JPH0473096B2 - - Google Patents
Info
- Publication number
- JPH0473096B2 JPH0473096B2 JP58224749A JP22474983A JPH0473096B2 JP H0473096 B2 JPH0473096 B2 JP H0473096B2 JP 58224749 A JP58224749 A JP 58224749A JP 22474983 A JP22474983 A JP 22474983A JP H0473096 B2 JPH0473096 B2 JP H0473096B2
- Authority
- JP
- Japan
- Prior art keywords
- platinum
- combustion
- palladium
- electromotive force
- detection element
- 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.)
- Expired - Lifetime
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 47
- 238000002485 combustion reaction Methods 0.000 claims description 43
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 34
- 229910052697 platinum Inorganic materials 0.000 claims description 23
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 21
- 238000001514 detection method Methods 0.000 claims description 18
- 229910052759 nickel Inorganic materials 0.000 claims description 16
- 229910052573 porcelain Inorganic materials 0.000 claims description 16
- 238000004519 manufacturing process Methods 0.000 claims description 12
- 229910052763 palladium Inorganic materials 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 6
- 229910010293 ceramic material Inorganic materials 0.000 claims description 5
- 150000003057 platinum Chemical class 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 150000002940 palladium Chemical class 0.000 claims description 4
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 description 11
- 229910052760 oxygen Inorganic materials 0.000 description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 238000007747 plating Methods 0.000 description 9
- 239000007789 gas Substances 0.000 description 7
- 239000000919 ceramic Substances 0.000 description 6
- 239000000446 fuel Substances 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- -1 oxygen ion Chemical class 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 229910020068 MgAl Inorganic materials 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 2
- 238000005192 partition Methods 0.000 description 2
- 238000007750 plasma spraying Methods 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000002941 palladium compounds Chemical class 0.000 description 1
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 1
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical compound Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 description 1
- NWAHZABTSDUXMJ-UHFFFAOYSA-N platinum(2+);dinitrate Chemical compound [Pt+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O NWAHZABTSDUXMJ-UHFFFAOYSA-N 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
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
- G01N27/4075—Composition or fabrication of the electrodes and coatings thereon, e.g. catalysts
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)
Description
【発明の詳細な説明】
産業上の利用分野
本発明は燃焼機器の燃焼雰囲気中の酸素濃度を
検知する燃焼検知素子の製造方法に関するもので
ある。DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a method for manufacturing a combustion detection element for detecting the oxygen concentration in the combustion atmosphere of combustion equipment.
従来例の構成とその問題点
従来、この種の燃焼検知素子の代表的なものに
酸素イオン伝導性磁器であるZrO2とY2O3または
ZrO2とCaOからなるジルコニア磁器を用いたも
のが挙げられる。Structure of conventional examples and their problems Traditionally, typical combustion detection elements of this type are oxygen ion conductive porcelains such as ZrO 2 and Y 2 O 3 or
Examples include those using zirconia porcelain made of ZrO 2 and CaO.
第１図はこのようなジルコニア焼結体磁器を用
いた燃焼検知素子を示す断面図であり、片方の先
端を封じた円筒状のジルコニア焼結体磁器１の
内、外表面に白金電極２，３が形成され、その白
金電極２，３が導電性金属端子４，５とそれぞれ
電気導通を得るように接続されている。 FIG. 1 is a cross-sectional view showing a combustion detection element using such zirconia sintered ceramic. Platinum electrodes 2, 3 is formed, and its platinum electrodes 2 and 3 are connected to conductive metal terminals 4 and 5, respectively, so as to obtain electrical continuity.
このような構造の燃焼検知素子において、焼結
体磁器１を約400℃以上の温度に保ち、白金電極
２，３を備えた前記磁器１の隔壁の両側を相異な
る分圧をもつた酸素ガスに接触させると、この隔
壁間に起電力を生じ、これにより酸素濃度を検出
することができる。ここで、導電性金属端子４，
５間に生じる起電力Ｅは、
Ｅ＝RT／4FlogP1／P2
P1：既知酸素分圧、P2：被測定酸素分圧、
Ｔ：絶対温度、Ｒ、Ｆ：定数。 In the combustion detection element having such a structure, the sintered porcelain 1 is maintained at a temperature of about 400° C. or higher, and oxygen gas having different partial pressures is applied to both sides of the partition wall of the porcelain 1 provided with platinum electrodes 2 and 3. When brought into contact with the barrier ribs, an electromotive force is generated between the partition walls, thereby allowing the oxygen concentration to be detected. Here, the conductive metal terminal 4,
The electromotive force E generated during 5 is: E=RT/4FlogP 1 /P 2 P 1 : Known oxygen partial pressure, P 2 : Measured oxygen partial pressure, T: Absolute temperature, R, F: Constant.
で表わされる。It is expressed as
この構造の燃焼検知素子の白金電極は、焼結体
磁器とガス雰囲気中の酸素分圧と、焼結体磁器中
の酸素イオンの濃度平衡における酸素のやりとり
に関係している。 The platinum electrode of the combustion detection element having this structure is related to the exchange of oxygen between the sintered porcelain and the oxygen partial pressure in the gas atmosphere and the oxygen ion concentration equilibrium in the sintered porcelain.
従来、このような構造を有する燃焼検知素子
は、可燃成分を含むガス雰囲気中では白金電極の
触媒作用による反応が白金電極表面で起り、第３
図ａのような起電力特性を示し、完全燃焼する理
論空燃比付近で急峻な起電力の変化をする特性が
一般的である。 Conventionally, in a combustion detection element having such a structure, in a gas atmosphere containing flammable components, a reaction occurs on the surface of the platinum electrode due to the catalytic action of the platinum electrode, and a third reaction occurs on the surface of the platinum electrode.
The electromotive force characteristic shown in Figure a is generally exhibited, and the electromotive force changes sharply near the stoichiometric air-fuel ratio for complete combustion.
しかしながら、燃焼機器では理論空燃比から相
当ずれた空気過剰側の雰囲気で使用されるのが一
般的である。 However, combustion equipment is generally used in an atmosphere with an excess of air that deviates considerably from the stoichiometric air-fuel ratio.
このため、実用上での起電力はきわめて微少な
もので、例えば、燃焼機器を最適な燃焼条件付近
で制御する場合、実用空燃比範囲ではこの検知素
子の起電力は小さく変化幅も微少であり、電気回
路での制御は不安定かつ困難であり、空気過剰側
雰囲気で大きな起電力を発生するか、または理論
空燃比付近で急峻な起電力の変化を示さず、ゆる
やかな起電力の勾配を示す燃焼検知素子が望まれ
ていた。 For this reason, the electromotive force in practical use is extremely small. For example, when controlling combustion equipment near optimal combustion conditions, the electromotive force of this sensing element is small and the range of change is minute in the practical air-fuel ratio range. , control with an electric circuit is unstable and difficult, and a large electromotive force is generated in an atmosphere with excess air, or the electromotive force does not show a steep change near the stoichiometric air-fuel ratio, but shows a gradual gradient of the electromotive force. A combustion sensing element shown in the figure has been desired.
発明の目的
本発明はこのような点に鑑みてなされたもので
あり、従来と異なる全く新らしい特性を示す燃焼
検知素子の製造方法を得ることを目的とし、比較
的簡単に安定な燃焼検知素子を提供しようとする
ものである。Purpose of the Invention The present invention has been made in view of the above points, and aims to provide a method for manufacturing a combustion detection element that exhibits completely new characteristics different from conventional ones, and to provide a method for manufacturing a combustion detection element that is relatively easy and stable. This is what we are trying to provide.
発明の構成
この目的を達成するために本発明における燃焼
検知素子の製造方法は、白金塩、パラジウム塩、
白金錯化合物の少なくとも一つを水または有機溶
剤に溶解して作成した溶液を燃焼検知素子を構成
する焼結体磁器に塗布した後、熱処理を施して前
記焼結体磁器表面に白金またはパラジウム膜層を
形成し、この白金またはパラジウム膜層上にニツ
ケルの化学めつきを施した後、500℃〜1000℃の
温度で熱処理し、その後、多孔性セラミツク材料
でコーテイングすることを特徴としている。Structure of the Invention In order to achieve this object, the method for manufacturing a combustion sensing element according to the present invention includes a method for manufacturing a combustion detection element using platinum salt, palladium salt,
A solution prepared by dissolving at least one platinum complex compound in water or an organic solvent is applied to the sintered porcelain constituting the combustion detection element, and then heat treated to form a platinum or palladium film on the surface of the sintered porcelain. After forming a layer and chemically plating nickel on the platinum or palladium film layer, it is heat treated at a temperature of 500°C to 1000°C, and then coated with a porous ceramic material.
実施例の説明
以下、本発明を実施例に基いて具体的に説明す
る。Description of Examples Hereinafter, the present invention will be specifically described based on Examples.
実施例 １
酸化イツトリウムをわずかに含んだ（８モル
％）酸化ジルコニウムを主成分とする第２図に示
す構造の燃焼検知素子の焼結体磁器６の内、外表
面に塩化白金酸1.0ｇを２−ブタノール50mlに溶
解した白金溶液し、これを空気中600℃で焼成し
た。Example 1 1.0 g of chloroplatinic acid was applied to the inner and outer surfaces of the sintered ceramic 6 of the combustion detection element having the structure shown in FIG. A platinum solution was prepared in 50 ml of 2-butanol and calcined in air at 600°C.
さらに、この上に市販のニツケルめつき液を用
いて60℃にて化学めつきすることにより、焼結体
磁器６の表面にニツケル膜厚1.0μｍの電極膜を形
成した後、ニツケル膜を十分に水洗し、乾燥させ
た。続いて空気中1000℃で１時間熱処理し、焼結
体磁器１の表面にニツケル電極７，８を形成し、
耐熱鋼板からなる導電性金属端子９，１０と電気
的導通を得るように接続した後、電極８の表面に
Al2O3粉末をプラズマ溶射にて溶射して多孔性セ
ラミツク膜１１を100〜150μｍの膜厚に形成し
た。 Furthermore, an electrode film with a thickness of 1.0 μm is formed on the surface of the sintered porcelain 6 by chemical plating at 60°C using a commercially available nickel plating solution. Washed with water and dried. Subsequently, heat treatment was performed in air at 1000°C for 1 hour to form nickel electrodes 7 and 8 on the surface of the sintered porcelain 1.
After connecting to the conductive metal terminals 9 and 10 made of heat-resistant steel plates so as to obtain electrical continuity, the surface of the electrode 8 is
A porous ceramic film 11 having a thickness of 100 to 150 μm was formed by spraying Al 2 O 3 powder using plasma spraying.
実施例 ２
酸化イツトリウムをわずかに含んだ（５モル
％）酸化ジルコニウムを主成分とする第２図に示
す構造の燃焼検知素子の焼結体磁器６の内、外表
面に塩化パラジウム1.0ｇを２−ブタノール50ml
に溶解したパラジウム溶液を塗布し、これを空気
中600℃で焼成した。さらに、この上に市販のニ
ツケルめつき液を用いて60℃にて化学めつきする
ことにより、焼結体磁器６の表面にニツケル膜厚
1.0μｍの電極膜を形成した後、ニツケル膜を十分
に水洗し、乾燥させた。続いて、窒素ガス雰囲気
中900℃で１時間処理し、焼結体磁器６の表面ニ
ツケル電極７，８を形成し、耐熱鋼板からなる導
電性金属端子９，１０と電気的導通を得るように
接続した後、電極８の表面にMgAl2O4粉末をプ
ラズマ溶射にして溶射して多孔性セラミツク膜１
０を100〜150μｍの膜厚に形成した。Example 2 1.0 g of palladium chloride was applied to the inner and outer surfaces of the sintered porcelain 6 of the combustion detection element having the structure shown in FIG. -Butanol 50ml
A palladium solution dissolved in water was applied, and this was fired at 600°C in air. Furthermore, by chemically plating at 60°C using a commercially available nickel plating solution, the surface of the sintered porcelain 6 is coated with a nickel film.
After forming a 1.0 μm electrode film, the nickel film was thoroughly washed with water and dried. Subsequently, treatment was performed at 900° C. for 1 hour in a nitrogen gas atmosphere to form nickel electrodes 7 and 8 on the surface of the sintered porcelain 6, and to obtain electrical continuity with conductive metal terminals 9 and 10 made of heat-resistant steel plates. After connection, MgAl 2 O 4 powder is plasma sprayed onto the surface of the electrode 8 to form a porous ceramic film 1.
0 was formed to a film thickness of 100 to 150 μm.
ここで、白金塩、パラジウム塩の熱処理は、白
金塩、パラジウム塩の化合物が熱分解して金属白
金または金属パラジウムが生成する温度以上で行
われ、用いる溶液の種類によりその熱処理温度は
それぞれ異なるが、およそ400〜800℃以上900℃
までの温度である。 Here, the heat treatment of the platinum salt and palladium salt is carried out at a temperature higher than the temperature at which the platinum salt and palladium salt compounds are thermally decomposed to produce metallic platinum or metallic palladium, and the heat treatment temperature varies depending on the type of solution used. , approximately 400~800℃ or more 900℃
The temperature is up to.
また、こうして得られた薄い白金またはパラジ
ウム膜層は、後に続く化学めつきの活性化工程も
兼ねており、この上に電気的導通と触媒作用を有
する電極を得るためにニツケルの化学めつきを行
うことを容易にする。 The thin platinum or palladium film layer thus obtained also serves as an activation step for the subsequent chemical plating, and is then chemically plated with nickel to obtain an electrode with electrical conductivity and catalytic action. make things easier.
そして、後者の熱処理は得られためつきニツケ
ル膜電極の強度を上げる目的で行われるものであ
り、この後に行う多孔性セラミツク材料のコーテ
イングによつて電極の保護、寿命の安定向上を図
つている。 The latter heat treatment is carried out for the purpose of increasing the strength of the resulting toughened nickel membrane electrode, and the subsequent coating with a porous ceramic material is intended to protect the electrode and stably improve its lifespan.
なお、本発明で用いる白金溶液の成分となる白
金塩、白金錯化合物またはパラジウム溶液の成分
となるパラジウム塩、パラジウム錯化合物として
は、塩化白金、硝酸白金、塩化パラジウム、硝酸
パラジウムなどそれぞれの化合物が使用できる。 In addition, platinum salts and platinum complex compounds that are components of the platinum solution used in the present invention, or palladium salts and palladium complex compounds that are components of the palladium solution, include platinum chloride, platinum nitrate, palladium chloride, palladium nitrate, and the like. Can be used.
また、有機溶剤としては、２−ｎブタノール、
エチレングリコールやｎ−ブチルカルビトールな
どの多くのアルコール系やエーテル系のものが使
用できる。さらに、用いる溶液の濃度は、それぞ
れの白金またはパラジウム化合物の種類にかかわ
らず、それぞれの化合物は１ｇ／10〜100mlが適
している。 In addition, as the organic solvent, 2-n butanol,
Many alcohols and ethers such as ethylene glycol and n-butyl carbitol can be used. Furthermore, the concentration of the solution to be used is suitably 1 g/10 to 100 ml of each compound, regardless of the type of each platinum or palladium compound.
また、多孔性セラミツク材料のコーテイング
は、Al2O3、MgAl2O4、ZrO2などの粉末をプラ
ズム溶射または無機バインダーを混ぜ塗布・焼成
する方法で形成することができる。 Further, the coating of the porous ceramic material can be formed by plasma spraying a powder of Al 2 O 3 , MgAl 2 O 4 , ZrO 2 or the like, or by mixing and applying an inorganic binder and firing.
本発明の製造方法は、燃焼検知素子を構成する
焼結体磁器表面に白金またはパラジウム膜を熱分
解法により形成するため、めつき法に比較して密
着性の良好な電極となる特徴がある。 The manufacturing method of the present invention is characterized by forming a platinum or palladium film on the surface of the sintered porcelain constituting the combustion sensing element by a thermal decomposition method, resulting in an electrode with better adhesion compared to the plating method. .
さらに、この上にめつき法によつてニツケル電
極を形成するため、従来の白金を用いて形成した
場合に比べ触媒反応の度合が異なり、理論空燃比
付近での急峻な起電力変化がなく、広範囲の空燃
比に対してゆるやかな起電力の勾配を示す従来に
ない全く新らしい特性を示す。 Furthermore, since the nickel electrode is formed on top of this by a plating method, the degree of catalytic reaction is different from that of conventional platinum electrodes, and there is no steep change in electromotive force near the stoichiometric air-fuel ratio. It exhibits a completely new characteristic that shows a gentle gradient of electromotive force over a wide range of air-fuel ratios.
また、ニツケル電極を用いており、従来の白金
電極と比較してきわめて安価であるうえに優れた
性能の燃焼検知素子が容易に得られる。 Furthermore, since a nickel electrode is used, it is extremely inexpensive compared to conventional platinum electrodes, and a combustion detection element with excellent performance can be easily obtained.
なお、本発明において化学めつきを施した後、
めつきニツケル膜の強度を上げる目的で、500℃
〜1000℃の温度で熱処理を行つているが、これは
温度が500℃より低いと強固な膜を形成すること
ができず、逆に1000℃より高いと熱によつてニツ
ケル膜が劣化するため好ましくないことによる。 In addition, in the present invention, after chemical plating is applied,
500℃ for the purpose of increasing the strength of the plated nickel film.
Heat treatment is performed at a temperature of ~1000℃, because if the temperature is lower than 500℃, a strong film cannot be formed, and if the temperature is higher than 1000℃, the nickel film will deteriorate due to heat. Due to undesirable things.
また、ニツケル膜が燃焼雰囲気中の有害物質に
犯され劣化するのを防ぐ目的で、フイルター効果
を多孔性セラミツク材料のコーデイングにより得
て寿命の安定向上を図つている。 In addition, in order to prevent the nickel membrane from deteriorating due to poisonous substances in the combustion atmosphere, a filter effect is obtained by coding the porous ceramic material to stably improve the lifespan.
このようにして作成した燃焼検知素子を以下に
示す可燃性ガス中にさらし、導電性金属電極端子
９，１０の間に発生する起電力を測定した。 The combustion detection element thus produced was exposed to the flammable gas shown below, and the electromotive force generated between the conductive metal electrode terminals 9 and 10 was measured.
すなわち、酸素ガス0.8容量％と残部窒素ガス
からなる基本ガス（流量2000ml／分）に水素ガス
を種々の割合（流量10、20、25、30、35、40、
50、60ml／分）で混合して被測定ガスを調整し
た。これを600℃に加熱させ、燃焼後のガスをそ
のまま燃焼検知素子の外側電極８側に接触させな
がら流して、この検知素子に発生する起電力を測
定した。なお、焼結体磁器６の内側電極７には参
照ガスとしての大気が接している。 That is, hydrogen gas was added in various proportions (flow rate 10, 20, 25, 30, 35, 40,
The gas to be measured was adjusted by mixing at a rate of 50, 60 ml/min). This was heated to 600° C., the gas after combustion was allowed to flow as it was in contact with the outer electrode 8 side of the combustion sensing element, and the electromotive force generated in this sensing element was measured. Note that the inner electrode 7 of the sintered ceramic 6 is in contact with the atmosphere as a reference gas.
すなわち、H2＋O2、Ni｜ZrO2−Y2O3｜Ni、
O2なる構成の酸素濃淡電池を形成して、水素量
を変化させることにより、その時発生する起電力
を測定した。 That is, H 2 + O 2 , Ni | ZrO 2 −Y 2 O 3 | Ni,
By forming an oxygen concentration battery with an O 2 configuration and varying the amount of hydrogen, the electromotive force generated at that time was measured.
第３図に測定結果を示す。第３図のａは前述し
たように従来の構成による燃焼検知素子の起電力
特性、ｂは本発明の実施例１による燃焼検知素
子、ｃは本発明の実施例２による燃焼検知素子の
それぞれの起電力特性で、燃焼後の被測定ガス中
に酸素が存在しはじめる状態にある酸素／水素の
モル比が0.5付近においてａの従来の構成による
燃焼検知素子はするどい起電力の立ち上がりを示
し、本発明による実施例１、２の燃焼検知素子
は、ｂおよびｃで示されるようにゆるやかな起電
力の勾配を示すことから、本発明による特性は従
来にない全く新しいものであることがわかる。 Figure 3 shows the measurement results. In FIG. 3, a shows the electromotive force characteristics of the combustion sensing element according to the conventional configuration as described above, b shows the electromotive force characteristics of the combustion sensing element according to the first embodiment of the present invention, and c shows the electromotive force characteristics of the combustion sensing element according to the second embodiment of the present invention. In terms of electromotive force characteristics, when the molar ratio of oxygen/hydrogen is around 0.5, which is the state in which oxygen begins to exist in the measured gas after combustion, the combustion detection element with the conventional configuration of a shows a sharp rise in electromotive force, and this The combustion sensing elements of Examples 1 and 2 according to the invention exhibit gentle gradients of electromotive force as shown by b and c, which shows that the characteristics according to the invention are completely new and unprecedented.
発明の効果
以上の説明から明らかなように、本発明の製造
方法は、従来の白金電極を用いたものとは全く異
なる新しい特性を示し、しかも燃焼機器において
も最も要望の多い燃焼雰囲気範囲できわめて大き
い起電力を発生し、燃焼機器の最適燃焼制御を安
定に行える十分な特性をもつ燃焼検知素子を製造
できるものである。Effects of the Invention As is clear from the above explanation, the manufacturing method of the present invention exhibits new characteristics that are completely different from those using conventional platinum electrodes, and is extremely effective in the combustion atmosphere range that is most desired in combustion equipment. It is possible to manufacture a combustion detection element that generates a large electromotive force and has sufficient characteristics to stably perform optimal combustion control of combustion equipment.
したがつて、本発明の製造方法を用いることに
より、簡単な製造方法でかつ高価な白金を用いな
いことから、きわめて安価で優れた性能を有する
燃焼検知素子が製造できるものである。 Therefore, by using the manufacturing method of the present invention, a combustion sensing element having excellent performance can be manufactured at an extremely low cost because it is a simple manufacturing method and does not use expensive platinum.
第１図は従来の燃焼検知素子を示す断面図、第
２図は本発明の製造方法を用いて構成された実施
例１、２により得られた燃焼検知素子を示す断面
図、第３図は従来例と本発明方法により得られた
燃焼検知素子の起電力特性をそれぞれ示す図であ
る。
６……焼結体磁器、７，８……ニツケル電極、
９，１０……電極端子、１１……多孔性セラミツ
ク膜。
FIG. 1 is a sectional view showing a conventional combustion sensing element, FIG. 2 is a sectional view showing combustion sensing elements obtained in Examples 1 and 2 using the manufacturing method of the present invention, and FIG. FIG. 3 is a diagram showing the electromotive force characteristics of the combustion sensing elements obtained by the conventional example and the method of the present invention, respectively. 6... Sintered porcelain, 7, 8... Nickel electrode,
9, 10... Electrode terminal, 11... Porous ceramic membrane.
Claims (1)
パラジウム錯化合物の少なくとも一つを水または
有機溶剤に溶解して作成した溶液を燃焼検知素子
を構成する焼結体磁器に塗布した後、熱処理を施
して前記焼結体磁器表面に白金またはパラジウム
膜層を形成し、この白金またはパラジウム膜層上
にニツケルの化学めつきを施した後、500℃〜
1000℃の温度で熱処理し、その後多孔性セラミツ
ク材料でコーテイングすることを特徴とする燃焼
検知素子の製造方法。1. After applying a solution prepared by dissolving at least one of a platinum salt, a palladium salt, a platinum complex compound, and a palladium complex compound in water or an organic solvent to the sintered porcelain constituting the combustion detection element, heat treatment is performed. A platinum or palladium film layer is formed on the surface of the sintered porcelain, and nickel is chemically plated on the platinum or palladium film layer.
A method for producing a combustion detection element, which is characterized by heat treatment at a temperature of 1000°C and subsequent coating with a porous ceramic material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58224749A JPS60115844A (en) | 1983-11-29 | 1983-11-29 | Production of combustion detecting element |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58224749A JPS60115844A (en) | 1983-11-29 | 1983-11-29 | Production of combustion detecting element |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60115844A JPS60115844A (en) | 1985-06-22 |
| JPH0473096B2 true JPH0473096B2 (en) | 1992-11-19 |
Family
ID=16818632
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP58224749A Granted JPS60115844A (en) | 1983-11-29 | 1983-11-29 | Production of combustion detecting element |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60115844A (en) |
-
1983
- 1983-11-29 JP JP58224749A patent/JPS60115844A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS60115844A (en) | 1985-06-22 |
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