CN116495992A - Glass ceramic slurry for temperature sensor and preparation method thereof - Google Patents
Glass ceramic slurry for temperature sensor and preparation method thereof Download PDFInfo
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- CN116495992A CN116495992A CN202310461578.6A CN202310461578A CN116495992A CN 116495992 A CN116495992 A CN 116495992A CN 202310461578 A CN202310461578 A CN 202310461578A CN 116495992 A CN116495992 A CN 116495992A
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- 239000002241 glass-ceramic Substances 0.000 title claims abstract description 71
- 239000002002 slurry Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title abstract description 10
- 239000000843 powder Substances 0.000 claims abstract description 44
- 239000003960 organic solvent Substances 0.000 claims abstract description 15
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims abstract description 12
- 229910004298 SiO 2 Inorganic materials 0.000 claims abstract description 11
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 claims abstract description 9
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229940116411 terpineol Drugs 0.000 claims abstract description 9
- 239000001856 Ethyl cellulose Substances 0.000 claims abstract description 3
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 3
- 229920001249 ethyl cellulose Polymers 0.000 claims abstract description 3
- 235000019325 ethyl cellulose Nutrition 0.000 claims abstract description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 3
- 239000011521 glass Substances 0.000 claims description 91
- 238000001816 cooling Methods 0.000 claims description 16
- 239000000156 glass melt Substances 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 12
- 238000000227 grinding Methods 0.000 claims description 10
- 229910052802 copper Inorganic materials 0.000 claims description 9
- 239000010949 copper Substances 0.000 claims description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 8
- 238000002425 crystallisation Methods 0.000 claims description 8
- 230000008025 crystallization Effects 0.000 claims description 8
- 238000002844 melting Methods 0.000 claims description 8
- 230000008018 melting Effects 0.000 claims description 8
- 238000010791 quenching Methods 0.000 claims description 8
- 230000000171 quenching effect Effects 0.000 claims description 8
- 238000007873 sieving Methods 0.000 claims description 8
- 238000005303 weighing Methods 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- 238000005245 sintering Methods 0.000 claims description 5
- 238000000465 moulding Methods 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 239000000523 sample Substances 0.000 abstract description 5
- 238000005538 encapsulation Methods 0.000 abstract description 2
- 239000011248 coating agent Substances 0.000 abstract 1
- 238000000576 coating method Methods 0.000 abstract 1
- 238000007598 dipping method Methods 0.000 abstract 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 21
- 239000002994 raw material Substances 0.000 description 17
- 238000007789 sealing Methods 0.000 description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 12
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 8
- 239000000919 ceramic Substances 0.000 description 8
- 230000001276 controlling effect Effects 0.000 description 8
- 239000000395 magnesium oxide Substances 0.000 description 8
- 238000004806 packaging method and process Methods 0.000 description 8
- 239000005394 sealing glass Substances 0.000 description 6
- 239000000377 silicon dioxide Substances 0.000 description 6
- 235000012239 silicon dioxide Nutrition 0.000 description 6
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 5
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 5
- 229910000019 calcium carbonate Inorganic materials 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000011161 development Methods 0.000 description 3
- 238000009413 insulation Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000001133 acceleration Effects 0.000 description 2
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 2
- 239000000347 magnesium hydroxide Substances 0.000 description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052810 boron oxide Inorganic materials 0.000 description 1
- 239000005388 borosilicate glass Substances 0.000 description 1
- 239000002419 bulk glass Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000001066 destructive effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000004807 localization Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 238000012858 packaging process Methods 0.000 description 1
- 238000012536 packaging technology Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000005365 phosphate glass Substances 0.000 description 1
- 238000004537 pulping Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
- C03C8/24—Fusion seal compositions being frit compositions having non-frit additions, i.e. for use as seals between dissimilar materials, e.g. glass and metal; Glass solders
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- 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
- C03C10/0036—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 containing SiO2, Al2O3 and a divalent metal oxide as main constituents
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C12/00—Powdered glass; Bead compositions
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/50—Glass production, e.g. reusing waste heat during processing or shaping
- Y02P40/57—Improving the yield, e-g- reduction of reject rates
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Ceramic Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Glass Compositions (AREA)
Abstract
The invention discloses glass ceramic slurry for a temperature sensor and a preparation method thereof. The glass ceramic slurry comprises the following components in percentage by mass: 70-80% of inorganic glass ceramic powder and 20-30% of organic solvent; wherein, the inorganic glass ceramic powder comprises the following components in percentage by mass: 45-60% SiO 2 、Al 2 O 3 10-25%, 15-30% CaO and 0-10% MgO; the organic solvent is at least one or more of terpineol, ethyl cellulose and polyvinyl alcohol Ding Quanzhi. The prepared glass ceramic slurry has good adhesiveness, strong insulativity and excellent durability, and the sensor element probe is coated in a dipping, coating and other modes, so that encapsulation protection is realized, the high temperature resistance of the sensor can be effectively improved, and the efficiency and the reliability of the automobile exhaust treatment device are improved.
Description
Technical Field
The invention belongs to the technical field of glass ceramic slurry, and particularly relates to glass ceramic slurry for a temperature sensor and a preparation method thereof.
Background
With the continuous development of the automobile industry, the upgrading and updating speeds of products are continuously increased, and the requirements on the working conditions of various equipment of the automobile are more and more severe. Particularly, the automobile exhaust emission, the detection and treatment standards of the automobile exhaust are continuously improved in consideration of environmental pollution. The core technology of the high-temperature sensor in the automobile exhaust treatment device plays a very important role in detection and secondary treatment of automobile exhaust.
The high-temperature sensor for the automobile exhaust is required to be accurate in measurement, and has the characteristics of thermal shock resistance, wide working temperature and the like. The sensitive element is a core device of the whole sensor, and high-temperature gas exhausted by an automobile has the characteristics of high temperature, high pressure and high speed, and is easy to form destructive impact on a rear end coupling wire and a welding spot, so that the protection of the sensitive element is an important point for researching the high-temperature gas temperature sensor. The glass slurry sintering mode is utilized to ensure that the inside of the probe is isolated from the outside air, so that a good sealing and packaging effect is achieved, and an insulating effect can be achieved between the thermocouple wire and the wall of the probe shell. However, the special glass is limited and exported abroad, and the research and development of the special glass in China currently has technical barriers, so that sealing products have certain problems, such as complex packaging technology, lower yield, poorer product consistency and unstable high-temperature insulating property, and the complete localization process of the high-temperature sensor is influenced. Therefore, aiming at the problems of wide working temperature range, high temperature, long working time and reliable sealing performance required by the sensor, development of special glass powder with stable performance, simple and convenient packaging process and high-temperature resistance and stable working is urgently needed, so that the production cost of the high-temperature sensor is reduced, the working stability of a connector is improved, and the guarantee is provided for the complete autonomous development of the high-temperature acceleration sensor.
Since the sensor probe is susceptible to external environmental effects, resulting in device failure, the sealability of the glass paste package is ensured, and the adhesiveness of the paste is also ensured when the sensor probe is operated in a high-temperature environment. The current packaging glass slurry has the problems that the slurry needs to be coated for many times, the adhesive force of the slurry is reduced at high temperature, the slurry is not compact during sintering, and the like, so that the reliability of the temperature sensor is greatly affected. In view of the above, the present inventors have studied and devised a glass ceramic paste with good adhesion, high temperature resistance, and high insulation for use in automobiles, but not limited to, in automobile exhaust gas sensors, and a method for preparing the same.
Chinese patent 201911395235.4 discloses a sealing glass material for a sensor and a preparation method thereof. Selecting P 2 O 5 -B 2 O 3 -Al 2 O 3 The glass system is taken as a main body, the performances of the glass such as the thermal expansion coefficient, the glass softening temperature, the chemical stability and the like are regulated by regulating the types and the contents of various metal oxides, and the obtained glass has the thermal expansion coefficient between 150 and 240 (10 -7 and/DEG C), can be used for sealing sensor glass of metals with high expansion coefficients such as Cu, al and the like and alloy materials thereof. However, the phosphate glass has poor chemical stability, lower sintering temperature and larger expansion coefficient, and is not beneficial to the use of a high-temperature sensor for automobile exhaust. Chinese patent 202111459033.9 discloses a method for preparing sealing glass for high-temperature vibration acceleration sensor and sealing process. Selecting SiO 2 -Al 2 O 3 The BaO-CaO system comprises the following sealing glass in mole percent: siO (SiO) 2 ：24％～40％；B 2 O 3 ：0％～11％；Al 2 O 3 ：5％～8％；BaO：34％～45％；CaO：15％～20％；Na 2 O：0％～1％；K 2 O：0％～2％；TiO 2 ：0％～0.5％；CeO 2 :0% -0.5%; znO:0% -1%. The glass components are controllably adjusted by adding the metal oxide, the thermal expansion coefficient of the glass is improved to change the matching property of the glass-metal sealing, and the high-temperature insulation performance of the sealing glass is improved by adjusting the component concentration. However, the glass has low use temperature, is not suitable for a high-temperature sensor, contains a certain content of boron oxide and alkali metal oxide, and has poor stability. Chinese patent 202111458380 discloses CaO-BaO-SiO for high temperature resistant sensor 2 A preparation method of sealing glass and a pulping process. The glass powder has the composition of SiO 2 45％～65％、CaO 5％～54％、7% -50% of BaO; coefficient of thermal expansion α= (78-89) ×10 -7 and/C. Softening temperature T of sealing glass f = 799.8 to 865.5 ℃. However, the glass softening temperature is low, the chemical stability of the pure glass powder is to be improved, and the coverage of the thermal expansion coefficient is small due to the limitation of the glass components.
Disclosure of Invention
The invention aims to provide glass ceramic slurry with good adhesiveness, high temperature resistance and strong insulativity and a preparation method thereof, wherein glass ceramic occupies a certain proportion, a crystalline phase part is used as a framework to adjust the thermal expansion coefficient of glass, and a glass part is used as a softening sealing material. Compared with glass powder, the glass ceramic powder provided by the scheme has better stability and large adjustable range of thermal expansion coefficient, and can effectively improve the high temperature resistance of the sensor, thereby improving the efficiency and reliability of the automobile exhaust treatment device.
The invention is realized by the following technical scheme:
a glass ceramic slurry for a temperature sensor, characterized by: the glass ceramic slurry comprises the following components in percentage by weight: 70-80% of inorganic glass ceramic powder and 20-30% of organic solvent;
wherein, the inorganic glass ceramic powder comprises the following components in percentage by mass of oxide:
SiO 2 45～60％
Al 2 O 3 10～25％
CaO 15～30％
MgO 0～10％；
the organic solvent is selected from one or more of terpineol, ethyl cellulose and polyvinyl alcohol Ding Quanzhi.
The invention also provides a preparation method of the packaging glass ceramic slurry.
The method is characterized in that: the method comprises the following steps:
a method for preparing glass ceramic slurry for a temperature sensor, which is characterized by comprising the following steps: the method comprises the following steps:
1) Accurately weighing the inorganic glass ceramic powder according to the composition ratio, uniformly mixing the inorganic glass ceramic powder, and then placing the mixture into a high-temperature melting furnace to fuse for 4 hours at 1600-1800 ℃ to obtain high-temperature glass fused solution;
2) Pouring the glass melt in the step 1) on a copper plate for rapid quenching to form massive glass;
3) Cooling and molding the glass in the step 2), rapidly transferring the glass into a muffle furnace for crystallization treatment, preserving heat for 10 hours at 850-950 ℃ and then cooling along with the furnace to obtain microcrystalline glass;
4) Pre-crushing the microcrystalline glass in the step 3), finely grinding in a ball mill, wherein the ball ratio is 1 (3-5), and sieving with a 800-mesh sieve to obtain inorganic glass ceramic powder with the granularity of 5-20 mu m;
5) Uniformly mixing the inorganic glass ceramic powder obtained in the step 4) with an organic solvent according to a proportion, stirring, grinding, and controlling the viscosity to be (150-250) Pa.s to obtain the glass ceramic slurry with the granularity of 5-20 mu m for the temperature sensor.
The thermal expansion coefficient of the inorganic glass ceramic powder is (60-80) 10 # -7 between/K.
The sintering temperature of the inorganic glass ceramic powder is 980-1100 ℃.
A thin glass slurry layer is spin-coated on the surface of sensitive ceramic of a temperature sensor, and kept in a furnace at 980-1100 ℃ for 10-30 min, so that a microcrystalline glass sealing structure can be formed.
By adopting the scheme, the invention has the following advantages:
1. the packaging glass slurry has good adhesiveness and uniformity stability of organic matters, and can be directly coated on a sensor port without repeated operation.
2. The borosilicate glass system used for packaging the glass ceramic slurry has high temperature resistance and good stability; and through microcrystallization treatment, the composite material has strong insulativity, strong corrosion resistance, good thermal stability and strong reliability.
3. The organic solvent and the glass ceramic powder of the packaging glass ceramic slurry are easy to mix, and the organic phase is easy to remove during heat treatment, so that the influence on the packaging performance is not required.
4. The preparation method of the packaging glass ceramic slurry is simple and easy to operate.
Drawings
FIG. 1 is an X-ray diffraction pattern of a bulk glass of example 1.
FIG. 2 is an X-ray diffraction chart of an inorganic glass ceramic powder of example 1
FIG. 3 is a schematic diagram of a glass-packaged temperature sensor
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The experimental methods in the following examples are all conventional methods unless otherwise specified, and the experimental reagents and materials involved are all conventional chemical reagents and materials unless otherwise specified.
Example 1
(1) Weighing glass raw materials according to the mass percentage: 25% CaO, 12% Al 2 O 3 56% SiO 2 7% MgO, caO derived from calcium carbonate, al 2 O 3 Derived from aluminium hydroxide, siO 2 From silicon dioxide, mgO from light magnesium oxide, and uniformly mixing the raw materials;
(2) Melting the glass raw material obtained in the step (1) for 4 hours at 1650 ℃ to obtain high-temperature glass melt, and then pouring the glass melt on a copper plate for rapid quenching to obtain blocky glass;
(3) And (3) after cooling and forming the glass in the step (2), rapidly transferring the glass into a muffle furnace for crystallization treatment, preserving heat at 930 ℃ for 10 hours, and cooling along with the furnace to obtain the microcrystalline glass.
(4) Pre-crushing the microcrystalline glass in the step (3), finely grinding in a ball mill, sieving with a 800-mesh sieve according to a ball ratio of 1:3, and obtaining inorganic glass ceramic powder with a granularity of 5-20 mu m;
(5) According to the proportion of 70% of inorganic glass ceramic powder and 30% of terpineol, fully and uniformly mixing the inorganic glass ceramic powder obtained in the step (4) with an organic solvent, and controlling the viscosity at 175 Pa.s to obtain a glass ceramic slurry finished product;
(6) A thin layer of glass paste is spin coated onto the surface of the sensitive ceramic of the temperature sensor. And kept in an oven at 1015 ℃ for 10 minutes to form a glass-ceramic sealing structure.
Example 2
(1) Weighing glass raw materials according to the mass percentage: 15% CaO, 23% Al 2 O 3 53% SiO 2 9% MgO, caO derived from calcium nitrate, al 2 O 3 Derived from aluminium hydroxide, siO 2 From silicon dioxide, mgO from magnesium hydroxide, and uniformly mixing the raw materials;
(2) Melting the glass raw material obtained in the step (1) for 4 hours at 1670 ℃ to obtain high-temperature glass melt, and then pouring the glass melt on a copper plate for rapid quenching to obtain massive glass;
(3) After cooling and forming the glass in the step (2), rapidly transferring the glass into a muffle furnace for crystallization treatment, preserving heat at 930 ℃ for 10 hours, and cooling along with the furnace to obtain microcrystalline glass;
(4) Pre-crushing the microcrystalline glass in the step (3), finely grinding in a ball mill, sieving with a 800-mesh sieve according to a ball ratio of 1:3, and obtaining inorganic glass ceramic powder with a granularity of 5-20 mu m;
(5) According to the proportion of 75% of inorganic glass ceramic powder and 25% of terpineol, fully and uniformly mixing the inorganic glass powder obtained in the step (4) with an organic solvent, and controlling the viscosity at 150 Pa.s to obtain a glass slurry finished product;
(6) A thin layer of glass paste is spin coated onto the surface of the sensitive ceramic of the temperature sensor. And kept in a furnace at 1000 ℃ for 15 minutes to form the microcrystalline glass sealing structure.
Example 3
(1) Weighing glass raw materials according to the mass percentage: 26% CaO, 24% Al 2 O 3 45% SiO 2 5% MgO, caO derived from carbonic acidCalcium, al 2 O 3 Derived from aluminium hydroxide, siO 2 The raw materials are uniformly mixed by the light magnesia from the silicon dioxide and the MgO from the light magnesia;
(2) Melting the glass raw material obtained in the step (1) for 4 hours at 1650 ℃ to obtain high-temperature glass melt, and then pouring the glass melt on a copper plate for rapid quenching to obtain blocky glass;
(3) After cooling and forming the glass in the step (2), rapidly transferring the glass into a muffle furnace for crystallization treatment, preserving heat at 910 ℃ for 10 hours, and cooling along with the furnace to obtain microcrystalline glass;
(4) Pre-crushing the microcrystalline glass in the step (3), finely grinding in a ball mill, sieving with a 800-mesh sieve according to a ball ratio of 1:3, and obtaining inorganic glass ceramic powder with a granularity of 5-20 mu m;
(5) According to the proportion of 80% of inorganic glass ceramic powder and 20% of terpineol, fully and uniformly mixing the inorganic glass ceramic powder obtained in the step (4) with an organic solvent, and controlling the viscosity at 250 Pa.s to obtain a glass ceramic slurry finished product;
(6) A thin layer of glass paste is spin coated onto the surface of the sensitive ceramic of the temperature sensor. And kept in a furnace at 980 ℃ for 20 minutes to form the microcrystalline glass sealing structure.
Example 4
(1) Weighing glass raw materials according to the mass percentage: 30% CaO, 20% Al 2 O 3 50% SiO 2 CaO is derived from calcium carbonate, al 2 O 3 From alumina powder, siO 2 The raw materials are uniformly mixed from silicon dioxide;
(2) Melting the glass raw material obtained in the step (1) for 4 hours at 1630 ℃ to obtain high-temperature glass melt, and then pouring the glass melt on a copper plate for rapid quenching to obtain massive glass;
(3) After cooling and forming the glass in the step (2), rapidly transferring the glass into a muffle furnace for crystallization treatment, preserving heat at 930 ℃ for 10 hours, and cooling along with the furnace to obtain microcrystalline glass;
(4) Pre-crushing the microcrystalline glass in the step (3), finely grinding in a ball mill, sieving with a 800-mesh sieve according to a ball ratio of 1:3, and obtaining inorganic glass ceramic powder with a granularity of 5-20 mu m;
(5) According to the proportion of 70% of inorganic glass ceramic powder and 30% of terpineol, fully and uniformly mixing the inorganic glass ceramic powder obtained in the step (4) with an organic solvent, and controlling the viscosity at 200 Pa.s to obtain a glass ceramic slurry finished product;
(6) A thin layer of glass paste is spin coated onto the surface of the sensitive ceramic of the temperature sensor. And kept in a furnace at 1030 ℃ for 25 minutes to form the microcrystalline glass sealing structure.
Example 5
(1) Weighing glass raw materials according to the mass percentage: 20% CaO, 20% Al 2 O 3 50% SiO 2 10% MgO, caO derived from calcium carbonate, al 2 O 3 Derived from aluminium hydroxide, siO 2 From silicon dioxide, mgO from magnesium hydroxide uniformly mixes raw materials;
(2) Melting the glass raw material obtained in the step (1) for 4 hours at 1600 ℃ to obtain high-temperature glass melt, and then pouring the glass melt on a copper plate for rapid quenching to obtain blocky glass;
(3) After cooling and forming the glass in the step (2), rapidly transferring the glass into a muffle furnace for crystallization treatment, preserving heat at 910 ℃ for 10 hours, and cooling along with the furnace to obtain microcrystalline glass;
(4) Pre-crushing the microcrystalline glass in the step (3), finely grinding in a ball mill, sieving with a 800-mesh sieve according to a ball ratio of 1:3, and obtaining inorganic glass ceramic powder with a granularity of 5-20 mu m;
(5) According to the proportion of 70% of inorganic glass ceramic powder and 30% of terpineol, fully and uniformly mixing the inorganic glass ceramic powder obtained in the step (4) with an organic solvent, and controlling the viscosity at 190 Pa.s to obtain a glass ceramic slurry finished product;
(6) A thin layer of glass paste is spin coated onto the surface of the sensitive ceramic of the temperature sensor. And kept in a furnace at 1020 ℃ for 30 minutes to form the microcrystalline glass sealing structure.
Example 6
(1) Weighing glass raw materialsThe weight percentages are as follows: 18% CaO, 25% Al 2 O 3 57% SiO 2 6% MgO, caO derived from calcium carbonate, al 2 O 3 Derived from aluminium hydroxide, siO 2 The raw materials are uniformly mixed by the light magnesia from the silicon dioxide and the MgO from the light magnesia;
(2) Melting the glass raw material obtained in the step (1) for 4 hours at 1750 ℃ to obtain high-temperature glass melt, and then pouring the glass melt on a copper plate for rapid quenching to obtain blocky glass;
(3) After cooling and forming the glass in the step (2), rapidly transferring the glass into a muffle furnace for crystallization treatment, preserving heat for 10 hours at 890 ℃ and then cooling along with the furnace to obtain microcrystalline glass;
(4) Pre-crushing the microcrystalline glass in the step (3), finely grinding in a ball mill, sieving with a 800-mesh sieve according to a ball ratio of 1:3, and obtaining inorganic glass ceramic powder with a granularity of 5-20 mu m;
(5) According to the proportion of 70% of inorganic glass ceramic powder and 30% of terpineol, fully and uniformly mixing the inorganic glass ceramic powder obtained in the step (4) with an organic solvent, and controlling the viscosity at 225 Pa.s to obtain a glass ceramic slurry finished product;
(6) A thin layer of glass paste is spin coated onto the surface of the sensitive ceramic of the temperature sensor. And kept in a furnace at 1100 ℃ for 20 minutes to form the microcrystalline glass sealing structure.
As shown in Table 1, the glass ceramic slurry for encapsulation prepared by the invention has better adhesiveness and better matching property with a ceramic substrate by adjusting the formula composition and controlling the heat treatment process. After the glass ceramic slurry prepared by the preparation method is applied to a high-temperature automobile exhaust temperature sensor, the glass ceramic slurry has the advantages of strong insulation, strong corrosion resistance, good thermal stability and high reliability.
Table 1: composition and related Performance test Table for examples 1-6
Claims (4)
1. A glass ceramic slurry for a temperature sensor, characterized by: the glass ceramic slurry comprises the following components in percentage by weight: 70-80% of inorganic glass ceramic powder and 20-30% of organic solvent;
wherein, the inorganic glass ceramic powder comprises the following components in percentage by mass of oxide:
SiO 2 45～60％
Al 2 O 3 10～25％
CaO15～30％
MgO0～10％；
the organic solvent is selected from one or more of terpineol, ethyl cellulose and polyvinyl alcohol Ding Quanzhi.
2. The method for preparing a glass ceramic slurry for a temperature sensor according to claim, wherein: the method comprises the following steps:
1) Accurately weighing the inorganic glass ceramic powder according to the composition ratio, uniformly mixing the inorganic glass ceramic powder, and then placing the mixture into a high-temperature melting furnace to fuse for 4 hours at 1600-1800 ℃ to obtain high-temperature glass fused solution;
2) Pouring the glass melt in the step 1) on a copper plate for rapid quenching to form massive glass;
3) Cooling and molding the glass in the step 2), rapidly transferring the glass into a muffle furnace for crystallization treatment, preserving heat for 10 hours at 850-950 ℃ and then cooling along with the furnace to obtain microcrystalline glass;
4) Pre-crushing the microcrystalline glass in the step 3), finely grinding in a ball mill, wherein the ball ratio is 1 (3-5), and sieving with a 800-mesh sieve to obtain inorganic glass ceramic powder with the granularity of 5-20 mu m;
5) Uniformly mixing the inorganic glass ceramic powder obtained in the step 4) with an organic solvent according to a proportion, stirring, grinding, and controlling the viscosity to be (150-250) Pa.s to obtain the glass ceramic slurry with the granularity of 5-20 mu m for the temperature sensor.
3. As claimed inThe glass ceramic slurry for a temperature sensor according to claim 1, wherein the inorganic glass ceramic powder has a thermal expansion coefficient of (60-80) x 10 -7 between/K.
4. The glass-ceramic slurry for a temperature sensor according to claim 1, wherein the sintering temperature of the inorganic glass-ceramic powder is between 980-1100 ℃.
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