High-strength high-expansion microcrystalline glass material, low-stress seal, and method of manufacture

Abstract

The application belongs to the technical field of glass-ceramics packaging, and relates to high-strength high-expansion glass-ceramics material, low-stress sealing element and a preparation method. The application provides a glass-ceramics material, which is composed of main crystal phase forming components, crystallization promoting regulators, crystallization inhibiting regulators, high-temperature performance regulators and transition oxides; the main crystal phase components are selected from 60-80 mol% SiO2, 0-20 mol% ZnO and 5-20 mol% Li2O; the crystallization promoting regulators are selected from 1-5 mol% R2O and 1-5 mol% P2O5, R is at least one of Na and K. The glass-ceramics material prepared by the application can precipitate crystal phases with high expansion coefficient and high mechanical strength, and the residual glass phase is rich in rare earth oxides with high molar ratio, so that the glass-ceramics material has high expansion coefficient and application temperature.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of microcrystalline glass packaging, and relates to a high-strength high-expansion microcrystalline glass material, a low-stress sealing element and a preparation method, which is suitable for being used as an insulating material for sealing with a metal or ceramic material having a large expansion coefficient, and is also suitable for being used as an insulating material for sealing with a glass or ceramic material having a matching expansion coefficient. BACKGROUND

[0002] Sealing glass is an advanced welding material, which has a suitable melting temperature and sealing temperature, good heat resistance and chemical stability, and high mechanical strength, and is widely used in many fields such as electric vacuum and microelectronic technology, laser and infrared technology, high-energy physics, energy, spaceflight, automobile and the like, to realize the mutual sealing of glass, ceramic, metal and semiconductor. Traditional sealing glass includes sodium borosilicate glass, sodium potassium lead silicate glass, sodium barium silicate glass, potassium lead silicate glass and potassium barium phosphate glass. With the development of microelectronic technology, electronic display and optoelectronic technology, the miniaturization of devices and the precision of structural elements, the sealing devices are applied in a wider and wider range, and the requirements for sealing are higher and higher, including the air tightness, reliability and sealing temperature. Especially for the sealing with high-expansion stainless steel or metal, the sealing material not only needs to have a high expansion coefficient, but also needs to have a high sealing temperature to adapt to a high use temperature. However, when the traditional sealing glass is sealed with metal, the problems such as high leakage rate, easy moisture absorption and unstable electrical insulation performance are common. Compared with the traditional sealing glass, the sealing microcrystalline glass has the characteristics of a large change range of thermal expansion coefficient, high electrical insulation performance, excellent mechanical properties, high chemical stability, dense structure and good sealing performance, and is the best candidate material for sealing with metal materials.

[0003] Li2O-ZnO-Al2O3-SiO2 system microcrystalline glass (including Li2O-Al2O3-SiO2 and Li2O-ZnO-SiO2) is an important sealing material, which has a wide composition range, a moderate sealing temperature (lower than 1100 DEG C), good chemical stability and the like, and the thermal expansion coefficient can be adjusted in a large range by adjusting the heat treatment system. How to control the performance parameters of the Li2O-ZnO-Al2O3-SiO2 system microcrystalline glass and further expand its application range is one of the important research directions for the person skilled in the art.

[0004] Li2O-Al2O3-SiO2 system glass-ceramics realize its thermal expansion coefficient control by regulating the precipitation of sealing glass crystals, such as Li2Si2O5, Li2SiO3, cristobalite phase, etc. Among them, the use of precipitated cristobalite obtains a high expansion coefficient of 15-22 ppm / °C, such as US005820989A by introducing nucleating agent Li3PO4 to obtain high expansion cristobalite glass-ceramics, which realizes the thermal expansion coefficient from 12.0-20.0 ppm / °C adjustable. However, cristobalite has a volume mutation of about 2% at about 273°C, resulting in a sudden change in thermal expansion coefficient, so a high expansion coefficient of 15-25 ppm / °C can be obtained in the temperature range of 100-300°C. US009878944B1 and the article (Sealing glass-ceramics with near-linear thermal strain, part III: Stress modeling of strain and strain rate matched glass-ceramic to metal seals, DOI: 10.1111 / jace.14821) confirmed that cristobalite leads to a large structural stress, which has a hidden danger for use, and a glass-ceramic material coexisting cristobalite and beta quartz is obtained by rapidly rising and falling temperature at 50-100°C / min across the crystallization interval of cristobalite. However, the sealing process requires very high, only suitable for chain furnace sealing process, not suitable for intermittent furnace sealing process, and rapid cooling will also cause structural stress due to the difference in thermal conductivity between metal and glass material. At the same time, in some application scenarios, such as aerospace engines, oil well drilling, solid oxide batteries, etc., the sealing glass is required to have a harsh application requirement of 350-1000°C. Although the SiO2 molar content in the Li2O-Al2O3-SiO2 system is higher than 70mol%, the relevant patents and researches do not clearly show the high temperature insulation, but the Li2O content higher than 20mol% may cause the high temperature resistance to drop above 500°C.

[0005] Similarly, Li2O-ZnO-SiO2 glass-ceramic sealing materials also have the same problem. The SiO2 content in this glass system is less than 60mol%, which can precipitate Li2Si2O5, Li2SiO3, Li2ZnSiO4, Li3Zn 0.5SiO4, cristobalite and the like phases, but as Chinese patent 201410790751.8 and documents (Crystallization behaviors thermo-physical properties and seal application of Li2O-ZnO-MgO-SiO2 glass-ceramics, DOI: 10.1016 / j.jallcom.2015.10.106; MgO-doping in the Li2O-ZnO-Al2O3-SiO2 glass-ceramics for better sealing with steel, DOI: 10.1016 / j.jnoncrysol.2014.09.022; ZnO content on Li2O-ZnO-SiO2 glass crystallization and performance, 1002-4026 (2011) 05-0026-04) all obtained a microcrystalline sealing glass material with a thermal expansion coefficient higher than 15 ppm / ℃, but also with the appearance of cristobalite phase, so there is a great structural stress caused by cristobalite, which exists hidden danger.

[0006] High borosilicate glass is a special glass material with high temperature resistance, high strength and high chemical stability. Because it has a similar linear expansion coefficient to Kovar alloy, it can be effectively matched and sealed with the RF coaxial connector. However, the dielectric constant of general high borosilicate glass is above 5.0. The RF connector sealed by it has acceptable performance when used at low frequency, but when the operating frequency is above 25 GHz, the voltage standing wave ratio and insertion loss are high, which seriously affects the microwave performance of the system. Therefore, in practical applications, there is an urgent need for a glass with lower dielectric constant and dielectric loss to improve the microwave performance indicators of the sealed device. However, there are few manufacturers who can provide low-dielectric sealing glass powder at present. The main problems existing at present include (1) the melting temperature of the glass powder is too high, and the high-temperature viscosity is large, resulting in high sealing temperature; (2) the dielectric constant or dielectric loss of the glass powder is large, which affects the practical application of low-dielectric sealing glass powder; (3) poor mechanical properties, insufficient resistance to temperature shock and mechanical impact; (4) the thermal expansion coefficient is too small, resulting in poor thermal matching performance with electrode materials (Ag, Cu, Au, etc.). SUMMARY

[0007] The present application aims to further expand the types of Li2O-ZnO-Al2O3-SiO2 system microcrystalline glass packaging materials and improve their performance parameters. The present application provides a high-strength high-expansion microcrystalline glass packaging material and its preparation method and application.

[0008] In a first aspect, the present application provides a glass-ceramic material, the composition of which comprises: main crystalline phase forming components, crystallization promoting regulators, crystallization inhibiting regulators, high temperature performance regulators and transition oxides;

[0009] The main crystalline phase components are selected from 60-80 mol% (preferably 60-75 mol%) SiO2, 0-20 mol% (preferably 0-15 mol%) ZnO, 5-20 mol% Li2O;

[0010] The crystallization promoting regulators are selected from 1-5 mol% R2O, 1-5 mol% P2O5, R = at least one of Na, K;

[0011] The crystallization inhibiting regulators are selected from 0-5 mol% Al2O3, 0-3 mol% B2O3, 0-3 mol% MgO, 0-3 mol% ZrO2;

[0012] The high temperature performance regulators are selected from 0-5 mol% Ln2O3 or / and 0-5 mol% M2O5, Ln = at least one of Sc, Y, La, Nd, Sm, Tb, Dy, Er, Tm, Yb, M = at least one of Ta, Nb;

[0013] The content of the transition oxides is 0-2 mol%.

[0014] Preferably, R = Na and K, and K2O + Na2O = 2-5 mol%.

[0015] Preferably, the transition metal oxides are at least one of manganese-containing oxides, nickel-containing oxides, iron-containing oxides, cobalt-containing oxides, copper-containing oxides, and chromium-containing oxides.

[0016] Preferably, the crystalline phase in the glass-ceramic material is at least one of β-quartz, cristobalite, tridymite, Li2O·SiO2, and Li2O·ZnO·SiO2, and the content of the crystalline phase is 50-90 wt%.

[0017] Preferably, the coefficient of thermal expansion of the glass-ceramic material is adjustable between 10-20 ppm / ℃.

[0018] The dielectric constant of the glass-ceramic material is ≤4-7, and the dielectric loss is ≤5×10 -3 ;

[0019] The bending strength of the glass-ceramic material is 150-400 MPa, and the elastic modulus is 80-120 GPa.

[0020] The insulation resistivity of the glass-ceramic material is ≥1×10 15 Ω·cm, and the material is resistant to plating.

[0021] The softening point of the glass-ceramic material is > 800℃;

[0022] The sealing temperature of the glass-ceramic material is 900-1050℃.

[0023] Preferably, the glass-ceramic material is in the form of powder or bulk.

[0024] Preferably, when the glass-ceramic material is in the form of glass powder, the particle size is D 50 = 20-50 μm, and D 90 = 60-100 μm.

[0025] In a second aspect, the present application provides a method for preparing a glass-ceramic material, wherein the glass-ceramic material is in the form of powder, and the method comprises:

[0026] (1) weighing each oxide according to the composition of the glass-ceramic material and mixing to obtain raw material powder;

[0027] (2) subjecting the obtained raw material powder to high-temperature melting to obtain glass melt;

[0028] (3) subjecting the obtained glass melt to quenching, ball milling and grading by the method of bottom leakage of the crucible to obtain the glass-ceramic material in the form of powder. Preferably, the solvent used for quenching is deionized water.

[0029] Preferably, the parameters of high-temperature melting include: heating to 1480-1600℃ and stirring at a rotation speed of 30-60 r / min for 4-12 hours.

[0030] In a third aspect, the present application provides a method for preparing a glass-ceramic material, wherein the glass-ceramic material is in the form of bulk, and the method comprises:

[0031] (1) weighing each oxide according to the composition of the glass-ceramic material and mixing to obtain raw material powder;

[0032] (2) subjecting the obtained raw material powder to high-temperature melting to obtain glass melt;

[0033] (3) pouring the obtained glass melt into a mold and then annealing to obtain the glass-ceramic material in the form of bulk.

[0034] Preferably, the parameters of high-temperature melting include: heating to 1480-1600℃ and stirring at a rotation speed of 30-60 r / min for 4-12 hours.

[0035] Preferably, the temperature of annealing is 400-500℃, and the time of annealing is 4-24 hours.

[0036] In a fourth aspect, the present invention provides a method for preparing a glass insulator, comprising:

[0037] (1) mixing a glass-ceramic material, ceramic powder, a binder, and a solvent to obtain a mixed slurry; the amount of the ceramic powder added is 0 to 20 wt% of the mass of the glass-ceramic material;

[0038] (2) granulating the obtained mixed slurry by spraying to obtain granulated powder;

[0039] (3) pressing the obtained granulated powder into a shape to obtain a preform;

[0040] (4) Debinding and sintering the obtained prefabricated part to obtain the glass insulator.

[0041] Preferably, the glass-ceramic material is in powder form with a particle size of D 50 =20~50μm, D 90 =60~100μm;

[0042] The ceramic powder is selected from at least one of β-quartz phase, magnesium oxide, magnesium silicate phase (MgSiO3 and / or Mg2SiO4), and barium silicate phase (BaSiO3 and / or BaSi2O5); the particle size of the ceramic powder is 10 μm to 100 μm.

[0043] Preferably, the particle size of the granulated powder is 80 to 300 μm;

[0044] The debinding temperature is 300-500°C and the time is 1-3 hours;

[0045] The sintering temperature is 650-800° C., and the sintering time is 10-60 min. Preferably, the sintering heating rate is 10-60° C. / min.

[0046] In a fifth aspect, the present invention provides a glass insulator prepared according to the above-mentioned preparation method, wherein the glass insulator is in an amorphous or partially crystallized state, and the content of the crystallized phase is 50 to 90 wt%; wherein the content of the cristobalite phase preferably does not exceed 20 wt% of the total mass of the crystallized phase; and the particle size of the crystallized phase is 1 to 50 μm.

[0047] In a sixth aspect, the present invention provides a method for encapsulating metal materials, comprising: assembling a glass insulator and the metal material to be encapsulated, placing the assembly in a mold, and then performing a sealing process in a protective atmosphere to complete the sealing of the metal material;

[0048] Preferably, the sealing treatment temperature is 900-1050°C, and the holding time is 10-60 min; more preferably, the sealing treatment heating rate is 10-100 min / °C;

[0049] Preferably, the protective atmosphere is at least one of nitrogen, helium and a mixture of nitrogen and helium.

[0050] Preferably, the mold is a graphite mold.

[0051] In a seventh aspect, the present application provides a method for preparing a sealing element, comprising:

[0052] (1) introducing the glass insulator into a surface of a connecting part to be connected or between surfaces of multiple connecting parts to be connected, and placing the assembled connecting part into a mold;

[0053] (2) first heating to a temperature T1 for a certain period of time, then heating to a temperature T2 for a certain period of time, and finally annealing at a temperature T3 to obtain the sealing element.

[0054] Preferably, the temperature T1 is 850-1050℃, and the holding time is 0-30min; preferably, the heating rate of the temperature T1 is 10-100min / ℃.

[0055] The temperature T2 is 600-850℃, and the holding time is 10-120min; preferably, the heating rate of the temperature T2 is 10-100min / ℃.

[0056] The temperature T3 is 500-700℃, and the holding time is 60-120min; preferably, the cooling rate of the temperature T3 is 5-20min / ℃.

[0057] In the present application, the material is heated to a temperature T1, so that the sintered glass insulator flows, thereby the material to be connected is wetted by the glass, and a shape-fitting airtight structure is provided between the material of the glass insulator and the material of the connecting part. The material connected in the shape-fitting manner is continuously heated to a temperature T2 greater than T1, so that the glass insulator is at least partially crystallized, thereby providing a microcrystalline glass sealing material with high strength and high-temperature service. The microcrystalline glass-metal sealing element is reduced to a temperature T3 for annealing treatment, thereby reducing the structural stress of the microcrystalline glass-metal sealing element.

[0058] In an eighth aspect, the present application provides a sealing element prepared by the above method.

[0059] In a ninth aspect, the present application provides a method for preparing a microcrystalline glass substrate material, characterized in that the method comprises: segmentally crystallizing a microcrystalline glass material by a rotating crystallization process to obtain the microcrystalline glass substrate material; and the microcrystalline glass material is in the form of a block.

[0060] Preferably, the rotating crystallization process comprises:

[0061] 1) First raise the temperature to 400-500℃ and keep it for 0.1-5h, then continue to raise the temperature to 500-600℃ and keep it for 0.1-5h and then cool it down to room temperature;

[0062] 2) Heating to 600-700℃, keeping the temperature for 0.1-5 hours and then cooling to room temperature along with the furnace;

[0063] 3) Finally, heat to 700-900°C and keep at this temperature for 0.1-5 hours, then cool to room temperature along with the furnace;

[0064] In the above steps 1) to 3), the rotation is maintained at a speed of 0.05 to 1 rpm;

[0065] Preferably, the heating rate of the heating is 0.1 to 5°C / min, and the cooling rate of the heating to room temperature is 0.1 to 5°C / min.

[0066] In a tenth aspect, the present invention provides a microcrystalline glass substrate material prepared according to the above preparation method.

[0067] In an eleventh aspect, the present invention provides a use of a glass-ceramic material as a sealing material in preparing a joint connection and / or a lead-through, wherein the joint connection and / or the lead-through comprises: a transition layer between ceramics and ceramics, or between ceramics and metals;

[0068] and / or a sensor from the group consisting of an exhaust gas sensor, a pressure sensor, a particle sensor, a soot particle sensor, a temperature sensor, a nitrogen oxide sensor, and an oxygen sensor;

[0069] and / or a feedthrough for a compressor and / or an electronic compressor;

[0070] and / or an electrical power feedthrough for an exhaust assembly; and / or a feedthrough for a chemical reactor.

[0071] Preferably, in these method steps, the material of the connecting fitting is preferably the housing material or the sealing element material, and the resulting joint preferably comprises: high expansion coefficient microwave dielectric ceramics and ferrite materials, such as M2SiO4 series, MgTiO3 series, LnAlO3 series, A(B 1 / 3 B 2 / 3 )O3 type, BaO-Ln2O3-TiO2-Ta2O3 tungsten bronze type and Ba 6-3x Ln 8+2x Ti 18 O 54such as YFe garnet gyromagnetic ferrite; or high-temperature stable ceramic compounds, such as alumina-based ceramics or zirconia-based ceramics, such as ceramics comprising Y2O3-stabilized zirconia; or metals, in particular metals chosen from the group comprising steel, such as standard steel, stainless steel, rust-resistant steel and high-temperature stable ferritic steel, or in iron-nickel alloys 5J50, 4J50; or 10 low-carbon steel; or Inconel alloys: Inconel 600 / NS312, Inconel 601 / NS313, Inconel 625 / NS336, Inconel 690 / NS315, Inconel 718 / GH4169, Inconel X-750 / GH4145; or high-temperature alloy steels: GH3030, GH2132, GH3039, GH3044, GH3128, GH4180, GH4169, GH4145, GH20, GH32, GH600, GH333, Inconel 725, Incoloy 925; or martensitic stainless steels: 403, 409, 410, 420, 430, 439, 441, 444, 446.

[0072] In a twelfth aspect, the application provides a microcrystalline glass material for use in the preparation of integrated circuit packaging substrates, resonators, microwave antenna sheets, filters.

[0073] Advantages of the application:

[0074] (1) The microcrystalline glass prepared by the application can precipitate crystal phases with high expansion coefficient and high mechanical strength, and the residual glass phase is rich in high-molar-ratio rare earth oxides, so it has high expansion coefficient and application temperature, and can have excellent thermal matching with stainless steel, high-temperature alloy, etc. and electrode materials such as gold and palladium, which also have high expansion coefficient, and can realize the preparation of low-stress seals;

[0075] (2) Excellent dielectric properties: low dielectric constant (4-7), low dielectric loss, can be used for the manufacture of integrated circuit packaging substrates, resonators, microwave antenna sheets, filters, millimeter wave communication equipment, etc. microwave devices and applied at high temperature;

[0076] (3) The material is simple to prepare, non-polluting and low in cost, and is a very promising microcrystalline glass material. BRIEF DESCRIPTION OF DRAWINGS

[0077] Figure 1XRD pattern of the glass-ceramic material in Example 1-3: from the figure, it can be found that the main crystal phase in Example 1-3 includes a quartz phase with high expansion coefficient and lamellar structure and a Li2SiO3 phase with high expansion coefficient and needle-like structure, the lamellar structure crystal phase and the needle-like structure crystal phase form an interlocking structure, which can significantly improve the mechanical properties and high-temperature resistance of the glass-ceramic; in addition, the composition of the high-field oxide changes slightly, and the subcrystal phase changes slightly;

[0078] Figure 2 XRD pattern of the glass-ceramic material in Example 4: from the figure, it can be found that the main crystal phase in Example 4 includes a quartz phase with high expansion coefficient, a quartz phase with high expansion coefficient and lamellar structure, and a Li2SiO3 phase with high expansion coefficient and needle-like structure, the lamellar structure crystal phase and the needle-like structure crystal phase form an interlocking structure, which further improves the mechanical properties of the glass-ceramic;

[0079] Figure 3 SEM image of the glass-ceramic material in Example 1: from the figure, it can be found that the microstructure of the glass-ceramic in Example 1 is formed by the interlocking structure of the lamellar structure crystal phase and the needle-like structure crystal phase, which further improves the mechanical properties of the glass-ceramic;

[0080] Figure 4 SEM image of the glass-ceramic material in Example 5: from the figure, it can be found that the microstructure of the glass-ceramic in Example 5 is composed of a quartz phase with spherical structure and a Li2Si2O5 phase with needle-like structure, and the needle-like structure can improve the mechanical properties of the glass-ceramic;

[0081] Figure 5 SEM image of the glass-ceramic material in Example 7: from the figure, it can be found that the microstructure of the glass-ceramic in Example 7 is formed by a quartz phase with high expansion coefficient and lamellar structure, and the lamellar structure can improve the mechanical properties of the glass-ceramic;

[0082] Figure 6 SEM image of the glass-ceramic material in Example 9: from the figure, it can be found that the microstructure of the glass-ceramic in Example 9 is composed of a Li2SiO3 phase with needle rod structure, and the needle rod structure can improve the mechanical properties of the glass-ceramic;

[0083] Figure 7 SEM image of the glass-ceramic material in Example 11: from the figure, it can be found that the microstructure of the glass-ceramic in Example 5 is composed of a quartz phase with spherical structure and a Li2Si2O5 phase with needle-like structure, and the needle-like structure can improve the mechanical properties of the glass-ceramic;

[0084] Figure 8SEM image of the microcrystalline glass material in Comparative Example 1: it can be found from the image that the microcrystalline glass in Comparative Example 1 has a microstructure composed of spherical structure Zn2SiO4 phase, and the high content of ZnO leads to the mechanical properties of the microcrystalline glass being insufficient due to the spherical structure Zn2SiO4 phase being dominant;

[0085] Figure 9 SEM image of the microcrystalline glass material in Comparative Example 2: it can be found from the image that the microcrystalline glass in Comparative Example 2 has a microstructure composed of rod-like structure Li2SiO3 phase, and the high content of Li2O leads to the mechanical properties of the microcrystalline glass being insufficient due to the excessive growth of Li2SiO3 phase;

[0086] Figure 10 SEM image of the microcrystalline glass material in Comparative Example 6: it can be found from the image that the microcrystalline glass in Comparative Example 6 has a microstructure composed of spherical structure cristobalite + Quartz phase, and the high content of SiO2 leads to the mechanical properties of the microcrystalline glass being insufficient due to the high spherical structure being dominant;

[0087] Figure 11 High-temperature resistance spectrum of the microcrystalline glass material in Examples 1-3 and Comparative Examples 2-3: it can be found from the image that the microcrystalline glass with high insulation performance is obtained by combining the composition design and crystallization process in the present patent, i.e. the resistivity is higher than 1×10 10 Ω·cm at 350℃;

[0088] Figure 12 Thermal expansion coefficient curve of the microcrystalline glass material in Examples 1-4 and Comparative Example 6: it can be found from the image that the microcrystalline glass with good linearity and high thermal expansion coefficient is obtained by combining the composition design and crystallization process in the present patent, and excessive cristobalite phase leads to the microcrystalline glass material having a significant expansion coefficient mutation at about 200℃;

[0089] Figure 13 SEM image of the interface of the microcrystalline glass material and copper alloy sealing in Example 1;

[0090] Figure 14 SEM image of the interface of the microcrystalline glass material, microwave dielectric material and ferrite sealing after electroplating in Example 1: the sealing interface is complete after electroplating, indicating that the microcrystalline glass sealing material has excellent electroplating resistance;

[0091] Figure 15 SEM image of the interface of the microcrystalline glass material, microwave dielectric material and ferrite sealing after electroplating in Comparative Example 2: the sealing interface appears to be corroded after electroplating, and the surface circuit can be seen to be disconnected, indicating that poor electroplating resistance of the glass can lead to device failure;

[0092] Figure 16This is an SEM image of the interface between the electroplated glass-ceramic material, microwave dielectric material, and ferrite after sealing in Comparative Example 6: Although the sealed interface is intact after electroplating, cracks appear on the interface, ferrite, and microwave dielectric ceramic due to stress.

[0093] Figure 17 Schematic diagram of the structure of microwave dielectric material and ferrite composite substrate;

[0094] Figure 18 It is a schematic diagram of the structure of a multi-core structure connector;

[0095] Figure 19 This is a schematic diagram of the integrated circuit package shell structure; the pins are optionally located on the side wall and bottom of the shell. DETAILED DESCRIPTION

[0096] The present invention is further described below through the following embodiments. It should be understood that the following embodiments are only used to illustrate the present invention, rather than to limit the present invention.

[0097] In the present disclosure, the high-strength and high-expansion microcrystalline glass comprises: a main crystal phase forming component, a crystallization promoting regulator, a crystallization inhibiting regulator, a high-temperature performance regulator and a transition metal oxide.

[0098] In an optional embodiment, the main crystalline phase composition is selected from 60-80 mol% SiO2, 0-20 mol% ZnO, and 5-20 mol% Li2O.

[0099] The SiO2 content in the present invention ranges from 60 to 80 mol%. The service environment of the glass-ceramics of the present invention must be above 500°C, and to maintain a low dielectric constant, an appropriate amount of quartz phase must be precipitated. When the SiO2 content is less than 60 mol%, on the one hand, it is not conducive to obtaining high-expansion β-quartz, sphene quartz, and cristobalite phases. On the other hand, the silicon content in the residual glass phase is too low, which is not conducive to sufficient electrical insulation properties during high-temperature use, thus failing to achieve the desired application effect. When the SiO2 content exceeds 80 mol%, the excessive amount may lead to excessively high melting temperatures and insufficient glass-forming properties.

[0100] The Li2O content in the present application is in the range of 5-20 mol%. If the content is less than 5 mol%, it is not conducive to the crystallization, on the one hand, Li2O and P2O5 act as nucleating agent of LiPO3, promoting the crystallization of high-strength phase Li2O·SiO2 and quartz phase, on the other hand, Li2O participates in the crystallization, if the content is too low, the content of the crystalline phase is too low, which will result in insufficient mechanical properties; and if the content is higher than 20 mol%, due to the small radius of Li+ ion, if Li+ is not fixed (such as the crystalline phase Li2O·SiO2 and Li2O·ZnO·SiO2), it is easy to move in the glass network structure under the coupling of electric field and temperature field, which will result in rapid decrease of the room temperature and high temperature resistance, which is not conducive to the application.

[0101] ZnO is an important glass network regulating oxide, which can reduce the softening point of the glass and adjust the thermal expansion coefficient, improve the chemical stability, thermal stability and refractive index of the glass. The content of ZnO in the present application is in the range of 0-20 mol%, preferably not more than 15 mol%. If the content is more than 15 mol%, the softening point temperature of the glass will increase, the glass flowability will be poor, and at the same time, the crystallization of high-strength phase Li2O·SiO2 and Li2O·ZnO·SiO2 will be inhibited.

[0102] In the optional embodiment, the crystallization promoting regulator is selected from 1-5 mol% R2O (R=Na, K), 1-5 mol% P2O5. Alkali metal oxide (one or more of Na2O, K2O) can improve the solubility in the glass melting process, reduce the melting temperature, and can reduce the softening temperature of the glass, but too much will result in the decrease of mechanical properties and resistivity. Preferably, K2O+Na2O=2-5 mol%.

[0103] In the optional embodiment, the crystallization inhibiting regulator is selected from 0-5 mol% Al2O3, 0-3 mol% MgO, 0-3 mol% ZrO2, 0-3 mol% (preferably 0.1-3 mol%) B2O3. The total content of the crystallization inhibiting regulator is preferably not 0.

[0104] In the present application, the addition of one or more of Al2O3, MgO, ZrO2 and B2O3 can reduce the crystallization tendency of the glass, increase the stability and mechanical strength of the glass, and adjust the thermal expansion coefficient and sealing temperature of the glass, but the addition amount should not be too much, which will increase the crystallization difficulty and softening temperature of the glass. In the present application, the total addition amount is 0-5 mol%.

[0105] In an alternative embodiment, the high temperature performance modifier is selected from 0-5 mol% (preferably 0.1-5 mol%) Ln2O3 or / and 0-5 mol% (preferably 0.1-5 mol%) M2O5, Ln = at least one of Sc, Y, La, Nd, Tb, Dy, Er, Tm, Yb, M = at least one of Ta, Nb. The total content of the high temperature performance modifier is preferably not 0.

[0106] In the present application, the glass composition comprises Ln2O3, M2O5, Ln = at least one of Sc, Y, La, Nd, Tb, Dy, Er, Tm, Yb, M = at least one of Ta, Nb. Compared with the prior art, the present application further provides the advantage that the high field strength oxide component does not participate in the crystallization process, i.e. will be present in the residual glass phase, thereby forming a glass matrix reinforced with high field strength oxides. This high field strength oxide reinforced residual glass phase is beneficial to improve the high temperature chemical and physical stability and the plating resistance of the encapsulated glass ceramic.

[0107] In an alternative embodiment, the transition metal oxide is 0-2 mol%, preferably including one or more of manganese-containing oxide, nickel-containing oxide, iron-containing oxide, cobalt-containing oxide, copper-containing oxide, chromium-containing oxide.

[0108] In the present application, in order to further improve the performance of the glass powder, the glass powder can further comprise a transition oxide, and the content of the colorant is ≤2 mol%. The transition oxide includes one or more of manganese-containing oxide, nickel-containing oxide, iron-containing oxide, cobalt-containing oxide, copper-containing oxide, chromium-containing oxide and a composite thereof.

[0109] Preferably, when the transition oxide is selected from a plurality of manganese-containing oxide, nickel-containing oxide, iron-containing oxide, cobalt-containing oxide, copper-containing oxide, chromium-containing oxide, the corresponding oxides are mixed according to the molar ratio, and then calcined at 500-1000°C for 2-6 hours.

[0110] In an alternative embodiment, the precipitated crystalline phase of the high expansion glass ceramic material comprises one or more of β-quartz phase, cristobalite phase, tridymite phase, Li2O·SiO2 phase and Li2O·ZnO·SiO2 phase, and the content of the precipitated crystalline phase is 50-90 wt%. The content of the tridymite phase cannot exceed 20%.

[0111] In the present application, the thermal expansion coefficient of the high expansion glass ceramic material is adjustable at 10-20 ppm / °C. The dielectric constant of the high expansion glass ceramic material is 4-7, and the dielectric loss is ≤1×10 -3The high-expansion glass-ceramic material has a bending strength of 150-400 MPa. The high-expansion glass-ceramic material has an elastic modulus of 80-120 GPa. The high-expansion glass-ceramic material has an insulation resistivity of ≥1×10 15 Ω·cm, and can resist plating. The high-expansion glass-ceramic material has a glass-ceramic softening point higher than 800℃, and a sealing temperature of 900-1100℃.

[0112] The following exemplary describes the preparation method of the glass-ceramic material.

[0113] The raw glass is melted. In the present application, according to the molar ratio of each component of the glass, the specific weight is introduced into the raw material in the three-dimensional mixer, and the glass mixed raw material is obtained by fully mixing. The crucible is selected from platinum-rhodium crucible or quartz crucible. The glass batch is placed in a high-temperature furnace at 1350-1450℃ for 2-4 hours to make the boric acid, nitric acid, and carbonic acid raw materials fully decompose. Then, the temperature is increased to 1450-1600℃ at a rate of 10-15℃ / min, and the stirring is performed at a rotation speed of 30-60r / min for 4-12 hours to obtain a uniform glass melt. The glass slag is quenched or poured into a block. Preferably, in the process of preparing the raw material powder, the R source is one or more of RCO3, R(NO3)2, and RCl2, with a purity of greater than 99%; the Ln source is Ln2O3, with a purity of greater than 99%; the Ta source is Ta2O5, with a purity of greater than 99%; the Nb source is Nb2O5, with a purity of greater than 99%; the Al source is Al2O3, with a purity of greater than 99%; the P source is NH4H2PO4 or (NH4)2HPO4, with a purity of greater than 99%; the B source is H3BO3 or boric anhydride, with a purity of greater than 99%; the Li source is Li2CO3, with a purity of greater than 99%; the Zn source is ZnO, with a purity of greater than 99%; and the Si source is SiO2, with a purity of greater than 99%. Using raw materials with a purity of greater than 99% to prepare the glass can ensure the stability of the glass crystallization phase and reduce the influence of impurities on the dielectric properties.

[0114] The glass is annealed. The glass melt is poured into a preheated graphite or metal mold, and heated to 400-600℃ in an annealing furnace for 4-24h to obtain a uniform and defect-free glass block.

[0115] Glass powder preparation. The glass fragments and zirconia balls (with a diameter of 1-5μm) are placed in a horizontal ball mill with a zirconia lining at a mass ratio of 1:(3-5), and ball milled at a speed of 30-100r / min for 12-36h. The glass powder with different particle sizes is obtained by sieving.

[0116] Glass granulation powder preparation. In the present invention, the glass powder, ceramic powder, binder and solvent are mixed to obtain a mixed slurry, and then the spherical granulation powder is obtained by spray granulation; the ceramic powder is selected from at least one of β-quartz phase, magnesium oxide, magnesium silicate phase (MgSiO3 or / and Mg2SiO4), barium silicate phase (BaSiO3 or / and BaSi2O5), and the addition amount is 0-20wt% of the mass of the glass powder.

[0117] Glass insulator preparation. In the present invention, when the glass powder is used as the sealing glass material of the radio frequency electrical connector, the glass granulation powder is formed into a specific shape by using an automatic press, placed in a muffle furnace, and then the degassing is completed at 300-500°C for 1-3h, and then the temperature is increased to 650-800°C at a rate of 10-60°C / min, and then sintering is performed for 10-60min, to obtain the glass insulator; the glass insulator is in a partially crystallized state, and the crystallization amount is 50-90wt%.

[0118] Microcrystalline glass-metal seal preparation. In the present invention, the glass insulator and the packaging metal material are assembled, placed in a graphite mold, and then placed in an atmosphere furnace, and then heated to 850-950°C under a protective atmosphere at a rate of 10-100min / °C, and then the temperature is maintained for 0-30min, and then the temperature is increased to 900-1050°C at a rate of 10-100min / °C, and then the temperature is maintained for 10-120min. If necessary, the temperature is decreased to 500-700°C at a rate of 5-20min / °C, and then the temperature is maintained for 60-120min, to complete the glass and metal sealing-glass microcrystallization-seal stress relief process, and obtain the microcrystalline glass-metal seal.

[0119] In an optional embodiment, microcrystalline glass substrate preparation. The microcrystalline glass substrate is placed in a rotating crystallization furnace, and then the temperature is maintained at 400-500°C for 0.1-5h, and then the temperature is maintained at 500-600°C for 0.1-5h, and then the temperature is decreased to room temperature, and then the temperature is maintained at 600-700°C for 0.1-5h, and then the temperature is decreased to room temperature, and then the temperature is maintained at 700-900°C for 0.1-5h, and then the temperature is decreased to room temperature. Preferably, the rotating speed is 0.05-1r / min. Preferably, the temperature increasing rate and the temperature decreasing rate of the microcrystallization process are both 0.1-5°C / min.

[0120] Test method:

[0121] (1) Thermal expansion analysis test: The thermal expansion test is performed by using a Netzsch DIL402 thermal expansion analyzer, and the temperature is increased from room temperature to 1000°C at a rate of 5°C / min.

[0122] (2) Differential thermal analysis (DSC): Differential thermal analysis was performed on sample powder passed through a 200-mesh sieve using a Netzsch DSC 404 differential scanning calorimeter (Germany) from room temperature to 1200℃ at a heating rate of 10℃ / min;

[0123] (3) X-ray diffraction analysis (XRD): After sintering, the sample was crushed with an agate mortar and passed through a 200-mesh sieve, and was tested using a Bruker D8 ADVANCE high-resolution powder X-ray diffractometer (Germany) at a test voltage of 40KV, a test current of 40mA, Cu / Kα rays, a scanning range of 10-80°, and a scanning speed of 5° / min. The obtained XRD pattern was searched using Jade software to determine the crystal phase type;

[0124] (4) Resistance performance test: The high-low temperature resistance / resistivity test system can perform variable temperature electrical insulation performance test;

[0125] (5) Mechanical properties:

[0126] The Instron-5566 universal material testing machine was used to test the mechanical standard sample, the bending strength (or flexural strength or flexural strength) sample was 3×4×34mm, and the test sample size for Young's modulus and Poisson's ratio was a strip sample of 3×10×34mm. Each group was tested for 5 times, and the average value was taken as the experimental parameter after the test was completed.

[0127] The following further examples are further illustrated to explain the present application. It should also be understood that the following examples are only used to further illustrate the present application, and cannot be understood as limiting the scope of protection of the present application. Some non-essential improvements and adjustments made by those skilled in the art according to the above content of the present application all belong to the protection scope of the present application. The specific process parameters in the following examples are only one example in the appropriate range, i.e. those skilled in the art can select within the appropriate range through the description herein, and are not limited to the specific values in the following examples.

[0128] Example 1

[0129] The preparation of the microcrystalline glass material includes:

[0130] (1) According to the total mass of 50 kg, the molar ratio of each component of the raw material is converted into a mass ratio. 33.283 kg SiO2, 3.839 kg Li2CO3, 4.659 kg ZnO, 0.944 kg H3BO3, 1.644 kg Al2O3, 0.719 kg Na2CO3, 0.986 kg K2CO3, 1.324 kg (NH4)2HPO4, and 1.324 kg Ta2O5 are accurately weighed, added to a three-dimensional mixer with an iron removal device, mixed for 12 hours, and then placed in a platinum crucible at 1600°C, stirred at 40 r / min, and kept warm for 8 hours. Then, the melted glass is directly poured into deionized water for quenching to obtain glass slag (or glass fragments);

[0131] (2) 30 kg of glass fragments obtained in step (1) and 120 kg of zirconia balls (with a diameter of 5 μm) were placed in a horizontal ball mill lined with zirconia, and ball milled for 24 h in a planetary ball mill at a speed of 50 r / min to obtain glass powder, i.e., a powdered microcrystalline glass material.

[0132] The preparation of glass insulators includes:

[0133] (1) Add 20 kg of glass powder, 4 kg of 10 wt% PVB alcohol solution, 5.6 kg of alcohol, and 0.2 kg of release agent into an alumina ceramic jar, stir at 100 r / min for 6 hours, and pass the slurry through a 120-mesh sieve to obtain a mixed slurry (or glass powder slurry); granulate the obtained glass powder slurry through a spray granulation tower to obtain granulated powder for use. The feed inlet temperature is 95°C, the discharge outlet temperature is 75°C, and the slurry is passed through a 60-mesh sieve;

[0134] (2) placing the obtained granulated powder into a mold and preforming it into a green blank with a porous structure through an automatic press;

[0135] (3) The green sample with a porous structure was placed in a muffle furnace and kept at 300°C for 2 hours, then at 450°C for 2 hours to complete the debinding. The temperature was then raised to 720°C at a rate of 20°C / min and sintered for 30 minutes to obtain a glass insulator.

[0136] The obtained glass insulator is assembled with the metal shell and the pin, placed in a graphite mold and then placed in an atmosphere furnace, and sintered at 20min / ℃ to 1050℃ for 20min under nitrogen protection to complete the sealing.

[0137] The obtained granulated powder is placed in a mold to be pre-formed into a rectangular block by an automatic press, and then is subjected to degassing and densification at a certain temperature regime (firstly, heat preservation at 300°C for 2h, and then heat preservation at 450°C for 2h to complete degassing; then, increase the temperature to 720°C at a rate of 20°C / min, and heat preservation sintering for 30min to complete densification), and then is cooled to room temperature to obtain a rectangular block sample. The rectangular block sample is placed in a graphite mold, and then is subjected to microcrystallization by a sealing regime (heat preservation sintering at 1050°C for 20min under nitrogen protection), and finally, the obtained sample is processed into various standard samples for performance tests such as thermal, mechanical, electrical, and chemical stability.

[0138] Example 2

[0139] The preparation of the glass-ceramic material comprises the following steps:

[0140] (1) According to the total mass of 50Kg, the molar ratio of each component of the raw material is converted into mass ratio, and 32.920Kg of SiO2, 3.803Kg of Li2CO3, 5.907Kg of ZnO, 0.937Kg of H3BO3, 0.705Kg of Na2CO3, 0.978Kg of K2CO3, 2.56Kg of (NH4)2HPO4, and 2.190Kg of Ta2O5 are accurately weighed and placed in a three-dimensional mixer with a deironing device for mixing for 12 hours, and then are placed in a platinum-gold crucible at 1600°C for stirring at 40r / min for 8h of heat preservation, and then the prepared glass melt is directly poured into deionized water for quenching to obtain glass slag;

[0141] (2) 30Kg of the glass slag obtained in step (1) + 120Kg of zirconia balls (diameter of 5μm) are placed in a horizontal ball mill with zirconia lining, and are subjected to planetary ball milling at a speed of 50r / min for 24h to obtain glass powder, i.e. the glass-ceramic material in powder form.

[0142] The preparation of the glass insulator comprises the following steps:

[0143] (1) 20Kg of the glass powder, 4Kg of 10wt% PVB alcohol solution, 5.6Kg of alcohol, and 0.2Kg of release agent are added into an alumina ceramic tank, and are stirred at a speed of 100r / min for 6h, and then the slurry is sieved through a 120 mesh sieve;

[0144] (2) The glass powder slurry milled in step (1) is completed by a spray granulation tower, wherein the temperature of the inlet is 95°C, the temperature of the outlet is 75°C, and the obtained glass granulated powder is sieved through a 60 mesh sieve for standby use;

[0145] (3) The granulated powder obtained in step (2) is placed in a mold to be pre-formed into a green body with a hole structure by an automatic press;

[0146] (4) Put the sample in step (3) into a muffle furnace, first at 300°C for 2h, then at 450°C for 2h, complete the degassing. Then increase the temperature to 720°C at a rate of 20°C / min, and sinter for 30min, to obtain a glass insulator.

[0147] Assemble the glass insulator obtained with the metal shell and the pin, put it into a graphite mold, and then place it in an atmosphere furnace, sinter at 1050°C for 20min under nitrogen protection, to complete the sealing.

[0148] Put the obtained granulated powder into a mold and pre-form it into a rectangular block by an automatic press. After degassing and densification (first at 300°C for 2h, then at 450°C for 2h, complete the degassing; then increase the temperature to 720°C at a rate of 20°C / min, and sinter for 30min, to complete the densification) at a certain temperature regime, and then decrease to room temperature, to obtain a rectangular block sample. Put the obtained rectangular block sample into a graphite mold, and then perform microcrystallization by a certain sealing regime (sinter at 1050°C for 20min under nitrogen protection). Finally, process the obtained sample into various standard samples for thermal, mechanical, electrical, and chemical stability performance tests.

[0149] Example 3

[0150] The preparation of the microcrystalline glass material includes:

[0151] (1) According to the total mass of 50Kg, convert the molar ratio of each component of the raw materials into mass ratio, accurately weigh 31.332Kg SiO2, 3.615Kg Li2CO3, 4.385Kg ZnO, 0.889Kg H3BO3, 1.543Kg Al2O3, 0.676Kg Na2CO3, 0.938Kg K2CO3, 2.455Kg (NH4)2HPO4, 4.167Kg Ta2O5, and put them into a three-dimensional mixer with iron removal device for mixing for 12 hours, then put them into a platinum-gold crucible at 1600°C for stirring at 40r / min for 8h, and then pour the prepared glass melt directly into deionized water for quenching, to obtain glass slag;

[0152] (2) Put 30Kg of the glass slag obtained in step (1) + 120Kg of zirconia balls (diameter of 5μm) into a horizontal ball mill with zirconia lining, and grind in a planetary ball mill at a speed of 50r / min for 24h, to obtain a glass powder, which is a powder-like microcrystalline glass material.

[0153] The preparation of the glass insulator includes:

[0154] (1) Put 20 Kg glass powder, 4 Kg 10wt% PVB alcohol solution, 5.6 Kg alcohol, and 0.2 Kg release agent into an alumina ceramic pot, stir at a speed of 100 r / min for 6 h, and sieve the slurry through a 120 mesh sieve;

[0155] (2) Complete granulation of the glass powder slurry prepared in step (1) by a spray granulator, wherein the temperature at the inlet is 95°C, the temperature at the outlet is 75°C, sieve through a 60 mesh sieve, and obtain glass granulated powder for standby use;

[0156] (3) Put the granulated powder obtained in step (2) into a mold and preform into a green body with a hole structure by an automatic press;

[0157] (4) Put the sample in step (3) into a muffle furnace, first heat at 300°C for 2 h, then at 450°C for 2 h to complete degassing, and then increase the temperature to 720°C at a rate of 20°C / min and heat for sintering for 30 min to obtain a glass insulator;

[0158] Assemble the obtained glass insulator with a metal shell and a pin, put them into a graphite mold, and then place them in an atmosphere furnace to complete sealing under nitrogen protection at a rate of 20 min / °C to 1050°C and heat for sintering for 20 min.

[0159] Put the obtained granulated powder into a mold and preform into a rectangular block by an automatic press, degas and densify by a certain temperature system (first heat at 300°C for 2 h, then at 450°C for 2 h to complete degassing, then increase the temperature to 720°C at a rate of 20°C / min and heat for sintering for 30 min to complete densification), and then reduce the temperature to room temperature, put the sample into a graphite mold, and then perform microcrystallization by a certain sealing system (under nitrogen protection at a rate of 20 min / °C to 1050°C and heat for sintering for 20 min). Finally, process the obtained sample into various standard samples for performance tests such as thermal, mechanical, electrical, and chemical stability.

[0160] Example 4

[0161] The preparation process of the powdered microcrystalline glass material in this example 4 is as described in example 1, the only difference is that in step (1), according to the total mass of 50 Kg, the mass ratio of each component is accurately weighed as follows: 31.500 Kg SiO2, 7.272 Kg Li2CO3, 4.177 Kg ZnO, 0.898 Kg H3BO3, 0.754 Kg Na2CO3, 0.836 Kg K2CO3, 2.462 Kg (NH4)2HPO4, and 2.100 Kg Nb2O5, put them into a three-dimensional mixer with iron removal device and mix for 12 hours, then put them into a platinum-gold crucible at 1580°C and stir at a speed of 40 r / min for 8 h, and then pour the prepared glass melt directly into deionized water for quenching to obtain glass slag.

[0162] Example 5

[0163] The preparation process of the powdered glass-ceramic material in this example 5 refers to example 1, the only difference is that in step (1), according to the total mass of 50Kg, the molar ratio of each component of the raw material is converted into mass ratio, 30.119Kg SiO2, 9.091Kg Li2CO3, 44.083Kg ZnO, 0.852Kg H3BO3, 0.753Kg Na2CO3, 0.756Kg K2CO3, 2.345Kg(NH4)2HPO4, 2.001Kg Nb2O5 are accurately weighed, mixed in a three-dimensional mixer with iron removal device for 12 hours, then placed in a platinum gold crucible at 1550℃ with stirring at 40r / min for 8h, then the prepared glass melt is directly poured into deionized water for quenching, and glass slag is obtained.

[0164] Example 6

[0165] The preparation process of the powdered glass-ceramic material in this example 6 refers to example 1, the only difference is that in step (1), according to the total mass of 50Kg, the molar ratio of each component of the raw material is converted into mass ratio, 29.410Kg SiO2, 10.424Kg Li2CO3, 3.613Kg ZnO, 0.834Kg H3BO3, 0.753Kg Na2CO3, 0.716Kg K2CO3, 2.288Kg(NH4)2HPO4, 1.963Kg Nb2O5 are accurately weighed, mixed in a three-dimensional mixer with iron removal device for 12 hours, then placed in a platinum gold crucible at 1550℃ with stirring at 40r / min for 8h, then the prepared glass melt is directly poured into deionized water for quenching, and glass slag is obtained.

[0166] Example 7

[0167] The preparation process of the powdered glass-ceramic material in this example 7 refers to example 1, the only difference is that in step (1), according to the total mass of 50Kg, the molar ratio of each component of the raw material is converted into mass ratio, 28.813Kg SiO2, 3.285Kg Li2CO3, 9.309Kg ZnO, 1.640Kg Al2O3, 0.943Kg H3BO3, 1.117Kg Na2CO3, 0.958Kg K2CO3, 2.601Kg(NH4)2HPO4, 1.333Kg La2O3 are accurately weighed, mixed in a three-dimensional mixer with iron removal device for 12 hours, then placed in a platinum gold crucible at 1550℃ with stirring at 40r / min for 8h, then the prepared glass melt is directly poured into deionized water for quenching, and glass slag is obtained.

[0168] Example 8

[0169] The preparation process of the powdered glass-ceramic material in this example 8 refers to example 1, the only difference is that in step (1), according to the total mass of 50Kg, the molar ratio of each component of raw materials is converted into mass ratio, 27.726Kg SiO2, 6.327Kg Li2CO3, 7.677Kg ZnO, 1.579Kg Al2O3, 0.910Kg H3BO3, 1.075Kg Na2CO3, 0.921Kg K2CO3, 2.494Kg (NH4)2HPO4, 1.290Kg La2O3 are accurately weighed, mixed in a three-dimensional mixer with iron removal device for 12 hours, then placed in a platinum gold crucible at 1550℃ with stirring at 40r / min for 8h, then the prepared glass melt is directly poured into deionized water for quenching, and glass slag is obtained.

[0170] Example 9

[0171] The preparation process of the powdered glass-ceramic material in this example 9 refers to example 1, the only difference is that in step (1), according to the total mass of 50Kg, the molar ratio of each component of raw materials is converted into mass ratio, 25.714Kg SiO2, 10.250Kg Li2CO3, 6.387Kg ZnO, 1.465Kg Al2O3, 0.841Kg H3BO3, 1.000Kg Na2CO3, 0.854Kg K2CO3, 2.311Kg (NH4)2HPO4, 1.176Kg La2O3 are accurately weighed, mixed in a three-dimensional mixer with iron removal device for 12 hours, then placed in a platinum gold crucible at 1520℃ with stirring at 40r / min for 8h, then the prepared glass melt is directly poured into deionized water for quenching, and glass slag is obtained.

[0172] Example 10

[0173] The preparation process of the powdered glass-ceramic material in this embodiment 10 is referred to the embodiment 1, the only difference is that in step (1), according to the total mass of 50 Kg, the molar ratio of each component of raw materials is converted into mass ratio, 27.498 Kg of SiO2, 6.275 Kg of Li2CO3, 7.616 Kg of ZnO, 1.562 Kg of Al2O3, 0.904 Kg of H3BO3, 1.060 Kg of Na2CO3, 0.915 Kg of K2CO3, 2.478 Kg of (NH4)2HPO4, 1.259 Kg of La2O3, and 0.433 Kg of Sm2O3 are accurately weighed, mixed in a three-dimensional mixer with iron removal device for 12 hours, then placed in a platinum gold crucible at 1550 ℃ with stirring at 40 r / min for 8 h, and then the prepared glass melt is directly poured into deionized water for quenching to obtain glass slag.

[0174] Embodiment 11

[0175] The preparation process of the powdered glass-ceramic material in this embodiment 11 is referred to the embodiment 1, the only difference is that in step (1), according to the total mass of 50 Kg, the molar ratio of each component of raw materials is converted into mass ratio, 26.585 Kg of SiO2, 6.088 Kg of Li2CO3, 7.364 Kg of ZnO, 1.514 Kg of Al2O3, 0.873 Kg of H3BO3, 1.033 Kg of Na2CO3, 0.882 Kg of K2CO3, 2.396 Kg of (NH4)2HPO4, 1.226 Kg of La2O3, and 2.039 Kg of Sm2O3 are accurately weighed, mixed in a three-dimensional mixer with iron removal device for 12 hours, then placed in a platinum gold crucible at 1550 ℃ with stirring at 40 r / min for 8 h, and then the prepared glass melt is directly poured into deionized water for quenching to obtain glass slag.

[0176] Embodiment 12

[0177] The preparation process of the powdered glass-ceramic material in this embodiment 12 is referred to the embodiment 1, the only difference is that in step (1), according to the total mass of 50 Kg, the molar ratio of each component of raw materials is converted into mass ratio, 25.546 Kg of SiO2, 5.832 Kg of Li2CO3, 7.077 Kg of ZnO, 1.454 Kg of Al2O3, 0.838 Kg of H3BO3, 0.994 Kg of Na2CO3, 0.855 Kg of K2CO3, 2.287 Kg of (NH4)2HPO4, 1.188 Kg of La2O3, and 3.929 Kg of Sm2O3 are accurately weighed, mixed in a three-dimensional mixer with iron removal device for 12 hours, then placed in a platinum gold crucible at 1550 ℃ with stirring at 40 r / min for 8 h, and then the prepared glass melt is directly poured into deionized water for quenching to obtain glass slag.

[0178] Example 13

[0179] The preparation process of the powdered glass-ceramic material in this example 13 refers to example 1, the only difference is that in step (1), according to the total mass of 50Kg, the molar ratio of each component of the raw material is converted into mass ratio, 25.552Kg SiO2, 8.489Kg Li2CO3, 5.865Kg ZnO, 1.785Kg H3BO3, 2.256Kg Na2CO3, 2.126Kg(NH4)2HPO4, 1.311Kg Yb2O3, 2.616Kg Ta2O5 are accurately weighed, mixed in a three-dimensional mixer with iron removal device for 12 hours, then placed in a platinum gold crucible at 1530℃ with stirring at 40r / min for 8h, then the prepared glass melt is directly poured into deionized water for quenching, and glass slag is obtained.

[0180] Example 14

[0181] The preparation process of the powdered glass-ceramic material in this example 14 refers to example 1, the only difference is that in step (1), according to the total mass of 50Kg, the molar ratio of each component of the raw material is converted into mass ratio, 28.276Kg SiO2, 9.992Kg Li2CO3, 1.985Kg ZnO, 1.445Kg Al2O3, 0.809Kg H3BO3, 1.648Kg K2CO3, 2.231Kg(NH4)2HPO4, 0.815Kg Y2O3, 2.800Kg Ta2O5 are accurately weighed, mixed in a three-dimensional mixer with iron removal device for 12 hours, then placed in a platinum gold crucible at 1550℃ with stirring at 40r / min for 8h, then the prepared glass melt is directly poured into deionized water for quenching, and glass slag is obtained.

[0182] Example 15

[0183] The preparation process of the powdered glass-ceramic material in this example 15 refers to example 1, the only difference is that in step (1), according to the total mass of 50Kg, the molar ratio of each component of the raw material is converted into mass ratio, 25.651Kg SiO2, 8.522Kg Li2CO3, 5.888Kg ZnO, 1.792Kg H3BO3, 2.265Kg Na2CO3, 2.134Kg(NH4)2HPO4, 1.312Kg Yb2O3, 2.331Kg Ta2O5, 0.101Kg Cr2O3 are accurately weighed, mixed in a three-dimensional mixer with iron removal device for 12 hours, then placed in a platinum gold crucible at 1500℃ with stirring at 40r / min for 8h, then the prepared glass melt is directly poured into deionized water for quenching, and glass slag is obtained.

[0184] Example 16

[0185] The preparation process of the powdered glass-ceramic material in this example 16 refers to example 1, the only difference is that in step (1), according to the total mass of 50Kg, the molar ratio of each component of the raw material is converted into mass ratio, 25.676Kg SiO2, 8.530Kg Li2CO3, 5.893Kg ZnO, 1.794Kg H3BO3, 2.267Kg Na2CO3, 2.136Kg(NH4)2HPO4, 1.317Kg Yb2O3, 2.333Kg Ta2O5, 0.053Kg CuO are accurately weighed, and then put into a three-dimensional mixer with iron removal device for mixing for 12 hours, then put in a platinum-gold crucible at 1500℃ with stirring at 40r / min for 8h, then pour the prepared glass melt directly into deionized water for quenching, and obtain glass slag.

[0186] Example 17

[0187] The preparation process of the bulk glass-ceramic material in this example 17 refers to example 1, the only difference is that in step (1), according to the total mass of 50Kg, the molar ratio of each component of the raw material is converted into mass ratio, 25.552Kg SiO2, 8.489Kg Li2CO3, 5.865Kg ZnO, 1.785Kg H3BO3, 2.256Kg Na2CO3, 2.126Kg(NH4)2HPO4, 1.311Kg Yb2O3, 2.616Kg Ta2O5 are accurately weighed, and then put into a three-dimensional mixer with iron removal device for mixing for 12 hours, then put in a platinum-gold crucible at 1500℃ with stirring at 40r / min for 8h, and obtain the prepared glass melt. Then pour the prepared glass melt directly into a preheated mold, and put it in an annealing furnace at 450℃ for 6 hours for annealing, and cool to room temperature with the furnace, and obtain glass slag; put the obtained glass bulk into a crystallization furnace, heat to 500℃ at 5℃ / min, and keep for 4 hours to complete nucleation, then heat to 850℃ at 1℃ / min, and keep for 4 hours to complete crystallization, and obtain the glass-ceramic material.

[0188] Example 18

[0189] The preparation process of the bulk glass-ceramic material in this example 18 is referred to example 1, the only difference is that in step (1), according to the total mass of 50Kg, the molar ratio of each component of the raw material is converted into mass ratio, 30.876Kg SiO2, 10.365Kg Li2CO3, 1.305Kg ZnO, 0.981Kg Al2O3, 0.952Kg ZrO2, 0.815Kg Na2CO3, 0.985Kg K2CO3, 3.537Kg (NH4)2HPO4, 0.952Kg La2O3 are accurately weighed, and then put into a three-dimensional mixer with iron removal device for mixing for 12 hours, then put into a platinum gold crucible at 1550℃ and stirred at 40r / min for 8h, to obtain a well-melted glass melt. Then the well-melted glass melt is directly poured into a preheated mold, and then placed in an annealing furnace at 450℃ for 6 hours for annealing, and then cooled to room temperature in the furnace to obtain glass slag. The obtained glass block is placed in a crystallization furnace, heated to 500℃ at a rate of 5℃ / min, and then kept for 4 hours to complete nucleation, and then heated to 850℃ at a rate of 1℃ / min and kept for 4 hours to complete crystallization, to obtain a glass-ceramic material.

[0190] Comparative example 1

[0191] The preparation process of the powder glass-ceramic material in this comparative example 1 is referred to example 1, the only difference is that in step (1), according to the total mass of 50Kg, the molar ratio of each component of the raw material is converted into mass ratio, 22.570Kg SiO2, 8.625Kg Li2CO3, 9.918Kg ZnO, 1.521Kg Al2O3, 1.032Kg Na2CO3, 1.820Kg K2CO3, 2.414Kg (NH4)2HPO4, 1.226Kg La2O3 are accurately weighed, and then put into a three-dimensional mixer with iron removal device for mixing for 12 hours, then put into a platinum gold crucible at 1450℃ and stirred at 40r / min for 8h, and then the well-melted glass melt is directly poured into deionized water for quenching, to obtain glass slag.

[0192] Comparative example 2

[0193] The preparation process of the powdered glass-ceramic material in the present comparative example 2 is as described in example 1, except that in step (1), 24.091 Kg of SiO2, 16.496 Kg of Li2CO3, 2.226 Kg of ZnO, 1.373 Kg of Al2O3, 0.932 Kg of Na2CO3, 0.800 Kg of K2CO3, 2.174 Kg of (NH4)2HPO4, and 1.114 Kg of La2O3 are accurately weighed according to the mass ratio converted from the molar ratio of the total mass of 50 Kg, and then added into a three-dimensional mixer with iron removal device for mixing for 12 hours, and then placed in a platinum-gold crucible at 1450 °C for stirring at 40 r / min for 8 h, and then the prepared glass melt is directly poured into deionized water for quenching, to obtain glass slag.

[0194] Comparative example 3

[0195] The preparation process of the powdered glass-ceramic material in the present comparative example 3 is as described in example 1, except that in step (1), 28.571 Kg of SiO2, 12.414 Kg of Li2CO3, 2.033 Kg of Al2O3, 2.863 Kg of K2CO3, and 1.855 Kg of (NH4)2HPO4 are accurately weighed according to the mass ratio converted from the molar ratio of the total mass of 50 Kg, and then added into a three-dimensional mixer with iron removal device for mixing for 12 hours, and then placed in a platinum-gold crucible at 1500 °C for stirring at 40 r / min for 8 h, and then the prepared glass melt is directly poured into deionized water for quenching, to obtain glass slag.

[0196] Comparative example 4

[0197] The preparation process of the powdered glass-ceramic material in the present comparative example 4 is as described in example 1, except that in step (1), 34.849 Kg of SiO2, 2.014 Kg of Li2CO3, 5.693 Kg of ZnO, 1.720 Kg of Al2O3, 2.009 Kg of K2CO3, and 2.726 Kg of (NH4)2HPO4 are accurately weighed according to the mass ratio converted from the molar ratio of the total mass of 50 Kg, and then added into a three-dimensional mixer with iron removal device for mixing for 12 hours, and then placed in a platinum-gold crucible at 1600 °C for stirring at 40 r / min for 8 h, and then the prepared glass melt is directly poured into deionized water for quenching, to obtain glass slag.

[0198] Comparative example 5

[0199] The preparation process of the powdered glass-ceramic material in Comparative Example 5 is the same as that in Example 1, except that in step (1), 36.152 kg of SiO2, 5.030 kg of Li2CO3, 2.033 kg of ZnO, 1.674 kg of Al2O3, 1.496 kg of Na2CO3, and 2.650 kg of (NH4)2HPO4 are accurately weighed according to the mass ratio converted from the molar ratio of the total mass of 50 kg, and then added into a three-dimensional mixer with a deironing device for mixing for 12 hours, and then placed in a platinum-gold crucible at 1600°C for stirring at 40 r / min for 8 h, and then the prepared glass melt is directly poured into deionized water for quenching to obtain glass slag.

[0200] Comparative Example 6

[0201] The preparation process of the powdered glass-ceramic material in Comparative Example 6 is the same as that in Example 1, except that in step (1), 33.730 kg of SiO2, 2.457 kg of Li2CO3, 5.506 kg of ZnO, 1.666 kg of Al2O3, 1.944 kg of K2CO3, 0.769 kg of (NH4)2HPO4, 1.400 kg of Yb2O3, and 1.570 kg of Ta2O5 are accurately weighed according to the mass ratio converted from the molar ratio of the total mass of 50 kg, and then added into a three-dimensional mixer with a deironing device for mixing for 12 hours, and then placed in a platinum-gold crucible at 1600°C for stirring at 40 r / min for 8 h, and then the prepared glass melt is directly poured into deionized water for quenching to obtain glass slag.

[0202] Table 1 is the composition and performance parameters of the powdered glass-ceramic materials prepared in Examples 1-6:

[0203]

[0204]

[0205] Table 2 is the composition and performance parameters of the powdered glass-ceramic materials prepared in Examples 7-12:

[0206]

[0207]

[0208] Table 3 is the composition and performance parameters of the glass-ceramic materials prepared in Examples 13-18:

[0209]

[0210]

[0211] Table 4 is the composition and performance parameters of the glass-ceramic materials prepared in Comparative Examples 1-6:

[0212]

[0213]

[0214] Table 5 is the performance parameters of the Inconel 718 seal prepared from the insulator prepared in Examples 1-5, Comparative Examples 3 and 6 under impact at 550°C:

[0215]

[0216] Pass requirement: < 1 x 10 -9 Pa-m 3 / s.

[0217] Table 6 is the performance parameters of the devices prepared from the microwave dielectric ceramic and ferrite composite using the glass-ceramic materials prepared in Example 6 and Comparative Example 2 as the sealing material in the C-Ku band:

[0218] Insertion loss Relative bandwidth Example 6 0.5 dB 70％ Comparative Example 2 X X

[0219] X represents that the parameter test cannot be performed. Mainly, the device is unqualified, resulting in that the electrical signal cannot be measured.

Claims

1. A glass-ceramic material, characterized in that: The glass-ceramic material comprises: a main crystal phase forming component, a crystallization promoting regulator, a crystallization inhibiting regulator, and a high temperature performance regulator; The main crystalline phase comprises: 68.94-77.62 mol% SiO2, 6.25-10.25 mol% ZnO, and 7.21-19.87 mol% Li2O; The crystallization promoting agent: 1-5 mol% R2O, 1.22-1.38 mol% P2O5, R = at least one of Na and K; The crystallization suppressing agent comprises: 0-5 mol% Al2O3, 0.95-1.07 mol% B2O3, 0-3 mol% MgO, and 0-3 mol% ZrO2; The high temperature performance regulator: 0.42-5 mol% M2O5, M=at least one of Ta and Nb.

2. The glass-ceramic material according to claim 1, wherein: R = Na and K, and K2O + Na2O = 2 ~ 5 mol%.

3. The glass-ceramic material according to claim 1, characterized in that The crystallized phase in the microcrystalline glass material is at least one of a β-quartz phase, a quartz phase, and a Li2O·SiO2 phase; and the content of the crystallized phase is 55.4 to 78.6 wt%.

4. The glass-ceramic material according to claim 1, wherein The thermal expansion coefficient of the glass-ceramic material is adjustable between 10 and 20 ppm / °C; The dielectric constant of the glass-ceramic material is ≤4-7, and the dielectric loss is ≤5×10 -3 ; The bending strength of the glass-ceramic material is 150-400 MPa, and the elastic modulus is 80-120 GPa; The insulation resistivity of the glass-ceramic material is ≥1×10 15 Ω·cm; The softening point of the glass-ceramic material is greater than 800°C; The sealing temperature of the microcrystalline glass material is 900-1050°C.

5. The glass-ceramic material according to claim 1, characterized in that: The glass-ceramic material is in the form of powder or block; When the microcrystalline glass material is in the form of glass powder, the particle size is D 50 =20~50μm, D 90 =60~100μm.

6. A method for preparing the glass-ceramic material according to claim 5, characterized in that: The glass-ceramic material is in the form of powder, and the preparation method includes: (1) Weighing and mixing the oxides according to the composition of the glass-ceramic material to obtain a raw material powder; (2) melting the raw material powder at high temperature to obtain a glass melt; (3) The obtained glass melt is quenched, ball-milled and classified by a crucible bottom leakage method to obtain a powdered microcrystalline glass material; the solvent used for the quenching is deionized water.

7. A method for preparing the glass-ceramic material according to claim 5, characterized in that: The glass-ceramic material is in the form of a block, and the preparation method includes: (1) Weighing and mixing the oxides according to the composition of the glass-ceramic material to obtain a raw material powder; (2) melting the raw material powder at high temperature to obtain a glass melt; (3) The obtained glass melt is cast into a mold and then annealed to obtain a bulk microcrystalline glass material.

8. The preparation method according to claim 7, characterized in that The parameters of the high temperature melting include: heating to 1480-1600° C. and stirring and keeping warm at a rotation speed of 30-60 r / min for 4-12 hours.

9. The preparation method according to claim 7, characterized in that The annealing temperature is 400-500° C.; the annealing time is 4-24 hours.

10. A method for preparing a glass insulator, characterized in that: include: (1) The glass-ceramic material according to claim 5, ceramic powder, a binder and a solvent are mixed to obtain a mixed slurry; the ceramic powder is selected from at least one of β-quartz phase, magnesium oxide, magnesium silicate phase and barium silicate phase, the magnesium silicate phase is MgSiO3 and / or Mg2SiO4, and the barium silicate phase is BaSiO3 and / or BaSi2O5; the amount of the ceramic powder added is 0 to 20 wt% of the mass of the glass-ceramic material; (2) granulating the obtained mixed slurry by spraying to obtain granulated powder; (3) Pressing the obtained granulated powder into a shape to obtain a preform; (4) The obtained preform is subjected to debinding and sintering to obtain the glass insulator.

11. The preparation method according to claim 10, characterized in that: The microcrystalline glass material is in the form of powder with a particle size of D 50 =20~50μm, D 90 =60~100μm; The particle size of the ceramic powder is 10 μm to 100 μm.

12. The preparation method according to claim 10, characterized in that The particle size of the granulated powder is 80 to 300 μm; The debinding temperature is 300-500°C and the time is 1-3 hours; The sintering temperature is 650-800° C., the sintering time is 10-60 min; and the sintering heating rate is 10-60° C. / min.

13. A glass insulator prepared by the method according to any one of claims 10 to 12, characterized in that: The glass insulator is in a partially crystallized state, the content of the crystallized phase is 30-80 wt %; and the particle size of the crystallized phase is 1-50 μm.

14. A method for packaging a metal material, characterized in that: include: Assembling the glass insulator according to claim 13 and the metal material to be encapsulated and placing them in a mold, and then sealing them in a protective atmosphere to complete the sealing of the metal material; The sealing treatment temperature is 900-1050°C, the holding time is 10-60 min; the heating rate of the sealing treatment is 10-100 min / °C; The protective atmosphere is at least one of nitrogen, helium and a mixture of nitrogen and helium; The mold is a graphite mold.

15. A method for preparing a sealing member, characterized in that: include: (1) The glass insulator according to claim 13 is introduced into the surface of a connecting fitting to be connected or between the surfaces of multiple connecting fittings to be connected, and after assembly is completed, is placed in a mold; (2) First, the temperature is raised to T1 and kept at this temperature for a certain time, then kept at T2 for a certain time, and finally, the temperature is lowered to T3 and annealed to obtain the sealing member.

16. The preparation method according to claim 15, characterized in that The T1 temperature is 850-1050°C, the holding time is 0-30 min; the heating rate of the T1 temperature is 10-100 min / °C; The T2 temperature is 600-850°C, the holding time is 10-120 min; the cooling rate of the T2 temperature is 10-100 min / °C; The T3 temperature is 500-700° C., and the holding time is 60-120 min. The cooling rate of the T3 temperature is 5-20 min / ° C.

17. A seal prepared according to the preparation method according to claim 15 or 16.

18. A method for preparing a microcrystalline glass substrate material, characterized in that: include: The glass-ceramic material according to any one of claims 1 to 5 is subjected to segmented microcrystallization treatment by a rotational crystallization process to obtain the glass-ceramic substrate material; The glass-ceramic material is in the form of a block; The system of the spin crystallization process includes: 1) First raise the temperature to 400-500℃ and keep it for 0.1-5h, then continue to raise the temperature to 500-600℃ and keep it for 0.1-5h and then cool it down to room temperature with the furnace; 2) Heat to 600-700℃, keep warm for 0.1-5 hours and cool to room temperature along with the furnace; 3) Finally, heat to 700-900℃ and keep warm for 0.1-5 hours, then cool to room temperature along with the furnace; In the above steps 1) to 3), the rotation is maintained at a speed of 0.05 to 1 rpm; The heating rate of the heating is 0.1-5°C / min, and the cooling rate of the heating down to room temperature is 0.1-5°C / min.

19. A microcrystalline glass substrate material prepared according to the preparation method according to claim 18.

20. Use of the glass-ceramic material according to any one of claims 1 to 5 as a sealing material for preparing joint connections and / or lead-throughs, characterized in that: The seam connection and / or lead-through includes: a transition layer between ceramic and ceramic, or between ceramic and metal; and / or a sensor from the group consisting of an exhaust gas sensor, a pressure sensor, a particle sensor, a temperature sensor, a nitrogen oxide sensor, and an oxygen sensor; and / or a feedthrough for a compressor and / or an electronic compressor; and / or an electrical power feedthrough for an exhaust assembly; and / or a feedthrough for a chemical reactor.

21. Use of the microcrystalline glass material according to any one of claims 1 to 5 in the preparation of integrated circuit packaging substrates, resonators, microwave antenna sheets, and filters.

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