JP3462993B2 - Slag oxidation measurement probe - Google Patents
Slag oxidation measurement probeInfo
- Publication number
- JP3462993B2 JP3462993B2 JP05034599A JP5034599A JP3462993B2 JP 3462993 B2 JP3462993 B2 JP 3462993B2 JP 05034599 A JP05034599 A JP 05034599A JP 5034599 A JP5034599 A JP 5034599A JP 3462993 B2 JP3462993 B2 JP 3462993B2
- Authority
- JP
- Japan
- Prior art keywords
- slag
- probe
- electrode
- oxidation degree
- measurement
- 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
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/10—Reduction of greenhouse gas [GHG] emissions
- Y02P10/134—Reduction of greenhouse gas [GHG] emissions by avoiding CO2, e.g. using hydrogen
Landscapes
- Measuring Oxygen Concentration In Cells (AREA)
- Treatment Of Steel In Its Molten State (AREA)
- Waste-Gas Treatment And Other Accessory Devices For Furnaces (AREA)
- Carbon Steel Or Casting Steel Manufacturing (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は、製鋼工程において使用
されるプローブに関し、さらに詳細に言えば、例えば取
鍋内で溶鋼の上に存在するスラグの酸化度を測定するプ
ローブに関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a probe used in a steelmaking process, and more particularly to a probe for measuring the degree of oxidation of slag existing on molten steel in a ladle, for example.
【０００２】[0002]
【従来の技術】溶鋼の精錬中に行われる不純物の除去、
例えば脱酸の程度は、スラグの酸化度に反映される。従
って鋳造後に得られる鋼材の清浄度は、例えば二次精錬
工程での取鍋内のスラグの酸化度により評価することが
できる。従来、このスラグの酸化度は、人手により分析
用の試料を採取し、化学分析によったり、又は固体電解
式起電力法（参考文献１：Ｔ．Ｏｇｕｒａ ｅｔ ａ
ｌ． Ｍｅｔ．Ｔｒａｎｓ． ｓｕｂｍｉｔｔｅｄ ｆ
ｏｒ ｐｕｂｌｉｃａｔｉｏｎ）を用いたスラグ中酸化
鉄活量自動測定装置によって求められていた。このよう
に、いずれの方法によっても、分析用試料を採取し、そ
の試料を分析、測定する必要があり、分析結果が得られ
るまでには相当の時間を要する。従って、分析結果が得
られたときには既にその分析の対象は二次精錬も鋳造も
終わって鋼材となっており、分析結果に基づく処理を施
してその鋼材の清浄度を高めるということは行えないの
が実情である。2. Description of the Related Art Removal of impurities, which is carried out during refining of molten steel,
For example, the degree of deoxidation is reflected in the degree of oxidation of slag. Therefore, the cleanliness of the steel material obtained after casting can be evaluated, for example, by the oxidation degree of the slag in the ladle in the secondary refining process. Conventionally, the degree of oxidation of this slag is measured by manually collecting a sample for analysis, by chemical analysis, or by a solid electrolytic electromotive force method (Reference 1: T. Ogura et a.
l. Met. Trans. submitted f
It was determined by an automatic iron oxide activity measuring device in slag using the or. As described above, it is necessary to collect a sample for analysis, analyze and measure the sample by any method, and it takes a considerable time to obtain the analysis result. Therefore, when the analysis result is obtained, the target of the analysis is already steel after the secondary refining and casting, and it is not possible to perform the processing based on the analysis result to improve the cleanliness of the steel. Is the reality.
【０００３】[0003]
【発明が解決しようとする課題】従って、製鋼工程例え
ば精錬工程で処理を行っている間にスラグの酸化度が即
時に判明すれば、その結果に基づき直ちにスラグの改質
を行い、溶鋼内の不純物の除去を更に進める等して、ス
ラグに起因する品質欠陥を減らし、鋼材の清浄度を高め
ることが出来る。Therefore, if the oxidation degree of the slag is immediately known during the treatment in the steelmaking process, for example, the refining process, the slag is immediately reformed based on the result, and By further promoting the removal of impurities, quality defects caused by slag can be reduced and the cleanliness of steel can be improved.
【０００４】本願発明は上記従来技術の問題点に鑑みな
されたものであり、本願発明者は、製鋼用酸素プローブ
を応用することにより、スラグの酸化度を簡易、迅速に
測定することが可能であることを見出した。すなわち、
本願発明が解決しようとする課題は、簡易且つきわめて
短時間にスラグの酸化度を測定することが可能な、スラ
グ酸化度測定プローブを提供することである。The present invention has been made in view of the above problems of the prior art, and the inventor of the present application can easily and quickly measure the oxidation degree of slag by applying an oxygen probe for steelmaking. I found that there is. That is,
The problem to be solved by the invention of the present application is to provide a slag oxidation degree measurement probe capable of measuring the oxidation degree of slag easily and in a very short time.
【０００５】[0005]
【課題を解決するための手段】上記課題を解決するため
に、本願発明に係るスラグ酸化度測定プローブにおいて
は、以下の構成とした。すなわち、一端閉管状の酸素イ
オン導電性を有する固体電解質と、前記固体電解質の内
部に配置された所定の酸素ポテンシャルを与える基準極
とを備えた標準電極に対し、鉄で構成した測定極を設け
る。そしてこの測定極には、スラグの流入を許容する開
口を備えた、内部にスラグを収容保持可能なスラグ収容
室を設け、標準電極は、少なくとも部分的にこのスラグ
収容室内位置するように挿入、配置したものである。こ
れにより、該プローブを溶鋼内に浸漬すると該スラグ収
容室にスラグが確実に溜められ、基準極と測定極との間
に鉄と酸化鉄との平衡反応部分が形成される。In order to solve the above problems, the slag oxidation degree measuring probe according to the present invention has the following constitution. That is, a measurement electrode made of iron is provided for a standard electrode provided with a solid electrolyte having a closed-ended tubular oxygen ion conductivity and a reference electrode provided inside the solid electrolyte to provide a predetermined oxygen potential. . Then, the measurement electrode is provided with an opening for allowing the inflow of slag, a slag accommodating chamber capable of accommodating and holding the slag is provided inside, and the standard electrode is inserted so as to be located at least partially in the slag accommodating chamber, It is arranged. As a result, when the probe is immersed in the molten steel, the slag is reliably stored in the slag accommodating chamber, and the equilibrium reaction part of iron and iron oxide is formed between the reference electrode and the measurement electrode.
【０００６】或る実施の態様では、スラグ収容室には、
スラグの進入に伴い該スラグ収容室内のガスを排出する
ガス抜き穴が設けられる。これにより、スラグのスラグ
収容室への進入が容易確実となるとともに、ガスを排出
することにより、酸化度のより正確な測定が可能とな
る。In one embodiment, the slag receiving chamber includes
A gas vent hole is provided for discharging the gas in the slag accommodating chamber as the slag enters. As a result, the slag can easily and surely enter the slag accommodating chamber, and by discharging the gas, the oxidation degree can be measured more accurately.
【０００７】ある実施の態様では、プローブの先端に、
スラグに浸漬されたときにスラグを飛散させない材質で
構成されたスラグ割り手段を備えている。これにより、
プローブの浸漬時に、固化したスラグを割り、スラグ収
容室へのスラグの進入を容易にする。In one embodiment, at the tip of the probe,
The slag splitting means is made of a material that does not scatter the slag when immersed in the slag. This allows
When the probe is dipped, the solidified slag is broken to facilitate the entry of the slag into the slag storage chamber.
【０００８】ある実施の態様では、溶鋼の温度を測定す
る温度測定手段を一体に備え、プローブが溶鋼に浸漬さ
れたときに、起電力の測定とともに温度の測定が同時に
行われる。In one embodiment, temperature measuring means for measuring the temperature of the molten steel is integrally provided, and when the probe is immersed in the molten steel, the temperature is measured simultaneously with the measurement of the electromotive force.
【０００９】ある実施の態様では、固体電解質はスラグ
収容室から、３ｍｍ以上１０ｍｍ以下の長さで突出して
いる。In one embodiment, the solid electrolyte projects from the slag accommodating chamber in a length of 3 mm or more and 10 mm or less.
【００１０】ある実施の態様では、スラグ収容室は、内
径が１０ｍｍ以上３０ｍｍ以下、深さが１０ｍｍ以上２
０ｍｍ以下である。In one embodiment, the slag accommodating chamber has an inner diameter of 10 mm or more and 30 mm or less and a depth of 10 mm or more 2
It is 0 mm or less.
【００１１】ある実施の態様では、標準電極と測定極と
からなる測定ユニットは保護管の一端に取り付けられ、
その保護管は、その一端から所定の長さの範囲で、少な
くともその外周は、セラミックファイバーで構成されて
いる。これにより、スラグの飛散が防止される。In one embodiment, a measuring unit consisting of a standard electrode and a measuring electrode is attached to one end of a protective tube,
The protective tube is formed from a ceramic fiber in a range of a predetermined length from one end thereof, and at least the outer circumference thereof. This prevents the slag from scattering.
【００１２】[0012]
【発明の実施の形態】以下、図面に基づき本願発明の具
体的実施の形態を説明するが、本願発明の範囲は以下に
説明される実施の形態に限定されるものではない。BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, specific embodiments of the present invention will be described with reference to the drawings, but the scope of the present invention is not limited to the embodiments described below.
【００１３】本願発明のスラグ酸化度測定プローブ（以
下、単に「プローブ」という）は、測定ユニットと該測
定ユニットが取り付けられる保護管からなるが、先ず図
１により、本発明のプローブ１に組み込まれる標準電極
３の構成を説明する。符号５は、下端５ａが閉じられ上
端５ｂが開いた管、即ち一端閉管状の形をしたジルコニ
ア固体電解質である。この固体電解質５の内部空所５ｃ
の下端５ａ側には、CrとCr２O３ の混合粉末からなる
基準極７が設けられている。The slag oxidation degree measuring probe of the present invention (hereinafter simply referred to as "probe") comprises a measuring unit and a protective tube to which the measuring unit is attached. First, referring to FIG. 1, it is incorporated in the probe 1 of the present invention. The structure of the standard electrode 3 will be described. Reference numeral 5 is a zirconia solid electrolyte in the shape of a tube whose lower end 5a is closed and whose upper end 5b is open, that is, a closed-end tube. Internal void 5c of this solid electrolyte 5
A reference electrode 7 made of a mixed powder of Cr and Cr2O3 is provided on the lower end 5a side.
【００１４】基準極７の上には石英ウールから構成され
た押さえ９が載置され、さらにその上に石英管１１が上
方へ延びて立設されている。固体電解質５の開口した上
端５ｂはキャップ１３として機能する無機質の接着剤に
より封止され、このキャップ１３は同時に石英管１１の
上端をも押さえることとなり、これにより基準極７は、
固体電解質５の下端５ａ及びその近傍において、固体電
解質５の内壁に接触した状態で固定されている。そし
て、符号１５はMo製の基準極リードであり、その先端が
固体電解質５の下端５ａ部の内壁に接触し、基準極７、
押さえ９、石英管１１及びキャップ１３を貫通して外部
へ引き出されている。A presser 9 made of quartz wool is placed on the reference electrode 7, and a quartz tube 11 is erected on the reference electrode 7 so as to extend upward. The open upper end 5b of the solid electrolyte 5 is sealed with an inorganic adhesive that functions as a cap 13, and this cap 13 simultaneously holds down the upper end of the quartz tube 11, whereby the reference electrode 7 is
The lower end 5a of the solid electrolyte 5 and its vicinity are fixed in contact with the inner wall of the solid electrolyte 5. Reference numeral 15 is a reference electrode lead made of Mo, the tip of which is in contact with the inner wall of the lower end 5a of the solid electrolyte 5, and the reference electrode 7,
It penetrates the retainer 9, the quartz tube 11 and the cap 13 and is drawn out to the outside.
【００１５】製鋼用酸素プローブの固体電解質としては
一般的に一端閉管状のジルコニア固体電解質が用いら
れ、基準極としては通常CrとCr２O３ 、MoとMoO２、Fe
とFeO、NiとNiO 等の金属の粉末とその金属の酸化物の
粉末との混合粉末が使用されるが、本願発明ではこれら
に限定されるものではなく、製鋼用酸素プローブに使用
できる材料であれば良い。As the solid electrolyte of the oxygen probe for steelmaking, a zirconia solid electrolyte having a closed-end tube is generally used, and the reference electrodes are usually Cr and Cr2O3, Mo and MoO2, Fe.
A mixed powder of a powder of a metal such as FeO, Ni and NiO, and a powder of an oxide of the metal is used, but the present invention is not limited to these, and is a material that can be used for an oxygen probe for steelmaking. I wish I had it.
【００１６】図２は上述した標準電極３を組み込んだプ
ローブ１の断面図であり、このプローブ１は、標準電極
３を備えた測定ユニット２と、この測定ユニット２が先
端に取り付けられる保護管４１からなる。そして測定ユ
ニット２は、標準電極３が取り付けられたハウジング２
１と、ハウジング２１の上部に取り付けられたコネクタ
ー２３と、ハウジングの下部に取り付けられた測定極２
７とで構成される。FIG. 2 is a cross-sectional view of a probe 1 incorporating the above-mentioned standard electrode 3. The probe 1 includes a measuring unit 2 equipped with the standard electrode 3 and a protective tube 41 to which the measuring unit 2 is attached at its tip. Consists of. And the measuring unit 2 includes a housing 2 to which the standard electrode 3 is attached.
1, a connector 23 attached to the upper part of the housing 21, and a measuring electrode 2 attached to the lower part of the housing
7 and 7.
【００１７】ハウジング２１はセラミック製であり、下
方から、標準電極３と、石英管に挿通された熱電対２５
の上端がそれぞれ挿入され、内部空所に耐火セメントを
詰めることにより、標準電極３及び熱電対２５即ち石英
管はハウジングに固定される。この構成は製鋼用酸素プ
ローブでは公知であるので、詳細な図示及び説明は省略
する。The housing 21 is made of ceramic, and the standard electrode 3 and a thermocouple 25 inserted through a quartz tube are inserted from below.
The standard electrode 3 and the thermocouple 25, i.e., the quartz tube, are fixed to the housing by inserting the upper ends of the two and filling the inner space with refractory cement. This configuration is known in the oxygen probe for steelmaking, and thus detailed illustration and description thereof will be omitted.
【００１８】測定極２７は、鉄製であり、短い円筒部２
９と、その上端を閉じる頂部壁３１を備え、内部に、後
述するようにこのプローブ１を使用する際にスラグを収
容するスラグ収容室３３を形成している。そして、円筒
部２９にはその上端部即ち頂壁部３１に繋がる位置で、
円周方向で適宜な間隔で、スラグ収容室３３と外部を連
通するガス抜き穴３４が貫通して、複数個設けられてい
る。頂部壁３１の上面側には、ハウジング２１の下端に
形成されたフランジ２１ａの形状に対応した窪み３１ａ
形成され、この窪み３１ａにフランジ２１ａが収受さ
れ、無機接着剤により固定されている。なお、ハウジン
グ２１に取り付けられた標準電極３と、熱電対２５と
は、頂部壁３１に設けられた穴を通ってスラグ収容室３
３内を下方へ延びている。その穴の空所には、耐火セメ
ントが充填されている。標準電極３の先端は、円筒部２
９の下端２９ａより下方へ僅かに突出している。熱電対
２５はさらに僅かながら下方に延びている。The measuring electrode 27 is made of iron and has a short cylindrical portion 2.
9 and a top wall 31 that closes the upper end thereof, and a slag storage chamber 33 that stores slag when the probe 1 is used is formed inside, as will be described later. Then, at the position connected to the upper end portion of the cylindrical portion 29, that is, the top wall portion 31,
A plurality of gas vent holes 34 that communicate with the outside of the slag accommodating chamber 33 are provided at appropriate intervals in the circumferential direction, and a plurality of gas vent holes 34 are provided. On the upper surface side of the top wall 31, a recess 31a corresponding to the shape of the flange 21a formed at the lower end of the housing 21.
The flange 21a is formed in the recess 31a and is fixed by an inorganic adhesive. The standard electrode 3 attached to the housing 21 and the thermocouple 25 pass through the holes provided in the top wall 31 and the slag accommodating chamber 3
3 extends downward. The void in the hole is filled with refractory cement. The tip of the standard electrode 3 has a cylindrical portion 2
It slightly projects downward from the lower end 29a of the plate 9. The thermocouple 25 further extends slightly downward.
【００１９】符号３５は、後に説明するスラグを割るた
めのスラグ割り部材であり、所定の長さの金属製の棒で
構成され、周方向適宜間隔で複数本設けられ、円筒部２
９の下端２９ａに取り付けられ、下方へ延びている。そ
の先端は、熱電対２５の先端を越えて延びている。Reference numeral 35 is a slag splitting member for splitting a slag, which will be described later, and is composed of a metal rod having a predetermined length, a plurality of which are provided at appropriate intervals in the circumferential direction, and the cylindrical portion 2 is provided.
It is attached to the lower end 29a of 9 and extends downward. Its tip extends beyond the tip of the thermocouple 25.
【００２０】コネクター２３は、ハウジング２１の上部
に形成された窪み（図示せず）に嵌入され、無機接着剤
によりハウジングに固定されている。このコネクター２
３には、標準電極３、熱電対２５及び測定極２７からの
リード線（図示せず）が繋がっており、使用時に保護管
４１の上部から挿入され、このコネクターに結合される
パイプ状の、一般にホルダーと称されるプローブ保持具
（図示せず）内に組み込まれた補償導線を通じて外部の
測定器に接続される。これらの構成は、製鋼用酸素プロ
ーブにおいて公知であり、詳細な図示及び説明は省略す
る。The connector 23 is fitted in a recess (not shown) formed in the upper portion of the housing 21 and fixed to the housing by an inorganic adhesive. This connector 2
A lead wire (not shown) from the standard electrode 3, the thermocouple 25, and the measurement electrode 27 is connected to 3, and a pipe-like member which is inserted from the upper portion of the protective tube 41 at the time of use and is connected to this connector, It is connected to an external measuring instrument through a compensating lead wire incorporated in a probe holder (not shown) generally called a holder. These configurations are known in the oxygen probe for steelmaking, and detailed illustration and description thereof will be omitted.
【００２１】保護管４１は内外２層構造になっている。
内側保護管４３は紙管である。そして外側保護管４５
は、上下二つの部材で構成され、下側の下部外側保護管
４７はセラミックファイバー製のスリーブであり、上側
の上部外側保護管４９は紙管である。この保護管４１の
下端に測定ユニット２のハウジング２１が挿入され、フ
ランジ２１ａと測定極２７の頂部壁３１の上面が保護管
４１の下端面に当接した状態で接着等適宜手段で固定さ
れる。The protective tube 41 has an inner and outer two-layer structure.
The inner protection tube 43 is a paper tube. And outer protection tube 45
Is composed of upper and lower members, the lower outer protective tube 47 on the lower side is a sleeve made of ceramic fiber, and the upper outer protective tube 49 on the upper side is a paper tube. The housing 21 of the measuring unit 2 is inserted into the lower end of the protective tube 41, and the flange 21a and the upper surface of the top wall 31 of the measuring electrode 27 are fixed to the lower end surface of the protective tube 41 by appropriate means such as adhesion. .
【００２２】使用に当たっては、上記の如く構成された
プローブ１をホルダーに装着して、図２に示す如く測定
ユニット２を下側にして溶鋼中に浸漬する。この際、溶
鋼の上に浮いているスラグ層を通過する時に、測定極２
７内に形成されたスラグ収容室３３内にスラグを溜め込
み、その状態で溶鋼内へ浸漬される。なお、測定極２７
の円筒部２９には、ガス抜き穴３４が設けられているの
で、スラグ収容室３３内にスラグが進入するに従い、収
容室３３内の空気がこのガス抜き穴３４から排出され、
確実にスラグ収容室３３内にスラグが溜められる。In use, the probe 1 configured as described above is mounted on a holder, and the measuring unit 2 is placed on the lower side as shown in FIG. 2 and immersed in molten steel. At this time, when passing through the slag layer floating on the molten steel, the measuring electrode 2
The slag is stored in the slag accommodating chamber 33 formed inside 7, and is immersed in the molten steel in that state. The measuring electrode 27
Since the cylindrical portion 29 is provided with the gas vent hole 34, as the slag enters the slag housing chamber 33, the air in the housing chamber 33 is discharged from the gas vent hole 34,
The slag is reliably stored in the slag storage chamber 33.
【００２３】ところで、このようにスラグ収容室３３内
にスラグが入った状態になると、測定極２７は鉄製なの
で、測定極２７と、スラグ収容室３３内に溜め込まれた
スラグ中の酸化鉄との間で下記の(１)式で示される平衡
反応が形成される。そしてその平衡定数(Ｋ)は(２)式の
関係となる。ここで鉄の活量［ａ（Ｆｅ）］は１又は一
定になるため、平衡反応部分の酸素活量［ａ（Ｏ）］を
測定することにより、スラグの酸化度すなわちスラグ中
の酸化鉄の活量［ａ（酸化鉄）］が求められる。平衡反
応部分の酸素活量は（３）式により求められる。ここで
実際に測定されるのは、基準極７と測定極２７との間の
起電力Ｅと、スラグ収容室３３内のスラグ或いは溶鋼の
温度Ｔである。By the way, when the slag is contained in the slag accommodating chamber 33 in this way, the measuring electrode 27 is made of iron, so that the measuring electrode 27 and the iron oxide in the slag stored in the slag accommodating chamber 33 are separated from each other. In the meantime, an equilibrium reaction represented by the following formula (1) is formed. Then, the equilibrium constant (K) has the relationship of equation (2). Since the iron activity [a (Fe)] is 1 or constant here, by measuring the oxygen activity [a (O)] of the equilibrium reaction part, the oxidation degree of the slag, that is, the iron oxide content of the slag The activity [a (iron oxide)] is obtained. The oxygen activity of the equilibrium reaction part is calculated by the equation (3). What is actually measured here is the electromotive force E between the reference electrode 7 and the measurement electrode 27 and the temperature T of the slag or molten steel in the slag accommodating chamber 33.
【００２４】[0024]
【数１】 [Equation 1]
【００２５】測定極２７を構成する鉄とスラグ中の酸化
鉄を平衡させ、その平衡反応部分の酸素活量を正確且つ
確実に測定するためには、固体電解質５すなわち標準電
極３の測定極２７から突出する部分の長さは、３ｍｍ以
上、１０ｍｍ以下とするのが適当であることが判明し
た。また、スラグ収容室３３内にスラグを確実に溜める
には、スラグ収容室３３の内径が１０ｍｍ以上、３０ｍ
ｍ以下で、深さが１０ｍｍ以上、２０ｍｍ以下が望まし
いことも判明した。スラグ収容室３３を大きくしすぎる
と測定極２７そのものが大きくなり、プローブの外径も
大きくなってしまい、製造コストが高くなる。また、ス
ラグ収容室３３が小さすぎると、スラグが入りにくくな
る。In order to equilibrate the iron constituting the measuring electrode 27 and the iron oxide in the slag and measure the oxygen activity of the equilibrium reaction portion accurately and reliably, the measuring electrode 27 of the solid electrolyte 5, that is, the standard electrode 3 is measured. It has been found that it is appropriate that the length of the portion protruding from is 3 mm or more and 10 mm or less. Further, in order to reliably collect the slag in the slag storage chamber 33, the inner diameter of the slag storage chamber 33 is 10 mm or more and 30 m.
It was also found that it is desirable that the depth is 10 mm or more and 20 mm or less when m or less. If the slag accommodating chamber 33 is made too large, the measuring electrode 27 itself becomes large and the outer diameter of the probe also becomes large, resulting in a high manufacturing cost. Further, if the slag accommodating chamber 33 is too small, it becomes difficult for the slag to enter.
【００２６】プローブ１の先端に設けたスラグ割り３５
は、プローブ１を溶鋼に浸漬するときに溶鋼の上に浮い
ているスラグを割るためである。すなわち、スラグの表
層は大気と接して温度が下がり、固まっていることが多
いため、測定部ユニット２の進入に先立ってこれを割
り、スラグのスラグ収納室３３内への進入を容易にし、
且つ、測定ユニット２の不測の損傷を防止するのが望ま
しい。なお、プローブ１を浸漬したとき、測定極２７は
スラグ層を突き抜け、その下の溶鋼内に留まるので、測
定極２７及び収容室３３内のスラグは溶鋼と同じ温度に
保たれ、収容室３３内のスラグが固化することはなく、
基準極７と測定極２７の間に平衡反応部分が確実に形成
される。なお、スラグ割り３５の材料としては、紙やプ
ラスチックは適しない。これらの材料素使用すると、ス
ラグ割り３５がスラグ層に進入したときにボイリングが
起こってスラグを飛散させてしまい、スラグをスラグ収
容室３３に溜めにくくなる。本実施の態様では鉄を使用
したが、モリブデン等も使用可能である。要するに、機
械的強度を有し、浸漬時にボイリングを生じさせない材
料であれば良い。A slag split 35 provided at the tip of the probe 1.
Is for breaking the slag floating on the molten steel when the probe 1 is immersed in the molten steel. That is, since the surface layer of the slag is cooled in contact with the atmosphere and often hardens, it is cracked prior to the entrance of the measurement unit 2 to facilitate the entrance of the slag into the slag storage chamber 33.
Moreover, it is desirable to prevent accidental damage of the measuring unit 2. When the probe 1 is immersed, the measuring electrode 27 penetrates the slag layer and stays in the molten steel below it, so that the measuring electrode 27 and the slag in the storage chamber 33 are kept at the same temperature as the molten steel, Slag does not solidify,
An equilibrium reaction portion is reliably formed between the reference electrode 7 and the measurement electrode 27. It should be noted that paper or plastic is not suitable as the material for the slag splitting 35. When these materials are used, when the slag split 35 enters the slag layer, boiling occurs and the slag is scattered, and it becomes difficult to store the slag in the slag accommodating chamber 33. Although iron is used in this embodiment, molybdenum or the like can also be used. In short, any material may be used as long as it has mechanical strength and does not cause boiling during immersion.
【００２７】下部外側保護管４５をセラミックファイバ
ー製のスリーブとしたのは、やはりこの部分がスラグや
溶鋼に接触したときにボイリングが起こるのを防止する
ためである。これにより、スラグ収容室へのスラグの進
入を妨げず、また、一端スラグ収容室に入ったスラグが
吐き出されるようなことはない。The lower outer protective tube 45 is made of a ceramic fiber sleeve in order to prevent boiling from occurring when this portion comes into contact with slag or molten steel. This does not prevent the slag from entering the slag storage chamber, and the slag that has once entered the slag storage chamber is not discharged.
【００２８】[0028]
【実施例】５００ｋｇ高周波誘導炉に３００ｋｇの市販
純鉄を溶解し、そこに造滓剤を投入してスラグを作り、
図１に示した構成のスラグ酸化度測定プローブを用いて
スラグ酸化度の測定を行った。スラグ組成のコントロー
ルによりスラグの酸化度を調整し、溶鋼側は未脱酸とア
ルミ脱酸の条件で行った。プローブを構成する部材やそ
の仕様は次の通りである。
ジルコニア固体電解質：ZrO２−８mol ％MgO （φ3.6mm
×φ2.2mm ×30mm）
基準極：Cr９８重量部とCr２O３ ２重量部の混合粉末
０．０５ｇ
基準極リード：φ0.5mm のMo線
測定極：外径34mmの炭素鋼
スラグ収納室の大きさ：内径26mm、深さ13mm
熱電対：φ0.075 のType−R
ジルコニア電解質の測定極先端からの突出長さ：5mm
スラグ割り：φ3mm の鉄棒４本を測定極に取付け
表１に測定データを示す。スラグ酸化度測定プローブの
測定値は、（３）式から計算した酸素活量であり、スラ
グ酸化度理論値は、スラグ酸化度プローブでの測定直後
に採取したスラグを分析し、そのスラグ組成から計算し
た酸素活量の理論計算値である。また、最右列に示した
酸素プローブ測定値は、スラグ酸化度測定プローブでの
測定直前に通常の酸素プローブで測定した溶鋼中での酸
素活量である。[Example] 300 kg of commercially pure iron was melted in a 500 kg high-frequency induction furnace, and a slag was added to make a slag.
The slag oxidation degree was measured using the slag oxidation degree measurement probe having the structure shown in FIG. The degree of oxidation of the slag was adjusted by controlling the slag composition, and the molten steel side was subjected to undeoxidized and aluminum deoxidized conditions. The members constituting the probe and their specifications are as follows. Zirconia solid electrolyte: ZrO2-8mol% MgO (φ3.6mm
× φ2.2mm × 30mm) Reference electrode: Mixed powder of 98 parts by weight of Cr and 2 parts by weight of Cr2O3 0.05g Reference electrode lead: Mo wire measuring electrode of φ0.5mm: Size of carbon steel slag storage chamber with outer diameter of 34mm: Inner diameter 26 mm, depth 13 mm Thermocouple: φ0.075 Type-R zirconia electrolyte Projection length from the measurement electrode tip: 5 mm Slag split: φ3 mm Four iron bars are attached to the measurement electrode and Table 1 shows the measurement data. The measured value of the slag oxidation degree measurement probe is the oxygen activity calculated from the equation (3), and the theoretical value of the slag oxidation degree is obtained by analyzing the slag collected immediately after the measurement with the slag oxidation degree probe, and from the slag composition thereof. It is a theoretical calculated value of the calculated oxygen activity. The oxygen probe measurement value shown in the rightmost column is the oxygen activity in molten steel measured with a normal oxygen probe immediately before the measurement with the slag oxidation degree measurement probe.
【００２９】[0029]
【表１】 [Table 1]
【００３０】表１から明らかなとおり、スラグ酸化度測
定プローブでの測定値と、通常の酸素プローブでの測定
値は全く異なっており、スラグ酸化度測定プローブでの
測定が溶鋼中の酸素活量を測定しているのではなく、ス
ラグ中の酸素活量を測定していることを示している。ま
た、図３にスラグ酸化度の理論計算値（参考文献２：萬
谷志郎 第１２２・１２３回西山記念技術講座「スラグ
の熱力学総論」（１９８８）Ｐ１１ 参考文献３：日本
学術振興会 製鋼第１９委員会編 製鋼反応の推奨平衡
値（１９８４））とスラグ酸化度測定プローブでの測定
値との比較を示す。絶対値は異なるが対応は良好であ
り、本願発明に係るプローブでのスラグ酸化度の測定は
十分可能であることを示している。また、スラグ酸化度
測定プローブでの測定に要する時間は１０秒乃至１５秒
ときわめて短時間であり、この測定結果に基づきスラグ
の改質を行っても、精錬工程の進行を妨げるほど時間を
要することはない。As is clear from Table 1, the values measured with the slag oxidation degree measurement probe and the values measured with the ordinary oxygen probe are completely different. The measurement with the slag oxidation degree measurement probe shows that the oxygen activity in molten steel is It means that the oxygen activity in the slag is measured instead of measuring. Further, FIG. 3 shows the theoretical calculated value of the slag oxidation degree (Reference 2: Shiro Mantani 122, 123rd Nishiyama Memorial Technical Course “General Introduction to Thermodynamics of Slag” (1988) P11 Reference 3: Japan Society for the Promotion of Science Steelmaking No. 19 The following is a comparison between the recommended equilibrium value of the steelmaking reaction (1984) by the committee and the value measured by the slag oxidation degree measurement probe. Although the absolute values are different, the correspondence is good, indicating that the slag oxidation degree can be sufficiently measured with the probe according to the present invention. Further, the time required for measurement with the slag oxidation degree measurement probe is extremely short, 10 seconds to 15 seconds, and even if the slag is reformed based on this measurement result, it takes time to hinder the progress of the refining process. There is no such thing.
【００３１】[0031]
【発明の効果】以上詳述したとおり、本発明に係るスラ
グ酸化度測定プローブによれば、簡易迅速に取鍋等にお
いて、スラグの酸化度を測定できる。従って、製鋼工程
の進行を妨げることなく、その測定結果に基づいてスラ
グの改質を行うことが可能となり、スラグに起因する鋼
材の品質欠陥を防止することだできる。また、危険な人
手によるスラグ試料採取作業をなくすことができる。As described above in detail, according to the slag oxidation degree measurement probe of the present invention, the oxidation degree of slag can be easily and quickly measured in a ladle or the like. Therefore, it becomes possible to modify the slag based on the measurement result without hindering the progress of the steelmaking process, and it is possible to prevent the quality defect of the steel material due to the slag. Further, it is possible to eliminate the dangerous manual work of slag sampling.
【００３２】本発明では、測定極を鉄で作り、この測定
極によりスラグ収容室を画成し、この収容室内に標準極
を挿入配置したので、スラグが確実にスラグ収容室に溜
められ、基準極と測定極とのあいだに鉄と酸化鉄の間の
平衡反応部分が確実に形成され、スラグの酸化度が確実
に測定できる。In the present invention, the measuring electrode is made of iron, the measuring electrode defines the slag accommodating chamber, and the standard electrode is inserted and arranged in the accommodating chamber, so that the slag is reliably stored in the slag accommodating chamber, An equilibrium reaction part between iron and iron oxide is reliably formed between the pole and the measurement electrode, and the degree of oxidation of the slag can be reliably measured.
【００３３】スラグ割り手段を備えた場合、大気との接
触によりスラグ表面が固化していた場合でも、これが破
砕され、スラグ収容室へのスラグの補足が確実におこな
われる。なお、スラグ割り手段として、スラグに浸漬さ
れた場合にボイリングを起こさない材質で構成されてい
るので、スラグが飛散することはない。When the slag splitting means is provided, even if the surface of the slag is solidified by contact with the atmosphere, it is crushed and the slag can be reliably captured in the slag accommodating chamber. Since the slag splitting means is made of a material that does not cause boiling when immersed in the slag, the slag does not scatter.
【００３４】保護管の下端から所定の長さの範囲で、そ
の外周をセラミックファイバーで構成すると、溶鋼への
浸漬時にボイリングが防止される。If the outer periphery of the protective tube is made of ceramic fibers within a predetermined length from the lower end of the protective tube, boiling will be prevented during immersion in molten steel.
【００３５】固体電解質が測定極の前記スラグ収容室か
ら、３ｍｍ以上１０ｍｍ以下の長さで突出して延びてい
ると、良好な測定結果が得られる。When the solid electrolyte extends from the slag accommodating chamber of the measuring electrode so as to protrude by a length of 3 mm or more and 10 mm or less, good measurement results can be obtained.
【００３６】スラグ収容室を、その内径が１０ｍｍ以上
３０ｍｍ以下、深さが１０ｍｍ以上２０ｍｍ以下とする
と、スラグの収容が良好に行え、且つプローブが大型化
しないですむ。If the inner diameter of the slag accommodating chamber is 10 mm or more and 30 mm or less and the depth is 10 mm or more and 20 mm or less, the slag can be well accommodated and the probe does not need to be large.
【００３７】[0037]
【図１】本発明の実施の形態で使用する標準電極を示す
断面図である。FIG. 1 is a cross-sectional view showing a standard electrode used in an embodiment of the present invention.
【図２】本発明の実施の形態に係るスラグ酸化度測定プ
ローブを示す断面図である。FIG. 2 is a cross-sectional view showing a slag oxidation degree measurement probe according to an embodiment of the present invention.
【図３】スラグ酸化度測定プローブでの測定値と理論値
との比較を示すグラフである。FIG. 3 is a graph showing a comparison between a measured value with a slag oxidation degree measurement probe and a theoretical value.
１ スラグ酸化度測定プローブ ２ 測定ユニット ３ 標準電極 ５ 固体電解質 ７ 基準極 １５ 基準極リード ２１ ハウジング ２３ コネクター ２５ 熱電対 ２７ 測定極 ３３ スラグ収容室 ３４ ガス抜き穴 ３５ スラグ割り部材 ４１ 保護管 ４３ 内側保護管 ４５ 外側保護管 ４７ 下部外側保護管 1 Slag oxidation degree measurement probe 2 Measuring unit 3 standard electrodes 5 Solid electrolyte 7 reference pole 15 Reference pole lead 21 housing 23 Connector 25 thermocouple 27 measuring pole 33 Slag storage room 34 Venting hole 35 Slag splitting member 41 Protection tube 43 inner protection tube 45 Outer protection tube 47 Lower outer protective tube
フロントページの続き (72)発明者 桜井 栄司 東京都千代田区丸の内一丁目１番２号 日本鋼管株式会社内 (72)発明者 古田 周良 大阪府大阪市淀川区宮原４丁目１番14号 住友生命新大阪北ビル 大阪酸素工業 株式会社内 (72)発明者 長塚 利男 大阪府大阪市淀川区宮原４丁目１番14号 住友生命新大阪北ビル 大阪酸素工業 株式会社内 (56)参考文献 特開2000−214127（ＪＰ，Ａ) 特開 昭58−213247（ＪＰ，Ａ) 特開 昭53−135696（ＪＰ，Ａ) 特開 平９−21780（ＪＰ，Ａ) 実開 昭59−195560（ＪＰ，Ｕ) (58)調査した分野(Int.Cl.7，ＤＢ名) G01N 27/411 C21C 5/46 C21C 7/00 F27D 21/00 (72) Inventor Eiji Sakurai 1-2-1, Marunouchi, Chiyoda-ku, Tokyo Within Nippon Steel Pipe Co., Ltd. (72) Inventor Shura Furuta 4-1-1-14, Miyahara, Yodogawa-ku, Osaka, Sumitomo Life Shin-Osaka Kita Building, Osaka Oxygen Industry Co., Ltd. (72) Inventor Toshio Nagatsuka 4-1-1 Miyahara, Yodogawa-ku, Osaka City, Osaka Prefecture Sumitomo Life Shin-Osaka Kita Building, Osaka Oxygen Industry Co., Ltd. (56) Reference JP 2000 -214127 (JP, A) JP 58-213247 (JP, A) JP 53-135696 (JP, A) JP 9-21780 (JP, A) Actual development JP 59-195560 (JP, U) ) (58) Fields investigated (Int.Cl. 7 , DB name) G01N 27/411 C21C 5/46 C21C 7/00 F27D 21/00
Claims (6)
固体電解質と、前記固体電解質の内部に配置された所定
の酸素ポテンシャルを与える基準極とを備えた標準電極
と、測定極とを含み、前記基準極と前記測定極との間の
電位差を測定可能に構成されたスラグ酸化度測定プロー
ブにおいて、前記測定極は鉄で構成され、スラグの流入
を許容する開口及び内部のガスを排出するためのガス抜
き穴を備えたスラグ収容室を備え、前記標準電極は、少
なくとも部分的に前記スラグ収容室内に挿入、配置され
ていることを特徴とする、スラグ酸化度測定プローブ。1. A standard electrode provided with a solid electrolyte having one end closed tubular shape and having oxygen ion conductivity, and a reference electrode provided inside the solid electrolyte to provide a predetermined oxygen potential, and a measurement electrode, In the slag oxidation degree measurement probe configured to be able to measure the potential difference between the reference electrode and the measurement electrode, the measurement electrode is made of iron, for discharging the gas and the opening that allows the inflow of slag. The slag oxidation degree measuring probe, comprising the slag accommodating chamber having the gas vent hole, and the standard electrode being at least partially inserted and arranged in the slag accommodating chamber.
ーブにおいて、前記プローブの先端には、スラグに浸漬
されたときにスラグを飛散させない材質で構成されたス
ラグ割り手段を備えていることを特徴とする、スラグ酸
化度測定プローブ。2. The slag oxidation degree measuring probe according to claim 1, wherein the tip of the probe is provided with a slag breaking means made of a material which does not scatter the slag when immersed in the slag. A characteristic slag oxidation degree measurement probe.
ーブにおいて、前記プローブが溶鋼に浸漬されたとき
に、該溶鋼の温度を測定する温度測定手段をさらに備え
ていることを特徴とする、スラグ酸化度測定プローブ。3. The slag oxidation degree measuring probe according to claim 1, further comprising temperature measuring means for measuring the temperature of the molten steel when the probe is immersed in the molten steel. Slag oxidation degree measurement probe.
ーブにおいて、前記固体電解質は前記測定極の前記スラ
グ収容室から、３ｍｍ以上１０ｍｍ以下の長さで突出し
て延びていることを特徴とする、スラグ酸化度測定プロ
ーブ。4. The slag oxidation degree measuring probe according to claim 1, wherein the solid electrolyte extends from the slag accommodating chamber of the measuring electrode in a length of 3 mm or more and 10 mm or less. , Slag oxidation probe.
ーブにおいて、前記スラグ収容室は、内径が１０ｍｍ以
上３０ｍｍ以下、深さが１０ｍｍ以上２０ｍｍ以下であ
ることを特徴とする、スラグ酸化度測定プローブ。5. The slag oxidation degree measurement probe according to claim 1, wherein the slag accommodation chamber has an inner diameter of 10 mm or more and 30 mm or less and a depth of 10 mm or more and 20 mm or less. probe.
ーブにおいて、前記プローブは、その一端に前記標準電
極と測定極とからなる測定ユニットが取り付けられる保
護管を備え、前記保護管は、前記一端から所定の長さの
範囲で、少なくともその外周は、セラミックファイバー
で構成されていることを特徴とする、スラグ酸化度測定
プローブ。6. The slag oxidation degree measurement probe according to claim 1, wherein the probe includes a protection tube to which a measurement unit including the standard electrode and the measurement electrode is attached at one end thereof, and the protection tube includes: A slag oxidation degree measuring probe, characterized in that at least a perimeter thereof is constituted by a ceramic fiber within a predetermined length from one end.
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|---|---|---|---|
| JP05034599A JP3462993B2 (en) | 1999-02-26 | 1999-02-26 | Slag oxidation measurement probe |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP05034599A JP3462993B2 (en) | 1999-02-26 | 1999-02-26 | Slag oxidation measurement probe |
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| Publication Number | Publication Date |
|---|---|
| JP2000249680A JP2000249680A (en) | 2000-09-14 |
| JP3462993B2 true JP3462993B2 (en) | 2003-11-05 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP05034599A Expired - Fee Related JP3462993B2 (en) | 1999-02-26 | 1999-02-26 | Slag oxidation measurement probe |
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| Country | Link |
|---|---|
| JP (1) | JP3462993B2 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100399238B1 (en) * | 2001-02-02 | 2003-09-22 | 주식회사 우진 | Sub lance combinations probe and thereof measuring method for converter |
| JP4806869B2 (en) * | 2001-07-31 | 2011-11-02 | Ｊｆｅスチール株式会社 | Manufacturing method of high clean steel |
| KR20050111422A (en) * | 2004-05-20 | 2005-11-25 | 주식회사 포스코 | Complex probe for level measurement of melting iron |
| DE102013208679A1 (en) | 2012-10-31 | 2014-04-30 | Heraeus Electro-Nite International N.V. | Measuring probe for measurement in metal or slag melts |
-
1999
- 1999-02-26 JP JP05034599A patent/JP3462993B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JP2000249680A (en) | 2000-09-14 |
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