JPH0222690Y2 - - Google Patents
Info
- Publication number
- JPH0222690Y2 JPH0222690Y2 JP15017882U JP15017882U JPH0222690Y2 JP H0222690 Y2 JPH0222690 Y2 JP H0222690Y2 JP 15017882 U JP15017882 U JP 15017882U JP 15017882 U JP15017882 U JP 15017882U JP H0222690 Y2 JPH0222690 Y2 JP H0222690Y2
- Authority
- JP
- Japan
- Prior art keywords
- electrolyte
- phosphorus concentration
- molten metal
- tube body
- tube
- 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
Links
- 229910052751 metal Inorganic materials 0.000 claims description 28
- 239000002184 metal Substances 0.000 claims description 28
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 25
- 239000003792 electrolyte Substances 0.000 claims description 25
- 229910052698 phosphorus Inorganic materials 0.000 claims description 25
- 239000011574 phosphorus Substances 0.000 claims description 25
- 239000013558 reference substance Substances 0.000 claims description 10
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 claims description 6
- 239000000523 sample Substances 0.000 description 7
- 238000004458 analytical method Methods 0.000 description 6
- 229910000831 Steel Inorganic materials 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000010959 steel Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 4
- 239000012925 reference material Substances 0.000 description 4
- 239000003779 heat-resistant material Substances 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 239000007784 solid electrolyte Substances 0.000 description 3
- 239000011575 calcium Substances 0.000 description 2
- 239000004568 cement Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- PGYDGBCATBINCB-UHFFFAOYSA-N 4-diethoxyphosphoryl-n,n-dimethylaniline Chemical compound CCOP(=O)(OCC)C1=CC=C(N(C)C)C=C1 PGYDGBCATBINCB-UHFFFAOYSA-N 0.000 description 1
- 239000006009 Calcium phosphide Substances 0.000 description 1
- 229910001096 P alloy Inorganic materials 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- -1 molten steel Chemical class 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
Landscapes
- Measuring Oxygen Concentration In Cells (AREA)
- Investigating And Analyzing Materials By Characteristic Methods (AREA)
Description
【考案の詳細な説明】
本考案は溶融金属のリン濃度測定装置に係り、
とくに固体電解質を用いる溶融金属のリン濃度測
定装置に関するものである。[Detailed description of the invention] The invention relates to a device for measuring phosphorus concentration in molten metal.
In particular, it relates to a molten metal phosphorus concentration measuring device using a solid electrolyte.
従来において溶融金属のリン濃度を測定するに
は精錬現場で自動あるいは手動の試料採取装置に
より採取した試料を分析室に送つて発光分析等を
行つていた。 Conventionally, in order to measure the phosphorus concentration in molten metal, a sample was collected at a smelting site using an automatic or manual sampling device and sent to an analysis laboratory for luminescence analysis.
しかしこの方法では測定結果を得るまで時間が
かかり、分析結果を連続精錬を行なう炉のコント
ロールに反映することが困難であつた。 However, with this method, it took time to obtain measurement results, and it was difficult to reflect the analysis results in the control of the continuous refining furnace.
それ故、リン量コントロールの為に多量の副資
材を用い大幅に安全範囲をふまえた操業がおこな
われることが多く、エネルギー面からのロスも多
かつた。 Therefore, in order to control the amount of phosphorus, large amounts of auxiliary materials were used and operations were often carried out far beyond the safe range, resulting in a large amount of energy loss.
固体電解質応用技術の進歩に伴い、溶融金属中
の各種成分量、例えば酸素量、硫黄量等の測定用
のセンサーが開発されてきている。 With advances in solid electrolyte application technology, sensors for measuring the amount of various components in molten metal, such as the amount of oxygen and the amount of sulfur, have been developed.
しかしながら溶融金属、例えば溶鋼のような高
温下で使用できるリン濃度測定用センサーは固体
電解質となりうるリン化物の特性上の制約から未
だ開発されるに至つていない。 However, a sensor for measuring phosphorus concentration that can be used at high temperatures in molten metals, such as molten steel, has not yet been developed due to limitations in the properties of phosphides, which can be used as solid electrolytes.
何故なら電解質として例えばリン化カルシウム
および、これに接して設けられるリン濃度測定の
基準極となるリン化物の基準物質は溶鋼温度のご
とき高温下では液状になることがあり、この様に
リン濃度測定時に溶鋼、電解質、基準物質がとも
に液状となれば相互に混合されて電池として機能
しなくなる点が解決されていなかつたからであ
る。 This is because, for example, calcium phosphide as an electrolyte and the phosphide reference material that is placed in contact with it and used as a reference electrode for measuring phosphorus concentration can become liquid at high temperatures such as the temperature of molten steel. This is because, at times, if the molten steel, the electrolyte, and the reference material become liquid, they will mix with each other and the battery will no longer function.
本考案は、以上の従来の問題を解決し、溶融金
属のリン濃度を迅速に測定するリン濃度測定装置
の提供を目的とする。 The present invention aims to solve the above-mentioned conventional problems and provide a phosphorus concentration measuring device that quickly measures the phosphorus concentration of molten metal.
以下本考案の溶融金属のリン濃度測定装置（以
下本考案のリン濃度測定装置という）を図面に示
す実施例に従い説明する。 DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The apparatus for measuring phosphorus concentration in molten metal of the present invention (hereinafter referred to as the apparatus for measuring phosphorus concentration of the present invention) of the present invention will be described below with reference to embodiments shown in the drawings.
第１図及び第２図は本考案のリン濃度測定装置
を示し、該リン濃度測定装置１はプローブ３の下
端に装着された耐熱性材料の支持体４を有する。 1 and 2 show a phosphorus concentration measuring device according to the present invention, which has a support 4 made of a heat-resistant material attached to the lower end of a probe 3. FIG.
該支持体４には測定管６が耐火セメント等の固
定材５により下方に突出して固定される。 A measuring tube 6 is fixed to the support 4 by projecting downward with a fixing material 5 such as refractory cement.
測定管６の詳細を第３図に示すが、該測定管６
はCa3P2と反応を生じない耐熱性材料の細管、例
えば、内面に白金コーテイングを施した石英管等
をＵ状に形成した管本体７を有する。 The details of the measuring tube 6 are shown in FIG.
has a U-shaped tube body 7 made of a thin tube made of a heat-resistant material that does not react with Ca 3 P 2 , such as a quartz tube whose inner surface is coated with platinum.
管本体７内には塊状又は粒状のCa3P2からなる
電解質１０が開口部から後退した位置に圧縮状に
押入、固化又は仮成型されて封入される。 An electrolyte 10 made of bulk or granular Ca 3 P 2 is compressed into the tube body 7 at a position retracted from the opening, solidified or temporarily molded, and sealed.
電解質１０の上方にはリン濃度が温度によつて
一義的に定まる基準物質１１、例えばFe−Ｐ合
金等が封入される。 A reference substance 11 whose phosphorus concentration is uniquely determined by temperature, such as an Fe-P alloy, is sealed above the electrolyte 10 .
更に電解質１０の上端には高温下での使用に耐
える金属、例えばMo又はＷ等のリード線１４が
該電解質１０と導通可能に導かれている。 Furthermore, a lead wire 14 made of a metal that can withstand use under high temperatures, such as Mo or W, is led to the upper end of the electrolyte 10 so as to be electrically conductive with the electrolyte 10.
基準物質１１の上方には耐熱性材料の充填体１
２が封入されて、管本体７内の残存空気の減少及
び電解質１０等の位置決めが図られる。 Above the reference substance 11 is a filling body 1 made of heat-resistant material.
2 is sealed to reduce the residual air in the tube body 7 and to position the electrolyte 10 and the like.
管本体７の上端は耐火セメント等の栓体１５に
より閉じられる。 The upper end of the tube body 7 is closed with a stopper 15 made of refractory cement or the like.
前記リード線１４は基準物質１１、充填体１２
及び栓体１５を貫通して外部に導かれている。 The lead wire 14 is connected to the reference material 11 and the filling body 12.
and is guided to the outside through the plug body 15.
一方、管本体７の先端はＵ状に屈曲されて開口
９が上方に向けられる。 On the other hand, the tip of the tube body 7 is bent into a U shape so that the opening 9 is directed upward.
第１図及び第２図に戻つて固定材５には熱電対
等の温度センサー１６及び高温下での使用に耐え
る金属、例えばMo又はＷ等の電極１７（これは
リード線１４と対になつて起電力を取出す）が突
出して設けられる。 Returning to FIGS. 1 and 2, the fixing material 5 includes a temperature sensor 16 such as a thermocouple and an electrode 17 made of a metal that can withstand use at high temperatures, such as Mo or W (this is paired with the lead wire 14). (takes out electromotive force) is provided protrudingly.
以上の実施例に示した本考案のリン濃度測定装
置の作用は次の通り。 The operation of the phosphorus concentration measuring device of the present invention shown in the above embodiments is as follows.
すなわち例えば溶鋼等の高温溶融金属中にリン
濃度測定装置１をプローブ３に装着した状態で挿
入する。 That is, the phosphorus concentration measuring device 1, attached to the probe 3, is inserted into a high-temperature molten metal such as molten steel.
これにより溶融金属は開口９から管本体７内に
流れ込む（管本体７内の空気は電解質１０、基準
物質１１、充填体１２及び栓体１５と管本体７と
の隙間から外部に排除される）。 As a result, the molten metal flows into the tube body 7 through the opening 9 (the air in the tube body 7 is expelled to the outside through the gap between the electrolyte 10, reference substance 11, filler 12, and plug body 15 and the tube body 7). .
従つて溶融金属は管本体７内において電解質１
０底部に接触する。 Therefore, the molten metal is mixed with the electrolyte 1 in the tube body 7.
0 contact the bottom.
溶融金属の温度（例えば、1600℃近辺の溶鋼温
度）によつては電解質１０および基準物質１１が
溶融し液体状になる場合があるが、測定管７が細
管であるため電解質１０が溶融金属中に混入する
ことはなく又電解質１０と基準物質１１とが密度
差により置換されることもなく濃淡電池の構成は
維持される。 Depending on the temperature of the molten metal (for example, the temperature of molten steel around 1600°C), the electrolyte 10 and reference substance 11 may melt and become liquid, but since the measuring tube 7 is a thin tube, the electrolyte 10 may not be in the molten metal. The electrolyte 10 and reference substance 11 are not replaced due to density difference, and the structure of the concentration battery is maintained.
液状の電解質１０と溶融金属も同様に置換され
ることがなく、また、溶融金属の静圧の作用によ
りこれら液状体が移動、流失することがないため
三液相共存状態が維持される。 Similarly, the liquid electrolyte 10 and the molten metal are not replaced, and the static pressure of the molten metal prevents these liquids from moving or flowing away, so that the three-liquid phase coexistence state is maintained.
従つて基準物質１１と溶融金属とにより上下に
挾まれた電解質１０には溶融金属のリン濃度に対
応した起電力が生じる。 Therefore, an electromotive force corresponding to the phosphorus concentration of the molten metal is generated in the electrolyte 10 which is sandwiched between the reference substance 11 and the molten metal.
この起電力はリード線１４と溶融金属中に挿入
された電極１７とにより外部に取出され温度セン
サー１６による測定温度に対応するリン濃度が決
定される。 This electromotive force is taken out to the outside by a lead wire 14 and an electrode 17 inserted into the molten metal, and the phosphorus concentration corresponding to the temperature measured by the temperature sensor 16 is determined.
溶融金属中に一定時間挿入された後プローブ３
は引上げられるが、溶融金属は管本体７の屈曲部
分において試料として採取され原子吸光等の機器
分析用あるいは化学分析用又は微量発光分析等に
用いられる。 Probe 3 after being inserted into the molten metal for a certain period of time
is pulled up, and the molten metal is collected as a sample at the bent portion of the tube body 7 and used for instrumental analysis such as atomic absorption, chemical analysis, trace emission analysis, etc.
以上の説明で明らかな様に管本体７がＵ状に形
成された理由は、三液相状態により長く安定に維
持するためと試料採取を同時に行うためである。 As is clear from the above explanation, the reason why the tube body 7 is formed in a U shape is to maintain the three-liquid phase stably for a long time and to collect samples at the same time.
従つて試料採取が不要な場合又は測定を短時間
で終る場合には、第４図に示す様に管本体７を直
管のままで使用しても差支えない。 Therefore, if sample collection is not necessary or if the measurement is to be completed in a short time, the tube main body 7 may be used as a straight tube as shown in FIG. 4.
更に以上の実施例においては管本体７に絞り込
み８が設けられていたが、これは電解質１０の位
置決めが目的であり他の方法で位置決めする場合
は省略可能である。 Furthermore, in the above embodiments, the tube body 7 is provided with a constriction 8, but this is for the purpose of positioning the electrolyte 10, and can be omitted when positioning is performed by other methods.
更に管本体７内の空気の排除を容易にするため
適所（例えば電解質１０の下端付近）において管
本体７に小穴を設けても良い。 Furthermore, in order to facilitate the removal of air within the tube body 7, a small hole may be provided in the tube body 7 at a suitable location (for example, near the lower end of the electrolyte 10).
本考案のリン濃度測定装置は以上の構成、作用
において次の効果を有する。 The phosphorus concentration measuring device of the present invention has the following effects in the above configuration and operation.
(1) 本考案の溶融金属のリン濃度測定装置は実用
新案登録請求の範囲に記載した構成であり、特
に細管の管本体７内に電解質１０を封入したた
め溶融金属の温度が高く電解質１０が溶融した
場合においても電解質１０が溶融金属中に混入
することがなく、電解質１０と基準物質１１と
が密度差により置換されることもなく濃淡電池
の構成が維持され、また、液状の電解質１０と
溶融金属も同様にして置換されることがなく、
更に、溶融金属の静圧の作用によりこれら液状
体が移動、流失することがないため三液相共存
状態が維持されその結果従来は困難とされたリ
ン濃度の迅速な測定が可能になつた。(1) The device for measuring the phosphorus concentration of molten metal of the present invention has the configuration described in the claims for utility model registration, and in particular, because the electrolyte 10 is sealed in the tube body 7 of the thin tube, the temperature of the molten metal is high and the electrolyte 10 melts. Even when the electrolyte 10 is mixed into the molten metal, the electrolyte 10 and the reference substance 11 are not replaced due to the density difference, and the structure of the concentration battery is maintained. Similarly, metals are not replaced,
Furthermore, because these liquids do not move or flow away due to the action of the static pressure of the molten metal, a three-liquid phase coexistence state is maintained, and as a result, it has become possible to quickly measure the phosphorus concentration, which was previously difficult.
(2) 本考案の溶融金属のリン濃度測定装置は同上
の構成であり、特に管本体７に電解質１０と基
準物質１１が封入されるため製造、保管及び品
質のバラツキ防止上極めて有利である。(2) The molten metal phosphorus concentration measuring device of the present invention has the same configuration as above, and in particular, since the electrolyte 10 and the reference substance 11 are sealed in the tube body 7, it is extremely advantageous in terms of manufacturing, storage, and preventing quality variations.
第１図は本考案のリン濃度測定装置の縦断面
図、第２図は同上底面図、第３図は同上測定管の
拡大縦断面図、第４図は同上他の測定管の拡大縦
断面図。
１……リン濃度測定装置、３……プローブ、４
……支持体、５……固定材、６……測定管、７…
…管本体、８……絞り込み、９……開口、１０…
…電解質、１１……基準物質、１２……充填体、
１４……リード線、１５……栓体、１６……温度
センサー、１７……電極。
Fig. 1 is a vertical cross-sectional view of the phosphorus concentration measuring device of the present invention, Fig. 2 is a top bottom view of the same, Fig. 3 is an enlarged longitudinal cross-sectional view of the same measuring tube, and Fig. 4 is an enlarged longitudinal cross-sectional view of another measuring tube of the same. figure. 1... Phosphorus concentration measuring device, 3... Probe, 4
...Support, 5...Fixing material, 6...Measuring tube, 7...
...tube body, 8...restriction, 9...opening, 10...
...Electrolyte, 11...Reference material, 12...Filling body,
14... Lead wire, 15... Plug, 16... Temperature sensor, 17... Electrode.
Claims (1)
本体７と、該管本体７内に開口部から後退させて
封入された塊状又は粒状のCa3P2からなる電解質
１０と、該電解質１０の上方に封入された既知の
リン濃度を有する基準物質１１と、電解質１０の
上端に導通可能にされたリード線１４と、支持体
４から突出する電極１７と、支持体４から突出す
る温度センサー１６とからなる溶融金属のリン濃
度測定装置。 A thin tube body 7 having an opening 9 and fixed to the support 4; an electrolyte 10 made of lump or granular Ca 3 P 2 sealed in the tube body 7 so as to be retracted from the opening; A reference substance 11 having a known phosphorus concentration sealed above the electrolyte 10 , a lead wire 14 connected to the upper end of the electrolyte 10 , an electrode 17 protruding from the support 4 , and a reference substance 11 having a known phosphorus concentration sealed above the electrolyte 10 . A molten metal phosphorus concentration measuring device comprising a temperature sensor 16.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15017882U JPS5954848U (en) | 1982-10-02 | 1982-10-02 | Phosphorus concentration measurement device for molten metal |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15017882U JPS5954848U (en) | 1982-10-02 | 1982-10-02 | Phosphorus concentration measurement device for molten metal |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5954848U JPS5954848U (en) | 1984-04-10 |
| JPH0222690Y2 true JPH0222690Y2 (en) | 1990-06-19 |
Family
ID=30333156
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP15017882U Granted JPS5954848U (en) | 1982-10-02 | 1982-10-02 | Phosphorus concentration measurement device for molten metal |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5954848U (en) |
-
1982
- 1982-10-02 JP JP15017882U patent/JPS5954848U/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5954848U (en) | 1984-04-10 |
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