JP5218477B2 - Gas sensor element and manufacturing method thereof - Google Patents

Description

  The present invention relates to a gas sensor element used for a gas sensor for measuring the concentration of a specific gas component contained in a gas to be measured such as combustion exhaust discharged from an internal combustion engine such as an automobile engine, and a manufacturing method thereof.

  Conventionally, a gas sensor for detecting the concentration of a specific gas component such as oxygen, nitrogen oxides, ammonia, and hydrogen contained in the combustion exhaust gas is disposed in the combustion exhaust flow path of the internal combustion engine such as an automobile engine, and the internal combustion engine. Combustion control and exhaust gas purification device control.

  As such a gas sensor, for example, in the case of an oxygen sensor, an oxygen ion conductive solid electrolyte layer formed in a flat plate shape, and a measurement electrode layer formed on one surface of the solid electrolyte layer and in contact with the gas to be measured A porous diffusion resistance layer that is formed on the measurement electrode layer side and transmits the gas to be measured; a reference electrode layer that is formed on the other surface of the solid electrolyte layer and is in contact with the reference gas; and the reference electrode layer side A so-called stacked gas sensor element is widely used by stacking and integrally forming a reference gas chamber forming layer having a reference gas chamber for introducing the reference gas and a heater portion having a heating element therein. .

On the other hand, the combustion exhaust as the gas to be measured contains poisonous substances composed of oil-containing components such as P, Ca, Zn, and Si and gasoline-added components such as K, Na, and Pb. There is a possibility that the measurement electrode layer and the porous diffusion layer are contaminated with these poisoning substances, causing problems such as deterioration in response of the gas sensor and abnormal output.
The combustion exhaust gas also contains water vapor, which may condense in the cold state to form water droplets and adhere to the gas sensor element.

In addition, such a gas sensor element heats and activates the solid electrolyte layer to a high temperature of, for example, 700 ° C. or higher by a built-in heating element in order to exhibit ion conductivity with respect to specific ions such as oxygen ions and protons. It is used in the state that was done.
For this reason, when water droplets in the gas to be measured adhere (water exposure), a large thermal shock is applied to the gas sensor element, and so-called water cracking may occur.

  Therefore, a porous protective layer having a predetermined thickness is formed on the outer peripheral surface of the gas sensor element, and the poisoning substance is captured in the porous protective layer to prevent malfunction, or water droplets are placed in the porous protective layer. It is widely practiced that the thermal shock is relaxed by being dispersed in the substrate and cracks are prevented from occurring in the entire device.

  Such a porous protective layer is, for example, a gas sensor element to be measured in a slurry in which a heat-resistant ceramic powder such as alumina having a predetermined particle size distribution is dispersed in a dispersion medium such as water or an organic solvent together with an inorganic binder and a dispersant. A part exposed to the fluid is immersed (dipped), and a film made of heat-resistant ceramic is formed on the outer peripheral surface thereof, and this is formed by heat treatment such as drying and sintering (for example, (See Patent Document 1, Patent Document 2, etc.).

  However, when a porous protective layer is formed by conventional dipping, it is extremely difficult to obtain a constant film thickness over the entire circumference of the surface of the gas sensor element due to the influence of surface tension and the like. On the other hand, the gas sensor element is formed in a substantially elliptical shape with a thin film thickness at the corner and a thick film at the center of the flat surface (see Patent Document 2, FIG. 3, etc.).

In particular, when the thickness is adjusted by repeating dipping a plurality of times, or when a protective layer having different particle diameters or porosity is formed in multiple layers, the packing density of the protective layer formed immediately before Affects the film thickness of the protective layer to be formed next.
For example, the portion having a high porosity of the protective layer that is the base has a high water absorption rate, and moisture in the slurry is quickly absorbed, so that the amount of adhesion increases, and the thickness of the protective layer to be formed increases. The portion having a low porosity has a relatively low water absorption rate, the amount of adhesion is reduced, and the thickness of the protective layer to be formed becomes thin.
Furthermore, the water dispersion type slurry generally used has a high surface tension, and a film thickness balance is generated according to the plane size of the gas sensor element. For this reason, there is a possibility that a part of the protective layer has an excessive film thickness, or a crack is generated on the surface of the protective layer due to a difference in shrinkage rate during drying and sintering.

  Therefore, in view of such circumstances, the present invention aims to make the thickness of the porous protective layer uniform, and to suppress cracking of the porous protective layer by reducing internal stress, and to have a highly durable porous protective layer. An object is to provide an element and a method for manufacturing the element.

In the first invention, a solid electrolyte layer in which a solid electrolyte material having specific ion conductivity is formed in a substantially flat plate shape, a reference electrode formed on one surface of the solid electrolyte layer and in contact with a reference gas, and another surface A sensor electrode that is in contact with the gas to be measured and is placed in the gas flow path to be measured, detects a concentration of a specific gas component in the gas to be measured, and a heating element that generates heat when energized. A gas sensor element comprising: a heater part that heats the sensor part; and a porous protective layer that is formed using a heat-resistant ceramic powder and covers a surface of the sensor part and the heater part,
The porous protective layer is constituted by a heat-resistant ceramic powder having a relatively large particle size that is aligned to a predetermined average particle size, and the average particle size of the large particle size is 2 with respect to the heat-resistant ceramic powder. A heat-resistant ceramic powder having a fine particle size having a particle size of 1 / min or less is added within a predetermined range, and the heat-resistant ceramic having a fine particle size is added to the surface of the heat-resistant ceramic powder having a large particle size or between the particles. Distribute the powder (Claim 1).

  According to 1st invention, when the said fine particle size particle | grain is filled between the said large particle size particle | grains, the intensity | strength of the said porous protective layer becomes high, and when the said porous protective layer is flooded, The porous protective layer is less likely to be peeled off or cracked, and a highly reliable gas sensor element can be realized.

  Specifically, as in the second invention, the porous protective layer comprises a large particle size particle having an average particle size of 22 μm ± 4 μm and a particle size of 10 μm distributed on the surface of the large particle particle or between the particles. The following fine particle size particles are used, and among the fine particle size particles, the frequency of particles having a particle size of 10 μm is 1.8% or less, and the cumulative amount of particles having a particle size of 10 μm or less is 8.4% or more. 13.0% or less (Claim 2).

  According to the second invention, a highly reliable gas sensor element having a high strength of the porous protective layer can be realized.

  In the third invention, the ratio of the minimum film thickness to the maximum film thickness of the porous protective layer is 2.5 or less (claim 3).

  According to the third invention, since the minimum film thickness can be maximized while suppressing the maximum film thickness of the porous protective layer within a range that can be incorporated in the gas sensor, the durability of the porous protective layer can be improved. it can.

  In the fourth invention, the heat-resistant ceramic powder is a metal oxide containing at least one of alumina, alumina magnesia spinel, titania, and mullite as a main component (invention 4).

  According to the fourth aspect of the invention, a gas sensor element having a highly durable porous protective layer can be realized.

In the fifth invention, a solid electrolyte layer in which a solid electrolyte material having specific ion conductivity is formed in a substantially flat plate shape, a reference electrode formed on one surface of the solid electrolyte layer and in contact with a reference gas, and another surface A sensor electrode that is in contact with the gas to be measured and is placed in the gas flow path to be measured, detects a concentration of a specific gas component in the gas to be measured, and a heating element that generates heat when energized. A heater unit that heats the sensor unit, and covers the surface of the sensor unit and the heater unit exposed to the gas to be measured from the moisture and poison components contained in the gas to be measured. A method for producing a gas sensor element, wherein a porous protective layer for protecting the heater part is formed using a heat-resistant ceramic powder,
At least a predetermined range of the sensor part and the heater part is immersed in a slurry for forming a porous protective layer in which the heat-resistant ceramic powder is dispersed in a predetermined dispersion medium, dried, heat-treated. Comprising a porous protective layer forming step of forming a porous protective layer,
The average particle size of the heat-resistant ceramic powder contained in the slurry is adjusted to 22 μm ± 4 μm, and among the fine particle size particles of 10 μm or less contained in the slurry, the frequency of 10 μm particles is 1.8% or less. The total amount of particles of 10 μm or less is adjusted to be 8.4% or more and 13.0% or less (Claim 5).

According to the fifth invention, when the predetermined range of the sensor part and the heater part is immersed in the slurry for forming the porous protective layer and dried, the fine particle size is between the particles of the heat-resistant ceramic powder. Since the particles are arranged and the packing density becomes high, it becomes easy to form a porous protective layer having high strength.
In addition, when the immersion into the slurry for forming the porous protective layer and the drying are repeated a plurality of times, the packing density of the porous protective layer formed earlier is increased and formed between the particles. Since the capillary attraction of the capillary is suppressed, there is no possibility that the next formed porous protective layer will be excessively thick, and a uniform film thickness can be formed.

  In the sixth aspect of the invention, the weight ratio of the slurry for forming the porous protective layer to the solid content contained in the slurry for forming the porous protective layer is 0.00 so that the surface tension of the slurry for forming the porous protective layer is 45 mN / m or less. A dispersion material of 5 wt% to 5.0 wt% is added (claim 6).

According to the sixth invention, since the surface tension of the porous protective layer forming slurry is low, the contact angle when the sensor part and the heater part are immersed in the porous protective layer forming slurry is small and wet. Therefore, a porous protective layer having a uniform film thickness can be formed.
In addition, the surface of the previously formed porous protective layer is immersed in the slurry for forming the porous protective layer when the immersion and drying in the porous protective layer forming slurry are repeated a plurality of times. When the contact angle is reduced, the capillary attractive force of the capillary formed between the particles of the heat-resistant ceramic powder constituting the underlying porous protective layer is reduced, and then the porous protective layer is formed. There is no fear that the film will become excessively thick, and a more uniform film thickness can be formed.

  In the seventh invention, the slurry for forming the porous protective layer uses a metal oxide mainly composed of at least one of alumina, alumina magnesia spinel, titania, and mullite as the heat-resistant ceramic powder, and the dispersion Water is used as a medium (Claim 7).

  According to the seventh invention, a gas sensor element including a highly durable porous protective layer can be manufactured by a simple method.

The outline | summary of the gas sensor element in the 1st Embodiment of this invention is shown, (a) is a perspective view which shows the whole, (b) is a cross-sectional view in the AA plane in this figure (a). The longitudinal cross-sectional view which shows the outline | summary of the gas sensor which comprises the gas sensor element of this invention. (A) is a Pareto chart showing the contribution ratio according to factors related to the uniform thickness of the porous protective layer, and (b) and (c) are protective layer slurries contributing to the uniformization of the porous protective layer. The characteristic view which shows the Example about the particle size distribution of the heat resistant rheramic powder contained in it with a comparative example. The correlation with the film thickness of the porous protective layer used for formation of the gas sensor element of this invention and the integrated amount of the specific particle size contained in a slurry is shown, (a) is a characteristic view with respect to the film thickness on a heater side ridge surface. (B) is a characteristic view with respect to the film thickness on a sensor side ridge surface. The correlation with the slurry for porous protective layer formation used for formation of the gas sensor element of this invention and a dispersing agent addition amount is shown, (a) is a characteristic view with respect to surface tension, (b) is a characteristic view with respect to slurry viscosity. Explanatory drawing of the test method performed in order to confirm the effect of this invention. (A) is a characteristic diagram which shows the effect of the dispersion material addition with respect to porous protective layer film thickness ratio, (b) is a characteristic diagram which shows the effect of this invention with respect to the uniformization of a porous protective layer with a comparative example. FIG. 5 is a drawing-substituting micrograph showing the characteristics of the porous protective layer in the cross section of the gas sensor element of the present invention. The drawing substitute photomicrograph which shows the characteristic of the porous protective layer in the cross section of the conventional gas sensor element shown as a comparative example. The drawing substitute electron micrograph (low magnification) which shows the characteristic of the porous protective layer in the surface of the gas sensor element of this invention. The drawing substitute electron micrograph which shows the characteristic of the porous protective layer in the surface of the conventional gas sensor element shown as a comparative example (low magnification). The drawing substitute electron micrograph (high magnification) which shows the characteristic of the porous protective layer in the surface of the gas sensor element of this invention. The drawing substitute electron micrograph (high magnification) which shows the characteristic of the porous protective layer in the surface of the conventional gas sensor element shown as a comparative example. (A)-(d) is a schematic diagram for demonstrating the influence of the surface tension of the slurry for porous protective layer formation given to the film thickness of a porous protective layer.

The gas sensor element 10 according to the first embodiment of the present invention is placed in a measured gas flow path such as a combustion exhaust flow path of an internal combustion engine such as an automobile engine, and includes oxygen contained in a measured gas such as combustion exhaust, It is used for the gas sensor 1 that detects specific gas components such as NO _X , NH ₃ , CH, etc., and uses them for combustion control, combustion exhaust treatment control, etc.
An outline of the gas sensor element 10 according to the first embodiment of the present invention will be described with reference to FIG. In this embodiment, a case where the present invention is applied to an oxygen sensor generally used as a gas sensor will be described as an example.
In addition, in this figure, the code | symbol D, W, and L shows the thickness direction D of the gas sensor element 10, the width direction W, and the longitudinal direction L, respectively.
The gas sensor element 10 is formed on a solid electrolyte layer 100 formed in a substantially flat plate shape, a reference gas electrode 110 formed on one surface of the solid electrolyte layer 100 and in contact with the atmosphere introduced as a reference gas, and on the other surface. The measurement electrode 120 in contact with the gas to be measured is laminated on the reference electrode 110 side, and the reference gas chamber forming layer 131 for forming the reference gas chamber 130 for introducing the reference gas is laminated on the measurement electrode 120 side for measurement. A sensor portion is formed by a porous diffusion resistance layer 140 having a predetermined diffusion resistance for introducing a gas to be measured to the surface of the electrode 120 and a shielding layer 150 covering the surface of the diffusion resistance layer 140.
Further, a heater portion is formed by a substantially flat insulating layer 180, a heating element 170 that is formed on the surface thereof and generates heat when energized, and an insulating layer 181 that covers the heating element 170 and ensures insulation.

The sensor part and the heater part are integrally laminated to form a substantially bottomed cylindrical gas sensor element 10, and is a main part of the present invention so as to cover a part of the gas sensor element 10 exposed to the gas to be measured, A porous protective layer 160 that protects the sensor unit from moisture and poisoning components contained in the gas to be measured is formed.
In addition, the sensor side ridge surface RS is trimmed in a taper shape or a C surface shape at a corner portion where the sensor side plane SS and the side surface SD of the gas sensor element 10 intersect, and a corner portion where the heater side plane SH and the side surface SD intersect with each other. The heater side ridge surface RH is provided in a taper shape or a C surface shape.

In the following description, the maximum film thickness of the porous protective layer 160 formed on the sensor side plane SS is t ₁ , the maximum film thickness of the porous protective layer formed on the heater side plane SH is t ₂ , and the side surface SD. The maximum thickness of the porous protective layer 160 formed thereon is t ₃ , the maximum thickness of the porous protective layer 160 formed on the sensor side ridge surface RS is t ₄ , and is formed on the heater side ridge surface RH. and the maximum film thickness of the porous protective layer 160 and t _5.
In the present embodiment, t ₁ is 350 μm or more and 450 μm or less, t ₂ is 400 μm or more and 450 μm or less, t ₃ is 350 μm or more and 450 μm or less, t ₄ is 400 μm or more and 500 μm or less, and t ₅ Is formed to be 200 μm or more and 250 μm or less.
Among thickness t ₄ of the porous protective layer 160 on sensor side edge surface SS of film thickness over the entire circumference of the porous protective layer 160, it has a maximum thickness, porous on RH heater-side edge surface The film thickness t ₅ of the protective layer 160 is the minimum film thickness among the film thickness over the entire circumference of the porous protective layer 160, and the film thickness ratio t ₄ / t ₅ of the minimum film thickness to the maximum film thickness is It is 2.5 or less.

The outline of the manufacturing method of the gas sensor element 10 of the present invention will be described.
In the solid electrolyte layer 100, an oxygen ion conductive ceramic material such as zirconia is dispersed in a dispersion medium such as toluene and ethanol together with a binder such as polyvinyl butyral (PVB), a plasticizer such as dibutyl phthalate (DBP), and a dispersant. The slurry is blended and formed into a substantially flat plate shape with a predetermined plate thickness by a known method such as a doctor blade method.

A measurement electrode layer 110 and a measurement electrode lead portion (not shown) are formed on the surface of the solid electrolyte layer 100 on the gas to be measured by a known method such as thick film printing, and the other surface has a reference electrode layer 120, A reference electrode lead portion (not shown) is formed by the same method.
For these print formations, a paste or the like in which a platinum paste and the above-described slurry for forming a solid electrolyte layer are mixed is used.
For example, a substantially flat insulating ceramic sheet is formed by a doctor blade method or the like using an alumina slurry in which an insulating ceramic material such as alumina is dispersed in a dispersion medium together with PVB, DBP, a dispersing agent, etc. The reference gas chamber forming layer 131 is punched into a reference gas chamber forming layer 131, and a plurality of the reference gas chamber forming layers 131 are stacked and bonded to the reference electrode side of the solid electrolyte layer 100, thereby forming the reference gas chamber 130.
Using a diffusion resistance layer slurry in which a heat-resistant ceramic material such as alumina having a particle size coarser than the above-described alumina sheet is dispersed in a dispersion medium together with a binder so as to cover the surface of the measurement electrode 120 of the solid electrolyte layer 100. The diffusion resistance layer 140 is formed by a known method such as a doctor blade method or a thick film printing method.
Further, a shielding layer 150 is laminated so as to cover the diffusion resistance layer 140. The shielding layer 150 may be the same as the alumina sheet used to form the reference gas introduction layer 131 described above.
The reference electrode 110 and the measurement electrode 120 are appropriately provided with a through-hole electrode or the like so as to be electrically connected to a later-described reference electrode terminal 111 and measurement electrode terminal 121 provided outside the shielding layer 150, respectively.
As described above, the reference electrode 110 is provided on one surface of the solid electrolyte layer 100, the measurement electrode 120 is provided on the other surface, and the reference gas chamber is formed so as to be laminated on the reference electrode 110 side and to have the reference gas chamber 130 inside. A sensor part provided with the layer 131 and laminated on the measurement electrode 120 side and provided with the diffusion resistance layer 140 and the shielding layer 150 can be formed.

The insulating ceramic sheet described above is formed into a substantially flat insulating layer 180 using a mold or the like, and a heating element 170 and a pair of unillustrated drawings are formed using a paste in which a platinum paste and the above-described alumina slurry are mixed on one surface thereof. A heating element lead part and a pair of heating element terminal parts 171a and 171b are printed and formed on the other surface, and the heating element lead part and the heating element terminal part are formed in a pair of through holes formed in the insulating layer 180. Through-hole electrodes that conduct to 171a and 171b are formed by suction printing or the like.
An insulating layer 181 similar to the insulating layer 180 is laminated on the printed side of the heating element 170 of the insulating layer 180 to form a heater portion in which the heating element 170 is built.
The gas sensor element 10 is formed by laminating the sensor part and the heater part formed in this way and firing them integrally.
Further, the sensor-side ridge surface RS and the heater-side ridge surface RH are formed in a tapered shape or a C-plane shape by a method such as grinding or polishing.
In addition, as a specific method for forming the sensor-side ridge surface RS and the heater-side ridge surface RH, either a method of forming a ridge surface before firing the gas sensor element 10 or a method of forming a ridge surface after firing may be used. .
When the sensor-side ridge surface RS and the heater-side ridge surface RH are formed before firing, the processing accuracy may be inferior, but the time required for processing is short and easy.
On the other hand, when the sensor-side ridge surface RS and the heater-side ridge surface RH are processed after firing, since the strength of the fired body is high, processing takes time, but the dimensional accuracy is excellent.

Further, a porous protective layer 160, which is a main part of the present invention, is formed in a portion exposed to the gas to be measured on the tip side of the gas sensor element 10 completed as described above.
The porous protective layer 160 diffuses moisture contained in the gas to be measured and collects poisonous substances composed of oil-containing components such as P, Ca, Zn, and Si and gasoline-added components such as K, Na, and Pb. In addition, the gas sensor element 10 is protected by suppressing water cracking and deterioration of the sensor portion.

Hereinafter, a specific porous protective layer forming step of the porous protective layer 160 which is a main part of the present invention will be described.
As the heat-resistant ceramic powder constituting the porous protective layer 160 applied to the gas sensor element 10 of the present invention, for example, alumina, alumina magnesia spinel, titania, mullite or the like can be used.
In the present invention, the heat-resistant ceramic powder having a relatively large particle size aligned to a predetermined average particle size is obtained by using a fine particle size particle having a particle size of 1/2 or less of the average particle size of the large particle size particle. Heat resistance ceramic powder is added within the specified range, and the heat resistance ceramic powder with fine particle size is distributed between the surface or particles of heat resistance ceramic powder with large particle size, so that packing density is increased and porous protection is achieved. Stabilization of the film thickness and improvement of strength when the layer 160 is formed are attempted.
Specifically, for example, alumina particles having an average particle diameter of 22 μm ± 4 μm are used as the heat-resistant ceramic powder composed of large particle diameter particles, whereas the heat-resistant ceramic powder composed of fine particle diameter particles is 10 μm or less. The particle size is adjusted so that alumina particles are included in the range of 8.4% to 13.0% as integrated amount, and the frequency of 10 μm in particle size is 1.8% or less.
Furthermore, in addition to these heat-resistant ceramic powders, a dispersing agent is added in a predetermined amount range, dispersed in a predetermined amount of dispersion medium, and a slurry for forming a porous protective layer adjusted to a predetermined surface tension range is prepared. .

At this time, the alumina particles contained in the slurry for forming the porous protective layer are adjusted to an average particle diameter of 22 μm ± 4 μm, and among the fine particle diameters of 10 μm or less, the frequency of 10 μm particles is 1.8%. The total amount of particles of 10 μm or less is adjusted to be 8.4% or more and 13.0% or less.
Specifically, a nonionic dispersant (for example, a solid content of alumina slurry adjusted to have a predetermined concentration using water as a dispersion medium, for example, a slurry viscosity of 500 to 1000 mPa · s, for example, Polyoxyalkylene glycol adduct, etc.) is added in a range of 0.5 wt% to 5.0 wt% with respect to the solid content of the alumina slurry, and the surface tension of the alumina slurry is adjusted to 45 mN / m or less. .

A predetermined range in which the measurement electrode 120 on the tip side of the gas sensor element 10 is formed is immersed in the slurry for forming a porous protective layer (alumina slurry) thus formed, pulled up at a predetermined speed, and dried. Then, a film to be the porous protective layer 160 is formed on the surface.
Repeated dipping and drying a plurality of times (for example, 3 times in the present embodiment), and when a predetermined film thickness is obtained, the porous protective layer 160 is fixed to the surface of the gas sensor element 10 by further heat treatment. Let
At this time, since the heat-resistant ceramic powder having a fine particle diameter is blended within the above-mentioned range, the packing density is improved at the time of coating formation, and the strength of the coating is increased. When the packing density of the formed porous protective layer serving as the base is high, the water absorption rate of the next dipped slurry is suppressed, and the film thickness can be made uniform without becoming an excessive film thickness.

  In addition, since the surface tension is adjusted to a predetermined range by the addition of the dispersant, the contact angle when the gas sensor element 10 is immersed in the slurry for forming the porous protective layer is reduced, so that the coating is easily wetted and spread. In addition, since the suction force of the capillaries formed between the particles of the dried protective layer becomes small, excessive film formation can be suppressed and the film thickness can be made uniform.

It should be noted that a predetermined amount of fine particle size particles is added to a large particle size heat resistant ceramic powder having a constant particle size distribution as described above, so that the cumulative amount of the heat resistant ceramic powder having a fine particle size falls within a predetermined range. Heat resistant ceramic powder may be added, or the particle size distribution may be adjusted by sieving heat resistant ceramic powder having a wide particle size distribution.
Further, in the following embodiment, alumina will be described as an example of the heat-resistant ceramic powder. However, surprisingly, a metal oxide containing at least one of alumina magnesia spinel, titania, and mullite as a main component may be used. it can.
Further, it is presumed that the film thickness can be further stabilized and the strength can be further improved by adjusting the alumina slurry so that the integrated amount of alumina particles of 5 μm or less is 4% or more.

With reference to FIG. 2, the outline | summary of the gas sensor 1 which comprises the gas sensor element 10 of this invention is demonstrated.
The gas sensor 1 includes a gas sensor element 10, a housing 30 that holds the gas sensor element 10 inside the insulating holding member 20, and cover bodies 60 and 61 that cover portions of the gas sensor element 10 that are exposed to the gas 700 to be measured. A pair of energization wires 171 a, 171 b to 174 a and 174 b for supplying power to the heater portion of the element 10 and a pair of signal lines 111 to 114 and 121 to 124 for taking out an output signal from the gas sensor element 10 are interposed via the sealing member 50. And a casing 40 for holding and fixing.

The housing 30 is made of a metal such as stainless steel and is formed in a substantially cylindrical shape. A casing 40 is fitted on the boss portion 32 on the proximal end side, and a double tubular shape is formed on the caulking portion 34 on the distal end side. Cover bodies 60 and 61 are fixed.
A threaded portion 31 is formed on the middle outer peripheral portion of the housing 30 and is screwed to a combustion exhaust passage 70 of an internal combustion engine (not shown) via a gasket or the like, so that a porous protective layer on the front end side of the gas sensor element 10 is formed. The portion covered with 170 is exposed to the gas 700 to be measured, and is fixed in a state covered with the cover bodies 60 and 61.
A hexagonal portion 33 for tightening the screw portion 31 is formed on the outer periphery on the proximal end side of the housing 30.

The cover bodies 60 and 61 are made of a heat-resistant metal such as stainless steel and have a double cylinder structure including a substantially bottomed cylindrical outer cover 60 and an inner cover 61.
The outer cover 60 and the inner cover 61 are respectively provided with introduction holes 601, 602, 611, 612 for introducing the measurement gas 700 into the inside and preventing the gas sensor element 10 from being exposed to water. The flange portion is caulked and fixed to the caulking portion 34 of the housing 30.

The gas sensor element 10 is fixed to the inside of the housing 30 via the sealing member 22 while ensuring insulation with the housing 30 by the insulator 20. The tip of the gas sensor element 10 exposed to the gas to be measured is covered with a porous protective layer 160 that is a main part of the present invention.
On the base end side of the gas sensor element 10, a reference electrode terminal portion 111 and a measurement electrode terminal portion 121 that aim to output the sensor, and heater terminal portions 171a and 171b that energize the heating element 170 are formed. Are elastically connected to the connection fittings 112, 122, 172a, and 172b held by.
The connection fittings 112, 122, 172a and 172b are connected to the signal lines 114 and 124 and the energization wires 174a and 174b via the crimp fittings 113, 123, 173a and 173b, respectively.
The pair of signal lines 114 and 124 and the pair of energization lines 174 a and 174 b are sealed and fixed to the base end portion 41 of the casing 40 through the sealing member 50.
Reference gas introduction holes 42 and 43 are formed in the base end portion 41, and the air introduced through the water repellent filter 44 is introduced into the reference gas chamber 130 of the gas sensor element 10.

When the heating element 170 is energized by an energization control device (not shown) and the solid electrolyte layer 100 is activated by the heating element 170, oxygen in the gas 700 to be measured that comes into contact with the measurement electrode layer 120 through the diffusion resistance layer 140. A potential difference is generated between the two electrodes due to the difference between the concentration and the oxygen concentration in the atmosphere introduced into the reference gas chamber 130 in contact with the reference electrode layer 110. By measuring this, the oxygen concentration in the gas 700 to be measured is determined. It can be detected.
In the above embodiment, the case where an oxygen ion conductive solid electrolyte material is used as a solid electrolyte body constituting a sensor unit used in an oxygen sensor, a NOx sensor, an air-fuel ratio sensor or the like has been described. The present invention is not limited to such a gas sensor that detects oxygen ions, but can be applied to any gas sensor such as a gas sensor that detects a hydrogen component-containing gas such as ammonia or hydrocarbon using a proton-conducting solid electrolyte.

With reference to FIG. 3, factors contributing to the uniform thickness of the porous protective layer 160 will be described. As shown in FIG. 3A, the most contributing to the uniform thickness of the porous protective layer 160 is the heat resistant ceramic powder contained in the slurry used to form the porous protective layer 160. It has been found that it is most important to control the integrated amount of fine particles of 10 μm or less. This is the result of the inventors' diligent investigations conducted under various conditions for the factors shown in FIG.
In past test investigations by the present inventors, it has been found that it is effective to use alumina having a relatively large particle size with an average particle size of 22 μm ± 4 μm as the heat-resistant ceramic powder forming the porous protective layer 160. doing.
However, since the heat-resistant ceramic powder such as alumina usually has a wide particle size distribution, the particle size can be reduced by sieving to form a porous protective layer having desired characteristics such as porosity and durability. In general, a classified one is used.
However, as shown in FIGS. 2B and 2C, for example, even an alumina powder having an average particle size of 22 μm ± 4 μm does not have a normal distribution with respect to the center particle size, and is not more than a certain particle size. There are fine particles and the distribution is biased.
It has been found that the presence of such fine particles greatly affects the behavior of the resulting slurry and also affects the thickness of the porous protective layer.
Therefore, the present inventors intentionally control the behavior of the slurry by controlling the abundance of finely sized particles, and aim to make the thickness of the porous protective layer uniform and increase the packing density. The present invention has been made by paying attention to the above.
The porous protective layer forming slurry of the present invention shown by solid lines as examples in FIGS. (B) and (c) is a conventional porous protective layer shown by dotted lines as comparative examples in FIGS. (B) and (c). The forming slurry and the average particle size are the same, but the frequency of particles having a particle size of 10 μm and the integrated amount of particles having a particle size of 10 μm or less are adjusted to be in a specific range.
By conducting an intensive test by the present inventors, a porous amount applied to the gas sensor element 10 is controlled by controlling an integrated amount of 10 μm or less, which is one half or less of the average particle size of the heat-resistant ceramic powder constituting the porous protective layer 160. It has been found that the film thickness of the quality protective layer 160 can be made uniform and the durability can be improved.

With reference to FIG. 4, the knowledge obtained as a result of the earnest examination investigation by the present inventors will be described.
This figure (a) is the film thickness of the protective layer 160 formed on the sensor side ridge surface RS and the integrated amount of the particle size of 10 μm or less present in the slurry prepared using alumina powder having an average particle size of 22 μm ± 4 μm. This is a result of investigating the correlation with t _4, and this figure (b) shows the frequency of the particle size of 10 μm present in the slurry prepared using the alumina powder having an average particle size of 22 μm ± 4 μm and the sensor side ridge surface RS. it is the result of investigation on the correlation between the film thickness t ₄ of the protective layer 160 to be formed.
In the present embodiment, the thickness t ₄ of the porous protective layer 160 formed on the sensor side edge surface RS is, among the film thickness over the entire circumference of the porous protective layer 160, the thickest maximum film thickness Prefecture It has become.
As shown in this figure (a), there is a negative correlation between the integrated amount of particles having a particle size of 10 μm or less and the film thickness t ₄ of the porous protective layer 160 formed on the sensor side ridge surface RS. There, the thickness t ₄ of the porous protective layer 160 integrated amount of particle size 10μm or less of the particles contained in the alumina slurry is formed with increasing sensor on the side edge surface RS has been found to be thinner.
To hardly occurs under water cracks, an attempt to form a thick film thickness t ₅ of the porous protective layer 160 formed on the RH heater-side edge surface, is formed on the relatively sensor side edge surface on RS porous thickness _{t 4} of the quality protective layer 160 is also increased.
Therefore, when the upper limit of the film thickness t4 of the porous protective layer 160 formed on the sensor side ridge surface RS having the shortest distance from the inner periphery of the inner cover 61 is 630 μm, 95% is considered in consideration of the variation. From the reliability limit, the film thickness t ₄ of the porous protective layer 160 formed on the sensor side ridge surface RS is formed to be 630 μm or less by setting the cumulative amount of alumina particles having a particle size of 10 μm or less to 8.4% or more. I understand that I can do it.
On the other hand, there is a positive correlation between the frequency of the particle diameter of 10 μm contained in the alumina slurry and the film thickness t ₄ of the protective layer 160 formed on the sensor side ridge surface RS, and is contained in the alumina slurry. thickness t ₄ of the porous protective layer 160 the frequency of particle size 10μm particles are formed with increasing sensor on the side edge surface RS has been found that thicker.
Therefore, it can be seen that the film thickness t ₄ of the porous protective layer 160 formed on the sensor side ridge surface RS can be formed to 630 μm or less by setting the frequency of particles having a particle size of 10 μm to 1.8% or less.
As described above, the lower limit for the integrated amount of particles having a particle size of 10 μm or less contained in the alumina powder having an average particle size of 22 μm ± 4 μm and the upper limit for the frequency of particles having a particle size of 10 μm were determined.

Next, with reference to FIG. 5, the results of tests conducted by the present inventors will be described regarding the relationship between the characteristics of the alumina slurry forming the porous protective layer 160 of the gas sensor element 10 of the present invention and the amount of dispersant added. .
As a result of investigating the change in the surface tension by changing the weight ratio of the dispersant to the solid content in the slurry, as shown in this figure (a), when 0.5 wt% or more of the dispersant is added, the surface tension is 45 mN / It became clear that it became m or less and became constant at 1.0 wt% or more. By reducing the surface tension, it is assumed that wetting and spreading properties when applied to the gas sensor element 10 are improved, and the thickness of the porous protective layer 160 can be made uniform.
Further, when the change in slurry viscosity was investigated by changing the weight ratio of the dispersant to the solid content in the slurry, as shown in FIG. It has been found that when the viscosity decreases and 5.0 wt% or more is added, the effect of the dispersant decreases, and alumina re-aggregates to increase the viscosity. As described above, the upper limit and the lower limit for the addition amount of the dispersant were determined.
The effect of uniformizing the film thickness of the porous protective layer 160 accompanying the decrease in surface tension and the decrease in slurry viscosity will be described later.

Next, with reference to FIG. 6, a test performed on the durability of the gas sensor element 10 of the present invention will be described.
When the porous protective layer 160 of the gas sensor element 10 of the present invention is formed, the condition is changed from 0.5% to 18.0% of the cumulative amount of particles having a particle size of 10 μm or less contained in the slurry for forming the porous protective layer Sample No. of gas sensor element manufactured As shown in FIG. 6, in a state where a plurality of levels 1 to 15 are prepared and the heating element 170 is energized, on the heater side ridge surface RH, which is close to the heating element 170 and easily affected by thermal shock, as shown in FIG. Using a dropping device, 1.0 μl of water drops are dropped so as to hit the protective layer 160 provided, and the state of the porous protective layer 160 is observed every time 500 drops of water are dropped. The number of drops was measured at the time when an abnormality such as cracking or peeling occurred in the film and evaluated. Table 1 shows the test results.
In addition, Table 1 shows a case where a conventional slurry for a porous protective layer in which an integrated amount having a particle size of 10 μm or less is not controlled is shown as Comparative Example 5.
The cumulative amount of particles having a particle size of 10 μm or less in Comparative Example 5 was 8.2%, and the number of drops until the occurrence of peeling was 5100. Based on this, the number of drops until the peeling occurred Is less than 5100 times, it is determined that there is no effect, the determination result is indicated by × mark, the case where the number of drops until the occurrence of peeling exceeds 5100 times is determined to be effective, the determination result is indicated by ○ mark, The case where the number of drops until the occurrence of peeling exceeded 7000 was judged as having a remarkable effect, and the judgment result was indicated by ◎.
In addition, as shown in the remarks column of Table 1, the sample No. in which the effect was not recognized. 1-5 and no. Samples Nos. 12 to 15 were identified as Comparative Examples 1 to 5 and Comparative Examples 6 to 9, respectively. 6 to 11 were set as Examples 1 to 6 of the present invention, respectively.
In addition, when a crack occurred during the dropping test, it was determined that there was no effect regardless of the number of times of dropping, and the determination result was indicated by x.
The numerical values in parentheses shown in the column of the film appearance in Table 1 indicate the number of test levels in the denominator and the number of levels in which the numerator has cracked.

  From the above results, the cumulative amount of particles having a particle size of 10 μm or less contained in a slurry in which alumina having an average particle size of 22 μm ± 4 μm is dispersed as the heat-resistant ceramic powder forming the porous protective layer 160 is 8.4% or more, 13 It was found that by setting the ratio to 0.0% or less, it is possible to form a highly durable porous protective layer 160 that hardly causes cracking and peeling when wet.

As described above, when the cumulative amount of particles of 10 μm or less is 8.4% or less, the film thickness t ₄ on the sensor-side ridge surface is 630 μm or more, so that the heat resistance for forming the porous protective layer 160 is also achieved. It has been confirmed that the cumulative amount of particles having a particle size of 10 μm or less contained in a slurry in which alumina having an average particle size of 22.0 μm is dispersed as ceramic powder is preferably 8.4% or more. Further, when the cumulative amount of particles having a particle size of 10 μm or less exceeds 13%, in addition to the decrease in durability, the surface roughness of the porous protective layer 160 may also decrease, and the toxicity to the object may also decrease.
In forming the porous protective layer of the gas sensor element, the heat-resistant ceramic powder having a specific average particle diameter constituting the porous protective layer is a fine particle having a specific range of 1/2 or less of the average particle diameter. By containing particles having a diameter within a predetermined range, it is presumed that the packing density of the porous protective layer is improved, and the water receiving strength is increased.

As described above, it was found that the surface tension and the viscosity of the slurry can be lowered by setting the addition amount of the dispersant to 0.5 wt% or more and 5.0 wt% or less. The effect on the uniform film thickness when the protective layer is formed will be described with reference to FIG.
As shown to this figure (a), when a dispersing agent is added 0.5 wt% or more with respect to solid content of the slurry for porous protective layer formation, the film thickness on the heater side ridge surface RH where the film thickness becomes the thinnest The ratio t ₄ / t ₅ of the film thickness t ₄ on the sensor-side ridge surface RS where the film thickness is the largest with respect to t ₅ can be set to 2.5 or less, and again when 5.0 wt% or more is added. It was found that the film thickness ratio t ₄ / t ₅ exceeded 2.5 and the difference in film thickness over the entire circumference of the porous protective layer 160 was increased.
Further, the film thickness (t _{1 to} t ₅ ) in each part when no dispersant is added to the conventional slurry for forming a porous protective layer shown as a comparative example in FIG. the thickness of each part of the case of adding .5～5.0Wt% showing a _(t 1 ~t _5). The subscripts R and L attached to the measurement positions mean the results of measurement at the right and left positions, respectively, in the cross section with the sensor-side plane SS shown in FIG. .
As shown in FIG. 5B, in the embodiment, t ₁ , t ₂ , t ₃ (R, L), and t ₄ (R, L) are thinner than the comparative example, and t ₅ (R, L) became thicker than the comparative example, and it was confirmed that the thickness of the porous protective layer 160 was made uniform as a whole.
Further, not only the film thickness of the entire porous protective layer 160 is made uniform, but also the variation between samples is reduced, and according to the present invention, it can be expected that the gas sensor element 10 with more stable quality can be formed.

The effect of the present invention will be further described with reference to FIGS. FIG. 8 is a photomicrograph observing the cross section of the gas sensor element 10 of the present invention, and FIG. 9 is a photomicrograph observing the cross section of the conventional gas sensor element 10z.
As an example of the present invention, a porous protective layer using an alumina slurry having an average particle size of 21.4 μm, an integrated amount of particles having a particle size of 10 μm or less of 13.0%, and a dispersant addition amount of 1.0 wt% As a comparative example, the gas sensor element 10 having 160 and an integrated amount of particles having an average particle diameter of 22.0 μm and a particle diameter of 10 μm or less are 0.5%, and porous protection is performed using an alumina slurry without addition of a dispersant. The gas sensor element 10z in which the layer 160z was formed was compared and examined.
The example and the comparative example are formed under the same conditions except for the slurry for forming the porous protective layer.
Compared to the porous protective layer 160z of thickness t _5z on the heater side edge surface of the conventional gas sensor element 10z as a comparative example in FIG. 9, the heater of the gas sensor element 10 of the present invention shown as an example of the present invention in FIG. 8 has become thicker thickness t ₅ of the porous protective layer 160 on the side edge surface, clearly it can be confirmed that the uniformity of the film thickness of the porous protective layer 160 is achieved.

With reference to FIGS. 10 to 13, the difference in characteristics between the gas sensor element 10 of the present invention and the conventional gas sensor element 10z will be further described.
10 and 11 are electron microscopes in which the surface of the porous protective layer 160z of the gas sensor element 10 of the present invention and the surface of the porous protective layer 160z of the conventional gas sensor element 10z are observed at a low magnification (× 200), respectively. FIGS. 12 and 13 are electron micrographs observed at a high magnification (× 2000), respectively.
As shown in FIGS. 10 and 11, there is no significant difference between the gas sensor element 10 of the present invention and the conventional gas sensor element 10z with respect to the distribution state of the holes, the roughness of the surface, and the distribution state of the particles having a large particle diameter. However, as shown in FIGS. 12 and 13, a large difference can be confirmed in the distribution of particles having a fine particle diameter of 10 μm or less between the example of the present invention and the conventional comparative example.

As shown in FIG. 12, in the porous protective layer 160 of the gas sensor element 10 of the present invention, primary particles having a size of about 1 μm are aggregated to form large secondary particles of 10 μm or more. It is observed that primary particles having a fine particle diameter of 10 μm or less are dispersed without agglomeration between the surfaces of the secondary particles and between the particles.
On the other hand, as shown in FIG. 13, in the porous protective layer 160z of the conventional gas sensor element 10z, primary particles having a size of about 1 μm are aggregated to form large secondary particles of 10 μm or more. As in the gas sensor element 10 of the present invention, it is not observed that particles having a fine particle diameter are dispersed without being aggregated between the surfaces of the secondary particles and the particles.

Here, addition of a dispersing material to the gas sensor element 10 of the present invention, and a surface by adding an integrated amount of particles of 10 μm or less contained in a slurry for forming a porous protective layer forming the porous protective layer 160 and a dispersant. The relationship between the decrease in tension and the film formation of the porous protective layer 160 will be described with reference to FIG.
As shown in this figure (a), when the surface tension σ _a of the porous protective layer forming slurry is large, the contact angle θ _a when the porous protective layer slurry is applied to the surface of the sensor element 10 becomes large. .
On the other hand, as shown in FIG. 4B, when the surface tension σ _{b of} the slurry is small, the contact angle θ _b when the slurry for the porous protective layer is applied to the surface of the sensor element 10 becomes small.
For this reason, when _a slurry having _a large surface tension σ _a is used when a porous film is formed on a flat surface, the film thickness at the center portion tends to become thicker, and a slurry having a small surface tension σ _b appears. When used, the wettability is improved and the entire film is easily spread, so that the film thickness can be made uniform.
Furthermore, as shown in the figure (c), when the surface tension sigma _a is large, increased capillary attraction P _Ca capillary (diameter 2r) formed between the porous protective layer particles, a plurality of times When a porous protective layer is formed across the substrate, the water absorption rate of the protective layer serving as a base is increased, and the formed film thickness is increased.
For this reason, when _a conventional slurry having a large surface tension σ _a is used, there is a tendency that the vicinity of the center of the film thickness t ₁ on the sensor side plane SS and the film thickness t ₂ on the heater side plane SH tends to be further thickened. There is a risk of excessive thickness.
On the other hand, as shown in this figure (d), when the surface tension σ _b is low, the capillary attractive force PCb of the capillary (diameter 2r) formed between the particles of the porous protective layer becomes small, and it is _repeated several times. Even when the porous protective layer is formed, the water absorption rate of the protective layer serving as a base is slowed down and an excessive film thickness is suppressed.
Furthermore, in the present invention, since the heat-resistant ceramic powder having a fine particle diameter is blended within the above-mentioned range, the packing density is improved during the formation of the coating, and the strength of the coating is increased. If the packing density of the porous protective layer, which is the base layer previously formed, is high, particles with a fine particle size exist in the capillaries formed between the particles, and the amount of water that can be absorbed decreases. The water absorption rate of the slurry thus obtained is further suppressed, and the film thickness can be made uniform without becoming an excessive film thickness.

The present invention is not limited to the above embodiment, and in forming the porous protective layer covering the surface of the gas sensor element, the average particle diameter of the heat-resistant ceramic powder constituting the porous protective layer is not more than one half. By specifying the cumulative amount of fine particles and adding a dispersant, the surface tension of the slurry is reduced, the packing density of the porous protective layer is increased, the film thickness is made uniform, and the porous protective layer As long as the strength of the present invention is not contrary to the gist of the present invention, it can be appropriately changed.
For example, in the above embodiment, an example in which one detection cell is configured by the reference electrode 110, the measurement electrode 120, and the solid electrolyte layer 100 as the gas sensor element has been described. It can be adopted as appropriate.

10 Gas sensor element 100 Solid electrolyte layer 110 Reference electrode 120 Measurement electrode 130 Reference gas chamber 131 Reference gas chamber forming layer 140 Diffusion resistance layer 150 Shielding layer 160 Porous protective layer 170 Heating element 180, 181 Insulating layer SS Sensor side plane SH Heater side Planar SD Side RS Sensor side ridge surface RH Heater side ridge surface

JP 2006-343297 A JP 2006-250537 A

Claims (6)

A solid electrolyte layer in which a solid electrolyte material having specific ion conductivity is formed in a substantially flat plate shape, a reference electrode formed on one surface of the solid electrolyte layer and in contact with a reference gas, and a gas to be measured formed on another surface A sensor unit that is placed in the measurement gas flow path and detects the concentration of a specific gas component in the measurement gas; and a heating element that generates heat when energized, and the sensor unit A gas sensor element comprising: a heater portion that heats; and a porous protective layer that is formed using a heat-resistant ceramic powder and covers a surface of the sensor portion and the heater portion,
The porous protective layer is composed of large particles having an average particle diameter of 22 μm ± 4 μm and fine particles having a particle diameter of 10 μm or less distributed on the surface of the large particles or between the particles. Among the diameter particles, the frequency of particles having a particle diameter of 10 μm is 1.8% or less, and the integrated amount of particles having a particle diameter of 10 μm or less is 8.4% to 13.0%. element.   The gas sensor element according to claim 1, wherein the ratio of the minimum film thickness to the maximum film thickness of the porous protective layer is 2.5 or less.   The gas sensor element according to claim 1 or 2, wherein the heat-resistant ceramic powder is a metal oxide containing at least one of alumina, alumina magnesia spinel, titania, and mullite as a main component. A solid electrolyte layer in which a solid electrolyte material having specific ion conductivity is formed in a substantially flat plate shape, a reference electrode formed on one surface of the solid electrolyte layer and in contact with a reference gas, and a gas to be measured formed on another surface A sensor unit that is placed in the measurement gas flow path and detects the concentration of a specific gas component in the measurement gas; and a heating element that generates heat when energized, and the sensor unit The heater part that heats the sensor, and covers the surface of the sensor part and the heater part exposed to the gas to be measured to protect the sensor part and the heater part from moisture and poisonous components contained in the gas to be measured A method for producing a gas sensor element, wherein a porous protective layer is formed using a heat-resistant ceramic powder,
At least a predetermined range of the sensor part and the heater part is immersed in a slurry for forming a porous protective layer in which the heat-resistant ceramic powder is dispersed in a predetermined dispersion medium, dried, heat-treated. Comprising a porous protective layer forming step of forming a porous protective layer,
The average particle size of the heat-resistant ceramic powder contained in the slurry is adjusted to 22 μm ± 4 μm, and among the fine particle size particles of 10 μm or less contained in the slurry for forming the porous protective layer, the frequency of 10 μm particles is set. A method for producing a gas sensor element, wherein the gas sensor element is adjusted to 1.8% or less so that an integrated amount of particles of 10 μm or less is 8.4% or more and 13.0% or less.   In order that the surface tension of the slurry for forming the porous protective layer is 45 mN / m or less, the weight ratio is 0.5 wt% or more and 5.0 wt% with respect to the solid content contained in the slurry for forming the porous protective layer. The manufacturing method of the gas sensor element of Claim 4 which adds a dispersion material of% or less.   The slurry for forming a porous protective layer uses a metal oxide mainly composed of at least one of alumina, alumina magnesia spinel, titania, and mullite as the heat-resistant ceramic powder, and uses water as the dispersion medium. Item 6. The method for producing a gas sensor element according to Item 4 or 5.