JP2002340843A - Manufacturing method for gas sensor element - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a manufacturing method for a gas sensor element having superior durability. SOLUTION: A raw sheet for a solid electrolyte plate 13 is provided with a printing part for forming an electrode, and a raw sheet for a heater board 15 is provided with a printing part for a heating element 150, grooving is performed for a raw sheet for a spacer plate 14, and a groove part having a closed end 102 and an open end 101 to form a reference gas chamber 10 is formed by pressing using a press die. In setting the raw sheet for the spacer plate 14, a porous sheet is used as a mold releasing sheet, the raw sheet for the spacer plate 14 is stacked on the raw sheet for the heater board 15, the raw sheet for the solid electrolyte plate 13 is stacked, the sheets are stuck to each other by an adhesive to form an unburnt layered product, and then the unburnt layered product is burnt.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for manufacturing various gas sensor elements mounted on an exhaust system of an internal combustion engine and used for controlling combustion.

[0002]

2. Description of the Related Art A gas sensor for use in combustion control is provided in an exhaust system of an automobile engine. As a gas sensor element incorporated therein, an element having a structure as disclosed in JP-A-9-26409 is known. ing.

As shown in FIG. 17, a gas sensor element 9 is provided in a reference gas chamber with a solid electrolyte plate 93 having a measured gas side electrode 11 in contact with a measured gas and a reference gas side electrode 12 in contact with a reference gas. Are formed by laminating a spacer plate 94 which constitutes a substrate with an alumina substrate 95. As shown in the figure, the spacer plate 94 has a U-shape and has a window 940 for forming a reference gas chamber.

One end of the reference gas chamber of the gas sensor element 9 is a closed end, and the other end is an open end open to the outside of the gas sensor element, and air or the like serving as a reference gas is introduced from the open end. It is configured to: In addition,
Although not shown, a heater substrate provided with a heating element is laminated on the alumina substrate 95.

[0005]

In the conventional gas sensor element 9, the spacer plate 94 and the alumina substrate 95 are separated during the manufacturing process or during use of the gas sensor element 9 to cause defects or troubles. was there. Therefore, in the gas sensor element 9 having the above configuration, it is conceivable to use a ceramic plate in which the spacer plate 94 and the alumina substrate 95 are integrated as a substitute for the spacer plate 94. That is, a groove is provided in the ceramic plate, and this groove is used as a reference gas chamber (see FIGS. 1 and 2 described later).

However, it is known that the following problems occur when a press die is used in manufacturing a spacer plate having a groove. That is, it is considered that an unsintered green sheet for a spacer plate is pressed using a press die to form a groove portion that can be used as a reference gas chamber (see FIG. 8 described later). At this time, air inside the raw sheet accumulates on the opposite side of the surface on which the groove is formed, and a void 70 may be formed as shown in FIG. Even after the green sheet is fired and turned into a spacer plate, the voids remain and reduce the strength of the spacer plate. Therefore, cracks, damages, and the like occur in the spacer plate, causing a reduction in the strength and durability of the gas sensor element.

The present invention has been made in view of such a conventional problem, and has as its object to provide a method of manufacturing a gas sensor element having excellent durability.

[0008]

According to a first aspect of the present invention, there is provided a solid electrolyte plate including a measured gas side electrode in contact with a measured gas and a reference gas side electrode in contact with a reference gas; A spacer plate having a closed end at one end and an open end open to the outside of the gas sensor element at the other end and having a reference gas chamber configured to introduce a reference gas; In manufacturing a gas sensor element in which a heater substrate having a heating element that generates heat by energization is laminated, a raw sheet for a solid electrolyte plate, a raw sheet for a spacer plate, and a raw sheet for a heater substrate are prepared, respectively.
A printed portion for forming electrodes is provided on the raw sheet for the solid electrolyte plate, and a printed portion for the heating element is provided on the raw sheet for the heater substrate.
The raw sheet for the spacer plate is grooved, and a groove having a closed end and an open end serving as a reference gas chamber is formed by press working using a press die. When setting the sheet, a porous sheet is used as a release sheet, a raw sheet for a spacer plate is laminated on a raw sheet for a heater substrate, and a raw sheet for a solid electrolyte plate is further laminated on these, and affixed with an adhesive. The present invention also provides a method for manufacturing a gas sensor element, in which an unsintered laminate is combined, and then the unsintered laminate is fired.

In the manufacturing method according to the present invention, the groove is formed by press working using a press die, and a porous sheet is used as a release sheet when a raw sheet for a spacer plate is set in the press die. As a result, as shown in FIG. 12, when the raw sheet is pressed, the air contained in the raw sheet escapes through the release sheet, so that voids are less likely to be generated in the raw sheet. Conventionally, Figure 1
As shown in FIG. 1, since there was no escape route of the air, the void 70 was formed in the raw sheet.

The spacer plate fired with the voids formed has low strength. Therefore, cracks, damages, and the like caused by the voids occur, which causes a decrease in the strength and durability of the gas sensor element. According to the present invention, since no void is formed, a gas sensor element having excellent strength and durability can be obtained.

As described above, according to the present invention, it is possible to provide a method for manufacturing a gas sensor element having excellent durability.

Each of the raw sheets can be manufactured in a size that can take one gas sensor element. However, from the viewpoint of manufacturing efficiency, each raw sheet is formed in a size that can take a plurality of gas sensor elements. It is preferable that a plurality of printed portions are formed, stacked, and then cut into pieces for each gas sensor element to be manufactured (see FIGS. 4 to 6).

Next, it is preferable that the release sheet has a thickness of 0.25 to 0.35 mm. As a result, voids are less likely to occur in the raw sheet. If the thickness of the release sheet is less than 0.25 mm, voids may remain in the raw sheet.
If the thickness is more than 0.35 mm, the price of the release sheet may be high and the cost may be high.

Next, it is preferable that the release sheet has a gas permeability of 20 seconds or less according to JIS P8117. As a result, voids are less likely to occur in the raw sheet. If the gas permeability of the release sheet is greater than 20 seconds, voids may remain in the raw sheet. The smaller the gas permeability, the better.

The gas permeability according to JIS P8117
The excess rate is an area of one square inch, or about 6.54 squares.
100 cm of air for 12.4 cm per cm sheet
H _TwoWhen pressurized with O pressure, 100cc of air
It is expressed by the time it takes to pass through the sheet.
Will be difficult to pass through. The above gas permeability is
For example, Oken type air permeability measurement device (Oji Paper Co., Ltd.)
Can be measured by using.

Next, as in the fourth aspect of the present invention, it is preferable that the water release pressure of the release sheet is 60 kPa or more. Thereby, breakage of the release sheet at the time of press working can be prevented. If the sheet waterproof pressure of the release sheet is less than 60 kPa, the release sheet may be damaged during press working. The greater the sheet withstand pressure, the better. Note that the sheet withstand pressure (WE
P: Water entry pressure) is 4 in diameter
7 mm sheet (pressure surface to which pressure is applied is 37 m in diameter
m area) is a pressure at which water flows slightly (confirmed visually) when a water pressure is applied at a rate of 0.2 N / sec.

Next, as in the fifth aspect of the present invention, the surface roughness of the release sheet is preferably 10 μm or less in ten-point average roughness. Thereby, the raw sheet can be laminated without forming a void at the interface with the release sheet. The smaller the surface roughness of the release sheet, the better. If the surface roughness of the release sheet is greater than 10 μm, the raw sheet may be laminated with the voids involved, due to the unevenness of the surface of the release sheet when laminated.

Next, a sixth aspect of the present invention is a solid electrolyte plate having a measured gas side electrode in contact with a measured gas and a reference gas side electrode in contact with a reference gas, and a solid electrolyte plate facing the reference gas side electrode. A spacer plate provided with a reference gas chamber configured to introduce a reference gas, the groove having a closed end at one end and an open end open to the outside of the gas sensor element at the other end; In manufacturing a gas sensor element in which a heater substrate provided with a heating element that generates heat is laminated, a raw sheet for a solid electrolyte plate, a raw sheet for a spacer plate, and a raw sheet for a heater substrate are prepared.
A printed portion for forming electrodes is provided on the raw sheet for the solid electrolyte plate, and a printed portion for the heating element is provided on the raw sheet for the heater substrate.
A groove was formed in the raw sheet for the spacer plate, and a groove having a closed end and an open end serving as a reference gas chamber was formed by pressing using a press die, and then the groove in the raw sheet was formed. The opposite surface is smoothed by cutting the opposite surface so as to be parallel to the surface on which the groove is formed, and the raw sheet for the spacer plate is laminated on the raw sheet for the heater substrate, and the solid electrolyte is further added thereto. There is provided a method for manufacturing a gas sensor element, which comprises stacking raw sheets for a plate, bonding them with an adhesive to form an unfired laminate, and thereafter firing the unfired laminate (see FIG. 14).

In the manufacturing method according to the present invention, in the raw sheet for the spacer, the opposite surface is cut in parallel with the surface provided with the groove. As a result, since the above-mentioned voids are almost removed, a gas sensor element having excellent strength and durability can be obtained as described above.

As described above, according to the present invention, a method of manufacturing a gas sensor element having excellent durability can be provided. The cutting can be performed by using, for example, a soft surface polishing method or the like. In addition, a raw sheet thicker than the spacer plate to be obtained can be manufactured by anticipating the cut portion in advance. In this case, the raw sheet has such a thickness that a desired spacer plate can be obtained after cutting.

Next, a seventh aspect of the present invention provides a solid electrolyte plate having a measured gas side electrode in contact with the measured gas and a reference gas side electrode in contact with the reference gas, and a solid electrolyte plate facing the reference gas side electrode. A spacer plate provided with a reference gas chamber configured to introduce a reference gas, the groove having a closed end at one end and an open end open to the outside of the gas sensor element at the other end; When manufacturing a gas sensor element comprising a heater substrate provided with a heating element that generates heat, a raw sheet for a solid electrolyte plate, a raw sheet for a spacer plate, and a raw sheet for a heater substrate, from which a plurality of gas sensor elements can be formed, are prepared. Each of them was prepared and the raw sheet for the solid electrolyte plate was provided with a printed part for electrode formation, and the raw sheet for the heater substrate was provided with a plurality of printed parts for the heating element so that a plurality of gas sensor elements could be installed. The raw sheet for the heater board is formed by forming a groove with a closed end and an open end serving as a reference gas chamber so that a plurality of grooves can be formed by pressing using a press die. The raw sheet for the spacer plate is laminated on top of this, and the raw sheet for the solid electrolyte plate is further laminated on them, and they are laminated with an adhesive to form an unfired laminate. A method of manufacturing a gas sensor element, comprising: performing singulation, removing the space between adjacent singulations, and firing the obtained singulations.

Usually, voids are formed on the opposite surface between the grooves (see FIG. 10). Therefore, as in the present invention, in the singulation, by cutting so as to remove the space between adjacent pieces, the portion where the voids are generated is removed, and a raw sheet for a heater substrate having no voids is obtained. be able to. Therefore, as described above, a gas sensor element having excellent strength and durability can be obtained.

As described above, according to the present invention, a method for manufacturing a gas sensor element having excellent durability can be provided.

The above-mentioned cutting can be performed using, for example, blade cutting using a cutting blade. In addition, the meaning that a plurality of gas sensor elements can be taken means that one unfired form produced by laminating green sheets is cut to produce a plurality of gas sensor elements, and the details are described in the first embodiment. .

[0025]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Embodiment 1 A method for manufacturing a gas sensor element according to an embodiment of the present invention will be described with reference to FIGS. 1 and 2
As shown in FIG. 1, the gas sensor element 1 of the present embodiment includes a solid electrolyte plate 13 having a measured gas side electrode 11 in contact with the measured gas and a reference gas side electrode 12 in contact with the reference gas. A spacer having a reference gas chamber 10 which is opposed to a closed end at one end and has an open end open to the outside of the gas sensor element 1 at the other end, and is configured to introduce a reference gas. A plate 14 and a heater substrate 15 having a heating element 150 that generates heat when energized are laminated.

A method for manufacturing the gas sensor element 1 will be briefly described. As shown in FIG. 4, a raw sheet 53 for a solid electrolyte plate, a raw sheet 54 for a spacer plate, and a raw sheet 55 for a heater substrate are prepared. As shown in FIG. 5, a printing section 530 for forming an electrode is formed on the raw sheet 53 for a solid electrolyte plate.
Is printed on the raw sheet 55 for the heater substrate by the printing section 55 for the heating element.
0 is provided for each.

Further, a groove is formed in the raw sheet 54 for a spacer plate, and a groove 540 having a closed end and an open end serving as the reference gas chamber 10 is formed as shown in FIG. When the raw sheet 54 for a spacer plate is formed by processing and the raw sheet 54 for a spacer plate is set in the press die, the release sheet 5
As 45, a porous sheet is used.

Then, as shown in FIG. 6, the raw sheet 54 for the spacer plate is laminated on the raw sheet 55 for the heater substrate.
A green sheet 53 for a solid electrolyte plate is further laminated on these, laminated with an adhesive to form an unfired laminate, and then fired.

The gas sensor element 1 of this embodiment will be described in detail. The gas sensor element 1 of this embodiment is incorporated in a gas sensor 2 as shown in FIG. 3, is mounted on an exhaust system of an automobile engine, and is used for engine combustion control. As shown in FIGS. 1 and 2, the gas sensor element 1 of the present embodiment includes a zirconia-based solid electrolyte plate 13 having oxygen ion conductivity, a spacer plate 14 made of an insulator made of alumina, and a heater substrate 15 made of alumina. Are laminated.

The measured gas side electrode 11 and the reference gas side electrode 12 are provided on the solid electrolyte plate 13. Also,
The measured gas side electrode 11 is covered with an electrode protection layer 135. Although not shown, the solid electrolyte plate 13 is provided with a terminal portion for output output and a lead portion which are electrically connected to the measured gas side electrode 11 and the reference gas side electrode 12. Further, the heater substrate 15 is provided with a lead portion 151 electrically connected to the heating element 150.

A gas sensor 2 incorporating the gas sensor element 1 according to the present embodiment will be described. As shown in FIG. 3, the gas sensor 2 of the present embodiment comprises a cylindrical housing 20, a double gas-to-be-measured cover 21 provided at the distal end of the housing 20, and an atmosphere-side cover provided at the proximal end. 22. At the base end side of the atmosphere side cover 22, a water repellent filter 2 is provided.
An outer cover 221 is provided through the center 20. The gas sensor element 1 inserted through the distal insulator 241 is disposed inside the housing 20, and the proximal insulator 2 is disposed inside the air-side cover at the proximal end of the gas sensor element 1.
42 are arranged.

A terminal 231 for taking out the output of the gas sensor element 1 is arranged inside the base-side insulator 242, and this terminal 231 is connected to a lead wire 233 led out of the gas sensor 1 via a connection fitting 232. ing. Further, an elastic insulating member 25 is provided inside the atmosphere-side cover 22 at the most proximal end side, and the lead wire 233 is inserted therethrough.

Next, a method for manufacturing the gas sensor element of this embodiment will be described. Each raw sheet 535 as shown in FIG.
53, 54 and 55 are prepared by an extrusion molding device (not shown). FIG. 4 shows, in order from the drawing, a raw sheet 535 for an electrode protective layer (alumina composition thickness 0.15 mm), a raw sheet 53 for a solid electrolyte plate (zirconia composition thickness 0.2 mm),
Raw sheet 54 for spacer plate (alumina composition thickness 1.5
mm), and a raw sheet 55 for a heater substrate (alumina composition thickness: 0.2 mm).

The dimensions of the raw sheet 53 for the solid electrolyte plate, the raw sheet 54 for the spacer plate, and the raw sheet 55 for the heater substrate are 70 mm × 90 mm.
Is 70 mm × 35 mm. The spacer sheet raw sheet 54 is adjusted to the above dimensions after performing the groove processing described below.

Next, the details of forming a groove 540 for the reference gas chamber 100 by forming a groove in the raw sheet 54 for a spacer plate will be described. First, the water content of the raw sheet for spacer plate 54 immediately after extrusion molding is adjusted.
As shown in FIG. 7, the raw sheet 54 is placed on a tray 549 with feet made of punched metal, and the tray 549 is stacked in a maximum of 10 steps and placed in an oven maintained at a temperature of 50 degrees for drying. I do. By this drying,
The water content of the raw sheet 54 is set to 11 ± 0.5%. If the amount of water is too small, the raw sheet 54 may be cracked. If the amount of water is too large, the shape may not be stable. After the drying, the raw sheet 54 is cut into a predetermined size.

Next, a description will be given of a mold used for press working of groove processing. As shown in FIG. 8, the mold includes an upper mold 61 and a lower mold 62, and a mold surface 610 of the upper mold 61 is provided with a convex portion 611 for forming a groove. A lower auxiliary tool 629 is arranged around the lower mold 62, and an upper auxiliary tool 619 is attached to the upper mold 61 on the side opposite to the mold surface 610. A packing 628 is arranged around the mold surface 620 of the lower mold 62.

The raw sheet 54 is set on the mold surface 620 of the lower mold 62 in such a state with the release sheet 545 interposed therebetween. The release sheet 545 has a sheet thickness of 0.3 ± 0.05 mm and a gas permeability of 20.
Seconds, sheet water pressure is 68.6 kPa or less, surface roughness is 1
PTFE (polytetrafluoroethylene) of 0 μm or less
It consists of a sheet made of.

Subsequently, the upper mold 61 is set with respect to the lower mold 62, and press molding is performed. At this time, the mold temperature is 80
C., the molding pressure was 77 MPa, and the molding time was 15 seconds.
After the molding is completed, the mold is opened, the raw sheet 54 having the groove formed thereon is taken out, and the release sheet 545 is peeled off.

Again, the raw sheet 54 was placed on a tray with feet made of punched metal (using the same tray 549 as in FIG. 10), and the trays were stacked in a maximum of 10 steps. This is dried in an oven maintained at a temperature of 95 ° C. for 2 hours. After the drying is completed, the raw sheet 54 has undulation as a whole, and the surface thereof has irregularities. In order to remove the undulations and irregularities, a smoothing press is applied to the raw sheet 54 in the following procedure.

As shown in FIG. 9, the upper and lower surfaces of the raw sheet 54 are sandwiched between release sheets 545 and set in a flat press mold. In this flat press die, the die surfaces 630 and 640 of the upper die 63 and the lower die 64 are each configured to be flat.

Then, the raw sheet 54 sandwiched between the release sheets 545 is arranged on the mold surface 640 of the lower mold 64, the upper mold 63 is set, and flat pressing is performed. At this time, the mold temperature is 95
C., the pressure was 8.5 MPa, and the time was 15 seconds. After the flat press, the mold is opened, the release sheet 545 is peeled off, and the raw spacer sheet 54 is taken out. After that, the groove pitch, groove shape, sheet warpage (need to be 1 mm or less), sheet surface roughness (need to be 5 μm or less), and appearance inspection are performed to remove defective products. As a result, a raw sheet 54 was obtained as shown in FIG.

Next, a printing section 530 is formed on the raw sheet 53 for the solid electrolyte plate, for the electrode to be measured and the electrode for the reference gas, for each terminal, and for the lead connecting the terminal and the electrode. Is provided. This printed part is made of conductive paste P
The t paste was formed by screen printing on the raw sheet 53. Similarly, the printing sheet 550 for the heating element and the lead section and the terminal section used when energizing the heating element is formed on the raw sheet 55 for the heater substrate by using a Pt paste as a conductive paste. The green sheet 55 was formed by screen printing.

Each raw sheet 535 processed as described above
As shown in FIG.
The layers are laminated as shown in FIG. The thus obtained unfired laminate is cut and singulated into one gas sensor element as shown in FIG. 6B. The obtained individual piece 56 is 147
Firing is performed at 0 ° C. for 2 hours to obtain the gas sensor element 1 as shown in FIG.

Further, the shape of the opposite surface 542 of the raw sheet for spacer 54 according to the present example at the end of the flat press was measured using a surface roughness meter. FIG. 13A is a diagram of the measurement result. The vertical axis is the thickness direction of the raw sheet 54, and the horizontal axis is the direction (portion) perpendicular to the groove of the raw sheet. In this diagram, the line in the thickness direction 0 is the ideal opposite surface 542 shape of the raw sheet 54, and the shape of the opposite surface 542 of the raw sheet 54 of this example is almost completely covered by the line in the thickness direction 0 in FIG. Recorded (see FIG. 10). As can be seen from FIG.
Is substantially overlapped with the line in the thickness direction 0. Also, FIG.
4 is a raw sheet 54 of this example. The opposite surface 542 is substantially flat as shown in FIG.

The operation and effect of this embodiment will be described. In this example, the above-mentioned PTFE sheet is used as the release sheet 545. By the way, as shown in FIG. 10A, the convex portion 611 for forming the groove of the upper die 61 is formed on the surface 5
41, and then, as shown in FIG.
And press it downward. A sink 7 occurs at a portion where the opposite surface 542 of the pressed surface 541 is not in contact with the convex portion 611. In other words, the sink 7 is formed on the opposite surface 542 between the grooves.

Conventionally, since a release sheet 79 made of Teflon (registered trademark) sheet is used, when sink marks 7 as shown in FIG. 11A occur, there is no place for air to escape. As shown in FIG. 11), the portion of the sink 7 is constricted with the progress of the press, and as shown in FIG. I do. This void 70
As a result, the strength of the gas sensor element 1 decreases. FIG. 13B is a diagram of a measurement result of the conventional release sheet 79. As can be seen from the figure, two small peaks a are recognized in the diagram. This is the void 70 in the trace of the sink 7.

In this embodiment, since the porous release sheet 545 is used, when sink 7 as shown in FIG. 12A occurs, air is released through the release sheet 545 and the lower mold. 12 to escape into the gap with
As shown in FIG. 13B, the sink 7 becomes smaller as the pressing progresses, and finally, as shown in FIG. 12C, the sink 7 closes and no void is formed (see FIG. 13A).

Therefore, it is possible to obtain a gas sensor element in which cracks, damages, and the like due to voids are unlikely to occur, and are excellent in strength and durability.

As described above, according to this embodiment, it is possible to provide a method of manufacturing a gas sensor element having excellent durability.

Embodiment 2 In this embodiment, a method for producing a raw sheet 54 provided with a groove 540 will be described. The raw sheet 54 prepared in the same procedure as in the first embodiment is dried in an oven as shown in FIG. 7 described above, and then a groove is formed by a die as shown in FIG. At this time, since a conventionally used Teflon sheet is used as the release sheet, air does not escape as shown in FIG. 11 described above, and as shown in FIG. 15, sink marks 7 and voids 70 are formed on the surface where the groove 540 is formed. 5
41 remains on the opposite surface 542.

Therefore, the opposite surface 542 is parallel to the surface 541.
The surface is dry-polished to remove the portions indicated by the broken lines in the same figure, and thereafter, as shown in FIG. 9 described above, flat pressing is performed to obtain a raw sheet 54 having a smooth opposite surface 542.
The other detailed manufacturing methods are the same, and the same effects as those of the first embodiment can be obtained from the method according to the present embodiment.

Embodiment 3 In this embodiment, a method for producing a raw sheet 54 provided with a groove 540 will be described. The raw sheet 54 prepared in the same procedure as in the first embodiment is dried in an oven as shown in FIG. 7 described above, and then a groove is formed by a die as shown in FIG. At this time, since a conventionally used Teflon sheet is used as the release sheet, air does not escape as shown in FIG. 11 described above, and as shown in FIG. 15, sink marks 7 and voids 70 are formed on the surface where the groove 540 is formed. 5
41 remains on the opposite surface 542.

The raw sheet 54 in this state is subjected to flat pressing as shown in FIG. 9 and laminated with other raw sheets 535, 53, 55, etc., as shown in FIG. Make up with the body. Thereafter, as shown in FIG. 6 (b) described above, singulation is performed. At the time of singulation, the separation between adjacent pieces is performed. That is, as shown in FIG.
Separation is performed so that the broken line portion is removed from the spacer raw sheet 54. The singulation was performed by blade cutting.

The above-described void 70 and sink 7 are formed in the groove 540.
Since it is often formed on the opposite surface 542 between the voids, if individualization is performed by the above-described method, the void 70 is naturally formed at the time of individualization.
The sink 7 is removed. The other detailed manufacturing methods are the same, and the same effects as those of the first embodiment can be obtained from the method according to the present embodiment.

[Brief description of the drawings]

FIG. 1 is an explanatory cross-sectional view in the central axis direction of a gas sensor element according to a first embodiment.

FIG. 2 is a cross-sectional explanatory view in a direction perpendicular to a central axis of the gas sensor element in the first embodiment.

FIG. 3 is an explanatory cross-sectional view of a gas sensor according to the first embodiment.

FIG. 4 is a perspective view of each raw sheet in the first embodiment.

FIG. 5 is a perspective view of each raw sheet provided with a printing unit and a groove in the first embodiment.

FIG. 6 is an explanatory view in the case where each raw sheet is laminated, separated into individual pieces, and fired to produce a gas sensor element in the first embodiment.

FIG. 7 is an explanatory diagram when a raw sheet is dried in the first embodiment.

FIG. 8 is an explanatory diagram when providing a groove in a raw sheet in the first embodiment.

FIG. 9 is an explanatory view of flat pressing of the raw spacer sheet provided with the grooves in the first embodiment.

FIG. 10 is an explanatory diagram showing the occurrence of sink marks when forming a groove in the first embodiment.

FIG. 11 is an explanatory view showing void generation when a conventional release sheet is used.

FIG. 12 is an explanatory diagram showing a state in which sink marks disappear in the first embodiment.

FIG. 13 is a diagram showing the shape of the opposite surface of the raw spacer sheet in the first embodiment.

FIG. 14 is a perspective view showing a raw sheet for spacer provided with grooves in the first embodiment.

FIG. 15 is an explanatory diagram illustrating a portion to be cut on the opposite surface of the raw spacer sheet according to the second embodiment.

FIG. 16 is an explanatory diagram illustrating a portion removed at the time of singulation in a raw sheet for a spacer according to the third embodiment.

FIG. 17 is a perspective development view showing a conventional gas sensor element.

[Explanation of symbols]

 1. . . 9. gas sensor element, . . Reference gas chamber, 101. . . Open end, 102. . . 10. closed end; . . 11. Gas electrode to be measured, . . 12. reference gas side electrode; . . 13. solid electrolyte plate; . . 14. spacer plate, . . Heater substrate, 150. . . Heating element,

Claims (7)

[Claims] 1. A solid electrolyte plate having a measured gas side electrode in contact with a measured gas and a reference gas side electrode in contact with a reference gas, a solid electrolyte plate facing the reference gas side electrode, one end of which is a closed end,
The other end has a groove shape configured as an open end open to the outside of the gas sensor element, and includes a spacer plate having a reference gas chamber configured to introduce a reference gas, and a heating element that generates heat when energized. In manufacturing a gas sensor element comprising a laminated heater substrate and a raw sheet for a solid electrolyte plate, a raw sheet for a spacer plate, and a raw sheet for a heater substrate, a raw sheet for a solid electrolyte plate is prepared. The printing part is provided with a printing part for the heating element on the raw sheet for the heater substrate, and the raw sheet for the spacer plate is grooved, and the groove having a closed end and an open end serving as a reference gas chamber is press-formed. When the raw sheet for the spacer plate is formed by press working using a mold, and the raw sheet for the spacer plate is set in the press die, a porous sheet is used as the release sheet, and the raw sheet for the heater substrate is It is characterized by laminating raw sheets for circulating boards, further laminating raw sheets for solid electrolyte boards, bonding them with an adhesive to form an unfired laminate, and then firing the unfired laminate. Of manufacturing a gas sensor element. 2. The method according to claim 1, wherein the release sheet has a thickness of 0.25 to 0.35 mm. 3. The method for manufacturing a gas sensor element according to claim 1, wherein the release sheet has a gas permeability according to JIS P8117 of 20 seconds or less. 4. The method according to claim 1, wherein:
A method for manufacturing a gas sensor element, wherein the sheet release pressure of the release sheet is 60 kPa or more. 5. The method according to claim 1, wherein:
A method for manufacturing a gas sensor element, wherein the surface roughness of the release sheet is 10 μm or less in ten-point average roughness. 6. A solid electrolyte plate comprising a measured gas side electrode in contact with the measured gas and a reference gas side electrode in contact with the reference gas, a solid electrolyte plate facing said reference gas side electrode, one end of which is a closed end,
The other end has a groove shape configured as an open end open to the outside of the gas sensor element, and includes a spacer plate having a reference gas chamber configured to introduce a reference gas, and a heating element that generates heat when energized. In manufacturing a gas sensor element comprising a laminated heater substrate and a raw sheet for a solid electrolyte plate, a raw sheet for a spacer plate, and a raw sheet for a heater substrate, a raw sheet for a solid electrolyte plate is prepared. The printing part is provided with a printing part for the heating element on the raw sheet for the heater substrate, and the raw sheet for the spacer plate is grooved, and the groove having a closed end and an open end serving as a reference gas chamber is press-formed. Formed by pressing using a mold, and then cutting the opposite surface of the raw sheet on which the groove is formed so as to be parallel to the surface on which the groove is formed. After smoothing, the raw sheet for the heater substrate is laminated with the raw sheet for the spacer plate, and then the raw sheet for the solid electrolyte plate is further laminated and bonded with an adhesive to form an unfired laminate. A method for manufacturing a gas sensor element, comprising firing a laminate. 7. A solid electrolyte plate comprising a measured gas side electrode in contact with the measured gas and a reference gas side electrode in contact with the reference gas, a solid electrolyte plate facing said reference gas side electrode, one end of which is a closed end,
The other end has a groove shape configured as an open end open to the outside of the gas sensor element, and includes a spacer plate having a reference gas chamber configured to introduce a reference gas, and a heating element that generates heat when energized. In manufacturing a gas sensor element having a laminated heater substrate, a raw sheet for a solid electrolyte plate, a raw sheet for a spacer plate, and a raw sheet for a heater substrate capable of taking a plurality of gas sensor elements are prepared. The printed part for forming electrodes on the raw sheet,
The raw sheet for the heater substrate is provided with a plurality of print portions for the heating elements so that a plurality of gas sensor elements can be respectively taken out. The raw sheet for the spacer plate is grooved, and has a closed end and an open end serving as a reference gas chamber. A plurality of grooves are formed by press working using a press die so that a raw sheet for a heater board is laminated with a raw sheet for a spacer plate, and a raw sheet for a solid electrolyte plate is further laminated on them. Then, the unsintered laminate is cut into pieces and cut into individual pieces, and at the same time, the adjacent pieces are removed. A method for manufacturing a gas sensor element, comprising firing the obtained individual pieces.