature of the glass powder is recorded by a high-definition camera; the thermal expansion coefficient of the glass powder is measured to be 9.830 multiplied by 10 -6 K -1 The hemispherical temperature is 825 deg.C;
(3) Mixing the glass powder with bonding glue (ethyl cellulose and terpineol with a mass ratio of 96;
(4) Coating the glass sealing material on the sealing part of 8YSZ ceramic and stainless steel SUS430, wherein the average coating thickness is 0.9mm, and applying 0.40kg/cm along the direction vertical to the sealing interface 2 Heating to a glue discharging temperature of 250 ℃, keeping the temperature for 2h for discharging glue, continuously heating to 750 ℃ after the glue discharging is finished, and controlling the extrusion force
Is 0.35kg/cm 2 Treating for 2.0h, then continuously heating to 830 ℃, and adjusting the extrusion force to be 0.20kg/cm 2 And treating for 2.0h, and then cooling to the use temperature of 780 ℃ to obtain the sealing body.
Example 2
The difference from example 1 is that step (4) is adjusted to:
coating the glass sealing material on the sealing part of 8YSZ ceramic and stainless steel SUS430, wherein the average coating thickness is 0.9mm, and applying 0.0.40kg/cm along the direction vertical to the sealing interface 2 Heating to the glue discharging temperature of 200 ℃ and keeping the temperature for 4hRemoving glue, after removing glue, continuously heating to 730 ℃, and controlling the extrusion force to be 0.30kg/cm 2 Treating for 1.5h, then continuously heating to 850 ℃, and adjusting the extrusion force to be 0.24kg/cm 2 And treating for 2.5h, and then cooling to the use temperature of 780 ℃ to obtain the sealing body.
The glass powder of example 2 has the same composition as that of the glass powder of example 1, and the thermal expansion coefficient of the glass powder is measured to be the same as that of example 1.
Example 3
The difference from example 1 is that step (4) is adjusted to:
coating the glass sealing material on the sealing part of 8YSZ ceramic and stainless steel SUS430, wherein the average coating thickness is 0.9mm, and applying 0.40kg/cm along the direction vertical to the sealing interface 2 Heating to the glue discharging temperature of 300 ℃, preserving the heat for 1h for discharging the glue, continuing heating to 780 ℃ after the glue discharging is finished, and controlling the extrusion force to be 0.40kg/cm 2 Treating for 2.5h, then continuously heating to 820 ℃, and adjusting the extrusion force to be 0.14kg/cm 2 And treating for 1.5h, and then cooling to the use temperature of 780 ℃ to obtain the sealing body.
The glass powder of example 3 had the same composition as that of example 1, and the thermal expansion coefficient of the glass powder was measured to be the same as that of example 1.
Example 4
The difference from example 1 is that step (4) is adjusted to:
coating the glass sealing material on the sealing part of 8YSZ ceramic and stainless steel SUS430, wherein the average coating thickness is 0.9mm, and applying 0.40kg/cm along the direction vertical to the sealing interface 2 Heating to 250 deg.C for 2h to discharge glue, heating to 800 deg.C, and controlling the extrusion force to 0.35kg/cm 2 And treating for 4h, and then cooling to the use temperature of 780 ℃ to obtain the sealing body.
The glass powder of example 4 had the same composition as that of the glass powder of example 1, and the thermal expansion coefficient of the glass powder was measured to be the same as that of example 1.
Example 5
The difference from example 1 is that step (4) is adjusted to:
coating the glass sealing material on the sealing part of 8YSZ ceramic and stainless steel SUS430, wherein the average coating thickness is 0.9mm, and applying 0.40kg/cm along the direction vertical to the sealing interface 2 Heating to 250 deg.C for 2h to discharge glue, heating to 850 deg.C, and controlling the extrusion force to 0.40kg/cm 2 And treating for 4h, and then cooling to the use temperature of 780 ℃ to obtain the sealing body.
The glass powder of example 5 had the same composition as that of example 1, and the thermal expansion coefficient of the glass powder was measured to be the same as that of example 1.
Example 6
The difference from example 1 is that step (4) is adjusted to:
coating the glass sealing material on the sealing part of 8YSZ ceramic and stainless steel SUS430, wherein the average coating thickness is 0.9mm, and applying 0.40kg/cm along the direction vertical to the sealing interface 2 Heating to 250 deg.C for 2h to discharge glue, heating to 800 deg.C, and controlling the extrusion force to 0.14kg/cm 2 And (4) treating for 4h, and then cooling to the using temperature of 780 ℃ to obtain the sealing body.
The glass powder of example 6 was identical in composition to the glass powder of example 1, and the thermal expansion coefficient of the glass powder was measured to be identical to that of example 1.
Example 7
The difference from example 1 is that:
the material composition of the composite glass material is calculated by oxides and prepared according to the following components:
63% by weight of SiO 2 3wt% of Al 2 O 3 6wt% CaO, 2.5wt% MgO, 9.5wt% K 2 O, 7wt% of Na 2 O, 8wt% BaO.
The same test method for the glass powder as in example 1 was used to determine that the thermal expansion coefficient of the glass powder obtained in example 7 was 10.021X 10 -6 K -1 The hemisphere temperature was 803 ℃.
Example 8
The difference from example 1 is that:
the material composition of the composite glass material is calculated by oxides and prepared according to the following components:
60wt% SiO 2 2.5wt% of Al 2 O 3 11.5wt% CaO, 5.5wt% MgO, 7.3wt% K 2 O, 5.3wt% of Na 2 O, 6.3wt% BaO.
The same test method for the glass powder as in example 1 was used to determine that the glass powder obtained in example 8 had a thermal expansion coefficient of 9.422X 10 -6 K -1 The hemisphere temperature was 851 ℃.
Example 9
The difference from example 1 is that:
the material composition of the composite glass material is calculated by oxides and prepared according to the following components:
59% by weight of SiO 2 2.5wt% of Al 2 O 3 15wt% CaO, 7wt% MgO, 6.5wt% K 2 O, 4.5wt% of Na 2 O, 5.5wt% BaO.
The same test method for the glass powder as in example 1 was used to determine that the glass powder obtained in example 9 had a thermal expansion coefficient of 9.434X 10 -6 K -1 The hemisphere temperature was 879 ℃.
Example 10
The difference from example 1 is that step (4) is adjusted to:
coating the glass sealing material on the sealing part of 8YSZ ceramic and stainless steel SUS430, wherein the average coating thickness is 0.9mm, and applying 0.0.40kg/cm along the direction vertical to the sealing interface 2 Heating to the glue discharging temperature of 200 ℃, keeping the temperature for 4 hours to discharge the glue, continuing heating to 700 ℃ after the glue discharging is finished, and controlling the extrusion force to be 0.50kg/cm 2 Treating for 3h, then continuously heating to 850 ℃, and adjusting the extrusion force to be 0.24kg/cm 2 And treating for 2.5h, and then cooling to the using temperature of 780 ℃ to obtain the sealing body.
The glass powder of example 10 has the same composition as that of the glass powder of example 1, and the thermal expansion coefficient of the glass powder is measured to be the same as that of example 1.
Example 11
The difference from example 1 is that step (4) is adjusted to:
coating the glass sealing material on the sealing part of 8YSZ ceramic and stainless steel SUS430, wherein the average coating thickness is 0.9mm, and applying 0.0.40kg/cm along the direction vertical to the sealing interface 2 Heating to the glue discharging temperature of 200 ℃, keeping the temperature for 4 hours to discharge the glue, continuing heating to 800 ℃ after the glue discharging is finished, and controlling the extrusion force to be 0.50kg/cm 2 Treating for 3h, then continuously heating to 850 ℃, and adjusting the extrusion force to be 0.24kg/cm 2 And treating for 2.5h, and then cooling to the use temperature of 780 ℃ to obtain the sealing body.
The glass powder of example 11 has the same composition as that of the glass powder of example 1, and the thermal expansion coefficient of the glass powder is measured to be the same as that of example 1.
Example 12
The difference from example 1 is that step (4) is adjusted to:
coating the glass sealing material on the sealing part of 8YSZ ceramic and stainless steel SUS430, wherein the average coating thickness is 0.9mm, and applying 0.0.40kg/cm along the direction vertical to the sealing interface 2 Heating to the glue discharging temperature of 200 ℃, keeping the temperature for 4h for discharging glue, continuously heating to 750 ℃ after the glue discharging is finished, and controlling the extrusion force to be 0.20kg/cm 2 Treating for 2h, then continuously heating to 850 ℃, and adjusting the extrusion force to be 0.24kg/cm 2 And treating for 2.5h, and then cooling to the using temperature of 780 ℃ to obtain the sealing body.
The glass powder of example 12 had the same composition as that of the glass powder of example 1, and the thermal expansion coefficient of the glass powder was measured to be the same as that of example 1.
Comparative example 1
The difference from example 1 is that:
the material composition of the composite glass material is calculated by oxides and prepared according to the following components:
52wt% SiO 2 6wt% of Al 2 O 3 12wt% CaO, 8wt% MgO, 8wt% K 2 O, 7wt% of Na 2 O、7wt% BaO.
Using the same test method for glass powder as in example 1, the glass powder obtained in comparative example 1 was found to have a thermal expansion coefficient of 9.478X 10 -6 K -1 The hemisphere temperature was 925 ℃.
Comparative example 2
The difference from example 1 is that:
the material composition of the composite glass material is calculated by oxides and prepared according to the following components:
60% by weight of SiO 2 5wt% of Al 2 O 3 4wt% CaO, 2wt% MgO, 12wt% K 2 O, 10wt% of Na 2 O, 7wt% BaO.
The same test method as in example 1 was used to measure that the thermal expansion coefficient of the glass powder obtained in comparative example 2 was 9.478X 10 -6 K -1 The hemisphere temperature was 750 ℃.
The composite glass materials of examples 1, 7 to 9 and comparative examples 1 to 2 were subjected to elemental analysis, and the compositions thereof in terms of oxides were measured as shown in table 1.
TABLE 1
| Make up of | Example 1 | Example 7 | Example 8 | Example 9 | Comparative example 1 | Comparative example2 |
| SiO 2 | 62.08 | 63.03 | 60.8 | 59.69 | 52.54 | 62.03 |
| Al 2 O 3 | 2.99 | 3.34 | 2.6 | 2.23 | 5.83 | 4.52 |
| CaO | 8.88 | 5.97 | 11.6 | 14.41 | 12.03 | 3.52 |
| MgO | 4.38 | 2.57 | 5.41 | 6.82 | 7.65 | 1.54 |
| K 2 O | 8.41 | 9.4 | 7.31 | 6.26 | 7.75 | 11.76 |
| Na 2 O | 5.95 | 6.87 | 5.34 | 4.58 | 7.02 | 9.54 |
| BaO | 6.89 | 8.13 | 6.32 | 5.41 | 6.75 | 6.86 |
| Impurities in the product | Allowance of | Balance of | Balance of | Balance of | Balance of | Balance of |
And (3) performance testing:
the following performance tests were performed on the seals obtained in the examples and comparative examples:
(1) The crystal phase composition is as follows: XRD (equipment model number is Smartlab (9)) is selected to carry out crystal phase determination under the room temperature condition;
(2) Coefficient of thermal expansion: selecting ZRPY-1000 equipment, measuring the thermal expansion coefficient under the conditions that the test temperature range is between room temperature and 700 ℃ and the heating rate is 5 ℃/min;
(3) Airtightness: introducing gas into the sealed object to enable the initial pressure to be 5kPa, measuring the gas overflow rate at 780 ℃, and recording as the gas tightness;
(4) Circulating air tightness: introducing gas into the sealed object to enable the initial pressure to be 5kPa, preserving the temperature for 30h at 780 ℃, then releasing the gas pressure, and cooling to the room temperature; then continuing to heat up and repeating the steps for 5 times, measuring the gas overflow rate when the temperature is raised to 780 ℃ in the last time, and recording as the cycle gas tightness;
the results are shown in Table 2.
TABLE 2
As can be seen from table 2, the sealing body provided by the application obtains a glass sealing body which has a diopside crystal phase while the amorphous phase content is high through the limitation on the composition, the sealing body has good air tightness, and can effectively seal a heterogeneous interface.
Figure 1 is an XRD spectrum of the seal of example 1. FIG. 1, a is the absorption peak of the seal of example 1 after sintering at 800 ℃ for 100 h; b is the absorption peak of the seal of example 1 after sintering at 800 ℃ for 10 h; c is the absorption peak of the seal of example 1 after sintering at 820 ℃ for 1 h; d is the absorption peak of the glass frit body of step (2) of example 1; has the advantages of
The absorption peak of (a) is information given by a JCPDS database, and is judged to be a diopside absorption peak.
As can be seen from fig. 1, the XRD spectrum of the seal of the present application can see that the main crystal phase is the orthorhombic diopside crystal phase (the marked peak is the absorption peak of the diopside crystal phase).
FIG. 2 is an electron microscope photograph showing cross-sectional shapes of the sealing body and stainless SUS430 of example 1, wherein the sealing body is provided at the upper part and the stainless SUS430 is provided at the lower part; FIG. 3 is a graph of element migration at the circled portion of FIG. 2. From fig. 2 and fig. 3, it can be seen that the silicon element and the chromium element are at the interface of 6.98 μm, and no chromium element is at 6.16 μm, which proves that the sealing body effectively blocks the migration of the chromium element.
FIG. 4 is a graph showing the measurement of the thermal expansion coefficient of the sealing body of example 1, and it can be seen from FIG. 4 that the thermal expansion coefficient of the sealing body of example 1 is 9.83016X 10 -6 K -1 . Since the thermal expansion coefficient is dependent on the composition of the glass material and is independent of the temperature rise process of the glass material, the sealing materials of examples 1 to 6 and example 10 have the same thermal expansion coefficient.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (9)
1. A preparation method of a sealing body based on a composite glass material is characterized by comprising the following steps:
(1) Mixing raw materials according to the material composition of the composite glass material, melting, and quenching in cold water to obtain a glass frit;
the composite glass material comprises the following components in terms of oxides:
58 to 64wt% of SiO 2 1.5 to 4.5wt% of Al 2 O 3 5 to 18wt% of CaO and 2 to 10wt% of CaO12wt% of MgO and 5 to 9wt% of K 2 O, 2.5 to 7wt% of Na 2 O, 1.5 to 8.5wt percent of BaO and the balance of impurities;
(2) Ball-milling the glass frit to obtain glass powder;
(3) Mixing the glass powder with adhesive to obtain a glass sealing material;
(4) Coating the glass sealing material on a part to be sealed, applying extrusion force along a direction vertical to a sealing interface, heating to a glue discharging temperature for discharging glue, continuing heating for crystallization after the glue discharging is finished, and cooling to obtain a sealing body;
the extrusion force in the step (4) is 0.14 to 0.40kg/cm 2 ；
The crystallization is carried out by heating to 730 to 850 ℃, and then keeping the temperature for 2 to 5 hours;
the temperature reduction is to reduce the temperature to the use temperature or to reduce the temperature to the storage temperature.
2. The method according to claim 1, wherein the melting temperature in the step (1) is 1400 to 1600 ℃ and the melting time is 2 to 5 hours.
3. The method according to claim 1, wherein the glass powder has a particle size of 0.070 to 0.090mm.
4. The preparation method according to claim 1, wherein the mass ratio of the glass powder to the adhesive in the step (3) is 4 to 1.
5. The method according to claim 1, wherein the crystallization comprises heating to 730 to 780 ℃ and controlling the extrusion pressure to be 0.30 to 0.40kg/cm 2 Treating for 1.5 to 2.5 hours, then continuously heating to 820 to 850 ℃, and adjusting the extrusion pressure to be 0.14 to 0.24kg/cm 2 Treating for 1.5 to 2.5 hours, and then cooling to obtain the sealing body.
6. A composite glass material-based seal, characterized in that it is produced by the method according to one of claims 1 to 5.
7. The seal of claim 6, wherein said seal has a hemisphere temperature of 800 ℃ to 880 ℃;
the thermal expansion coefficient of the sealing body is 8.0 multiplied by 10 -6 K -1 ~12.0×10 -6 K -1 。
8. The sealing body according to claim 6, wherein the sealing body comprises the following components in terms of oxides, in terms of composition of matter:
58 to 64wt% of SiO 2 1.5 to 4.5wt% of Al 2 O 3 CaO 5 to 18wt%, mgO 2 to 12wt%, and K5 to 9wt% 2 O, 2.5 to 7wt% of Na 2 O, 1.5 to 8.5wt percent of BaO and the balance of impurities.
9. Use of a composite glass material based seal according to claim 6 as any one of, or in combination with at least two of, a solid fuel cell seal, an electrolytic cell seal, a sensor seal, an actuator seal, a display screen seal, a microelectronic seal.
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| CN101148322B (en) * | 2007-06-29 | 2011-05-11 | 清华大学 | Microcrystal glass sealing material used for solid oxide fuel battery and sealing method thereof |
| DE102013209970B3 (en) * | 2013-05-28 | 2014-07-24 | Schott Ag | Glassy or at least partially crystalline joining material and its use and jointing |
| CN103274601B (en) * | 2013-06-07 | 2016-01-06 | 福州大学 | A kind of containing Nb 2o 5seal glass and preparation and application thereof |
| DE102015207285B4 (en) * | 2015-04-22 | 2019-05-02 | Schott Ag | Glassy or at least partially crystallized sealing material, joint, barrier layer, and layer system with the melted material and its integration in components |
| CN104961337A (en) * | 2015-07-01 | 2015-10-07 | 京东方科技集团股份有限公司 | Lead-free sealing glass and preparation method thereof |
| CN111302639A (en) * | 2020-04-20 | 2020-06-19 | 北京北旭电子材料有限公司 | Preparation method of glass powder and glass powder |
| CN112521011B (en) * | 2020-11-04 | 2022-03-08 | 中国科学院上海硅酸盐研究所 | Solid oxide fuel cell composite sealing material and preparation method and application thereof |
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