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EP0491040A1 - Materiau constituant l'electrode d'un four de verrerie - Google Patents

Materiau constituant l'electrode d'un four de verrerie Download PDF

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Publication number
EP0491040A1
EP0491040A1 EP90910178A EP90910178A EP0491040A1 EP 0491040 A1 EP0491040 A1 EP 0491040A1 EP 90910178 A EP90910178 A EP 90910178A EP 90910178 A EP90910178 A EP 90910178A EP 0491040 A1 EP0491040 A1 EP 0491040A1
Authority
EP
European Patent Office
Prior art keywords
melting furnace
electrode material
nickel
balance
glass
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.)
Granted
Application number
EP90910178A
Other languages
German (de)
English (en)
Other versions
EP0491040A4 (en
EP0491040B1 (fr
Inventor
Toshio 3-48-11 Tajiri-Cho Masaki
Noriaki 2774-20 Mawatari Sasaki
Shin-Ichiro C-301 Aza-Tsukanoue Takaba Torata
Hiroshi 1-4-11 Ushirono Igarashi
Tetsuya 15-7 Ubakoyama Kasadera-Cho Shimizu
Tomohito 1-20-34 Ichiban Atsuta-Ku Iikubo
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Doryokuro Kakunenryo Kaihatsu Jigyodan
Original Assignee
Doryokuro Kakunenryo Kaihatsu Jigyodan
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Doryokuro Kakunenryo Kaihatsu Jigyodan filed Critical Doryokuro Kakunenryo Kaihatsu Jigyodan
Publication of EP0491040A1 publication Critical patent/EP0491040A1/fr
Publication of EP0491040A4 publication Critical patent/EP0491040A4/en
Application granted granted Critical
Publication of EP0491040B1 publication Critical patent/EP0491040B1/fr
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Classifications

    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B3/00—Ohmic-resistance heating
    • H05B3/60—Heating arrangements wherein the heating current flows through granular powdered or fluid material, e.g. for salt-bath furnace, electrolytic heating
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C19/00—Alloys based on nickel or cobalt
    • C22C19/03—Alloys based on nickel or cobalt based on nickel
    • C22C19/05—Alloys based on nickel or cobalt based on nickel with chromium
    • C22C19/058—Alloys based on nickel or cobalt based on nickel with chromium without Mo and W
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B3/00—Ohmic-resistance heating
    • H05B3/02—Details
    • H05B3/03—Electrodes

Definitions

  • the present invention relates to an electrode material of a glass melting furnace having an excellent corrosion resistance in molten glass in an energized state and utilizable as an electrode material of glass melting furnace.
  • Examples of electrode material of a glass melting furnace which have hitherto been used include a molybdenum-base alloy comprising 10 to 60% of copper and 0.5 to 5% of barium (see Japanese Patent Laid-Open No. 88739/1974), a platinum-base alloy comprising 1 to 20% of rhodium and 0.5 to 5% of tungsten (see Japanese Patent Laid-Open No. 51124/1978), and further those using tin oxide and those using a nickel-base alloy.
  • Examples of the nickel-base alloy include Inconel 690 which is a nickel-base alloy comprising about 30% of chromium and about 9% of iron.
  • this type of electrode of a glass melting furnace is used in molten glass in an energized state, it must have not only an excellent corrosion resistance in molten glass in an energized state but also a high melting point for the purpose of improving the operability of the melting furnace.
  • Conventional electrode materials had problems such as poor corrosion resistance im molten glass and low melting point.
  • Inconel 690 which is a nickel-base alloy comprising the above-described ingredients is not always excellent in the corrosion resistance im molten glass and has also a drawback that the melting point is as low as about 1350 o C.
  • the present invention has been made in view of the problem accompanying conventional electrodes particularly comprising a nickel-base alloy.
  • An object of the present inventiion is to provide a nickel-base electrode material of a glass melting furnace which has an excellent corrosion resistance in molten glass in an energized state and a melting point above 1350 o C, i.e., the melting point of the above-described conventional nickel-base Inconel, and is suitable as an electrode material of a glass melting furnace.
  • the electrode material of a glass melting furnace excellent in the corrosion resistance in molten glass in an energized state is characterized by having a chemical composition comprising by weight 25 to 40% of chromium, 10 to 45% of cobalt, optionally 0.1 to 1.5% of titanium and optionally 0.01 to 0.50% of at least one element selected from amoung REMs (rare earth metals) with the balance consisting of nickel and unavoidable impurities.
  • Chromium is added for ensuring the corrosion resistance of an electrode used for electric melting of glass in a glass melting furnace and is limited to 25% or more for the purpose of ensuring the corrosion resistance of such an electrode.
  • the upper limit of the chromium content is set to 40% or less because the addition of an excessive amount of chromium not only causes the effect to be saturated but also lowers the melting point and deteriorates the toughness of the electrode.
  • Cobalt is an element useful for improving the operability of the glass melting furnace through a rise of the melting point of the electrode and, at the same time, improving the corrosion resistance of the electrode in molten glass in an energized state.
  • the cobalt content is limited to 10% or more for the purpose of attaining the effect of raising the melting point and improving the corrosion resistance of the electrode.
  • the upper limit of the cobalt content is set to 45% or less because the addition of an excessive amount of cobalt not only causes the effect to be saturated but also deteriorates the toughness of the electrode.
  • Titanium 0.1 - 1.5%
  • Titanium is an element useful for improving the resistance of the electrode to molten glass in an energized state and, at the same time, attaining an improvement in the releasability of scale and may be optionally added in amount of 0.1% or more for attaining the effect of improving the above-described corrosion resistance and releasability of scale.
  • the addition of an excessive amount of titanium however, not only causes the effect to be saturated but also unfavorably lowers the melting point of the electrode. Therefore, when the titanium is added, the content should be 1.5% or less.
  • REM is an element useful for improving the corrosion resistance of the electrode in molten glass in an energized state and may be optionally added in an amount of 0.01% or more for the purpose of attaining such an effect.
  • the addition of an excessive amount of REM however, not only causes the effect to be saturated but also unfavorably deteriorates the toughness of the electrode. Therefore, when REM is added, the content should be 0.50% or less.
  • Nickel is effective in ensuring the corrosion resistance of the electrode in molten glass as well as in improving the operability of a glass melting furnace by virtue of its high melting point. Therefore, nickel is usd as the balance.
  • the electrode material of a glass melting furnace according to the present invention has the above-described chemical composition and comprises nickel having a high melting point and an excellent corrosion resistance as a matrix, and a suitable amount of chromium added for the purpose of ensuring the resistance of the electrode to corrosion by molten galss, a suitable amount of cobalt added for the purpose of improving the melting point of the electrode and the resistance to corrosion by molten glass, a suitable amount of titanium optionally added for the purpose of further improving the corrosion resistance and also the releasability of scale, and a suitable amount of at least one REM optionally added for allowing voides to stay inside the alloy to further improve the corrosion resistance.
  • the electrode material of the present invention has an excellent corrosion resistance in molten glass in an energized state, and the high melting point thereof serves to improve the operability of the melting furnace.
  • Nickel-base alloys comprising various chemical ingredients listed in Tabale 1 were molten by vacuum, induction melting to prepare ingots each having a weight of 30Kg.
  • Mm represents mischmetal (La + Ce) among REMs and Inconel 690 was used in Comparative Example 1.
  • each ingot was hot-forged to make a round bar having a diameter of 20 mm and a current was allowed to flow at a density of 0.8 A/cm2 through the round bar at 1250 o C in a molten borosilicate glass to determine the extent of corrosion (the extent of wearing out) under immersion for 100 hr in an energized state to thereby evaluate the resistance of the electrode to corrosion by molten glass.
  • Table 1 The results are given in Table 1.
  • Example 1 28.6 Fe:9.0 0.32 Al:0.28 the balance 356 1341 2 33.6 ⁇ 0.01 - - the balance 216 1378 3 32.2 52.2 - - the balance 254 1414 4 42.0 ⁇ 0.01 - - the balance 209 1356 5 42.0 15.9 - - the balance 207 1363 6 20.2 40.3 - - the balance 211 1430
  • the electrode materials comprising nickle-base alloys of Examples 1 to 14 according to the present invention exhibited a less extent of corrosion in a molten borosilicate glass in an energized state, i.e., were found to have a superior resistance to corrosion by molten glass in an energized state. Further, they had a melting point above that of Inconel 690 (Comparative Example 1) which is a conventional nickel-base alloy, i.e., have been confirmed to be able to improve the operability of a glass melting furnace.
  • the nickel-base alloys of Comparative Examples 1 to 6 exhibited a larger extent of corrosion in molten glass in an energized state. This brings about a problem of durability when then are used as an electrode material. Further, some of them has a low melting point.
  • the electrode material of a glass melting furnace according to the present invention has a composition comprising by weight 25 to 40% of chromium, 10to45% of cobalt, optionally 0.1 to 1.5% of titanium and optionally 0.01 to 0.50% of at least one element selected from among REMs with the balance consisting of nickel and unavoidable impurities and, by virture of this constitution, brings about such a remarkably excellent effect that it exhibits an excellent resistance to corrosion by molten glass in an energized state when used as an electrode material of a glass melting furnace and, at the same time, improves the operability of the glass melting furnace because of its higher melting point than that of Inconel 690, i.e., the conventional nickle-base alloy.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Glass Melting And Manufacturing (AREA)

Abstract

Un matériau constituant une électrode pour un four de verrerie comprend de 25 à 40 % en poids de chrome, de 10 à 45 % en poids de cobalt, éventuellement de 0,1 à 1,5 % en poids de titane, et éventuellement de 0,01 à 0,50 % en poids d'un ou plusieurs métaux des terres rares, le solde étant constitué de nickel et des inévitables impuretés.
EP90910178A 1989-01-09 1990-07-09 Materiau constituant l'electrode d'un four de verrerie Expired - Lifetime EP0491040B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP341689A JPH0819505B2 (ja) 1989-01-09 1989-01-09 通電下における溶融ガラス中での耐侵食性に優れたガラス溶融炉用電極材料
PCT/JP1990/000880 WO1992001077A1 (fr) 1989-01-09 1990-07-09 Materiau constituant l'electrode d'un four de verrerie

Publications (3)

Publication Number Publication Date
EP0491040A1 true EP0491040A1 (fr) 1992-06-24
EP0491040A4 EP0491040A4 (en) 1992-12-09
EP0491040B1 EP0491040B1 (fr) 1995-03-01

Family

ID=11556782

Family Applications (1)

Application Number Title Priority Date Filing Date
EP90910178A Expired - Lifetime EP0491040B1 (fr) 1989-01-09 1990-07-09 Materiau constituant l'electrode d'un four de verrerie

Country Status (4)

Country Link
EP (1) EP0491040B1 (fr)
JP (1) JPH0819505B2 (fr)
DE (1) DE69017460T2 (fr)
WO (1) WO1992001077A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6772921B2 (en) * 2001-07-10 2004-08-10 Heraeus Electro-Nite International N.V. Refractory nozzle

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
IL112648A (en) * 1994-02-22 2000-02-17 Curtis Helene Ind Inc Transparent antiperspirant deodorant compositions comprising a borate crosslinker

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CH597364A5 (fr) * 1974-04-11 1978-03-31 Bbc Sulzer Turbomaschinen
JPS5662943A (en) * 1979-10-26 1981-05-29 Hitachi Ltd Gas turbine nozzle material
JPS6059039A (ja) * 1983-09-09 1985-04-05 Mitsubishi Metal Corp 溶融ガラス接触部材用Ｃｏ基耐熱合金
JPS6277446A (ja) * 1985-09-30 1987-04-09 Toshiba Corp ガラス溶融炉用電極合金
JPS62185851A (ja) * 1986-02-13 1987-08-14 Toshiba Corp ガラス製品製造用工具
US4774149A (en) * 1987-03-17 1988-09-27 General Electric Company Oxidation-and hot corrosion-resistant nickel-base alloy coatings and claddings for industrial and marine gas turbine hot section components and resulting composite articles
JPH0225535A (ja) * 1988-07-14 1990-01-29 Daido Steel Co Ltd 溶融ガラス接触部材用Ｎｉ基合金

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6772921B2 (en) * 2001-07-10 2004-08-10 Heraeus Electro-Nite International N.V. Refractory nozzle

Also Published As

Publication number Publication date
JPH02213439A (ja) 1990-08-24
EP0491040A4 (en) 1992-12-09
EP0491040B1 (fr) 1995-03-01
JPH0819505B2 (ja) 1996-02-28
DE69017460T2 (de) 1995-08-10
DE69017460D1 (de) 1995-04-06
WO1992001077A1 (fr) 1992-01-23

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