WO2014051176A1 - Composition d'isolant pour sonde à oxygène et sonde à oxygène l'utilisant - Google Patents

Composition d'isolant pour sonde à oxygène et sonde à oxygène l'utilisant Download PDF

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WO2014051176A1
WO2014051176A1 PCT/KR2012/007830 KR2012007830W WO2014051176A1 WO 2014051176 A1 WO2014051176 A1 WO 2014051176A1 KR 2012007830 W KR2012007830 W KR 2012007830W WO 2014051176 A1 WO2014051176 A1 WO 2014051176A1
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composition
aluminosilicate glass
oxygen sensor
insulator composition
glass powder
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Korean (ko)
Inventor
김경원
윤상옥
정광현
김관수
강현규
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Kyungwon Industry Co Ltd
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Kyungwon Industry Co Ltd
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Priority to PCT/KR2012/007830 priority Critical patent/WO2014051176A1/fr
Priority to KR1020157007693A priority patent/KR20150073164A/ko
Publication of WO2014051176A1 publication Critical patent/WO2014051176A1/fr
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/02—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of inorganic substances
    • H01B3/12—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of inorganic substances ceramics
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B18/00—Layered products essentially comprising ceramics, e.g. refractory products
    • 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
    • C03C14/00—Glass compositions containing a non-glass component, e.g. compositions containing fibres, filaments, whiskers, platelets, or the like, dispersed in a glass matrix
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    • 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
    • C03C3/00—Glass compositions
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    • C03C3/00—Glass compositions
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    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/083—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
    • C03C3/085—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal
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    • C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
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    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/03—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on magnesium oxide, calcium oxide or oxide mixtures derived from dolomite
    • C04B35/04—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on magnesium oxide, calcium oxide or oxide mixtures derived from dolomite based on magnesium oxide
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    • 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
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    • G01N27/403—Cells and electrode assemblies
    • G01N27/406—Cells and probes with solid electrolytes
    • G01N27/407—Cells and probes with solid electrolytes for investigating or analysing gases
    • G01N27/4071—Cells and probes with solid electrolytes for investigating or analysing gases using sensor elements of laminated structure
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    • 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
    • C03C2214/00—Nature of the non-vitreous component
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    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
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    • C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3427—Silicates other than clay, e.g. water glass
    • C04B2235/3436—Alkaline earth metal silicates, e.g. barium silicate
    • C04B2235/3445—Magnesium silicates, e.g. forsterite
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    • C04B2237/345—Refractory metal oxides
    • C04B2237/348—Zirconia, hafnia, zirconates or hafnates

Definitions

  • the present invention relates to an insulator composition for an oxygen sensor, and more particularly to an insulator composition for an oxygen sensor that is excellent in airtightness and electrical insulation as an insulating layer and has excellent adhesion to a solid electrolyte layer.
  • the present invention also relates to an oxygen sensor using the insulator composition.
  • the engine of an automobile changes the output, fuel consumption and exhaust gas amount of the engine according to the air-fuel ratio, which is a mixture ratio of air and fuel, it is necessary to control the engine to maintain an optimum air-fuel ratio at all times. In particular, such efficient control results in energy savings and reduction of harmful emissions.
  • This air-fuel ratio is obtained by measuring the content of oxygen contained in the exhaust gas emitted from the engine of the vehicle, the oxygen sensor is usually used for such a measurement.
  • the oxygen sensor transmits the internal both ends of the voltage generated according to the oxygen content of the exhaust gas to the ECU (Electronic Control Unit), which is an engine control device, and the ECU flows into the engine based on the voltage data received from the oxygen sensor.
  • the air-fuel ratio is controlled by adjusting the fuel supply amount.
  • the flat plate type oxygen sensor can have a smaller size than the tube type and can shorten the time to start the sensor.
  • Such a plate-type oxygen sensor is well disclosed in DE2907032 A1 (published on August 28, 1980) and WO 1998/30984 (published on July 16, 1998).
  • FIG. 1 schematically shows a structure of a general flat plate type oxygen sensor.
  • the general flat plate type oxygen sensor 100 includes a sensor unit 120 on a substrate 170 such as alumina, and a heater unit 140 connected to the electrical insulating layer 140. .
  • the sensor unit 120 includes a measurement electrode 122 and a reference electrode 124 disposed to face each other with the solid electrolyte layer 123 interposed therebetween.
  • a solid electrolyte layer 125 having a reference channel 127 through which (reference) air flows is positioned below the reference electrode 124, and an upper end of the measurement electrode 122 is a protective layer that is a porous oxide film ( 121).
  • the solid electrolyte layers 123 and 125 have oxygen ion conductivity and generally have a stabilized zirconia (YSZ) composition.
  • the measuring electrode 122 faces the exhaust gas and the reference electrode 124 faces the (reference) atmosphere, an electric potential difference is generated between the two electrodes, thereby detecting such a voltage, and thus the oxygen content in the exhaust gas. Is detected.
  • the heater unit 13 includes a heating element, that is, a resistance heating element 142, the operation of the sensor unit 120 by heating to the operating temperature of the oxygen sensor (for example, 450 ⁇ 900 °C) Make it happen quickly.
  • a heating element that is, a resistance heating element 142
  • the insulating layer 140 is generally made of alumina (Al 2 O 3 ) composition.
  • alumina (Al 2 O 3 ) composition has a different sintering behavior than that of the stabilized zirconia (YSZ) composition of the solid electrolyte layer 125, so that the alumina (Al 2 O 3 ) composition is inevitably formed as a porous body to compensate for the thermal expansion coefficient. Due to the porosity, since the exhaust gas easily diffuses into the reference atmosphere in the reference channel 127 and contaminates it, the measurement value of the sensor unit 120 becomes unstable and causes a fatal problem that causes damage to the heater unit.
  • WO 1998/30984 discloses a composition composed of a crystalline nonmetallic material such as alumina and a glass forming material of alkaline earth silicate glass. Such a composition can control the plastic deformation according to the compressive stress and form an insulating layer having excellent airtightness by using the softening property of the glass, thereby compensating for the different sintering behavior and coefficient of thermal expansion between alumina and stabilized zirconia.
  • a fine powder having a particle size of d 50 ⁇ 0.4 ⁇ m of crystalline nonmetallic materials such as alumina should be used, and a large amount of glass forming material made of alkaline earth silicate glass is used at 50 wt%. Accordingly, there is a problem that the lifetime of the oxygen sensor is limited as the thermal conductivity of the insulating layer decreases.
  • an object of the present invention is to provide an insulator composition for an oxygen sensor having excellent airtightness and electrical insulation and excellent adhesion with a solid electrolyte layer.
  • Insulator composition for an oxygen sensor according to an aspect of the present invention for achieving the above object may include one or more of magnesia, sodium aluminosilicate glass and calcium aluminosilicate glass as a sintering aid.
  • the content of the sintering aid may be 10 ⁇ 40wt%, preferably 10 ⁇ 30wt% relative to the total amount of the insulator composition.
  • composition of the sodium aluminosilicate glass may include components in the following contents:
  • composition of the calcium aluminosilicate glass may include components of the following contents:
  • the firing temperature of the insulator composition may be in the range of 1300 ⁇ 1500 °C.
  • the oxygen sensor according to another aspect of the present invention comprises a solid electrolyte layer, a measurement electrode attached to each surface of the solid electrolyte layer, respectively, the measurement electrode facing the exhaust gas and the reference electrode facing the atmosphere and A sensor unit for detecting oxygen concentration by detecting a potential difference between the reference electrodes;
  • An insulating layer which is integrally bonded to the lower surface of the sensor part and is made of an insulator composition comprising at least one of sodium aluminosilicate glass and calcium aluminosilicate glass as magnesia and a sintering aid and bonded to the solid electrolyte layer;
  • Including a heating element embedded therein may include a heater unit for heating the sensor unit.
  • FIG. 1 is a schematic structural diagram of a general flat plate type oxygen sensor.
  • Figure 2 is a flow chart of the manufacturing process by the oxide mixing method according to an embodiment of the present invention.
  • Figure 3 is a graph of the change in relative density according to the addition ratio and sintering temperature when low alkali aluminosilicate glass powder is added to magnesia as embodiments of the present invention.
  • Figure 4 is a graph of the change in relative density according to the addition ratio and sintering temperature when the alkali-free aluminosilicate glass powder is added to magnesia as another embodiment of the present invention.
  • FIG. 5 is a crystal phase analysis of a laminate co-fired at 1350 ° C. by stacking an insulating layer made of a composition in which calcium aluminosyl case glass powder is added to magnesia and a solid electrolyte layer of a stabilized zirconia (YSZ) composition according to the present invention.
  • XRD X-ray diffraction analysis
  • FIG. 6 is a scanning electron microscope (FE-SEM) photograph of the laminate of FIG.
  • the present invention relates to an insulator composition that can be effectively used as an insulating layer (eg, "140" in FIG. 1) in the aforementioned flat plate oxygen sensor (eg, "100" in FIG. 1).
  • an insulator composition that can be effectively used as an insulating layer (eg, "140" in FIG. 1) in the aforementioned flat plate oxygen sensor (eg, "100” in FIG. 1).
  • excellent airtightness and insulation resistance are required for the insulator composition, and as a requirement for having such characteristics, the insulator composition should have a relative density of 95% or more and a specific resistance of 1 M ⁇ ⁇ cm or more.
  • magnesia (MgO) composition can replace the conventional alumina composition as the insulator composition for the oxygen sensor.
  • the thermal conductivity of alumina is 28 ⁇ 32W / (m * K), while magnesia is 45 ⁇ 60W / (m * K), which is twice as good as alumina. That is, the magnesia composition has a similar thermal expansion coefficient and high thermal conductivity to Yttria Stabilized Zirconia (YSZ) ceramic of the solid electrolyte layer (eg, “125” in FIG. 1).
  • YSZ Yttria Stabilized Zirconia
  • the inventors of the present invention when the alkali aluminosilicate and / or alkali-free aluminosilicate glass powder is added to the magnesia (MgO) as a sintering aid, it is possible to co-fire with the solid electrolyte layer, thermal conductivity, insulation and It was found that the sintering characteristics were excellent.
  • MgO magnesia
  • composition formula of the insulator composition for an oxygen sensor according to the present invention is as follows:
  • x is a wt% unit and the glass powder is a low alkali aluminosilicate glass powder or an alkali free aluminosilicate glass powder.
  • the particle size of these powders is preferably in the range of 1 to 2 ⁇ m.
  • the low alkali aluminosilicate glass powder composition may be sodium aluminosilicate, and includes the following components. Wherein each wt% is relative to the total low alkali aluminosilicate glass powder composition:
  • the components of the low alkali aluminosilicate glass powder composition preferably have the following composition ratio. Wherein each wt% is relative to the total low alkali aluminosilicate glass powder composition:
  • alkali-free aluminosilicate glass composition may be calcium aluminosilicate, and includes the following. Wherein each wt% is relative to the total alkali free aluminosilicate glass powder composition:
  • the components of the alkali-free aluminosilicate glass powder composition preferably have the following composition ratio. Wherein each wt% is relative to the total alkali free aluminosilicate glass powder composition:
  • the insulator composition for an oxygen sensor according to the present invention may be prepared by various manufacturing methods known in the art, including an oxide mixing method and a thick film printing method such as a doctor blade.
  • Fig. 2 illustrates a manufacturing process by the oxide mixing method, but the manufacturing method of the present invention is not limited thereto.
  • the low alkali aluminosilicate or alkali free aluminosilicate glass is milled as a sintering aid to grind to a particle size of about 1 to 2 ⁇ m (S202).
  • the sintering aid prepared as described above is added to magnesia (MgO), and the alcohol is milled with a solvent to be mixed and ground (S204). Thereafter, the ground mixture is dried (S206).
  • the dried mixed powder is molded at a predetermined pressure (for example, molded by applying a pressure of 100 MPa to a mold having a diameter of 15 mm), and sintered at a temperature of 1300 to 1500 ° C. for 2 hours (S208).
  • a predetermined pressure for example, molded by applying a pressure of 100 MPa to a mold having a diameter of 15 mm
  • the sintered body thus prepared was evaluated for sintering characteristics through relative density measurements, and then, electrodes and lead wires made of materials known in the art including silver (Ag), platinum (Pt), and palladium (Pd) were formed on both surfaces thereof. Attached and heat treated at 800 °C for 1 hour to prepare an insulator for oxygen sensor (S210).
  • Example 1 10 wt% of a low alkali aluminosilicate glass powder was added to 90 wt% of magnesia, and the alcohol was mixed with a solvent in a ball mill and pulverized to dry. The mixed powder thus dried was molded at a pressure of 100 MPa in a 15 mm diameter metal mold, and then sintered at a temperature of 1350 ° C. for 2 hours using an electric furnace.
  • the manufactured sintered body was evaluated for its sintering characteristics by measuring its relative density, and the silver (Ag) electrode and silver (Ag) lead wire were attached to both surfaces, and heat-treated at 800 ° C for 1 hour, and then the insulation characteristics were measured at 700 ° C through specific resistance measurement. Evaluated.
  • the relative density was 97.4%
  • the porosity was 2.6%
  • the specific resistance was 1.1Mcm.
  • Example 2 the mixed powder composition and the manufacturing process are the same as those in Example 1, except that the sintering temperature is different. That is, 10 wt% of a low alkali aluminosilicate glass powder was added to 90 wt% of magnesia in the same composition and process as in Example 1, followed by mixing, pulverizing and drying to form a dried mixed powder. However, this molded body was sintered at a temperature of 1400 ° C. for 2 hours.
  • the relative density was 98.1%
  • the porosity was 1.9%
  • the specific resistance was 1.4Mcm.
  • Example 3 20 wt% of a low alkali aluminosilicate glass powder was added to 80 wt% of magnesia, and the alcohol was mixed with a solvent in a ball mill and pulverized to dry. The dried mixed powder was molded at a pressure of 100 MPa in a 15 mm diameter metal mold, and then sintered for 2 hours at a temperature of 1350 ° C. using an electric furnace.
  • the relative density was 99.7%
  • the porosity was 0.3%
  • the specific resistance was 1.8Mcm.
  • Example 4 the mixed powder composition and the manufacturing process are the same as those in Example 3, except that the sintering temperature is different. That is, in the same composition and process as in Example 3, 20 wt% of a low alkali aluminosilicate glass powder was added to 80 wt% of magnesia, mixed, pulverized and dried, and then the dried mixed powder was molded. However, this molded body was sintered at a temperature of 1400 ° C. for 2 hours.
  • the relative density was 99.8%
  • the porosity was 0.2%
  • the resistivity was 2.0 Mcm.
  • Example 5 a low alkali aluminosilicate glass powder was added to 70 wt% of magnesia, and alcohol was mixed with a solvent in a ball mill and pulverized to dry. The dried mixed powder was molded at a pressure of 100 MPa in a 15 mm diameter metal mold, and then sintered for 2 hours at a temperature of 1350 ° C. using an electric furnace.
  • the relative density was 99.8%
  • the porosity was 0.2%
  • the specific resistance was 1.5Mcm.
  • Example 6 the mixed powder composition and manufacturing process were the same as those in Example 5, except that the sintering temperature was different. That is, 30 wt% of a low alkali aluminosilicate glass powder was added to 70 wt% of magnesia in the same composition and process as in Example 5, followed by mixing, pulverizing and drying to form a dried mixed powder. However, this molded body was sintered at a temperature of 1400 ° C. for 2 hours.
  • the relative density was 99.5%
  • the porosity was 0.5%
  • the specific resistance was 1.1Mcm.
  • Example 7 40 wt% of low alkali aluminosilicate glass powder was added to 60 wt% of magnesia, and the alcohol was mixed and pulverized in a ball mill and dried. The dried mixed powder was molded at a pressure of 100 MPa in a 15 mm diameter metal mold, and then sintered for 2 hours at a temperature of 1350 ° C. using an electric furnace.
  • the relative density was 99.8%
  • the porosity was 0.2%
  • the specific resistance was 1.2Mcm.
  • Example 8 the mixed powder composition and the manufacturing process were the same as those in Example 7, except that the sintering temperature was different. That is, in the same composition and process as in Example 7, 40 wt% of a low alkali aluminosilicate glass powder was added to 60 wt% of magnesia, followed by mixing, pulverizing and drying to form a dried mixed powder. However, this molded body was sintered at a temperature of 1400 ° C. for 2 hours.
  • the relative density was 99.3%
  • the porosity was 0.7%
  • the specific resistance was 0.9Mcm.
  • Example 9 10 wt% of alkali-free aluminosilicate glass powder was added to 90 wt% of magnesia, and alcohol was mixed and pulverized in a ball mill and dried. The dried mixed powder was molded at a pressure of 100 MPa in a 15 mm diameter metal mold, and then sintered for 2 hours at a temperature of 1350 ° C. using an electric furnace.
  • the relative density was 92.5%
  • the porosity was 7.5%
  • the specific resistance was 0.7Mcm.
  • Example 10 the mixed powder composition and the manufacturing process were the same as those in Example 9, except that the sintering temperature was different. That is, in the same composition and process as in Example 9, 10 wt% of alkali-free aluminosilicate glass powder was added to 90 wt% of magnesia, mixed, pulverized and dried, and then the dried mixed powder was molded. However, this molded body was sintered at a temperature of 1400 ° C. for 2 hours.
  • the relative density was 96.5%
  • the porosity was 3.5%
  • the specific resistance was 0.9Mcm.
  • Example 11 20 wt% of alkali-free aluminosilicate glass powder was added to 80 wt% of magnesia, and alcohol was mixed and pulverized in a ball mill to dry. The dried mixed powder was molded at a pressure of 100 MPa in a 15 mm diameter metal mold, and then sintered for 2 hours at a temperature of 1350 ° C. using an electric furnace.
  • the relative density was 95.7%
  • the porosity was 4.3%
  • the specific resistance was 1.0Mcm.
  • Example 12 the mixed powder composition and the manufacturing process were the same as those in Example 11, except that the sintering temperature was different. That is, 20 wt% of alkali-free aluminosilicate glass powder was added to 80 wt% of magnesia in the same composition and process as in Example 11, followed by mixing, pulverizing and drying to form a dried mixed powder. However, this molded body was sintered at a temperature of 1400 ° C. for 2 hours.
  • the relative density was 98.6%
  • the porosity was 1.4%
  • the specific resistance was 1.3Mcm.
  • Example 13 an alkali free aluminosilicate glass powder was added to 70 wt% of magnesia, and alcohol was mixed with a solvent in a ball mill and pulverized to dry. The dried mixed powder was molded at a pressure of 100 MPa in a 15 mm diameter metal mold, and then sintered for 2 hours at a temperature of 1350 ° C. using an electric furnace.
  • the prepared sintered body was evaluated for the sintering characteristics and the insulating characteristics in the same process as in Example 1.
  • the relative density was 99.5%
  • the porosity was 0.5%
  • the specific resistance was 2.1 Mcm.
  • Example 14 the mixed powder composition and the manufacturing process were the same as those in Example 13, except that the sintering temperature was different. That is, 30 wt% of alkali-free aluminosilicate glass powder was added to 70 wt% of magnesia in the same composition and process as in Example 13, followed by mixing, pulverizing and drying to form a dried mixed powder. However, this molded body was sintered at a temperature of 1400 ° C. for 2 hours.
  • the relative density was 99.8%
  • the porosity was 0.2%
  • the resistivity was 2.2Mcm.
  • Example 15 40 wt% of alkali-free aluminosilicate glass powder was added to 60 wt% of magnesia, and the alcohol was mixed with a solvent in a ball mill and pulverized to dry. The dried mixed powder was molded at a pressure of 100 MPa in a 15 mm diameter metal mold, and then sintered for 2 hours at a temperature of 1350 ° C. using an electric furnace.
  • the relative density was 99.6%
  • the porosity was 0.4%
  • the specific resistance was 1.9Mcm.
  • Example 16 the mixed powder composition and the manufacturing process were the same as those in Example 15, except that the sintering temperature was different. That is, 40 wt% of alkali-free aluminosilicate glass powder was added to 60 wt% of magnesia in the same composition and process as in Example 15, followed by mixing, pulverizing and drying to form a dried mixed powder. However, this molded body was sintered at a temperature of 1400 ° C. for 2 hours.
  • the relative density was 99.8%
  • the porosity was 0.2%
  • the specific resistance was 1.9Mcm.
  • Example 17 20 wt% of low alkali aluminosilicate glass powder and 10 wt% of alkali free aluminosilicate glass powder were added to 70 wt% of magnesia, and the alcohol was mixed with a solvent in a ball mill and pulverized to dry. The dried mixed powder was molded at a pressure of 100 MPa in a 15 mm diameter metal mold, and then sintered for 2 hours at a temperature of 1350 ° C. using an electric furnace.
  • the relative density was 99.8%
  • the porosity was 0.2%
  • the specific resistance was 1.6Mcm.
  • Example 18 a low alkali aluminosilicate glass powder and 15 wt% alkali-free aluminosilicate glass powder were added to 70 wt% of magnesia, and alcohol was mixed with a solvent in a ball mill and pulverized to dry. The dried mixed powder was molded at a pressure of 100 MPa in a 15 mm diameter metal mold, and then sintered for 2 hours at a temperature of 1350 ° C. using an electric furnace.
  • the relative density was 99.7%
  • the porosity was 0.3%
  • the specific resistance was 1.6Mcm.
  • Example 19 10 wt% of low alkali aluminosilicate glass powder and 20 wt% of alkali free aluminosilicate glass powder were added to 70 wt% of magnesia, and the alcohol was mixed and pulverized in a ball mill and dried. The dried mixed powder was molded at a pressure of 100 MPa in a 15 mm diameter metal mold, and then sintered for 2 hours at a temperature of 1350 ° C. using an electric furnace.
  • the relative density was 99.5%
  • the porosity was 0.5%
  • the specific resistance was 1.8Mcm.
  • the addition amount (ie, x of Formula 1) of the low alkali aluminosilicate glass powder and / or the glass powder which is an alkali free aluminosilicate glass powder is added in an amount of 10 to 40 wt%, particularly preferably. 10-30 wt%.
  • Figure 3 is a graph of the change in relative density according to the addition ratio and sintering temperature when low alkali aluminosilicate glass powder is added to magnesia as embodiments of the present invention.
  • the low alkali aluminosilicate glass powder at a sintering temperature of 1350 °C or more it can be seen that the relative density is more than 95% at 10 ⁇ 40wt%.
  • the relative densities were similar at 20 to 40 wt%, but the relative density also increased as the specific gravity of the low alkali aluminosilicate glass powder was increased at 1300 ° C, but the same at 1350 ° C but almost the same at 1400 ° C. It can be seen that the relative density decreases as the specific gravity of the low alkali aluminosilicate glass powder increases.
  • FIG. 4 is a graph showing changes in relative density according to addition ratio and sintering temperature when alkali-free aluminosilicate glass powder is added to magnesia as another embodiment of the present invention.
  • the relative density is also increased.
  • the relative density is more than 95% at 10 to 40wt% at the sintering temperature of 1400 ° C.
  • a solid electrolyte layer composition (e.g., "123" of FIG. 1) of a conventional stabilized zirconia (YSZ) composition and an insulating layer of the insulator composition according to the present invention (e.g., " 140 ") were laminated and cofired, and the heterojunction properties of these layers were observed.
  • YSZ stabilized zirconia
  • FIG. 5 is a laminate of an insulating layer made of a composition in which 20 wt% of calcium aluminosyl case glass powder is added to a magnesia and a solid electrolyte layer of a stabilized zirconia (YSZ) composition and co-fired at 1350 ° C. Crystal phase analysis (XRD, X-ray diffraction analysis) is shown.
  • the solid electrolyte composition is a zirconia crystal phase to which yttria (Y 2 0 3 ) is added, and the insulator composition is formed of a forsterite (Mg 2) formed by reaction of magnesia and glass powder in addition to the magnesia (MgO) main phase. It can be seen that SiO 4 ) secondary phase was produced.
  • Mg 2 forsterite
  • the insulating layer (B) made of the composition according to the present invention has a very good heterojunction without a delamination with the solid electrolyte layer (A) of YSZ composition. It can be confirmed that it has excellent adhesion.
  • the insulator composition according to the present invention is excellent in airtightness and electrical insulation as an insulating layer in application to the oxygen sensor, and in particular, by providing excellent adhesion and thermal conductivity with the solid electrolyte layer, Durability can be improved.
  • the powder characteristics such as the average particle size, distribution, and specific surface area of the composition powder, the purity of the raw material, the amount of impurity addition, and the heat treatment conditions vary slightly within a normal error range. It can be quite natural for one of ordinary skill in the art to be there.
  • the insulator composition according to the present invention may be applied to the oxygen sensor of FIG. 1, which is attached to each surface of the solid electrolyte layer, the solid electrolyte layer and the measurement electrode facing the exhaust gas and the atmosphere.

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PCT/KR2012/007830 2012-09-27 2012-09-27 Composition d'isolant pour sonde à oxygène et sonde à oxygène l'utilisant Ceased WO2014051176A1 (fr)

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Publication number Priority date Publication date Assignee Title
US4127463A (en) * 1976-07-17 1978-11-28 Brown, Boveri & Cie Ag Probe for an electrochemical oxygen measurement pickup
JP2005077127A (ja) * 2003-08-28 2005-03-24 Kyocera Corp 酸素センサ素子
US20100050739A1 (en) * 2008-08-29 2010-03-04 Jesse Nachlas Sintered and bonded multilayer sensor

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4127463A (en) * 1976-07-17 1978-11-28 Brown, Boveri & Cie Ag Probe for an electrochemical oxygen measurement pickup
JP2005077127A (ja) * 2003-08-28 2005-03-24 Kyocera Corp 酸素センサ素子
US20100050739A1 (en) * 2008-08-29 2010-03-04 Jesse Nachlas Sintered and bonded multilayer sensor

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Title
G. V. SAMSONOV. ET AL.: "Study of elementary mechanisms during sintering of MgO with Mn203, Mn02 and NiO additives", JOURNAL DE PHYSIQUE, COLLOQUE, vol. 37, December 1976 (1976-12-01), pages C7415 - C7422 *
YU-HAI SUN ET AL.: "Microstructure and bending strength of 3Y-TZP ceramics by liquid- phase sintering with CAS addition", CERAMICS INTERNATIONAL, vol. 29, 2003, pages 229 - 232 *

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