CN116143411A - Application of high-temperature-resistant high-expansion rare earth-rich glass material in high-temperature alloy/stainless steel sealing glass material - Google Patents
Application of high-temperature-resistant high-expansion rare earth-rich glass material in high-temperature alloy/stainless steel sealing glass material Download PDFInfo
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- C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
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- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
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Abstract
The invention relates to an application of a high-temperature-resistant high-expansion rare earth-rich glass material in a 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 glass powder; (2) Mixing glass powder, ceramic powder, a binder and a solvent to obtain mixed slurry, and performing spray granulation to obtain granulated powder; the ceramic powder is at least one of alumina, zirconia and magnesia, and the addition amount is 0-20wt% of the mass of the glass powder; (3) Molding the obtained granulated powder by an automatic press, and vitrifying at 1100-1300 ℃; (4) Finally, the metal equipment and the pre-oxidized metal equipment are placed in a protective atmosphere, and sealing and melting are completed at 1200-1400 ℃.
Description
The invention relates to a high-temperature-resistant high-expansion rare earth-rich glass material, which is a divisional application of an invention patent application with application number 202210467814.0, application date 2022, 04 month and 29, and the invention name of the invention.
Technical Field
The invention relates to a preparation method of rare earth-containing microcrystalline glass material, which prepares a rare earth-rich RO-Ln with high application temperature, high thermal expansion coefficient and low dielectric constant (6-12) 2 O 3 -SiO 2 -B 2 O 3 (RLSB) glass ceramic.
Background
In recent years, wireless communication technology has been rapidly developed, and thus, demands for antenna, resonator, and filter materials have been increasing. In addition, as millimeter wave devices that can rapidly transmit data are also being developed, materials used as millimeter wave communication devices are required to have a low dielectric constant (ε) r ) Thereby reducing the cross coupling effect of the conductors and improving the transmission efficiency. At the same time, such devices require a high quality factor (q×f) to make data transmission more stable.
The microcrystalline glass combines the advantages of ceramic and glass materials, such as high mechanical strength, easy regulation of component properties, and the like, and is a promising microwave dielectric material. Several low dielectric constant glass ceramics have been developed, such as ZnO-B described in Chinese patent 1 (application number 02124133.3) 2 O 3 -SiO 2 -Li 2 CuO-ZnO-B described in the O series, chinese patent No. 2 (application No. 201810151957.4) 2 O 3 -Li 2 O-CeO 2 -Ga 2 O 3 Y introduced in patent 3 (201710006401.1) 2 O 3 -Al 2 O 3 -ZnO-B 2 O 3 They are microcrystalline glass, and have respective limitations, such as that the practical use temperature of the microcrystalline glass is not more than 500 ℃, the microcrystalline glass can only be used in low-temperature environments, and extremely severe high-temperature application cannot be satisfied.
Disclosure of Invention
Aiming at the problems, the invention aims to provide a high-temperature-resistant high-expansion rare earth-rich glass material, and a preparation method and application thereof.
In a first aspect, the invention provides a high-temperature-resistant high-expansion rare earth-rich glass material, which has the composition of aRO-bLn 2 O 3 -cSiO 2 -dB 2 O 3 The method comprises the steps of carrying out a first treatment on the surface of the Wherein at least one of r= Ba, ca, mg, sr, ln= Sc, Y, la, ce, pr, nd, sm, eu, cd, tb, dy, ho, er, tm, yb, lu; a=20 to 45moL%, b=2.5 to 20moL%, c=52.5 to 77.5moL%, d=0 to 10moL%, and a+b+c+d=100 moL%.
The inventor has found through preliminary research that SiO 2 The glass of the BaO system has higher sintering temperature, the rare earth element lanthanum has higher field intensity, surrounding atoms can be adsorbed to enable a glass network to be more compact, polar ions are bound by the glass network, and the polarization of a bond dipole moment is weakened under the action of an electric field, so that a lower dielectric constant can be finally obtained, and the dielectric properties of the series of glass are studied in detail. Further, the present inventors have provided a rare earth-enriched RO-Ln 2 O 3 -SiO 2 -B 2 O 3 The glass ceramic can be used as a microwave medium material and also can be used as high-temperature sealing glass by changing the content of each component to regulate and control the performance of the glass ceramic.
Preferably, the glass transition temperature of the high-temperature-resistant high-expansion rare earth-rich glass material is 700-850 ℃, and the initial crystallization temperature is 800-1000 ℃.
Preferably, the densification temperature of the high-temperature-resistant high-expansion rare earth-rich glass material is between 1100 and 1300 ℃, the sealing temperature is between 1200 and 1450 ℃, and the highest use temperature is between 900 and 1250 ℃.
In a second aspect, the invention provides a high-temperature-resistant high-expansion rare earth-rich microcrystalline glass material, which is characterized in that the high-temperature-resistant high-expansion rare earth-rich microcrystalline glass material is subjected to densification and crystallization at a crystallization temperature of 850-1200 ℃ for 10 minutes to 4 hours, so that the high-temperature-resistant high-expansion rare earth-rich microcrystalline glass material is obtained.
Preferably, the main crystal phase of the high-temperature-resistant high-expansion rare earth-rich microcrystalline glass material comprises: magnesium silicate phase (MgSiO) 3 Or/and Mg 2 SiO 4 ) Barium silicate phase (BaSiO) 3 Or/and BaSi 2 O 5 ) Calcium silicate phase (CaSiO) 3 Or/and Ca 2 SiO 4 ) Strontium silicate phase (SrSiO) 3 Or/and Sr 2 SiO 4 ) At least one of them.
Preferably, the thermal expansion coefficient of the high-temperature-resistant high-expansion rare earth-rich microcrystalline glass material is 10-18 ppm/DEG C; the dielectric constant of the high-temperature-resistant high-expansion rare earth-rich microcrystalline glass material is between 6 and 12, and the quality factor is 5000-25000 GHz.
Preferably, the material can be used for manufacturing materials of devices such as resonators, microwave antenna sheets, filters, millimeter wave communication equipment, sensor substrates and the like and is applied at high temperature; meanwhile, the high-expansion-coefficient metal sealing material can be used as sealing materials of high-expansion-coefficient metals such as stainless steel, high-temperature alloy and the like, and can be applied to electric connectors in the fields of aerospace, nuclear energy and the like.
In a third aspect, the invention provides a method for preparing a rare earth-rich glass material with high temperature resistance and high expansion, comprising the following steps:
(1) R source, ln source, si source and B source are selected as raw materials, and the raw materials are weighed and mixed according to the composition of the high-temperature-resistant high-expansion rare earth-rich glass material to obtain a batch;
(2) Heating the obtained batch to 1550-1650 ℃ and preserving heat for 2-6 hours to obtain uniform glass melt, and then rapidly quenching to obtain the high-temperature-resistant high-expansion rare earth-rich glass material;
preferably, the R source is RCO 3 、R(NO 3 ) 2 And RCl 2 One or more of the above-mentioned materials are more than 99% pure; the Ln source is Ln 2 O 3 Purity is greater than 99%; the source B is H 3 BO 3 Purity is greater than 99%; the Si source is SiO 2 The purity is more than 99 percent. Can be used as a microwave medium material and also can be used as a sealing material matched with stainless steel and high-temperature alloy.
In a fourth aspect, the present invention provides a method for preparing a microwave dielectric material, which is characterized by comprising:
(1) Grinding the high-temperature-resistant high-expansion rare earth-rich glass material into glass powder;
(2) Mixing glass powder, a binder and a solvent to obtain mixed slurry, and then carrying out spray granulation to obtain granulated powder; the ceramic powder is at least one of alumina, zirconia and magnesia, and the addition amount is 0-20wt% of the mass of the glass powder;
(3) Molding the obtained granulated powder by an automatic press, and performing glue discharging and vitrification-microcrystallization at 1100-1300 ℃ to obtain the microwave medium material;
preferably, in the step (1), the particle size distribution of the glass frit is in the range of 1 to 50 μm;
preferably, in the step (2), the particle size of the granulated powder is 100 to 300 μm;
preferably, in the step (3), the temperature of the adhesive discharging is 300-550 ℃ and the time is 1-6 hours; the temperature rising rate of the vitrification-microcrystallization is 3-10 ℃/min, and the heat preservation time of the vitrification-microcrystallization is 60-180 minutes. Ceramic powder is added to regulate and control the thermal expansion coefficient, sintering temperature, dielectric property and other properties of the glass.
In a fifth aspect, the present invention provides a method for preparing a microwave dielectric material, which is characterized by comprising:
(1) Grinding the high-temperature-resistant high-expansion rare earth-rich glass material into glass powder;
(2) Mixing glass powder, a binder and a solvent to obtain mixed slurry, and forming a raw material belt by a tape casting method; the ceramic powder is at least one of alumina, zirconia and magnesia, and the addition amount is 0-20wt% of the mass of the glass powder;
(3) Laminating a plurality of green tapes with printed electrode materials to obtain a device green body;
(4) Discharging glue from the green body of the device and completing matching co-firing at 1100-1500 ℃;
preferably, in the step (1), the particle size distribution of the glass frit is in the range of 1 to 10 μm;
preferably, in the step (4), the temperature rising rate of the completed matched cofiring is 1-10 ℃/min, and the heat preservation time of the completed matched cofiring is 60-180 minutes. Ceramic powder is added to regulate and control the thermal expansion coefficient, sintering temperature, dielectric property and other properties of the glass.
In a sixth aspect, the present invention provides an application of a high temperature resistant and high expansion rare earth-rich glass material in a superalloy/stainless steel sealing glass material, which is characterized by comprising:
(1) Grinding the high-temperature-resistant high-expansion rare earth-rich glass material into glass powder;
(2) Mixing glass powder, a binder and a solvent to obtain mixed slurry, and performing spray granulation to obtain granulated powder; the ceramic powder is at least one of alumina, zirconia and magnesia, and the addition amount is 0-20wt% of the mass of the glass powder;
(3) Molding the obtained granulated powder by an automatic press, and vitrifying at 1100-1300 ℃;
(4) Finally, placing the metal equipment and the pre-oxidized metal equipment in a protective atmosphere, and finishing sealing and melting at 1150-1400 ℃;
preferably, in the step (1), the particle size distribution of the glass frit is in the range of 1 to 50 μm;
preferably, in the step (2), the particle size of the granulated powder is 100 to 300 μm;
preferably, in the step (4), the heating rate of the sealing and melting is 5-30 ℃/min, and the heat preservation time of the sealing and melting is 10-120 minutes. Ceramic powder is added to regulate and control the thermal expansion coefficient, sintering temperature, dielectric property and other properties of the glass.
The invention has the beneficial effects that:
(1) The microcrystalline glass prepared by the invention can separate out crystalline phases with high expansion coefficients, and meanwhile, the residual glass phase is enriched with rare earth oxide with high molar ratio, so that the microcrystalline glass has both high expansion coefficients and application temperature, and can have excellent thermal matching property with stainless steel, high-temperature alloy and the like with high expansion coefficients and electrode materials such as gold, palladium and the like;
(2) Has excellent dielectric properties: low dielectric constant (6-12), low dielectric loss and high quality factor (about more than or equal to 5000 GHz), and can be used for manufacturing microwave devices such as dielectric resonators, microwave antenna sheets, filters, millimeter wave communication equipment and the like and applied at high temperature;
(3) The material is simple to prepare, pollution-free and low in cost;
(4) Preferably, the glass ceramic can be used for high-temperature sealing of an oxygen/nitrogen-oxygen sensor after the thermal expansion coefficient is regulated, and is potential glass ceramic.
Drawings
FIG. 1 shows a rare earth oxide glass network modifier La 2 O 3 、Sm 2 O 3 、Yb 2 O 3 Attempts to obtain BaO-La by replacing alkaline earth oxide BaO modifications respectively 2 O 3 -SiO 2 (BSL)、BaO-Sm 2 O 3 -SiO 2 (BSS) and BaO-Yb 2 O 3 -SiO 2 (BSY) glass, prepared by a high temperature melt-rapid quench method to obtain a glass forming region at 1600 ℃ of: BSL-La 2 O 3 2.5 to 10mol percent, 10 to 50mol percent of BaO and SiO 2 47.5 to 77.5mol percent, BSS-Sm 2 O 3 2.5 to 15mol percent, 10 to 50mol percent of BaO and SiO 2 47.5 to 77.5mol percent of BSY-Yb 2 O 3 2.5 to 12.5mol percent, 10 to 60mol percent of BaO and SiO 2 40 to 75mol percent;
FIG. 2 is a DSC graph of the rare-earth-enriched glass material prepared in examples 1-6, wherein the glass transition temperature Tg and the crystallization peak temperature Tc of the glass are changed along with the change of the composition, but the glass transition temperature ranges from 700 ℃ to 850 ℃ and the initial crystallization temperature ranges from 800 ℃ to 1000 ℃;
FIG. 3 is a graph showing the coefficient of thermal expansion of glass ceramics obtained after crystallization of the corresponding rare earth-rich glasses prepared in examples 1-6, wherein the coefficient of thermal expansion of the glass ceramics is higher than or equal to 10 ppm/DEG C;
FIG. 4 shows the X-ray diffraction patterns (XRD) of the crystallized glass ceramics obtained after crystallization of the corresponding rare earth-rich glasses prepared in examples 1 to 6, in which the main phase of the crystallized glass is barium silicate phase (Ba 2 SiO 4 And BaSiO 3 ) And with different compositions, the crystallization phases and crystallization amounts are different, so that the thermal expansion coefficients are different, and the realization of performance regulation by adjusting the glass components is described;
FIG. 5 is a Scanning Electron Microscope (SEM) image of the crystallized glass obtained from examples 1-6, wherein the obtained samples are dense and pore-free, indicating that dense glass crystals can be obtained at a certain temperature, and the knitting structure is barium silicate crystal phase;
FIG. 6 is an EDS point scan and surface scan element diagram of the glass-ceramic prepared in example 1, from which it is known that the glass-ceramic is BaSiO with a high expansion coefficient 3 Phase and 36BaO-30La 2 O 3 -34SiO 2 (mol%) residual glass phase composition, the crystallization process further improves the rare earth content in the residual glass phase, which is helpful for improving the temperature resistance of the microcrystalline glass;
FIG. 7 is a DSC graph of the rare-earth-rich glass material prepared in examples 7-8, from which La is seen 2 O 3 Tg and Tc temperatures of the glass materials obtained by increasing the BaO ratio gradually increase, indicating La 2 O 3 The polymerization degree of the glass network structure is improved, and the glass transition temperature and the crystallization temperature are improved;
FIG. 8 is a DSC graph of the rare-earth-rich glass material prepared in examples 8, 11-13, from which it can be seen that SiO follows 2 The Tg and Tc temperatures of the glass material obtained by reducing the BaO proportion are gradually reduced, which shows that the BaO serving as a glass network modifier can reduce the polymerization degree of a glass network structure, thereby reducing the glass transition temperature and crystallization temperature;
FIG. 9 is a DSC curve of the glasses prepared in examples 25 and 26, comparative examples 1 and 2; b) Comparative example 1 glass, example 25, example 26, comparative example 2 glass ceramics, and thermal expansion coefficients and softening point curves thereof; c) Comparative example 1 glass, example 25, example 26, comparative example 2 glass ceramics, and temperature change curves. From the figure, it can be seen that the multicomponent rare earth doped BaO- (La, sm, yb) 2 O 3 -SiO 2 And multicomponent rare earth doped BaO- (Y, la, nd, sm, tb, er, yb) 2 O 3 -SiO 2 Microcrystalline glass sealing material in comparison with NEG company-BaO-Na 2 O-SiO 2 Amorphous glass sealing material (ST), baO-B from Schott company 2 O 3 -Al 2 O 3 -SiO 2 High-temperature stability of glass-ceramic sealing material (G18)The qualitative aspect has obvious advantages: a) The glass has high glass transition temperature, and the glass ceramics has softening temperature higher than 1100 ℃ and far higher than ST (575 ℃) and G18 glass ceramics (810 ℃); b) The resistivity of the microcrystalline glass is still higher than 5 multiplied by 10 at 1000 DEG C 5 Omega cm; c) The doping of the multi-element rare earth oxide is more obvious than the high temperature resistance of single components;
FIG. 10 is a DIL graph of the glass-ceramic and ceramic composites prepared in examples 26-28, showing that the oxide species (Al 2 O 3 ZrO with a thermal expansion coefficient of 8 ppm/DEG C 2 The thermal expansion coefficient is 10.8 ppm/DEG C) and the content can realize the composite material and the sealed material (5 mol%Y) 2 O 3 -ZrO 2 ) The thermal expansion coefficient of the glass tube is matched and sealed;
FIG. 11 is a graph showing the surface polishing morphology of the glass-ceramic and ceramic composite and 5YZ ceramic prepared in example 27 after 2 hours of heat preservation at 1450 ℃, wherein the interface is clear, and the glass-ceramic and ceramic composite and 5YZ ceramic are sintered densely, indicating that matching co-firing can be achieved.
Detailed Description
The invention is further illustrated by the following embodiments, which are to be understood as merely illustrative of the invention and not limiting thereof.
In the invention, the high-temperature-resistant high-expansion rare earth-rich glass material (RLSB glass) has the composition of RO-Ln 2 O 3 -SiO 2 -B 2 O 3 (RLSB; r= Ba, ca, mg, sr one or more, ln= Sc, Y, la, ce, pr, nd, sm, eu, cd, tb, dy, ho, er, tm, yb, lu one or more), the molar percentage composition ranges of the respective oxides being RO:20 to 45mol percent of SiO 2 ：52.5～77.5mol％，Ln 2 O 3 ：2.5～20mol％，B2O3：0～10mol％。
In an alternative embodiment, the high temperature and high expansion resistant rare earth-rich glass material is microcrystallized glass, the glass transition temperature is 700-850 ℃, and the initial crystallization temperature is 800-1000 ℃.
In an alternative embodiment, the densification temperature of the high temperature and high expansion resistant rare earth-rich glass material is between 1100 and 1300 ℃, the sealing temperature is between 1200 and 1450 ℃, and the maximum use temperature is 900 to 1250 ℃.
In the invention, the main crystal phase of the RLSB microcrystalline glass comprises: magnesium silicate phase (MgSiO) 3 Or/and Mg 2 SiO 4 ) Barium silicate phase (BaSiO) 3 Or/and BaSi 2 O 5 ) Calcium silicate phase (CaSiO) 3 Or/and Ca 2 SiO 4 ) Strontium silicate phase (SrSiO) 3 Or/and Sr 2 SiO 4 ) One or more of them.
In an alternative embodiment, the RLSB glass crystallites have a coefficient of thermal expansion of from 10 to 18ppm/°c. The dielectric constant of the RLSB microcrystalline glass is between 6 and 12, and the quality factor is 5000 to 25000GHz.
Preferably, the method comprises the steps of,
the high-temperature-resistant high-expansion rare earth-rich glass material can be used as a manufacturing material of devices such as resonators, microwave antenna sheets, filters, millimeter wave communication equipment, sensor substrates and the like and can be applied at high temperature, and can be used as a sealing material of metals with high expansion coefficients such as stainless steel, high-temperature alloy and the like and applied to electric connectors in the fields such as aerospace, nuclear energy and the like. The following illustrates exemplary methods for preparing high temperature and high expansion resistant rare earth-rich glass materials.
And melting the original glass. The molar ratio of each component of the RLSB glass is converted into mass ratio. Accurately weighing the weight of the corresponding raw materials, ball milling, sieving with a 80-mesh sieve, and uniformly mixing to prepare the batch. Preparation of RO-Ln 2 O 3 -SiO 2 -B 2 O 3 In the process of the glass powder, the R source is RCO with the purity of more than 99 percent 3 、R(NO 3 ) 2 And RCl 2 One or more Ln sources are Ln with purity more than 99% 2 O 3 One or more of the sources B are H with the purity of more than 99 percent 3 BO 3 The Si source is SiO with purity more than 99% 2 . Preparing RO-Ln by adopting raw materials with purity of more than 99 percent 2 O 3 -SiO 2 -B 2 O 3 The glass powder can ensure the stability of a glass crystallization phase and reduce the influence of impurities on dielectric properties.
And (5) rapidly cooling and extracting the glass. Pouring the batch into a platinum crucible, heating to 1550-1650 ℃ in a molybdenum rod furnace, and preserving heat for 2-6 h to obtain uniform glass melt. And rapidly quenching the melted glass melt to obtain clear and uniform glass.
And (5) preparing glass powder. Pressing the glass blocks: zirconium ball: absolute ethanol = 1: (3-6): and (3) putting the mixture into an alumina ceramic pot in a proportion of (0) to (3) for ball milling for 0.5 to (3) hours, putting the obtained slurry into a constant temperature drying oven at a temperature of between 90 and 110 ℃ for drying for 2 to 12 hours, and sieving (for example, 200 meshes) after drying to obtain glass powder. And (5) obtaining glass powder with different particle sizes by controlling the mesh number of the sieves.
And (5) preparing glass granulating powder. The glass powder is added with PVB alcohol solution (preferably 3 to 15 wt%) with the weight percentage of 5 to 20 percent, and then the mixture is granulated. And then sieving with a 60-mesh sieve, drying at 70-110 ℃ for 20-60 min, and grading with a 60-200-mesh sieve to obtain the spherical-like granulating powder.
And (5) preparing a performance test sample. Placing the granulated powder into a specific mould, and pressing into the product by using a hydraulic press
And (3) placing the cylindrical and 7X 30mm long blanks in a muffle furnace, heating to 450 ℃ at a heating rate of 3-5 ℃/min, preserving heat for 2 hours to remove the gelatin, heating to 1100-1500 ℃ and preserving heat for 2 hours, and cooling to room temperature along with the furnace to obtain a test sample for measuring density, dielectric property and thermal expansion coefficient.
The testing method comprises the following steps: .
(1) Thermal expansion analysis test: the thermal expansion test adopts a Germany Netzsch DIL4002 thermal expansion analyzer, and the temperature is raised from room temperature to 1300 ℃ at a speed of 10 ℃/min;
(2) Differential thermal analysis (DSC): sample powder passing through a 200 mesh sieve was subjected to differential thermal analysis using a Netzsch DSC 404 differential scanning calorimeter (germany) at a rate of rise from room temperature to 1200 ℃:10 ℃/min;
(3) X-ray diffraction analysis (XRD): grinding the sintered sample with an agate mortar, sieving with a 200-mesh sieve, testing with a high-resolution powder X-ray diffractometer of Bruzu D8 ADVANCE, testing voltage of 40KV, testing current of 40mA, cu/K alpha rays, scanning range: 10-80 deg. and scanning speed 5 deg./min. Obtaining an XRD pattern, searching a JCPDS card by using Jade software, and determining the type of a crystal phase;
(4) Scanning electron microscope analysis (SEM): the sintered sample was subjected to single-sided polishing, surface-etched for 10s with 10% hf alcohol solution, rinsed 3 times with deionized water, and dried. Observing the surface morphology by using a Magellan 400FESEM electron scanning microscope, and performing qualitative analysis on the crystal phase type in the sample;
(5) Microwave dielectric properties: the microwave dielectric property is tested by adopting a Hakki-Coleman open cylinder network dielectric resonance method, and the TE011 mode is used for measuring the relative dielectric constant (epsilon) under the microwave frequency r ) And quality factor (q×f), samples were tested using an Agilent E8362B vector network analyzer. The measured data are all averages of 5 groups of samples.
The present invention will be further illustrated by the following examples. It is also to be understood that the following examples are given solely for the purpose of illustration and are not to be construed as limitations upon the scope of the invention, since numerous insubstantial modifications and variations will now occur to those skilled in the art in light of the foregoing disclosure. The specific process parameters and the like described below are also merely examples of suitable ranges, i.e., one skilled in the art can make a suitable selection from the description herein and are not intended to be limited to the specific values described below.
Example 1:
the molar ratio of each component of the raw materials is converted into mass ratio, and 345.01g of BaCO is accurately weighed 3 、123.05g SiO 2 、31.94g La 2 O 3 Uniformly mixing, placing in a platinum crucible, heating to 1500 ℃ in a molybdenum rod furnace at a heating rate of 3 ℃/min, preserving heat for 2 hours to obtain glass liquid, and water-cooling to obtain glass blocks. And adding alcohol into the glass blocks in an alumina ball milling tank, ball milling for 1h, and drying to obtain glass powder (powder: zirconium balls: alcohol=1:5:3). Granulating the glass powder with the PVB alcohol solution (3 wt%) with the weight percentage of 6%, and sieving with a 60-mesh sieve to obtain the granulated powder. The granulated powder is placed in a specific die and pressed into a cylindrical blank of phi 15 x 8 by using a hydraulic press. Placing the blanks in horsesIn a furs furnace, heating to 450 ℃ at a heating rate of 5 ℃/min, preserving heat for 2 hours to remove the gelatin, heating to 1000-1400 ℃ and preserving heat for 2 hours, and cooling to room temperature along with the furnace to obtain a test sample for measuring density and dielectric properties. The sintered compact samples were tested for thermal expansion to give CTE of 14.06 ppm/deg.C over a test range of 30-900 deg.C as shown in FIG. 3. The sample was subjected to X-ray diffraction analysis as shown in FIG. 4, and its main crystal phase was determined to be barium silicate. The sample was polished and etched and then SEM images were obtained using a scanning electron microscope, as shown in fig. 5 and 6, to clearly see the barium silicate phase. Determination of relative permittivity (. Epsilon.) at microwave frequency Using TE011 mode r ) And quality factor (q×f), samples were tested using an Agilent E8362B vector network analyzer. The data are shown in Table 2 as the average of 5 samples.
Example 2:
the molar ratio of each component of the raw materials is converted into mass ratio, and 203.15g of BaCO is accurately weighed 3 、161.47g SiO 2 、135.38g La 2 O 3 Uniformly mixing, placing in a platinum crucible, preserving heat for 2 hours at 1500 ℃ in a molybdenum rod furnace to obtain glass liquid, and water-cooling to obtain glass blocks. And adding alcohol into the glass blocks in an alumina ball milling tank, ball milling for 1h, and drying to obtain glass powder. After the glass powder is granulated and pressed according to the method, the temperature is firstly increased to 450 ℃ in a muffle furnace at a heating rate of 5 ℃/min to remove the gelatin, and then the temperature is increased to 1200 ℃ to keep the temperature for 2 hours to obtain a compact sample. The sintered compact samples were tested for thermal expansion to give CTE of 13.69 ppm/deg.C over a test range of 30-900 deg.C as shown in FIG. 3. The sample was subjected to X-ray diffraction analysis as shown in fig. 4, the main crystal phase thereof was determined to be barium silicate, and after polishing and etching the sample, SEM images were obtained by scanning electron microscopy, as can be clearly seen in fig. 5. Determination of relative permittivity (. Epsilon.) at microwave frequency Using TE011 mode r ) And the quality factor (Q.times.f), the data are shown in Table 2.
Example 3:
the molar ratio of each component of the raw materials is converted into mass ratio, and 275.96g of BaCO is accurately weighed 3 、144.62g SiO 2 、79.42g Yb 2 O 3 Uniformly mixing, placing in a platinum crucible, preserving heat for 2 hours at 1500 ℃ in a molybdenum rod furnace to obtain glass liquid, and water-cooling to obtain glass blocks. Glass block is put in an alumina ball milling tankAdding alcohol, ball milling for 1h and drying to obtain glass powder. After the glass powder is granulated and pressed according to the method, the temperature is firstly increased to 450 ℃ in a muffle furnace at the heating rate of 5 ℃/min, the gel is removed after the temperature is maintained for 2 hours, and then the temperature is increased to 1150 ℃ and the temperature is maintained for 2 hours, so as to obtain a compact sample. The sample was subjected to X-ray diffraction analysis, as shown in fig. 4, and the main crystal phase was determined to be barium silicate, and after the sample was polished and corroded, SEM images were obtained by scanning electron microscopy, as can be clearly seen in fig. 5. Determination of relative permittivity (. Epsilon.) at microwave frequency Using TE011 mode r ) And the quality factor (Q.times.f), the data are shown in Table 2.
Example 4:
the molar ratio of each component of the raw materials is converted into mass ratio, and 169.19g of BaCO is accurately weighed 3 、181.02g SiO 2 、149.79g Sm 2 O 3 Uniformly mixing, placing in a platinum crucible, preserving heat for 2 hours at 1500 ℃ in a molybdenum rod furnace to obtain glass liquid, and water-cooling to obtain glass blocks. And adding alcohol into the glass blocks in an alumina ball milling tank, ball milling for 1h, and drying to obtain glass powder. After the glass powder is granulated and pressed according to the method, the temperature is firstly increased to 450 ℃ in a muffle furnace at a heating rate of 5 ℃/min to remove the gelatin, and then the temperature is increased to 1200 ℃ to keep the temperature for 2 hours to obtain a compact sample. The sintered compact samples were tested for thermal expansion to give CTE of 14.26 ppm/deg.C over a test range of 30-900 deg.C, as shown in FIG. 3. The sample was subjected to X-ray diffraction analysis as shown in fig. 4, the main crystal phase thereof was determined to be barium silicate, and after polishing and etching the sample, SEM images were obtained by scanning electron microscopy, as can be clearly seen in fig. 5. Determination of relative permittivity (. Epsilon.) at microwave frequency Using TE011 mode r ) And the quality factor (Q.times.f), the data are shown in Table 2.
Example 5:
the molar ratio of each component of the raw materials is converted into mass ratio, and 199.75g of BaCO is accurately weighed 3 、158.77g SiO 2 、141.48g Sm 2 O 3 Uniformly mixing, placing in a platinum crucible, preserving heat for 2 hours at 1500 ℃ in a molybdenum rod furnace to obtain glass liquid, and water-cooling to obtain glass blocks. And adding alcohol into the glass blocks in an alumina ball milling tank, ball milling for 1h, and drying to obtain glass powder. Granulating the glass frit according to the method described aboveAfter sample pressing, the temperature is firstly increased to 450 ℃ in a muffle furnace at a heating rate of 5 ℃/min to remove the gelatin, and then the temperature is increased to 1150 ℃ to keep the temperature for 2 hours to obtain a compact sample. The sintered compact samples were tested for thermal expansion to give CTE of 12.40 ppm/deg.C over a test range of 30-900 deg.C as shown in FIG. 3. The sample was subjected to X-ray diffraction analysis, as shown in fig. 4, and the main crystal phase was determined to be barium silicate, and after the sample was polished and corroded, SEM images were obtained by scanning electron microscopy, as can be clearly seen in fig. 5. Determination of relative permittivity (. Epsilon.) at microwave frequency Using TE011 mode r ) And the quality factor (Q.times.f), the data are shown in Table 2.
Example 6:
the molar ratio of each component of the raw materials is converted into mass ratio, and 219.01g of BaCO is accurately weighed 3 、133.90g SiO 2 、147.09g Yb 2 O 3 Uniformly mixing, placing in a platinum crucible, preserving heat for 2 hours at 1500 ℃ in a molybdenum rod furnace to obtain glass liquid, and water-cooling to obtain glass blocks. And adding alcohol into the glass blocks in an alumina ball milling tank, ball milling for 1h, and drying to obtain glass powder. After the glass powder is granulated and pressed according to the method, the temperature is firstly increased to 450 ℃ in a muffle furnace at a heating rate of 5 ℃/min to remove the gelatin, and then the temperature is increased to 1150 ℃ to keep the temperature for 2 hours to obtain a compact sample. The sintered compact samples were tested for thermal expansion to give CTE of 12.21 ppm/DEG C over a test range of 30-900 ℃ as shown in FIG. 3. The sample was subjected to X-ray diffraction analysis as shown in fig. 4, the main crystal phase thereof was determined to be barium silicate, and after polishing and etching the sample, SEM images were obtained by scanning electron microscopy, as can be clearly seen in fig. 5. Determination of relative permittivity (. Epsilon.) at microwave frequency Using TE011 mode r ) And the quality factor (Q×f), see Table 2.
Example 7:
this example 7 is different from example 1 in that: a=37.5 mol%, b=2.5 mol%, c=60 mol%.
Example 8:
this example 8 is different from example 1 in that: a=35 mol%, b=5 mol%, c=60 mol%.
Example 9:
this embodiment 9 is different from embodiment 1 in that: a=32.5 mol%, b=7.5 mol%, c=60 mol%.
Example 10:
this embodiment 10 is different from embodiment 1 in that: a=25 mol%, b=15 mol%, c=60 mol%.
Example 11:
this embodiment 11 is different from embodiment 1 in that: a=25 mol%, b=5 mol%, c=70 mol%.
Example 12:
this embodiment 12 is different from embodiment 1 in that: a=45 mol%, b=5 mol%, c=50 mol%.
Example 13:
this example 13 is different from example 1 in that: a=50 mol%, b=5 mol%, c=45 mol%.
Example 14:
this example 7 is different from example 4 in that: a=20 mol%, b=2.5 mol%, c=77.5 mol%.
Example 15:
this example 8 is different from example 4 in that: a=20 mol%, b=5 mol%, c=75 mol%.
Example 16:
this example 9 is different from example 4 in that: a=20 mol%, b=15 mol%, c=65 mol%.
Example 17:
this embodiment 10 is different from embodiment 4 in that: a=20 mol%, b=20 mol%, c=65 mol%.
Example 18:
this embodiment 18 is different from embodiment 2 in that: the alkaline earth oxide is CaO.
Example 19:
this example 19 is different from example 2 in that: the alkaline earth oxide is SrO.
Example 20:
this embodiment 20 is different from embodiment 2 in that: the alkaline earth oxide is MgO.
Example 21:
this embodiment 21 is different from embodiment 2 in that: the alkaline earth oxide was 20mol% BaO+20mol% CaO.
Example 22:
this embodiment 22 is different from embodiment 2 in that: the alkaline earth oxide was 20mol% BaO+20mol% SrO.
Example 23:
this embodiment 23 is different from embodiment 2 in that: the alkaline earth oxide was 20mol% BaO+20mol% MgO.
The glass formulations in examples 1-23 of the present invention are shown in Table 1 (mol%)
The key parameters and dielectric properties of the specific examples 1-16 of the present invention are shown in Table 2:
example 24:
the molar ratio of each component of the raw materials is converted into mass ratio, and 560.65g of BaCO is accurately weighed 3 、293.81g SiO 2 、44.48g La 2 O 3 、47.27g Sm 2 O 3 、53.79g Yb 2 O 3 Uniformly mixing, placing in a platinum crucible, heating to 1600 ℃ in a molybdenum rod furnace at a heating rate of 3 ℃/min, preserving heat for 2 hours to obtain glass liquid, and water-cooling to obtain glass blocks. And adding alcohol into the glass blocks in an alumina ball milling tank, ball milling for 1h, and drying to obtain glass powder (powder: zirconium balls: alcohol=1:5:3). Granulating the glass powder with the PVB alcohol solution (3 wt%) with the weight percentage of 6%, and sieving with a 60-mesh sieve to obtain the granulated powder. Placing the granulated powder into a specific die, and pressing into test sample by using hydraulic pressSize. Placing the blank in a muffle furnace, heating to 450 ℃ at a heating rate of 5 ℃/min, preserving heat for 2 hours to remove the gelatin, heating to 1200 ℃ and preserving heat for 2 hours, and cooling to room temperature along with the furnace to obtain a test sample for performance test.
Example 25:
the molar ratio of each component of the raw materials is converted into mass ratio, and 345.01g of BaCO is accurately weighed 3 、123.05g SiO 2 、13.3g Y 2 O 3 、19.19g La 2 O 3 、19.81g Nd 2 O 3 、20.4g Sm 2 O 3 、21.33g Tb 2 O 3 、22.54g Er 2 O 3 、23.21g Yb 2 O 3 Uniformly mixing, placing in a platinum crucible, heating to 1600 ℃ in a molybdenum rod furnace at a heating rate of 3 ℃/min, preserving heat for 2 hours to obtain glass liquid, and water-cooling to obtain glass blocks. And adding alcohol into the glass blocks in an alumina ball milling tank, ball milling for 1h, and drying to obtain glass powder (powder: zirconium balls: alcohol=1:5:3). Granulating the glass powder with the PVB alcohol solution (3 wt%) with the weight percentage of 6%, and sieving with a 60-mesh sieve to obtain the granulated powder. The granulated powder was placed in a specific mold and pressed into the desired dimensions of the test sample using a hydraulic press. Placing the blank in a muffle furnace, heating to 450 ℃ at a heating rate of 5 ℃/min, preserving heat for 2 hours to remove the gelatin, heating to 1200 ℃ and preserving heat for 2 hours, and cooling to room temperature along with the furnace to obtain a test sample for performance test.
The formulations of the glasses according to the invention in examples 24 to 25 and comparative example 2 are shown in Table 3 (mol%)
Example 26:
880g of the glass frit of example 1, 120g of zirconia (ZrO 2 ) Placing the powder in a planetary ball milling tank, ball milling with alcohol for 1h, and drying to obtain sealed glass powder which is denoted as RSL-7. Weighing 100g of RSL-7, adding 40g of xylene solvent, and placing 1g of fish oil (dispersing agent) into a ball milling tank for ball milling for 1h; adding 8g PVB (binder) and 4gSL04 (plasticizer) to continue ball milling for 1h to obtain slurry, and obtaining the slurry of YSZ ceramic by the same method; vacuum itDefoaming, pouring the slurry on a PET bottom die for casting, and driving the PET bottom die to move forwards at the speed of 0.25 m/min, wherein the thickness of the slurry is controlled at 200 mu m by a scraper, the temperature in a casting chamber is controlled at 60 ℃, and after the slurry is formed into a film strip, removing the bottom die to obtain a biscuit, and casting and forming on a casting machine to obtain a film bag; removing the bottom die, shearing into a 5X 5mm sample, laminating the glass biscuit and the YSZ biscuit, and performing hot isostatic pressing, wherein the pressure is controlled to be 20-40 MPa, the temperature is 40-80 ℃, and the pressure maintaining time is 10-40 min; and (3) placing the obtained sample in a muffle furnace, heating to 500 ℃ to remove the plain glue, and heating to 1400 ℃ to obtain the compact sealing piece.
Example 27:
900g of the glass frit of example 2, 100g of alumina (Al 2 O 3 ) Placing the powder in a planetary ball milling tank, ball milling with alcohol for 1h, and drying to obtain sealed glass powder which is denoted as RSL-8. Weighing 100g of RSL-8, adding 40g of xylene solvent, and placing 1g of fish oil (dispersing agent) into a ball milling tank for ball milling for 1h; adding 8g PVB (binder) and 4gSL (plasticizer), and continuing ball milling for 1h to obtain slurry, and obtaining the slurry of YSZ ceramic by the same method; pouring the slurry on a PET bottom die for casting, and driving the PET bottom die to move forward at the speed of 0.25 m/min, wherein the thickness of the slurry is controlled at 200 mu m by a scraper, the temperature in a casting chamber is controlled at 60 ℃, and after the slurry is formed into a film strip, the bottom die is removed to obtain a biscuit, and casting and forming are carried out on a casting machine to obtain a film bag; removing the bottom die, shearing into a 5X 5mm sample, laminating the glass biscuit and the YSZ biscuit, and performing hot isostatic pressing, wherein the pressure is controlled to be 20-40 MPa, the temperature is 40-80 ℃, and the pressure maintaining time is 10-40 min; and (3) placing the obtained sample in a muffle furnace, heating to 500 ℃ to remove the plain glue, and heating to 1400 ℃ to obtain the compact sealing piece.
Example 28:
950g of the glass frit of example 3, 50g of zirconia (ZrO 2 ) Placing the powder in a planetary ball milling tank, ball milling with alcohol for 1h, and drying to obtain sealed glass powder which is denoted as RSL-8. Weighing 100g of RSL-8, adding 40g of xylene solvent, and placing 1g of fish oil (dispersing agent) into a ball milling tank for ball milling for 1h; adding 8g PVB (binder), 4gSL04 (plasticizer) and ball milling for 1h to obtain slurry, and performing the same methodObtaining slurry of YSZ ceramic; pouring the slurry on a PET bottom die for casting, and driving the PET bottom die to move forward at the speed of 0.25 m/min, wherein the thickness of the slurry is controlled at 200 mu m by a scraper, the temperature in a casting chamber is controlled at 60 ℃, and after the slurry is formed into a film strip, the bottom die is removed to obtain a biscuit, and casting and forming are carried out on a casting machine to obtain a film bag; removing the bottom die, shearing into a 5X 5mm sample, laminating the glass biscuit and the YSZ biscuit, and performing hot isostatic pressing, wherein the pressure is controlled to be 20-40 MPa, the temperature is 40-80 ℃, and the pressure maintaining time is 10-40 min; and (3) placing the obtained sample in a muffle furnace, heating to 500 ℃ to remove the plain glue, and heating to 1400 ℃ to obtain the compact sealing piece.
The thermal expansion coefficients of specific examples 26-28 of the present invention are detailed in Table 4:
| sequence number | CTE：30～800℃(×10 -6 ) |
| 5YZ | 10.47 |
| Example 26 | 12.05 |
| Example 27 | 11.05 |
| Example 28 | 9.98 |
。
Claims (6)
1. The application of the high-temperature-resistant high-expansion rare earth-rich glass material in the high-temperature alloy/stainless steel sealing glass material is characterized by comprising the following steps:
(1) Grinding the high-temperature-resistant high-expansion rare earth-rich glass material into glass powder; the high-temperature-resistant high-expansion rare earth-rich glass material has the composition of aRO-bLn 2 O 3 -cSiO 2 -dB 2 O 3 The method comprises the steps of carrying out a first treatment on the surface of the Wherein at least one of r= Ba, ca, mg, sr, ln= Sc, Y, la, ce, pr, nd, sm, eu, cd, tb, dy, ho, er, tm, yb, lu; a=20 to 45moL%, b=2.5 to 20moL%, c=52.5 to 77.5moL%, d=0 to 10moL%, and a+b+c+d=100 moL%;
(2) Mixing glass powder, ceramic powder, a binder and a solvent to obtain mixed slurry, and performing spray granulation to obtain granulated powder; the ceramic powder is at least one of alumina, zirconia and magnesia, and the addition amount is 0-20wt% of the mass of the glass powder;
(3) Molding the obtained granulated powder by an automatic press, and vitrifying at 1100-1300 ℃;
(4) Finally, the metal equipment and the pre-oxidized metal equipment are placed in a protective atmosphere, and sealing and melting are completed at 1200-1400 ℃.
2. The use according to claim 1, wherein in step (1), the glass frit has a particle size distribution ranging from 1 to 50 μm;
in the step (2), the particle size of the granulated powder is 100-300 mu m;
in the step (4), the heating rate of the sealing and melting is 5-30 ℃/min, and the heat preservation time of the sealing and melting is 10-120 minutes.
3. The use according to claim 1, wherein the glass transition temperature of the high temperature and high expansion resistant rare earth rich glass material is between 700 and 850 ℃ and the initial crystallization temperature is between 800 and 1000 ℃.
4. The use according to claim 1, wherein the high temperature and high expansion resistant rare earth rich glass material has a densification temperature between 1100 and 1300 ℃, a sealing temperature between 1200 and 1450 ℃ and a maximum use temperature between 900 and 1250 ℃.
5. The use according to any one of claims 1 to 4, wherein the method for preparing the high temperature and high expansion resistant rare earth-rich glass material comprises:
(1) R source, ln source, si source and B source are selected as raw materials, and the raw materials are weighed and mixed according to the composition of the high-temperature-resistant high-expansion rare earth-rich glass material to obtain a batch;
(2) Heating the obtained batch to 1550-1650 ℃ and preserving heat for 2-6 hours to obtain uniform glass melt, and then rapidly quenching to obtain the high-temperature-resistant high-expansion rare earth-rich glass material.
6. The use of claim 5, wherein the R source is RCO 3 、R(NO 3 ) 2 And RCl 2 One or more of the above-mentioned materials are more than 99% pure; the Ln source is Ln 2 O 3 Purity is greater than 99%; the source B is H 3 BO 3 Purity is greater than 99%; the Si source is SiO 2 The purity is more than 99 percent.
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