TW201441611A - 用於測量鑄鐵熔液氧含量之感測器 - Google Patents

用於測量鑄鐵熔液氧含量之感測器 Download PDF

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TW201441611A
TW201441611A TW103123876A TW103123876A TW201441611A TW 201441611 A TW201441611 A TW 201441611A TW 103123876 A TW103123876 A TW 103123876A TW 103123876 A TW103123876 A TW 103123876A TW 201441611 A TW201441611 A TW 201441611A
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cast iron
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oxygen content
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D27/00—Treating the metal in the mould while it is molten or ductile ; Pressure or vacuum casting
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F27—FURNACES; KILNS; OVENS; RETORTS
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    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
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    • C21—METALLURGY OF IRON
    • C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
    • C21C7/00—Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00
    • C21C7/0006—Adding metallic additives
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
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    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/12—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the method of spraying
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
    • C21C5/00—Manufacture of carbon-steel, e.g. plain mild steel, medium carbon steel or cast steel or stainless steel
    • C21C5/28—Manufacture of steel in the converter
    • C21C5/42—Constructional features of converters
    • C21C5/46—Details or accessories
    • C21C5/4673—Measuring and sampling devices
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
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    • G01N27/406—Cells and probes with solid electrolytes
    • G01N27/411—Cells and probes with solid electrolytes for investigating or analysing of liquid metals
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
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    • G01N33/205—Metals in liquid state, e.g. molten metals
    • 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
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    • 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

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Abstract

本發明係關於一種藉由向鑄鐵熔液中添加鎂而影響鑄鐵性質之方法，其包括測量鑄鐵熔液之氧含量且將鎂添加入鑄鐵熔液中直至鑄鐵熔液中氧含量在大約1,420℃之溫度下達到大約0.005至0.2 ppm；本發明進一步關於一種用於測量鑄鐵熔液中氧含量之感測器，該感測器係利用一種包括一固態電解質管之電化學測量單元。

Description

用於測量鑄鐵熔液氧含量之感測器
本發明係關於一種藉由向鑄鐵熔液中添加鎂而影響鑄鐵性質之方法。本發明進一步關於一種用於測量鑄鐵熔液中氧含量之感測器，該感測器係利用一種包括一固態電解質管之電化學測量單元。
一般而言，鑄鐵熔液中之自由鎂含量被視為係在經鎂處理之鑄鐵中形成球體或毛蟲狀石墨之一決定性因素。用於調節延性鑄鐵之生產的現今實物係由借助於攝譜儀分析樣品測定鎂總含量(即自由及束縛鎂)所組成。然而，由於不知曉自由鎂的含量且測量並未提供任何關於氧活性的資訊，因而此方法所提供的圖像並不完整。然而，與自由鎂平衡之氧活性係石墨形態形成之一決定性因素。所謂的延性鑄鐵係經球形成添加劑處理，以致鑄鐵中大部分的石墨碳呈所謂的球狀石墨或球形石墨之常規灰色鑄件。鑄鐵中之球狀石墨必須根據形態、大小及顆粒數量進行分析，因為該等參數會影響鑄鐵之機械性能。視覺分析係複雜或主觀的，即使係在部分自動化分析中亦然。已知曉此方面之測量法，舉例而言，US 5,675,097。DE 19928456A1描述用於測定鑄鐵中石墨之空間結構的測量法，該方法係基於氧測定且無視覺方法之缺點。因此，其可更迅速地反應且鑄造過程中生產之特定影響會分別增加產量或減少廢料。鑄鐵品質可得到良好控制。
鑄鐵中鎂處理之成功可(例如)藉由白色凝固樣品之金相學或攝譜儀分析或也可藉由熱分析而獲證實。
一般而言，純鎂或鎂合金通常可促進鑄鐵之球形形態。一部分添加鎂吸收鐵中的氧及硫；剩餘部分即所謂的自由鎂部分，其控制氧活性。熔液中之自由鎂含量係鑄鐵球化之決定性因素。經過一段時間熔液中自由鎂部分減少而氧活性提高。該現象影響鑄鐵之結構及機械性能。
舉例而言，已由DE 10310387B3獲知用於測定金屬熔液之氧活性之感測器。本案揭示之固態電解質管，其外表面具有一鋯酸鈣及氟化物之混合物的塗層，使得舉例而言可測量鐵熔液中之硫、矽或碳濃度。
本發明之目的係提出一種藉以改良先前技術，及在液相中即明確影響鑄鐵之機械性能的方法，以及一種用於調節該方法的感測器。
獨立請求項之特徵解決了該問題。附屬請求項指出有利之實施例。特定言之，根據本發明之方法的特徵在於測量鑄鐵熔液中氧含量，且將鎂添加進鑄鐵熔液中直至鑄鐵熔液中氧含量在大約1,420℃之參考溫度下達到大約0.005至0.2ppm。由於氧測量比迄今為止可能的鎂測量(熔液中鎂以自由鎂及束縛鎂存在，使得精確分析不可能)更精確，因此鑄鐵機械性能之測定將更精確。熟習此項技術者能偵測並利用一方面在低氧含量下存在一些大石墨顆粒與另一方面在較高氧含量下存在許多小石墨顆粒之間的相互關係。因而，可建立與機械性能之相互關係，如已在US 5,675,097中描述，例如就抗張強度、伸長率及變形阻力而言。對於鑄鐵令人驚訝地顯示當添加鎂直至氧含量小於0.1ppm，較佳介於0.08至0.1ppm之間時，其具有最大伸長率。在較低或較高的氧含量下，鑄鐵之伸長率又降低。向鑄鐵熔液中添加大約 200至750ppm鎂以達到所需氧含量係有利的。
根據本發明之感測器之特徵在於在固態電解質管之朝外表面上施加一層二氧化鋯。特定言之，該層之二氧化鋯可藉由氧化鈣、氧化釔及/或氧化鎂而穩定。該層藉由至高達30重量%之氧化鈣、至高達25重量%之氧化鎂及/或至高達52重量%之氧化釔穩定係有利的。特定言之，該層藉由大約4至6重量%之氧化鈣穩定係有利的。有利地，感測器之該層係經電漿噴塗。其厚度較佳大約為30至50μm，特定言之，大約為40μm。其上具有該層之固態電解質管較佳係可經大約2重量%之氧化鎂穩定的二氧化鋯管。
1‧‧‧金屬管
2‧‧‧電線
3‧‧‧砂填充體
4‧‧‧連接片
5‧‧‧熱電偶
6‧‧‧電化學測量單元
7‧‧‧熱電偶密封粘合膠
8‧‧‧黏合膠
9‧‧‧密封塞
10‧‧‧塑膠夾子
11‧‧‧熱絕緣部分
12‧‧‧砂體
13‧‧‧載體管
14‧‧‧潑濺保護管
15‧‧‧金屬蓋帽
圖1顯示石墨顆粒數量與氧含量(氧活性aO)之間的相互關係；圖2顯示相對伸長率與氧含量之間的相互關係；圖3顯示穿過根據本發明之感測器頂部的橫截面圖；及圖4顯示穿過感測器之另一個實施例的部分剖視圖。
以下以圖式為基礎描述本發明之一個示範實施例。
圖1顯示石墨顆粒數量隨著氧含量(氧活性aO)的增加而增加。因而，可藉由通過鎂之添加調節氧含量，從而調整石墨顆粒之數量。因此，鑄鐵之性能已在熔液中受明確影響。在氧活性處於大約0.10及0.12ppm(1,420℃下有效)之間時提供最大量球化。當氧活性降至0.10ppm以下時球化減少。此現象與鑄造實務中已知之經驗一致，即過量的鎂對球化有負面影響。
圖2顯示鑄鐵之相對伸長率與氧含量之間的相互關係。在大約0.08ppm下可注意到最大伸長率。氧活性較低時，伸長率略微較小，此大概係由於較低球化所致。如果氧活性超過最適宜值，則伸長率穩定減小。圖解介紹顯示可藉由通過鎂之添加調節鑄鐵熔液中之氧含 量，從而影響鑄鐵之相對伸長率。
圖3顯示一根據本發明之感測器。在金屬管1中，電線2(Cu/CuNi/導體)安裝在砂填充體3中。經由連接片4，該等電線與一矛狀器或另一固定器連接，且又與一分析單元連接。電線2之另一端與一熱電偶5及電化學測量單元6相連。電化學測量單元6有一固態電解質管(ZrO2單元)，該管有一鋼震屏蔽作為一外殼。ZrO2單元在其外表面上有一經5重量%氧化鈣穩定之二氧化鋯層。該層之厚度大約為40μm。因為固態電解質管基本上已為吾人所知，故圖中不詳細顯示。
熱電偶5被定位於一熱電偶密封粘合膠7內。測量單元6也被定位於一黏合膠8內；其位於感測器內部之一端藉由有電接點通過之密封塞9而封閉。該兩個感測元件5、6藉由一塑膠夾子10連接。電線延伸通過熱絕緣部分11而穿過金屬管1之內部。在感測器之浸沒端，於金屬管1之外部設有一砂體12以保護感測器。
圖4顯示一類似配置，其中呈現感測器於載體管13中之接觸。載體管13係由紙板形成，且其面朝砂體12之前側被一潑濺保護管14所環繞，該潑濺保護管14係由鑄砂或水泥所製成。為了運輸期間及沉浸進熔液期間之保護，感測元件5、6自身最初經金屬蓋帽15環繞，該蓋帽分別在感測器沉浸進金屬熔液期間或之後熔化，從而暴露感測元件5、6。
1‧‧‧金屬管
2‧‧‧電線
3‧‧‧砂填充體
4‧‧‧連接片
5‧‧‧熱電偶
6‧‧‧電化學測量單元
7‧‧‧熱電偶密封粘合膠
8‧‧‧黏合膠
9‧‧‧密封塞
10‧‧‧塑膠夾子
11‧‧‧熱絕緣部分
12‧‧‧砂體

Claims (7)

  1. 一種用於測量鑄鐵熔液中氧含量之感測器，其中該感測器包含具有外表面之固態電解質管之電化學測量單元，且其中在該固態電解質管之該外表面上施加一層經大約4至6重量%之氧化鈣穩定化之二氧化鋯層，其中該層之厚度大約為30至50μm。
  2. 如請求項1之感測器，其特徵在於該層之二氧化鋯係經氧化釔及/或氧化鎂穩定化。
  3. 如請求項2之感測器，其特徵在於該層係經至高達25重量%之氧化鎂、或至高達52重量%之氧化釔穩定化。
  4. 如請求項1至3中任一項之感測器，其特徵在於該層係經電漿噴塗。
  5. 如請求項1之感測器，其特徵在於該層之厚度大約為40μm。
  6. 如請求項1之感測器，其特徵在於該固態電解質管係經設計成一種二氧化鋯管。
  7. 如請求項6之感測器，其特徵在於該二氧化鋯管係經大約2重量%之氧化鎂穩定化。
TW103123876A 2007-01-22 2008-01-17 用於測量鑄鐵熔液氧含量之感測器 TWI530678B (zh)

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US20100018348A1 (en) 2010-01-28
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JP2010516469A (ja) 2010-05-20
AU2011202140A1 (en) 2011-06-02
JP5101634B2 (ja) 2012-12-19
EP2228643A1 (de) 2010-09-15
AU2011202140B2 (en) 2012-01-12
CN102944601A (zh) 2013-02-27
CA2668841C (en) 2016-03-15
BRPI0805850B1 (pt) 2018-08-28
CA2855425A1 (en) 2008-07-31
CN101595382B (zh) 2013-08-14
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UA101660C2 (ru) 2013-04-25
EP2113079A1 (de) 2009-11-04
AU2008209133B2 (en) 2011-05-12
PL2228643T3 (pl) 2017-06-30
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US8449741B2 (en) 2013-05-28
US8557176B2 (en) 2013-10-15
TWI530678B (zh) 2016-04-21
KR101441713B1 (ko) 2014-09-17
ES2617429T3 (es) 2017-06-19
TW200846658A (en) 2008-12-01
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