CN112255296B - Partial pressure type oxygen sensor based on ceramic co-firing technology and preparation method thereof - Google Patents
Partial pressure type oxygen sensor based on ceramic co-firing technology and preparation method thereof Download PDFInfo
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Abstract
A partial pressure type oxygen sensor based on a ceramic co-firing technology and a preparation method thereof relate to the technical field of sensor structure design and manufacture. The invention aims to solve the problems that the traditional partial pressure type oxygen sensor has poor mechanical resistance and temperature impact resistance and short service life, and the coating process is difficult when a sealed cavity is enclosed by a glass sealing glaze sealing pump pool and a concentration pool. The method comprises the following steps: stacking the pump pool and the concentration pool together to form a closed air cavity, printing volatile layer slurry in the air cavity by adopting a screen printing technology, filling the air cavity with the volatile layer slurry, and prepressing from top to bottom by adopting an isostatic pressing technology to obtain a prefabricated member; and cutting and separating the prefabricated part by adopting a scribing technology to obtain a plurality of sensors, and sintering and molding the sensors by adopting a sintering technology. The invention can obtain the partial pressure type oxygen sensor based on the ceramic co-firing technology and the preparation method thereof.
Description
Technical Field
The invention relates to the technical field of sensor structure design and manufacture, in particular to a partial pressure type oxygen sensor based on a ceramic co-firing technology and a preparation method thereof.
Background
The measurement and control of oxygen concentration are widely applied in the fields of medical instruments, biotechnology, food industry, production safety and the like, and oxygen sensors are installed in anesthesia machines, breathing machines, oxygen detectors, greenhouse gas detectors, oxygen generators, fire detectors and other equipment.
The good oxygen ion conductivity of YSZ solid electrolytes is utilized to fabricate partial pressure type oxygen sensors and limiting current type oxygen sensors. The boundary current type oxygen sensor has the characteristics of high measurement accuracy and no need of reference gas, but has the defects of poor sensor consistency and great reduction of measurement accuracy due to small hole blocking deformation and over-sensitivity of a compact diffusion barrier to temperature.
The traditional partial pressure type oxygen sensor (also called frequency conversion type oxygen sensor) is composed of a pump pool, a concentration pool and a glass sealing glaze. The glass sealing glaze has a thermal expansion coefficient which is greatly different from that of a pump pool and a concentration pool due to the difference of material properties, so that the glass sealing glaze is the weakest link of the sensor in resistance to mechanical impact and temperature impact, and an oxygen sensor prepared by adopting a glass sealing glaze sealing process is difficult to realize high-precision and high-reliability oxygen concentration measurement, so that the further development of the oxygen sensor is limited.
Disclosure of Invention
The invention aims to solve the problems of poor mechanical resistance and temperature impact resistance, short service life and high coating process difficulty when a sealed chamber is enclosed by a glass sealing glaze sealing pump pool and a concentration pool in the traditional partial pressure type oxygen sensor, and provides a partial pressure type oxygen sensor based on a ceramic co-firing process technology and a preparation method thereof.
The partial pressure type oxygen sensor based on the ceramic co-firing technology comprises a pump pool, a concentration pool, a bonding layer and an insulating layer; the periphery of the inner surface of the pump pond is provided with a bonding layer, the periphery of the inner surface of the concentration pond is provided with a bonding layer, and the bonding layer on the pump pond is connected with the bonding layer on the concentration pond through an insulating layer, so that a closed air cavity is formed inside the pump pond and the concentration pond; the inner surface of the pump pool is provided with a pump pool inner electrode, the pump pool inner electrode is positioned in the air cavity, the outer surface of the pump pool is provided with a pump pool outer electrode and a pump pool outer electrode lead wire, the pump pool is provided with a through hole a, and the pump pool inner electrode penetrates through the through hole a to reach the outer surface of the pump pool; the inner surface of the concentration tank is provided with a concentration tank inner electrode, the concentration tank inner electrode is positioned in the air chamber, the outer surface of the concentration tank is provided with a concentration tank outer electrode and a concentration tank outer electrode lead, the concentration tank is provided with a through hole b, and the concentration tank inner electrode penetrates through the through hole b to reach the outer surface of the concentration tank.
The preparation method of the partial pressure type oxygen sensor based on the ceramic co-firing technology comprises the following steps:
1. manufacturing two zirconia casting substrates to obtain a pump pool and a concentration pool, firstly, adopting a punching technology to open a through hole a on the pump pool and open a through hole b on the concentration pool, then adopting a screen printing technology to print an electrode material on the inner surface of the pump pool to form an electrode in the pump pool, respectively printing the electrode material and the electrode lead material on the outer surface of the pump pool to form an electrode outside the pump pool and an electrode lead outside the pump pool, printing the electrode material on the inner surface of the concentration pool to form an electrode in the concentration pool, respectively printing the electrode material and the electrode lead material on the outer surface of the concentration pool to form an electrode lead outside the concentration pool and an electrode lead outside the concentration pool, respectively adopting the screen printing technology to print adhesive layer slurry on the peripheral edges of the inner surfaces of the pump pool and the concentration pool to form an adhesive layer, printing the insulating layer slurry on the adhesive layer of the pump pool or the concentration pool to form an insulating layer, and finally overlapping the pump pool and the concentration pool together in a mode that the inner surfaces of the pump pool and the concentration pool are opposite to each other, and forming a closed air cavity between the pump pool and the concentration pool;
2. printing volatile layer slurry in the air chamber by adopting a screen printing technology, filling the air chamber with the volatile layer slurry, and then pre-pressing from top to bottom by adopting an isostatic pressing technology to obtain a prefabricated member; cutting and separating the prefabricated member by adopting a scribing technology to obtain a plurality of sensors, and finally sintering and molding the sensors at 1400-1500 ℃ by adopting a sintering technology to obtain a partial pressure type oxygen sensor based on a ceramic co-firing technology; the volatile layer slurry is composed of terpineol, graphite powder, a binder and a dispersing agent.
The invention has the beneficial effects that:
1. the invention relates to a preparation method of a partial pressure type oxygen sensor based on a ceramic co-firing technology, wherein a pump pool and a concentration pool are bonded together by adopting bonding layer slurry and insulating layer slurry, a closed air cavity is filled with volatile layer slurry, the volatile layer slurry disappears by glue removal and combustion to form a closed cavity, and the pump pool, the concentration pool, the insulating layer slurry and the bonding layer slurry are sintered to form the co-firing ceramic body oxygen sensor. The traditional partial pressure type oxygen sensor adopts a glass sealing glaze to bond a pump pool and a concentration pool, and because of the difference of material properties, the thermal expansion coefficient of the glass sealing glaze is greatly different from that of the pump pool and the concentration pool, so that the glass sealing glaze is the weakest link of the sensor in resisting mechanical impact and temperature impact. The bonding slurry and the insulating slurry are designed according to the formula, the sintering shrinkage and the thermal expansion coefficient of the bonding slurry and the insulating slurry are matched with the pump pool and the concentration pool, the pump pool and the concentration pool can be well connected, and the defects that the traditional partial pressure type oxygen sensor has poor mechanical resistance and temperature impact resistance and short service life, and a coating process is difficult and large-scale production is not facilitated when a sealed cavity is enclosed by the glass sealing glaze sealing pump pool and the concentration pool are overcome. The partial pressure type oxygen sensor has stable working performance under the high-temperature environment of 400-700 ℃, can detect the oxygen concentration range of 0.1-99 percent, improves the mechanical impact resistance strength from 4G to 10G, and prolongs the service life from 2 years to 5 years.
2. The processes of through hole conduction, cavity formation, electrode formation and insulating layer and bonding layer formation of the partial pressure type oxygen sensor all adopt printing processes, so that the preparation process flow of the oxygen sensor is simple, the automation degree is high, the yield is greatly improved, and the mass production of the sensor can be realized.
3. The invention is based on the ceramic co-firing process technology, the process mainly comprises the ceramic co-firing process technology including the punching process, the screen printing process, the laminating process, the cutting process and the like, the bonding layer slurry and the insulating layer slurry are prepared and used for replacing the glass sealing glaze, the two slurries play the roles of insulation and bonding, and the invention has the characteristics of simple manufacturing method and process, mature technology, low cost, batch production and the like.
The invention can obtain the partial pressure type oxygen sensor based on the ceramic co-firing technology and the preparation method thereof.
Drawings
Fig. 1 is a schematic structural view of a partial pressure type oxygen sensor of a conventional structure, wherein 1 represents a pump cell, 2 represents a concentration cell, 3 represents an air chamber, 4 represents an external electrode of the pump cell, 5 represents an external electrode of the concentration cell, 6 represents an internal electrode of the pump cell, 7 represents an internal electrode of the concentration cell, and 14 represents a glass sealing glaze;
fig. 2 isbase:Sub>A cross-sectional viewbase:Sub>A-base:Sub>A of the partial pressure type oxygen sensor based on the ceramic co-firing process technology of example 1, wherein 1 representsbase:Sub>A pumping cell, 2 representsbase:Sub>A concentration cell, 3 represents an air chamber, 4 represents an external electrode of the pumping cell, 5 represents an external electrode of the concentration cell, 6 represents an internal electrode of the pumping cell, 7 represents an internal electrode of the concentration cell, 8 represents an adhesive layer, and 9 represents an insulating layer;
FIG. 3 is a schematic assembly diagram of a partial pressure type oxygen sensor based on the ceramic co-firing process technology in example 1;
fig. 4 is a schematic front structure diagram of a partial pressure type oxygen sensor based on the ceramic co-firing process technology in embodiment 1, where 10 represents a through hole a, and 11 represents an external electrode lead of a pump chamber;
fig. 5 is a schematic diagram of a reverse structure of the partial pressure type oxygen sensor based on the ceramic co-firing technology in example 1, where 12 represents a through hole b, and 13 represents an external electrode lead of the concentration cell.
Detailed Description
The first specific implementation way is as follows: the partial pressure type oxygen sensor based on the ceramic co-firing technology comprises a pump pool 1, a concentration pool 2, a bonding layer 8 and an insulating layer 9; the periphery of the inner surface of the pump pool 1 is provided with a bonding layer 8, the periphery of the inner surface of the concentration pool 2 is provided with the bonding layer 8, the bonding layer 8 on the pump pool 1 is connected with the bonding layer 8 on the concentration pool 2 through an insulating layer 9, so that a closed air cavity 3 is formed in the pump pool 1 and the concentration pool 2; the inner surface of the pump pool 1 is provided with a pump pool inner electrode 6, the pump pool inner electrode 6 is positioned in the air cavity 3, the outer surface of the pump pool 1 is provided with a pump pool outer electrode 4 and a pump pool outer electrode lead 11, the pump pool 1 is provided with a through hole a 10, and the pump pool inner electrode 6 penetrates through the through hole a 10 to reach the outer surface of the pump pool 1; the inner surface of the concentration tank 2 is provided with a concentration tank inner electrode 7, the concentration tank inner electrode 7 is positioned in the air chamber 3, the outer surface of the concentration tank 2 is provided with a concentration tank outer electrode 5 and a concentration tank outer electrode lead 13, the concentration tank 2 is provided with a through hole b 12, and the concentration tank inner electrode 7 penetrates through the through hole b 12 to reach the outer surface of the concentration tank 2.
The second embodiment is as follows: the first difference between the present embodiment and the present embodiment is: the pump pool inner electrode 6 and the pump pool outer electrode 4 are same in size and symmetrically arranged, the concentration pool inner electrode 7 and the concentration pool outer electrode 5 are same in size and symmetrically arranged, and the through hole a 10 and the through hole b 12 are same in inner diameter and coincide in central line.
Other steps are the same as in the first embodiment.
The third concrete implementation mode: the preparation method of the partial pressure type oxygen sensor based on the ceramic co-firing technology is completed according to the following steps:
1. manufacturing two zirconium oxide casting substrates to obtain a pump pool 1 and a concentration pool 2, firstly, adopting a punching technology to open a through hole a 10 on the pump pool 1 and open a through hole b 12 on the concentration pool 2, then adopting a screen printing technology to print an electrode material on the inner surface of the pump pool 1 to form a pump pool inner electrode 6, respectively printing an electrode material and an electrode lead material on the outer surface of the pump pool 1 to form a pump pool outer electrode 4 and a pump pool outer electrode lead 11, respectively printing an electrode material on the inner surface of the concentration pool 2 to form a concentration pool inner electrode 7, respectively printing an electrode material and an electrode lead material on the outer surface of the concentration pool 2 to form a concentration pool outer electrode 5 and a concentration pool outer electrode lead 13, then adopting a screen printing technology to respectively print paste on the peripheral edges of the inner surfaces of the pump pool 1 and the concentration pool 2 to form an adhesive layer 8, printing insulating layer paste on the adhesive layer 8 of the pump pool 1 or the concentration pool 2 to form an insulating layer 9, and finally overlapping the pump pool 1 and the concentration pool 2 in a mode that the inner surfaces of the pump pool 1 and the concentration pool 2 are opposite to each other, and forming an air cavity of the concentration pool 2;
2. printing volatile layer slurry in the air chamber 3 by adopting a screen printing technology, filling the air chamber 3 with the volatile layer slurry, and then pre-pressing from top to bottom by adopting an isostatic pressing technology to obtain a prefabricated member; cutting and separating the prefabricated member by adopting a scribing technology to obtain a plurality of sensors, and finally sintering and molding the sensors at 1400-1500 ℃ by adopting a sintering technology to obtain a partial pressure type oxygen sensor based on a ceramic co-firing technology; the volatile layer slurry is composed of terpineol, graphite powder, a binder and a dispersing agent.
The beneficial effects of the embodiment are as follows:
1. according to the preparation method of the partial pressure type oxygen sensor based on the ceramic co-firing technology, the pump pool and the concentration pool are bonded together by adopting the bonding layer slurry and the insulating layer slurry, the closed air cavity is filled with the volatile layer slurry, the volatile layer slurry disappears through binder removal combustion to form the closed cavity, and the pump pool, the concentration pool, the insulating layer slurry and the bonding layer slurry are sintered to form the co-firing ceramic body oxygen sensor. The traditional partial pressure type oxygen sensor adopts a glass sealing glaze to bond a pump pool and a concentration pool, and because of the difference of material properties, the thermal expansion coefficient of the glass sealing glaze is greatly different from that of the pump pool and the concentration pool, so that the glass sealing glaze is the weakest link of the sensor in resisting mechanical impact and temperature impact. According to the embodiment, the bonding slurry and the insulating slurry are designed according to the formula, the sintering shrinkage and the thermal expansion coefficient of the bonding slurry are matched with those of the pump pool and the concentration pool, the pump pool and the concentration pool can be well connected, and the defects that the traditional partial pressure type oxygen sensor is poor in mechanical resistance and temperature impact resistance and short in service life, and a coating process is difficult and large-scale production is not facilitated when a sealed cavity is defined by sealing the pump pool and the concentration pool with glass sealing glaze are overcome. The partial pressure type oxygen sensor has stable working performance in a high-temperature environment of 400-700 ℃, can detect the oxygen concentration range of 0.1-99%, improves the mechanical impact resistance strength from 4G to 10G, and prolongs the service life from 2 years to 5 years.
2. The processes of through hole conduction, cavity formation, electrode formation and insulating layer and bonding layer formation of the partial pressure type oxygen sensor of the embodiment all adopt printing processes, so that the preparation process flow of the oxygen sensor is simple, the automation degree is high, the yield is greatly improved, and the mass production of the sensor can be realized.
3. The embodiment is based on a ceramic co-firing process technology, the process mainly comprises a punching process, a screen printing process, a laminating process, a cutting process and the like, the bonding layer slurry and the insulating layer slurry are prepared and used for replacing the glass sealing glaze, the two slurries play roles of insulation and bonding, and the ceramic co-firing process technology has the characteristics of simple manufacturing method and process, mature technology, low cost, batch production and the like.
The fourth concrete implementation mode: the third difference between the present embodiment and the specific embodiment is: the zirconia casting substrate in the step one is formed by Y 2 O 3 Stabilized ZrO 2 Solid electrolyte ceramic, said Y 2 O 3 Stabilized ZrO 2 Y in solid electrolyte ceramics 2 O 3 The molar content of (b) is 5% -8%.
The other steps are the same as those in the third embodiment.
The fifth concrete implementation mode: the third or fourth difference between the present embodiment and the specific embodiment is: and the electrode material and the electrode lead material in the step one are both metal platinum.
The other steps are the same as those of the third or fourth embodiment.
The sixth specific implementation mode is as follows: the difference between this embodiment and one of the third to fifth embodiments is: the bonding layer slurry in the first step is prepared from a solvent, a binder, an organic additive and solid-phase powder, wherein the mass ratio of the solvent to the binder to the organic additive to the solid-phase powder is (20-40): (4-6): (1-1.5): (55-65).
The other steps are the same as those in the third to fifth embodiments.
The seventh concrete implementation mode: the third to sixth differences from the present embodiment are as follows: the solvent is terpineol or carbitol, the binder is polyvinyl butyral or ethyl cellulose, the organic additive is dioctyl phthalate, dibutyl phthalate or castor oil, the solid phase powder is zirconia powder, and the zirconia powder is Y 2 O 3 Stabilized zirconia powder, Y 2 O 3 Stabilized zirconia powder Y 2 O 3 The molar content of (A) is 5-8%.
The other steps are the same as those in the third to sixth embodiments.
The specific implementation mode eight: the difference between this embodiment and one of the third to seventh embodiments is: the insulating layer slurry in the first step is prepared from a solvent, a binder, an organic additive and solid-phase powder, wherein the mass ratio of the solvent to the binder to the organic additive to the solid-phase powder is (25-35): (4-6): (1-1.5): (60 to 70).
The other steps are the same as those of the third to seventh embodiments.
The specific implementation method nine: the third to eighth differences from the present embodiment are: the solvent is terpineol or carbitol, the binder is polyvinyl butyral or ethyl cellulose, the organic additive is dioctyl phthalate, dibutyl phthalate or castor oil, the solid phase powder body is composed of alumina powder and zirconia powder body, and the zirconia powder body is Y 2 O 3 The stable zirconia powder comprises 20-50% of the mass fraction; said Y is 2 O 3 Stabilized zirconia powder Y 2 O 3 The molar content of (A) is 3-8%.
The other steps are the same as those in the third to eighth embodiments.
The detailed implementation mode is ten: the third to ninth differences from the present embodiment are as follows: the bonding layer slurry and the insulating layer slurry are prepared according to the following steps: putting the weighed solid phase powder into a drying oven, and drying for 12 hours at the temperature of 100-120 ℃ to obtain a substance A; mixing and stirring the weighed solvent, the binder and the organic additive for 24 hours to obtain a substance B; and placing the substance A and the substance B in a ball milling tank, ball milling for 24 hours at the rotating speed of 80-150 rpm, and then degassing and defoaming in a vacuum environment to obtain slurry, wherein the vacuum pressure is-1 kPa.
The other steps are the same as those in the third to ninth embodiments.
The following examples were used to demonstrate the beneficial effects of the present invention:
example 1: the partial pressure type oxygen sensor based on the ceramic co-firing technology comprises a pump pool 1, a concentration pool 2, a bonding layer 8 and an insulating layer 9; the periphery of the inner surface of the pump pool 1 is provided with an adhesive layer 8, the periphery of the inner surface of the concentration pool 2 is provided with the adhesive layer 8, the adhesive layer 8 on the pump pool 1 is connected with the adhesive layer 8 on the concentration pool 2 through an insulating layer 9, so that a closed air cavity 3 is formed inside the pump pool 1 and the concentration pool 2; the inner surface of the pump pool 1 is provided with a pump pool inner electrode 6, the pump pool inner electrode 6 is positioned in the air cavity 3, the outer surface of the pump pool 1 is provided with a pump pool outer electrode 4 and a pump pool outer electrode lead 11, the pump pool 1 is provided with a through hole a 10, and the pump pool inner electrode 6 penetrates through the through hole a 10 to reach the outer surface of the pump pool 1; the inner surface of the concentration tank 2 is provided with a concentration tank inner electrode 7, the concentration tank inner electrode 7 is positioned in the air chamber 3, the outer surface of the concentration tank 2 is provided with a concentration tank outer electrode 5 and a concentration tank outer electrode lead 13, the concentration tank 2 is provided with a through hole b 12, and the concentration tank inner electrode 7 penetrates through the through hole b 12 to reach the outer surface of the concentration tank 2.
The pump pool inner electrode 6 and the pump pool outer electrode 4 are same in size and are symmetrically arranged, the concentration pool inner electrode 7 and the concentration pool outer electrode 5 are same in size and are symmetrically arranged, and the through hole a 10 and the through hole b 12 are same in inner diameter and coincide in central line.
Example 2: the preparation method of the partial pressure type oxygen sensor based on the ceramic co-firing technology comprises the following steps:
temperature and humidity data of a production site are collected, and the component proportion is finely adjusted to enable the viscosity of the slurry to meet the requirements of different screen printing machines on the plasticity, thixotropy and dispersion uniformity of the slurry.
1. Preparing bonding layer slurry and insulating layer slurry: putting the weighed solid phase powder into a drying oven, and drying for 12 hours at 120 ℃ to obtain a substance A; mixing and stirring the weighed solvent, the binder and the organic additive for 24 hours to obtain a substance B; and placing the substance A and the substance B in a ball milling tank, carrying out ball milling for 24h at the rotating speed of 150rpm, and then carrying out degassing and defoaming in a vacuum environment to obtain slurry, wherein the vacuum pressure is-1 kPa.
2. Using Y 2 O 3 Stabilized ZrO 2 Preparing two zirconia tape-casting substrates by using solid electrolyte ceramics to obtain a pump pool 1 and a concentrateA difference pool 2, the Y 2 O 3 Stabilized ZrO 2 Y in solid electrolyte ceramics 2 O 3 Is 8%; firstly, a through hole a 10 is formed in a pump pool 1 by adopting a punching technology, a through hole b 12 is formed in a concentration pool 2 by adopting a punching technology, then an electrode material is printed on the inner surface of the pump pool 1 by adopting a screen printing technology to form a pump pool inner electrode 6, an electrode material and an electrode lead material are respectively printed on the outer surface of the pump pool 1 to form a pump pool outer electrode 4 and a pump pool outer electrode lead 11, an electrode material is printed on the inner surface of the concentration pool 2 to form a concentration pool inner electrode 7, an electrode material and an electrode lead material are respectively printed on the outer surface of the concentration pool 2 to form a concentration pool outer electrode 5 and a concentration pool outer electrode lead 13, then an adhesive layer slurry is printed on the peripheral edges of the inner surfaces of the pump pool 1 and the concentration pool 2 by adopting a screen printing technology to form an adhesive layer 8 by adopting a thick film technology, an insulating layer slurry is printed on the adhesive layer slurry of the pump pool 1 or the adhesive layer 8 of the concentration pool 2 to form an insulating layer 9 by adopting a thick film technology, and finally the pump pool 1 and the concentration pool 2 are stacked together in a mode that the pump pool 1 and the inner surface of the concentration pool 2 are opposite, a sealed air cavity 3 is formed between the pump pool 1 and the concentration pool 2, and plays a supporting role;
the electrode material and the electrode lead material are both metal platinum; the bonding layer slurry is prepared from a solvent, a binder, an organic additive and solid-phase powder through the working procedures of mixing, ball milling, defoaming and the like, wherein the mass ratio of the solvent to the binder to the organic additive to the solid-phase powder is 40:6:1.5:65, the solvent is terpineol, the binder is polyvinyl butyral, the organic additive is dioctyl phthalate, the solid phase powder is zirconia powder, and the zirconia powder is Y 2 O 3 Stabilized zirconia powder, Y 2 O 3 Stabilized zirconia powder Y 2 O 3 The molar content of (a) is 8%. The insulating layer slurry is prepared from a solvent, a binder, an organic additive and solid-phase powder through the procedures of mixing, ball milling, defoaming and the like, wherein the mass ratio of the solvent to the binder to the organic additive to the solid-phase powder is 35:6:1.5:70, the solvent is terpineol, the binder is polyvinyl butyral, and the organic additive is o-butylDioctyl phthalate, solid phase powder body is composed of alumina powder body and zirconia powder body, the zirconia powder body is Y 2 O 3 Stable zirconia powder with the mass fraction of 50 percent; said Y 2 O 3 Y in stabilized zirconia powder 2 O 3 The molar content of (b) is 8%.
3. Printing volatile layer slurry in the air chamber 3 by adopting a screen printing technology, filling the air chamber 3 with the volatile layer slurry, and then pre-pressing from top to bottom by adopting an isostatic pressing technology to obtain a prefabricated member; cutting and separating the prefabricated part by adopting a scribing technology to obtain a plurality of sensors, and finally sintering and molding the sensors at 1500 ℃ by adopting a sintering technology to obtain a partial pressure type oxygen sensor based on a ceramic co-firing technology; the volatile layer slurry consists of terpineol, graphite powder, a binder and a dispersing agent.
The constant current source applies current with constant magnitude and alternating direction to the pump pool 1 to realize the concentration voltage inside and outside the concentration pool 2 at E 1 To E 2 The range is alternatively changed, and the concentration difference voltage inside and outside the concentration pool 2 is measured to be E by a time measuring instrument 1 To E 2 The time t of the range change realizes the oxygen partial pressure P of the detected gas 1 The measurement of (2).
The partial pressure type oxygen sensor based on the ceramic co-firing technology prepared in the embodiment is subjected to related performance tests, and the test results show that: the partial pressure type oxygen sensor has stable working signals in a high-temperature environment of 400-700 ℃, can detect the oxygen concentration range of 0.1-99%, improves the mechanical impact resistance strength from 4G to 10G, and prolongs the service life from 2 years to 5 years.
Claims (9)
1. The preparation method of the partial pressure type oxygen sensor based on the ceramic co-firing technology is characterized by comprising the following steps of:
1. manufacturing two zirconia tape casting substrates to obtain a pump pool (1) and a concentration pool (2), firstly, adopting a punching technology to open a through hole a (10) on the pump pool (1) and open a through hole b (12) on the concentration pool (2), then, an electrode material is printed on the inner surface of the pump pool (1) by adopting a screen printing technology to form a pump pool inner electrode (6), electrode materials and electrode lead materials are respectively printed on the outer surface of the pump pool (1) to form a pump pool outer electrode (4) and a pump pool outer electrode lead (11), and printing electrode material on the inner surface of the concentration cell (2) to form an electrode (7) in the concentration cell, respectively printing an electrode material and an electrode lead material on the outer surface of the concentration cell (2) to form a concentration cell outer electrode (5) and a concentration cell outer electrode lead (13), respectively printing bonding layer slurry on the peripheral edges of the inner surfaces of the pump cell (1) and the concentration cell (2) by adopting a screen printing technology to form a bonding layer (8), printing insulating layer slurry on a bonding layer (8) of the pump pool (1) or the concentration pool (2) to form an insulating layer (9), and finally stacking the pump pool (1) and the concentration pool (2) together in a mode that the pump pool (1) is opposite to the inner surface of the concentration pool (2), wherein a closed air cavity (3) is formed between the pump pool (1) and the concentration pool (2);
2. printing volatile layer slurry in the air chamber (3) by adopting a screen printing technology, filling the air chamber (3) with the volatile layer slurry, and then pre-pressing from top to bottom by adopting an isostatic pressing technology to obtain a prefabricated member; cutting and separating the prefabricated member by adopting a scribing technology to obtain a plurality of sensors, and finally sintering and molding the sensors at 1400-1500 ℃ by adopting a sintering technology to obtain a partial pressure type oxygen sensor based on a ceramic co-firing technology;
the partial pressure type oxygen sensor based on the ceramic co-firing technology comprises a pump pool (1), a concentration pool (2), a bonding layer (8) and an insulating layer (9); the periphery of the inner surface of the pump pool (1) is provided with a bonding layer (8), the periphery of the inner surface of the concentration pool (2) is provided with the bonding layer (8), the bonding layer (8) on the pump pool (1) is connected with the bonding layer (8) on the concentration pool (2) through an insulating layer (9), so that a closed air cavity (3) is formed inside the pump pool (1) and the concentration pool (2); the inner surface of the pump pool (1) is provided with a pump pool inner electrode (6), the pump pool inner electrode (6) is positioned in the air cavity (3), the outer surface of the pump pool (1) is provided with a pump pool outer electrode (4) and a pump pool outer electrode lead (11), the pump pool (1) is provided with a through hole a (10), and the pump pool inner electrode (6) penetrates through the through hole a (10) to reach the outer surface of the pump pool (1); the inner surface of the concentration tank (2) is provided with a concentration tank inner electrode (7), the concentration tank inner electrode (7) is positioned in the air chamber (3), the outer surface of the concentration tank (2) is provided with a concentration tank outer electrode (5) and a concentration tank outer electrode lead (13), the concentration tank (2) is provided with a through hole b (12), and the concentration tank inner electrode (7) penetrates through the through hole b (12) to reach the outer surface of the concentration tank (2).
2. The method for preparing the partial pressure type oxygen sensor based on the ceramic co-firing process technology as claimed in claim 1, wherein the zirconia casting substrate in the first step is Y 2 O 3 Stabilized ZrO 2 Solid electrolyte ceramic, said Y 2 O 3 Stabilized ZrO 2 Y in solid electrolyte ceramic 2 O 3 The molar content of (b) is 5% -8%.
3. The method for preparing the partial pressure type oxygen sensor based on the ceramic co-firing process technology as claimed in claim 1, wherein the electrode material and the electrode lead material in the first step are both platinum metal.
4. The method for preparing the partial pressure type oxygen sensor based on the ceramic co-firing process technology as claimed in claim 1, wherein the bonding layer slurry in the step one is prepared from a solvent, a binder, an organic additive and solid-phase powder, and the mass ratio of the solvent, the binder, the organic additive and the solid-phase powder is (20-40): (4-6): (1-1.5): (55 to 65).
5. The method for preparing the pressure-dividing type oxygen sensor based on the ceramic co-firing process technology as claimed in claim 4, wherein the solvent is terpineol or carbitol, the binder is polyvinyl butyral or ethyl cellulose, the organic additive is dioctyl phthalate, dibutyl phthalate or castor oil, the solid phase powder is zirconia powder, and the zirconia powder is Y 2 O 3 Stabilized zirconia powder, Y 2 O 3 Stabilized zirconia powder Y 2 O 3 The molar content of (A) is 5-8%.
6. The method for preparing the partial pressure type oxygen sensor based on the ceramic co-firing process technology as claimed in claim 1, wherein the insulating layer slurry in the step one is prepared from a solvent, a binder, an organic additive and solid-phase powder, and the mass ratio of the solvent, the binder, the organic additive and the solid-phase powder is (25-35): (4-6): (1-1.5): (60-70).
7. The method for preparing a pressure-dividing type oxygen sensor based on the ceramic co-firing technology of claim 6, wherein the solvent is terpineol or carbitol, the binder is polyvinyl butyral or ethyl cellulose, the organic additive is dioctyl phthalate, dibutyl phthalate or castor oil, the solid phase powder is composed of alumina powder and zirconia powder, and the zirconia powder is Y 2 O 3 The stable zirconia powder comprises 20-50% of the mass fraction; said Y is 2 O 3 Y in stabilized zirconia powder 2 O 3 The molar content of (A) is 3-8%.
8. The method for preparing the partial pressure type oxygen sensor based on the ceramic co-firing process technology as claimed in claim 4 or 6, wherein the bonding layer slurry and the insulating layer slurry are prepared by the following steps: putting the weighed solid phase powder into a drying oven, and drying for 12 hours at the temperature of 100-120 ℃ to obtain a substance A; mixing and stirring the weighed solvent, the binder and the organic additive for 24 hours to obtain a substance B; and placing the substance A and the substance B in a ball milling tank, ball milling for 24 hours at the rotating speed of 80-150 rpm, and then degassing and defoaming in a vacuum environment to obtain slurry, wherein the vacuum pressure is-1 kPa.
9. The method for preparing the partial pressure type oxygen sensor based on the ceramic co-firing process technology according to claim 1, wherein the pump cell inner electrode (6) and the pump cell outer electrode (4) are the same in size and are symmetrically arranged, the concentration cell inner electrode (7) and the concentration cell outer electrode (5) are the same in size and are symmetrically arranged, and the through hole a (10) and the through hole b (12) have the same inner diameter and coincide with each other.
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