Glass for encapsulating a device of a titanium-containing metallic material, and method of manufacturing and use thereof

Abstract

The application relates to a glass for packaging a titanium-containing metal material device and a preparation method and application thereof. The glass comprises, in terms of mass percentage of oxides: 10-25% of Al2O3, 40-60% of B2O3, 10-30% of CaO, 1-8% of SiO2, 0.1-2% of Co2O3, 1-5% of TiO2, 1-5% of MgO, 1-10% of ZnO, 0.5-5% of ZrO2, and the sum of mass percentages of Al2O3 and B2O3 is less than 75%. The application solves the technical problem of how to provide a glass for packaging a titanium-containing metal material device, and the packaged device can be used reliably at high temperature, high pressure and in a corrosive environment.

Description

Technical Field

[0001] This invention belongs to the field of sealing glass, and in particular relates to a glass for packaging devices containing titanium metal materials, its preparation method and application. Background Technology

[0002] Titanium-containing metal materials possess unique properties such as low density, high strength, high temperature resistance, corrosion resistance, and high mechanical strength. Furthermore, titanium alloys are non-magnetic, resulting in minimal signal loss during transmission and resistance to interference from strong magnetic environments. Based on these characteristics, titanium and titanium alloys have been widely used in recent years as housing materials for electronic components such as connectors and sensors, replacing traditional Kovar alloys, stainless steel, and high-temperature alloys. They are widely applied in fields such as aerospace, marine engineering, oil exploration, electronic information, and medical technology.

[0003] Because the crystal form of titanium-containing metal materials can easily transform during the encapsulation process when the sealing temperature of the glass used for packaging titanium-containing metal materials is too high, researchers in this field are currently trying to prepare low-temperature glass with a low sealing temperature, keeping the sealing temperature below 600°C, to avoid the transformation of the crystal form of titanium-containing metal materials during the encapsulation process.

[0004] A literature describes the preparation of a borosilicate-titanium alloy sealing glass. By adding a high content of Na₂O and K₂O, its glass sealing temperature reaches 700–825℃, and its glass transition temperature T₀ is [not specified]. g The temperatures range from 450 to 650°C, but the chemical stability of the glass prepared by these methods deteriorates, and the high-temperature insulation resistance decreases, making it difficult to meet the application requirements of titanium-containing metal materials in high-temperature, high-pressure, and corrosive environments. Summary of the Invention

[0005] The main objective of this invention is to provide a glass for packaging devices containing titanium metal materials, its preparation method, and its application. The technical problem to be solved is how to provide a glass for packaging devices containing titanium metal materials that has a sealing temperature lower than the crystal transformation temperature of the titanium metal material, good chemical stability, high mechanical strength, and good corrosion resistance, so as to meet the application requirements of titanium metal materials in high temperature, high pressure, and corrosive environments.

[0006] The objective of this invention and the technical problem it solves are achieved by the following technical solution. According to this invention, a glass for packaging titanium-containing metal materials for devices comprises, by mass percentage of oxides: 10-25% Al₂O₃; 40-60% B₂O₃; 10-30% CaO; 1-8% SiO₂; 0.1-2% Co₂O₃; 1-5% TiO₂; 1-5% MgO; 1-10% ZnO; 0.5-5% ZrO₂; and the sum of the mass percentages of Al₂O₃ and B₂O₃ is <75%.

[0007] The objectives of this invention and the technical problems it addresses can be further achieved by the following technical measures.

[0008] Preferably, in the aforementioned encapsulation glass, m1 is the sum of the mass percentages of CaO and MgO; m2 is the sum of the mass percentages of Al2O3 and B2O3; and the ratio of m1 to m2 is 0.15 to 0.62.

[0009] Preferably, the aforementioned encapsulation glass further comprises: 0-1.0% Li2O.

[0010] Preferably, the aforementioned encapsulation glass has a sealing temperature of 780–850°C and a glass transition temperature T0. g The temperature ranges from 430 to 620℃; the glass softening temperature T f The thermal expansion coefficient is 5×10⁻⁶ for temperatures ranging from 580 to 660℃ and from 25 to 300℃. -6 / ℃~7×10 -6 / ℃; water chemical stability is above level IV.

[0011] The objective of this invention and the technical problem it solves are further achieved by the following technical solution. The method for preparing glass for packaging titanium-containing metal material devices according to this invention includes the following steps:

[0012] Weigh the following raw materials, which, by mass percentage of oxides, include: 10–25% Al₂O₃; 40–60% B₂O₃; 10–30% CaO; 1–8% SiO₂; 0.1–2% Co₂O₃; 1–5% TiO₂; 1–5% MgO; 1–10% ZnO; and 0.5–5% ZrO₂; wherein the sum of the mass percentages of Al₂O₃ and B₂O₃ is <75%; mix the raw materials evenly to obtain a batching material.

[0013] The batch material is melted, clarified, and homogenized to form molten glass; the molten glass is then quenched and ball-milled to obtain glass powder.

[0014] The objectives of this invention and the technical problems it addresses can be further achieved by the following technical measures.

[0015] Preferably, in the aforementioned preparation method, the melting process includes holding at 1300–1500°C for 2–5 hours.

[0016] Preferably, in the aforementioned preparation method, the quenching is tablet quenching.

[0017] Preferably, the aforementioned preparation method further includes the following step:

[0018] The glass powder is mixed with solvent and binder at a ratio of 100:60-80:6-10, granulated, pressed into shape, and vitrified by debinding to prepare precast glass.

[0019] The solvent is any one or a mixture of water, alcohol, and ethyl acetate; the binder is polyethylene glycol and / or polyvinyl alcohol; the molecular weight of the binder is 5000 to 40000.

[0020] Preferably, the aforementioned preparation method involves a gradient temperature process for vitrification, which includes: a first stage of heating to 150–300°C and holding for 1–3 hours; a second stage of further heating to 300–450°C and holding for 1–3 hours; a third stage of further heating to 680–750°C and holding for 15–30 minutes; and then cooling to obtain the pre-made glass.

[0021] The objective of this invention and the solution to its technical problem are also achieved by the following technical solution. The method for preparing a titanium-containing metal material packaged device according to this invention comprises: assembling the glass described in the aforementioned solution with a titanium-containing metal material shell, Kovar pins, and a graphite mold to form an assembly; sintering the assembly in a nitrogen or argon atmosphere, heating to 780–850°C; holding at this temperature for 0.5–1 hour; and then cooling to below 100°C to obtain the finished product.

[0022] By employing the above technical solution, the present invention provides a glass for packaging titanium-containing metal devices, its preparation method, and its application, which have at least the following advantages:

[0023] 1. This invention provides a glass for packaging titanium-containing metal material devices and its preparation method. By adjusting the glass composition, the sealing temperature of the glass is reduced; and by avoiding the presence of sodium and potassium ions in the glass composition, the number of mobile conductive ions in the glass is reduced, thereby improving the chemical stability and high-temperature insulation performance of the glass. The sealing temperature of the final glass is lower than the crystal transformation temperature of the internal elements of the titanium-containing metal material, reducing the surface tension. Furthermore, its coefficient of thermal expansion matches the corresponding coefficient of the titanium-containing metal material well, improving the wettability between the glass and the titanium-containing metal material. The glass has a high softening temperature and transformation temperature, which broadens the application temperature range of the packaged device. Therefore, the glass for packaging titanium-containing metal material devices provided by this invention is more practical and has good application prospects.

[0024] 2. The present invention provides a glass application for packaging titanium-containing metal material devices. During the packaging process, there is no need to apply external force to the glass body for compression sintering, which reduces the operation process and improves production efficiency and yield. Moreover, the sintering temperature during sealing is low, which avoids the problem of shell deformation caused by the phase transformation of titanium alloy during traditional silicate glass sealing, and at the same time reduces the energy consumption required for packaging.

[0025] The above description is merely an overview of the technical solution of the present invention. In order to better understand the technical means of the present invention and to implement it in accordance with the contents of the specification, the preferred embodiments of the present invention are described in detail below. Attached Figure Description

[0026] Figure 1 The expansion curve of the titanium-containing metal material device packaging glass prepared in Example 3 includes the glass expansion coefficient, transition temperature and softening temperature from 25 to 300°C. Detailed Implementation

[0027] To further illustrate the technical means and effects adopted by the present invention to achieve the intended purpose, the following describes, in conjunction with preferred embodiments, a glass for packaging titanium-containing metal materials devices according to the present invention, its preparation method, and its application. Its specific implementation methods, structure, features, and effects are detailed below.

[0028] Through research and analysis, the inventors discovered that the low-temperature glass used for packaging titanium-containing metal devices produced by existing technologies, due to the high levels of sodium and potassium in its glass composition, not only exhibits poor chemical resistance and mechanical strength, but also weak corrosion resistance. Furthermore, when applied to the packaging of titanium-containing metal devices, the resulting devices exhibit poor insulation, especially at higher temperatures such as 350°C, where their insulation performance is far below 1×10⁻⁶. 8 Ω, even below 1×10 6 Furthermore, the sealing glass produced by this process, when used for sealing titanium-containing metal materials, still exhibits leakage issues in high-temperature (≥350℃) environments, thus failing to meet the requirements for use in high-temperature (≥350℃), high-pressure, and corrosive environments for titanium-containing metal material devices. However, currently, titanium alloy TC4 materials often maintain their operational state for extended periods at 350℃. 11 The material often remains operational at temperatures up to 500℃ for extended periods. Therefore, the low-temperature sealing glass produced using existing technologies is limited in practical applications.

[0029] The inventors further investigated and analyzed the existing technology and found that high-temperature sealing glasses with sealing temperatures exceeding 900°C are publicly available. When using the sealing glass prepared in this literature to encapsulate titanium-containing metal materials, the heat treatment temperature needs to reach above 900°C. However, the intermorphic (α, β) transition temperature of titanium alloys is 882°C. During the encapsulation process, the heat treatment temperature exceeds the intermorphic (α, β) transition temperature of the titanium alloy, causing a transformation in the titanium alloy's crystal structure and a change in its internal microstructure, resulting in a sharp decline in its mechanical strength and stability. Furthermore, titanium-containing metal materials are prone to oxidation under high-temperature conditions, forming a complex and thick oxide layer on their surface. This further reduces the sealing performance of the connector and increases the difficulty of subsequent surface treatment. When the sealing temperature is too high, components such as silicates and phosphates in the glass generate titanate complex phases and O, H, and N atoms at the titanium alloy interface. These substances penetrate the titanium alloy surface, causing embrittlement and ultimately reducing the strength of the material itself and the connector, as well as decreasing the sealing performance.

[0030] Based on the above findings, the inventors intend to design and research a new type of glass for packaging titanium-containing metal devices. This glass avoids the presence of sodium and potassium elements and, through formula adjustments, ensures that its sealing temperature is lower than the crystal transformation temperature of the elements within the titanium-containing metal material. It also enables the glass to have high temperature resistance, high pressure resistance, and corrosion resistance, thus meeting the requirements for high reliability of titanium-containing metal device applications in high-temperature, high-pressure, and corrosive environments.

[0031] This invention provides a glass for encapsulating titanium-containing metal materials. By adding Al₂O₃, B₂O₃, CaO, SiO₂, and MgO to the glass, the sealing temperature of the sealing glass is lowered. Co₂O₃ is also added to the glass to further reduce the sealing temperature and promote good wettability between the glass and the titanium-containing metal material during the sealing process, thereby helping to ensure good sealing performance. Furthermore, this application also improves the chemical stability of the glass by adding ZnO and ZrO₂. To improve the compatibility between the titanium-containing metal material and the glass, and to further enhance the chemical stability and wettability of the glass and the titanium-containing metal material, TiO₂ is also added to the glass.

[0032] The composition range of each component in the glass material of this invention is described below. In this invention, unless otherwise specified, the content of each component and the total content are all expressed as mass percentages, that is, the mass percentage of the content of each component and the total content relative to the total mass of the glass material composed of oxides.

[0033] This invention provides a glass for packaging devices containing titanium-containing metal materials, comprising, by mass percentage of oxides: 10-25% Al₂O₃; 40-60% B₂O₃; 10-30% CaO; 1-8% SiO₂; 0.1-2% Co₂O₃; 1-5% TiO₂; 1-5% MgO; 1-10% ZnO; 0.5-5% ZrO₂; and the sum of the mass percentages of Al₂O₃ and B₂O₃ is <75%. In some embodiments, the titanium-containing metal material is titanium metal or titanium alloy.

[0034] Al2O3, as an intermediate in glass networks, can increase network stability, reduce the coefficient of thermal expansion of glass, and improve the chemical stability of glass. However, excessive Al2O3 content may increase the difficulty of glass melting and the sealing temperature. Therefore, this invention strictly limits the Al2O3 content to 10-25%.

[0035] B2O3 is a glass network forger, serving as a framework structure that improves glass-forming properties, lowers the sealing temperature, and enhances the sealing ability between the glass and titanium metal materials. If its content is too low, the sealing temperature of the glass may not meet the preset requirements; however, if its content is too high, the chemical stability of the glass may decrease. Therefore, this invention strictly controls the B2O3 content to be 40-60%.

[0036] When the contents of Al2O3 and B2O3 are high, most of the B2O3 in the glass exists as trigonal [BO3], while Al2O3 exists as aluminum oxide octahedron [AlO6]. This reduces the degree of glass network connectivity and may lead to a decrease in the water resistance and chemical stability of the glass. Therefore, this invention strictly limits the sum of the contents of Al2O3 and B2O3 to <75%.

[0037] SiO2 is a crucial component of the basic framework structure of glass. This invention strictly limits the SiO2 content in the glass to 1-8% by mass to maintain the glass's strength, chemical stability, viscosity, and coefficient of thermal expansion. If the SiO2 content in the glass is less than 1%, it may lead to a decrease in the glass's strength and chemical stability; while if the SiO2 content is greater than 8%, it will result in increased viscosity, higher sealing temperature, and an excessively low coefficient of thermal expansion, potentially causing the glass's coefficient of thermal expansion to be incompatible with that of titanium-containing metal materials during encapsulation.

[0038] CaO and MgO form the outer layer of the glass network, providing free oxygen. + Mg +It can fill the gaps in the network and produce a "mixed alkaline earth effect" and a pressing effect, improving the glass's insulation performance. Both can increase the glass's chemical stability and effectively reduce its viscosity, making the glass easier to melt and clarify. If its content is too low, the sealing temperature of the glass may not reach the preset requirements; however, if the content is too high, it will reduce the glass's water resistance and chemical stability, and may also lead to a decrease in insulation performance. Therefore, this invention strictly controls the CaO content to 10-30% and the MgO content to 1-5%.

[0039] Co2O3 partially enters the glass network, reducing the interfacial energy between the sealing glass and the titanium-containing metal material, and significantly improving the various properties of the sealing glass. However, when its content is too high, it will hinder the improvement of the sealing performance between the sealing glass and the titanium-containing metal material. Therefore, the present invention strictly controls its content to be 0.1-2%.

[0040] ZrO2 can significantly improve the acid and alkali resistance and water resistance of glass, but if its content is too high, the glass melting and clarification will be difficult, and the sealing temperature may increase. Therefore, this invention strictly limits the ZrO2 content to 0.5% to 5%.

[0041] Preferably, in the aforementioned technical solution, the sum of the mass percentages of CaO and MgO is m1; the sum of the mass percentages of Al2O3 and B2O3 is m2; and the ratio of m1 to m2 is 0.15 to 0.62. Under these conditions, it helps to ensure that the glass has good water resistance and chemical stability, high temperature insulation, high mechanical strength, and good pressure resistance.

[0042] Preferably, in some embodiments of the aforementioned scheme, the glass for packaging titanium-containing metal material devices further includes 0-1.0% Li2O; adding an appropriate amount of Li2O helps to improve the chemical stability of the glass, reduce the viscosity and sealing temperature of the glass, and reduce the crystallization tendency of the glass. However, if its content is too high, it will not be conducive to reducing the chemical stability of the glass, and the coefficient of thermal expansion of the glass may increase, thereby making the matching between the sealing glass and the titanium-containing metal material poor, thus affecting the sealing performance of the sealing glass and the titanium-containing metal material.

[0043] The glass for packaging titanium-containing metal devices provided by this invention has a sealing temperature of 780–850°C and a glass transition temperature T0. g The temperature ranges from 430 to 620℃; the glass softening temperature T f The thermal expansion coefficient is 5×10⁻⁶ for temperatures ranging from 580 to 660℃ and from 25 to 300℃. -6 / ℃~7×10 -6 / ℃; water chemical stability is above level IV.

[0044] This invention also provides a method for preparing glass for packaging devices containing titanium metal materials, which includes the following steps:

[0045] 1) Preparation of glass powder, the preparation method is as follows:

[0046] Preparation of the batch: Weigh the following raw materials, based on the mass percentage of oxides, including: 10-25% Al2O3; 40-60% B2O3; 10-30% CaO; 1-8% SiO2; 0.1-2% Co2O3; 1-5% TiO2; 1-5% MgO; 1-10% ZnO; 0.5-5% ZrO2; and the sum of the mass percentages of Al2O3 and B2O3 is <75%. Mix the raw materials evenly to obtain the batch.

[0047] Preferably, in some embodiments, the sum of the mass percentages of CaO and MgO is m1; the sum of the mass percentages of Al2O3 and B2O3 is m2; and the ratio of m1 to m2 is 0.13 to 0.62. More preferably, in other embodiments, the batch material further includes 0 to 1.0% Li2O.

[0048] Melting: The above-mentioned batch material is added to the crucible of a high-temperature melting furnace for high-temperature melting. In order to completely melt the batch material and quickly form a clear and homogenized glass liquid, the glass liquid is continuously stirred with a stirring rod and kept at 1300-1500°C for 2-5 hours. More preferably, in some embodiments, the melting temperature is 1350-1500°C, which can improve the glass melting efficiency.

[0049] The crucibles and stirring rods used in this invention are preferably made of corrosion-resistant materials. In some embodiments, pure platinum crucibles are used, and in other embodiments, platinum alloy crucibles are used.

[0050] Quenching: The homogenized glass melt described above is quenched to prepare glass shards. Preferably, in some embodiments, pressing quenching is used because the glass of the present invention contains a large number of BO-Ca bonds. If the glass shards are prepared by traditional water quenching, the BO-Ca groups react with water to easily generate Ca(OH)2, which destroys the original structure of Ca... 2+ The charge balance with the [BO4] tetrahedron leads to the decomposition of Ca(OH)2 during the later sintering process, affecting the stability of the surface glass network structure. This invention employs tablet pressing and quenching, with the tablet press rotating at 20–40 rpm. This avoids contact with water during glass preparation, thus resolving the impact of water on the glass structure during boroaluminate glass formation and ensuring the stability of the formed surface glass network structure.

[0051] Ball milling: The sharded glass formed by quenching in the aforementioned method is placed in a ball mill jar and ball-milled to form glass powder. The material of the ball mill jar is not specifically limited, as long as it enables ball milling. In some embodiments, the ball mill jar is a corundum ball mill jar. To improve ball milling efficiency, in some embodiments, the ball milling speed is 30–50 rpm, and the ball milling time is 24–28 hours. To make the glass powder formed by ball milling more uniform and finer, preferably, a ball milling solvent is added during the ball milling process. In some embodiments, the ball milling solvent is alcohol, ethanol of 95% or higher, etc.

[0052] 2) Preparation of pre-fabricated glass, the preparation method is as follows:

[0053] Mixing: The glass powder prepared by the aforementioned method is mixed with solvent and binder at a ratio of 100:60 to 80:6 to 10 to form a mixture. The ratio range of molten glass to solvent and binder is strictly limited. The binder and glass powder have good solubility in the solvent and are evenly dispersed, which is beneficial for subsequent glass powder bonding and granulation. Preferably, in some embodiments, the glass powder prepared by the aforementioned method is also passed through a 150-180 mesh sieve, resulting in a uniform particle size distribution during granulation, which further facilitates the smooth progress of the pressing step.

[0054] Preferably, in some embodiments, the solvent is any one or a mixture of water, alcohol, and ethyl acetate; the binder is any one or a mixture of polyethylene glycol (hereinafter referred to as "PEG") or polyvinyl alcohol (hereinafter referred to as "PVP"). Using these solvents and binders allows the binder to dissolve completely in the solvent, and the binder helps the glass powder bond better, which is beneficial for subsequent granulation and pressing steps. In other embodiments, the molecular weight of the binder is preferably 5000–40000; more preferably, the molecular weight of the binder is 6000–30000. Strictly limiting the molecular weight range of the binder is beneficial for the bonding of the glass powder and also facilitates the smooth progress of subsequent granulation, pressing, and vitrification processes.

[0055] Granulation: The mixture formed by mixing the above glass powder with solvent and binder is granulated to prepare particulate matter. The granulation method can be any one of spray drying granulation, manual granulation, or pressure granulation.

[0056] Preferably, in some embodiments, a spray drying granulation method is used, with the inlet temperature of the atomizing dryer being 200–350°C and the outlet temperature being 100–200°C during the granulation process. This invention preferably uses the spray drying granulation method, further strictly limiting the temperature conditions during the spray drying granulation process. This not only results in high preparation efficiency but also helps to obtain particles with uniform particle size. If the temperature is too low, the resulting particles will have excessive viscosity, easily causing blockage of the atomizing dryer; furthermore, if the temperature is too high, carbonization of the glass components will affect the various properties of the subsequently prepared glass.

[0057] Preferably, in some embodiments of the aforementioned technical solution, spray drying granulation is used, and the granulated particles are 50 to 200 mesh. Strictly limiting the particle size not only helps to avoid clogging of the atomizing drying equipment and ensures smooth atomizing granulation, but also facilitates the smooth progress of subsequent pressing processes.

[0058] Compression molding: The granules formed by granulation are compressed into shape. This invention does not specifically limit the compression equipment, as long as it can achieve compression molding. In some embodiments, a molding press is used to compress and form a glass preform. More preferably, the speed of the press is 20-40 rpm, which can quickly form the glass preform and achieve good molding results.

[0059] Vitrification with adhesive removal: This invention employs a gradient temperature method for vitrification of the pressed glass preform, comprising: a first stage, heating from room temperature (20-25°C) to 150-300°C at a rate of 2-10°C / min, and holding at this temperature for 1-3 hours; a second stage, further heating at a rate of 2-10°C / min, increasing the temperature to 300-450°C, and holding at this temperature for 1-3 hours; and a third stage, further heating at a rate of 10-20°C / min, increasing the temperature to 680-750°C, and holding at this temperature for 15-30 minutes, thus obtaining pre-formed glass. By employing the above process method and parameters, and strictly controlling the heating rate and holding temperature conditions at each stage, this process avoids uneven heating within the glass due to excessively rapid heating or excessively high temperatures, which can easily lead to carbonization. Furthermore, the process parameters of this invention also facilitate the complete removal of adhesives from the glass preform, ensuring that the properties of the formed pre-formed glass meet the design requirements. This invention does not specifically limit the apparatus used for placing and pressing the glass preform for vitrification and adhesive removal, as long as it can achieve vitrification and adhesive removal of the glass preform prepared by the above scheme. Preferably, in some embodiments, the third stage is heated to the range of 680-730°C. Under this condition, energy is saved and input costs are reduced while ensuring that the adhesive in the glass preform can be completely removed.

[0060] This invention also provides a method for preparing a titanium-containing metal material encapsulation device, comprising: assembling the glass described in the aforementioned scheme with a titanium-containing metal material shell, Kovar pins, and a graphite mold to form an assembly; then sintering the assembly in a nitrogen or argon atmosphere, heating from room temperature (20-25°C) to 780-850°C at a heating rate of 5-20°C / min; holding at this temperature for 0.5-1 hour; and then cooling down to below 100°C at a cooling rate of 5-10°C / min to obtain the finished product. This invention strictly limits the heating rate during the sintering process because an excessively rapid heating rate will cause the glass to melt too quickly, resulting in gaps between the glass and the titanium-containing metal material shell / contact surface, with gas trapped within these gaps. This leads to poor strength, low sealing performance, and poor insulation properties in the titanium-containing metal material encapsulation device. Preferably, in some embodiments, a heating rate of 5-15°C / min and a cooling rate of 5-8°C / min further ensure good performance of the prepared titanium-containing metal material encapsulation device.

[0061] The titanium-containing metal packaged device prepared by this invention has a leakage rate of <1×10⁻⁶. -10 Pa·m 3 / s; Insulation resistance (350℃) > 1×10 8 Ω has excellent performance in all aspects.

[0062] The present invention will be further described below with reference to specific embodiments, but this should not be construed as a limitation on the scope of protection of the present invention. Some non-essential improvements and adjustments made by those skilled in the art based on the above description of the present invention still fall within the scope of protection of the present invention.

[0063] Unless otherwise specified, all materials and reagents mentioned below are commercially available products well known to those skilled in the art; unless otherwise specified, all methods described are methods known in the art. Unless otherwise defined, the technical or scientific terms used should have the ordinary meaning understood by those skilled in the art to which this invention pertains.

[0064] The testing methods for various performance indicators in the embodiments and comparative examples of this invention are as follows:

[0065] Thermal expansion coefficient test: The test shall be conducted in accordance with the method specified in GB / T 7962.16-2010;

[0066] Glass transition temperature T g and glass softening temperature T f Test: According to GB / T 7962.16-2010 Test Method for Colorless Optical Glass;

[0067] Bending strength test: The test shall be conducted in accordance with the test method for bending strength of glass materials in GB / T 37781-2019.

[0068] Water resistance chemical stability test: The test was conducted according to the test method and classification of water resistance of glass particles at 98℃ in GB / T6582—2021.

[0069] Sealing temperature test: The test shall be conducted in accordance with the method specified in SJ / T 3231-2005;

[0070] Leakage rate test: The leakage rate of the sealed product is determined using a helium mass spectrometer leak detector.

[0071] Insulation resistance test: The insulation of the sealed product at 25°C and 350°C is measured using an ultra-high resistance tester.

[0072] Example 1

[0073] This embodiment describes the preparation of a titanium-containing metal material for device packaging, its preparation method, and its application. The process includes the following steps:

[0074] 1) The specific method for preparing pre-formed glass powder is as follows:

[0075] S1: Weigh the raw materials according to the glass component ratio in Table 1, and mix these raw materials evenly to obtain the batch material.

[0076] S2: The batch material obtained in S1 is placed in a platinum crucible in a high-temperature melting furnace, and the melting temperature is 1350℃. The mixture is held at this temperature for 4 hours and continuously stirred with a platinum stirring rod to form a homogenized glass melt.

[0077] S3: The glass melt obtained in S2 is quenched by pressing and quenching. The speed of the pressing machine is 30 rpm.

[0078] S4: Place the broken glass formed in S3 into a corundum ball mill jar and ball mill it. During the ball milling process, add an appropriate amount of ball milling solvent. The ball milling speed is 40 rpm. The ball milling time is 24 h to obtain glass powder.

[0079] 2) The specific method for preparing pre-fabricated glass is as follows:

[0080] The preparation of glass preforms using the above-mentioned glass powder includes the following steps:

[0081] 1) Mixing: Pass the glass powder through a 160-mesh sieve, and then mix it with water and PEG (PEG molecular weight is 8000) at a mass ratio of 100:70:8 to form a mixture;

[0082] 2) Granulation: The mixture formed in step 1) is spray-dried in a spray drying equipment to form granules with a particle size of 50-200 mesh;

[0083] 3) Press molding: The granules prepared by granulation are pressed into glass preforms using a molding press.

[0084] 4) Adhesive removal vitrification: The glass preform is vitrified by removing adhesive using a gradient temperature method.

[0085] First stage: At room temperature, heat to 230℃ at a rate of 5℃ / min and hold for 2 hours;

[0086] Second stage: Based on the temperature of the first stage, continue to increase the temperature to 400℃ at a rate of 5℃ / min, and hold for 2 hours;

[0087] The third stage: Based on the temperature of the second stage, the temperature is increased to 700℃ at a rate of 15℃ / min and held for 15 minutes; then cooled to obtain the pre-made glass.

[0088] 3) The specific method for preparing titanium alloy packaged devices is as follows:

[0089] The titanium alloy shell, Kovar pin, and graphite mold are cleaned and dried, and then assembled with the pre-fabricated glass prepared in this embodiment. The assembly is then sintered in a nitrogen atmosphere, heated to 800°C at a rate of 10°C / min and held for 0.5 hours. The temperature is then lowered to below 100°C at a rate of 15°C / min to obtain the finished product.

[0090] 4) Preparation and detection:

[0091] The glass transition temperature T of pre-fabricated glass g Glass softening temperature T f The coefficient of thermal expansion, water resistance and chemical stability were tested; the bending strength and glass sealing temperature were tested; the test methods are as described above.

[0092] Leakage rate and insulation resistance (350℃, 25℃) tests were performed on the titanium alloy packaged devices. The specific methods are as described above. The test results are shown in Table 5.

[0093] Example 2

[0094] The difference between this embodiment and embodiment 1 is that the composition of each group in the raw materials in this embodiment is as shown in Table 1, while the remaining steps and parameters are the same as in embodiment 1, and the detection indicators and methods are the same as in embodiment 1.

[0095] Example 3

[0096] The difference between this embodiment and Embodiment 1 is that the component distribution of the raw materials in this embodiment is as shown in Table 1. The remaining steps and parameters are the same as in Embodiment 1, and the detection indicators and methods are the same as in Embodiment 1. An expansion curve of the titanium-containing metal material for device packaging prepared in this embodiment is plotted (see attached figure). Figure 1 .

[0097] Example 4

[0098] The difference between this embodiment and embodiment 1 is that the composition of each group in the raw materials in this embodiment is as shown in Table 1, while the remaining steps and parameters are the same as in embodiment 1, and the detection indicators and methods are the same as in embodiment 1.

[0099] Example 5

[0100] The difference between this embodiment and embodiment 1 is that the composition of each group in the raw materials in this embodiment is as shown in Table 1, while the remaining steps and parameters are the same as in embodiment 1, and the detection indicators and methods are the same as in embodiment 1.

[0101] Example 6

[0102] The difference between this embodiment and embodiment 1 is that the composition of each group in the raw materials in this embodiment is as shown in Table 1, while the remaining steps and parameters are the same as in embodiment 1, and the detection indicators and methods are the same as in embodiment 1.

[0103] Example 7

[0104] The difference between this embodiment and embodiment 1 is that the composition of each group in the raw materials in this embodiment is as shown in Table 1, while the remaining steps and parameters are the same as in embodiment 1, and the detection indicators and methods are the same as in embodiment 1.

[0105] Example 8

[0106] The difference between this embodiment and embodiment 1 is that the composition of each group in the raw materials in this embodiment is as shown in Table 1, while the remaining steps and parameters are the same as in embodiment 1, and the detection indicators and methods are the same as in embodiment 1.

[0107] Example 9

[0108] The difference between this embodiment and embodiment 1 is that the process parameters in this embodiment are shown in Table 2, and the speed of the tablet press is 20 rpm during the tableting and quenching process; the remaining steps are the same as in embodiment 1, and the detection indicators and methods are the same as in embodiment 1.

[0109] Example 10

[0110] The difference between this embodiment and embodiment 1 is that the process parameters in this embodiment are shown in Table 2. In the process of preparing the pre-fabricated glass, the glass powder is passed through a 140-mesh sieve. The other process parameters and steps are the same as in embodiment 1, as shown in Tables 3 and 4.

[0111] Comparative Example 1

[0112] The difference between this comparative example and Example 1 is that the mass percentage of SiO2 in the glass composition is 10%, which exceeds the maximum limit of SiO2 in the glass composition of this invention; the remaining components are shown in Table 3, the process parameters are shown in Table 4, and the process steps and parameters are basically the same as those in Example 1.

[0113] Comparative Example 2

[0114] The difference between this comparative example and Example 1 is that the glass composition does not contain SiO2; the remaining components are shown in Table 3, the process parameters are shown in Table 4, and the process steps and parameters are basically the same as those in Example 1.

[0115] Comparative Example 3

[0116] The difference between this comparative example and Example 1 is that the mass percentage of B2O3 in the glass component is 63%, which exceeds the maximum limit of B2O3 in the glass component of this invention; the remaining components are shown in Table 3, the process parameters are shown in Table 4, and the process steps and parameters are basically the same as those in Example 1.

[0117] Comparative Example 4

[0118] The difference between this comparative example and Example 1 is that the mass percentage of CaO in the glass component is 32%, which exceeds the maximum limit of CaO in the glass component of this invention; the remaining components are shown in Table 3, the process parameters are shown in Table 4, and the process steps and parameters are basically the same as those in Example 1.

[0119] Comparative Example 5

[0120] The difference between this comparative example and Example 1 is that the quenching method used in the preparation of chopped glass is the traditional water quenching method. Specifically, the molten glass is poured into deionized water, quenched into glass particles, and then dried in an oven. The remaining process parameters and steps are the same as in Example 1, as shown in Tables 3 and 4.

[0121] Comparative Example 6

[0122] The difference between this comparative example and Example 1 is that the binder used in the granulation process is PEG with a molecular weight of 4000; the other process parameters and steps are the same as in Example 1, as shown in Tables 3 and 4.

[0123] Comparative Example 7

[0124] The difference between this comparative example and Example 1 is that the binder used in the granulation process is PEG with a molecular weight of 60,000; the other process parameters and steps are the same as in Example 1, as shown in Tables 3 and 4.

[0125] In the table below, Table 1 shows the glass composition of each embodiment; Table 2 shows the process conditions of each embodiment; Table 3 shows the glass composition of each comparative example; Table 4 shows the process conditions of each comparative example; and Table 5 shows the test results of the embodiments and comparative examples.

[0126] In Tables 1 and 3, all components are expressed as mass percentages, in %. In Tables 1 and 3, m1 represents the sum of the mass percentages of Al2O3 and B2O3; m2 represents the sum of the mass percentages of CaO and MgO.

[0127] The units and letters for each process stage in Tables 2 and 4 are as follows:

[0128] Glass powder preparation stage: melting temperature in °C; melting time in h; ball milling speed in rpm; ball milling time in h.

[0129] In the precast glass stage, the meanings of each letter are as follows:

[0130] M represents the molecular weight of the adhesive;

[0131] η represents the ratio of glass powder:water:binder;

[0132] α1 represents the heating rate of the first stage of gradient debinding, in °C / min;

[0133] T1 represents the insulation temperature of the first stage of gradient adhesive removal, in °C;

[0134] t1 represents the heat preservation time of the first stage of gradient glue removal, in hours;

[0135] α2 represents the heating rate in the second stage of gradient debinding, in °C / min;

[0136] T2 represents the insulation temperature of the second stage of gradient adhesive removal, in °C;

[0137] t2 represents the heat preservation time in the second stage of gradient glue removal, in hours;

[0138] α3 represents the heating rate of the third stage of gradient debinding, in °C / min;

[0139] T3 indicates the insulation temperature of the third stage of gradient adhesive removal, in °C;

[0140] t3 represents the heat preservation time of the third stage of gradient glue removal, in minutes;

[0141] Sealing device stage: Sintering temperature is in °C; heating rate and cooling rate are both in °C / min.

[0142] In Table 5, the meanings of each letter are as follows:

[0143] α: represents the coefficient of thermal expansion of glass under temperature conditions of 25–300℃, with units of ×10⁻¹⁰.-7 / ℃;

[0144] T g : Indicates the glass transition temperature, in °C;

[0145] T f : Indicates the glass softening temperature, in °C;

[0146] T 封 : Indicates the sealing temperature of the packaged device, in °C;

[0147] Water resistance and chemical stability: Refer to the water resistance classification of glass particles at 98℃ in GB / T6582—2021;

[0148] Leakage rate: This indicates the leakage rate of the packaged device, measured in ×10⁻⁶. -10 Pa·m 3 / s;

[0149] Insulation resistance (350℃): This indicates the insulation resistance of the packaged device under a high temperature condition of 350℃, and the unit is ×10. 8 Ω;

[0150] Insulation resistance (25℃): This indicates the insulation resistance of the packaged device at 25℃, measured in ×10⁻⁶. 14 Ω;

[0151] Bending resistance: This indicates the glass's resistance to bending, measured in MPa.

[0152] - indicates that the relevant data could not be tested or was not tested.

[0153] Table 1. Raw material component distribution ratios for each embodiment.

[0154]

[0155] Table 2. Process conditions for preparing glass powder in each embodiment.

[0156]

[0157]

[0158] Table 3 shows the distribution ratio of raw material groups for each comparative example.

[0159]

[0160] Table 4. Preparation process conditions for each comparative example

[0161]

[0162]

[0163] Table 5. Test results for the examples and comparative examples.

[0164]

[0165]

[0166] In conjunction with the embodiments, the data in Tables 1, 2, and 5, and the appendix... Figure 1 As can be seen, the sealing temperature of the titanium-containing metal material device packaging glass prepared by this invention is 780-850℃; the glass transition temperature T g The temperature ranges from 430 to 620℃; the glass softening temperature T f The thermal expansion coefficient is 5×10⁻⁶ for temperatures ranging from 580 to 660℃ and from 25 to 300℃. -6 / ℃~7×10 -6 / ℃; water chemical stability is above level IV.

[0167] Comparing Example 10 with Example 1, it can be seen that during the preparation of the pre-fabricated glass, the glass powder still has a relatively coarse particle size after sieving. The airtightness of the device will be reduced after sealing. This is because the glass powder is too coarse, and the surface of the glass pre-fabricated part is rougher. During the sealing process, the wettability between the glass and the shell is poor, resulting in a reduction in the airtightness of the device.

[0168] Comparing Comparative Example 1 with Example 1, it can be seen that the mass percentage of SiO2 in the glass composition exceeds the maximum limit of SiO2 in the glass composition of the present invention. The prepared glass will show an increase in sealing temperature. This is because the increase in SiO2 content improves the compactness of the glass network structure, resulting in an increase in the glass characteristic temperature point and sealing temperature.

[0169] Comparing Comparative Example 2 with Example 1, it can be seen that when the glass composition does not contain SiO2, the glass prepared there is a problem of reduced glass bending strength. This is because the glass does not contain SiO2 network aggregator, the density of the glass network structure decreases, resulting in a decrease in the bending strength of the glass.

[0170] Comparing Comparative Example 3 with Example 1, it can be seen that the mass percentage of B2O3 in the glass component exceeds the maximum limit of B2O3 in the glass component of the present invention. The glass prepared by it has problems of poor chemical stability and low bending strength. This is because the glass contains too much B2O3, which exists mainly in the form of boron-oxygen trigonometric bodies in the glass network structure, reducing the degree of connection of the glass network, making the glass easier to peel off, resulting in decreased chemical stability and reduced bending strength.

[0171] Comparing Comparative Example 4 with Example 1, it can be seen that the mass percentage of CaO in the glass component exceeds the maximum limit of CaO in the glass component of the present invention. The prepared glass will have poor chemical stability. This is because a large amount of CaO in the glass provides more free oxygen, which reduces the degree of connection of the glass network structure, making the glass more susceptible to corrosion and resulting in decreased chemical stability.

[0172] Comparing Comparative Example 5 with Example 1, it can be seen that the glass prepared by the traditional water quenching method has the problem of reduced chemical stability. This is because there are a large number of BO-Ca bonds in the glass during the water quenching process. The BO-Ca groups react with water to generate Ca(OH)2, which is easily corroded in a humid environment.

[0173] Comparing Comparative Example 6 with Example 1, it can be seen that the molecular weight of the binder used is too low, and its bonding effect on the glass powder is weak. Therefore, the glass preform has low density and is relatively loose.

[0174] Comparing Comparative Example 7 with Example 1, it can be seen that the molecular weight of the adhesive used is too large, and its bonding effect on the glass powder is strong. This makes it difficult to remove adhesive and other steps in the preparation of pre-fabricated glass. As a result, the glass prepared has the problem of incomplete removal of organic matter, and a large number of bubbles appear in the glass body after encapsulation. At high temperature, the insulation resistance of the glass decreases, and the glass is more easily broken down by current.

[0175] The technical features in the claims and / or specification of this invention can be combined, and the combination is not limited to the combinations obtained through reference in the claims. Technical solutions obtained by combining the technical features in the claims and / or specification are also within the scope of protection of this invention.

[0176] The above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention in any way. Any simple modifications, equivalent changes, and alterations made to the above embodiments based on the technical essence of the present invention shall still fall within the scope of the technical solution of the present invention.

Claims

1. A glass for encapsulating a device containing a titanium metal material, characterized by comprising: 0 It comprises, in terms of mass percentage of oxides: 10-25% Al2O3; 40-60% B2O3; 10-30% CaO; 1-8% SiO2; 0.1-2% Co2O3; 1-5% TiO2; 1-5% MgO; 1-10% ZnO; 0.5-5% ZrO2; and the sum of mass percentage of Al2O3 and B2O3 is less than 75%.

2. The glass of claim 1, wherein, The sum of mass percentage of CaO and MgO is m1; the sum of mass percentage of Al2O3 and B2O3 is m2; m1:m2 is 0.15-0.

62.

3. The glass of claim 1, wherein, It further comprises: 0-1.0% Li2O.

4. The glass of claim 1, wherein, The sealing temperature thereof is 780-850°C; the glass transition temperature T g is 430-620°C; the glass softening temperature T f is 580-660°C; the thermal expansion coefficient at 25-300°C is 5x10 -6 / °C-7x10 -6 / °C; the water chemical resistance is above grade IV.

5. A method for producing a glass for a device package of a titanium-containing metallic material, characterized by, It comprises the following steps: The following raw materials are weighed, which comprise, in terms of mass percentage of oxides: 10-25% Al2O3; 40-60% B2O3; 10-30% CaO; 1-8% SiO2; 0.1-2% Co2O3; 1-5% TiO2; 1-5% MgO; 1-10% ZnO; 0.5-5% ZrO2; and the sum of mass percentage of Al2O3 and B2O3 is less than 75%; the raw materials are mixed uniformly to prepare a batch; The batch is subjected to melting, refining and homogenizing to form a glass liquid; the glass liquid is subjected to quenching and ball milling in sequence to obtain a glass powder.

6. The production method according to claim 5, wherein The melting comprises keeping at 1300-1500℃ for 2-5h.

7. The preparation method according to claim 5, characterized in that, The quenching is tablet quenching.

8. The production method according to any one of claims 5 to 7, characterized by, It further comprises the following steps: The glass powder is mixed with a solvent and a binder in a ratio of 100:60-80:6-10, granulated, and pressed into shape; the binder is removed and vitrified to prepare a preform glass. The solvent is any one or a mixture of more than one of water, alcohol and ethyl acetate; the binder is polyethylene glycol and / or polyvinyl alcohol; the molecular weight of the binder is 5000-40000.

9. The production method according to claim 8, characterized by, The binder removal and vitrification are performed in a gradient temperature mode, which comprises: a first stage of heating to 150-300℃ for 1-3h; a second stage of continuously heating to 300-450℃ for 1-3h; a third stage of continuously heating to 680-750℃ for 15-30min; and then cooling to obtain the preform glass.

10. A method for producing a device encapsulated with a titanium-containing metallic material, characterized by The glass of any one of claims 1-4 is assembled with a shell of titanium-containing metal material, a kovar pin and a graphite mold to form an assembly; the assembly is sintered in a nitrogen or argon environment, heated to 780-850℃; kept for 0.5-1h; and then cooled to below 100℃ to obtain a finished product.

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