Solid-electrolyte oxygen concentration detector and method of making the detector

IPC classes for russian patent Solid-electrolyte oxygen concentration detector and method of making the detector (RU 2298176):

G01N27/406 -

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FIELD: measuring technique.

SUBSTANCE: method and detector can be used in metallurgy, power engineering, and chemical industry for measuring activity of oxygen in different media. Solid-electrolyte oxygen concentration detector has ceramic sensitive element placed hermetically inside case, comparison electrode and central electrode, both displaced inside cavity of ceramic sensitive element. Ceramic sensitive element is completely made of solid electrolyte in form of conjugated cylindrical element and part of sphere. External cylindrical part of ceramic sensitive element is connected with internal side surface of case by means of connecting material. Detector is additionally provided with plug made of metal oxide. Plug has opening and it overlaps cross-section of cavity of ceramic sensitive element. Comparison electrode is disposed in cavity formed by internal surface of ceramic sensitive element and surface of plug. Comparison electrode occupies at least part of cavity which part is turned to part of sphere. Free end of central electrode is withdrawn into space of comparison electrode through opening in plug. Electrical contact is provided between comparison electrode and lower part of central electrode. At least part of sphere of ceramic sensitive element protrudes out of case. Material of case, of ceramic sensitive element and of connecting material have similar temperature expansion coefficient. The materials have to be chemically resistant in relation to working medium. Bushing is soldered to internal part free part of case. Top part of central electrode protrudes out of bushing. Ring-shaped cavity between bushing and top part of central electrode is filled with dielectric material providing air-tightness of internal cavity of detector. Detector shows excellent operation under cyclical thermal shocks and at temperatures higher than 500C.

EFFECT: prolonged service life; higher reliability of operation.

23 cl, 1 dwg

The invention relates to measuring technique and can be used in metallurgy, power industry, chemical industry for determining the oxygen activity in different environments.

Known solid electrolyte sensor of oxygen concentration / Blokhin, VA, Budilov Mrs x, Velikanova R.I., I. Gorelov. and other Experience of creation and operation of the solid electrolyte activaero oxygen in the coolant lead-bismuth. // Proceedings of the conference on Heavy liquid metal coolants in nuclear technology", Obninsk, IPPE. T2, 1999 s./, where as a solid electrolyte is used, the tube of zirconium dioxide stabilized with yttrium oxide, a length of 250 mm, an outer diameter of 10 mm and a wall thickness of about 1 mm as the reference electrode used air. The tube and potential conclusions compacted rubber seal of the flange connection, which is cooled by flowing water.

The disadvantage of the design is the narrow range of temperatures (350-450°C) and low temperature resistance (up to 2°C/min). This is due to design features. The lower part of the tube is at operating temperature, the upper part is sealed with a rubber stopper and is cooled to a temperature of 20-40°C. When this temperature difference along the length of the tube is 300-430°that more is frequently leads to the destruction of ceramics. Thus, this design does not exclude the likelihood of cracking tubes in place its seal. In addition, over time, is the penetration of oxygen from the environment into the tubes through the rubber seal and the deterioration of properties of the reference electrode.

Closest to the claimed device is an oxygen sensor, discussed in the patent RU No. 2085928 (priority from 27.07.97). The specified sensor includes a housing, consistently placed in the bore of the housing sealing ring, bulb sensing element with an external annular flange, with the measuring electrode and the reference electrode in the form of conductive coatings on the inner and outer surfaces of the bulb sensing element, one of which bears on one of the ends of the annular flange of the sensing element, the contact element and the insulating sleeve. Part of the bore of the body is threaded and is threaded sleeve, tucked up to the insulating sleeve, the outer cylindrical surface of which is made a longitudinal groove in which is placed the tooth body. The contact element is made in the form of a sleeve with the annular contact located coaxially on the outside of the sleeve.

The disadvantage of this sensor is a low life and reliability, especially when working in the services is of significant TurboCache and temperatures above 500° With due to the following:

- leaking connection "bulb sensing element - conduit";

- destruction bulb sensing element and insulating tubes under cyclic thermal shocks and temperatures above 500°due to the difference of coefficient of thermal expansion of the materials of the bulb sensing element and the insulation tube.

The authors faced the task of creating a sensor thermodynamic activity of oxygen devoid of these shortcomings.

To solve the problem in the solid electrolyte sensor oxygen containing ceramic sensing element is hermetically accommodated in the housing, the reference electrode and the Central electrode, placed in the cavity of the ceramic sensor element, it is proposed;

- ceramic sensing element to perform the whole of the solid electrolyte in the form of a conjugate between a cylindrical member and part of the sphere;

- case run of ferritic-martensitic steel EI-852 (HMS) or ferritic-martensitic steel EP-823 (SP);

- side surface of the cylindrical element to be joined with the inner side surface of the housing via a connecting material;

- the sensor is additionally provided with a tube from a metal oxide having a hole and elecrama cross-section of the cavity of the ceramic sensing element;

a reference electrode positioned in the cavity formed by the inner surface of the ceramic sensing element and the surface of the tube so as to cover at least part of it;

- facing part of the spherical element, the free end of the Central electrode to withdraw the reference electrode through the opening in the tube;

to ensure electrical contact between the reference electrode and the lower part of the Central electrode;

at least part of the sphere ceramic sensing element out of the housing;

- materials, ceramic sensing element and the connecting material to choose such that they have the same coefficients of thermal expansion, and was chemically resistant to the working environment;

- free part of the body to weld the sleeve;

- from the cavity of the sleeve to bring the upper portion of the Central electrode;

- the annular cavity between the sleeve and the upper part of the Central electrode to fill dielectric material, ensuring the integrity of the internal cavity of the sensor.

In private cases, perform sensor features.

As the connecting material to use Sitall consisting of silicon oxide (SiO₂) - 20-30 wt.%, aluminium oxide Al ₂O₃) - 6-7 wt.%, oxide of boron (₂About₃) - 20-21 wt.%, peroxide zinc (ZnO₂) - 10-12 wt.%, zirconium oxide (ZrO₂) - 5-6 wt.%, tin oxide (SnO₂) - 5-7 wt.%, of calcium oxide (Cao) - 15-21 wt.%, sodium oxide (Na₂O) - 3-4 wt.% and potassium oxide (K₂O) - 3-4 wt.%.

As the connecting material to use extruded carbon-graphite fiber.

As a dielectric material to use Sitall.

Ceramic sensing element to perform one of the following materials: partially stabilized Zirconia or fully stabilized zirconium dioxide or hafnium oxide.

In the composition of the ceramic material of the sensing element to use nanostructured ultra-fine ceramic material.

The reference electrode to perform one of the following chemical elements: bismuth, lead, indium or gallium.

The lower portion of the Central electrode located in the internal cavity of the housing, placed in a detention center.

Tube manufacture of nanostructured ultra-fine ceramic material.

The casing is made of ferritic-martensitic steel EI-852 (HMS) or ferritic-martensitic steel EP-823 (SP).

The lower portion of the Central electrode made of 12CR18NI10TI steel or molybdenum, or operaf the postal threads.

A known method of manufacturing a sensor, provided in the patent of the Russian Federation No. 2085928 (priority from 27.07.97).

The method includes placing the sealing ring in the bore of the housing, insert the grommets into the housing, the installation in the housing of the bulb sensing element with an external annular flange at an open end having a measuring electrode and a reference electrode in the form of a conductive coating on the outer and inner surfaces of the flask, the force for moving the sensing element to compress o-ring, installation of the contact element with the application of force to compress it to the internal conductive coating on the bulb sensing element, the installation of the grommets in the case after installing the bulb sensing element and a contact element, the formation of the tooth from the body material, for example by stamping, in the area of the longitudinal groove of the insulating sleeve on the body, screwed into the threaded hole on the housing threaded bushing.

The disadvantages of this method are:

- lack of reliability of the sensor, because the microdefects inevitably formed on the bulb sensing element during mechanical processing, are stress concentrators and lead to the occurrence of microcracks and destruction;

mechanical connection method is ri using threads do not provide 100% yield, because a tight seal is ensured by the accuracy of machining surfaces;

- the complexity of the Assembly process;

- the need to use qualified personnel for carrying out a thin hand Assembly operations.

To eliminate these disadvantages in the method of manufacturing a solid-electrolyte sensor of oxygen concentration, including the manufacturing of ceramic sensing element, a tight connection with the casing, the space inside the ceramic sensing element of the reference electrode, the measuring electrode and the welding sleeve, features:

to connect a ceramic sensing element with the body to use Sitall consisting of silicon oxide (SiO₂) - 20-30 wt.%, aluminum oxide (Al₂O₃) - 6-7 wt.%, oxide of boron (₂About₃) - 20-21 wt.%, peroxide zinc (ZnO₂) - 10-12 wt.%, zirconium oxide (ZrO₂) - 5-6 wt.%, tin oxide (SnO₂) - 5-7 wt.%, of calcium oxide (Cao) - 15-21 wt.%, sodium oxide (Na₂O) - 3-4 wt.% and potassium oxide (K₂O) - 3-4 wt.%;

- case run of ferritic-martensitic steel EI-852 (HMS) or ferritic-martensitic steel EP-823 (SP);

- powdered Sitall to fill in the annular gap between the ceramic sensor element and the housing;

Assembly of eroticheskoe sensitive element, housing and powdered glass-ceramic to install in oven;

- in the furnace as a gas environment to use the air;

Assembly to heat to a temperature of 900-930°C;

Assembly to cool in the furnace and to extract from it;

in the inner cavity of the ceramic sensing element to fill the reference electrode to install the tube from the metal oxide and the measuring electrode in isolation;

- through sleeve skip the upper portion of the Central electrode and to bring its free end beyond the outer dimensions of the sleeve;

- the annular gap between the outer surface of the upper part of the Central electrode and the inner surface of the sleeve to fill dielectric material;

the site, consisting of an upper part of the Central electrode, a dielectric material, a metal sleeve, set in a furnace, in which the gaseous environment to use the air;

node reheated to a temperature of 900-930°C;

to produce the extract node in the furnace to provide uniform heating and melting of the glass-ceramic,

to provide mechanical strength and vacuum tightness of the dielectric material with the electrode and sleeve, then the node is allowed to cool with the oven and remove from the oven;

- to carry out the electrical contact of the free ends of the lower part of the Central electrode with the upper part of the Central nervous system, the second electrode;

- to the body to weld the sleeve.

In private cases, the implementation of the method proposed ceramic sensing element to produce a slip casting or pressing.

The invention is illustrated in the drawing, which shows a longitudinal axial section of the sensor.

In the drawing, the following notation: 1 - ceramic sensing element; 2 - reference electrode; 3 - tube; 4 - connecting material; 5 - housing; 6 - lower part of the center electrode; 7 - insulator; 8 - Bush; 9 - upper portion of the Central electrode; 10 - dielectric material.

The solid electrolyte sensor of oxygen concentration contains ceramic sensor element 1, a hermetically accommodated in the housing 5, the reference electrode 2 and the Central electrode, which consists of two parts - the bottom 6 and top 9, is placed in the cavity of the sensor.

Ceramic sensing element 1 is made entirely of solid electrolyte in the form of a conjugate between a cylindrical member and part of the sphere. A side surface of a cylindrical member connected with the inner side surface of the housing 5 via a connecting material 4.

The sensor is supplied with a plug 3 of a metal oxide having an aperture and overlying the cross-section of the cavity of the ceramic sensing element 1. The tube is DL the fixation of the electrode 2 in the inner cavity of the ceramic sensor element 1.

The reference electrode 2 is located in the cavity formed by the inner surface of the ceramic sensor element 1 and the surface of the tube 3, and occupies at least a part of it.

Facing the part of the spherical element, the free end of the lower part of the Central electrode 6 is displayed in the volume of the electrode 2 through the hole in the tube 3. This provided an electrical contact between the electrode 2 and the lower part of the Central electrode 6.

At least part of the sphere ceramic sensing element 1 protrudes outside of the housing 5. In the process of this sensor protruding portion is immersed, for example, in a melt of molten metal, which is determined by the activity of oxygen.

Materials 5, ceramic sensing element 1 and the connecting material 4 have the same coefficient of thermal expansion and are chemically resistant to the working environment, for example to melt lead at temperatures not exceeding 650°C. It allows you to keep health gauge at the speed of change of temperature (thermal shock) in the liquid metal to 100°C/s in the temperature range 300-650°C.

To free part of the body 5 is welded to the sleeve 8. From the cavity of the sleeve 8 extends the upper portion of the Central electrode 9.

The annular cavity m is waiting for the sleeve 8 and the upper part of the Central electrode 9 is filled with a dielectric material 10, ensuring the integrity of the internal cavity of the sensor. This is necessary to prevent the ingress of oxygen from the air into the internal cavity of the sensor and change the properties of the electrode 2.

Special cases of the performance of the sensor.

Connecting material 4 is a Sitall consisting of silicon oxide (SiO₂) - 20-30 wt.%, aluminum oxide (Al₂About₃) - 6-7 wt.%, oxide of boron (₂O₃) - 20-21 wt.%, peroxide zinc (ZnO₂) - 10-12 wt.%, zirconium oxide (ZrO₂) - 5-6 wt.%, tin oxide (SnO₂) - 5-7 wt.%, of calcium oxide (Cao) - 15-21 wt.%, sodium oxide (Na₂O) - 3-4 wt.%, of potassium oxide (K₂O) - 3-4 wt.%.

Connecting material 4 is a pressed carbon-graphite fiber.

As the dielectric material 10 used Sitall.

Ceramic sensing element 1 is made of one of the following materials: partially stabilized Zirconia fully stabilized zirconium dioxide or hafnium oxide.

The ceramic material of the sensing element 1 may contain nanostructured ultra-fine ceramic material.

The reference electrode 2 is made of one of the following chemical elements: bismuth, lead, indium or gallium.

The lower portion of the Central electrode 6, the location is cited in the internal cavity of the housing 5, placed in the insulator 7 made of aluminum oxide.

The tube 3 is made of nanostructured ultradispersed aluminum.

The housing 5 is made of ferritic-martensitic steel EI-852 (HMS) or ferritic-martensitic steel EP-823 (SP).

The lower portion of the Central electrode 6 is made of steel 12X18H10T or molybdenum, or graphite filaments.

The solid electrolyte sensor of oxygen concentration can be produced by the following method.

The method of slip casting or extrusion is made of a ceramic sensor element 1.

Ceramic sensing element 1 is hermetically connected to the housing 5 by means of a connecting material 4. As the connecting material 4 used Sitall consisting of silicon oxide (SiO₂) - 20-30 wt.%, aluminum oxide (Al₂O₃) - 6-7 wt.%, oxide of boron (₂O₃) - 20-21 wt.%, peroxide zinc (ZnO₂) - 10-12 wt.%, zirconium oxide (ZrO₂) - 5-6 wt.%, tin oxide (SnO₂) - 5-7 wt.%, of calcium oxide (Cao) - 15-21 wt.%, sodium oxide (Na₂O) - 3-4 wt.%, of potassium oxide (K₂O) - 3-4 wt.%.

Powdered Sitall fall asleep in the annular gap between the ceramic sensor element 1 and the housing 5.

The Assembly of the ceramic sensor element 1, the housing 5 and powdered glass-ceramic set is in the oven. In the furnace as a gas environment of the use of the air.

The Assembly is heated to a temperature of 900-930°C. a Temperature of 900° corresponds to the melting temperature of glass-ceramic and the temperature of 930°corresponds to the temperature at which irreversible chemical transformations that can impair the adhesion and sealing properties of the glass-ceramic.

After holding at this temperature the Assembly is cooled in the furnace.

Then the Assembly is extracted, and into the internal cavity of the ceramic sensor element 1 fall asleep electrode 2, install the tube 3 inside the ceramic sensing element 1, the lower portion of the Central electrode 6 in isolation 7.

Through the sleeve 8 is passed the upper part of the Central electrode 9 and deduce its free end beyond the outer dimensions of the sleeve 8.

The annular gap between the outer surface of the upper part of the Central electrode 9 and the inner surface of the sleeve is filled powdered dielectric material, which is used Sitall.

The site, consisting of an upper part of the Central electrode 9, the dielectric material 10, a metal sleeve 8, is installed in the furnace, in which the gas medium used by the air.

The site is heated to a temperature of 900-930°C.

Produce the extract node in the furnace to ensure it is equal to REGO warming and melting of the glass-ceramic.

Then the node is cooled together with the furnace. After cooling, the sleeve 8 with the upper part of the Central electrode 9 forms a mechanically rigid dielectric vacuum-tight connection, ensuring the integrity of the internal cavity of the sensor.

After cooling, the node is removed from the oven and using a soldering carry out the electrical contact of the free ends of the lower part of the Central electrode 6 with the upper part of the Central electrode 9.

The sleeve 8 are welded to the housing 5, for example, using electron beam welding.

A method of manufacturing a sensor allows you to:

to avoid defects and internal stresses, leading to the destruction of the ceramic sensor element 1, since the product obtained by casting without the need for mechanical handling;

to get the absolute tightness of the ceramic sensor element 1 in the form of capsules, which is constructive, because the product is not integral, and integral;

- significantly increase the reliability and tightness of the connection of the ceramic sensor element 1 - case 5, which is provided by the selection of materials of the solid electrolyte, metal and glass-ceramic with close values of the coefficient of thermal expansion ˜10 1/°·10^-6and good adhesive properties of the glass-ceramic of the composition in relation to the s to the ceramic material of the sensing element 1 and the housing 5.

The method does not require special equipment (high-temperature furnaces and gas-static installation). The process of connecting a ceramic sensing element 1 with the housing 5 is carried out in a conventional muffle furnace. This reduces the complexity of the manufacturing process.

A specific example of the sensor.

Manufactured and demonstrated its functionality sensor of oxygen concentration.

The main characteristics of the sensor.

The conversion range of the relative values of thermodynamic activity of oxygen to the working environment - from 1·10^-6to 1, the permissible relative deviation EMF sensor - ±10%, the pressure of working medium is not more than 0.5 MPa, the speed of movement of the working environment is not more than 1.0 m/s, the rate of temperature change of the working environment - no more than 100°C/C, ambient temperature is from 300 to 650°C, ambient temperature is from 5 to 40°C, relative humidity environment at 25°With no more than 80%, atmospheric pressure - from 84,0 to 106.7 kPa (350 to 600 mm Hg), the time of the ramp-up during initial installation of the sensor in a working environment - no more than 10 hours, the average time to failure - at least 38,000 h, the average life of not less than 6 years.

Dimensions of sensor: length 600 mm, diameter 27 mm, weight sensor is not more than 0,022 kg

Ceramic sensitive El the element 1 is made of partially stabilized Zirconia, having the following composition: ZrO₂97 mol % + Y₂About₃3 mol % in the form of a conjugate between a cylindrical member and a portion of a sphere and has the form of capsules with an outer diameter of 10 mm, an inner diameter of 4 mm and a length of 15 mm.

The reference electrode 2 lot 1 gram made of powdered bismuth.

The tube 3 is made of nanostructured, ultrafine aluminum oxide, has the shape of a cylinder with a diameter of 4 mm and a height of 2 mm At the center of the tube 3 along the axis is a through hole with a diameter of 0.5 mm.

The housing 5 is made of ferritic-martensitic steel EP-823 (SP) in the form of a tube outer diameter of 16 mm and a length of 200 mm With one side of the housing 5 has a cylindrical groove for installation of ceramic sensing element 1.

The outer cylindrical surface of the ceramic sensor element 1 is connected with the inner side surface of the groove of the housing 5 via a connecting material 4 of a glass-ceramic consisting of silicon oxide (SiO₂- up to 20 wt.%, aluminum oxide (Al₂O₃) - 6 wt.%, oxide of boron (₂O₃) - 21 wt.%, peroxide zinc (ZnO₂) - 12 wt.%, zirconium oxide (ZrO₂) - 6 wt.%, tin oxide (SnO₂) - 7 wt.%, of calcium oxide (Cao) - 21 wt.%, sodium oxide (Na₂O) - 3 wt.% and potassium oxide (K₂O) - 4 wt.%.

Ceramic sensitivity is the first element 1, the housing 5 and the connecting material 4 have a similar coefficient of thermal expansion.

The lower portion of the Central electrode 6 is made of molybdenum with a diameter of 0.5 mm and is located in the internal cavity of the housing 5, passes through the through hole in the tube 3 has an electrical contact with the reference electrode 2 and placed in the insulator 7 made of aluminum oxide.

The upper portion of the Central electrode 9 made of steel 12X18H10T and is located inside the sleeve 8 of the same steel.

The annular gap between the upper part of the Central electrode and the sleeve 8 is filled with a dielectric material 10, which used Sitall consisting of silicon oxide (SiO₂- up to 20 wt.%, aluminum oxide (Al₂O₃) - 6 wt.%, oxide of boron (₂O₃) - 21 wt.%, peroxide zinc (ZnO₂) -12 wt.%, zirconium oxide (ZrO₂) - 6 wt.%, tin oxide (SnO₂) - 7 wt.%, of calcium oxide (Cao) - 21 wt.%, sodium oxide (Na₂O) - 3 wt.%, of potassium oxide (K₂O) - 4 wt.%.

The sleeve 8 is connected to the housing 5 of the electron-beam welding.

An example of a specific implementation of the method.

When implementing the method had the following characteristic modes, materials and devices for its implementation.

To connect ceramic sensing element with case used Sitall consisting of silicon oxide (SiO_{2/sub> - up to 20 wt.%, aluminum oxide (Al₂O₃) - 6 wt.%, oxide of boron (₂About₃) - 21 wt.%, peroxide zinc(ZnO₂) - 12 wt.%, zirconium oxide (ZrO₂) - 6 wt.%, tin oxide (SnO₂) - 7 wt.%, of calcium oxide (Cao) - 21 wt.%, sodium oxide (Na₂O) - 3 wt.%, of potassium oxide (K₂O) - 4 wt.%.}

The Assembly of the ceramic sensing element, the housing and powdered glass-ceramic was established in the furnace MIN-U, in which the gas medium used air, and warmed up to 900°C.

Made shutter Assembly at the temperature for 1 hour, then cooled it with the oven. After removing the Assembly from the furnace into the internal cavity of the ceramic sensing element through the internal cavity of the housing 5 has included a reference electrode of bismuth 2 mass of 1 gram.

The upper portion of the Central electrode 9 is placed coaxially inside the sleeve 8. Ring gap with a thickness of 1 mm between the outer surface of the upper part of the Central electrode and the inner surface of the sleeve was filled with powdered glass-ceramic 10 consisting of silicon oxide (SiO₂- up to 20 wt.%, aluminum oxide (Al₂About₃) - 6 wt.%, oxide of boron (₂O₃) - 21 wt.%, peroxide zinc(ZnO₂) - 12 wt.%, zirconium oxide (ZrO₂) - 6 wt.%, tin oxide (SnO₂) - 7 wt.%, of calcium oxide (Cao) - 21 wt.%, sodium oxide (Na₂About - 3 wt.%, of potassium oxide (K₂O) - 4 wt.%.

The site, consisting of an upper part of the Central electrode 9, the dielectric material 10 and the metal sleeve 8, was installed in the furnace MIN-U, in which the gas medium used air, and warmed to a temperature of 900°C. Produced exposure at this temperature for 1 hour, then cooled together with the furnace for 10 hours.

After cooling, the site was removed from the oven and using a soldering was carried out by the electrical contact of the free ends of the bottom 6 and top 9 parts of the Central electrode.

The sleeve 8 was welded to the chassis 5 of the electron-beam welding.

1. The solid electrolyte sensor oxygen containing ceramic sensing element is hermetically accommodated in the housing, the reference electrode and the Central electrode, placed in the cavity of the ceramic sensor element, characterized in that the ceramic sensing element is made entirely of solid electrolyte in the form of a conjugate between a cylindrical member and the outer cylindrical surface of the ceramic sensing element is connected with the inner side surface of the housing via a connecting material, the sensor is further provided with a tube from a metal oxide having an aperture and overlapping the second cross-section of the cavity of the ceramic sensor element, the reference electrode is positioned in the cavity formed by the inner surface of the ceramic sensing element and the surface of the tube, and covers at least part of it, facing towards the free end of the Central electrode is displayed in the volume of the electrode through the hole in the tube, thus provided an electrical contact between the reference electrode and the lower part of the Central electrode, at least part of the sphere ceramic sensing element protrudes outside of the housing, the housing materials, ceramic sensing element and the connecting material have the same coefficient of thermal expansion, are chemically resistant to the working environment, free of the hull is welded to the sleeve from the cavity which is the upper part of the Central electrode, the annular cavity between the sleeve and the upper part of the Central electrode is filled with a dielectric material, ensuring the integrity of the internal cavity of the sensor.

2. The sensor according to claim 1, characterized in that the connecting material is a Sitall consisting of silicon oxide (SiO₂) 20-30 wt.%, aluminum oxide (Al₂O₃) 6-7 wt.%, oxide of boron (₂About₃) 20-21 wt.%, peroxide zinc (ZnO₂) 10-12 wt.%, zirconium oxide (ZrO₂) 5-6 wt.%, is xida tin (SnO ₂) 5-7 wt.%, of calcium oxide (Cao) 15-21 wt.%, sodium oxide (Na₂O) 3-4 wt.%, of potassium oxide (K₂O) 3-4 wt.%.

3. The sensor according to claim 1, characterized in that the connecting material is a pressed carbon-graphite fiber.

4. The sensor according to claim 1, characterized in that the dielectric material used Sitall.

5. The sensor according to claim 1, characterized in that the ceramic sensing element is made of partially stabilized Zirconia.

6. The sensor according to claim 1, characterized in that the ceramic sensing element is made of fully stabilized Zirconia.

7. The sensor according to claim 1, characterized in that the ceramic sensing element is made of hafnium oxide.

8. The sensor according to claim 1, characterized in that the ceramic material of the sensing element comprises nanostructured ultra-fine ceramic material.

9. The sensor according to claim 1, characterized in that the reference electrode is made of bismuth.

10. The sensor according to claim 1, characterized in that the reference electrode is made of lead.

11. The sensor according to claim 1, characterized in that the reference electrode is made of indium.

12. The sensor according to claim 1, characterized in that the reference electrode is made of gallium.

13. The sensor according to claim 1, characterized in that the lower part of the Central electrode, is the th in the internal cavity of the housing, placed in an isolation cell.

14. The sensor according to claim 1, characterized in that the tube is made of nanostructured ultra-fine ceramic material.

15. The sensor according to claim 1, characterized in that the casing is made of a ferritic-martensitic steel EI-852 (HMS).

16. The sensor according to claim 1, characterized in that the casing is made of a ferritic-martensitic steel EP-823 (SP).

17. The sensor according to claim 1, characterized in that the lower part of the Central electrode is made of steel 12X18H10T.

18. The sensor according to claim 1, characterized in that the lower part of the Central electrode is made of molybdenum.

19. The sensor according to claim 1, characterized in that the lower part of the Central electrode is made of carbon-graphite threads.

20. A method of manufacturing a solid-electrolyte sensor of oxygen concentration, including the manufacturing of ceramic sensing element, a tight connection with the casing, the space inside the ceramic sensing element of the reference electrode, the lower part of the Central electrode and the welding sleeve, characterized in that for connecting the ceramic sensing element with a use case Sitall consisting of silicon oxide (SiO₂) 20-30 wt.%, aluminum oxide (Al₂O₃) 6-7 wt.%, oxide of boron (₂O₃) 20-21 wt.%, peroxide zinc (ZnO₂) 10-12 wt.%, oxide zircon is I (ZrO ₂) 5-6 wt.%, tin oxide (SnO₂) 5-7 wt.%, of calcium oxide (Cao) 15-21 wt.%, sodium oxide (Na₂O) 3-4 wt.% and potassium oxide (K₂O) 3-4 wt.%, Sitall in the form of powder is poured into the annular gap between the ceramic sensor element and the housing, the Assembly of the ceramic sensing element, the housing and powdered glass-ceramic is installed in the furnace, in which the gaseous environment of the use of air, and is heated to a temperature of 900-930°C, after which the Assembly is cooled in the oven, then remove and into the internal cavity of the ceramic sensing element fall asleep reference electrode, install the tube from the metal oxide and the lower portion of the Central electrode in the ceramic insulation, pass through the sleeve upper portion of the Central electrode and derive its free end beyond the outer dimensions of the sleeve, the annular gap between the outer surface of the upper part of the Central electrode and the inner surface of the sleeve is filled by a dielectric material, node, consisting of the upper part of the Central electrode, a dielectric material, a metal sleeve, is installed in the furnace, in which the gas medium used is air, the node is heated to a temperature of 900-930°To produce the extract node in the furnace to provide uniform heating and melting of the glass-ceramic to ensure Ecevit mechanical strength and vacuum tightness of the dielectric material with the upper part of the Central electrode and the sleeve, expand cool with the oven, remove from the oven and carry out the electrical contact of the free ends of the lower part of the Central electrode with the upper part of the Central electrode to the body weld nut.

21. The method according to claim 20, characterized in that the ceramic sensing element made slip casting.

22. The method according to claim 20, characterized in that the ceramic sensor element is manufactured by pressing.