US20090285717A1 - Iron-Nickel-Chrome-Silicon-Alloy - Google Patents

Iron-Nickel-Chrome-Silicon-Alloy Download PDF

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US20090285717A1
US20090285717A1 US12/086,822 US8682208A US2009285717A1 US 20090285717 A1 US20090285717 A1 US 20090285717A1 US 8682208 A US8682208 A US 8682208A US 2009285717 A1 US2009285717 A1 US 2009285717A1
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alloy
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nickel
pwe
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Heike Hattendorf
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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 having improved service life and dimensional stability.
  • Austenitic iron-nickel-chromium-silicon alloys having different nickel, chromium, and silicon contents have been used for some time as heat conductors in temperatures ranging up to 1100° C.
  • This alloy group is standardized in DIN 17470 (Table 1) and ASTM B344-83 (Table 2).
  • Table 3 lists a number of commercially available alloys for this standard.
  • the chromium content is slowly consumed for building the protective layer. Therefore the service life is increased by a higher chromium content because a higher content of the element chromium, which forms the protective layer, delays the point in time at which the Cr content is below the critical limit and oxides other than Cr 2 O 3 form, which are e.g. iron-containing oxides.
  • EP-A 0 531 775 is a heat-resistant thermally moldable austenitic nickel alloy having the following composition (in % by weight):
  • EP-A 0 386 730 describes a nickel-chromium-iron alloy that has very good oxidation resistance and heat resistance as is desired for advanced heat conductor applications and that proceeds from the known heat conductor alloy NiCr6015 and in which it was possible to attain significant improvements in usage properties by adjusting to one another modifications made to the composition.
  • the alloy is distinguished from the known NiCr6015 material in particular in that the rare earth metals are replaced with yttrium, in that they also contain zirconium and titanium, and in that the nitrogen content is adjusted in a special manner to the zirconium and titanium content.
  • the creep mechanisms that have a negative impact on dimensional stability in the application temperature range are all influenced toward greater creep resistance by a large grain size (except for dislocation creep). Dislocation creep is not a function of grain size. Producing a wire with a large grain size increases creep resistance and therefore dimensional stability. Grain size should therefore also be considered as an important factor.
  • NiCr3020 and 35Ni, 20Cr (Table 1 and Table 2), which are distinguished by significantly lower costs, do not satisfactorily fulfill the service life requirements.
  • the object is thus to design an alloy that, with significantly lower nickel content than NiCr6015 and thus with significantly lower costs, has
  • This object is attained using an iron-nickel-chromium-silicon alloy having (in % by weight) 34 to 42% nickel, 18 to 26% chromium, 1.0 to 2.5% silicon, and additives 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, remainder iron and the usual impurities resulting from the production process.
  • this alloy Due to its special composition, this alloy has a longer service life than the alloys according to the prior art that have the same nickel and chromium content. In addition, with 0.04 to 0.10% carbon it is possible to attain increased dimensional stability and less sagging than with the alloys according to the prior art.
  • the range for the element nickel is between 34 and 42%, wherein, depending on employment, the nickel content can be as follows:
  • the chromium content is between 18 and 26%, wherein depending on the area of employment, here as well, the chromium content can be as follows:
  • the silicon content is between 1.0 and 2.5%, wherein, depending on the area of application, the defined content can be adjusted within the range:
  • the element aluminum is provided as an additive, specifically aluminum content is 0.05 to 1%. It can preferably also be adjusted as follows in the alloy:
  • the inventive subject-matter preferably proceeds from the fact that the material properties provided in the examples are largely adjusted by adding the element lanthanum for a lanthanum content of 0.01 to 0.26%. Depending on the area of application, defined values can be adjusted in the alloy here as well:
  • Carbon is added to the alloy analogously, specifically to attain carbon content between 0.01 and 0.14%. Content can be adjusted specifically as follows in the alloy:
  • Magnesium is also among the elements that can be added to attain magnesium content of 0.0005 to 0.05%. Specifically it is possible to adjust this element as follows in the alloy:
  • the elements sulfur and boron can be present in the alloy as follows:
  • the calcium content of the alloy can be between 0.005 and 0.07%, in particular 0.001 to 0.05% or 0.01 to 0.05%.
  • the alloy can moreover contain at least one of the elements Ce, Y, Zr, Hf, Ti at a content of 0.01 to 0.3%, which can also be defined additives as needed.
  • Additions of elements with an affinity for oxygen improve service life. They do this in that they are included in the oxide layer and there block the diffusion path of the oxygen on the grain boundaries.
  • the quantity of the element available for this mechanism must therefore be calibrated to the atomic weight in order to be able to compare the quantities of different elements to one another.
  • E is the element in question and X E is the content of the element in question in percent.
  • the alloy can contain 0.01 to 0.3% of one or more of the elements La, Ce, Y, Zr, Hf, Ti, wherein
  • the alloy can moreover have a phosphorous content between 0.01 to 0.20%, in particular 0.005 to 0.020%.
  • the alloy can contain between 0.01 and 1.0% of one or more of the elements Mo, W, V, Nb, Ta, Co, which can furthermore be limited as follows:
  • the elements copper, lead, zinc, and tin can be present as impurities in contents as follows:
  • the inventive alloy is to be used in electrical heating elements, in particular electrical heating elements that require high dimensional stability and not much sagging.
  • One specific application for the inventive alloy is its use in constructing furnaces.
  • Tables 4a and 4b depict industrial-scale melted iron-nickel-chromium-silicon alloys according to the prior art T1 through T7, an alloy melted on the laboratory scale according to the prior art T8, and a plurality of inventive test alloys V771 through V777, V1070 through V1076, V1090 through V1093, melted on the laboratory scale, for optimizing the alloy composition.
  • the heat conductor service life test is performed on wires having a 0.40 mm diameter.
  • the wire is clamped between 2 current supplies spaced 150 mm apart and heated by applying a voltage up to 1150° C. Heating at 1150° C. is performed for 2 minutes, then the current supply is interrupted for 15 seconds.
  • the burn time is sum of the “on” times during the service life of the wire.
  • the relative burn time tb is the % of the burn time for a reference batch.
  • the sagging behavior of heating coils at the application temperature is investigated in a sagging test.
  • coil sagging from the horizontal is determined after a certain period of time. The less sagging, the greater the dimensional stability and creep resistance of the material.
  • T1 and T2 are alloys having approx. 30% nickel, approx. 20% Cr, and approx. 2% Si. They contain additions of rare earths (SE), in this case cerium mixed metal, which means that SE comprises 60% Ce, approx. 35% La, and the remainder Pr and Nd. The relative burn time is 24% or 335%.
  • SE rare earths
  • Example T3 is an alloy having approx. 40% nickel, approx. 20% Cr, and approx. 1.3% Si. It contains additions of rare earths (SE), in this case cerium mixed metal, which means that SE is approx. 60% Ce, approx. 35% La, and the remainder Pr and Nd. The relative burn time is 72%.
  • SE rare earths
  • Examples T4 through T7 are alloys having approx. 60% nickel, approx. 16% Cr, and approx. 1.2-1.5% Si. They contain additions of rare earths (SE), in this case cerium mixed metal, which means that SE is approx. 60% Ce, approx. 35% La, and the remainder Pr and Nd.
  • SE rare earths
  • the relative burn time ranges from 100 to 130%.
  • Tables 4a and 4b contain a number of alloys melted on the laboratory scale.
  • the alloy according to the prior art T8 melted on the laboratory scale is an alloy having 36.2% nickel, 20.8% Cr, and 1.87% Si.
  • T1-T7 Like the industrially produced alloys T1-T7, it contains additions of rare earths (SE) in the form of cerium mixed metal, which means that SE is approx. 60% Ce, approx. 35% La, and the remainder Pr and Nd, and, apart from the Ni, Cr, and Si content, was melted in the same way as the industrial batches.
  • SE rare earths
  • the batches according to the prior art T1 through T8 are thus directly comparable.
  • the relative burn time for T8 is 53%.
  • Ce and La are added to V771 through V777, V1070, V1071, and V1076 by adding cerium mixed metal.
  • these batches therefore contain slight quantities of Pr and Nd, but these have not been explicitly added to Table 4a because the quantities are so small.
  • elements with an affinity for oxygen improve service life. They do this in that they are included in the oxide layer and there block the diffusion paths of the oxygen on the grain boundaries.
  • the quantity of the elements available for this mechanism must therefore be scaled to the atomic weight in order to be able to compare the quantities of different elements to one another.
  • E is the element in question and X E is the content of the element in question in percent.
  • FIG. 1 is a graphic depiction of the relative burn time tb and the potential PwE for the various alloys listed in Tables 4a and 4b.
  • Area A Usual content of effective elements
  • Area B possible content of effective elements
  • Area C content of effective elements is too high.
  • PwE is between 0.11 (T2 and T4) and 0.15 (T6 and T7).
  • V1090 and V1072 to which no cerium mixed metal was added, i.e. no Ce or La, but rather Y, demonstrate a shorter relative burn time than T8, although, at 0.10, V1090 has a slightly lower PwE, but, at 0.18, V1072 has a greater PwE.
  • the effect of Y does not seem to be as good as that of Ce and/or La, so that replacing Se with Y leads to worse results compared to the prior art.
  • Zr and Ti V1074) or Zr and Hf(V1092, V1073, V1091, V1093) in different quantities it was possible to attain the service life for T8.
  • Test melts V771 through V777, V1070, V1071 were all melted with cerium mixed metal, V1075 contains only La. Of these test melts, test melts V1075 and V777 attained the highest relative burn time, approx. 70%. At 0.36, the PwE of V777 is significantly greater than in V1075, at 0.20, which is on the edge of the PwE for the alloys according to the prior art. It is thus apparent that a high quantity of elements with an affinity to oxygen is not critical for attaining a high relative burn time, but rather it is much more important to add defined elements with an affinity to oxygen. V77 attained a similarly good relative burn time with a combination of 0.06% Ce, 0.02% La, 0.03% Zr, and 0.04% Ti.
  • V1071 has the same content of Ce, La, and Zr as V777, but its T1 content is significantly higher, which means a PwE of 0.44 and, in comparison to V777, a significantly lower burn time of only 49%.
  • V775 has a relative burn time of only 46%, which indicates that adding Y and Zr to Ce and La is not very effective.
  • FIG. 2 is a graphic depiction of the relative burn time and PwE to help clarify the information in the foregoing.
  • FIG. 2 depicts the relative burn times for the alloys T1 through T8 according to the prior art as a function of the nickel content.
  • the straight lines limit the relative burn time scatter band into which the alloys according to the prior art fall as a function of nickel content.
  • test alloy V1075 with the addition of the most effective element, La. Its service life is clearly above the scatter band.
  • Table 4b summarizes sagging and the grain size of the wires.
  • the alloys according to the prior art T1 through T8 exhibit sagging between 4.5 and 6.2 mm with comparable grain sizes between 20 and 25 ⁇ m.
  • FIG. 3 plots nickel content. However, nickel content does not appear critical for sagging.
  • FIG. 4 plots C content for alloys T1 through T8 and the test alloys. Since the test alloys have different grain sizes, they were divided into 2 categories: grain sizes of 19 to 26 ⁇ m and grain sizes of 11 to 16 ⁇ m. The alloys T1 through T8 and the test alloys having a grain size of 19 ⁇ m to 26 ⁇ m that have comparable grain sizes all exhibit similar sagging, ranging from 4.5 to 6.2 mm. The test alloys that have a grain size of 11 to 16 ⁇ m and a carbon content less than 0.042% exhibit greater sagging, approx. 8 mm, as is to be expected due to the smaller grain size. The test alloys having a grain size of 11 to 16 ⁇ m and a carbon content greater than 0.044% unexpectedly exhibit less sagging, 2.8 to 5 mm.
  • FIG. 5 plots N content for the alloys T1 through T8 and the test melts.
  • the alloys T1 through T8 and the test alloys having a grain size of 19 ⁇ m to 26 ⁇ m that all have comparable grain sizes exhibit reduced sagging as the N content rises.
  • the test alloys that have a grain size of 11 to 16 ⁇ m and an N content less than 0.010% exhibit greater sagging than all of the alloys having a grain size of 19 to 26 ⁇ m.
  • FIG. 6 plots the total C+N. It again illustrates how C+N together significantly reduce sagging.
  • the test alloys that have a grain size of 11 to 16 ⁇ m and a C+N content less than 0.060% exhibit greater sagging than all of the alloys having a grain size of 19 to 26 ⁇ m.
  • test alloys having a grain size from 11 to 16 ⁇ m and a C+N content greater than 0.09%, comprising a carbon content greater than 0.044% and at the same time a nitrogen content greater than 0.045%, unexpectedly exhibit sagging equal to or less than all alloys having a grain size of 19 to 26 ⁇ m.
  • test alloys were all subjected to a standard heat treatment.
  • the alloy V777 exhibits the least sagging of all of the alloys. It has the highest C content and the N content is in the top third. High C content consequently seems particularly effective in reducing sagging.
  • Nickel contents below 34% have too negative an impact on service life (relative burn times), the specific electrical resistance, and the ct value. Therefore 34% is the lower limit for nickel content. Nickel content that is too high increases costs due to the high cost of nickel. Therefore 42% should be the upper limit for nickel content.
  • Cr content that is too low means that the Cr concentration drops below the critical limit too fast. Therefore 18% Cr is the lower limit for chromium. Cr content that is too high has a negative impact on the processability of the alloy. Therefore 26% Cr is the upper limit.
  • Formation of a silicon oxide layer beneath the chromium oxide layer reduces the oxidation rate. Below 1% the silicon oxide layer has too many gaps to attain its full potential. Si content that is too high has a negative effect on the processability of the alloy. Therefore an Si content of 2.5% is the upper limit.
  • a minimum content of 0.01% La is necessary to retain the effect of the La, which increases oxidation resistance.
  • the upper limit is 0.26%, which corresponds to a PwE of 0.38. Greater PwE values do not make sense, as explained in the examples.
  • Al is required for improving the processability of the alloy. Therefore a minimum content of 0.05% is necessary. If the content is too high, this has a negative effect on processability. The Al content is therefore limited to 1%.
  • a minimum content of 0.01% C is necessary for good dimensional stability and 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 and low sagging. N is limited to 0.14% because this element reduces oxidation resistance and processability.
  • Mg a minimum content of 0.001% is necessary because this improves the processability of the material.
  • the limit is set at 0.05% in order not to soften the positive effect of this element.
  • the sulfur and boron content should be kept as low as possible because these surfactant elements have a negative effect on oxidation resistance. Therefore limits are set at max. 0.01% S and max. 0.005% B.
  • Copper is limited to max. 1% because this element reduces oxidation resistance.
  • Pb is limited to max. 0.002% because this element reduces oxygen resistance. The same applies to Sn.
  • a minimum content of 0.01% Mn is necessary for improving processability.
  • Manganese is limited to 1% because this element reduces oxidation resistance.
  • Chg Batch Variant Chg Tb in % Ni Cr Si Al Mn Se Ce La Zr Y Hf Cronifer III T1 24 30.7 20.3 2.05 0.05 0.34 0.10 ⁇ 0.01 ⁇ Cronifer III T2 35 31.0 21.0 2.13 0.06 0.37 0.08 ⁇ 0.01 ⁇ Ni40Cr20Si T3 72 41.6 20.7 1.36 0.31 0.46 0.06 ⁇ 0.01 0 Cronifer II T4 97 59.2 16.2 1.23 0.30 0.30 0.08 ⁇ 0.01 0 Cronifer II T5 106 59.5 16.1 1.5 0.22 0.25 0.05 0.01 0 Cronifer II T6 122 59.1 16.2 1.41 0.28 0.26 0.06 0.01 0 Cronifer II T7 128 59.4 16.1 1.26 0.30 0.29 0.06 0.01 0 Ni36Cr20Si T8 53 36.2 20.8 1.87 0.03 0.43 0.08 0.06 0.02 ⁇ 0.01 ⁇ 0.01 ⁇ 0.01 ⁇ Ni36Cr20S
  • TABLE 4b continued: Relative burn time tb and composition of test batches (batch no. begins with V) and batches according to the prior art (T1 through T8). Provided in % by weight.
  • Tb Sagging KG Variant Variant Chg in % in mm in ⁇ m
  • C N P S Mo B Co Nb Cronifer III Cronifer III T1 24 0.036 0.047 0.011 0.002 0.04 0.001 0.05 ⁇ 0.
  • Cronifer III Cronifer III T2 35 0.047 0.043 0.01 0.002 0.03 0.001 0.08 ⁇ 0.

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  • Refinement Of Pig-Iron, Manufacture Of Cast Iron, And Steel Manufacture Other Than In Revolving Furnaces (AREA)
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US12/086,822 2007-01-31 2008-01-15 Iron-Nickel-Chrome-Silicon-Alloy Abandoned US20090285717A1 (en)

Applications Claiming Priority (3)

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DE102007005605.4 2007-01-31
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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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)
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US10174397B2 (en) 2014-02-13 2019-01-08 Vdm Metals International Gmbh Titanium-free alloy
WO2023208278A1 (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

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DE102011077893A1 (de) 2011-06-21 2012-12-27 Robert Bosch Gmbh Verwendung einer heißgaskorrosionsbeständigen duktilen Legierung
CN104313395A (zh) * 2014-10-14 2015-01-28 杨雯雯 一种弹性合金
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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
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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MX2009007535A (es) 2009-08-20
ES2341151T3 (es) 2010-06-15
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JP2010516902A (ja) 2010-05-20
DE102007005605B4 (de) 2010-02-04
CN101595236B (zh) 2011-08-31
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