CN117602838A - High-temperature sealing microcrystalline glass and preparation and application thereof - Google Patents
High-temperature sealing microcrystalline glass and preparation and application thereof Download PDFInfo
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- 239000011521 glass Substances 0.000 title claims abstract description 101
- 238000007789 sealing Methods 0.000 title claims abstract description 96
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 38
- 229910000833 kovar Inorganic materials 0.000 claims abstract description 20
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims abstract description 15
- 229910004298 SiO 2 Inorganic materials 0.000 claims abstract description 15
- 239000013078 crystal Substances 0.000 claims description 31
- 238000000137 annealing Methods 0.000 claims description 26
- 238000002425 crystallisation Methods 0.000 claims description 25
- 230000008025 crystallization Effects 0.000 claims description 25
- 238000002844 melting Methods 0.000 claims description 24
- 239000005394 sealing glass Substances 0.000 claims description 24
- 230000008018 melting Effects 0.000 claims description 23
- 238000010899 nucleation Methods 0.000 claims description 17
- 230000006911 nucleation Effects 0.000 claims description 17
- 239000006121 base glass Substances 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 13
- 239000002241 glass-ceramic Substances 0.000 claims description 12
- 239000000919 ceramic Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 229910045601 alloy Inorganic materials 0.000 abstract description 18
- 239000000956 alloy Substances 0.000 abstract description 18
- 239000007788 liquid Substances 0.000 description 14
- 238000012360 testing method Methods 0.000 description 11
- 239000002994 raw material Substances 0.000 description 10
- 238000005266 casting Methods 0.000 description 7
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- 238000005520 cutting process Methods 0.000 description 7
- 239000006066 glass batch Substances 0.000 description 7
- 238000000465 moulding Methods 0.000 description 7
- 238000011056 performance test Methods 0.000 description 7
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- 238000005303 weighing Methods 0.000 description 7
- 238000009413 insulation Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- XGCTUKUCGUNZDN-UHFFFAOYSA-N [B].O=O Chemical compound [B].O=O XGCTUKUCGUNZDN-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 230000007704 transition Effects 0.000 description 4
- 239000000969 carrier Substances 0.000 description 3
- 238000010292 electrical insulation Methods 0.000 description 3
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 229910001413 alkali metal ion Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
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- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
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- 229910021193 La 2 O 3 Inorganic materials 0.000 description 1
- 229910017709 Ni Co Inorganic materials 0.000 description 1
- 229910003267 Ni-Co Inorganic materials 0.000 description 1
- 229910003262 Ni‐Co Inorganic materials 0.000 description 1
- CFOAUMXQOCBWNJ-UHFFFAOYSA-N [B].[Si] Chemical compound [B].[Si] CFOAUMXQOCBWNJ-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
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Abstract
The invention discloses high-temperature sealing microcrystalline glass, and preparation and application thereof, wherein the high-temperature sealing microcrystalline glass comprises the following components in parts by mass: 55-65 parts of SiO 2 8-15 parts of Al 2 O 3 10-20 parts of B 2 O 3 4-10 parts of ZnO and 4-10 parts of R 2 O, 4-10 parts of CaO, 4-10 parts of ZrO 2 The method comprises the steps of carrying out a first treatment on the surface of the Wherein R is 2 O is Na 2 O、K 2 One or more of O; the softening point of the obtained high-temperature sealing microcrystalline glass is more than 600 ℃, the matching degree of the high-temperature sealing microcrystalline glass and the thermal expansion coefficient of kovar alloy is high, and the resistivity is always more than 3.72 multiplied by 10 within the temperature range of room temperature to 600 DEG C 9 The high-temperature sealing microcrystalline glass has good insulativity when the resistivity is high and the density of the high-temperature sealing microcrystalline glass is 2.39g/cm 3 ‑2.46g/cm 3 High-temperature sealing microcrystalline glass and kovar alloy protection of the application at high temperatureGood matching and sealing and good insulativity are maintained.
Description
Technical Field
The invention relates to the technical field of glass products, in particular to high-temperature sealing microcrystalline glass, and preparation and application thereof.
Background
The sealing glass is used as a non-aging and temperature-resistant glue, has the functions of electric insulation, physical support, signal transmission and the like, and is an intermediate transition material for realizing reliable connection among metal, ceramic, other glass and composite materials. Compared with the common sealing technology, the sealing glass has obvious superiority, and is mainly characterized by good mechanical property and high air tightness.
The sealing glass is classified into low temperature type sealing glass and high temperature type sealing glass according to the sealing temperature. The low-temperature sealing glass is also called as low-melting point sealing glass, and the melting point of the low-temperature sealing glass is obviously lower than that of common glass, and is generally lower than 600 ℃. The high-temperature sealing glass is glass for sealing at a higher temperature (the sealing temperature is more than 800 ℃), and the glass transition temperature, the softening temperature and the melting point of the high-temperature sealing glass are higher. The kovar alloy is an Fe-Ni-Co alloy with Fe as a main matrix element, and the expansion coefficient of the kovar alloy is similar to that of the silicon-boron hard glass by about 50+/-5 multiplied by 10 -7 ℃ -1 . Therefore, kovar alloy and glass sealing are widely applied to the field of electronic packaging of incandescent lamps, electronic tubes, semiconductor shells and the like, and glass for sealing the kovar alloy is required to have the characteristics of insulation, high temperature resistance and sealing effect at high temperature. In the related art, sealing glass for kovar alloy has a thermal expansion coefficient of 3 to 5×10 -6 ℃ -1 SiO of (2) 2 -B 2 O 3 Glass systems (7070, corning). However, as the working temperature increases from 25℃to 350℃the volume resistivity of the sealing glass is from 10 12 Omega cm to 10 7 Omega cm, the maximum use temperature of the sealing glass is limited to 350 ℃. In addition, when the operating temperature is higher than the glass transition temperature Tg, since alkali or alkaline earth metal ions become more likely to migrate in the glass network structure, the electrical insulation property is deteriorated due to a rapid decrease in the sealing glass resistivity, thus limiting the use temperature of the sealing glass device and adversely affecting the electrical properties thereof. Other high temperature sealing glasses, e.g. La 2 O 3 -BaO-SiO 2 High-temperature sealing glass of system still 10 at 350 DEG C 11 Resistivity of Ω cm, and still possess 10 when the temperature is raised to 600 c 9 Resistivity of Ω·cm, and insulation property. However, the thermal expansion coefficient is 12.48-13.18X10 -6 ℃ -1 The expansion coefficient difference with the kovar alloy is large, and the kovar alloy cannot be used for matching and sealing of the kovar alloy, otherwise, the problems of cracking and the like are caused.
Therefore, it is desirable to provide a sealing glass that maintains the insulating properties of the glass at high temperatures and has a moderate expansion coefficient to achieve sealing with kovar.
Disclosure of Invention
In view of the above, the present application provides a high-temperature sealing glass ceramic, and preparation and application thereof, which solves the problem of how to achieve good sealing between the sealing glass and the kovar alloy at high temperature and good insulation.
In order to achieve the technical purpose, the application adopts the following technical scheme:
in a first aspect, the application provides high-temperature sealing glass ceramic, which comprises the following components in parts by mass: 55-65 parts of SiO 2 8-15 parts of Al 2 O 3 10-20 parts of B 2 O 3 4-10 parts of ZnO and 4-10 parts of R 2 O, 4-10 parts of CaO, 4-10 parts of ZrO 2 The method comprises the steps of carrying out a first treatment on the surface of the Wherein R is 2 O is Na 2 O、K 2 One or more of O.
Preferably, the main crystal phase is Al 0.52 Zr 0.48 O 1.74 And ZrO(s) 2 The crystallinity of the main crystal phase is 5-19%.
More preferably, R 2 O is K 2 O。
In a second aspect, the present application provides a method for preparing high temperature sealing glass ceramics, comprising the following steps:
s1, mixing powdered SiO according to parts by mass 2 、Al 2 O 3 、B 2 O 3 、ZnO、R 2 O、CaO、ZrO 2 Uniformly mixing, forming after melting, homogenizing and clarifying, and then annealing to obtain base glass;
s2, sequentially carrying out nucleation and crystallization heat treatment on the base glass to obtain the high-temperature sealing microcrystalline glass.
Preferably, in step S1, the melting temperature is 1500-1600 ℃, and the melting time is 2-4h.
Preferably, in step S1, the annealing temperature is 580-650 ℃ and the annealing time is 1-3h.
Preferably, in step S2, the temperature of the nucleation is 850-950 ℃ and the time of the nucleation is 0.5-3h.
Preferably, in step S2, the crystallization temperature is 1100-1350 ℃ and the crystallization time is 0.5-3h.
In a third aspect, the application provides an application of high-temperature sealing microcrystalline glass in kovar sealing.
Preferably, the sealing temperature is 800-1025 ℃.
The beneficial effects of this application are as follows:
under the component proportion of the application, the high-temperature sealing microcrystalline glass is obtained through heat treatment, the glass after heat treatment has different degrees of crystallization, and the precipitated main crystal phase is Al 0.52 Zr 0.48 O 1.74 (PDF# 53-0294) and ZrO 2 (PDF#37-1484) with crystallinity of about 5-19% for the main crystal phase, the two main crystal phases having high melting point, high resistivity, low expansion coefficient; meanwhile, in the process of forming the high-temperature sealing microcrystalline glass, the boron-oxygen triangle body [ BO ] 3 ]To boron oxygen tetrahedra [ BO 4 ]The transition is caused to be converted from a part of the layered structure in the two-dimensional space to a frame-shaped structure in the three-dimensional space, so that the network structure is increased to enable the structure to be compact, and the effects of reducing the thermal expansion coefficient and improving the resistivity are achieved; furthermore, the precipitated crystals still exist under the high temperature condition and have a larger blocking effect on the migration of alkali metal ions, so that the resistivity is kept relatively stable, namely, when alkali metal is used as a carrier to move in an oriented mode, the alkali metal is subjected to the resistance effect of a main crystal phase on one hand, and is limited by the range of a frame-shaped structure of a three-dimensional space on the other hand, so that the resistivity of the high-temperature sealing microcrystalline glass is large, and the insulativity of the high-temperature sealing microcrystalline glass is further improved.
The softening point temperature of the high-temperature sealing microcrystalline glass obtained by the application is more than 600 ℃, and the thermal expansion coefficient of the high-temperature sealing microcrystalline glass within the temperature range of 20-600 ℃ is (47+/-10) multiplied by 10 7 ℃ -1 In the range, the thermal expansion coefficient matching degree with the kovar alloy is high. In the present application Al 2 O 3 With ZrO 2 Al can enter into ZrO under the limit of the amount of the catalyst 2 Lattice of Al 0.52 Zr 0.48 O 1.74 If Al is 2 O 3 Excessive use of Al 0.52 Zr 0.48 O 1.74 Reduction of crystalline phase content，ZrO 2 The crystal phase content is increased, and the overall crystallization degree is reduced. The normal temperature resistivity of the sealing microcrystalline glass is 1.58 multiplied by 10 12 -8.01×10 14 Omega cm, resistivity of 3.72X10 at room temperature-600deg.C 9 Omega cm, high resistivity and good insulation. And the density of the sealing microcrystalline glass is 2.39g/cm 3 -2.46g/cm 3 The high-temperature sealing microcrystalline glass and the kovar alloy keep good matching sealing and good insulativity at high temperature.
Drawings
FIG. 1 is an X-ray test result of the glass ceramics of examples 1 to 5;
FIG. 2 is a scanning electron microscope test result of the glass ceramics of example 4;
FIG. 3 shows the X-ray test results of the glass ceramics of comparative examples 1-2.
Detailed Description
The present invention will be described in further detail with reference to the following examples in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
The application provides high-temperature sealing microcrystalline glass which comprises the following components in parts by weight: 55-65 parts of SiO 2 8-15 parts of Al 2 O 3 10-20 parts of B 2 O 3 4-10 parts of ZnO and 4-10 parts of R 2 O, 4-10 parts of CaO, 4-10 parts of ZrO 2 The method comprises the steps of carrying out a first treatment on the surface of the Wherein R is 2 O is Na 2 O、K 2 One or more of O. Al of the present application 2 O 3 With ZrO 2 Al forming tetragonal phase under the limitation of the amount of (C) 0.52 Zr 0.48 O 1.74 And ZrO of monoclinic phase 2 . ZrO during the preparation process 2 Will change from tetragonal phase to monoclinic phase, al can enter ZrO in the system at high temperature 2 Forming tetragonal Al 0.52 Zr 0.48 O 1.74 If Al is 2 O 3 Excessive use of Al 0.52 Zr 0.48 O 1.74 Reduced crystalline phase content, zrO 2 The content of crystal phase is increased, and the whole analysis is carried outThe degree of crystallinity is reduced. Wherein R is 2 O is all-purpose K 2 The crystallization effect of O is better, but Na is used 2 The sealing temperature at O is lower.
The main crystal phase of the high-temperature sealing microcrystalline glass is Al 0.52 Zr 0.48 O 1.74 And ZrO(s) 2 The crystallinity of the main crystal phase is 5-19%.
The application provides a preparation method of high-temperature sealing microcrystalline glass, which comprises the following steps:
s1, mixing powdered SiO according to parts by mass 2 、Al 2 O 3 、B 2 O 3 、ZnO、R 2 O、CaO、ZrO 2 Uniformly mixing, forming after melting, homogenizing and clarifying, and then annealing to obtain base glass;
s2, sequentially carrying out nucleation and crystallization heat treatment on the base glass to obtain the high-temperature sealing microcrystalline glass.
The microcrystalline glass for high-resistance high-temperature sealing uses SiO 2 As a glass network skeleton, the relative content of each component is adjusted to provide sufficient free oxygen in the glass structure, znO and R in a certain total amount 2 An increase in the O content will return an increase in free oxygen. At the same time, when the non-bridging oxygen increases, the boron-oxygen triangle [ BO ] 3 ]To boron oxygen tetrahedra [ BO 4 ]The transition results in the transition from the layered structure of the two-dimensional space to the rack-like structure of the three-dimensional space, thereby increasing the network structure, making the structure compact, and achieving the effects of reducing the thermal expansion coefficient and improving the resistivity. In addition, due to the shelf-like structure of the three-dimensional space of the present application, the space for directional movement of carriers can be limited, the conductivity is reduced, in some embodiments, compared to Na + K with larger radius + As a carrier, the resistance in motion is larger, and the conductivity is worse and the resistivity is higher.
In the present application, zrO 2 As a nucleating agent, under the definition of the components of the present application, when the nucleating agent is ZrO 2 The Al is most likely to be precipitated 0.52 Zr 0.48 O 1.74 And ZrO(s) 2 When the crystal nucleus agent such as TiO is replaced 2 Then only other crystal phases can be separated out to prepareThe temperature mainly affects the quantity and the size of the precipitated crystals.
Through proper component proportion, the content of the network exosome is regulated to change the content of free oxygen, so that the optimal crystallization temperature is changed, and crystallization of different degrees occurs under the same heat treatment system. Wherein the precipitated main crystal phase is Al 0.52 Zr 0.48 O 1.74 (PDF# 53-0294) and ZrO 2 (PDF # 37-1484) with crystallinity of about 5-19%. ZrO at room temperature 2 (PDF # 37-1484) is a monoclinic phase structure with a space group P21/c, lattice constant a=5.142, b=5.206, c= 5.313, β=99° 18, chemically inert, and has properties of high melting point, high resistivity, high refractive index, and low thermal expansion coefficient. Al (Al) 0.52 Zr 0.48 O 1.74 (PDF # 53-0294) ZrO 2 as Al atoms into tetragonal phase at high temperature 2 The lattice replaces the uniform solid solution formed by partial Zr atoms, maintains the tetragonal phase structure at room temperature, and has the characteristics of high resistivity and low thermal expansion coefficient. The larger the resistance of the main crystal relative to carriers, the larger the volume resistivity of the material. In addition, the characteristics of high resistivity of the two crystals enable the material to have excellent electrical insulation performance from room temperature to 600 ℃, so that the application temperature range of the material is greatly improved. It is noted that the reason why the main crystal has a large resistance to carriers is that, firstly, the two generated crystal phases have high electrical insulation properties, and secondly, the higher the crystallinity is, the more the number of crystals is, the stronger the obstruction to ion movement is, and the higher the resistivity is. The microcrystalline glass for high-temperature sealing has high-temperature insulation property, and is used for better meeting the requirement that a device can normally work in a high-temperature environment after sealing.
In the step S1, the melting temperature is 1500-1600 ℃, the melting time is 2-4h, the melting temperature is too low, and the raw materials cannot be melted and cannot be formed.
In the step S1, the annealing temperature is 580-650 ℃, the annealing time is 1-3h, the annealing temperature is too low, the thermal stress cannot be eliminated, and the cracking is easy.
In the step S2, the nucleation temperature is 850-950 ℃, the nucleation time is 0.5-3h, and the number of crystal nucleation is reduced when the nucleation temperature is too high or too low.
In the step S2, the crystallization temperature is 1100-1350 ℃, the crystallization time is 0.5-3h, the crystallization temperature is too low, and the size of the crystal is small; the crystallization temperature is too high, the grain size increases, and even secondary recrystallization/remelting.
The softening point of the high-temperature sealing microcrystalline glass obtained by the application is more than 600 ℃, and the thermal expansion coefficient of the high-temperature sealing microcrystalline glass is (47+/-10) multiplied by 10 within the temperature range of 20-600 DEG C 7 ℃ -1 In the range, the thermal expansion coefficient matching degree with the kovar alloy is high, and the normal temperature resistivity is 1.58 multiplied by 10 12 -8.01×10 14 Omega cm, and resistivity of 3.72X10 at room temperature-600deg.C 9 The high-temperature sealing microcrystalline glass has good insulativity when the resistivity is high and the density of the high-temperature sealing microcrystalline glass is 2.39g/cm 3 -2.46g/cm 3 The high-temperature sealing microcrystalline glass and the kovar alloy keep good matching sealing and good insulativity at high temperature.
The application provides application of high-temperature sealing microcrystalline glass in kovar alloy sealing, the sealing temperature is 800-1025 ℃, and the sealing temperature is slightly higher than the softening temperature of a glass material, because the glass is required to have certain fluidity during sealing.
The present application is further illustrated by the following detailed description.
The raw materials used in the examples of the present invention are all chemically pure raw materials, but allow for trace amounts of unavoidable impurities; a high-temperature melting furnace is used for melting glass; a crystallization furnace is used for crystallization; annealing is performed in an annealing furnace.
Example 1
The high-temperature sealing microcrystalline glass comprises the following components in parts by weight: 58 parts of SiO 2 9 parts of Al 2 O 3 13 parts of B 2 O 3 5 parts of ZnO and 5 parts of Na 2 O, 5 parts of CaO, 5 parts of ZrO 2 The sum of the mass ratio of the components is 100 percent.
The preparation method of the high-temperature sealing microcrystalline glass comprises the following steps:
s1, weighing raw materials according to the dosage of the components, preparing a basic glass batch, melting and preserving heat of the batch at 1600 ℃ for 3 hours, homogenizing at high temperature, clarifying to obtain glass liquid, molding the glass liquid by a casting method, and then, entering an annealing furnace to preserve heat at 620 ℃ for 2 hours for annealing treatment to obtain the basic glass.
S2, carrying out nucleation treatment on the base glass at 900 ℃ for 0.5h, then carrying out crystallization heat treatment at 1300 ℃ for 0.5h, cooling along with a furnace to obtain high-temperature sealing microcrystalline glass, and then cutting, polishing and carrying out subsequent performance test.
The main crystal phase of the high-temperature sealing microcrystalline glass obtained in the embodiment is Al 0.52 Zr 0.48 O 1.74 (PDF# 53-0294) and ZrO 2 (PDF # 37-1484) with crystallinity of about 5-7%; the test result of the X-ray of the glass ceramics is shown in figure 1; the softening point is 630 ℃; a thermal expansion coefficient of 52.3X10 at a temperature of 20℃to 600 DEG C 7 ℃ -1 The method comprises the steps of carrying out a first treatment on the surface of the Density of about 2.395g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the Room temperature resistivity of about 1.58×10 12 Omega cm; the sealing temperature is 900-950 ℃.
Example 2
The high-temperature sealing microcrystalline glass comprises the following components in parts by weight: 55 parts of SiO 2 11.5 parts of Al 2 O 3 10 parts of B 2 O 3 6 parts of ZnO and 1.98 parts of Na 2 O, 3.02 parts of K 2 O, 7 parts of CaO, 5 parts of ZrO 2 The method comprises the steps of carrying out a first treatment on the surface of the The sum of the mass ratio of the components is 100 percent.
The preparation method of the high-temperature sealing microcrystalline glass comprises the following steps:
s1, weighing raw materials according to the dosage of the components, preparing a basic glass batch, melting and preserving heat of the batch at 1600 ℃ for 3 hours, homogenizing at high temperature, clarifying to obtain glass liquid, molding the glass liquid by a casting method, and then, entering an annealing furnace to preserve heat at 620 ℃ for 2 hours for annealing treatment to obtain the basic glass.
S2, carrying out nucleation treatment on the base glass at 900 ℃ for 0.5h, then carrying out crystallization heat treatment at 1200 ℃ for 0.5h, cooling along with a furnace to obtain high-temperature sealing microcrystalline glass, and then cutting, polishing and carrying out subsequent performance test.
The main crystal phase of the high-temperature sealing microcrystalline glass obtained in the embodiment is Al 0.52 Zr 0.48 O 1.74 (PDF# 53-0294) and ZrO 2 (PDF # 37-1484) with crystallinity of about 10-12%, and the X-ray test results of glass ceramics are shown in FIG. 1; softening point is 692 ℃; thermal expansion coefficient of 46.7X10 at 20-600deg.C 7 ℃ -1 The method comprises the steps of carrying out a first treatment on the surface of the Density of about 2.431g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the Room temperature resistivity of about 1.51X10 13 Omega cm; the sealing temperature is 900-975 ℃.
Example 3
The high-temperature sealing microcrystalline glass comprises the following components in parts by weight: 55 parts of SiO 2 11.5 parts of Al 2 O 3 10 parts of B 2 O 3 6 parts of ZnO and 1.98 parts of Na 2 O, 3.02 parts of K 2 O, 7 parts of CaO, 5 parts of ZrO 2 The method comprises the steps of carrying out a first treatment on the surface of the The sum of the mass ratio of the components is 100 percent.
The preparation method of the high-temperature sealing microcrystalline glass comprises the following steps:
s1, weighing raw materials according to the dosage of the components, preparing a basic glass batch, melting and preserving heat of the batch at 1600 ℃ for 3 hours, homogenizing at high temperature, clarifying to obtain glass liquid, molding the glass liquid by a casting method, and then, entering an annealing furnace to preserve heat at 620 ℃ for 2 hours for annealing treatment to obtain the basic glass.
S2, carrying out nucleation treatment on the base glass at 900 ℃ for 0.5h, then carrying out crystallization heat treatment at 1300 ℃ for 0.5h, cooling along with a furnace to obtain high-temperature sealing microcrystalline glass, and then cutting, polishing and carrying out subsequent performance test.
The main crystal phase of the high-temperature sealing microcrystalline glass obtained in the embodiment is Al 0.52 Zr 0.48 O 1.74 (PDF# 53-0294) and ZrO 2 (PDF # 37-1484) with crystallinity of about 15-18%, and the X-ray test results of glass ceramics are shown in FIG. 1; the softening point is 696 ℃; a thermal expansion coefficient of 45.5X10 at a temperature of 20℃to 600 DEG C 7 ℃ -1 The method comprises the steps of carrying out a first treatment on the surface of the Density of about 2.449g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the Room temperature resistivity of about 2.10X10 14 Omega cm; the sealing temperature is 925-975 ℃.
Example 4
The high-temperature sealing microcrystalline glass comprises the following components in parts by weight: 56.5 parts of SiO 2 11.5 parts of Al 2 O 3 13 parts of B 2 O 3 5 parts of ZnO and 1.24 parts of Na 2 O, 3.76 parts of Na 2 O, 4 parts of CaO, 5 parts of ZrO 2 The method comprises the steps of carrying out a first treatment on the surface of the The sum of the mass ratio of the components is 100 percent.
The preparation method of the high-temperature sealing microcrystalline glass comprises the following steps:
s1, weighing raw materials according to the dosage of the components, preparing a basic glass batch, melting and preserving heat of the batch at 1600 ℃ for 3 hours, homogenizing at high temperature, clarifying to obtain glass liquid, molding the glass liquid by a casting method, and then, entering an annealing furnace to preserve heat at 620 ℃ for 2 hours for annealing treatment to obtain the basic glass.
S2, carrying out nucleation treatment on the base glass at 900 ℃ for 0.5h, then carrying out crystallization heat treatment at 1300 ℃ for 0.5h, then cooling with a furnace to obtain high-temperature sealing microcrystalline glass, then cutting, polishing and carrying out subsequent performance tests, wherein the scanning electron microscope test result of the high-temperature sealing microcrystalline glass is shown in figure 2.
The main crystal phase of the high-temperature sealing microcrystalline glass obtained in the embodiment is Al 0.52 Zr 0.48 O 1.74 (PDF# 53-0294) and ZrO 2 (PDF#37-1484), crystallinity about 16-19%, glass ceramics X-ray test results are shown in FIG. 1; the softening point is 743 ℃; a thermal expansion coefficient of 44.7X10 at a temperature of 20℃to 600 DEG C 7 ℃ -1 The method comprises the steps of carrying out a first treatment on the surface of the Density of about 2.448g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the Room temperature resistivity of about 7.10X10 14 Omega cm; the sealing temperature is 925-975 ℃.
Example 5
The high-temperature sealing microcrystalline glass comprises the following components in parts by weight: 57.5 parts of SiO 2 8.5 parts of Al 2 O 3 15 parts of B 2 O 3 4 parts of ZnO and 5 parts of K 2 O, 4 parts of CaO, 6 parts of ZrO 2 The method comprises the steps of carrying out a first treatment on the surface of the The sum of the mass ratio of the components is 100 percent.
The preparation method of the high-temperature sealing microcrystalline glass comprises the following steps:
s1, weighing raw materials according to the dosage of the components, preparing a basic glass batch, melting and preserving heat of the batch at 1600 ℃ for 3 hours, homogenizing at high temperature, clarifying to obtain glass liquid, molding the glass liquid by a casting method, and then, entering an annealing furnace to preserve heat at 620 ℃ for 2 hours for annealing treatment to obtain the basic glass.
S2, carrying out nucleation treatment on the base glass at 900 ℃ for 0.5h, then carrying out crystallization heat treatment at 1300 ℃ for 0.5h, cooling along with a furnace to obtain high-temperature sealing microcrystalline glass, and then cutting, polishing and carrying out subsequent performance test.
The main crystal phase of the high-temperature sealing microcrystalline glass obtained in the embodiment is Al 0.52 Zr 0.48 O 1.74 (PDF# 53-0294) and ZrO 2 (PDF#37-1484), crystallinity about 16-19%, glass ceramics X-ray test results are shown in FIG. 1; the softening point is 650 ℃; a thermal expansion coefficient of 46.3X10 at a temperature of 20℃to 600 DEG C 7 ℃ -1 The method comprises the steps of carrying out a first treatment on the surface of the Density of about 2.445g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the Room temperature resistivity of about 8.00X 10 14 Omega cm; the sealing temperature is 950-1025 ℃.
Comparative example 1
The high-temperature sealing microcrystalline glass comprises the following components in parts by weight: 50 parts of SiO 2 16 parts of Al 2 O 3 14 parts of B 2 O 3 5 parts of ZnO and 5 parts of K 2 O, 5 parts of CaO, 5 parts of TiO 2 The method comprises the steps of carrying out a first treatment on the surface of the The sum of the mass ratio of the components is 100 percent.
The preparation method of the high-temperature sealing microcrystalline glass comprises the following steps:
s1, weighing raw materials according to the dosage of the components, preparing a basic glass batch, melting and preserving heat of the batch at 1600 ℃ for 3 hours, homogenizing at high temperature, clarifying to obtain glass liquid, molding the glass liquid by a casting method, and then, entering an annealing furnace to preserve heat at 620 ℃ for 2 hours for annealing treatment to obtain the basic glass.
S2, carrying out nucleation treatment on the base glass at 900 ℃ for 0.5h, then carrying out crystallization heat treatment at 1300 ℃ for 0.5h, cooling along with a furnace to obtain high-temperature sealing microcrystalline glass, and then cutting, polishing and carrying out subsequent performance test.
The main crystal phase of the high-temperature sealing microcrystalline glass obtained in the comparative example is ZnAl 2 O 4 (PDF # 05-0669) and SiO 2 (PDF # 52-1425) with crystallinity of about 12-15%, and the X-ray test result of glass ceramics is shown in FIG. 3; the softening point is 693 ℃; a thermal expansion coefficient of 46.1X10 at a temperature of 20℃to 600 DEG C 7 ℃ -1 The method comprises the steps of carrying out a first treatment on the surface of the Density of about 2.44g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the Room temperature resistivity of about 1.73X10 13 Omega cm; the sealing temperature is 900-1025 ℃.
Comparative example 2
The high-temperature sealing microcrystalline glass comprises the following components in parts by weight: 50 parts of SiO 2 16 parts of Al 2 O 3 14 parts of B 2 O 3 5 parts of ZnO and 5 parts of K 2 O, 5 parts of CaO, 1.4 parts of ZrO 2 3.6 parts of TiO 2 The method comprises the steps of carrying out a first treatment on the surface of the The sum of the mass ratio of the components is 100 percent.
The preparation method of the high-temperature sealing microcrystalline glass comprises the following steps:
s1, weighing raw materials according to the dosage of the components, preparing a basic glass batch, melting and preserving heat of the batch at 1600 ℃ for 3 hours, homogenizing at high temperature, clarifying to obtain glass liquid, molding the glass liquid by a casting method, and then, entering an annealing furnace to preserve heat at 620 ℃ for 2 hours for annealing treatment to obtain the basic glass.
S2, carrying out nucleation treatment on the base glass at 900 ℃ for 0.5h, then carrying out crystallization heat treatment at 1300 ℃ for 0.5h, cooling along with a furnace to obtain high-temperature sealing microcrystalline glass, and then cutting, polishing and carrying out subsequent performance test.
The main crystal phase of the high-temperature sealing microcrystalline glass obtained in the comparative example is ZnAl 2 O 4 (PDF # 05-0669) and SiO 2 (PDF # 52-1425) with crystallinity of about 7-10%, and the X-ray test result of glass ceramics is shown in FIG. 3; the softening point is 676 ℃; thermal expansion coefficient of 4.32X10 at 20-600deg.C 7 ℃ -1 The method comprises the steps of carrying out a first treatment on the surface of the Density of about 2.39g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the Room temperature resistivity of about 6.9X10 11 Omega cm; the sealing temperature is 900-1025 ℃.
Through reasonable component design, the glass ceramic for sealing has the thermal expansion coefficient similar to that of metals such as kovar alloy, has the performances of high softening point, high density, high strength, excellent chemical stability and the like, improves the sintering strength, and has a wide application prospect, and the preparation method is simple.
The present invention is not limited to the above-mentioned embodiments, and any changes or substitutions that can be easily understood by those skilled in the art within the technical scope of the present invention are intended to be included in the scope of the present invention.
Claims (9)
1. The high-temperature sealing microcrystalline glass is characterized by comprising the following components in parts by weight: 55-65 parts of SiO 2 8-15 parts of Al 2 O 3 10-20 parts of B 2 O 3 4-10 parts of ZnO and 4-10 parts of R 2 O, 4-10 parts of CaO, 4-10 parts of ZrO 2 The method comprises the steps of carrying out a first treatment on the surface of the Wherein R is 2 O is Na 2 O、K 2 One or more of O.
2. The high-temperature sealing glass-ceramic according to claim 1, wherein the main crystal phase is Al 0.52 Zr 0.48 O 1.74 And ZrO(s) 2 The crystallinity of the main crystal phase is 5-19%.
3. A method for preparing high temperature sealing glass ceramics according to any one of claims 1 to 2, comprising the steps of:
s1, mixing powdered SiO according to parts by mass 2 、Al 2 O 3 、B 2 O 3 、ZnO、R 2 O、CaO、ZrO 2 Uniformly mixing, forming after melting, homogenizing and clarifying, and then annealing to obtain base glass;
s2, sequentially carrying out nucleation and crystallization heat treatment on the base glass to obtain the high-temperature sealing microcrystalline glass.
4. A method according to claim 3, wherein in step S1, the melting temperature is 1500-1600 ℃ and the melting time is 2-4 hours.
5. A method according to claim 3, wherein in step S1, the annealing temperature is 580-650 ℃ and the annealing time is 1-3h.
6. The method according to claim 3, wherein in step S2, the nucleation is performed at a temperature of 850 to 950 ℃ for a time of 0.5 to 3 hours.
7. The method according to claim 3, wherein in the step S2, the crystallization temperature is 1100-1350 ℃ and the crystallization time is 0.5-3h.
8. Use of the high temperature sealing glass ceramics obtained by the preparation method of any one of claims 3-7 in sealing of kovar.
9. The use according to claim 8, wherein the sealing temperature is 800-1025 ℃.
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