EP2162558B1 - Eisen-nickel-chrom-silizium-legierung - Google Patents

Eisen-nickel-chrom-silizium-legierung Download PDF

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Publication number
EP2162558B1
EP2162558B1 EP08773262.4A EP08773262A EP2162558B1 EP 2162558 B1 EP2162558 B1 EP 2162558B1 EP 08773262 A EP08773262 A EP 08773262A EP 2162558 B1 EP2162558 B1 EP 2162558B1
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EP
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Prior art keywords
alloy according
elements
max
content
alloy
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EP08773262.4A
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German (de)
English (en)
French (fr)
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EP2162558A1 (de
Inventor
Heike Hattendorf
Jürgen WEBELSIEP
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VDM Metals International GmbH
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VDM Metals International GmbH
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Priority to SI200831882T priority Critical patent/SI2162558T1/sl
Priority to PL08773262T priority patent/PL2162558T3/pl
Publication of EP2162558A1 publication Critical patent/EP2162558A1/de
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    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/001—Ferrous alloys, e.g. steel alloys containing N
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/002—Ferrous alloys, e.g. steel alloys containing In, Mg, or other elements not provided for in one single group C22C38/001 - C22C38/60
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/005—Ferrous alloys, e.g. steel alloys containing rare earths, i.e. Sc, Y, Lanthanides
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/06—Ferrous alloys, e.g. steel alloys containing aluminium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/08—Ferrous alloys, e.g. steel alloys containing nickel
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • 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
    • H05B3/10—Heating elements characterised by the composition or nature of the materials or by the arrangement of the conductor
    • H05B3/12—Heating elements characterised by the composition or nature of the materials or by the arrangement of the conductor characterised by the composition or nature of the conductive material

Definitions

  • the invention relates to iron-nickel-chromium-silicon alloys with improved life and dimensional stability.
  • Austenitic iron-nickel-chromium-silicon alloys with different nickel, chromium and silicon contents have long been used as heat conductors in the temperature range up to 1100 ° C.
  • this alloy group is standardized in DIN 17470 (Table 1) and ASTM B344-83 (Table 2). There are a number of commercially available alloys listed in Table 3 for this standard.
  • the lifetime is increased by a higher chromium content, since a higher content of the protective layer forming element chromium Delaying time when the Cr content is below the critical limit and other oxides form as Cr 2 O 3, which are, for example iron-containing oxides.
  • the composition (in% by mass) is as follows: C not more than 0.2% Si 0.01-4% Mn 0.05-2% P not more than 0.04% S not more than 0.015% Cr 10-35% Ni 30-78% al not less than 0.005 but not more than 4.5% N 0.005-0.2% and one or more of Cu 0.015 - 3% as well Co 0.015-3%
  • thermoformable austenitic nickel alloy of the following composition (in wt .-%) has become known: C 0.05-0.15% Si 2.5-3.0% Mn 0.2-0.5% P Max. 0.015% S Max. 0.005% Cr 25-30% Fe 20-27% al 0.05-0.15% Cr 0.001-0.005% SE 0.05-0.15% N 0.05-0.20%
  • the EP-A 0 386 730 describes a nickel-chromium-iron alloy with very good oxidation resistance and high temperature resistance, as desired for advanced heat conductor applications, which emanates from the known NiCr6015 Schuleiterlegmaschine and in which by matching modifications of the composition considerable improvements in performance could be achieved.
  • the alloy differs from the known material NiCr6015 in particular in that the rare earth metals are replaced by yttrium, that it additionally contains zirconium and titanium, and that the nitrogen content is specially adapted to the contents of zirconium and titanium.
  • an austenitic Fe-Cr-Ni alloy for use in the high-temperature range is to be taken, which has essentially the following chemical composition (in% by weight): Ni 38-48% Cr 18-24% Si 1.0-1.9% C ⁇ 0.1% Fe Rest.
  • dislocation creep dislocation creep, grain boundary slippage, or diffusion creep
  • dislocation creep does not depend on the grain size.
  • the production of a wire with a large grain size increases the creep resistance and thus the dimensional stability.
  • grain size should therefore also be taken into account as an important influencing factor.
  • Another important factor for a heat conductor material is the highest possible specific electrical resistance and the lowest possible change in the ratio of heat resistance / cold resistance to temperature (temperature coefficient ct).
  • This object is achieved by an iron-nickel-chromium-silicon alloy, with (in wt .-%) 19 to 34% nickel, 12 to 26% chromium, 0.75 to 2.5% silicon, and 0 additions , 05 to 1% Al, 0.01 to 1% Mn, 0.01 to 0.26% lanthanum, 0.0005 to 0.05% magnesium, 0.04 to 0.14% carbon, 0.02 to 0 , 14% nitrogen, further containing 0.0005 to 0.07% Ca, 0.002 to 0.020% P, max. 0.01% sulfur, max.
  • these alloys Due to their special composition, these alloys have a longer service life than the alloys of the prior art with comparable nickel and chromium contents. In addition, an increased dimensional stability or a lower sagging can be achieved than the alloys according to the prior art.
  • the spreading range for the element nickel is either between 19 and 34%, whereby, depending on the application, nickel contents can be given as follows and adjusted depending on the application in the alloy.
  • the alloy may further include calcium at levels between 0.0005 and 0.07%, especially 0.001 to 0.05% or 0.01 to 0.05%.
  • the alloy may further include phosphorus at levels of between 0.002 and 0.020%, especially 0.005 to 0.02%.
  • the elements sulfur and boron may be given in the alloy as follows: sulfur Max. 0.005% boron Max. 0.003%.
  • the alloy may further comprise at least one of the elements Ce, Y, Zr, Hf, Ti with a content of 0.01 to 0, 3%, where necessary, the elements can also be defined additions.
  • oxygen affinity elements such as preferred La and, if necessary, Ce, Y, Zr, Hf, Ti
  • improve the lifetime by incorporating them into the oxide layer and blocking the diffusion paths of the oxygen there on the grain boundaries.
  • the amount of elements available for this mechanism must therefore be normalized to the atomic weight in order to be able to compare the amounts of different elements among each other.
  • PwE 200 • ⁇ X e / Atomic weight of E where E is the relevant element and X E is the content of that element in percent.
  • impurities may still contain the elements copper, lead, zinc and tin in amounts as follows: Cu Max. 1.0% pb Max. 0.002% Zn Max. 0.002% sn Max. 0.002%.
  • the alloy according to the invention should preferably be used for use in electrical heating elements, in particular in electrical heating elements which require high dimensional stability and low sagging.
  • Another concrete application for the alloy according to the invention is the use in furnace construction.
  • Tables 1 to 3 reflect - as already mentioned at the beginning - the state of the art.
  • the sagging behavior of heating coils at the application temperature is investigated in a sagging test.
  • the sagging of the coils from the horizontal is recorded after a certain time on heating coils. The lower the sag, the greater the dimensional stability or creep resistance of the material.
  • a soft annealed wire with a diameter of 1.29 mm is wound into spirals with an inner diameter of 14 mm.
  • All heating coils are controlled at the start of the experiment to a uniform outlet temperature of 1000 ° C. The temperature is determined with a pyrometer. The test is carried out with a switching cycle of 30 s "on” / 30 s “off” at constant voltage. After 4 hours, the experiment is terminated. After the heating coils have cooled, the sagging of the individual turns (sagging) from the horizontal is measured and the mean value of the 6 values of the heating coils is formed.
  • FIG. 1 the dependence of the relative burning time on the La content is shown, the influences of the Ni, Cr, Si content have been excluded. It turns out that the relative burning time greatly increases with increasing La content.
  • a La content of 0.04 to 0.15% is particularly advantageous.
  • FIG. 2 shows the dependence of the Saggings on the N-content, whereby the influences of the Ni, Cr, Si and C content were excluded. It can be seen that sagging decreases strongly with increasing N content. In particular, an N content of 0.05 to 0.09% is advantageous.
  • FIG. 3 the dependency of the Saggings on the C-content is shown, whereby the effects of the Ni, Cr, Si and N content were excluded. It can be seen that sagging decreases significantly with increasing C content. In particular, a C content of 0.04 to 0.10% is advantageous.
  • Alloys with lower nickel contents are particularly cost-effective. Therefore, the alloys in the range of 19% to 34% Ni are of great interest, despite the lower temperature coefficient and lower resistivity compared to alloys with higher nickel contents. Below 19% nickel, there is an increasing risk of sigma phase formation, which causes the alloy to become brittle. Therefore, 19% is the lower limit for the nickel content.
  • Too low Cr contents mean that the Cr concentration drops very quickly below the critical limit. That's why 12% Cr is the lower limit for chromium. Too high Cr contents deteriorate the workability of the alloy. Therefore, 26% Cr is considered the upper limit.
  • PwE 200 ⁇ ⁇ X e / Atomic weight of E where E is the element in question and X E is the content of the relevant element in%.
  • a minimum content of 0.01% La is necessary to obtain the oxidation resistance-enhancing effect of La.
  • the upper limit is set at 0.26%, which corresponds to a PwE of 0.38. Larger values of PwE are not useful here.
  • Al is needed to improve the processability of the alloy. It is therefore necessary a minimum content of 0.05%. Too high contents in turn affect the processability.
  • the Al content is therefore limited to 1%.
  • N A minimum content of 0.02% N is required for good dimensional stability or low sagging. N is limited to 0.14% because this element reduces oxidation resistance and processability.
  • Mg a minimum content of 0.0005% is required, which improves the processability of the material.
  • the limit is set at 0.05% because too much Mg has proved negative.
  • the levels of sulfur and boron should be adjusted as low as possible, as these surfactants impair oxidation resistance. It will therefore max. 0.01% S and max. 0.005% B is set.
  • Copper is heated to max. 1% limited as this element reduces the oxidation resistance.
  • Pb is set to max. 0.002% limited because this element reduces the oxidation resistance. The same applies to Sn.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Soft Magnetic Materials (AREA)
  • Resistance Heating (AREA)
  • Conductive Materials (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Refinement Of Pig-Iron, Manufacture Of Cast Iron, And Steel Manufacture Other Than In Revolving Furnaces (AREA)
  • Fuel Cell (AREA)
EP08773262.4A 2007-06-26 2008-06-12 Eisen-nickel-chrom-silizium-legierung Active EP2162558B1 (de)

Priority Applications (2)

Application Number Priority Date Filing Date Title
SI200831882T SI2162558T1 (sl) 2007-06-26 2008-06-12 Zlitina železo-nikelj-krom-silicij
PL08773262T PL2162558T3 (pl) 2007-06-26 2008-06-12 Stop żelaza-niklu-chromu-krzemu

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102007029400.1A DE102007029400B4 (de) 2007-06-26 2007-06-26 Eisen-Nickel-Chrom-Silizium-Legierung
PCT/DE2008/000965 WO2009000230A1 (de) 2007-06-26 2008-06-12 Eisen-nickel-chrom-silizium-legierung

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Publication Number Publication Date
EP2162558A1 EP2162558A1 (de) 2010-03-17
EP2162558B1 true EP2162558B1 (de) 2017-08-09

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US (2) US20100172790A1 (enrdf_load_stackoverflow)
EP (1) EP2162558B1 (enrdf_load_stackoverflow)
JP (2) JP5447864B2 (enrdf_load_stackoverflow)
KR (1) KR101335009B1 (enrdf_load_stackoverflow)
CN (1) CN101707948B (enrdf_load_stackoverflow)
BR (1) BRPI0813917A8 (enrdf_load_stackoverflow)
CA (1) CA2690637C (enrdf_load_stackoverflow)
DE (1) DE102007029400B4 (enrdf_load_stackoverflow)
ES (1) ES2643635T3 (enrdf_load_stackoverflow)
MX (1) MX2009013253A (enrdf_load_stackoverflow)
PL (1) PL2162558T3 (enrdf_load_stackoverflow)
SI (1) SI2162558T1 (enrdf_load_stackoverflow)
WO (1) WO2009000230A1 (enrdf_load_stackoverflow)

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US9174309B2 (en) * 2012-07-24 2015-11-03 General Electric Company Turbine component and a process of fabricating a turbine component
DE102012015828B4 (de) * 2012-08-10 2014-09-18 VDM Metals GmbH Verwendung einer Nickel-Chrom-Eisen-Aluminium-Legierung mit guter Verarbeitbarkeit
CN102952990A (zh) * 2012-11-20 2013-03-06 无锡康柏斯机械科技有限公司 一种精密电阻丝合金
CN103422003B (zh) * 2013-05-15 2015-06-17 锡山区羊尖泓之盛五金厂 一种镍铬合金
CN105579607A (zh) * 2013-09-13 2016-05-11 伊顿公司 耐磨合金
CN104911405A (zh) * 2014-03-15 2015-09-16 紫旭盛业（昆山）金属科技有限公司 一种镍铬模具合金
WO2015196357A1 (zh) * 2014-06-24 2015-12-30 深圳麦克韦尔股份有限公司 电子烟及其发热丝
JP6186043B1 (ja) 2016-05-31 2017-08-23 日本冶金工業株式会社 Ｆｅ−Ｎｉ−Ｃｒ合金、Ｆｅ−Ｎｉ−Ｃｒ合金帯、シーズヒーター、Ｆｅ−Ｎｉ−Ｃｒ合金の製造方法及びシーズヒーターの製造方法
CN106567012A (zh) * 2016-11-07 2017-04-19 杨俊� 深海油田控制阀门材质配方
CN110972343A (zh) * 2018-09-29 2020-04-07 中新三三仁智科技江苏有限公司 智能致密化金属纳米负离子热源导体
KR102396584B1 (ko) * 2019-06-12 2022-05-10 엘지전자 주식회사 면상 발열체 및 그 제조방법
CN110819850A (zh) * 2019-12-18 2020-02-21 江苏兄弟合金有限公司 一种镍铬电热合金及其制备方法
JP2022049630A (ja) * 2020-09-16 2022-03-29 優章 荒井 発熱体
EP4350757A4 (en) * 2021-06-01 2025-06-11 Lg Innotek Co., Ltd. PRINTED CIRCUIT BOARD AND CHIP HOUSING
JP2023032217A (ja) * 2021-08-26 2023-03-09 新報国マテリアル株式会社 オーステナイト・ステンレス鋼鋳物
CN115233040B (zh) * 2022-09-21 2022-12-20 广东腐蚀科学与技术创新研究院 一种控温用镍铬铁合金材料及其制备方法和应用
CN115233039B (zh) * 2022-09-21 2022-12-20 广东腐蚀科学与技术创新研究院 一种镍铬铁合金材料及其制备方法和应用
CN116005038B (zh) * 2022-12-08 2024-08-02 北京首钢吉泰安新材料有限公司 一种镍铬铁合金及其制备方法
CN116396094B (zh) * 2023-03-24 2024-03-01 中铝郑州有色金属研究院有限公司 一种铁酸镍基陶瓷惰性阳极与金属导电块的连接方法
CN116287870B (zh) * 2023-03-27 2024-11-22 昆明理工大学 一种快速响应加热的耐碳腐蚀镍铬基合金材料及其制备方法与应用
JP7647792B2 (ja) * 2023-04-11 2025-03-18 大同特殊鋼株式会社 抵抗体及びその製造方法
CN117026013A (zh) * 2023-08-21 2023-11-10 北京首钢吉泰安新材料有限公司 一种镍铬电热合金及其制备方法

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Also Published As

Publication number Publication date
WO2009000230A1 (de) 2008-12-31
US20130200068A1 (en) 2013-08-08
CN101707948A (zh) 2010-05-12
JP2010532425A (ja) 2010-10-07
BRPI0813917A2 (pt) 2014-12-30
CA2690637A1 (en) 2008-12-31
JP5626815B2 (ja) 2014-11-19
EP2162558A1 (de) 2010-03-17
SI2162558T1 (sl) 2017-11-30
PL2162558T3 (pl) 2018-01-31
DE102007029400B4 (de) 2014-05-15
CA2690637C (en) 2014-03-11
JP2013177691A (ja) 2013-09-09
KR20100022488A (ko) 2010-03-02
ES2643635T3 (es) 2017-11-23
US20100172790A1 (en) 2010-07-08
MX2009013253A (es) 2010-01-25
JP5447864B2 (ja) 2014-03-19
KR101335009B1 (ko) 2013-11-29
CN101707948B (zh) 2014-10-15
BRPI0813917A8 (pt) 2016-05-03
DE102007029400A1 (de) 2009-01-02

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