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WO2002088404A2 - Alliage fer-chrome-aluminium - Google Patents

Alliage fer-chrome-aluminium Download PDF

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Publication number
WO2002088404A2
WO2002088404A2 PCT/EP2002/004571 EP0204571W WO02088404A2 WO 2002088404 A2 WO2002088404 A2 WO 2002088404A2 EP 0204571 W EP0204571 W EP 0204571W WO 02088404 A2 WO02088404 A2 WO 02088404A2
Authority
WO
WIPO (PCT)
Prior art keywords
max
chromium
iron
aluminum
aluminum alloy
Prior art date
Application number
PCT/EP2002/004571
Other languages
German (de)
English (en)
Other versions
WO2002088404A3 (fr
Inventor
Heike Hattendorf
Jürgen WEBELSIEP
Hans-Joachim Balke
Michael Eckhardt
Original Assignee
Thyssenkrupp Vdm Gmbh
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
Priority claimed from DE10157749A external-priority patent/DE10157749B4/de
Application filed by Thyssenkrupp Vdm Gmbh filed Critical Thyssenkrupp Vdm Gmbh
Priority to AU2002302575A priority Critical patent/AU2002302575A1/en
Priority to BRPI0209166-6A priority patent/BR0209166B1/pt
Priority to US10/476,170 priority patent/US20040131493A1/en
Priority to DE50200904T priority patent/DE50200904D1/de
Priority to EP02730208A priority patent/EP1381701B1/fr
Priority to AT02730208T priority patent/ATE274605T1/de
Publication of WO2002088404A2 publication Critical patent/WO2002088404A2/fr
Publication of WO2002088404A3 publication Critical patent/WO2002088404A3/fr

Links

Classifications

    • 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
    • C22C38/28—Ferrous alloys, e.g. steel alloys containing chromium with titanium or zirconium
    • 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
    • C22C38/06—Ferrous alloys, e.g. steel alloys containing aluminium

Definitions

  • the invention relates to a deformable, ferritic steel alloy.
  • Alloys of this type are used, inter alia, for the production of electrical heating elements and catalyst supports. These materials form a dense, firmly adhering aluminum oxide layer, which protects them from destruction. This protection is improved by the addition of so-called reactive elements such as Ca, Ce, La, Y, Zr, Hf, Ti, Nb, which improve the adhesiveness and / or reduce the layer growth, as described in the “Handbook of High-Temperature Materials Technology, Ralf Bürgel, Vieweg Verlag, Braunschweig 1998 ", from page 274.
  • the aluminum oxide layer protects the metallic material from rapid oxidation. It grows itself, albeit very slowly. This growth takes place with the consumption of the aluminum content of the material. If there is no more aluminum, other oxides (chromium and iron oxides) grow. The metal content of the material is consumed very quickly and the material fails. The time to failure is called lifespan. Increasing the aluminum content therefore extends the service life.
  • EP-B 0387670 an alloy with (in mass%) 20 to 25% Cr, 5 to 8% Al and additions of 0.03 to 0.08% yttrium 0.004 to 0.008% nitrogen, 0.020 up to 0.040% carbon, and approximately equal parts 0.035 to 0.07% Ti and 0.035 to 0.07% zirconium, and max. 0.01% phosphorus, max. 0.01% magnesium, max. 0.5% manganese, max. 0.005% sulfur, remainder iron addressed, whereby the sum of the contents of Ti and Zr in% is 1.75 to 3.5 times as large as the sum of the contents of C and N in mass% as well as impurities due to melting. All or part of Ti and Zr can be replaced by hafnium and / or tantalum or vanadium.
  • EP-B 0290719 an alloy with (in mass%) 12 to 30% Cr, 3.5 to 8% Al, 0.008 to 0.10% carbon, max. 0.8% silicon, 0.10 to 0.1% manganese, max. 0.035% phosphorus, max. 0.020% sulfur, 0.1 to 1.0% molybdenum, max.
  • nickel 1% nickel, and the additives 0.010 to 1.0% zirconium, 0.003 to 0.3% titanium and 0.003 to 0.3% nitrogen, calcium plus magnesium 0.005 to 0.05%, and rare earth metals from 0.003 to 0.80 %, Niobium of 0.5%, rest of iron described with usual accompanying elements, which is used for example as wire for heating elements for electrically heated furnaces and as a construction material for thermally stressed parts and as a film for the production of catalyst supports.
  • the iron-chromium-aluminum alloy Cr AI 14 4 can be manufactured more easily by the aluminum content lowered to approx. 4 to 4.5 mass% than the alloys described above with more than 5 mass% aluminum. But it shows still embrittlement phenomena, which lead to increased production costs for hot forming.
  • GB-A 476,115 shows an iron alloy, particularly suitable as electrical resistance, which contains the following elements: 6.1 - 30% Cr, 3 - 12% Al, 0.07 - 0.2% C, 4% Ti , Rest of Fe as well as contamination due to melting.
  • the Ti content is bound to the C content in such a way that it should not be less than 3 times the C content.
  • Preferred ranges for Cr are> 8%, for AI> 5%, for C> 0.085%.
  • the metal composite foil contains a carrier layer made of ferritic steel strip, which is provided on both sides with an outer layer made of aluminum or an aluminum alloy.
  • the carrier layer is formed from an alloy, with (in mass%) 16-25% Cr, rare earths, Y or Zr in contents between 0.01-0.1%, Fe rest. Furthermore, AI in contents between 2 and 6% can be added. Preferred Cr contents are above 20%.
  • EP-A 0402 640 discloses a stainless steel foil as a carrier element for catalysts and their production.
  • the foil is formed from an alloy of the following composition (in mass%): 1.0-20% Al, 5-30% Cr, up to 2% Mn, up to 3% Si, up to 1% C, balance Fe and manufacturing-related impurities.
  • Preferred ranges for AI are between 5.5 and 20%.
  • Y, Sc or rare earths can be added in limits up to 0.3% are, wherein at least one of the elements Ti, Nb, Zr, Hf, V, Ta, Mo, W can be provided in contents up to 2%.
  • Levels ⁇ 4% AI require Cr contents> 25%.
  • the invention has for its object to provide an inexpensive iron-chromium-aluminum alloy that has a similar or better life than Cr AI 14 4, but has an even lower brittleness and thus improved formability, but at the same time the same technical functionality as Cr AI 14 4 has.
  • an iron-chromium-aluminum alloy with a long service life with (in mass%)> 2 to 3.6 mass% aluminum and> 10 to 20% chromium and additions of 0.1 to 1% Si, Max. 0.5% Mn, 0.01 to 0.2% yttrium and / or 0.01 to 0.2% Hf and / or 0.01 to 0.3% Zr, max. 0.01% Mg, max. 0.01% Ca, max. 0.08% carbon, max. 0.04% nitrogen, max. 0.04% phosphorus, max. 0.01% sulfur, max. 0.05% copper, and max. 0.1% molybdenum and / or tungsten and manufacturing-related impurities, the rest iron
  • the Al content can preferably be set within limits of 2.5-3.55% and the Cr content within limits of 13-17%.
  • the most effective way to reduce brittleness is to reduce the aluminum content.
  • this has the disadvantage that the specific electrical resistance also decreases and the service life decreases.
  • the brittleness is also increased by chromium, silicon, carbon and nitrogen, which is why these elements should also be kept as low as possible.
  • the same technical functionality for a heating conductor which is used for the electrical generation of heat, can be achieved if the surface power, the power on the heating element, the total resistance of the heating element and the service life of the heating element remain constant with any change in the material.
  • Weight M B / M A * jp B lp A • ⁇ B l ⁇ A
  • Example: Material A: PA 1, 25 ⁇ mm 2 / m
  • the oxidation constant k is a measure of the quality of the oxide layer k smaller than with a poorer oxide layer, the smaller k is, the longer the life.
  • the subject of the invention is in addition to heating conductors for heating elements, for. B. a household appliance, or as a construction material in furnace construction can also be used as a film, for example as a carrier film for catalysts.
  • Table 1 shows various iron-chromium-aluminum alloys, the table containing batches that have been melted on an industrial scale as well as in a laboratory.
  • the test is carried out on wires with a diameter of 0.40 mm, from which wire coils with 12 turns, a coil diameter of 4 mm and a coil length of 50 mm are produced.
  • the wire coils are clamped between two power supplies and heated up to 1200 ° C by applying a voltage. The heating takes place for 2 minutes each, then the power supply is interrupted for 15 seconds. At the end of the service life, the wire fails because the remaining cross-section melts. The total time that the wire was heated, without the interruption times, is given as the service life in the following.
  • the large-scale batch T1 and the laboratory batches T2 and T3 represent the state of the art for Cr AI 14 4, with (in mass%) approx. 14.5% chromium, 4.5% aluminum, approx. 0.3% manganese , approx. 0.2% silicon and as a reactive element 0.17 to 0.18% zircon. They have lifetimes of 49 hours for the T3 laboratory batch, 63 hours for the T2 laboratory batch and 77 hours for the T1 industrial batch.
  • Batches H1 to H6 are batches with an aluminum content of more than 5% by mass and various additions of silicon, manganese, zirconium, titanium, hafnium and yttrium and other additives such as calcium, magnesium, carbon and nitrogen.
  • the aluminum content has been reduced from 4.5 to 3.55 mass% compared to the laboratory batch according to the prior art T2.
  • the service life was reduced from 63 hours to 34 hours.
  • Batch L3 with an aluminum content of 3.55% and a zirconium content of 0.053% and a hafnium content of 0.042% and an yttrium content of 0.02% has a service life of 90 hours.
  • Batch M1 has a lifetime of 92 hours with an aluminum content of 2.78% and a zircon content of 0.05% and a hafnium content of 0.03% and an yttrium content of 0.02%.
  • Charge M2 has a life of 126 hours with an aluminum content of 2.71% and a zirconium content of 0.05% and a hafnium content of 0.03% and an yttrium content of 0.04%.
  • Batch M4 has a lifetime of 85 hours with an aluminum content of 2.8% and a zircon content of 0.03% and a hafnium content of 0.03% and an yttrium content of 0.03%.
  • the alloy according to the invention must contain additions of 0.01 to 0.2% yttrium, and / or 0.01 to 0.2% Hf and / or 0.01 to 0.3% Zr.
  • Batch L1 shows that even with the addition of zirconium, hafnium and yttrium with an aluminum content of 1.55%, only a service life of 9.3 hours is achieved. Even with the addition of zirconium, hafnium and yttrium and an aluminum content of only 2.24%, Charge M3 only has a lifespan of 72 hours, which is in the range of the batches according to the prior art.
  • the Alloy according to the invention should therefore have an aluminum content of more than 2%.
  • Chromium contents between 14 and 17% have no decisive influence on the service life like the comparison of the batches M1 containing zirconium, hafnium and yttrium with 14.85% chromium and 2.78% aluminum and batch L2 with 16.86% chromium and 2.55 % Aluminum shows.
  • a certain chromium content is necessary, since chromium promotes the formation of the particularly stable and protective ⁇ - A 0 3 layer. According to HM Herbelin, M Mantel, Colloque C7, Suppleement au Journal de Physique III, Vol. 5, Novembre 1995, pages C7-365 to 374, this still happens with a chromium content of 13%, but a chromium content of 6% is no longer sufficient ,
  • Table 1 lists the impact energy at room temperature, 50 ° C, 100 ° C and 150 ° C on standard DMV samples (see W. Domke, Materials Science and Testing, Verlag W. Gerardet, Essen, 1981, from page 336).
  • the impact energy is low for a ferritic steel in the case of the brittle fracture occurring at low temperatures (low position), in the case of ductile, easily deformable behavior high (high position) with a steep increase within a few degrees from the low position to the high position. In this area, the impact energy can be widely scattered.
  • the temperature at which the transition from the high position to the low position takes place is called the notch impact transition temperature.
  • a material is the more brittle the larger the grain size or, in the case of iron-chromium-aluminum materials, the higher the content of alloying elements such as aluminum, chromium, silicon, nitrogen, carbon, phosphorus and sulfur. Due to your manufacturing route as a laboratory batch, all impact tests in Table 1 have one very large grain size of approximately 200 to 400 ⁇ m, which is very unfavorable. Therefore, all samples are in the low position at room temperature, with the samples with the lowest aluminum content, the lowest chromium content and the lowest carbon content having the highest impact energy, as shown by batches M1, M2, M3, M4 and L1.
  • Charge M4 has a slightly lower notch impact energy than Charge M2 with a similar aluminum and chromium content, since it has a higher carbon content.
  • Charge L2 has a slightly lower impact energy than Charge M2 because it has a higher chromium content. Nitrogen, phosphorus and sulfur act similarly to carbon, the contents of which should therefore advantageously be kept low. It turns out that the aluminum content must not exceed 3.6% in order to keep the embrittling effect of the aluminum as low as possible.
  • the brittle behavior of the iron-chromium-aluminum alloys is significantly reduced by lowering the aluminum content to below 3.6%.
  • This is further supported by low levels of silicon, carbon, nitrogen, phosphorus and sulfur.
  • the carbon content is therefore limited to max. 0.08%, the nitrogen content to max. 0.04%, the phosphorus content to max. 0.04% and the sulfur content to max. 0.01 Mass% limited.
  • Phosphorus and sulfur also have an unfavorable effect on the service life, so that the lowest possible levels of these elements are also advantageous from this point of view.
  • the chromium content should also be as low as possible. Due to the requirements regarding the service life, the silicon and chromium content cannot be reduced to almost zero, but must be at least 0.1% silicon and 10% chromium. However, no more than 20% chromium and 1% silicon should be added in order to achieve the lowest possible brittleness.
  • the alloy according to the invention must have an at least 10% longer lifespan in order to compensate for the disadvantage of the smaller wire diameter.
  • the batches according to the invention all have an at least 50% longer lifespan, the use of the alloy according to the invention additionally has the advantage of an increased lifespan.
  • Manganese is limited to 0.5% by mass because this element reduces the resistance to oxidation. The same applies to copper.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Resistance Heating (AREA)
  • Powder Metallurgy (AREA)
  • Catalysts (AREA)
  • Treatment Of Steel In Its Molten State (AREA)
  • Conductive Materials (AREA)
  • Cookers (AREA)
  • Carbon Steel Or Casting Steel Manufacturing (AREA)
  • Refinement Of Pig-Iron, Manufacture Of Cast Iron, And Steel Manufacture Other Than In Revolving Furnaces (AREA)

Abstract

L'invention concerne un alliage fer-chrome-aluminium de durée de vie étendue, comprenant (en % en masse) > 2 à 3,6 % d'aluminium et > 10 à 12 % de chrome, ainsi que des apports de l'ordre de 0,1 à 1 % de Si, au maximum 0,5 de Mn, 0,01 à 0,2 % d'yttrium et/ou 0,01 à 0,2 % de Hf et/ou 0,01 à 0,3 % de Zr, au maximum 0,01 % de Ca, au maximum 0,08 % de carbone, au maximum 0,04 % d'azote, au maximum 0,04 % de phosphore, au maximum 0,01 % de soufre, au maximum 0,05 % de cuivre et dans chaque cas, au maximum 0,1 % de molybdène et/ou de tungstène, ainsi que les impuretés habituelles inhérentes au processus de production, le reste étant du fer.
PCT/EP2002/004571 2001-04-26 2002-04-25 Alliage fer-chrome-aluminium WO2002088404A2 (fr)

Priority Applications (6)

Application Number Priority Date Filing Date Title
AU2002302575A AU2002302575A1 (en) 2001-04-26 2002-04-25 Iron-chrome-aluminium-alloy
BRPI0209166-6A BR0209166B1 (pt) 2001-04-26 2002-04-25 liga de ferro-cromo-alumìnio.
US10/476,170 US20040131493A1 (en) 2001-04-26 2002-04-25 Iron-chrome aluminium-alloy
DE50200904T DE50200904D1 (de) 2001-04-26 2002-04-25 Eisen-chrom-aluminium-legierung
EP02730208A EP1381701B1 (fr) 2001-04-26 2002-04-25 Alliage fer-chrome-aluminium
AT02730208T ATE274605T1 (de) 2001-04-26 2002-04-25 Eisen-chrom-aluminium-legierung

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
DE10120561.9 2001-04-26
DE10120561 2001-04-26
DE10157749.4 2001-11-24
DE10157749A DE10157749B4 (de) 2001-04-26 2001-11-24 Eisen-Chrom-Aluminium-Legierung

Publications (2)

Publication Number Publication Date
WO2002088404A2 true WO2002088404A2 (fr) 2002-11-07
WO2002088404A3 WO2002088404A3 (fr) 2003-11-06

Family

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Application Number Title Priority Date Filing Date
PCT/EP2002/004571 WO2002088404A2 (fr) 2001-04-26 2002-04-25 Alliage fer-chrome-aluminium

Country Status (6)

Country Link
EP (1) EP1381701B1 (fr)
CN (1) CN1226439C (fr)
AT (1) ATE274605T1 (fr)
AU (1) AU2002302575A1 (fr)
BR (1) BR0209166B1 (fr)
WO (1) WO2002088404A2 (fr)

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CN115961118A (zh) * 2022-12-15 2023-04-14 湖南华菱涟源钢铁有限公司 一种高铝钢及其制备方法和制品
CN116790988A (zh) * 2023-06-28 2023-09-22 中子时代(青岛)创新科技有限公司 一种适用于铅基堆的铁铬铝合金及其热处理方法

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DE102008018135B4 (de) 2008-04-10 2011-05-19 Thyssenkrupp Vdm Gmbh Eisen-Chrom-Aluminium-Legierung mit hoher Lebensdauer und geringen Änderungen im Warmwiderstand
CN104637640A (zh) * 2013-11-07 2015-05-20 丹阳智盛合金有限公司 一种铁铬铝电阻丝的加工工艺
CN103949863A (zh) * 2014-05-14 2014-07-30 河南飞孟金刚石工业有限公司 一种金刚石或立方氮化硼合成用钢片及其制作方法
CN104911492B (zh) * 2015-05-11 2017-02-01 安徽先锋门业科技有限公司 一种使用寿命长的伸缩门
CN113088830B (zh) * 2016-04-22 2023-09-01 山特维克知识产权股份有限公司 铁素体合金
CN107400835B (zh) * 2017-05-23 2021-12-03 上海大学 耐硫酸盐还原菌腐蚀用钢、其应用及其制备方法
CN108188196B (zh) * 2017-12-04 2019-10-11 中国科学院金属研究所 一种FeCrAl/Zr双金属复合管及其制备方法
CN108950415B (zh) * 2018-07-17 2020-10-09 山东瑞泰新材料科技有限公司 表面具有高温绝缘性能的合金及其制备工艺
CN110172648B (zh) * 2019-06-10 2020-06-16 苏州大学 一种含锆电热合金及含锆合金的制备方法
CN111057937A (zh) * 2019-12-31 2020-04-24 江苏新华合金有限公司 一种电热合金铁铬铝丝材及其制备方法
CN116065096B (zh) * 2023-03-05 2023-08-04 襄阳金耐特机械股份有限公司 一种铁素体耐热铸钢
CN117512402B (zh) * 2023-10-17 2024-07-12 北京首钢吉泰安新材料有限公司 一种铁镍电热合金及其制备方法

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5110805B2 (fr) * 1972-07-07 1976-04-07
JP3247162B2 (ja) * 1992-10-06 2002-01-15 川崎製鉄株式会社 耐酸化性に優れたＦｅ−Ｃｒ−Ａｌ系合金およびその箔
JPH06330248A (ja) * 1993-05-20 1994-11-29 Kawasaki Steel Corp 製造性および耐酸化性に優れた触媒コンバーター担体用Ｆｅ−Ｃｒ−Ａｌ合金
JPH08269730A (ja) * 1995-03-31 1996-10-15 Kawasaki Steel Corp 耐酸化性に優れるＦｅ−Ｃｒ−Ａｌ合金板
DE19834552A1 (de) * 1998-07-31 2000-02-03 Krupp Vdm Gmbh Oxidationsbeständige Metallfolie
DE19928842C2 (de) * 1999-06-24 2001-07-12 Krupp Vdm Gmbh Ferritische Legierung

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115961118A (zh) * 2022-12-15 2023-04-14 湖南华菱涟源钢铁有限公司 一种高铝钢及其制备方法和制品
CN116790988A (zh) * 2023-06-28 2023-09-22 中子时代(青岛)创新科技有限公司 一种适用于铅基堆的铁铬铝合金及其热处理方法

Also Published As

Publication number Publication date
EP1381701A2 (fr) 2004-01-21
BR0209166A (pt) 2004-08-03
CN1226439C (zh) 2005-11-09
BR0209166B1 (pt) 2011-01-11
AU2002302575A1 (en) 2002-11-11
EP1381701B1 (fr) 2004-08-25
WO2002088404A3 (fr) 2003-11-06
CN1537177A (zh) 2004-10-13
ATE274605T1 (de) 2004-09-15

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