EP2115179B1 - Eisen-nickel-chrom-silizium-legierung - Google Patents

Eisen-nickel-chrom-silizium-legierung Download PDF

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Publication number
EP2115179B1
EP2115179B1 EP08706757A EP08706757A EP2115179B1 EP 2115179 B1 EP2115179 B1 EP 2115179B1 EP 08706757 A EP08706757 A EP 08706757A EP 08706757 A EP08706757 A EP 08706757A EP 2115179 B1 EP2115179 B1 EP 2115179B1
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Prior art keywords
alloy according
content
elements
nickel
alloy
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German (de)
English (en)
French (fr)
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EP2115179A2 (de
Inventor
Heike Hattendorf
Jürgen WEBELSIEP
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VDM Metals GmbH
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ThyssenKrupp VDM GmbH
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    • 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
    • C22C38/001—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
    • C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
    • 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
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel

Definitions

  • the invention relates to an iron-nickel-chromium-silicon alloy 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 Time delays at which the Cr content is below the critical limit and form other oxides than Cr 2 O 3 , which are, for example, iron-containing oxides.
  • EP A 0 531 775 discloses a heat-resistant thermoformable austenitic nickel alloy of the following composition (in% by weight): 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% Balance Ni and impurities caused by melting.
  • 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).
  • iron-nickel-chromium-silicon alloy with (in wt .-%) 34 to 42% nickel, 18 to 26% chromium, 1.0 to 2.5% silicon and additions of 0, 05 to 1% Al, 0.01 to 1% Mn, 0.01 to 0.26% lanthanum, 0.0005 to 0.05% magnesium, 0.01 to 0.14% carbon, 0.01 to 0, 14% nitrogen, max. 0.01% sulfur, max. 0.005% B, balance iron and the usual process-related impurities.
  • This alloy due to its special composition, has a longer service life than the alloys of the prior art with the same nickel and chromium contents. In addition, increased dimensional stability or sagging can be achieved than the prior art alloys with 0.04 to 0.10% carbon.
  • sulfur and boron may be given in the alloy as follows: sulfur max, 0.01%, preferably max. 0.005% boron Max. 0.005%, preferably max. 0.003%.
  • 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 comprise at least one of the elements Ce, Y, Zr, Hf, Ti with a content of 0.01 to 0, 3%, which can also be defined supplements as needed.
  • oxygen-affinity elements such as La, Ce, Y, Zr, Hf, Ti improve the lifetime. They do this 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.
  • the alloy can have a phosphorus content between 0.001 to 0.020%, in particular from 0.005 to 0.020%.
  • 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 is to be used for use in electric heating elements, in particular in electrical heating elements which require high dimensional stability and low sagging.
  • a 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.
  • Tables 4a and 4b are industrially molten iron-nickel-chromium-silicon alloys according to the prior art T1 to T7, one on a laboratory scale Prior art molten alloy T8 and a plurality of bench scale inventive experimental alloys V771 to V777, V1070 to V1076, V1090 to V1093 melted to optimize the alloy composition.
  • the heat conductor life test is carried out on wires with a diameter of 0.40 mm.
  • the wire is clamped between 2 power supply lines at a distance of 150 mm and heated by applying a voltage up to 1150 ° C.
  • the heating at 1150 ° C takes place for 2 minutes, then the power supply is interrupted for 15 seconds.
  • the burning time is the addition of the "on" times during the life of the wire.
  • the relative burning time tb is the indication in% related to the burning time of a reference batch.
  • the sagging behavior of heating coils at the application temperature is investigated in a sagging test. This is on heating coils, the sagging of the helices of the Horizontal captured after a certain time. The lower the sag, the greater the dimensional stability or creep resistance of the material.
  • T1 and T2 are alloys with about 30% nickel, about 20% Cr and about 2% Si. They contain rare earth (SE) additions in this case, cerium misch metal, which means that SE consists of about 60% Ce, about 35% La and the rest Pr and Nd. The relative burning time is 24% or 35%.
  • SE rare earth
  • the example T3 is an alloy with about 40% nickel, about 20% Cr and about 1.3% Si. It contains rare earth (SE) additions in this case, cerium misch metal, which means that SE is about 60% Ce, about 35% La, and the balance is Pr and Nd. The relative burning time is 72%.
  • SE rare earth
  • Examples T4 to T7 are alloys with about 60% nickel, about 16% Cr and about 1.2-1.5% Si. They contain rare earth (SE) additions in this case, cerium misch metal, which means that SE is about 60% Ce, about 35% La, and the balance is Pr and Nd. The relative burning time is in the range of about 100 to 130%.
  • SE rare earth
  • Tables 4a and 4b contain a number of alloys melted on a laboratory scale.
  • the laboratory-scale melted prior art alloy T8 is an alloy of 36.2% nickel, 20.8% Cr, and 1.87% Si.
  • T1-T7 Like the industrially produced alloys T1-T7, it contains rare earth (SE) additions in the form of cerium misch metal, which means that SE is and was about 60% Ce, about 35% La and the rest Pr and Nd, apart from the Ni, Cr, and Si contents, melted to the same specifications as the large-scale batches.
  • SE rare earth
  • the batches according to the prior art T1 to T8 are thus directly comparable.
  • the relative burning time of T8 is 53%.
  • the Ni content is about 36%, the Cr content about 20% and the Si content about 1.8%.
  • the additions to Ce, La, Y, Zr, Hf, Ti, Al, Ca, Mg C, N were varied. These batches can therefore be compared directly with the prior art alloys T8, thus serving as a reference alloy for optimization serves.
  • PwE 200 * total X e / Atomic weight of E where E is the element in question and X E is the content of the relevant element in%.
  • Fig. 1 shows a graphical representation of the relative burning time tb and the potential PwE for the indicated in the tables 4a and 4b different alloys.
  • Range A typical content of active elements
  • range B possible content of active elements
  • range C too high content of active elements.
  • PwE is between 0.11 (T2 and T4) and 0.15 (T6 and T7).
  • V1090 and V1072 which did not add cerium mischmetal, ie Ce and La, but Y instead, show a lower relative burn time than T8, although V1090 at 0.10 has a slightly lower PwE but V1072 at 0, 18 has a higher PwE. Y does not appear to work as well as Ce and / or La, so replacement of SE by Y leads to a deterioration over the prior art. Further additions of Zr and Ti (V1074) or Zr and Hf (V1092, V1073, V1091, V1093) in different proportions have succeeded in achieving the service life of T8 again.
  • V771 to V777, V1070, V1071 have all been melted with cerium mischmetal, V1075 contains only La.
  • the experimental melts V1075 and V777 achieved the highest relative burning time of about 70% of these experimental melts.
  • the PwE of V777 is significantly larger at 0.36 than in V1075 at 0.20, which is at the limit of the PwE of the prior art alloys.
  • a similar good burning time was achieved with V777 with a combination of 0.06% Ce, 0.02% La, 0.03% Zr and 0.04% Ti.
  • V775 with 0.07% Ce and 0.03% La, 0.05% Y and 0.03% Hf with a PwE of 0.30 only has a relative burning time of 46%, indicating that additional doses of Y and Zr to Ce and La are not as effective.
  • Figure 2 is a plot of relative burn time and PwE to illustrate the previously described.
  • Figure 2 shows the relative burning time of the alloys T1 to T8 according to the prior art as a function of the nickel content.
  • the straight lines limit the scattering band in the relative burning time into which the alloys of the prior art fall as a function of the nickel content.
  • the trial alloy V1075 with the addition of the best acting element La. Their life is well above the scattering range.
  • Table 4b summarizes sagging along with the grain size of the wires.
  • the alloys of the prior art T1 to T8 show sagging between 4.5 and 6.2 mm at comparable grain sizes between 20 and 25 microns.
  • Figure 3 shows a plot of the nickel content. However, this does not seem to be decisive for sagging.
  • Figure 4 shows a plot of the alloys T1 to T8 and the experimental alloys on the C content. Since the experimental alloys have different particle sizes, they were divided into 2 classes: particle sizes from 19 to 26 ⁇ m and particle sizes from 11 to 16 ⁇ m. The alloys T1 to T8 and the trial alloys with a grain size of 19 microns to 26 microns, the comparable Grain sizes all show a similar sagging in the range of 4.5 to 6.2 mm. The experimental alloys, which have a particle size of 11 to 16 microns and a carbon content less than 0.042% have a larger Sagging of about 8 mm, as it is to be expected due to the smaller grain size. The experimental alloys with a grain size of 11 to 16 microns and a carbon content of greater than 0.044% unexpectedly show a lower sagging of 2.8 to 5 mm.
  • Figure 5 shows a plot of the alloys T1 to T8 and the experimental melts on the N content.
  • Figure 6 shows a plot over the sum C + N. It illustrates once again how C + N significantly reduce sagging.
  • a higher C- or N-content thus reduces sagging so much that the sagging-enhancing effect of a smaller grain size is not fully compensated.
  • the trial alloys have all been subjected to a standard heat treatment.
  • the alloy V777 shows the lowest sagging of all alloys. It has the highest C content and an N content in the upper third. A high C content therefore seems to be particularly effective in reducing sagging.
  • Nickel contents below 34% degrade the lifetime (relative burning time), the electrical resistivity and the ct value too much. Therefore, 34% is the lower limit for the nickel content. Too high nickel contents cause higher costs due to the high nickel price. Therefore, 42% should be the upper limit for the nickel content.
  • Too low Cr contents mean that the Cr concentration falls too fast below the critical limit. That is why 18% Cr is the lower limit for chromium. Too high Cr contents deteriorate the workability of the alloy. Therefore, 26% Cr is the upper limit.
  • 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 meaningful as explained in the examples.
  • 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%.
  • a minimum content of 0.01% C is necessary for good dimensional stability or low sagging. C is limited to 0.14% because this element reduces oxidation resistance and processability.
  • N A minimum content of 0.01% N is necessary 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 as it improves the processability of the material.
  • the threshold is set at 0.05%, so as not to soften the positive effect of this element.
  • the levels of sulfur and boron should be kept as low as possible, since these surface-active elements affect the 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)
  • Refinement Of Pig-Iron, Manufacture Of Cast Iron, And Steel Manufacture Other Than In Revolving Furnaces (AREA)
  • Continuous Casting (AREA)
  • Heat Treatment Of Steel (AREA)
  • Fuel Cell (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Treatment Of Steel In Its Molten State (AREA)
  • Conductive Materials (AREA)
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EP08706757A 2007-01-31 2008-01-15 Eisen-nickel-chrom-silizium-legierung Active EP2115179B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PL08706757T PL2115179T3 (pl) 2007-01-31 2008-01-15 Stop żelaza-niklu-chromu-krzemu

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102007005605A DE102007005605B4 (de) 2007-01-31 2007-01-31 Eisen-Nickel-Chrom-Silizium-Legierung
PCT/DE2008/000060 WO2008092419A2 (de) 2007-01-31 2008-01-15 Eisen-nickel-chrom-silizium-legierung

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EP2115179A2 EP2115179A2 (de) 2009-11-11
EP2115179B1 true EP2115179B1 (de) 2010-04-07

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US (1) US20090285717A1 (zh)
EP (1) EP2115179B1 (zh)
JP (1) JP5404420B2 (zh)
CN (1) CN101595236B (zh)
AT (1) ATE463589T1 (zh)
DE (2) DE102007005605B4 (zh)
ES (1) ES2341151T3 (zh)
MX (1) MX2009007535A (zh)
PL (1) PL2115179T3 (zh)
WO (1) WO2008092419A2 (zh)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102011077893A1 (de) 2011-06-21 2012-12-27 Robert Bosch Gmbh Verwendung einer heißgaskorrosionsbeständigen duktilen Legierung

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CN114000032A (zh) * 2014-02-13 2022-02-01 Vdm金属国际有限公司 无钛合金
CN104313395A (zh) * 2014-10-14 2015-01-28 杨雯雯 一种弹性合金
CN106567004B (zh) * 2016-11-08 2017-12-22 北京首钢吉泰安新材料有限公司 一种钢化玻璃炉用电热材料及其制取方法
CN107641735A (zh) * 2017-08-18 2018-01-30 南通聚星铸锻有限公司 一种电热丝的配方及其制备工艺
CN107699806A (zh) * 2017-11-20 2018-02-16 广西双宸贸易有限责任公司 一种铁基高温材料
CN108085569A (zh) * 2017-12-15 2018-05-29 重庆友拓汽车零部件有限公司 一种汽车用离合器盖的配方及其制备工艺
CN114231795A (zh) * 2021-12-23 2022-03-25 佛山市天禄智能装备科技有限公司 用于回转窑的耐高温合金的制备方法及回转窑窑体
DE102022110383A1 (de) 2022-04-28 2023-11-02 Vdm Metals International Gmbh Verwendung einer Nickel-Eisen-Chrom-Legierung mit hoher Beständigkeit in aufkohlenden und sulfidierenden und chlorierenden Umgebungen und gleichzeitig guter Verarbeitbarkeit und Festigkeit
DE102022110384A1 (de) 2022-04-28 2023-11-02 Vdm Metals International Gmbh Verwendung einer Nickel-Eisen-Chrom-Legierung mit hoher Beständigkeit in hoch korrosiven Umgebungen und gleichzeitig guter Verarbeitbarkeit und Festigkeit
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

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102011077893A1 (de) 2011-06-21 2012-12-27 Robert Bosch Gmbh Verwendung einer heißgaskorrosionsbeständigen duktilen Legierung
WO2012175271A2 (de) 2011-06-21 2012-12-27 Robert Bosch Gmbh Verwendung einer heissgaskorrosionsbeständigen duktilen legierung
WO2012175271A3 (de) * 2011-06-21 2013-09-26 Robert Bosch Gmbh Verwendung einer heissgaskorrosionsbeständigen duktilen legierung

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Publication number Publication date
ATE463589T1 (de) 2010-04-15
EP2115179A2 (de) 2009-11-11
WO2008092419A3 (de) 2008-10-16
MX2009007535A (es) 2009-08-20
ES2341151T3 (es) 2010-06-15
WO2008092419A2 (de) 2008-08-07
US20090285717A1 (en) 2009-11-19
DE502008000536D1 (de) 2010-05-20
JP2010516902A (ja) 2010-05-20
DE102007005605B4 (de) 2010-02-04
CN101595236B (zh) 2011-08-31
DE102007005605A1 (de) 2008-08-07
PL2115179T3 (pl) 2010-09-30
JP5404420B2 (ja) 2014-01-29
CN101595236A (zh) 2009-12-02

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