CN1106574C - 在玻璃熔液或盐熔液中进行电化学测量所用的装置 - Google Patents
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Abstract
本发明涉及一种用于在玻璃熔液或盐熔液中进行电化学测量的装置,该装置具有至少一个测量电极和一个参考电极装置。为了能实现甚精确的测量,测量电极的确定用于浸入熔液中的尖端是用铱或一种含有其它贵金属的铱合金做成的,并气密地用一耐热管支承着;其中,测量电极被引过该耐热管。
Description
本发明涉及一种在玻璃熔液或盐熔液中进行电化学测量所用的装置,具有至少一个测量电极和一个参考电极装置。
这类装置已反复被公开,例如已由专利GB 2057695A公开。在该专利公开的装置中,利用一个电化学的测量元件,亦称之为参考电极装置,对氧分压进行测量,该测量元件经过一个常规的指示装置和/或计值装置(测量系统)而与一个对应电极(亦称测量电极)相连接。采用铂丝作测量电极,铂丝被引导穿过一个氧化铝体。铂丝在氧化铝体的尖端是显露的,所以一当对应电极浸入熔液中,铂丝便能立即与熔液接触。氧化铝体被夹持在一根氧化铝管中。在实际工作中已证明:在铂电极和氧化铝体之间不可能实现气密。因此,氧气从熔液上方的大气中一直渗入到与熔液相接触的测量电极部分,致使在那里测得的值与熔液中的实际情况不符,测量因此有误差。
类似的测量装置例如还在专利DE 38 11 915A1中公开过。在这里,测量电极也是用铂做的。
例如在《Glastechnische Berichte》(玻璃技术报导)68(1995)NO.9,S.273 ff上介绍了:利用三个电极进行电计量分析以测定玻璃熔液中的铁、硫或铬。但在这里也出现了所述及的问题。为此例如必须准确地知道处在玻璃熔液中的电极表面的大小。
本发明的任务是:根据从现有技术所公开的装置出发,提高在玻璃熔液或盐熔液中进行例如氧分压测量的测量精度。
仿照本发明,上述任务是采用下述措施加以解决的:测量电极的被定作浸入熔液中的尖端是用铱或含有其它贵金属的一种铱合金做成的,并气密地夹持在一支耐热管的一端中,其中,测量电极被引导穿过该耐热管(从熔液中引出一直引到计值装置)。所谓气密的夹持意味着没有足以影响测量结果的氧气量通过耐热管从外部渗入到待测量的熔液(特别是玻璃熔液)。铱或铱合金是具有高熔点的,因此可以通过热处理而与耐热管实现气密性的连接。用石英玻璃管做耐热管是有利的,当然也可以用陶瓷管,例如氧化铝陶瓷管。在采用陶瓷管的情况下,自然有必要做到:所用的材料在大约1000至1500℃时不会成为离子或电子导体。
最好是将铱或铱合金烧结在或熔封在耐热管中。铱的熔点达2447℃,因此它能耐高温加热,如为了熔化或致密烧结氧化铝或者为了软化石英玻璃所需用的高温。
可以设想,测量电极熔接在石英玻璃管中,主要是为了实现瞬时测量,而熔封在氧化铝陶瓷管中的测量电极也可以用于实现长时测量(配用所谓的连续性探针)。
可取的做法是,测量电极和耐热管之间的连接点应气密地处于耐热管的确定用于浸入熔液中的尖端上。向后,从熔液中出来,耐热管可以是开口的。用铱或一种铱合金做的测量电极尖端在耐热管中最好同一根测量丝相连,该测量丝最好用钼、钨或一种铬-镍合金(例如Cronix)做成。这样可使得用作为电极的铱丝的长度短一些,以达到节省铱的目的。
在用钼或钨做测量丝时,可在用铱或铱合金做的测量电极尖端和测量丝之间安置一个用钼做的金属条。铱和测量丝之间的连接点可以熔封在耐热管中。特别是所熔封的钼金属条确保了几乎是绝对的气密性。
铬-镍丝不可熔封在耐热管中,这是因为在所需的温度下它有熔化的危险;为此,连接点最好安置在耐热管中的熔封点后面。
为了获得高的测量精度,有利的做法是:在一支一端封闭的固化电解质小管中安置一个参考电极,该小管以它的背向其封闭端的那一端夹持在一支陶瓷管中,参考电极被引过该陶瓷管;在固体电解质小管中的参考电极端部被一种参考物质包围,这种参考物质是一种金属-金属氧化物粉末混合物,最好是一种镍-镍氧化物粉末混合物;参考电极本身最好用一种铬-镍合金制成。
此外,一种有利的做法是:耐热管和陶瓷管都用刚玉填充。再者,最好将耐热管和陶瓷管夹持在一根共同的支承管中,该支承管最好用陶瓷制成,而且在它的背向浸入端的那一端上有一个普通的连接件,借以实现测量电极和参考电极同一测量系统的机械性耦联和连接。支承管可用氧化铝制成,并填充刚玉球粒。
下面根据附图对本发明的一个实施例做详细的说明。
附图所示:
图1本发明的装置的示意图;
图2本发明的装置的纵剖面图;
图3被熔封在耐热管中的测量电极的一个纵剖面图;及
图4具有三个电极的装置的截面图。
图1中所示用于测量气分压的装置具有一个用氧化铝制做的支承管1。在支承管的背向浸入端的那一端上安置了一个连接件2,连接件插在一个图中未示出的夹持件例如一金属套中。被引过支承管1的金属丝、测量丝3和参考电极4均经过连接件2而与一测量系统即一常规指示单元和/或计值单元相连。在支承管1内,测量丝3和参考电极4被引过一石英玻璃小管5,并埋入刚玉球粒6内。
在支承管1的朝向本装置浸入端的那一端上,安置了参考电极装置7和作为耐热管的石英管8。参考电极装置7有一根氧化铝陶瓷管9,参考电极4被引过该陶瓷管,一直被引入到固体电解质小管10中。固体电解质小管10是用氧化锆做的,在其内部有一种镍-镍氧化物粉末混合物,用铬-镍合金(Cronix)做成的参考电极4便是夹持在这种混合物中。测量电极连同测量丝3被引过石英管8。测量电极的尖端11是用铱丝做的,它也可用一种合金即主要含有铱和其它的贵金属的合金做成。用铱做的尖端11一直伸入到石英玻璃管8中。尖端11被气密地熔封在石英玻璃管8的端部12中,熔接的区段约为2cm(厘米)。然后改换测量电极的材料。为了节省颇为昂贵的铱丝,测量电极的其余部分是用Cronix(一种铬-镍合金)做的测量丝3。代替Cronix,例如也可以用钼或钨做测量丝3。
还有一个制做测量电极的可能性,见图3中所示。在这里,用铱做的尖端11在石英玻璃管8内同一钼条13相连,该钼条的另一端则与测量丝3相连。在这种条件下,测量丝3例如可以用钼或钨做成。在所示的实施例中,钼条13完全被熔封在石英玻璃管8的端部12中。这样便能获得完善的气密性。
图中未示出的可能性是,将钼条13从石英玻璃管8的熔封的端部12中引出来,然后在开着的管中与测量丝3相连。在这种情况下,还是可用Cronix做测量丝3的。
石英玻璃管8和陶瓷管9都填充了刚玉球粒,借以固定金属丝在上述管子中的位置。
图4中所示的装置适用于例如对玻璃熔液中的铁的、硫的或铬的含量进行电计量测量。为此所采用的测量方法例如在《GlastechnischeBerichte》68(1995)NO.9,S.273 ff上做了介绍。在用氧化铝陶瓷做的支承管1中安置了一个测量电极和一个参考电极4。测量电极的尖端11是用铱做的,并被熔封在一石英玻璃管8中。参考电极4是用铂做的,并被安置在一陶瓷管9中,在支承管1的浸入端上安置了一个用铂做的对应电极14。
用上述装置进行测量可以获得极可靠的结果,尤其在瞬时测量中。由于本装置的制造成本很合算,所以作为一次性探针制造是可行的。在采用耐热的氧化铝陶瓷管8的情况下,还可进行长时间测量。
Claims (14)
1.用于在玻璃熔液或盐熔液中进行电化学测量的装置,具有至少一个测量电极和一个参考电极装置,其特征在于,测量电极的用于浸入熔液中的尖端(11)是用铱或含有其它贵金属的一种铱合金做成的,并气密地被夹持在一耐热管(8)中,其中,测量电极被引过该耐热管(8)。
2.按照权利要求1所述的装置,其特征在于,耐热管(8)是一石英玻璃管。
3.按照权利要求1所述的装置,其特征在于,铱或铱合金是被烧结在或被熔封在耐热管(8)中。
4.按照权利要求1所述的装置,其特征在于,测量电极和耐热管(8)之间的连接点是气密地处于耐热管(8)的被定作浸入熔液中的端部(12)上。
5.按照权利要求1所述的装置,其特征在于,测量电极的用铱做的尖端(11)在耐热管(8)内同一测量丝(3)相连。
6.按照权利要求5所述的装置,其特征在于,在测量电极的用铱做的尖端(11)和测量丝(3)之间设置了一个用钼做的金属条(13)。
7.按照权利要求6所述的装置,其特征在于,测量丝(3)是用钼或钨做的。
8.按照权利要求5所述的装置,其特征在于,在铱和测量丝(3)之间的连接点是熔封在耐热管(8)中的。
9.按照权利要求5所述的装置,其特征在于,测量丝(3)是用一种铬-镍合金做的。
10.按照权利要求1所述的装置,其特征在于,参考电极(4)安置在一个一端封闭的固化电解质小管中,该小管以它的与封闭端相对的一端夹持在一陶瓷管(9)中,参考电极(4)被引过该陶瓷管,在固体电解质小管(10)中的参考电极(4)的端部被一种参考物质所包围,该参考物质是由一种金属-金属氧化物粉末混合物,最好是镍-镍氧化物粉末混合物构成的。
11.按照权利要求1所述的装置,其特征在于,参考电极(4)是用一种铬-镍合金做的。
12.按照权利要求10或11所述的装置,其特征在于,耐热管(8)和陶瓷管(9)中填充有刚玉球粒。
13.按照权利要求10所述的装置,其特征在于,耐热管(8)和陶瓷管(9)被支承在一共同的支承管(1)中,该支承管最好用陶瓷做成,在它的背向浸入端的端部上有一连接件(2),借以使测量电极和参考电极(4)同一测量系统实现机械性耦联和连接。
14.按照权利要求13所述的装置,其特征在于,支承管(1)是用氧化铝做的,它填充有刚玉球粒(6)。
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19623683.5 | 1996-06-14 | ||
DE19623683A DE19623683C1 (de) | 1996-06-14 | 1996-06-14 | Vorrichtung zur Durchführung von elektrochemischen Messungen in Glas- oder Salzschmelzen |
Publications (2)
Publication Number | Publication Date |
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CN1177103A CN1177103A (zh) | 1998-03-25 |
CN1106574C true CN1106574C (zh) | 2003-04-23 |
Family
ID=7796898
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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CN97112720A Expired - Fee Related CN1106574C (zh) | 1996-06-14 | 1997-06-13 | 在玻璃熔液或盐熔液中进行电化学测量所用的装置 |
Country Status (11)
Country | Link |
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EP (1) | EP0813057B1 (zh) |
JP (1) | JPH1062382A (zh) |
KR (1) | KR100443555B1 (zh) |
CN (1) | CN1106574C (zh) |
AT (1) | ATE425453T1 (zh) |
AU (1) | AU2487597A (zh) |
BR (1) | BR9703578A (zh) |
CZ (1) | CZ179297A3 (zh) |
DE (2) | DE19623683C1 (zh) |
PL (1) | PL184157B1 (zh) |
TR (1) | TR199700502A3 (zh) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN107367536A (zh) * | 2017-08-31 | 2017-11-21 | 常州市丰瑞电子有限公司 | 一种稳定型碳糊电极的制备方法 |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE10103701C1 (de) * | 2001-01-26 | 2002-09-12 | Heraeus Electro Nite Int | Messeinrichtung zur Bestimmung der Sauerstoffaktivität in Metallschmelzen oder Schlackeschmelzen |
DE102004028789B3 (de) * | 2004-06-16 | 2006-01-05 | Heraeus Electro-Nite International N.V. | Vorrichtung zur Durchführung von Messungen und/oder Probennahmen in Metallschmelzen |
DE102010040057A1 (de) * | 2010-08-31 | 2012-03-01 | Endress + Hauser Conducta Gesellschaft für Mess- und Regeltechnik mbH + Co. KG | Elektrochemischer Sensor |
JP6198134B2 (ja) * | 2013-11-22 | 2017-09-20 | 国立研究開発法人日本原子力研究開発機構 | 溶融ガラスの電気化学測定に用いる酸化ニッケル/ニッケル参照極およびそれを用いた電気化学測定装置 |
Family Cites Families (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1277751A (en) * | 1969-04-17 | 1972-06-14 | Pilkington Brothers Ltd | Method of and apparatus for removing dissolved oxygen from molten tin |
DE2001012C3 (de) * | 1970-01-10 | 1978-05-11 | Robert Bosch Gmbh, 7000 Stuttgart | Elektrochemisches Verfahren zur Bestimmung von metallischem Calcium in Blei-Calcium-Legierungen |
US3816269A (en) * | 1970-04-14 | 1974-06-11 | Kennecott Copper Corp | Method for determining the concentration of a metal in an alloy melt |
FR2122758A6 (en) * | 1971-01-22 | 1972-09-01 | Siderurgie Fse Inst Rech | Solid electrolyte electrochemical cell - with a molybdenum wire reference couple |
GB2057695B (en) * | 1979-08-31 | 1983-10-12 | Unisearch Ltd | Method and apparatus for measuring the oxygen potential of an ionic conducting melt |
US4313799A (en) * | 1980-04-04 | 1982-02-02 | Owens-Corning Fiberglas Corporation | Oxygen sensor and method for determining the oxygen activity in molten glass |
DE3028270C2 (de) * | 1980-07-25 | 1986-08-14 | Schott Glaswerke, 6500 Mainz | Meßanordnung zur Messung von Sauerstoff-Partialdrücken |
DE3109454A1 (de) * | 1981-03-12 | 1982-09-23 | Schott Glaswerke | Sonde zur messung von sauerstoffpartialdruecken in hochaggressiven medien |
JPS58139060A (ja) * | 1982-02-05 | 1983-08-18 | リ−ズ・アンド・ノ−スラツプ・カンパニ− | 高速感応性酸素セル |
DE3709196A1 (de) * | 1986-03-27 | 1987-10-01 | Wissenschaftlich Tech Betrieb | Sauerstoffmesssonde fuer hohe temperaturen |
DE3811915A1 (de) * | 1988-04-09 | 1989-10-19 | Schott Glaswerke | Messvorrichtung zum messen des sauerstoffpartialdruckes in aggressiven fluessigkeiten hoher temperatur |
DE3811865C1 (en) * | 1988-04-09 | 1989-05-24 | Schott Glaswerke, 6500 Mainz, De | Measurement device for measuring the oxygen partial pressure in aggressive liquids at high temperature |
DE3811864A1 (de) * | 1988-04-09 | 1989-10-19 | Schott Glaswerke | Messvorrichtung zum messen des sauerstoffpartialdruckes in aggressiven fluessigkeiten hoher temperatur |
-
1996
- 1996-06-14 DE DE19623683A patent/DE19623683C1/de not_active Expired - Fee Related
-
1997
- 1997-04-25 DE DE59712996T patent/DE59712996D1/de not_active Expired - Lifetime
- 1997-04-25 AT AT97106854T patent/ATE425453T1/de not_active IP Right Cessation
- 1997-04-25 EP EP97106854A patent/EP0813057B1/de not_active Expired - Lifetime
- 1997-06-02 JP JP9157345A patent/JPH1062382A/ja not_active Withdrawn
- 1997-06-10 PL PL97320466A patent/PL184157B1/pl not_active IP Right Cessation
- 1997-06-11 KR KR1019970024072A patent/KR100443555B1/ko not_active IP Right Cessation
- 1997-06-11 CZ CZ971792A patent/CZ179297A3/cs unknown
- 1997-06-13 CN CN97112720A patent/CN1106574C/zh not_active Expired - Fee Related
- 1997-06-13 AU AU24875/97A patent/AU2487597A/en not_active Abandoned
- 1997-06-13 TR TR97/00502A patent/TR199700502A3/tr unknown
- 1997-06-16 BR BR9703578A patent/BR9703578A/pt not_active Application Discontinuation
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN107367536A (zh) * | 2017-08-31 | 2017-11-21 | 常州市丰瑞电子有限公司 | 一种稳定型碳糊电极的制备方法 |
CN107367536B (zh) * | 2017-08-31 | 2019-10-29 | 东阳市天齐知识产权运营有限公司 | 一种稳定型碳糊电极的制备方法 |
Also Published As
Publication number | Publication date |
---|---|
EP0813057A2 (de) | 1997-12-17 |
JPH1062382A (ja) | 1998-03-06 |
TR199700502A2 (xx) | 1998-01-21 |
DE19623683C1 (de) | 1997-11-13 |
CN1177103A (zh) | 1998-03-25 |
KR100443555B1 (ko) | 2005-06-17 |
EP0813057A3 (de) | 1998-07-15 |
KR980003575A (ko) | 1998-03-30 |
AU2487597A (en) | 1997-12-18 |
PL320466A1 (en) | 1997-12-22 |
EP0813057B1 (de) | 2009-03-11 |
BR9703578A (pt) | 1998-11-03 |
DE59712996D1 (de) | 2009-04-23 |
ATE425453T1 (de) | 2009-03-15 |
PL184157B1 (pl) | 2002-09-30 |
TR199700502A3 (tr) | 1998-01-21 |
CZ179297A3 (cs) | 1998-01-14 |
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