CN110398525B - ZrO2Sealing method of oxygen-based sensitive element and metal flange - Google Patents

ZrO2Sealing method of oxygen-based sensitive element and metal flange Download PDF

Info

Publication number
CN110398525B
CN110398525B CN201910807272.5A CN201910807272A CN110398525B CN 110398525 B CN110398525 B CN 110398525B CN 201910807272 A CN201910807272 A CN 201910807272A CN 110398525 B CN110398525 B CN 110398525B
Authority
CN
China
Prior art keywords
oxygen
metal flange
zro
atmosphere furnace
temperature atmosphere
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201910807272.5A
Other languages
Chinese (zh)
Other versions
CN110398525A (en
Inventor
向蓝翔
李重
邵长贵
黄继东
高会玲
丛中斗
韩月奇
尹卫
王维华
贾铁军
张谦
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
China Institute of Atomic of Energy
Original Assignee
China Institute of Atomic of Energy
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by China Institute of Atomic of Energy filed Critical China Institute of Atomic of Energy
Priority to CN201910807272.5A priority Critical patent/CN110398525B/en
Publication of CN110398525A publication Critical patent/CN110398525A/en
Application granted granted Critical
Publication of CN110398525B publication Critical patent/CN110398525B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

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
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Biochemistry (AREA)
  • Immunology (AREA)
  • Physics & Mathematics (AREA)
  • Analytical Chemistry (AREA)
  • Molecular Biology (AREA)
  • General Health & Medical Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Electrochemistry (AREA)
  • Pathology (AREA)
  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Oxide Ceramics (AREA)

Abstract

The invention provides ZrO2The sealing method of the oxygen-based sensitive element and the metal flange comprises the following steps: s1. preparationPreparing a glass blank; s2, pre-oxidizing the metal flange; and S3, passing the ZrO through the glass body2A oxygen-based sensitive element sealed to the metal flange, wherein the glass body, the metal flange and the ZrO2The oxygen-based sensitive elements have similar coefficients of thermal expansion. According to the sealing method of the present invention, ZrO is minimized2The thermal expansion coefficient difference among the oxygen-based sensitive element, the metal flange and the glass body ensures that three materials of the sealing piece have basically similar deformation under the condition of temperature change, thereby avoiding glass body cracking or ZrO caused by larger difference of deformation amount in the sealing or using process2The breakage of the oxygen-based sensitive element, thereby greatly improving the sealing yield and prolonging the service life of the sealing part.

Description

ZrO2Sealing method of oxygen-based sensitive element and metal flange
Technical Field
The invention relates to the field of sealing of oxygen sensors, and more particularly to ZrO2ZrO in oxygen sensors2A sealing method of an oxygen-based sensitive element and a metal flange.
Background
ZrO2An oxygen sensor is a precision instrument for measuring the oxygen content in a gas. The working principle is ZrO2The reference electrode of the oxygen-based sensor is in contact with a reference gas (usually air) and the measurement electrode is in contact with the gas to be measured (the reference gas is strictly isolated from the gas to be measured). Under high temperature, when the oxygen concentration or pressure on the surfaces of the two electrodes are not equal, electromotive force is generated between the two electrodes, the electromotive force and the oxygen concentration or pressure conform to the Nernst equation, and the oxygen content in the gas to be measured can be calculated according to the Nernst equation.
At present, ZrO2The oxygen sensor is widely applied to the aspects of boiler combustion and automobile air-fuel ratio monitoring, the working temperature of the oxygen sensor is between 600 ℃ and 900 ℃, and the requirement on oxygen content measurement is very strict. To obtain accurate measurement results, the gases must be strictly separated between the two electrodes, so ZrO2The sealing of the oxygen-based sensitive element to the metal flange holding the element is of critical importance. At ZrO2In the sealing process of the oxygen-based sensitive element and the metal flange, firstly, ZrO is sealed2The sealing material of the oxygen-based sensitive element and the metal flange has strict requirements on components, the sealing material has good thermal stability, chemical stability and insulativity under the high-temperature condition, and ZrO is also required2The thermal expansion coefficients of the oxygen-based sensitive element, the metal flange and the sealing material are matched and compatible. Furthermore, there are strict requirements on the sealing process and sealing technique.
At present, ZrO2The sealing method of the oxygen-based sensitive element and the metal flange mainly comprises the following steps: (1) sealing with high temperature resistant inorganic adhesive; (2) the glass material is sealed at normal pressure and high temperature. However, the high-temperature inorganic adhesive has poor thermal expansion coefficient matching with the metal flange, and the adhesive cracks and falls off when the temperature changes violently. The glass sealing material has become ZrO because it can better meet the use requirements in the aspects of insulating property, thermal expansion coefficient matching property, thermal stability, chemical stability, compatibility, interface bonding property and the like2The research on the sealing material of the oxygen-based sensitive element is focused.
Because the glass sealing is carried out under normal pressure, air atmosphere or oxygen at presentThe sealing effect can not meet the design requirement. Firstly, when the glass material is melted under normal pressure, gas can be generated by the glass material or can be entrained from the surrounding environment, and the gas cannot be effectively discharged, so that a large number of air holes are remained in the glass sealing body, and the sealing effect is influenced; secondly, glass material and ZrO at atmospheric pressure2The infiltration angle of the oxygen-based sensitive element or the metal flange is large, the viscosity and the fluidity of the glass body are poor, the stress generated in the sintering process cannot be released to the maximum extent, and finally the stress is concentrated and acts on ZrO2The surface of the oxygen-sensitive element, causing it to break; in addition, the metal flange can undergo a severe oxidation reaction under a high-temperature air atmosphere or an oxidizing atmosphere, and the oxide layer on the surface can reduce the conductivity of the metal flange material and affect the conductivity of the metal flange material (in an oxygen sensor, the metal flange is required to have a function of leading out a potential signal of the sensor). Thus, ZrO2The sealing between the oxygen-based sensitive element and the metal flange has become ZrO2Technical bottlenecks in the development and production of oxygen sensors.
Disclosure of Invention
To solve at least one aspect of the above technical problems, embodiments of the present invention provide a ZrO2The sealing method of the oxygen-based sensitive element and the metal flange comprises the following steps:
s1, preparing a glass blank;
s2, pre-oxidizing the metal flange; and
s3, the ZrO is pressed through the glass body2A oxygen-based sensitive element sealed to the metal flange, wherein the glass body, the metal flange and the ZrO2The oxygen-based sensitive elements have similar coefficients of thermal expansion.
ZrO according to the invention2In a preferred embodiment of the sealing method of the oxygen-based sensitive element and the metal flange, step S1 includes: mixing the raw materials of the glass body according to the proportion of 65-80 percent of glass powder, 5-10 percent of binder, 5-10 percent of plasticizer and 10-15 percent of solvent by weight ratio, performing ball milling treatment on the mixed raw materials, and pressingAnd (4) forming a glass body.
In the ZrO according to the invention2In another preferred embodiment of the method for sealing a base oxygen sensor to a metal flange, the adhesive comprises an epoxy resin, the plasticizer comprises dimethyl phthalate, and the solvent comprises ethanol.
ZrO according to the invention2In another preferred embodiment of the sealing method of the oxygen-based sensitive element and the metal flange, step S2 includes: and (3) placing the metal flange in a muffle furnace at 300-600 ℃ in air for pre-oxidation treatment.
In the ZrO according to the invention2In another preferred embodiment of the sealing method of the oxygen-based sensitive element and the metal flange, step S3 includes:
s31, enabling the metal flange, the glass blank and ZrO to be arranged2The oxygen-based sensitive elements are sequentially and fixedly placed in the high-temperature atmosphere furnace;
s32, carrying out air tightness inspection on the high-temperature atmosphere furnace;
s33, removing oxygen in the high-temperature atmosphere furnace; and
and S34, heating the high-temperature atmosphere furnace and cooling to room temperature.
ZrO according to the invention2In another preferred embodiment of the sealing method of the oxygen-based sensitive element and the metal flange, step S32 includes: and vacuumizing the high-temperature atmosphere furnace, and checking the air tightness of the high-temperature atmosphere furnace.
In the ZrO according to the invention2In another preferred embodiment of the method for sealing an oxygen-based sensitive element and a metal flange, step S33 includes introducing high-purity nitrogen gas into the high-temperature atmosphere furnace, opening an outlet of the high-temperature atmosphere furnace, cleaning the high-temperature atmosphere furnace for a certain time, closing the outlet of the atmosphere furnace, stopping or reducing the introduction of nitrogen gas when the pressure in the high-temperature atmosphere furnace reaches 0.01MPa-0.03MPa, and maintaining the pressure.
ZrO according to the invention2In still another preferred embodiment of the method for sealing a base oxygen sensor to a metal flange, step S34 includes subjecting the high temperature toHeating the atmosphere furnace to 1020 ℃, preserving heat at 1020 ℃ for 20min-30min, introducing nitrogen when heating to 300 ℃ -400 ℃, opening a gas outlet of the high-temperature atmosphere furnace, keeping the pressure in the high-temperature atmosphere furnace at 0.04MPa-0.06MPa, stopping introducing nitrogen when cooling to 300 ℃ -400 ℃, and closing the gas outlet.
In the ZrO according to the invention2In still another preferred embodiment of the sealing method of the oxygen-based sensitive element and the metal flange, the process of heating the high temperature atmosphere furnace to 1020 ℃ comprises:
heating to 300 ℃ at the heating rate of 2-5 ℃/min;
heating to 900 ℃ at the heating rate of 4-6 ℃/min; and
heating to 1020 ℃ at a heating rate of 8-10 ℃/min.
ZrO according to the invention2In another preferred embodiment of the sealing method of the oxygen-based sensitive element and the metal flange, step S34 further includes reducing the temperature of the high temperature atmosphere furnace to 600 ℃ at a temperature reduction rate of 2 ℃/min to 5 ℃/min, and then naturally cooling to room temperature.
Compared with the prior art, the invention has at least one of the following beneficial effects:
(1) by subjecting ZrO to a positive pressure2The oxygen-based sensitive element and the metal flange are sealed, so that the glass melt is subjected to an external pressure, the gas in the glass melt is promoted to be discharged, and the ZrO content is reduced2The infiltration angle of an oxygen-based sensitive element or a metal flange; the effective discharge of the gas can reduce the residue of air holes in the glass body and enhance the compactness of the glass body, thereby achieving the purpose of enhancing the air tightness; the reduction of the wetting angle between the materials can increase the viscous fluidity of the glass body, thereby effectively releasing the stress generated in the sintering process and avoiding ZrO2The oxygen-based sensitive element cracks or breaks at the seal.
(2) Through nitrogen protection, the oxidation degree of the metal flange can be effectively reduced, and the metal flange is ensured to have good conductivity.
(3) By minimising ZrO2Oxygen sensitive elementThe difference of thermal expansion coefficients among the piece, the metal flange and the glass body ensures that three materials of the sealing piece have basically similar deformation under the condition of temperature change, thereby avoiding the cracking or ZrO of the glass body caused by larger difference of deformation in the sealing or using process2The breakage of the oxygen-based sensitive element, thereby greatly improving the sealing yield and prolonging the service life of the sealing piece.
Drawings
Other objects and advantages of the present invention will become apparent from the following description of the invention which refers to the accompanying drawings, and may assist in a comprehensive understanding of the invention.
FIG. 1 is a view of ZrO according to the present invention2A flow chart of a sealing method of an oxygen-based sensitive element and a metal flange.
It is noted that the drawings are not necessarily to scale and are merely illustrative in nature and not intended to obscure the reader.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be described clearly and completely with reference to the accompanying drawings of the embodiments of the present invention. It should be apparent that the described embodiment is one embodiment of the invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the described embodiments of the invention without any inventive step, are within the scope of protection of the invention.
Unless defined otherwise, technical or scientific terms used herein shall have the ordinary meaning as understood by one of ordinary skill in the art to which this invention belongs.
Embodiments of the present invention provide a ZrO2Method for sealing between an oxygen-based sensitive element and a metal flange, wherein the metal flange is used for supporting ZrO2The sealing method of the oxygen-based sensitive element comprises the following steps:
s1, preparing a glass blank;
s2, pre-oxidizing the metal flange; and
s3, the ZrO is pressed through the glass body2A oxygen-based sensitive element sealed to the metal flange, wherein the glass body, the metal flange and the ZrO2The oxygen-based sensitive elements have similar coefficients of thermal expansion.
ZrO2The oxygen-based sensitive element is of a cylindrical structure, preferably cylindrical, and is mounted in the central hole of the metal flange, in ZrO2An annular gap (the width of the gap is in the range of 1.5mm-2.0 mm) is arranged between the oxygen-based sensitive element and the metal flange, and a glass body can be placed in the annular gap, thereby realizing ZrO2And sealing the oxygen-based sensitive element and the metal flange. The metal flange is pre-oxidized to generate a layer of chromium oxide on the surface of the metal flange, and the chromium oxide layer has two functions on the premise of not influencing the conductivity of the metal flange, wherein one function is to prevent the metal flange from nitriding in a high-temperature nitrogen environment, avoid the reduction of the mechanical property of the metal flange caused by nitriding, and the other function is to facilitate the sealing treatment with a glass body.
Due to ZrO2The oxygen-based sensitive element, the metal flange and the glass body have matched thermal expansion coefficients, so that the sealing piece has basically similar deformation under the condition of temperature change, thereby avoiding cracking or ZrO of the glass body caused by large difference of deformation amount in the sealing or using process2The breakage of the oxygen-based sensitive element, thereby greatly improving the sealing yield and prolonging the service life of the sealing part.
In the above step S1, the preparing of the glass body includes: preparing raw materials of a glass blank according to the proportioning relation of 65-80% of glass powder, 5-10% of binder, 5-10% of plasticizer and 10-15% of solvent by weight ratio, mixing the raw materials, carrying out ball milling treatment on the mixed raw materials for 6 hours (namely 6 hours), and finally pressing the mixed raw materials after ball milling treatment into the glass blank. In this case, the thermal expansion coefficient of the glass frit and ZrO2The thermal expansion coefficients of the oxygen-based sensitive element and the metal flange are basically similar, wherein the metal flange can be formed by310 stainless steel, 310S stainless steel or kovar alloy, etc., thereby obtaining the ZrO after sealing2The oxygen-based sensitive element can not cause the cracking of a glass body or the ZrO of the glass body because of the larger difference of the thermal expansion coefficients of the three combined together under the high-temperature environment2The breakage of the oxygen-based sensitive element, thereby greatly improving the sealing yield and prolonging the service life of the sealing part.
In the above embodiment, the binder is preferably an epoxy resin, the plasticizer is preferably dimethyl phthalate, and the solvent may include ethanol. Of course, the above is only a preferred embodiment, and other corresponding materials commonly used in the art can be used for the binder, plasticizer and solvent.
In the ZrO of the invention2In the method for sealing a base oxygen sensor and a metal flange, the step S2 includes: in the air, the metal flange is placed in a muffle furnace at 300-600 ℃ for pre-oxidation treatment. For example, the glass blank can be pre-oxidized in a muffle furnace at 300 ℃ to 600 ℃ for 15 minutes to 30 minutes (i.e. 15 minutes to 30 minutes), so that an oxide film is formed on the surface of the metal flange, and the sealing treatment with the glass blank is more convenient.
Further, the step S3 includes the following steps:
s31, enabling the metal flange, the glass blank and ZrO to be arranged2The oxygen-based sensitive elements are sequentially and fixedly placed in the high-temperature atmosphere furnace;
s32, carrying out air tightness inspection on the high-temperature atmosphere furnace;
s33, removing oxygen in the high-temperature atmosphere furnace; and
and S34, heating the high-temperature atmosphere furnace and cooling to room temperature.
In step S31, the pre-oxidized metal flange and ZrO are treated by a special equipment2The oxygen-based sensitive element and the glass blank are fixed in place and then fixed in a high-temperature atmosphere furnace together with special equipment, and the subsequent steps are carried out. Of course, it is also possible to first place a special apparatus in the high-temperature atmosphere furnace and then sequentially place the metal flange, the glass blank and the ZrO2The oxygen-based sensitive element is fixed and put at high temperatureAn atmosphere furnace.
In step S32, the high-temperature atmosphere furnace is vacuumized and checked for airtightness to determine whether it satisfies the use requirement. Here, it is necessary to inspect the inlet and the outlet of the high-temperature atmosphere furnace to check whether the inlet and the outlet can be tightly sealed in a vacuum state. Whether the high-temperature atmosphere furnace has good air tightness can be judged according to the pressure maintaining time in the high-temperature atmosphere furnace.
In step S33, the removing of the oxygen in the high temperature atmosphere furnace may include introducing high purity nitrogen gas into the high temperature atmosphere furnace, for example, the nitrogen gas may be introduced for 10min to 15min, so as to reduce the oxygen content in the high temperature atmosphere furnace as much as possible. And closing the gas outlet of the atmosphere furnace, stopping introducing nitrogen or reducing the introduction amount of the nitrogen when the pressure in the high-temperature atmosphere furnace reaches 0.01-0.03 MPa, and keeping the pressure in the high-temperature atmosphere furnace within the range of 0.01-0.03 MPa.
In step S34, the high temperature atmosphere furnace is heated to 1020 ℃, and the temperature is kept at 1020 ℃ for 20min-30min, wherein nitrogen is introduced when the high temperature atmosphere furnace is heated to 300 ℃ -400 ℃, meanwhile, the air outlet of the high temperature atmosphere furnace is opened, the pressure in the high temperature atmosphere furnace is kept at 0.04MPa-0.06MPa, and the introduction of nitrogen is stopped when the high temperature atmosphere furnace is cooled to 300 ℃ -400 ℃, and the air outlet is closed.
The process of heating the high-temperature atmosphere furnace to 1020 ℃ comprises the following stages, firstly, heating the high-temperature atmosphere furnace to 300 ℃ at the heating rate of 2 ℃/min-5 ℃/min, then, heating the high-temperature atmosphere furnace to 900 ℃ at the heating rate of 4 ℃/min-6 ℃/min, starting to introduce nitrogen into the high-temperature atmosphere furnace during the heating to 300 ℃ to 400 ℃, simultaneously opening a gas outlet of the high-temperature atmosphere furnace so as to discharge the nitrogen in the high-temperature atmosphere furnace to the outside, finally, heating the high-temperature atmosphere furnace to 1020 ℃ at the heating rate of 8 ℃/min-10 ℃/min, and then entering the heat preservation treatment stage of 20min-30 min.
After the heat preservation treatment at 1020 ℃, the temperature of the high-temperature atmosphere furnace is reduced to 600 ℃ at the cooling rate of 2 ℃/min-5 ℃/min, and then the furnace is naturally cooled to the room temperature. And during the temperature reduction, stopping introducing nitrogen when the furnace is naturally cooled to 300-400 ℃, and closing the gas outlet at the same time to cool the furnace under the condition of keeping a certain gas amount in the high-temperature atmosphere furnace.
By sealing under a certain positive pressure, the glass melt is subjected to an external pressure, so that the discharge of gas in the glass melt is promoted, and the ZrO content is reduced2The infiltration angle of an oxygen-based sensitive element or a metal flange; the effective discharge of the gas can reduce the residue of air holes in the glass body and enhance the compactness of the glass body, thereby achieving the purpose of enhancing the air tightness; the reduction of the wetting angle between the materials can increase the viscous fluidity of the glass body, thereby effectively releasing the stress generated in the sintering process and avoiding ZrO2The oxygen-based sensitive element cracks or breaks at the seal. Furthermore, through nitrogen protection, the oxidation degree of the metal flange can be effectively reduced, and the metal flange is ensured to have good conductivity.
The ZrO of the present invention is illustrated by the following specific examples2The steps of the sealing method of the oxygen-based sensitive element and the metal flange are more specifically explained.
Experimental example 1:
first, preparation of a glass body is performed: respectively mixing 75% of glass powder, 8% of epoxy resin, 6% of dimethyl phthalate and 11% of ethanol according to the weight ratio to obtain a pasty substance, carrying out ball milling on the mixture for 6 hours by using a ball mill, and pressing the ball-milled mixture into a glass blank.
Then, the metal flange is pre-oxidized: a metal flange made of 310 stainless steel was pre-oxidized in a muffle furnace at 500 ℃ for 20 min.
Subsequently, ZrO is carried out2Glass sealing of the oxygen-based sensitive element and the metal flange: (1) preparing a high-temperature atmosphere furnace; (2) pre-oxidized metal flange and ZrO2The oxygen-based sensitive element is fixed in a special sealing device, and the glass body is placed in ZrO2In the gap between the oxygen-based sensitive element and the metal flange; (3) placing the sealing equipment into a high-temperature atmosphere furnace, and carrying out vacuumizing operation on the high-temperature atmosphere furnace to check the air tightness of the high-temperature atmosphere furnace; (4) is introduced intoCleaning the high-temperature atmosphere furnace for 10min by using nitrogen, closing a gas outlet of the high-temperature atmosphere furnace, and finally keeping the pressure in the atmosphere furnace at 0.02 MPa; (5) heating the high-temperature atmosphere furnace, namely firstly heating the high-temperature atmosphere furnace to 300 ℃ at the heating rate of 5 ℃/min, then heating the high-temperature atmosphere furnace to 900 ℃ at the heating rate of 6 ℃/min, and in the process, when the temperature of the high-temperature atmosphere furnace is raised to 300 ℃, introducing nitrogen, simultaneously opening a gas outlet of the high-temperature atmosphere furnace, and keeping the pressure in the high-temperature atmosphere furnace at 0.05 MPa; then heating the high-temperature atmosphere furnace to 1020 ℃ at the heating rate of 10 ℃/min, and preserving the heat at 1020 ℃ for 30 min; and finally, cooling the high-temperature atmosphere furnace to 600 ℃ at a cooling rate of 5 ℃/min, stopping heating, starting natural cooling of the atmosphere furnace, stopping introducing nitrogen when the temperature is reduced to 300 ℃, closing an air outlet of the high-temperature atmosphere furnace, and cooling to room temperature.
Finally, the ZrO sealed in example 1 was tested2The performance of the oxygen-based sensitive element and the metal flange is verified: ZrO (ZrO)2The sealing performance of the oxygen-based sensitive element and the metal flange is good under the high temperature and temperature change states, and ZrO2No damage to the oxygen-sensitive element and ZrO2The conductivity between the oxygen-based sensitive element and the metal flange is good, the compressive strength of the sealing piece is greater than 200MPa, and the performance requirement on the sealing piece in actual production is met.
Experimental example 2:
first, preparation of a glass body is performed: mixing 70% of glass powder, 7% of epoxy resin, 8% of dimethyl phthalate and 15% of ethanol according to the weight ratio, wherein the mixture is in a pasty state, performing ball milling treatment on the mixture by using a ball mill for 6 hours, and pressing the ball-milled mixture into a glass blank.
Then, carrying out pre-oxidation treatment on the metal flange: the metal flange made of kovar alloy material was pre-oxidized in a muffle furnace at 600 ℃ for 25 min.
Subsequently, ZrO is performed2Glass sealing of the oxygen-based sensitive element and the metal flange: (1) preparing a high-temperature atmosphere furnace; (2) pre-oxidized metal flange and ZrO2The oxygen-based sensitive element is fixed in a special sealing device, and the glass body is placed in ZrO2In the gap between the oxygen-based sensitive element and the metal flange; (3) placing the sealing equipment into a high-temperature atmosphere furnace, and vacuumizing the high-temperature atmosphere furnace to check the air tightness of the high-temperature atmosphere furnace; (4) introducing nitrogen to clean the high-temperature atmosphere furnace for 15min, closing an air outlet of the atmosphere furnace, and keeping the pressure in the high-temperature atmosphere furnace at 0.03 MPa; (5) and heating and cooling the high-temperature atmosphere furnace. Firstly, heating a high-temperature atmosphere furnace to 300 ℃ at the heating rate of 3 ℃/min; heating the furnace to 900 ℃ at the heating rate of 5 ℃/min, introducing nitrogen when the temperature of the high-temperature atmosphere furnace is raised to 400 ℃, simultaneously opening a gas outlet of the high-temperature atmosphere furnace, and keeping the pressure in the high-temperature atmosphere furnace at 0.04 MPa; then heating the high-temperature atmosphere furnace to 1020 ℃ at the heating rate of 8 ℃/min, and preserving the heat for 20min at the environment of 1020 ℃; and finally, cooling the high-temperature atmosphere furnace to 600 ℃ at a cooling rate of 3 ℃/min, stopping heating, enabling the high-temperature atmosphere furnace to enter a natural cooling state, stopping introducing nitrogen when the high-temperature atmosphere furnace is cooled to 300 ℃, simultaneously closing an air outlet of the high-temperature atmosphere furnace, and then naturally cooling the high-temperature atmosphere furnace to a room temperature state.
Finally, the ZrO sealed in example 2 was tested2The performance of the oxygen-based sensitive element and the metal flange is verified: ZrO (ZrO)2The sealing performance of the oxygen-based sensitive element and the metal flange is good under the high temperature and temperature change states, and ZrO2No damage of the oxygen-based sensitive element and ZrO2The conductivity between the oxygen-based sensitive element and the metal flange is good, the compressive strength of the sealing piece is greater than 200MPa, and various performance requirements on the sealing piece in actual production are met.
It should also be noted that, in the case of the embodiments of the present invention, features of the embodiments and examples may be combined with each other to obtain a new embodiment without conflict.
The above description is only an embodiment of the present invention, but the scope of the present invention is not limited thereto, and the scope of the present invention is subject to the scope of the claims.

Claims (8)

1. ZrO (ZrO)2The sealing method of the oxygen-based sensitive element and the metal flange comprises the following steps:
s1, preparing a glass blank;
s2, pre-oxidizing the metal flange; and
s3, the ZrO is pressed through the glass body2A oxygen-based sensitive element sealed to the metal flange, wherein the glass body, the metal flange and the ZrO2The oxygen-based sensitive elements have similar thermal expansion coefficients;
wherein, step S2 includes: in the air, placing the metal flange in a muffle furnace at 300-600 ℃ for pre-oxidation treatment;
step S3 includes:
s31, enabling the metal flange, the glass blank and ZrO to be arranged2The oxygen-based sensitive elements are fixedly placed into a high-temperature atmosphere furnace in sequence;
s32, carrying out air tightness inspection on the high-temperature atmosphere furnace;
s33, removing oxygen in the high-temperature atmosphere furnace; and
s34, heating the high-temperature atmosphere furnace and cooling to room temperature;
wherein the step S33 includes introducing high-purity nitrogen gas into the high-temperature atmosphere furnace.
2. ZrO according to claim 12A sealing method of an oxygen-based sensitive element and a metal flange is characterized in that,
step S1 includes: mixing the raw materials of the glass body according to the proportioning relation of 65-80% of glass powder, 5-10% of binder, 5-10% of plasticizer and 10-15% of solvent by weight ratio, carrying out ball milling treatment on the mixed raw materials, and pressing into the glass body.
3. ZrO according to claim 22A sealing method of an oxygen-based sensitive element and a metal flange is characterized in that,
the adhesive comprises an epoxy resin, the plasticizer comprises dimethyl phthalate, and the solvent comprises ethanol.
4. ZrO according to claim 12A sealing method of an oxygen-based sensitive element and a metal flange is characterized in that,
step S32 includes performing vacuum-pumping processing on the high-temperature atmosphere furnace and checking the airtightness of the high-temperature atmosphere furnace.
5. ZrO according to claim 12A sealing method of an oxygen-based sensitive element and a metal flange is characterized in that,
and step S33, opening an air outlet of the high-temperature atmosphere furnace, cleaning the high-temperature atmosphere furnace for a certain time, closing the air outlet of the atmosphere furnace, stopping or reducing the introduction of nitrogen when the pressure in the high-temperature atmosphere furnace reaches 0.01MPa-0.03MPa, and keeping the pressure.
6. ZrO according to claim 12A sealing method of an oxygen-based sensitive element and a metal flange is characterized in that,
and the step S34 comprises the steps of heating the high-temperature atmosphere furnace to 1020 ℃, preserving heat at 1020 ℃ for 20min-30min, introducing nitrogen when heating to 300 ℃ -400 ℃, opening a gas outlet of the high-temperature atmosphere furnace, keeping the pressure in the high-temperature atmosphere furnace at 0.04MPa-0.06MPa, stopping introducing nitrogen when cooling to 300 ℃ -400 ℃, and closing the gas outlet.
7. ZrO according to claim 62A sealing method of an oxygen-based sensitive element and a metal flange is characterized in that,
the process of heating the high temperature atmosphere furnace to 1020 ℃ comprises:
heating to 300 ℃ at the heating rate of 2-5 ℃/min;
heating to 900 ℃ at the heating rate of 4-6 ℃/min; and
heating to 1020 ℃ at a heating rate of 8-10 ℃/min.
8. ZrO according to claim 62A sealing method of an oxygen-based sensitive element and a metal flange is characterized in that,
and the step S34 also comprises the step of reducing the temperature of the high-temperature atmosphere furnace to 600 ℃ at the temperature reduction rate of 2-5 ℃/min, and then naturally cooling to the room temperature.
CN201910807272.5A 2019-08-28 2019-08-28 ZrO2Sealing method of oxygen-based sensitive element and metal flange Active CN110398525B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201910807272.5A CN110398525B (en) 2019-08-28 2019-08-28 ZrO2Sealing method of oxygen-based sensitive element and metal flange

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201910807272.5A CN110398525B (en) 2019-08-28 2019-08-28 ZrO2Sealing method of oxygen-based sensitive element and metal flange

Publications (2)

Publication Number Publication Date
CN110398525A CN110398525A (en) 2019-11-01
CN110398525B true CN110398525B (en) 2020-11-10

Family

ID=68329393

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201910807272.5A Active CN110398525B (en) 2019-08-28 2019-08-28 ZrO2Sealing method of oxygen-based sensitive element and metal flange

Country Status (1)

Country Link
CN (1) CN110398525B (en)

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3977540B2 (en) * 1999-02-16 2007-09-19 日本特殊陶業株式会社 Manufacturing method of temperature sensor
JP4225273B2 (en) * 2004-11-25 2009-02-18 株式会社デンソー Glow plug
CN101148322B (en) * 2007-06-29 2011-05-11 清华大学 Microcrystal glass sealing material used for solid oxide fuel battery and sealing method thereof
CN103672182A (en) * 2012-09-05 2014-03-26 北京航天试验技术研究所 Sealing method of sensor at low temperature and under high pressure
CN205347576U (en) * 2015-11-12 2016-06-29 阜南明环化工有限公司 Prevent that naphthenic acid corrodes thermocouple sleeve pipe
CN108822740B (en) * 2018-05-22 2020-08-21 中国原子能科学研究院 High-temperature-resistant inorganic sealant and preparation and sealing methods thereof

Also Published As

Publication number Publication date
CN110398525A (en) 2019-11-01

Similar Documents

Publication Publication Date Title
CN109641784B (en) Joining element made of at least partially crystallized glass and method for the production thereof
US9964502B2 (en) Thermal conductivity detector comprising a sealed cavity
JPH0536426A (en) Solid electrolytic fuel cell
GB2425605A (en) Gas Sensor For The Detection Of Combustible Gases Wherein The Electrical Contacts Pass Through Glass Bushings
CN110398525B (en) ZrO2Sealing method of oxygen-based sensitive element and metal flange
US4123344A (en) Two fire ceramic sealed oxygen sensing device and method of forming same
CN105776868A (en) High temperature-resistant and high-insulation sealing glass and preparation method thereof
CN102276150A (en) High-temperature and high-pressure resistant glass material for sealing and preparation method thereof
CN209261682U (en) It is a kind of avoid soldering when thread failure sparking plug structure
Li et al. Thermal properties and joinability investigation of BaO–SrO–SiO2–B2O3 glasses for oxygen transport membrane application
CN108822740B (en) High-temperature-resistant inorganic sealant and preparation and sealing methods thereof
RU2339028C1 (en) Detecting element of oxygen analyser and method of making it
Wei et al. Role of bonding temperature and voltage in silicon-to-glass anodic bonding
JP6769478B2 (en) Thermal mass flow sensor, manufacturing method of the thermal mass flow sensor, and thermal mass flow meter using the thermal mass flow sensor
US4270691A (en) Method of joining ceramic members and its application to oxygen sensor element manufacture
RU2298176C2 (en) Solid-electrolyte oxygen concentration detector and method of making the detector
JP2005329330A (en) Structure of window for high temperature and high pressure vessel
CN210401286U (en) Crack detection device for ceramic element of gas sensor
Holden et al. Healing of glass in humid environments
Gross-Barsnick et al. Repair Joining of Glass-Ceramic Sealants for SOC Stacks
Hatcher et al. Development and testing of an intermediate temperature glass sealant for use in mixed ionic and electronic conducting membrane reactors
CN109854388A (en) A kind of micro semiconductor sparking plug structure
KR20170077827A (en) Sensor for detecting at least one property of a measuring gas in a measuring gas chamber
CN212321501U (en) Miniature high temperature oxygen sensor based on diffusion bonding
Dai et al. The process and reliability research of glass tube sealed diode

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant