A sealing glass well-matched with titanium alloy in wettability and a preparation method thereof

Abstract

This invention discloses a sealing glass with good wettability to titanium alloys, comprising the following components in weight percentage (wt.%): 30-50 wt.% SiO2, 1-5 wt.% Al2O3, 10-30 wt.% B2O3, 10-20 wt.% TiO2, 5-9 wt.% CaO, 1-5 wt.% SrO, 0.1-0.5 wt.% BaO, 2-8 wt.% ZrO2, 1-2 wt.% La2O3, 0-1 wt.% CeO2, and 0.1-0.5 wt.% CoO. This invention also provides a method for preparing sealing glass, comprising the following steps: weighing raw materials according to a mass percentage of a glass composition, mixing them evenly, heating and melting them into a glass melt; after the glass melt is uniform, pouring the molten glass melt into deionized water for rapid cooling and quenching, then drying to obtain glass melt fragments; then ball milling the dried glass fragments into glass powder, drying and sieving to ensure the glass powder particle size is less than 100 micrometers, thus obtaining the desired sealing glass material powder. This invention has a linear thermal expansion coefficient of (50-70)×10⁻⁶ in the range of 20-300 °C. ‑7 / ℃; glass softening temperature is 610-660℃; advantages include chemical stability of level IV or above.

Description

Technical Field

[0001] This invention relates to a sealing glass material with good wettability to titanium alloys and its preparation method, belonging to the field of sealing technology for glass materials and electronic materials. Background Technology

[0002] Sealing glass is a special type of glass used to seal together similar or dissimilar materials through heating. It enables the interconnection and hermetic encapsulation of glass, ceramics, metals, and semiconductors. Sealing glass possesses excellent heat resistance and chemical stability, as well as high mechanical strength, hermeticity, and electrical insulation properties. Therefore, sealing glass is widely used in various fields such as vacuum sealing, electronic component sealing, microelectronics sealing, and semiconductor chip packaging, particularly in the semiconductor industry, consumer electronics industry, and aerospace systems.

[0003] With the rapid development of science and technology and the increasing demands for lightweight, high-strength, and corrosion-resistant equipment in key fields such as automotive electronics, home appliances, information and communication technology, national defense, microelectronics, new energy, and aerospace, titanium alloys have become an irreplaceable material in these fields. This is mainly due to the following advantages of titanium alloys: (1) Titanium alloy has a low density (4.5 g / cm³). 3 Compared to stainless steel (7.9 g / cm³), 3 Titanium alloys are 43% lighter than stainless steel for the same volume. They have advantages such as low density, light weight, high specific strength, and corrosion resistance, which can meet the requirements of lightweight equipment. (2) Titanium alloys have high thermal strength and can work for a long time at temperatures of 450 to 550°C while maintaining the required strength, while aluminum alloys can only be used below 200°C. (3) Titanium alloys have good corrosion resistance. When working in humid atmospheres and seawater, their corrosion resistance is far superior to that of stainless steel. In addition, they also have excellent corrosion resistance to alkalis, chlorides, chlorinated organics, nitric acid and sulfuric acid. (4) Titanium alloys have good low-temperature resistance and high-temperature resistance. They can still maintain their mechanical properties at low and ultra-low temperatures, making them suitable for use as low-temperature structural materials. (5) Titanium alloys have low thermal conductivity. The thermal conductivity of pure titanium is λ = 15.24 W / (mK), which is about 1 / 4 of that of nickel, 1 / 5 of that of iron, and 1 / 14 of that of aluminum. The thermal conductivity of various titanium alloys is 50% lower than that of pure titanium. (6) Titanium alloy is also a non-magnetic material. When it is used to transmit signals, the signal loss is small and it can resist interference from strong magnetic environment.

[0004] Based on these properties, titanium alloys have found widespread application in automotive electronics, home appliances, information and communication technology, national defense, microelectronics, new energy, and aerospace. They are commonly used as housing materials for electronic components such as connectors and sensors. Particularly in aerospace applications, such as turbine engines, the demand for various electrical connectors is enormous; a single aircraft can use thousands of connectors. Furthermore, these connectors and sensors are required to withstand temperatures above 500°C for over 24 hours, making their reliability and stability paramount. However, there are currently no sealing glass materials specifically designed for titanium alloys. This is primarily due to the poor wettability of titanium alloys and the fact that excessively high temperatures can cause crystal transformation during sealing, potentially leading to sealing defects. Especially when subjected to environmental changes, numerous microcracks can form at the sealing interface, resulting in poor airtightness and low insulation resistance. Additionally, titanium alloys are highly susceptible to high-temperature oxidation, forming different types of oxide layers at different temperatures, increasing the difficulty of subsequent surface treatment.

[0005] Currently used sealing glass materials mainly include lead-acid glass, vanadate glass, phosphate glass, and bismuthate glass. Lead-acid glass has advantages such as low dielectric loss, low softening temperature, and good chemical stability. However, due to its PbO content, lead-acid glass can cause pollution and toxicity to humans and the environment during its preparation and use. Vanadate sealing glass is the main material for airtight bonding below 400℃, but it is prone to crystallization during use, has poor chemical stability, requires oxygen purging during melting, and the V₂O₅ in the glass raw material has a chronic toxic effect on humans. Furthermore, V₂O₅ is a semiconductor material, and its high conductivity after melting into glass negatively impacts the insulation performance of the sealed device. Phosphate glass generally has a high coefficient of thermal expansion and poor chemical stability. Bismuthate glass has good electrical insulation properties and a wide adjustable range of its coefficient of thermal expansion, but it has low sealing strength and poor chemical stability.

[0006] Therefore, improving the wettability of the sealing glass and titanium alloy to improve the sealing quality is a technical problem that urgently needs to be solved in this field. Summary of the Invention

[0007] To address the problem of poor wettability between sealing glass and titanium alloy, which leads to a higher probability of sealing defects, the present invention aims to provide a sealing glass with good wettability matching with titanium alloy. The present invention also provides a method for preparing a sealing glass with good wettability matching with titanium alloy.

[0008] To solve the above-mentioned technical problems, the present invention adopts the following technical solution: A sealing glass with good wettability to titanium alloys comprises the following components in weight percentage (wt.%):

[0009] Preferably, the sealing glass used to prepare a material with good wettability to titanium alloy comprises the following components in weight percentage (wt.%):

[0010] The sealing glass of the present invention, which has good wettability with titanium alloy, is characterized in that it does not substantially contain any of the alkali metal oxides, wherein the alkali metal oxides refer to any of the following: Li2O, Na2O, K2O, Rb2O, Cs2O, Fr2O, etc.

[0011] The sealing glass of the present invention has good wettability with titanium alloys and does not contain any of the environmentally harmful metal oxides such as As2O3, Sb2O5, PbO, Tl2O, CdO, BeO, V2O5, etc.

[0012] Furthermore, the sealing glass with good wettability to titanium alloys is characterized in that the average linear coefficient of thermal expansion of the glass in the temperature range of 20-300 °C is (50-70)×10⁻⁶. -7 / ℃; the softening temperature of the glass is 610-660℃; the chemical stability is above level IV.

[0013] The present invention discloses a method for preparing sealing glass, characterized by comprising the following steps: weighing raw materials such as SiO2, Al2O3, B2O3, TiO2, CaO, SrO, BaO, ZrO2, La2O3, CeO2, and CoO according to their mass percentages, mixing them evenly, and heating them to melt them into a glass melt. After the glass melt is uniformly melted, the molten glass melt is poured into deionized water for rapid cooling and quenching, and then dried to obtain glass melt fragments. The dried glass fragments are then ball-milled into glass powder, dried, and sieved to make the particle size of the sealing glass powder less than 100 micrometers, thereby obtaining the desired sealing glass material powder.

[0014] Compared with the prior art, the significant advantage of the sealing glass provided by the present invention, which has good wettability matching with titanium alloy, is that: (1) The sealing glass material provided by the present invention has the characteristics of good wettability sealing matching with titanium alloy and high chemical stability; (2) The preparation method of the sealing glass of the present invention is simple, the raw materials are inexpensive, the cost is low, and it has good airtightness after sealing, and can be used in high temperature environment; (3) The sealing glass of the present invention has a suitable coefficient of thermal expansion, and its average linear coefficient of thermal expansion in the range of 20-300 °C is (50-70)×10. －7 / ℃; (4) After the sealing glass of the present invention is sealed with the titanium alloy material, and then baked at 450°C for 1 hour, the air leakage rate is less than 1×10⁻⁶. －10 Pa·m 3 / s; (5) The sealing glass of the present invention has a high softening temperature and transition temperature, which broadens the application temperature range of the encapsulation device. Therefore, the sealing glass provided by the present invention, which has good wettability matching with titanium alloy, is more practical and has good application prospects. Detailed Implementation

[0015] To make the objectives, technical solutions, and advantages of the present invention clearer, the embodiments of the present invention will be described in further detail below.

[0016] The present invention will be further described in detail below with reference to specific embodiments, but this is not intended to limit the present invention.

[0017] This invention provides a sealing glass with good wettability to titanium alloys, comprising the following components in weight percentage (wt.%):

[0018] Preferably, the sealing glass used to prepare a material with good wettability to titanium alloy comprises the following components in weight percentage (wt.%):

[0019]

[0020] In this invention, SiO2 is the main component constituting the glass skeleton, forming a unified network within the glass. Introducing SiO2 into the glass can improve its mechanical strength, viscosity, thermal stability, and reduce its coefficient of thermal expansion. If the SiO2 content is below 30 wt.%, the overall performance of the glass will be poor, making it difficult to obtain high-strength sealing glass. However, if its content is above 50 wt.%, the required temperature during glass melting will be too high, and defects such as stone formation may occur, affecting the final sealing performance.

[0021] Al₂O₃ is an intermediate oxide of glass. 3+Al2O3 exists in two coordination states: tetrahedral or octahedral. When there is sufficient oxygen in the glass, aluminum-oxygen tetrahedra [AlO4] are formed, creating a continuous network with silicon-oxygen tetrahedra. When there is insufficient oxygen in the glass, aluminum-oxygen octahedra [AlO6] are formed, existing as outer bodies within the voids of the silicon-oxygen network. Therefore, within a certain content range, it can form the main body of the glass network with SiO2 and B2O3, and together with SiO2, it can form a network structure, making the glass structure more compact. Introducing an appropriate amount of Al2O3 can significantly improve the chemical stability, mechanical strength, and resistance to crystallization of the glass. By forming strong Al-O bonds, it strengthens the network structure, effectively inhibits the migration of alkaline earth metal ions, and enhances hydrolysis resistance. If the Al2O3 content is less than 1 wt.%, the internal network structure of the glass is weak, resulting in low strength and viscosity, as well as small network gaps. If its content is higher than 5 wt.%, the melting temperature is too high, which will cause defects such as stones, reduce the thermal expansion coefficient of the glass, worsen the matching with the sealing device, and affect the final sealing performance.

[0022] In this invention, B2O3 is a glass-forming oxide and a component of the glass framework. It is also a flux that reduces the viscosity of molten glass and a major component in lowering the glass softening temperature. Boron-oxygen trigonal [BO3] and boron-oxygen tetrahedron [BO4] are structural components. Under different conditions, boron may exist as trigonal [BO3] or boron-oxygen tetrahedron [BO4]. Under high-temperature melting conditions, it is generally difficult to form boron-oxygen tetrahedra, and it can only exist as trihedrons. However, at low temperatures, under certain conditions, B2O3... 3+ B₂O₃ tends to capture free oxygen to form tetrahedrons, resulting in a more compact structure and increased low-temperature viscosity of the glass. However, its properties of decreasing glass viscosity at high temperatures and increasing it at low temperatures limit its content range. The mass percentage (wt.%) of B₂O₃ is 10-30, preferably 20-30 wt.%. A B₂O₃ content below 10 wt.% fails to act as a solubilizer and reduces the chemical stability of the glass; a B₂O₃ content above 30 wt.% reduces the glass's coefficient of thermal expansion and mechanical strength, while also increasing its tendency for phase separation.

[0023] To improve the compatibility between titanium alloy materials and glass, enhance the chemical stability of the glass, and improve the wettability of both materials, this invention also incorporates TiO2 into the glass. TiO2 primarily functions as a stabilizer and improves compatibility with the titanium alloy, thereby increasing the mechanical strength and chemical stability of the glass and lowering its softening and sealing temperatures. The mass percentage (wt.%) of TiO2 is 10-20%. If the TiO2 content is below 10 wt.%, it cannot provide a fluxing effect and results in poor wettability with the titanium alloy material. If the TiO2 content is above 20 wt.%, it increases the tendency of the glass to crystallize.

[0024] CaO, SrO, and BaO are alkaline earth metal oxides, which are divalent network exooxides. The strong alkalinity of alkaline earth metal ions increases the density, gloss, and chemical stability of glass. They also increase the coefficient of thermal expansion of the glass, matching the expansion coefficient of the sealing material to reduce interfacial thermal stress. CaO and SrO effectively lower the melting temperature and high-temperature viscosity of glass, improving fluidity and spreadability, thus ensuring the formation of a dense, defect-free sealing layer. CaO also improves the chemical stability of glass, especially its alkali resistance, and effectively inhibits its crystallization tendency; while SrO can adjust the coefficient of thermal expansion, allowing for better matching with the sealing device and reducing thermal stress. Introducing small amounts of CaO and SrO into the glass network structure enhances its chemical stability. The mass percentage (wt.%) of CaO is 5-9%. A CaO content below 5 wt.% decreases the chemical stability of the glass; a CaO content above 9 wt.% increases the coefficient of thermal expansion and also increases the glass's tendency for phase separation. The mass percentage (wt.%) of SrO is 1-5%. When the SrO content is below 1%, its effect on fluxing and enhancing chemical stability is limited; if the content is above 5%, crystallization may occur due to exceeding its solubility, which will lead to a decrease in the chemical stability of the glass. The introduction of BaO helps to improve the dielectric constant of the glass and reduce dielectric loss. As a high field strength cation, barium ions will generate induced charges at the film layer after sealing and passivation, forming negative charge centers and reducing reverse leakage current. A small amount of barium oxide can accelerate the melting of glass, but too much content will cause secondary bubbles to appear during clarification. If the BaO content is less than 0.1%, its effect on accelerating glass melting is not obvious and cannot meet the requirements of glass processability and thermal matching; when the BaO content is greater than 0.5%, it will lead to a decrease in the chemical stability and structural strength of the glass, and may increase the tendency of the glass to crystallize. It will also react with oxygen, making it difficult to clarify the melt, causing more severe corrosion to refractory materials, and hindering ion exchange, thus affecting the final performance.

[0025] ZrO2 primarily functions as a network intermediate, enhancing chemical stability and mechanical strength. Its high field strength Zr... 4＋ Zirconium ions can effectively strengthen the glass network, especially significantly enhancing its resistance to alkali corrosion. The mass percentage (wt.%) of ZrO2 is 2-8%. If its content is less than 2%, the strengthening effect is not obvious, and the improvement in the chemical stability of the glass is limited. If the content is higher than 8%, due to the low solubility of zirconium ions in the glass melt, they are very easy to crystallize, which will seriously damage the uniformity and density of the glass and drastically increase the melt viscosity, making glass melting, homogenization and forming extremely difficult.

[0026] Furthermore, by synergistically combining the fluxing and wetting properties of TiO2 with the chemical stability and strength-enhancing characteristics of ZrO2, a balance is achieved between suitable processing temperature, a thermal expansion coefficient matching the titanium alloy material, excellent chemical stability, and long-term structural stability in the sealing glass. If the ZrO2 to TiO2 mass ratio is less than 0.1, the glass network structure will become too loose due to excessive TiO2. Although this helps to lower the melting temperature, it will severely degrade the chemical stability of the passivation layer, reducing its chemical resistance and significantly increasing the thermal expansion coefficient, leading to the risk of thermal stress mismatch with the sealing device. If the barium oxide to zinc oxide mass ratio is greater than 0.8, the high-temperature viscosity of the glass melt will increase sharply, deteriorating its fluidity and spreadability, leading to increased processing temperature and easily inducing the precipitation of zirconium-related crystalline phases, thus compromising the uniformity of the sealing glass.

[0027] La₂O₃ is a rare earth oxide that can reduce the coefficient of thermal expansion and softening temperature of glass, improve its chemical stability, and effectively inhibit crystallization, thus lowering the sealing temperature. This is achieved by introducing a high-field-strength La₂O₃. 3＋ Ions can effectively strengthen the glass network structure, significantly improve the density and chemical stability of the passivation layer, especially enhancing its resistance to active corrosive media such as fluoride ions, which have a strong corrosive effect on titanium alloys. Simultaneously, the introduction of La2O3 can effectively suppress the glass's phase separation tendency, improve high-temperature viscosity stability, and ensure that the sealing glass maintains an amorphous and uniform state during heat treatment. Furthermore, its trivalent nature can effectively compensate for the space charge formed by the migration of alkaline earth metal ions in the glass network, optimizing the interfacial electric field distribution and dielectric properties. The mass percentage (wt.%) of La2O3 is 1-2. If the La2O3 content is less than 1 wt.%, the glass network structure will lack the high electric field strength of La2O3. 3＋ The strengthening effect of ions leads to insufficient compactness, resulting in a significant decrease in the chemical stability of the glass, especially its chemical resistance and ability to inhibit ion migration; when the La2O3 content is greater than 2 wt.%, the excess La... 3＋ Ions, limited by their solubility in the glass melt, can become heterogeneous nucleation sites, greatly increasing the glass's tendency to crystallize. This not only causes devitrification but also introduces micro-stress due to the difference in thermal expansion coefficients between the crystalline phase and the glass phase, deteriorating the mechanical strength and insulation properties of the sealing glass.

[0028] CeO2 can act as an oxidant, helping to control the redox environment of glass and preventing excessive crystallization during application and sealing. The mass percentage (wt.%) of CeO2 is 0-1; a CeO2 content higher than 1 wt.% will reduce the chemical stability and mechanical strength of the glass. Titanium alloys are easily oxidized at high temperatures, forming a complex and thick oxide layer on their metal surface. This further reduces the sealing performance of the device, increases the difficulty of subsequent surface treatment, and leads to embrittlement of the titanium alloy, ultimately resulting in reduced sealing strength and decreased sealing performance of both the sealing material and the device. Using La2O3 and CeO2 in the aforementioned amounts can further optimize the mechanical strength and chemical properties of the resulting glass powder after sealing. Simultaneously, under appropriate conditions, CeO2 can partially function as an oxidant, more effectively controlling the atmosphere during glass sealing.

[0029] CoO partially enters the glass network, which can reduce the interfacial energy between the sealing glass and the titanium-containing metal material, and significantly improve 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 alloy material. Therefore, the present invention strictly controls the mass percentage (wt.%) of CoO to 0.1-0.5%.

[0030] The sealing glass of this invention, which exhibits good wettability with titanium alloys, is characterized by being substantially free of any alkali metal oxides. Alkali metal oxides refer to any one of Li₂O, Na₂O, K₂O, Rb₂O, Cs₂O, Fr₂O, etc., and any trace amounts are due to other glass raw materials. Because glass is a typical ionic conductor, its conductivity mechanism is caused by the movement of alkali metal ions under the influence of an electric field, which increases the conductivity of the glass. Therefore, for titanium alloy sealing devices with high insulation requirements, the presence of Na₂O in the sealing glass composition should be avoided. ＋ K ＋ Alkali metal ions can reduce the number of mobile conductive ions in glass, improve the chemical stability and high-temperature insulation performance of glass; ultimately, the sealing temperature of the sealing glass is lower than the crystal transformation temperature of the internal elements of the titanium alloy material, reducing surface tension, and making the thermal expansion coefficient of the sealing glass match the corresponding coefficient of the titanium alloy material well, thus improving the wettability of the glass and the titanium alloy material.

[0031] The sealing glass composition formulation of this invention, which exhibits good wettability with titanium alloys, does not contain any environmentally harmful metal oxides such as As₂O₃, Sb₂O₅, PbO, Tl₂O, CdO, BeO, V₂O₅, etc. In particular, the addition of Sb₂O₃, as extensive experiments by the inventors have shown, reduces the resistance of the sealing glass powder composition to acid and alkali corrosion after sintering, thus affecting the long-term stability and reliability of the final sealed device. Furthermore, the oxygen absorption and re-release properties of Sb₂O₃ are detrimental to the wettability of the sealing glass powder composition system provided by this invention with the titanium alloy surface.

[0032] Furthermore, the sealing glass of the present invention, which has good wettability with titanium alloy, is characterized in that the average linear thermal expansion coefficient of the glass in the temperature range of 20-300 °C is (50-70)×10⁻⁶. -7 / ℃; the softening temperature of the glass is 610-660℃; the chemical stability is above level IV.

[0033] The sealing glass material of this invention reacts with titanium alloy at high temperatures to form high-strength TiB2, which improves the sealing strength and thus enhances the insulation and hermeticity of the sealed assembly. Furthermore, the sintering temperature of the sealing glass material and titanium alloy during sealing is lower than the phase transformation temperature of the titanium alloy, avoiding the phase transformation problem of titanium alloy during traditional sealing glass sealing. This ensures the dimensional stability of the sintered titanium alloy workpiece and reduces energy consumption during sealing. Before sealing, the titanium alloy shell undergoes low-temperature pre-oxidation, which increases the wettability between the metal and glass. The low-temperature oxide layer acts as a protective layer to prevent excessive oxidation of the metal at high temperatures, further ensuring the consistency of the sintered assembly and facilitating subsequent surface treatment.

[0034] The present invention discloses a method for preparing sealing glass, characterized by comprising the following steps: weighing raw materials such as SiO2, Al2O3, B2O3, TiO2, CaO, SrO, BaO, ZrO2, La2O3, CeO2, and CoO according to their mass percentages, mixing them evenly, and heating them to melt them into a glass melt. After the glass melt is uniformly melted, the molten glass melt is poured into deionized water for rapid cooling and quenching, and then dried to obtain glass melt fragments. The dried glass fragments are then ball-milled into glass powder, dried, and sieved to make the particle size of the sealing glass powder less than 100 micrometers, thereby obtaining the desired sealing glass material powder.

[0035] Fine raw material particle size is fundamental to obtaining highly chemically homogeneous glass melts free of unmelted grains and streak defects. Precisely reducing the particle size through ball milling significantly increases the contact area between components, thereby greatly promoting solid-state reaction rates and mass transfer efficiency during subsequent melting. Effectively lowering the complete melting temperature of the glass and shortening the melting time not only contributes to energy conservation and consumption reduction but also avoids excessive loss of volatile components such as B2O3 caused by prolonged high-temperature heating. This ensures the consistency of the final glass composition with the designed ratio, guaranteeing a uniform composition and structure of the final passivation layer at the microscale. It avoids problems such as uneven electrical performance, internal stress concentration, or decreased corrosion resistance caused by localized compositional fluctuations, significantly improving the reliability and yield of sealing devices. If the raw material particle size is greater than 100 micrometers, it will significantly reduce the specific surface area of ​​each component, severely hindering the solid-state reaction kinetics and mass transfer efficiency during high-temperature melting. Furthermore, incompletely melted coarse particles or incompletely reacted intermediate phases will remain as foreign matter in the glass melt, forming microscopic inhomogeneities. These defects, after subsequent molding into glass seals, can become stress concentration points, rapid ion migration channels, or electrical weaknesses, severely degrading the density, insulation strength, and chemical stability of the passivation layer. Therefore, this invention preferably uses raw materials with a particle size of less than 100 μm after ball milling.

[0036] The parameters, measurement methods, and instruments used for the sealing glass of this invention that has good wettability with titanium alloy are as follows: the average linear expansion coefficient α of the glass at 20-300℃. 20 / 300 [10 -7 [Temperature / ℃] Measured using a horizontal dilatometer, expressed as the average linear expansion coefficient. The linear expansion coefficient and glass softening temperature T d The test was conducted according to GB / T 7962.16-2010 "Test Methods for Colorless Optical Glass - Part 16: Coefficient of Linear Expansion, Transition Temperature and Sag Temperature"; the bending strength was tested according to GB / T37781-2019 "Test Method for Bending Strength of Glass Materials"; the airtightness test was conducted using a helium mass spectrometer leak detector to detect the airtightness and leakage rate of the sealed products; the chemical stability test was conducted according to the test method and classification of water resistance of glass particles at 98℃ in GB / T6582—2021.

[0037] Table 1 Chemical composition (wt.%) and glass properties of the examples

[0038] The following are the raw materials used in the examples and their requirements: Quartz sand (high purity, less than 1% of the material on a 150 μm sieve, less than 30% of the material under a 45 μm sieve, and Fe2O3 content less than 0.01 wt.%), aluminum hydroxide (analytical grade, average particle size 50 μm), boric acid (less than 10% of the material on a 400 μm sieve and less than 10% of the material under a 63 μm sieve), titanium dioxide (analytical grade), calcium carbonate (analytical grade), strontium carbonate (analytical grade), barium nitrate (analytical grade), zirconium oxide (analytical grade), lanthanum oxide (analytical grade), cerium oxide (analytical grade), and cobalt oxide (analytical grade).

[0039] Example 1: First, raw materials were selected according to the glass composition in Example 1 (Table 1), and the alkali metal content in the glass raw materials was strictly controlled to ensure that the formulation met the glass chemical composition in Table 1. After being mixed evenly, the mixture was heated and melted into molten glass. After the glass melt was uniform, the molten glass was poured into a preheated heat-resistant steel mold with dimensions of 70mm×70mm×10mm and cast into shape. Then, it was annealed. The molten glass was poured into deionized water for rapid cooling and quenching, and then dried to obtain glass melt fragments. The dried glass fragments were then ball-milled into glass powder, dried, and sieved to make the particle size of the sealing glass powder less than 100 micrometers. The required sealing glass material powder was thus obtained, and its test performance is shown in Table 1.

[0040] Example 2: Raw materials were selected according to the glass composition of Example 2 in Table 1, and the alkali metal content in the glass raw materials was strictly controlled to ensure that the formula met the glass chemical composition in Table 1. After being mixed evenly, the mixture was heated and melted into a glass melt. After the glass melt was uniform, the glass melt was poured into a preheated heat-resistant steel mold with dimensions of 70mm×70mm×10mm and cast into shape. Then, it was annealed. The molten glass melt was poured into deionized water for rapid cooling and quenching, and then dried to obtain glass melt fragments. The dried glass fragments were then ball-milled into glass powder, dried and sieved to make the particle size of the sealing glass powder less than 100 micrometers, thus obtaining the required sealing glass material powder. Its test performance is shown in Table 1.

[0041] Example 3: Raw materials were selected according to the glass composition in Example 3 of Table 1, and the alkali metal content in the glass raw materials was strictly controlled to ensure that the formula met the glass chemical composition in Table 1. After being mixed evenly, the mixture was heated and melted into a glass melt. After the glass melt was uniform, the glass melt was poured into a preheated heat-resistant steel mold with dimensions of 70mm×70mm×10mm and cast into shape. Then, it was annealed. The molten glass melt was poured into deionized water for rapid cooling and quenching, and then dried to obtain glass melt fragments. The dried glass fragments were then ball-milled into glass powder, dried and sieved to make the particle size of the sealing glass powder less than 100 micrometers, thus obtaining the required sealing glass material powder. Its test performance is shown in Table 1.

[0042] Example 4: Raw materials were selected according to the glass composition of Example 4 in Table 1, and the alkali metal content in the glass raw materials was strictly controlled to ensure that the formula met the glass chemical composition in Table 1. After being mixed evenly, the mixture was heated and melted into a glass melt. After the glass melt was uniform, the glass melt was poured into a preheated heat-resistant steel mold with dimensions of 70mm×70mm×10mm and cast into shape. Then, it was annealed. The molten glass melt was poured into deionized water for rapid cooling and quenching, and then dried to obtain glass melt fragments. The dried glass fragments were then ball-milled into glass powder, dried and sieved to make the particle size of the sealing glass powder less than 100 micrometers, thus obtaining the required sealing glass material powder. Its test performance is shown in Table 1.

[0043] Example 5: Raw materials were selected according to the glass composition of Example 5 in Table 1, and the alkali metal content in the glass raw materials was strictly controlled to ensure that the formula met the glass chemical composition in Table 1. After being mixed evenly, the mixture was heated and melted into a glass melt. After the glass melt was uniform, the glass melt was poured into a preheated heat-resistant steel mold with dimensions of 70mm×70mm×10mm and cast into shape. Then, it was annealed. The molten glass melt was poured into deionized water for rapid cooling and quenching, and then dried to obtain glass melt fragments. The dried glass fragments were then ball-milled into glass powder, dried and sieved to make the particle size of the sealing glass powder less than 100 micrometers, thus obtaining the required sealing glass material powder. Its test performance is shown in Table 1.

[0044] In summary, the data obtained from the embodiments show that each component in the formulation provided by the present invention has a direct impact on the performance of the glass powder, and the compatibility between them ensures that the glass powder can meet the requirements of the sealing process. The sealing glass of the present invention, which has good wettability with titanium alloy, has advantages such as being free of harmful heavy metals, having good chemical stability, high mechanical strength, good wettability, and matching coefficient of thermal expansion. By adjusting the proportion of each component, the performance of the sealing glass powder can be optimized to meet the special sealing requirements of titanium alloy wettability.

[0045] The above description is merely a preferred embodiment of the present invention and is not intended to limit the invention. The scope of protection of the present invention is defined by the claims. Any modifications, equivalent substitutions, or improvements made by those skilled in the art to the present invention within its spirit and scope are also considered to fall within the scope of protection of the present invention.

Claims

1. A sealing glass with good wettability to titanium alloys, characterized in that, The components include the following mass percentages (wt.%): 。 2. The sealing glass with good wettability to titanium alloy according to claim 1, characterized in that, The components include the following mass percentages (wt.%): 。 3. The sealing glass with good wettability to titanium alloy according to claims 1-2, characterized in that, The mass ratio of ZrO2 to TiO2 is 0.1-0.

8.

4. A sealing glass with good wettability to titanium alloys according to claims 1-2, characterized in that, It does not actually contain any of the alkali metal oxides, which here refer to any of the following: Li2O, Na2O, K2O, Rb2O, Cs2O, Fr2O, etc.

5. A sealing glass with good wettability to titanium alloys according to claims 1-2, characterized in that, It does not contain any of the environmentally harmful metal oxides or heavy metal oxides such as As2O3, Sb2O5, PbO, Tl2O, CdO, BeO, V2O5, etc.

6. A method for preparing a sealing glass with good wettability to titanium alloys as described in any one of claims 1-5, characterized in that, The process includes the following steps: weighing the raw materials such as SiO2, Al2O3, B2O3, TiO2, CaO, SrO, BaO, ZrO2, La2O3, CeO2, and CoO according to their mass percentages, mixing them evenly, and heating them to melt them into a glass liquid. After the glass melts evenly, pour the molten glass liquid into deionized water for rapid cooling and quenching, and then dry it to obtain glass melt fragments. The dried glass fragments are then ball-milled into glass powder, dried, and sieved to obtain the required sealing glass material powder.

7. The preparation method according to claim 6, characterized in that, The glass powder after ball milling and sieving has a particle size of less than 100 micrometers.

8. A sealing glass with good wettability to titanium alloys, characterized in that, The sealing glass, prepared according to any one of claims 6-7, has an average linear thermal expansion coefficient of (50-70)×10⁻⁶ in the temperature range of 20-300℃, and is well matched with the wettability of titanium alloy. -7 / ℃; the softening temperature of the glass is 610-660℃; the chemical stability is above level IV.

9. The use of the sealing glass according to claim 8, which has good wettability with titanium alloys, characterized in that, The sealing glass, which has good wettability with titanium alloys, is suitable for automotive electronics, home appliances, information and communication technology, national defense, microelectronics, new energy, and aerospace.

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