JPH0750061B2 - Sensor for measuring silicon concentration - Google Patents
Sensor for measuring silicon concentrationInfo
- Publication number
- JPH0750061B2 JPH0750061B2 JP60242166A JP24216685A JPH0750061B2 JP H0750061 B2 JPH0750061 B2 JP H0750061B2 JP 60242166 A JP60242166 A JP 60242166A JP 24216685 A JP24216685 A JP 24216685A JP H0750061 B2 JPH0750061 B2 JP H0750061B2
- Authority
- JP
- Japan
- Prior art keywords
- silicon concentration
- sensor
- silicate
- measuring
- 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.)
- Expired - Lifetime
Links
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims description 41
- 229910052710 silicon Inorganic materials 0.000 title claims description 41
- 239000010703 silicon Substances 0.000 title claims description 41
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 44
- 239000007784 solid electrolyte Substances 0.000 claims description 25
- 229910000831 Steel Inorganic materials 0.000 claims description 17
- 239000010959 steel Substances 0.000 claims description 17
- 229910000805 Pig iron Inorganic materials 0.000 claims description 14
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 12
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 12
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 12
- 150000003839 salts Chemical class 0.000 claims description 11
- 239000011230 binding agent Substances 0.000 claims description 7
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000004115 Sodium Silicate Substances 0.000 claims description 4
- 239000008119 colloidal silica Substances 0.000 claims description 4
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 4
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 claims description 3
- 239000000378 calcium silicate Substances 0.000 claims description 3
- 229910052918 calcium silicate Inorganic materials 0.000 claims description 3
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 claims description 3
- 239000000391 magnesium silicate Substances 0.000 claims description 3
- 229910052919 magnesium silicate Inorganic materials 0.000 claims description 3
- 235000019792 magnesium silicate Nutrition 0.000 claims description 3
- ZADYMNAVLSWLEQ-UHFFFAOYSA-N magnesium;oxygen(2-);silicon(4+) Chemical compound [O-2].[O-2].[O-2].[Mg+2].[Si+4] ZADYMNAVLSWLEQ-UHFFFAOYSA-N 0.000 claims description 3
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 3
- 235000012239 silicon dioxide Nutrition 0.000 claims description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims 1
- 229910052726 zirconium Inorganic materials 0.000 claims 1
- 229910052760 oxygen Inorganic materials 0.000 description 10
- 239000001301 oxygen Substances 0.000 description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 239000000126 substance Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 239000000395 magnesium oxide Substances 0.000 description 7
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 229910017625 MgSiO Inorganic materials 0.000 description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 3
- 229910004298 SiO 2 Inorganic materials 0.000 description 3
- 239000004568 cement Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 229910002077 partially stabilized zirconia Inorganic materials 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000011812 mixed powder Substances 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 229910002076 stabilized zirconia Inorganic materials 0.000 description 2
- 229910004762 CaSiO Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RQFRTWTXFAXGQQ-UHFFFAOYSA-N [Pb].[Mo] Chemical compound [Pb].[Mo] RQFRTWTXFAXGQQ-UHFFFAOYSA-N 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- -1 oxygen ions Chemical class 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Landscapes
- 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、溶融銑鋼中のケイ素濃度を迅速に測定可能と
するケイ素濃度測定用センサーに関し、更に詳細には安
定化或いは部分安定化ジルコニア固体電解質表面に特定
物質を付着構成せしめてなる溶融銑鋼中のケイ素濃度測
定用センサーに関するものである。Description: TECHNICAL FIELD The present invention relates to a sensor for measuring silicon concentration that enables rapid measurement of silicon concentration in molten pig iron steel, and more particularly to stabilized or partially stabilized zirconia. The present invention relates to a sensor for measuring the silicon concentration in molten pig iron, which comprises a specific substance adhered to the surface of a solid electrolyte.
（従来の技術） 従来より極高純度鋼は溶銑段階において必要な酸素を確
保するため、事前に溶銑中のケイ素濃度を0.20〜0.25％
程度以下まで低減させ、脱リン用酸素の不足を回避する
とか、又一般鋼の製造においても転炉の精錬コストを安
価にするため、溶銑中のケイ素濃度を0.20〜0.25％レベ
ルに安定させる必要があるとして、溶銑中に処理剤を添
加し、脱ケイ素処理に付される。脱ケイ素処理において
は当然のことながら、溶銑中のケイ素濃度により処理剤
の添加量を変化させる必要があるが、従来法である機器
分析ではサンプル採取から測定結果を得るまでに長時間
を要し、工程時間内に分析結果を勘案して処理剤を投入
することができず、結果として初期の目的を十分に達成
できない等の不都合を有していた。(Prior Art) Conventionally, ultra-high purity steel has a silicon concentration of 0.20 to 0.25% in advance in order to secure necessary oxygen in the hot metal stage.
It is necessary to stabilize the silicon concentration in the hot metal to a level of 0.20 to 0.25% in order to reduce the oxygen content for dephosphorization to avoid the lack of oxygen for dephosphorization and to reduce the refining cost of the converter even in the production of general steel. If so, a treating agent is added to the hot metal and the silicon is desiliconized. Naturally, in the desiliconization treatment, it is necessary to change the amount of the treatment agent added depending on the silicon concentration in the hot metal, but in the conventional instrumental analysis, it takes a long time to obtain the measurement result from the sample collection. However, the processing agent cannot be added in consideration of the analysis result within the process time, and as a result, there is a disadvantage that the initial purpose cannot be sufficiently achieved.
（発明が解決しようとする問題点） かかる事情下に鑑み、本発明者らは溶融銑鋼中のケイ素
濃度を極めて迅速に測定し得るケイ素濃度測定用センサ
ーを得るべく鋭意検討した結果、従来溶鋼中の酸素濃度
測定用に使用されていた安定化或いは部分安定化ジルコ
ニア固体電解質表面に特定物質を被覆する場合には副電
極型固体電池となり、溶融銑鋼中のケイ素濃度を迅速に
精度よく測定し得ることを見出し、本発明を完成するに
至った。(Problems to be Solved by the Invention) In view of the above circumstances, the present inventors have earnestly studied to obtain a silicon concentration measuring sensor capable of extremely rapidly measuring the silicon concentration in molten pig steel, and as a result, the conventional molten steel has been obtained. When the surface of a stabilized or partially stabilized zirconia solid electrolyte, which was used to measure the oxygen concentration in the interior, is coated with a specific substance, it becomes a sub-electrode type solid battery, and the silicon concentration in molten pig steel can be measured quickly and accurately. They have found that they can do so and have completed the present invention.
（問題点を解決するための手段） すなわち本発明は、溶融銑鋼とケイ素濃度測定用センサ
ーの間に生じる起電力により溶融銑鋼中のケイ素濃度を
測定する、ジルコニア固体電解質の管内に参照電極を充
填してなるケイ素濃度測定用センサーであって、ケイ酸
塩と該ケイ酸の塩を構成する元素の酸化物および酸化ジ
ルコニウムにバインダーとしてケイ酸ソーダ又はコロイ
ダルシリカ溶液を添加、混合し、これをジルコニア固体
電解質表面に固着せしめてなる溶融銑鋼中のケイ素濃度
測定用センサーを提供するにある。(Means for Solving the Problems) That is, the present invention provides a reference electrode in a tube of a zirconia solid electrolyte for measuring the silicon concentration in molten pig steel by an electromotive force generated between the molten pig steel and a sensor for measuring silicon concentration. A sensor for measuring silicon concentration, which is obtained by filling a silicate and an oxide of an element constituting the salt of silicate and zirconium oxide with a sodium silicate or colloidal silica solution added as a binder and mixed, Another object of the present invention is to provide a sensor for measuring the silicon concentration in molten pig steel, which is obtained by sticking the above to the surface of a zirconia solid electrolyte.
以下、本発明を更に詳細に説明する。Hereinafter, the present invention will be described in more detail.
本発明において使用するケイ酸塩としては、ケイ酸カル
シウム、ケイ酸マグネシウム及びケイ酸アルミニウムの
単独或いはこれらの混合物で、該ケイ酸の塩を構成する
元素の酸化物（以下単に該塩の酸化物という）とは、ケ
イ酸カルシウムの場合には酸化カルシウム、ケイ酸マグ
ネシウムの場合には酸化マグネシウム、ケイ酸アルミニ
ウムの場合には酸化アルミニウムで、その使用粒度は酸
化ジルコニウムも含め、通常20μ以下、好ましくは10〜
0.3μのものが適当する。As the silicate used in the present invention, calcium silicate, magnesium silicate and aluminum silicate are used alone or in a mixture thereof, and oxides of the elements constituting the salt of the silicic acid (hereinafter simply referred to as oxides of the salt). ) Means calcium oxide in the case of calcium silicate, magnesium oxide in the case of magnesium silicate, aluminum oxide in the case of aluminum silicate, the particle size of which is usually 20 μm or less, including zirconium oxide, preferably Is 10 ~
0.3μ is suitable.
固体電解質表面に固着せしめるケイ酸塩と該塩の酸化物
との混合割合は重量％で10〜90:90〜10、好ましくは30
〜70:70〜30であり、ケイ酸塩に対する酸化物の混合割
合が上記範囲より少ない場合には副電極としての効果が
なくなり好ましくなく、他方上記範囲を越える場合には
測定値のバラツクの原因となり好ましくない。The mixing ratio of the silicate to be fixed on the surface of the solid electrolyte and the oxide of the salt is 10 to 90:90 to 10, preferably 30 by weight%.
~ 70: 70 ~ 30, and when the mixing ratio of the oxide to the silicate is less than the above range, the effect as a sub-electrode is lost, which is not preferable. On the other hand, when the mixing ratio exceeds the above range, the cause of variation in measured values Is not preferable.
本発明においては、副電極構成物質として酸化ジルコニ
ウムの添加を必須とする。副電極の機能としては、ケイ
酸塩及び該塩の酸化物より構成される組成で満足し得る
が、該組成中に酸化ジルコニウムが存在しない場合に
は、後の副電極成分の焼成工程で該成分がジルコニア固
体電解質表面から剥離、更には溶融銑鋼中での剥離脱落
が生じ、実用に耐えない。In the present invention, it is essential to add zirconium oxide as a sub-electrode constituent substance. The function of the sub-electrode can be satisfied by a composition composed of silicate and an oxide of the salt. However, when zirconium oxide is not present in the composition, the sub-electrode can be used in the subsequent firing step of the sub-electrode component. The components are peeled off from the surface of the zirconia solid electrolyte and further peeled off in the molten pig steel, which is not practical.
該酸化ジルコニウムの添加量は、ケイ酸塩及び該塩の酸
化物の総量に対し10〜70重量％、好ましくは20〜50重量
％の範囲で使用される。酸化ジルコニウムの量が上記範
囲以下の場合には添加効果がなく、他方上記範囲を越え
る場合には副電極としての安定性が悪くなり、測定値が
バラツクため好ましくない。The amount of zirconium oxide added is in the range of 10 to 70% by weight, preferably 20 to 50% by weight, based on the total amount of silicate and oxides of the salt. If the amount of zirconium oxide is less than the above range, there is no effect of addition. On the other hand, if it exceeds the above range, the stability as a sub-electrode deteriorates and the measured values are not preferable.
このようにして調整されたケイ酸塩と該塩の酸化物及び
酸化ジルコニウムは通常均一に分散するよう十分攪拌、
混合した後バインダーとしてのケイ酸ソーダ又はコロイ
ダルシリカ溶液と混合し、ペースト状或いはスラリー状
物質を形成せしめた後、これをジルコニア固体電解質表
面に付着せしめる。The silicate thus prepared, the oxide of the salt and zirconium oxide are usually sufficiently stirred so as to be uniformly dispersed,
After mixing, it is mixed with sodium silicate or colloidal silica solution as a binder to form a paste-like or slurry-like substance, which is then attached to the surface of the zirconia solid electrolyte.
ケイ酸塩と該塩の酸化物及び酸化ジルコニウムに対する
バインダーとしてのケイ酸ソーダ又はコロイダルシリカ
の混合割合は、該混合物のジルコニア固体電解質表面へ
の付着作業性により自ずと決定されるが、通常ケイ酸塩
と該塩の酸化物及び酸化ジルコニウムの総量に対し５〜
40％重量％の割合で使用される。The mixing ratio of sodium silicate or colloidal silica as a binder to the silicate and the oxide and zirconium oxide of the salt is naturally determined by the workability of the mixture to adhere to the surface of the zirconia solid electrolyte. And 5 to the total amount of oxide and zirconium oxide of the salt
Used at a rate of 40% by weight.
本発明で用いられるジルコニア固体電解質は、通常の鉄
鋼用の酸素センサーとして使用されている耐熱衝撃性の
良好なものであればいかなるものであってもよく、例え
ばMgOを３〜15モル％含有してなる部分安定化ジルコニ
ア等が使用される。The zirconia solid electrolyte used in the present invention may be any as long as it has good thermal shock resistance used as an oxygen sensor for ordinary iron and steel, and contains, for example, 3 to 15 mol% of MgO. Partially stabilized zirconia or the like is used.
ジルコニア固体電解質表面への該ペースト或いはスラリ
ー状物質の付着方法としては刷毛塗法、スプレー法、浸
漬法等公知の付着方法でよく、付着面積は該付着物が溶
融銑鋼中の酸素イオンのジルコニア固体電解質表面への
移動を妨げないのであれば、例えば付着物を多孔質状態
に構成することにより全面被覆でもよいが、通常は付着
物質がジルコニア固体電解質表面の約10〜90％、好まし
くは30〜70％を均一に分散付着、例えば網目状或いは斑
点状に付着せしめる方法等が推奨される。As a method for adhering the paste or slurry-like substance to the surface of the zirconia solid electrolyte, a known adhering method such as a brush coating method, a spray method or a dipping method may be used, and the adhering area is zirconia of oxygen ions in molten pig steel. If it does not hinder the transfer to the solid electrolyte surface, for example, the entire surface may be covered by forming the deposit in a porous state, but usually the deposit is about 10 to 90% of the zirconia solid electrolyte surface, preferably 30. It is recommended to uniformly disperse and deposit 70% to 70%, for example, a method of depositing in the form of a mesh or spots.
ジルコニア固体電解質表面への付着物質の付着厚は2mm
以下、好ましくは0.02〜1mmであればよい。付着厚が厚
過ぎると溶融銑鋼中に浸漬する際、剥離脱落が生じ、又
薄過ぎると副電極としての効果を発揮しない。Zirconia solid electrolyte surface has a deposit thickness of 2 mm
Hereafter, it is preferably 0.02 to 1 mm. If the adhered thickness is too thick, peeling and dropping occur when immersed in molten pig iron, and if too thin, the effect as a sub-electrode is not exerted.
このようにして固体電解質表面に被覆されたペースト状
物質は次いで乾燥され、1000〜1600℃の温度で焼成さ
れ、ジルコニア固体電解質表面に固着せしめる。The paste-like substance coated on the surface of the solid electrolyte in this manner is then dried and calcined at a temperature of 1000 to 1600 ° C. to adhere it to the surface of the zirconia solid electrolyte.
ケイ素濃度測定用センサーとしては通常のジルコニア固
体電解質による酸素濃度測定用センサーと同様、第１図
に示す如く上記方法により得た副電極（２）を固着せし
めた一端閉塞型のジルコニア固体電解質の管（１）内に
参照電極（３）となるMo/MoO2、Cr/Cr2O3、Ni/NiO、Fe/
FeO等の混合物を充填し、Mo等のリード線（４）を配設
した後アルミナセメント等（５）を封入することにより
作成し得る。As a sensor for measuring silicon concentration, as in the case of a sensor for measuring oxygen concentration using a normal zirconia solid electrolyte, a tube of zirconia solid electrolyte with one end closed to which the sub-electrode (2) obtained by the above method is fixed as shown in FIG. Mo / MoO 2 , Cr / Cr 2 O 3 , Ni / NiO, Fe / which becomes the reference electrode (3) in (1)
It can be prepared by filling a mixture of FeO or the like, disposing the lead wire (4) of Mo or the like, and then enclosing alumina cement or the like (5).
該センサーの適用は通常のジルコニア固体電解質による
酸素濃度測定用センサーと同様に測定すればよく、より
具体的には、上記構成のケイ素濃度測定用センサーの先
端を溶融銑鋼中に浸漬すると共に、センサーからのリー
ド線４と、該センサー近傍の溶融銑鋼中に浸漬したモリ
ブデン等よりなる金属からのリード線を起電力測定装置
に接続する。The application of the sensor may be measured in the same manner as a sensor for measuring oxygen concentration using a normal zirconia solid electrolyte, and more specifically, while immersing the tip of the sensor for measuring silicon concentration having the above configuration in molten pig iron, A lead wire 4 from the sensor and a lead wire made of metal such as molybdenum immersed in molten pig steel near the sensor are connected to an electromotive force measuring device.
溶融銑鋼と副電極を挟んで参照電極の間では、電池が形
成され、ケイ素濃度に応じた起電力が発生するので、こ
れを起電力測定装置で検知する。A battery is formed between the molten pig iron and the reference electrode with the sub-electrode interposed therebetween, and an electromotive force corresponding to the silicon concentration is generated. This is detected by the electromotive force measuring device.
以上詳述した本発明のケイ素濃度測定用センサーは溶融
銑鋼中のケイ素の活量をAl2O3／Al2O3・SiO2／ZrO2、Ca
O/CaSiO3／ZrO2、MgO/MgSiO3／ZrO2を主体とする副電極
を用いて酸素ポテンシャルに変換し、これをジルコニア
固体電解質によって測定するもので、副電極としての選
定物質である酸化物がSiO2に比較して解離圧が小さく、
又ケイ酸塩が安定であり、SiO2の活量を一定として近似
できるため、溶融銑鋼中のケイ素濃度の変化と起電力値
が敏感に対応し、迅速なケイ素濃度の測定を可能ならし
めるものと推測される。The sensor for measuring silicon concentration of the present invention described in detail above shows the activity of silicon in molten pig iron as Al 2 O 3 / Al 2 O 3 .SiO 2 / ZrO 2 , Ca.
Oxygen potential is converted by using a sub-electrode composed mainly of O / CaSiO 3 / ZrO 2 and MgO / MgSiO 3 / ZrO 2 , and this is measured by a zirconia solid electrolyte. The material has a smaller dissociation pressure than SiO 2 .
In addition, since the silicate is stable and the activity of SiO 2 can be approximated to be constant, changes in the silicon concentration in the molten pig steel and the electromotive force value can be sensitively responded to, enabling rapid measurement of the silicon concentration. It is supposed to be.
（実施例） 以下、実施例により本発明を更に詳細に説明するが、実
施例は本発明の一実施態様を示すものであって、本発明
はかかる実施例に限定されるものではない。(Examples) Hereinafter, the present invention will be described in more detail with reference to examples, but the examples show one embodiment of the present invention, and the present invention is not limited to the examples.
実施例１ 外径5.5mm、内径3.6mm、長さ35mmの一端閉管型のMgOを
７モル％含有するジルコニア管の表面にMgSiO330重量
部、MgO40重量部及びZrO230重量部、バインダーとして
の３号水ガラス30重量部を混合した後、刷毛で第１図に
示すように斑点状（直径2mm、膜厚約0.2mm、固体電解質
外表面に占める割合50％）に塗布し、120℃で乾燥さ
せ、更に1400℃の温度で２時間焼成した。Example 1 30 parts by weight of MgSiO 3 , 40 parts by weight of MgO and 30 parts by weight of ZrO 2 as a binder on the surface of a zirconia tube containing 7 mol% of MgO having an outer diameter of 5.5 mm, an inner diameter of 3.6 mm and a length of 35 mm and containing 7 mol% of MgO. After mixing 30 parts by weight of No. 3 water glass, it was applied with a brush in spots (diameter: 2 mm, film thickness: about 0.2 mm, 50% of the outer surface of the solid electrolyte) and 120 ° C. And dried at 1400 ° C. for 2 hours.
次いで得られたMgSiO3/MgO/ZrO2被覆ジルコニア管内に
モリブデン１重量部と酸化モリブデン４重量部の混合粉
末を充填し、リード線として1mmのモリブデン線を挿入
し、アルミナセメントを封入固定し、副電極付固体電解
質センサー10本を作成した。Then, fill the mixed powder of 1 part by weight of molybdenum and 4 parts by weight of molybdenum oxide into the obtained MgSiO 3 / MgO / ZrO 2 coated zirconia tube, insert a 1 mm molybdenum wire as a lead wire, and seal and fix alumina cement, Ten solid electrolyte sensors with sub-electrodes were created.
このようにして得られたセンサーと溶融銑鋼用のモリブ
デンリード線をアルミナルツボ内で1450℃の温度で溶
解、保持した炭素約4.2重量％を含有し、ケイ素濃度を
0.1〜1.0重量％の範囲で調整した銑鉄中に投入し、各ケ
イ素濃度に於ける起電力値測定し、その値を第２図に示
した。第２図においてケイ素濃度は対数目盛りで示して
あるが、第２図から明らかなように本発明のセンサーを
用いた場合には、ケイ素濃度の変化に起電力値がほぼ直
線関係に敏感に対応しており、溶融銑鉄中のケイ素濃度
と起電力値との相関が高いことがわかる。The sensor thus obtained and the molybdenum lead wire for molten pig steel were melted at a temperature of 1450 ° C in an alumina crucible and contained about 4.2% by weight of retained carbon.
It was put into pig iron adjusted in the range of 0.1 to 1.0% by weight, and the electromotive force value at each silicon concentration was measured. The value is shown in FIG. In FIG. 2, the silicon concentration is shown on a logarithmic scale. As is clear from FIG. 2, when the sensor of the present invention is used, the electromotive force value is sensitive to the change in silicon concentration in a substantially linear relationship. Therefore, it can be seen that the correlation between the silicon concentration in the molten pig iron and the electromotive force value is high.
なお、副電極の組成としてZrO2を用いず、またバインダ
ー添加量を20重量部に変更した以外は上記方法と同様に
して得たセンサー10本を溶融銑鉄中に投入し、ケイ素濃
度を測定したところ４本のセンサーにクラックが生じ、
剥離脱落し測定不能であった。ちなみに本発明のセンサ
ーは全て副電極の剥離脱落はなく、測定可能であった。Incidentally, without using ZrO 2 as the composition of the sub-electrode, except that the binder addition amount was changed to 20 parts by weight, 10 sensors obtained in the same manner as the above method were put into molten pig iron, and the silicon concentration was measured. However, cracks occurred in the four sensors,
It was peeled off and unmeasurable. By the way, all the sensors of the present invention were measurable without peeling off of the auxiliary electrode.
実施例２ ジルコニア管への被覆物質を第１表の組成のものに変え
た以外は実施例１と同様の方法でセンサーを作成し、溶
融銑鉄中でその性能を測定した。Example 2 A sensor was prepared in the same manner as in Example 1 except that the coating material for the zirconia tube was changed to the composition shown in Table 1, and its performance was measured in molten pig iron.
その結果を第２図に示す。The results are shown in FIG.
第２図より本発明のセンサーは、溶融銑鉄中のケイ素濃
度と起電力値が直線関係にあり、ケイ素濃度の測定がで
きることが分かる。 It can be seen from FIG. 2 that the sensor of the present invention has a linear relationship between the silicon concentration in molten pig iron and the electromotive force value, and can measure the silicon concentration.
又、比較のため副電極組成として酸化ジルコニウムを用
いない他は第２表中に示す組成（但しバインダー量は実
験No1で20重量部、No2で15重量部、No3で25重量部、No4
で25重量部とした）と同様にしてセンサー各10本作成
し、同様にテストした結果、実験No1対応品で５本、以
下４本、２本、６本が副電極にクラックが生じ、剥離脱
落し、ケイ素濃度の測定ができなかった。なお、本発明
のセンサーはいずれも剥離脱落はながった。For comparison, the composition shown in Table 2 was used except that zirconium oxide was not used as the auxiliary electrode composition (however, the binder amount was 20 parts by weight in experiment No1, 15 parts by weight in No2, 25 parts by weight in No3, No4.
10 parts of each sensor were prepared in the same manner as above), and the same test was performed. As a result, 5 pieces, 4 pieces, 2 pieces, and 6 pieces of the product corresponding to Experiment No. 1 were cracked in the sub-electrode and peeled. It fell off and the silicon concentration could not be measured. All the sensors of the present invention did not peel off.
（発明の効果） 以上詳述した本発明のケイ素濃度測定用センサーは、溶
融銑鋼中のケイ素の活量を副電極を用いて酸素ポテンシ
ャルに変換し、これをジルコニア固体電解質によって測
定するもので、作動原理が明確であり、かつ溶融銑鋼中
のケイ素濃度を極めて迅速に測定することを可能ならし
めたもので、その工業的価値は頗る大なるものである。(Effects of the Invention) The sensor for measuring silicon concentration of the present invention, which has been described in detail above, converts the activity of silicon in molten pig iron into oxygen potential using a sub-electrode, and measures this with a zirconia solid electrolyte. The operating principle is clear, and it is possible to measure the silicon concentration in molten pig iron extremely quickly, and its industrial value is extremely large.
第１図は、本発明のケイ素濃度測定用センサーの概略図
であり、図中 １……ジルコニア固体電解質管 ２……ケイ酸塩、該ケイ酸の塩を構成する元素の酸化物
及び酸化ジルコニウムよりなる固着物 ３……MoとMoO2の混合粉末よりなる充填物 ４……リード線 ５……アルミナセメント を示す。 又第２図は、本発明のケイ素濃度測定用センサーで観測
されたケイ素濃度と起電力値との関係図を示す。FIG. 1 is a schematic view of a sensor for measuring silicon concentration according to the present invention. In the figure, 1 ... Zirconia solid electrolyte tube 2 ... Silicate, oxides of elements constituting the salt of silicic acid, and zirconium oxide Adhered substance 3 ... Filling substance composed of mixed powder of Mo and MoO 2 4 ... Lead wire 5 ... Alumina cement. Further, FIG. 2 shows a relationship diagram between the silicon concentration and the electromotive force value observed by the sensor for measuring silicon concentration of the present invention.
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 昭61−142455（ＪＰ，Ａ) 特開 昭61−260155（ＪＰ，Ａ) 特開 昭61−260156（ＪＰ，Ａ) 特開 昭59−73763（ＪＰ，Ａ) ─────────────────────────────────────────────────── ─── Continuation of front page (56) Reference JP-A-61-142455 (JP, A) JP-A-61-260155 (JP, A) JP-A-61-260156 (JP, A) JP-A-59- 73763 (JP, A)
Claims (2)
に生じる起電力により溶融銑鋼中のケイ素濃度を測定す
る、ジルコニア固体電解質の管内に参照電極を充填して
なるケイ素濃度測定用センサーであって、ケイ酸塩と該
ケイ酸の塩を構成する元素の酸化物および酸化ジルコニ
ウムにバインダーとしてケイ酸ソーダ又はコロイダルシ
リカ溶液を添加、混合し、これをジルコニア固体電解質
表面に固着せしめてなる溶融銑鋼中のケイ素濃度測定用
センサー。1. A sensor for measuring silicon concentration, comprising a zirconia solid electrolyte tube filled with a reference electrode for measuring the silicon concentration in molten pig steel by an electromotive force generated between the molten pig steel and the sensor for measuring silicon concentration. A solution of sodium silicate or colloidal silica as a binder is added to and mixed with oxides of zirconium and elements constituting the salt of silicic acid and zirconium oxide, and these are fixed to the surface of the zirconia solid electrolyte. Sensor for measuring silicon concentration in molten pig iron.
ネシウム及びケイ酸アルミニウムから選ばれた少なくと
も１種である特許請求の範囲第１項記載のケイ素濃度測
定用センサー。2. The sensor for measuring silicon concentration according to claim 1, wherein the silicate is at least one selected from calcium silicate, magnesium silicate and aluminum silicate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60242166A JPH0750061B2 (en) | 1985-10-29 | 1985-10-29 | Sensor for measuring silicon concentration |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60242166A JPH0750061B2 (en) | 1985-10-29 | 1985-10-29 | Sensor for measuring silicon concentration |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62102150A JPS62102150A (en) | 1987-05-12 |
| JPH0750061B2 true JPH0750061B2 (en) | 1995-05-31 |
Family
ID=17085310
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60242166A Expired - Lifetime JPH0750061B2 (en) | 1985-10-29 | 1985-10-29 | Sensor for measuring silicon concentration |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0750061B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0786499B2 (en) * | 1989-07-10 | 1995-09-20 | 株式会社陶研産業 | Component concentration sensor for molten metal using composite solid electrolyte |
-
1985
- 1985-10-29 JP JP60242166A patent/JPH0750061B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS62102150A (en) | 1987-05-12 |
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