JPS6151558A - Manufacture of oxygen sensor element - Google Patents
Manufacture of oxygen sensor elementInfo
- Publication number
- JPS6151558A JPS6151558A JP59173759A JP17375984A JPS6151558A JP S6151558 A JPS6151558 A JP S6151558A JP 59173759 A JP59173759 A JP 59173759A JP 17375984 A JP17375984 A JP 17375984A JP S6151558 A JPS6151558 A JP S6151558A
- Authority
- JP
- Japan
- Prior art keywords
- electrode
- sensor element
- oxygen sensor
- platinum
- solid electrolyte
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/403—Cells and electrode assemblies
- G01N27/406—Cells and probes with solid electrolytes
- G01N27/407—Cells and probes with solid electrolytes for investigating or analysing gases
- G01N27/4073—Composition or fabrication of the solid electrolyte
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Molecular Biology (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Measuring Oxygen Concentration In Cells (AREA)
Abstract
Description
【発明の詳細な説明】 （産業上の利用分野） 本発明は酸素センサ素子の製造法に関する。[Detailed description of the invention] (Industrial application field) The present invention relates to a method for manufacturing an oxygen sensor element.
（従来技術） 酸素センサ素子は１例えば第１図に示すようＫ。(Conventional technology) The oxygen sensor element may be 1K, for example, as shown in FIG.
袋管状のジルコニア固体電解質体１の内外表面に耐熱性
金屑の内側電便２及び外側電極３を形成し。An inner electrode 2 and an outer electrode 3 made of heat-resistant metal scraps are formed on the inner and outer surfaces of a bag-tubular zirconia solid electrolyte body 1.
内外側電極表面の酸素０度差によって生ずる起電力を測
定して燃焼ガスの燃焼制御、不完全燃焼の検知等に使用
される。同図において４及び５は電極２及び３を電圧計
（図示せず］Ｋ接続するり−ド線である。The electromotive force generated by the 0 degree difference in oxygen between the inner and outer electrode surfaces is measured and used for combustion control of combustion gas, detection of incomplete combustion, etc. In the figure, 4 and 5 are lead wires connecting the electrodes 2 and 3 to a voltmeter (not shown).
ところで酸素センサ素子は、燃料中に含有する硫黄分忙
よシ第１図のような形状の場合は燃焼中に前記外側電極
３が腐蝕されて固体電解質体との接着力が低下し、又は
内部抵抗が増大して酸素センサとしての機能が低下し、
甚だしいときには電極の剥離脱落１機能停止に至ること
がある。By the way, if the oxygen sensor element has a shape as shown in Fig. 1 due to the sulfur content contained in the fuel, the outer electrode 3 will corrode during combustion and the adhesive force with the solid electrolyte body will decrease, or the internal The resistance increases and the function as an oxygen sensor decreases,
In severe cases, the electrodes may peel off or fall off, leading to malfunction.
（発明の目的）
本発明は上記した欠点を改良した酸素センサ素子の製造
法を提供することを目的とする。(Objective of the Invention) An object of the present invention is to provide a method for manufacturing an oxygen sensor element that improves the above-mentioned drawbacks.
（発明の構成）
本発明は、固体電解質の成形体、仮焼体又は焼結体の表
面に耐熱性電極を被着したのち焼成するｒＲ素センサ素
子の製造法忙おいて、固体電解質原料に白金粉大分散含
有させたのち成形焼成することを特徴とする酸素センサ
素子の製造法に関する。(Structure of the Invention) The present invention relates to a method for manufacturing an rR element sensor element in which a heat-resistant electrode is deposited on the surface of a solid electrolyte molded body, calcined body, or sintered body and then fired. The present invention relates to a method for manufacturing an oxygen sensor element, which comprises containing a large amount of platinum powder and then molding and firing it.
本発明において固体電解質原料は、主成分としてのジル
コニア、ドリア等の粉末に安定化剤としてイツトリア、
カルシア、マグネシア、セリア。In the present invention, the solid electrolyte raw materials include powders such as zirconia and doria as main components, and itria and yttrias as stabilizers.
Calcia, Magnesia, Celia.
ストロンチア等の粉末を添加し粉砕混合し、約１４００
℃で焙焼してジルコニア、トリア等の主成分の結晶を安
定化させ、（ｌ）この焙焼物に焼結助剤のアルミナ、シ
リカ等を加えて再度粉砕したもの、 （２１（１１に可
塑剤、結合剤等を加え湿式混合したのち乾燥造粒したも
の、 （３１（１）を泥漿にしたもの等である。この固
体電解質原料に白金粉を添加し。Add powder such as strontia, grind and mix, approximately 1400
℃ to stabilize the crystals of main components such as zirconia and thoria, (l) sintering aids alumina, silica, etc. are added to this roasted product and crushed again, (21 (11) (31(1) is made into a slurry.Platinum powder is added to this solid electrolyte raw material.)
混合機等により混合し、固体電解質原料中に均一分散さ
せたのちプレス成形、鋳込み成形等により成形品とされ
る。白金粉は２粒度が１０〜３００μ、添加量が固体電
解質原料に対して１〜１０重量％の範囲が好ましい。鋳
込み成形の場合は前記した泥漿に白金粉を添加分散させ
る。After being mixed using a mixer or the like and uniformly dispersed in the solid electrolyte raw material, a molded product is formed by press molding, casting molding, etc. It is preferable that the platinum powder has a particle size of 10 to 300 microns and an amount added of 1 to 10% by weight based on the solid electrolyte raw material. In the case of cast molding, platinum powder is added and dispersed in the slurry described above.
本発明において耐熱性電極は白金、ロジウム。In the present invention, the heat-resistant electrode is platinum or rhodium.
パラジウム等の高融点金属であるが通常は白金が使用さ
れる。A high melting point metal such as palladium, but platinum is usually used.
固体電解質の成形品は機械加工等によシ所定形状例えば
袋管状の成形体としたのち、１０００〜１３００°Ｃで
仮焼して仮焼体とし、更に１４００〜１７００℃で焼成
して焼結体とされる。白金等の耐熱性ＴＬ＠は成形体、
仮焼体、焼結体のいずれの固体１！解質体に被着しても
よいが、焼結体に被着したときは１４００〜１７００’
Ｃで再度焼成する。The solid electrolyte molded product is formed into a predetermined shape, for example, a bag tube shape, by machining, etc., then calcined at 1000 to 1300°C to form a calcined body, and further fired at 1400 to 1700°C to sinter. It is considered a body. Heat-resistant TL@ of platinum etc. is a molded body,
Both calcined and sintered solids 1! It may be adhered to the disintegrated body, but when it is adhered to the sintered body, it is 1400 to 1700'
Bake again at C.
第１図のような酸素センサ素子の場合は燃焼ガＩ？−
スな接触する外側電極２が損傷するから、固体電解質体
１中の白金粉が外周から１／２〜１１５の部分に分布す
るように固体電解質体を内側と外側に分けて仮成形及び
加工したのち（外側成形体にのみ白金粉を分散含有せし
め）、外側成形体と内側成形体を合わせて一体成形する
方法を採用してもよい。In the case of an oxygen sensor element like the one shown in Fig. 1, the combustion gas I? - To prevent damage to the outer electrode 2 that comes in direct contact with the solid electrolyte body 1, the solid electrolyte body 1 is temporarily formed and processed by dividing it into an inside and an outside part so that the platinum powder in the solid electrolyte body 1 is distributed over 1/2 to 115 points from the outer periphery. After that (platinum powder is dispersed and contained only in the outer molded body), a method may be adopted in which the outer molded body and the inner molded body are combined and integrally molded.
（作用）
固体電解質体内に分散した白金粉は焼成することによシ
白金の溶融粒子となシ、第２図の拡大図に示すように電
極７の近傍の白金の溶融粒子６＃−ｉ電極７と融着し、
電極７は固体電解質体１と強固に結合して電極の腐蝕及
び剥離を防止する。(Function) The platinum powder dispersed in the solid electrolyte becomes molten platinum particles by firing, and as shown in the enlarged view of FIG. Fused with 7,
The electrode 7 is firmly bonded to the solid electrolyte body 1 to prevent corrosion and peeling of the electrode.
（実施例）
ジルコニア粉９４ｍｏｌ−忙イットリア６ｍｏ１％を加
えて平均粒径０．５μに微粉砕して混合後。(Example) After adding 94 mol of zirconia powder and 6 mol % of yttria and pulverizing to an average particle size of 0.5 μm and mixing.
１３５０℃で２時間焙焼してジルコニアとイツトリアの
固溶体を得た。この固溶体９９重量−にアルミナ１重量
％を加え再度、平均粒径０．５μに微粉砕したのちこの
粉砕品忙対し、ポリビニールアルコール２ Ｍｆｊｆ（
％及びマイクロワックス０．５ｉ４１％を加え、水を４
５重量％含有するように加えてスラリーとし、スプレー
ドライヤーで乾燥造粒した。It was roasted at 1350°C for 2 hours to obtain a solid solution of zirconia and ittria. After adding 1% by weight of alumina to 99% by weight of this solid solution and pulverizing it again to an average particle size of 0.5μ, the pulverized product was prepared using polyvinyl alcohol 2Mfjf (
% and microwax 0.5i41%, and water
The slurry was added to contain 5% by weight, and dried and granulated using a spray dryer.
この造粒粉に平均粒径１００μの白金粉を２重量％添加
し、Ｖ型混合機で３時間混合し、ラバープレスにより
１．０ ”Ｊ／ｃｍ”の圧力で成形した。成形品を外径
１０ｎ＋ｙｎ、内径ｓｍｍ、厚さ１ｍｍの袋管に加工し
、１１００℃で仮焼成後、白金ペーストを袋管の内外周
に塗布し、１５００℃で１時間保持焼成して第１図に示
すような酸素センサ素子を得た。2% by weight of platinum powder with an average particle size of 100μ was added to this granulated powder, mixed for 3 hours with a V-type mixer, and then mixed with a rubber press.
Molding was carried out at a pressure of 1.0 "J/cm". The molded product was processed into a bag tube with an outer diameter of 10n+yn, an inner diameter of smm, and a thickness of 1mm, and after pre-firing at 1100°C, platinum paste was applied to the inner and outer periphery of the bag tube, and the first tube was held and fired at 1500°C for 1 hour. An oxygen sensor element as shown in the figure was obtained.
比較例として、実施例における白金粉を分散含有させな
い酸素センナ素子を作成した。As a comparative example, an oxygen senna element was prepared in which the platinum powder in the example was not dispersed.
上記酸素センサ素子の電極の剥離強度を測定した結果、
比較例のものが５ｋｇ／ｍｍｔであるのに対し。As a result of measuring the peel strength of the electrode of the above oxygen sensor element,
While that of the comparative example is 5 kg/mmt.
実施例のものは１０ｋｇ／ｗ”の値を示した。また実施
例の一つをと９．破断面を顕微鏡で観察した結果、白金
粉が一様に分散していることが確認された。The sample of the example showed a value of 10 kg/w''.The fracture surface of one of the examples was observed under a microscope, and it was confirmed that the platinum powder was uniformly dispersed.
（発明の効果） 木兄９４によれば、燃焼ガスによる電極の腐蝕。(Effect of the invention) According to Kien 94, electrode corrosion due to combustion gas.
剥離及びこれらに起因する機能の低下を防止できるので
長期間の使用に耐える酸素センサ素子の提供が可能とな
る。Since peeling and functional deterioration caused by these can be prevented, it is possible to provide an oxygen sensor element that can be used for a long period of time.
第１図は酸素セ／す素子の一例を示す断面図。
第２図は本発明の実施例になる酸素センサ素子の部分拡
大断面図である。
符号の説明
１・・・固体電解質体 ２・・・外側電極３・・
・内側電極 ４・・・リード線５・・・リ
ード線 ６・・・溶融粒子７・・・電極
第１図
′）一覧”ｔ’！ｌ！ｃFIG. 1 is a cross-sectional view showing an example of an oxygen sensor element. FIG. 2 is a partially enlarged sectional view of an oxygen sensor element according to an embodiment of the present invention. Explanation of symbols 1...Solid electrolyte body 2...Outer electrode 3...
・Inner electrode 4... Lead wire 5... Lead wire 6... Molten particle 7... Electrode Figure 1') List "t'!l!c
Claims (1)
熱性電極を被着したのち焼成する酸素センサ素子の製造
法において，固体電解質原料に白金粉を分散含有させた
のち成形焼成することを特徴とする酸素センサ素子の製
造法。1. In a method for manufacturing an oxygen sensor element in which a heat-resistant electrode is attached to the surface of a solid electrolyte molded body, calcined body, or sintered body and then fired, platinum powder is dispersed in the solid electrolyte raw material and then shaped and fired. A method for manufacturing an oxygen sensor element characterized by:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59173759A JPS6151558A (en) | 1984-08-21 | 1984-08-21 | Manufacture of oxygen sensor element |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59173759A JPS6151558A (en) | 1984-08-21 | 1984-08-21 | Manufacture of oxygen sensor element |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS6151558A true JPS6151558A (en) | 1986-03-14 |
Family
ID=15966610
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP59173759A Pending JPS6151558A (en) | 1984-08-21 | 1984-08-21 | Manufacture of oxygen sensor element |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6151558A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02133659U (en) * | 1989-04-12 | 1990-11-06 | ||
| JP2005077194A (en) * | 2003-08-29 | 2005-03-24 | Nippon Steel Corp | Oxygen concentration measuring device in high-temperature gas |
-
1984
- 1984-08-21 JP JP59173759A patent/JPS6151558A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02133659U (en) * | 1989-04-12 | 1990-11-06 | ||
| JP2005077194A (en) * | 2003-08-29 | 2005-03-24 | Nippon Steel Corp | Oxygen concentration measuring device in high-temperature gas |
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