JPH0812176B2 - Sensor for measuring phosphorus concentration- - Google Patents
Sensor for measuring phosphorus concentration-Info
- Publication number
- JPH0812176B2 JPH0812176B2 JP61256601A JP25660186A JPH0812176B2 JP H0812176 B2 JPH0812176 B2 JP H0812176B2 JP 61256601 A JP61256601 A JP 61256601A JP 25660186 A JP25660186 A JP 25660186A JP H0812176 B2 JPH0812176 B2 JP H0812176B2
- Authority
- JP
- Japan
- Prior art keywords
- phosphorus concentration
- phosphate
- sensor
- 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 - Fee Related
Links
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims description 41
- 229910052698 phosphorus Inorganic materials 0.000 title claims description 41
- 239000011574 phosphorus 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
- 229910019142 PO4 Inorganic materials 0.000 claims description 17
- 229910000831 Steel Inorganic materials 0.000 claims description 17
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 17
- 239000010452 phosphate Substances 0.000 claims description 17
- 239000010959 steel Substances 0.000 claims description 17
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 11
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 11
- 239000011230 binding agent Substances 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 6
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 claims description 4
- WAKZZMMCDILMEF-UHFFFAOYSA-H barium(2+);diphosphate Chemical compound [Ba+2].[Ba+2].[Ba+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O WAKZZMMCDILMEF-UHFFFAOYSA-H 0.000 claims description 3
- 239000001506 calcium phosphate Substances 0.000 claims description 3
- 229910000389 calcium phosphate Inorganic materials 0.000 claims description 3
- 235000011010 calcium phosphates Nutrition 0.000 claims description 3
- GVALZJMUIHGIMD-UHFFFAOYSA-H magnesium phosphate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GVALZJMUIHGIMD-UHFFFAOYSA-H 0.000 claims description 3
- 239000004137 magnesium phosphate Substances 0.000 claims description 3
- 229910000157 magnesium phosphate Inorganic materials 0.000 claims description 3
- 229960002261 magnesium phosphate Drugs 0.000 claims description 3
- 235000010994 magnesium phosphates Nutrition 0.000 claims description 3
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 claims description 3
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims description 2
- 229910000805 Pig iron Inorganic materials 0.000 description 12
- 239000000203 mixture Substances 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- 238000000034 method Methods 0.000 description 8
- 150000003839 salts Chemical class 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 6
- 239000000395 magnesium oxide Substances 0.000 description 6
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 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
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 3
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 3
- 239000004568 cement Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910002077 partially stabilized zirconia Inorganic materials 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 239000000292 calcium oxide Substances 0.000 description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000002474 experimental method Methods 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
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 229910017119 AlPO Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- RQFRTWTXFAXGQQ-UHFFFAOYSA-N [Pb].[Mo] Chemical compound [Pb].[Mo] RQFRTWTXFAXGQQ-UHFFFAOYSA-N 0.000 description 1
- 230000001464 adherent effect Effects 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
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000006866 deterioration Effects 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
- 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
- 235000011837 pasties Nutrition 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000012545 processing Methods 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
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 229910002076 stabilized zirconia Inorganic materials 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052726 zirconium Inorganic materials 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、溶融銑鋼中のリン濃度を迅速に測定可能と
するリン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リン濃度測定用
センサーに関するものである。Description: TECHNICAL FIELD The present invention relates to a phosphorus concentration measuring sensor capable of quickly measuring the phosphorus concentration in molten pig steel, and more specifically, stabilized or partially stabilized zirconia. The present invention relates to a sensor for measuring the phosphorus concentration in molten pig steel, which comprises a specific substance adhered to the surface of a solid electrolyte.
〈従来の技術〉 従来より鋼材中のリンは鋼材の機械的強度等の物性低
下を招くとして、転炉工程の前段で溶銑中に処理剤を添
加し、脱リン処理に付される。<Prior Art> Since phosphorus in steel has conventionally been known to cause deterioration of physical properties such as mechanical strength of steel, a treating agent is added to the hot metal in the preceding stage of the converter process, and phosphorus is subjected to dephosphorization treatment.
脱リン処理においては当然のことながら、溶銑中のリ
ン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、結果として均
一な品質を有する製品が得られないという不都合を有し
ていた。Naturally, in the dephosphorization treatment, it is necessary to change the amount of the treatment agent added depending on the phosphorus concentration in the hot metal, but in the conventional instrumental analysis, it takes a long time from sample collection to obtaining the measurement result. However, the processing agent cannot be added in consideration of the analysis result within the process time, and as a result, a product having uniform quality cannot be obtained.
〈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リン
濃度を極めて迅速に測定し得るリン濃度測定用センサー
を得るべく鋭意検討した結果、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、溶融銑鋼中のリン濃度を迅
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 such circumstances, the present inventors have earnestly studied to obtain a phosphorus concentration measurement sensor capable of extremely rapidly measuring the phosphorus concentration in molten pig steel, and as a result, stabilization. Alternatively, when a partially stabilized zirconia solid electrolyte surface is coated with a specific substance, it becomes a secondary electrode type solid battery, and it was found that the phosphorus concentration in molten pig steel can be measured quickly and accurately, and the present invention has been completed. It was
〈問題点を解決するための手段〉 すなわち本発明は、溶融銑鋼とリン濃度測定用センサ
ーの間に生じる起電力により溶融銑鋼中のリン濃度を測
定する、ジルコニア固体電解質の管内に参照電極を充填
してなるリン濃度測定用センサーであって、リン酸塩と
該リン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可溶性リン酸塩溶液を添加、
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リン濃度測定用センサーを提供する
にある。<Means for Solving Problems> That is, the present invention is to measure the phosphorus concentration in the molten pig steel by the electromotive force generated between the molten pig steel and the sensor for measuring phosphorus concentration, the reference electrode in the tube of the zirconia solid electrolyte. A sensor for measuring phosphorus concentration, which comprises a phosphate and a soluble phosphate solution as a binder in oxides of zirconium and the oxides of the elements constituting the phosphate salt,
Another object of the present invention is to provide a sensor for measuring phosphorus concentration in molten pig iron, which is obtained by mixing and adhering this 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リン酸塩としては、リン酸カ
ルシウム、リン酸マグネシウム、リン酸バリウム及びリ
ン酸アルミニウムの単独或いはこれらの混合物で、該リ
ン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、リン酸カルシウムの場合には酸化カル
シウム、リン酸マグネシウムの場合には酸化マグネシウ
ム、リン酸バリウムの場合には酸化バリウム、リン酸ア
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、通常約40μ以下、好まし
くは約10〜約0.3μのものが適当する。As the phosphate used in the present invention, calcium phosphate, magnesium phosphate, barium phosphate and aluminum phosphate alone or in a mixture thereof, an oxide of an element constituting the salt of phosphoric acid (hereinafter simply referred to as The term `` oxide '' means calcium oxide in the case of calcium phosphate, magnesium oxide in the case of magnesium phosphate, barium oxide in the case of barium phosphate, and aluminum oxide in the case of aluminum phosphate. Including zirconium oxide, those having a thickness of about 40 μm or less, preferably about 10 to about 0.3 μm are suitable.
固体電解質表面に固着せしめるリン酸塩と該塩の酸化
物との混合割合は重量％で約10〜約90:約90〜約10、好
ましくは約30〜約70:約70〜約30であり、リン酸塩に対
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キの原因となり好ま
しくない。The mixing ratio of the phosphate to be fixed on the surface of the solid electrolyte and the oxide of the salt is about 10 to about 90: about 90 to about 10, preferably about 30 to about 70: about 70 to about 30. If the mixing ratio of the oxide with respect to the phosphate is less than the above range, the effect as the sub-electrode is lost, which is not preferable, while if the mixing ratio exceeds the above range, the measured values are varied, which 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。In the present invention, it is essential to add zirconium oxide as a sub-electrode constituent substance.
副電極の機能としては、リン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
には溶融鋼中での剥離脱落が生じ、実用に耐えない。The function of the sub-electrode can be satisfied by a composition composed of a phosphate and an oxide of the salt. However, when zirconium oxide is not present in the composition, the function of the sub-electrode in the subsequent firing step of the sub-electrode component is The components are peeled off from the surface of the zirconia solid electrolyte and further peeled off in the molten steel, which is not practical.
該酸化ジルコニウムの添加量は、リン酸塩及び該塩の
酸化物の総量に対し約10〜約70重量％、好ましくは約20
〜約50重量％の範囲で使用される。The amount of zirconium oxide added is about 10 to about 70% by weight, preferably about 20% by weight, based on the total amount of phosphate and oxides of the salt.
Used in the range of about 50% by weight.
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。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リン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可溶性リン酸塩溶液
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 phosphate thus prepared, the oxide of the salt, and zirconium oxide are usually sufficiently stirred and mixed so as to be uniformly dispersed, and then mixed with a soluble phosphate solution as a binder to form a paste-like or slurry-like substance. After being formed, it is attached to the surface of the zirconia solid electrolyte.
リン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可溶性リン酸塩の混合割合は、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、通常リン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約５〜約40重量％の割
合で使用される。The mixing ratio of the phosphate and the soluble phosphate as a binder with respect to the oxide of the salt and zirconium oxide is naturally determined by the workability of adhering the mixture to the surface of the zirconia solid electrolyte, but usually the phosphate and the It is used in a proportion of about 5 to about 40% by weight, based on the total amount of salt oxide and zirconium oxide.
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〜約90％、好
ましくは約30〜約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 brush coating method, a spray method,
A known adhesion method such as a dipping method may be used, and if the adhesion area does not hinder the transfer of oxygen ions in the molten pig iron to the zirconia solid electrolyte surface, for example, the adhesion material should be formed in a porous state. Although it may be coated over the entire surface, usually the adhesion substance is about 10 to about 90% of the surface of the zirconia solid electrolyte, preferably about 30 to about 70% is uniformly dispersed and adhered, for example, a method of adhering to a mesh or spots. Recommended.
ジルコニア固体電解質表面への付着物質の付着は約2m
m以下、好ましくは約0.02〜約1mmであればよい。Approximately 2 m of adherent substance adheres to the surface of zirconia solid electrolyte
It may be m or less, preferably about 0.02 to about 1 mm.
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、また薄過ぎると副電極としての効果を発揮し
ない。If the adhesion thickness is too thick, peeling and dropping occurs when immersed in molten pig iron, and if it is 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、約1000〜約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 pasty material thus coated on the solid electrolyte surface is then dried and calcined at a temperature of about 1000 to about 1600 ° C. to adhere to the zirconia solid electrolyte surface.
リン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 the sensor for measuring phosphorus concentration, as in the case of the sensor for measuring oxygen concentration using a normal zirconia solid electrolyte, a tube of one-end closed type zirconia solid electrolyte 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 / FeO that will become the reference electrode (3) in (1)
It can be prepared by filling a mixture such as, and arranging a lead wire (4) such as Mo and then enclosing alumina cement (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、上記構成のリン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 phosphorus 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、リン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 phosphorus concentration is generated, which is detected by the electromotive force measuring device.
以上詳述した本発明のリン濃度測定用センサーは溶融
銑鋼中のリンの活量をAl2O3／AlPO4／ZrO2,CaO/Ca3(P
O4)2／ZrO2,MgO/Mg3(PO4)2／ZrO2,BaO/Ba3(PO4)2／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P2O5に比較
して解離圧が小さく、またリン酸塩が安定であり、P2O5
の活量を一定として近似できるため、溶融銑鋼中のリン
濃度の変化と起電力値が敏感に対応し、迅速なリン濃度
の測定を可能ならしめるものと推測される。The phosphorus concentration measuring sensor of the present invention described in detail above shows the activity of phosphorus in molten pig iron as Al 2 O 3 / AlPO 4 / ZrO 2 , CaO / Ca 3 (P
O 4 ) 2 / ZrO 2 , MgO / Mg 3 (PO 4 ) 2 / ZrO 2 , BaO / Ba 3 (PO 4 ) 2 / ZrO 2
Is converted into oxygen potential using a sub-electrode mainly composed of, and is measured by a zirconia solid electrolyte, the oxide selected as the sub-electrode has a smaller dissociation pressure than P 2 O 5 , Also, the phosphate is stable and P 2 O 5
Since it can be approximated as a constant activity, it is presumed that the change in the phosphorus concentration in the molten pig steel and the electromotive force value are sensitively related to each other, which enables the rapid measurement of the phosphorus concentration.
〈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。<Example> Hereinafter, the present invention will be described in more detail with reference to Examples.
The example shows one embodiment of the present invention, and the present invention is not limited to the example.
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菅の表面にMg3(PO4)230
重量部、MgO 40重量部及びZrO230重量部、バインダー
としてのリン酸アルミニウム溶液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（直径約1mm、膜
厚約0.3mm、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３時間焼
成した。Example 1 Outer diameter 5.5 mm, inner diameter 3.6 mm, length 35 mm, one-end closed tube type MgO
Mg 3 (PO 4 ) 2 30 on the surface of a zirconia tube containing 7 mol% of
1 part by weight, 40 parts by weight of MgO and 30 parts by weight of ZrO 2 and 30 parts by weight of an aluminum phosphate solution as a binder were mixed, and then, as shown in FIG. 1, a spotted shape (diameter about 1 mm, film thickness about 0.3 mm , 50% of the outer surface of the solid electrolyte), dried at 120 ° C., and baked at a temperature of 1400 ° C. for 3 hours.
次いで得られたMg3(PO4)2/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1mmφ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 obtained Mg 3 (PO 4 ) 2 / MgO / ZrO 2 coated zirconia tube with a mixed powder of 1 part by weight of molybdenum and 4 parts by weight of molybdenum oxide, insert a 1 mmφ molybdenum wire as a lead wire, and form an alumina cement. Then, 10 solid electrolyte sensors with sub-electrodes were prepared.
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、リン濃度を0.0
05〜0.3重量％の範囲で調整した銑鉄中に投入し、リン
濃度に於ける起電力値を測定し、その値を第２図に示し
た。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 carbon, and the phosphorus concentration was 0.0
It was put into pig iron adjusted in the range of 05 to 0.3% by weight, and the electromotive force value in phosphorus concentration was measured, and the value is shown in FIG.
第２図においてリン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、リン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、溶融銑鉄中のリン濃度と起電力
値との相関が高いことがわかる。In FIG. 2, the phosphorus concentration is shown on a logarithmic scale, but as is clear from FIG. 2, when the sensor of the present invention is used, the electromotive force value sensitively responds to the change in phosphorus concentration in a substantially linear relationship. Therefore, it is understood that the correlation between the phosphorus 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25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、リン濃
度を測定したところ６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。Incidentally, without using ZrO 2 as the composition of the sub-electrode, except that the binder addition amount was changed to 25 parts by weight, 10 sensors obtained in the same manner as the above method were put into molten pig iron, and the phosphorus concentration was measured. However, cracks occurred in the six sensors,
It was peeled off and unmeasurable.
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。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.
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、溶融銑鉄中のリン濃
度と起電力値が直線関係にあり、リン濃度の測定ができ
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 phosphorus concentration in the molten pig iron and the electromotive force value, and the phosphorus concentration can be measured.
また、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１表中に示す組成（但しバインダー量
は実験No.1で15重量部、No.2で20重量部、No.3で25重量
部、No.4で20重量部、No.5で10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No.1対応品で５本、以下６本、３本、７本、６本が
副電極にクラックが生じ、剥離脱落し、リン濃度の測定
ができなかった。For comparison, the composition shown in Table 1 was used except that zirconium oxide was not used as the auxiliary electrode composition (however, the amount of the binder was 15 parts by weight in experiment No. 1, 20 parts by weight in No. 2 and 25 parts in No. 3). Parts, 20 parts by weight for No.4 and 10 parts by weight for No.5.)
In the products corresponding to the experiment No. 5, 5 pieces, 6 pieces, 3 pieces, 7 pieces, and 6 pieces were cracked in the sub-electrodes, peeled off, and could not measure the phosphorus concentration.
なお、本発明のセンサーはいずれも剥離脱落はなかっ
た。Note that none of the sensors of the present invention peeled off.
〈発明の効果〉 以上詳述した本発明のリン濃度測定用センサーは、溶
融銑鋼中のリン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
リン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 phosphorus concentration of the present invention described in detail above converts the activity of phosphorus 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 phosphorus concentration in the molten pig steel extremely quickly, and its industrial value is enormous.
第１図は、本発明のリン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……リン酸塩、該リン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。 また第２図は、本発明のリン濃度測定用センサーで観測
されたリン濃度と起電力値との関係図を示す。FIG. 1 is a schematic diagram of a sensor for measuring phosphorus concentration according to the present invention. In the figure, 1 ... Zirconia solid electrolyte tube 2 ... Phosphate, oxides of elements constituting the salt of phosphoric 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 phosphorus concentration and the electromotive force value observed by the sensor for measuring phosphorus 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61−260157（ＪＰ，Ａ) 特開 昭62−102150（ＪＰ，Ａ) ─────────────────────────────────────────────────── ─── Continuation of the front page (56) Reference JP 61-142455 (JP, A) JP 61-260157 (JP, A) JP 62-102150 (JP, A)
Claims (2)
生じる起電力により溶融銑鋼中のリン濃度を測定する、
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
リン濃度測定用センサーであって、リン酸塩と該リン酸
の塩を構成する元素の酸化物及び酸化ジルコニウムにバ
インダーとして可溶性リン酸塩溶液を添加、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
銑鋼中のリン濃度測定用センサー。1. A phosphorus concentration in molten pig steel is measured by an electromotive force generated between the molten pig steel and a phosphorus concentration measuring sensor.
A sensor for measuring phosphorus concentration, which is obtained by filling a reference electrode in a tube of zirconia solid electrolyte, wherein a soluble phosphate solution is used as a binder for a phosphate and zirconium oxide, which is an element of the phosphate salt. A sensor for measuring phosphorus concentration in molten pig steel, which is prepared by adding and mixing and fixing it to the surface of zirconia solid electrolyte.
ネシウム、リン酸バリウム及びリン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
載のリン濃度測定用センサー。2. The sensor for measuring phosphorus concentration according to claim 1, wherein the phosphate is at least one selected from calcium phosphate, magnesium phosphate, barium phosphate and aluminum phosphate.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60-242167 | 1985-10-29 | ||
| JP24216785 | 1985-10-29 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62174649A JPS62174649A (en) | 1987-07-31 |
| JPH0812176B2 true JPH0812176B2 (en) | 1996-02-07 |
Family
ID=17085325
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61256601A Expired - Fee Related JPH0812176B2 (en) | 1985-10-29 | 1986-10-27 | Sensor for measuring phosphorus concentration- |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0812176B2 (en) |
Families Citing this family (2)
| 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 |
| JP4734570B2 (en) * | 2006-08-09 | 2011-07-27 | 国立大学法人北見工業大学 | Cyclone separation device and residential air supply hood using the same |
-
1986
- 1986-10-27 JP JP61256601A patent/JPH0812176B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPS62174649A (en) | 1987-07-31 |
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