Use of a high temperature and high expansion rare earth-rich glass material in high temperature alloy / stainless steel sealing glass materials

Abstract

The application relates to application of a high-temperature-resistant high-expansion rare-earth-rich glass material in high-temperature alloy / stainless steel sealing glass material, which comprises the following steps: (1) grinding the high-temperature-resistant high-expansion rare-earth-rich glass material into a glass powder; (2) mixing the glass powder, ceramic powder, binder and solvent to obtain a mixed slurry, and then spraying and granulating to obtain granulated powder; the ceramic powder is at least one selected from alumina, zirconia and magnesia, and the adding amount is 0-20 wt% of the mass of the glass powder; (3) forming the obtained granulated powder through an automatic press, and vitrifying at 1100-1300 DEG C; (4) finally, pre-oxidized metal equipment is arranged, and sealing melting is completed at 1200-1400 DEG C in a protective atmosphere.

Description

[0001] The present application is a divisional application of the invention patent application with application number 202210467814.0, application date April 29, 2022, and invention name “A high-temperature-resistant and high-expansion rare earth-rich glass material and its preparation method and application”. TECHNICAL FIELD

[0002] The present application relates to the preparation of rare earth-containing microcrystalline glass material, and a high-temperature-resistant and high-expansion rare earth-rich RO-Ln2O3-SiO2-B2O3 (RLSB) system microcrystalline glass with low dielectric constant (6-12) is prepared. BACKGROUND

[0003] In recent years, wireless communication technology has developed rapidly, and thus the demand for antenna, resonator, and filter materials has been increasing. In addition, millimeter wave devices that can quickly transmit data are also being developed, and materials used for millimeter wave communication devices need to have a low dielectric constant (ε r ) to reduce the cross-coupling effect of the conductor and improve transmission efficiency. At the same time, such devices need a high quality factor (Qxf) to make data transmission more stable.

[0004] Microcrystalline glass combines the advantages of ceramic and glass materials, such as high mechanical strength and easy adjustment of component performance, and is a very promising microwave dielectric material. Several low-dielectric-constant microcrystalline glasses have been developed, such as the ZnO-B2O3-SiO2-Li2O system introduced in Chinese Patent 1 (application number 02124133.3), the CuO-ZnO-B2O3-Li2O-CeO2-Ga2O3 system introduced in Chinese Patent 2 (application number 201810151957.4), and the Y2O3-Al2O3-ZnO-B2O3 system microcrystalline glass introduced in Chinese Patent 3 (201710006401.1), each of which has its own limitations, such as their actual use temperature not exceeding 500℃, and they can only be used in some low-temperature environments, which cannot meet the extremely harsh high-temperature applications. SUMMARY

[0005] To solve the above problems, the present application aims to provide a high-temperature-resistant and high-expansion rare earth-rich glass material and its preparation method and application.

[0006] In a first aspect, the present application provides a high-temperature-resistant and high-expansion rare-earth-rich glass material, which has a composition of aRO-bLn2O3-cSiO2-dB2O3, wherein R is at least one of Ba, Ca, Mg and Sr, Ln is at least one of Sc, Y, La, Ce, Pr, Nd, Sm, Eu, Cd, Tb, Dy, Ho, Er, Tm, Yb and Lu, a is 20-45 mol%, b is 2.5-20 mol%, c is 52.5-77.5 mol%, d is 0-10 mol%, and a+b+c+d=100 mol%.

[0007] The present inventors have found through previous research that the SiO2-BaO system glass has a high sintering temperature, and the rare earth element lanthanum has a high field strength, can adsorb surrounding atoms to make the glass network more dense, and can bind the polar ions in the glass network. Under the action of an electric field, the bond dipole moment polarization is weakened, and finally a low dielectric constant can be obtained. Therefore, the dielectric properties of this series of glasses are studied in detail. Further, the present inventors provide a rare-earth-rich RO-Ln2O3-SiO2-B2O3 system glass-ceramic, the performance of which is regulated by changing the content of each component, and the glass-ceramic can be used as a microwave dielectric material and a high-temperature sealing glass.

[0008] Preferably, the high-temperature-resistant and high-expansion rare-earth-rich glass material has a glass transition temperature of 700-850°C and an initial crystallization temperature of 800-1000°C.

[0009] Preferably, the high-temperature-resistant and high-expansion rare-earth-rich glass material has a densification temperature of 1100-1300°C, a sealing temperature of 1200-1450°C, and a maximum use temperature of 900-1250°C.

[0010] In a second aspect, the present application provides a high-temperature-resistant and high-expansion rare-earth-rich glass-ceramic material, which is obtained by densifying and crystallizing the high-temperature-resistant and high-expansion rare-earth-rich glass material described above at a crystallization temperature of 850-1200°C for 10 minutes to 4 hours.

[0011] Preferably, the high-temperature-resistant and high-expansion rare-earth-rich glass-ceramic material has a main crystal phase including at least one of a magnesium silicate phase (MgSiO3 or / and Mg2SiO4), a barium silicate phase (BaSiO3 or / and BaSi2O5), a calcium silicate phase (CaSiO3 or / and Ca2SiO4), and a strontium silicate phase (SrSiO3 or / and Sr2SiO4).

[0012] Preferably, the high-temperature-resistant and high-expansion rich-rare-earth glass-ceramic material has a thermal expansion coefficient of 10-18 ppm / ℃, a dielectric constant of 6-12, and a quality factor of 5000-25000 GHz.

[0013] Preferably, the material can be used for manufacturing resonators, microwave antenna sheets, filters, millimeter wave communication devices, sensor substrates, and the like, and can be applied at high temperatures. The material can also be used as a sealing material for high-expansion coefficient metals such as stainless steel and high-temperature alloys, and can be applied to electrical connectors in the fields of aerospace and nuclear energy.

[0014] In a third aspect, the present application provides a method for preparing a high-temperature-resistant and high-expansion rich-rare-earth glass material, comprising:

[0015] (1) selecting R sources, Ln sources, Si sources, and B sources as raw materials, weighing the raw materials according to the composition of the high-temperature-resistant and high-expansion rich-rare-earth glass material, and mixing the raw materials to obtain a batch;

[0016] (2) heating the obtained batch to 1550-1650℃ and maintaining the temperature for 2-6 hours to obtain a uniform glass melt, and then rapidly quenching the glass melt to obtain the high-temperature-resistant and high-expansion rich-rare-earth glass material;

[0017] Preferably, the R source is one or more of RCO3, R(NO3)2, and RCl2, and has a purity of greater than 99%; the Ln source is Ln2O3, and has a purity of greater than 99%; the B source is H3BO3, and has a purity of greater than 99%; and the Si source is SiO2, and has a purity of greater than 99%. The material can be used as a microwave dielectric material and as a sealing material matched with stainless steel and high-temperature alloys.

[0018] In a fourth aspect, the present application provides a method for preparing a microwave dielectric material, comprising:

[0019] (1) grinding the high-temperature-resistant and high-expansion rich-rare-earth glass material into a glass powder;

[0020] (2) mixing the glass powder, a binder, and a solvent to obtain a mixed slurry, and then spray granulating the mixed slurry to obtain a granulated powder; the ceramic powder is selected from at least one of alumina, zirconia, and magnesia, and is added in an amount of 0-20 wt% of the mass of the glass powder;

[0021] (3) forming the obtained granulated powder through an automatic press, and then vitrifying and crystallizing the formed granulated powder at 1100-1300℃ to obtain the microwave dielectric material;

[0022] Preferably, in step (1), the particle size distribution of the glass powder ranges from 1 to 50 μm.

[0023] Preferably, in step (2), the particle size of the granulated powder is 100-300 μm.

[0024] Preferably, in step (3), the temperature of the degassing is 300-550 ℃, and the time is 1-6 hours; the heating rate of the vitrification-microcrystallization is 3-10 ℃ / min, and the holding time of the vitrification-microcrystallization is 60-180 minutes. The ceramic powder is added to regulate the thermal expansion coefficient, sintering temperature, dielectric properties and other properties of the glass.

[0025] In a fifth aspect, the present application provides a preparation method of a microwave dielectric material, characterized in that, comprising:

[0026] (1) grinding a high-temperature-resistant and high-expansion rare earth-rich glass material into a glass powder;

[0027] (2) mixing the glass powder, a binder and a solvent to obtain a mixed slurry, and forming a green tape by a tape casting method; the ceramic powder is selected from at least one of alumina, zirconia and magnesia, and the addition amount is 0-20 wt% of the mass of the glass powder;

[0028] (3) printing an electrode material on a plurality of green tapes and stacking them to obtain a device green body;

[0029] (4) degassing the device green body and completing matching co-firing at 1100-1500 ℃;

[0030] Preferably, in step (1), the particle size distribution range of the glass powder is 1-10 μm.

[0031] Preferably, in step (4), the heating rate of the completed matching co-firing is 1-10 ℃ / min, and the holding time of the completed matching co-firing is 60-180 minutes. The ceramic powder is added to regulate the thermal expansion coefficient, sintering temperature, dielectric properties and other properties of the glass.

[0032] In a sixth aspect, the present application provides an application of a high-temperature-resistant and high-expansion rare earth-rich glass material in a high-temperature alloy / stainless steel sealing glass material, characterized in that, comprising:

[0033] (1) grinding a high-temperature-resistant and high-expansion rare earth-rich glass material into a glass powder;

[0034] (2) mixing the glass powder, a binder and a solvent to obtain a mixed slurry, and then granulating by spraying to obtain a granulated powder; the ceramic powder is selected from at least one of alumina, zirconia and magnesia, and the addition amount is 0-20 wt% of the mass of the glass powder;

[0035] (3) forming the obtained granulated powder by an automatic press, and vitrifying at 1100-1300 ℃;

[0036] (4) Finally, the pre-oxidized metal equipment is sealed and melted at 1150-1400℃ in a protective atmosphere;

[0037] Preferably, in step (1), the particle size of the glass powder is in the range of 1-50 μm;

[0038] Preferably, in step (2), the particle size of the granulated powder is in the range of 100-300 μm;

[0039] Preferably, in step (4), the heating rate of the sealing and melting is in the range of 5-30℃ / min, and the holding time of the sealing and melting is in the range of 10-120 min. The ceramic powder is added to control the thermal expansion coefficient, sintering temperature, dielectric properties and other properties of the glass.

[0040] The beneficial effects of the present application are:

[0041] (1) The microcrystalline glass prepared by the present application can precipitate crystal phase with high expansion coefficient, and the residual glass phase is rich in high molar ratio of rare earth oxides, so it has high expansion coefficient and application temperature, and has excellent thermal matching with stainless steel, high-temperature alloy and electrode materials such as gold and palladium which also have high expansion coefficient;

[0042] (2) It has excellent dielectric properties: low dielectric constant (6-12), low dielectric loss and high quality factor (about ≥5000 GHz), and can be used for the manufacture of microwave devices such as dielectric resonator, microwave antenna sheet, filter, millimeter wave communication equipment, etc. and applied at high temperature;

[0043] (3) The material is simple to prepare, non-polluting and low in cost;

[0044] (4) Preferably, after adjusting the thermal expansion coefficient, it can be used for high-temperature sealing of oxygen / nitrogen oxygen sensors, and is a very potential microcrystalline glass. BRIEF DESCRIPTION OF DRAWINGS

[0045] Figure 1The rare earth oxide glass network modifier La2O3, Sm2O3, Yb2O3 respectively replaces the alkaline earth oxide BaO modifier to attempt to obtain BaO-La2O3-SiO2(BSL), BaO-Sm2O3-SiO2(BSS) and BaO-Yb2O3-SiO2(BSY) system glass, and the glass forming region at 1600 DEG C is obtained by high temperature melting-rapid quenching method: BSL-La2O3 is 2.5-10mol%, BaO is 10-50mol%, SiO2 is 47.5-77.5mol%, BSS-Sm2O3 is 2.5-15mol%, BaO is 10-50mol%, SiO2 is 47.5-77.5mol%, BSY-Yb2O3 is 2.5-12.5mol%, BaO is 10-60mol%, SiO2 is 40-75mol%;

[0046] Figure 2 The DSC curve of the rare earth-rich glass material prepared in Example 1-6 is shown in the figure, and it can be seen from the figure that the glass transition temperature Tg and the crystallization peak temperature Tc of the glass change with the composition, but the glass transition temperature range is between 700-850 DEG C, and the initial crystallization temperature is in the range of 800-1000 DEG C;

[0047] Figure 3 The thermal expansion coefficient curve of the microcrystalline glass obtained by crystallizing the corresponding rare earth-rich glass prepared in Example 1-6 is shown in the figure, and it can be seen from the figure that the thermal expansion coefficient of the microcrystalline glass is all≥10ppm / ℃;

[0048] Figure 4 The X-ray diffraction pattern (XRD) of the microcrystalline glass obtained by crystallizing the corresponding rare earth-rich glass prepared in Example 1-6 is shown in the figure, and it can be seen from the figure that the main crystalline phase of the microcrystalline glass is barium silicate phase (Ba2SiO4 and BaSiO3), and with different compositions, the crystalline phase and the crystallization amount are different, thereby causing different thermal expansion coefficients, which shows that the performance can be controlled by adjusting the glass composition;

[0049] Figure 5 The scanning electron microscope (SEM) of the microcrystalline glass obtained by crystallizing the corresponding rare earth-rich glass prepared in Example 1-6 is shown in the figure, and it can be seen from the figure that the obtained sample is a dense body without air holes, which shows that dense microcrystalline glass can be obtained under a certain temperature sintering, and the needle structure is barium silicate phase;

[0050] Figure 6EDS point scanning and surface scanning element map of the glass-ceramics prepared in Example 1, from the figure, it can be seen that the glass-ceramics is composed of high expansion coefficient BaSiO3 phase and 36BaO-30La2O3-34SiO2(mol%) residual glass phase, and further increasing the rare earth content in the residual glass phase during crystallization process is helpful to improve the temperature resistance of the glass-ceramics;

[0051] Figure 7 DSC curve of the rare earth-rich glass material prepared in Example 7-8, from the figure, it can be seen that with the increase of La2O 3 / BaO ratio, the Tg and Tc temperatures of the obtained glass material gradually increase, which indicates that La2O3 is beneficial to increase the polymerization degree of the glass network structure, and further increase the glass transition temperature and crystallization temperature;

[0052] Figure 8 DSC curve of the rare earth-rich glass material prepared in Example 8, 11-13, from the figure, it can be seen that with the decrease of SiO2 / BaO ratio, the Tg and Tc temperatures of the obtained glass material gradually decrease, which indicates that BaO as a glass network modifier can reduce the polymerization degree of the glass network structure, and further reduce the glass transition temperature and crystallization temperature;

[0053] Figure 9 DSC curve of the glass prepared in Example 25 and 26, and Comparative Example 1 and 2; b) thermal expansion coefficient and softening point curve of the glass of Comparative Example 1 and the glass-ceramics of Example 25, Example 26, and Comparative Example 2; c) resistivity-temperature curve of the glass of Comparative Example 1 and the glass-ceramics of Example 25, Example 26, and Comparative Example 2. From the figure, it can be seen that the multi-component rare earth doped BaO-(La, Sm, Yb)2O3-SiO2 and multi-component rare earth doped BaO-(Y, La, Nd, Sm, Tb, Er, Yb)2O3-SiO2 glass-ceramics sealing materials have obvious advantages in high temperature stability compared with NEG company-BaO-Na2O-SiO2 amorphous glass sealing material (ST) and Schott company-BaO-B2O3-Al2O3-SiO2 glass-ceramics sealing material (G18): a) the glass has a high glass transition temperature, and the softening temperature of the glass-ceramics is higher than 1100℃, which is much higher than that of ST (575℃) and G18 glass-ceramics (810℃); b) the resistivity of the glass-ceramics at 1000℃ is still higher than 5×10 5 Ω·cm; c) the high temperature resistance of the multi-component rare earth oxide doped glass is more obvious than that of the single-component;

[0054] Figure 10The DIL curve of the glass-ceramic and ceramic composite material prepared in Example 26-28 is shown in the figure, and it can be seen from the figure that the thermal expansion coefficients of the composite material and the sealed material (5mol% Y2O3-ZrO2) can be matched by adjusting the types and contents of the oxide of the rare earth-rich glass (the thermal expansion coefficient of Al2O3 is 8ppm / ℃, and the thermal expansion coefficient of ZrO2 is 10.8ppm / ℃).

[0055] Figure 11 The surface polishing morphology of the glass-ceramic and ceramic composite material prepared in Example 27 and the 5YZ ceramic after co-firing at 1450℃ for 2 hours is shown in the figure, and it can be seen from the figure that the interface is clear, and the glass-ceramic and ceramic composite material and the 5YZ ceramic have been sintered to be dense, which indicates that the matched co-firing can be achieved. DETAILED DESCRIPTION

[0056] The application is further illustrated by the following examples, and it should be understood that the following examples are only used to illustrate the application, but not to limit the application.

[0057] In the application, the high-temperature-resistant and high-expansion rare earth-rich glass material (RLSB glass) has a composition of RO-Ln2O3-SiO2-B2O3 (RLSB; R = one or more of Ba, Ca, Mg, and Sr, and Ln = one or more of Sc, Y, La, Ce, Pr, Nd, Sm, Eu, Cd, Tb, Dy, Ho, Er, Tm, Yb, and Lu), and the molar percentage composition of each oxide ranges from 20mol% to 45mol% for RO, from 52.5mol% to 77.5mol% for SiO2, from 2.5mol% to 20mol% for Ln2O3, and from 0mol% to 10mol% for B2O3.

[0058] In an optional embodiment, the high-temperature-resistant and high-expansion rare earth-rich glass material is a glass that can be crystallized, the glass transition temperature is 700-850℃, and the initial crystallization temperature is 800-1000℃.

[0059] In an optional embodiment, the dense temperature of the high-temperature-resistant and high-expansion rare earth-rich glass material is between 1100-1300℃, the sealing temperature is between 1200-1450℃, and the maximum use temperature is 900-1250℃.

[0060] In the application, the main crystal phase of the RLSB glass-ceramic includes one or more of a magnesium silicate phase (MgSiO3 or / and Mg2SiO4), a barium silicate phase (BaSiO3 or / and BaSi2O5), a calcium silicate phase (CaSiO3 or / and Ca2SiO4), and a strontium silicate phase (SrSiO3 or / and Sr2SiO4).

[0061] In an optional embodiment, the RLSB glass-ceramics has a coefficient of thermal expansion of 10-18 ppm / °C. The RLSB glass-ceramics has a dielectric constant of 6-12 and a quality factor of 5000-25000 GHz.

[0062] Preferably,

[0063] The high-temperature-resistant and high-expansion rare earth-rich glass material can be used for manufacturing materials of resonators, microwave antenna sheets, filters, millimeter wave communication devices, sensor substrates and other devices and applied at high temperatures. Meanwhile, the high-temperature-resistant and high-expansion rare earth-rich glass material can be used as a sealing material for high-expansion coefficient metals such as stainless steel and high-temperature alloy and applied to electrical connectors in the fields of aerospace and nuclear energy. The following exemplarily illustrates a preparation method of the high-temperature-resistant and high-expansion rare earth-rich glass material.

[0064] The original glass is melted. The molar ratio of each component of the RLSB glass is converted into mass ratio. The weights of the corresponding raw materials are accurately weighed, ball milled, sieved through an 80-mesh sieve, and uniformly mixed to prepare the batch. In the process of preparing the RO-Ln2O3-SiO2-B2O3 glass powder, the R source is one or more of RCO3, R(NO3)2 and RCl2 with a purity greater than 99%, the Ln source is one or more of Ln2O3 with a purity greater than 99%, the B source is H3BO3 with a purity greater than 99%, and the Si source is SiO2 with a purity greater than 99%. The use of raw materials with a purity greater than 99% to prepare the RO-Ln2O3-SiO2-B2O3 glass powder can ensure the stability of the glass crystallization phase and reduce the influence of impurities on the dielectric properties.

[0065] The glass is rapidly cooled and extracted. The batch is poured into a platinum crucible, heated to 1550-1650°C in a molybdenum rod furnace for 2-6 h, and a uniform glass melt is prepared. The melted glass melt is rapidly quenched to obtain a clear and uniform glass.

[0066] Glass powder preparation. The glass block is placed in an alumina ceramic jar in a ratio of 1:(3-6):(0-3) of material: zirconium balls: anhydrous ethanol, ball milled for 0.5-3 h, and the obtained slurry is placed in a constant temperature drying box at 90-110°C for 2-12 h. After drying, sieving (for example, 200 mesh) is performed to obtain the glass powder. By controlling the mesh number of the sieve, glass powders with different particle sizes are obtained.

[0067] Glass granulation powder preparation. 5-20% of PVB alcohol solution (preferably 3-15 wt%) is added to the glass powder, and then granulation is performed. After sieving through a 60-mesh sieve, drying at 70-110°C for 20-60 min is performed, and then classification is completed using a 60-mesh to 200-mesh sieve to obtain spherical granulation powder.

[0068] Performance test sample preparation. The granulation powder is placed in a specific mold and pressed into a Cylindrical and 7x7x30 mm long bar samples were first heated to 450 °C at a heating rate of 3-5 °C / min for 2 h to remove organic binder, then heated to 1100-1500 °C for 2 h and furnace cooled to room temperature to obtain the test samples for measuring density, dielectric properties and thermal expansion coefficient.

[0069] Test method:

[0070] (1) Thermal expansion analysis test: Thermal expansion test was performed using Netzsch DIL4002 thermal expansion analyzer, from room temperature to 1300 °C, at a heating rate of 10 °C / min;

[0071] (2) Differential thermal analysis (DSC): Differential thermal analysis was performed on sample powder sieved through a 200 mesh sieve using Netzsch DSC 404 differential scanning calorimeter (Germany), from room temperature to 1200 °C, at a heating rate of 10 °C / min;

[0072] (3) X-ray diffraction analysis (XRD): The sintered samples were crushed with an agate mortar and sieved through a 200 mesh sieve, and tested using a Bruker D8 ADVANCE high-resolution powder X-ray diffractometer (Germany) at a test voltage of 40 KV, a test current of 40 mA, Cu / Ka rays, a scanning range of 10-80°, and a scanning speed of 5 ° / min. The XRD patterns obtained were searched using Jade software to determine the crystal phase type;

[0073] (4) Scanning electron microscope analysis (SEM): The sintered samples were single-sided polished, surface etched with 10% HF alcohol solution for 10 s, rinsed with deionized water for 3 times, and then dried. The surface morphology was observed using a Magellan 400 FESEM electron scanning microscope, and the crystal phase type in the sample was qualitatively analyzed;

[0074] (5) Microwave dielectric properties: Microwave dielectric properties were tested using the Hakki-Coleman open-cylinder network dielectric resonance method, using TE011 mode to determine the relative dielectric constant (ε r ) and quality factor (Qxf) at microwave frequency, using an Agilent E8362B vector network analyzer to test the sample. The measured data are the average values of 5 groups of samples.

[0075] The following further illustrates the embodiments in detail. It should also be understood that the following embodiments are only used to further illustrate the present application and cannot be understood as limiting the scope of the present application. Some non-essential improvements and adjustments made by those skilled in the art according to the above content of the present application are within the scope of the present application. The specific process parameters in the following examples are only one example in the appropriate range, i.e. those skilled in the art can select within the appropriate range according to the description herein, and are not limited to the specific values in the following examples.

[0076] Example 1

[0077] The molar ratio of each component of the raw material was converted into mass ratio, and 345.01 g of BaCO3, 123.05 g of SiO2, and 31.94 g of La2O3 were accurately weighed and uniformly mixed. The mixture was placed in a platinum crucible and heated to 1500°C at a heating rate of 3°C / min in a molybdenum rod furnace for 2 h to obtain a glass liquid. The glass liquid was water-cooled to obtain a glass block. The glass block was ball-milled in an alumina ball mill tank with alcohol for 1 h and dried to obtain a glass powder (powder: zirconium ball: alcohol = 1:5:3). The glass powder was granulated with an additional 6% PVB alcohol solution (3 wt%) and sieved through a 60 mesh sieve to obtain a granulated powder. The granulated powder was placed in a special mold and pressed into a Φ15x8 cylindrical blank using a hydraulic press. The blank was placed in a muffle furnace and heated to 450°C at a heating rate of 5°C / min for 2 h to remove the binder, and then heated to 1000-1400°C for 2 h and cooled to room temperature in the furnace to obtain a test sample for measuring density and dielectric properties. The sintered and dense sample was tested for thermal expansion, and the CTE was 14.06 ppm / °C in the test range of 30-900°C, as shown in Figure 3 . The sample was analyzed by X-ray diffraction as shown in Figure 4 , and it was determined that the main crystal phase was barium silicate. After polishing and etching, the sample was observed by scanning electron microscopy to obtain a SEM image, as shown in Figure 5 and Figure 6 The barium silicate phase can be clearly seen. The relative dielectric constant (ε r ) and quality factor (Qxf) at microwave frequency were measured using TE011 mode, and the sample was tested using an Agilent E8362B vector network analyzer. The measured data are the average values of 5 groups of samples, and the data are shown in Table 2.

[0078] Example 2

[0079] The molar ratio of each component of the raw materials was converted into a mass ratio. 203.15g BaCO3, 161.47g SiO2 and 135.38g La2O3 were accurately weighed and evenly mixed. The mixture was placed in a platinum crucible and kept at 1500℃ in a molybdenum rod furnace for 2h to obtain glass liquid, which was then water-cooled to obtain a glass block. The glass block was ball-milled in an alumina ball mill with alcohol for 1h and dried to obtain glass powder. After the glass powder was granulated and pressed according to the method described above, it was first heated to 450℃ in a muffle furnace at a heating rate of 5℃ / min and kept warm for 2h to remove the plain glue, and then heated to 1200℃ and kept warm for 2h to obtain a dense sample. The sintered dense sample was subjected to a thermal expansion test, and the CTE was 13.69ppm / ℃ in the test range of 30-900℃. Figure 3 The sample was subjected to X-ray diffraction analysis, as shown in Figure 4 As shown, the main crystal phase was determined to be barium silicate. After the sample was polished and etched, a SEM image was obtained using a scanning electron microscope, as shown in FIG. Figure 5 The barium silicate phase can be clearly seen. The relative dielectric constant (ε r ) and quality factor (Q×f), the data are shown in Table 2.

[0080] Example 3:

[0081] The molar ratio of each component of the raw materials was converted into a mass ratio. 275.96g BaCO3, 144.62g SiO2 and 79.42g Yb2O3 were accurately weighed and evenly mixed. The mixture was placed in a platinum crucible and kept at 1500℃ in a molybdenum rod furnace for 2h to obtain glass liquid, which was then water-cooled to obtain a glass block. The glass block was ball-milled in an alumina ball mill with alcohol for 1h and dried to obtain glass powder. After the glass powder was granulated and pressed according to the method described above, it was first heated to 450℃ in a muffle furnace at a heating rate of 5℃ / min and kept warm for 2h to remove the plain glue, and then heated to 1150℃ and kept warm for 2h to obtain a dense sample. The sintered dense sample was subjected to a thermal expansion test, and the CTE was 12.61ppm / ℃ in the test range of 30-900℃. Figure 3 The sample was subjected to X-ray diffraction analysis, as shown in Figure 4 As shown, the main crystalline phase was determined to be barium silicate. After polishing and etching the sample, a SEM image was obtained using a scanning electron microscope, as shown in FIG. Figure 5 The barium silicate phase can be clearly seen. The relative dielectric constant (ε r ) and quality factor (Q×f), the data are shown in Table 2.

[0082] Example 4:

[0083] Convert the molar ratio of each component of the raw materials into a mass ratio, accurately weigh 169.19g BaCO3, 181.02g SiO2, and 149.79g Sm2O3, mix them evenly, place them in a platinum crucible, keep them warm at 1500℃ in a molybdenum rod furnace for 2h to obtain glass liquid, and water-cool them to obtain glass blocks. Add alcohol to the glass block in an alumina ball mill for 1h and dry it to obtain glass powder. After the glass powder is granulated and pressed according to the method described above, it is first heated to 450℃ in a muffle furnace at a heating rate of 5℃ / min and kept warm for 2h to remove the plain glue, and then heated to 1200℃ and kept warm for 2h to obtain a dense sample. The sintered dense sample is subjected to a thermal expansion test, and the CTE is 14.26ppm / ℃ in the test range of 30-900℃, as shown in FIG. Figure 3 The sample was subjected to X-ray diffraction analysis, as shown in Figure 4 As shown, the main crystal phase was determined to be barium silicate. After the sample was polished and etched, a SEM image was obtained using a scanning electron microscope, as shown in FIG. Figure 5 The barium silicate phase can be clearly seen. The relative dielectric constant (ε r ) and quality factor (Q×f), the data are shown in Table 2.

[0084] Example 5:

[0085] Convert the molar ratio of each component of the raw materials into a mass ratio, accurately weigh 199.75g BaCO3, 158.77g SiO2, and 141.48g Sm2O3, mix them evenly, place them in a platinum crucible, keep them warm at 1500℃ in a molybdenum rod furnace for 2h to obtain glass liquid, and water-cool them to obtain glass blocks. Add alcohol to the glass block in an alumina ball mill for 1h and dry it to obtain glass powder. After the glass powder is granulated and pressed according to the method described above, it is first heated to 450℃ in a muffle furnace at a heating rate of 5℃ / min and kept warm for 2h to remove the plain glue, and then heated to 1150℃ and kept warm for 2h to obtain a dense sample. The sintered dense sample is subjected to a thermal expansion test, and the CTE is 12.40ppm / ℃ in the test range of 30-900℃, as shown in the figure. Figure 3 The sample was subjected to X-ray diffraction analysis, as shown in Figure 4 As shown, the main crystal phase was determined to be barium silicate. After the sample was polished and etched, a SEM image was obtained using a scanning electron microscope, as shown in FIG. Figure 5 The barium silicate phase can be clearly seen. The relative dielectric constant (ε r ) and quality factor (Q×f), the data are shown in Table 2.

[0086] Example 6:

[0087] The molar ratio of each component of the raw materials was converted into a mass ratio. 219.01g BaCO3, 133.90g SiO2 and 147.09g Yb2O3 were accurately weighed and evenly mixed. The mixture was placed in a platinum crucible and kept at 1500℃ in a molybdenum rod furnace for 2h to obtain glass liquid, which was then water-cooled to obtain a glass block. The glass block was ball-milled in an alumina ball mill with alcohol for 1h and dried to obtain glass powder. After the glass powder was granulated and pressed according to the method described above, it was first heated to 450℃ in a muffle furnace at a heating rate of 5℃ / min and kept warm for 2h to remove the plain glue, and then heated to 1150℃ and kept warm for 2h to obtain a dense sample. The sintered dense sample was subjected to a thermal expansion test, and the CTE was 12.21ppm / ℃ in the test range of 30-900℃. Figure 3 The sample was subjected to X-ray diffraction analysis, as shown in Figure 4 As shown, the main crystal phase was determined to be barium silicate. After the sample was polished and etched, a SEM image was obtained using a scanning electron microscope, as shown in FIG. Figure 5 The barium silicate phase can be clearly seen. The relative dielectric constant (ε r ) and quality factor (Q×f), see Table 2.

[0088] Example 7:

[0089] This Example 7 refers to Example 1, except that: a=37.5 mol%, b=2.5 mol%, and c=60 mol%.

[0090] Example 8:

[0091] This Example 8 refers to Example 1, except that: a=35 mol%, b=5 mol%, and c=60 mol%.

[0092] Example 9:

[0093] This Example 9 refers to Example 1, except that: a=32.5 mol%, b=7.5 mol%, and c=60 mol%.

[0094] Example 10:

[0095] This Example 10 refers to Example 1, except that: a=25 mol%, b=15 mol%, and c=60 mol%.

[0096] Example 11:

[0097] This Example 11 refers to Example 1, except that: a=25 mol%, b=5 mol%, and c=70 mol%.

[0098] Example 12:

[0099] This example 12 refers to example 1, with the difference that a = 45 mol%, b = 5 mol%, c = 50 mol%.

[0100] Example 13:

[0101] This example 13 refers to example 1, with the difference that a = 50 mol%, b = 5 mol%, c = 45 mol%.

[0102] Example 14:

[0103] This example 7 refers to example 4, with the difference that a = 20 mol%, b = 2.5 mol%, c = 77.5 mol%.

[0104] Example 15:

[0105] This example 8 refers to example 4, with the difference that a = 20 mol%, b = 5 mol%, c = 75 mol%.

[0106] Example 16:

[0107] This example 9 refers to example 4, with the difference that a = 20 mol%, b = 15 mol%, c = 65 mol%.

[0108] Example 17:

[0109] This example 10 refers to example 4, with the difference that a = 20 mol%, b = 20 mol%, c = 65 mol%.

[0110] Example 18:

[0111] This example 18 refers to example 2, with the difference that the alkaline earth oxide is CaO.

[0112] Example 19:

[0113] This example 19 refers to example 2, with the difference that the alkaline earth oxide is SrO.

[0114] Example 20:

[0115] This example 20 refers to example 2, with the difference that the alkaline earth oxide is MgO.

[0116] Example 21:

[0117] This example 21 refers to example 2, with the difference that the alkaline earth oxide is 20 mol% BaO + 20 mol% CaO.

[0118] Example 22:

[0119] This example 22 refers to example 2, except that the alkaline earth oxide is 20 mol% BaO + 20 mol% SrO.

[0120] Example 23:

[0121] This example 23 refers to example 2, except that the alkaline earth oxide is 20 mol% BaO + 20 mol% MgO.

[0122] The formulations of the glasses in the specific embodiments 1-23 of the present application are shown in Table 1 (in mol%)

[0123]

[0124]

[0125] The key parameters and the results of the dielectric properties of the glasses in the specific embodiments 1-16 of the present application are shown in Table 2:

[0126]

[0127]

[0128] Example 24:

[0129] The molar ratios of the raw materials were converted into mass ratios and accurately weighed 560.65 g of BaCO3, 293.81 g of SiO2, 44.48 g of La2O3, 47.27 g of Sm2O3, and 53.79 g of Yb2O3, and uniformly mixed. The mixture was placed in a platinum crucible and heated to 1600°C at a heating rate of 3°C / min in a molybdenum rod furnace for 2 h to obtain a glass liquid. The glass liquid was water-cooled to obtain a glass block. The glass block was ball-milled in an alumina ball mill tank with alcohol for 1 h, and then dried to obtain a glass powder (powder: zirconium ball: alcohol = 1:5:3). The glass powder was granulated by adding 6% PVB alcohol solution (3 wt%) by weight, and then sieved through a 60-mesh sieve to obtain a granulated powder. The granulated powder was placed in a specific mold, and a hydraulic press was used to press the granulated powder into a test sample with the required size. The blank was placed in a muffle furnace and heated to 450°C at a heating rate of 5°C / min for 2 h to remove the binder, and then heated to 1200°C for 2 h. The furnace was cooled to room temperature to obtain a test sample, which was used for performance testing.

[0130] Example 25:

[0131] The raw material components were accurately weighed in molar ratio and converted to mass ratio. 345.01 g of BaCO3, 123.05 g of SiO2, 13.3 g of Y2O3, 19.19 g of La2O3, 19.81 g of Nd2O3, 20.4 g of Sm2O3, 21.33 g of Tb2O3, 22.54 g of Er2O3, and 23.21 g of Yb2O3 were uniformly mixed and placed in a platinum crucible. The mixture was heated to 1600°C at a rate of 3°C / min in a molybdenum rod furnace and held for 2 h to obtain a glass liquid. The glass liquid was water-cooled to obtain a glass block. The glass block was ball-milled in an alumina ball mill tank with alcohol for 1 h, and dried to obtain a glass powder (powder: zirconium ball: alcohol = 1:5:3). The glass powder was granulated with 6% PVB alcohol solution (3 wt%) and sieved through a 60 mesh sieve to obtain a granulated powder. The granulated powder was placed in a special mold, and a hydraulic press was used to press the powder into a test sample of the required size. The blank was placed in a muffle furnace and heated to 450°C at a rate of 5°C / min to remove the binder, and then heated to 1200°C for 2 h. The sample was cooled to room temperature in the furnace to obtain a test sample for performance testing.

[0132] The glass formulations in Examples 24-25 and Comparative Example 2 are shown in Table 3 (mol%)

[0133]

[0134] Example 26:

[0135] A 880 g of the glass powder in Example 1 and 120 g of zirconia (ZrO2) powder were accurately weighed and placed in a planetary ball mill tank for alcohol ball milling for 1 h, and dried to obtain a sealed glass powder, which was labeled as RSL-7. 100 g of RSL-7, 40 g of xylene solvent, and 1 g of fish oil (dispersant) were placed in a ball mill tank for ball milling for 1 h. Then, 8 g of PVB (binder) and 4 g of SLO4 (plasticizer) were added, and the ball milling was continued for 1 h to obtain a slurry. A slurry for YSZ ceramic was obtained in the same manner. The slurry was vacuum degassed, and then cast on a PET bottom mold. The PET bottom mold was driven forward at a speed of 0.25 m / min, and the thickness of the slurry was controlled at 200 μm by a doctor blade. The temperature in the casting room was controlled at 60°C. After the slurry was formed into a film strip, the bottom mold was removed to obtain a green body. The film strip was cut into 5x5 mm samples. The glass green body and the YSZ green body were stacked and hot isostatic pressed at a pressure of 20-40 MPa and a temperature of 40-80°C for 10-40 min. The obtained sample was heated to 500°C in a muffle furnace to remove the binder, and then heated to 1400°C to obtain a dense sealing member.

[0136] Example 27:

[0137] Precisely weigh 900g of glass powder in Example 2, 100g of alumina (Al2O3) powder is placed in a planetary ball mill jar and ball milled for 1h, dried to obtain a sealing glass powder, which is marked as RSL-8. Weigh 100g of RSL-8, add 40g of xylene solvent, 1g of fish oil (dispersant) into the ball mill jar and ball mill for 1h; then add 8g of PVB (binder) and 4g of SLO4 (plasticizer) and continue to ball mill for 1h to obtain a slurry. In the same way, a slurry of YSZ ceramic is obtained. The slurry is vacuum degassed, and the slurry is poured onto a PET bottom mold for casting, and the PET bottom mold is driven forward at a speed of 0.25m / min, wherein the thickness of the slurry is controlled to be 200μm by a scraper, and the temperature in the casting chamber is controlled to be 60℃. After the slurry is formed into a film strip, the bottom mold is removed to obtain a green body on the casting machine, and a film bag is obtained. The bottom mold is removed, and the sample is cut into a 5x5mm sample. The glass green body and the YSZ green body are stacked and hot isostatic pressed, wherein the pressure is controlled to be 20-40MPa, the temperature is 40-80℃, and the holding time is 10-40min. The obtained sample is placed in a muffle furnace and heated to 500℃ to remove the green glue, and then heated to 1400℃ to obtain a dense sealing piece.

[0138] Example 28:

[0139] Precisely weigh 900g of glass powder in Example 2, 100g of alumina (Al2O3) powder is placed in a planetary ball mill jar and ball milled for 1h, dried to obtain a sealing glass powder, which is marked as RSL-8. Weigh 100g of RSL-8, add 40g of xylene solvent, 1g of fish oil (dispersant) into the ball mill jar and ball mill for 1h; then add 8g of PVB (binder) and 4g of SLO4 (plasticizer) and continue to ball mill for 1h to obtain a slurry. In the same way, a slurry of YSZ ceramic is obtained. The slurry is vacuum degassed, and the slurry is poured onto a PET bottom mold for casting, and the PET bottom mold is driven forward at a speed of 0.25m / min, wherein the thickness of the slurry is controlled to be 200μm by a scraper, and the temperature in the casting chamber is controlled to be 60℃. After the slurry is formed into a film strip, the bottom mold is removed to obtain a green body on the casting machine, and a film bag is obtained. The bottom mold is removed, and the sample is cut into a 5x5mm sample. The glass green body and the YSZ green body are stacked and hot isostatic pressed, wherein the pressure is controlled to be 20-40MPa, the temperature is 40-80℃, and the holding time is 10-40min. The obtained sample is placed in a muffle furnace and heated to 500℃ to remove the green glue, and then heated to 1400℃ to obtain a dense sealing piece.

[0140] The thermal expansion coefficients of the specific embodiments 26-28 of the present application are shown in Table 4:

[0141] Figure 3 CTE: 30-800°C (x 10 -6 )]]> Figure 4 10.47 Figure 5 12.05 Figure 3 11.05 Figure 4 Figure 5 Figure 3 Figure 4 Figure 5 Figure 3 Figure 4 Figure 5 Figure 3 Figure 4 Figure 5 Figure 3 Figure 4 Figure 5 Figure 3 Figure 4 Figure 5 Figure 3 Figure 4 Figure 5 Figure 9.98 .

Claims

1. Application of a high temperature resistant and high expansion rare earth rich glass material in high temperature alloy / stainless steel sealing glass material, characterized in that: include: (1) Grinding a high-temperature resistant and high-expansion rare-earth-rich glass material into a glass powder; the composition of the high-temperature resistant and high-expansion rare-earth-rich glass material is aRO-bLn2O3-cSiO2-dB2O3; wherein R = at least one of Ba, Ca, Mg, and Sr, and Ln = at least one of Sc, Y, La, Ce, Pr, Nd, Sm, Eu, Cd, Tb, Dy, Ho, Er, Tm, Yb, and Lu; a = 20 to 30 mol%, b = 5 to 20 mol%, c = 65 to 75 mol%, d = 0 to 10 mol%, and a+b+c+d = 100 mol%; (2) glass powder, ceramic powder, binder and solvent are mixed to obtain a mixed slurry, and then granulated by spraying to obtain granulated powder; the ceramic powder is selected from at least one of aluminum oxide, zirconium oxide and magnesium oxide, and the amount added is 0 to 20 wt% of the mass of the glass powder; (3) The obtained granulated powder is formed by an automatic press and vitrified at 1100-1300°C; (4) Finally, the pre-oxidized high-temperature alloy / stainless steel equipment is placed in a protective atmosphere and sealed at 1200-1400°C.

2. The use according to claim 1, characterized in that In step (1), the particle size distribution range of the glass powder is 1 to 50 μm; In step (2), the particle size of the granulated powder is 100 to 300 μm; In step (4), the heating rate of the sealing melt is 5 to 30°C / min, and the insulation time of the sealing melt is 10 to 120 minutes.

3. The use according to claim 1, characterized in that The glass transition temperature of the high-temperature resistant and high-expansion rare-earth-rich glass material is between 760.3°C and 850°C, and the initial crystallization temperature is between 800°C and 1000°C.

4. The use according to any one of claims 1 to 3, characterized in that The method for preparing the high-temperature resistant and high-expansion rare-earth-rich glass material comprises: (1) selecting R source, Ln source, Si source, and B source as raw materials, weighing and mixing the raw materials according to the composition of the high temperature resistant and high expansion rare earth rich glass material to obtain a batch material; (2) The obtained batch material is heated to 1550-1650° C. and kept at this temperature for 2-6 hours to obtain a uniform glass melt, and then rapidly quenched to obtain the high-temperature resistant and high-expansion rare earth-rich glass material.

5. The use according to claim 4, characterized in that The R source is one or more of RCO3, R(NO3)2 and RCl2, with a purity greater than 99%; the Ln source is Ln2O3, with a purity greater than 99%; the B source is H3BO3, with a purity greater than 99%; and the Si source is SiO2, with a purity greater than 99%.

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