US20100172790A1 - Iron-nickel-chromium-silicon alloy - Google Patents

Iron-nickel-chromium-silicon alloy Download PDF

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Publication number
US20100172790A1
US20100172790A1 US12/646,756 US64675609A US2010172790A1 US 20100172790 A1 US20100172790 A1 US 20100172790A1 US 64675609 A US64675609 A US 64675609A US 2010172790 A1 US2010172790 A1 US 2010172790A1
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Prior art keywords
alloy
content
accordance
weight
nickel
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US12/646,756
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English (en)
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Heike Hattendorf
Juergen Webelsiep
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VDM Metals GmbH
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ThyssenKrupp VDM GmbH
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Assigned to THYSSENKRUPP VDM GMBH reassignment THYSSENKRUPP VDM GMBH ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: WEBELSIEP, JUERGEN, HATTENDORF, HEIKE
Publication of US20100172790A1 publication Critical patent/US20100172790A1/en
Assigned to OUTOKUMPU VDM GMBH reassignment OUTOKUMPU VDM GMBH CHANGE OF NAME (SEE DOCUMENT FOR DETAILS). Assignors: THYSSENKRUPP VDM GMBH
Priority to US13/837,325 priority Critical patent/US20130200068A1/en
Abandoned legal-status Critical Current

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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 having a longer service life and enhanced 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 the temperature range up to 1100° C.
  • This alloy group is standardized in DIN 17470 (Table 1) and ASTM B344-01 (Table 2) for use as heat conductor alloys.
  • ASTM B344-01 Table 2
  • the chromium content is slowly depleted for building up the protective layer. Therefore a higher chromium content increases service life since a higher content of chromium, the element that forms the protective layer, delays the point in time at which the Cr content drops below the critical limit and oxides other than Cr 2 O 3 form, which are e.g. iron-containing ferrous oxides.
  • EP-A 0 531 775 is a heat-resistant hot-formable austenitic nickel alloy having the following composition (in wt. %):
  • EP-A 0 386 730 describes a nickel-chromium-iron alloy having very good oxidation resistance and thermal strength, these being desired for advanced heat conductor applications that proceed from the known heat conductor alloy NiCr6015 and in which significant improvements in the usage properties could be attained using modifications to the composition that were matched to one another.
  • the alloy is distinguished from the known NiCr6015 material especially in that the rare earth metals are replaced by yttrium, in that it also includes zirconium and titanium, and in that the nitrogen content is matched to the content of zirconium and titanium in a special manner.
  • WO-A 2005/031018 describes an austenitic Fe—Cr—Ni alloy for use in the high temperature range that essentially has the following chemical composition (in wt. %):
  • dislocation creep Apart from dislocation creep, the creep mechanisms that have a negative impact on dimensional stability in the application temperature range (dislocation creep, grain boundary slip, and diffusion creep) are all influenced by a large grain size to have greater creep resistance. Displacement creep is not solely a function of grain size. Producing a wire having a larger grain size increases creep resistance and thus dimensional stability. In any considerations grain size should therefore be included as a factor that has significant influence.
  • heat conductor material Also important for a heat conductor material is the greatest possible specific electrical resistance and the lowest possible change in the ratio of heat resistance/cold resistance to temperature (temperature coefficient ct).
  • the underlying object of the invention is to design alloys with contents of nickel, chromium, and Si similar to the alloys in accordance with the prior art in Tables 1 and 2, but that have
  • This object is attained using an iron-nickel-chromium-silicon alloy having (in wt. %) 19 to 34% or 42 to 87% nickel, 12 to 26% chromium, 0.75 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, 0.04 to 0.14% carbon, 0.02 to 0.14% nitrogen, moreover including 0.0005 to 0.07% Ca, 0.002 to 0.020% P, max. 0.01% sulfur, max. 0.005% B, the remainder iron and the usual process-related impurities.
  • these alloys Due to their special composition, these alloys have a longer service life than the alloys in accordance with the prior art that have comparable nickel and chromium contents. In addition, it is possible to attain enhanced dimensional stability and less sagging than the alloys in accordance with the prior art.
  • FIG. 1 is a plot of relative burn time as a function of La content
  • FIG. 2 is a plot of sagging as a function of N content
  • FIG. 3 is a plot of sagging as a function of C content.
  • the range for the element nickel is either between 19 to 34% or 42 to 87%, the following nickel contents being possible depending on use and being adjusted in the alloy regardless of the use.
  • Preferred Ni ranges between 19 and 34% are provided as follows:
  • Preferred Ni ranges between 42 and 87% are provided as follows:
  • the chromium content is between 12 and 26%, it being possible for there to be chromium content as follows, again depending on the area in which the alloy will be employed:
  • the silicon content is between 0.75 and 2.5%, it being possible to adjust defined contents within the range depending on the area of application:
  • the element aluminum is provided as an additive, specifically in contents of 0.05 to 1%. It can preferably be adjusted in the alloy as follows:
  • inventive subject matter preferably proceeds from the fact that the material properties provided in the examples are essentially adjusted with the addition of the element lanthanum in contents of 0.01 to 0.26%. In this case, as well, defined values can be adjusted in the alloy, depending on the area of application:
  • Carbon is added to the alloy in the same manner, in contents between 0.04 and 0.14%. Specifically content can be adjusted in the alloy as follows:
  • Magnesium is also among the added elements, in contents of 0.0005 to 0.05%. Specifically, it is possible to adjust this element in the alloy as follows:
  • the alloy can include calcium in contents between 0.0005 and 0.07%, especially 0.001 to 0.05% or 0.01 to 0.05%.
  • the alloy can include phosphorus in contents between 0.002 and 0.020%, especially 0.005 to 0.02%.
  • the elements sulfur and boron can be in the alloy as follows:
  • the alloy can moreover include at least one of the elements Ce, Y, Zr, Hf, Ti, with contents of 0.01 to 0.3%, wherein when needed the elements may also be defined additives,
  • E is the element in question and X E is the content of the element in question in percent.
  • the alloy can include 0.01 to 0.3% of one or a plurality of the elements La, Ce, Y, Zr, Hf, Ti, whereby
  • the alloy can contain between 0.01 to 1.0% of one or a plurality of the elements Mo, W, V, Nb, Ta, Co, which can additionally be further limited as follows:
  • the inventive alloy should preferably be used for employment in electrical heating elements, especially in electrical heating elements that require good dimensional stability and low sagging.
  • Another specific application for the inventive alloy is use in furnace construction.
  • the heat conductor service life test is performed on wires that have a diameter of 0.40 mm.
  • the wire is clamped between 2 power supplies spaced 150 mm apart and is heated to 1150° C. by applying a voltage. Each heating interval to 1150° C. is performed for 2 minutes and then the power supply is interrupted for 15 seconds.
  • the wire fails at the end of its service life in that the rest of the cross-section melts through.
  • the burn time is the sum of the “On” times during the service life of the wire.
  • the relative burn time tb is this figure as a percentage of the burn time for a reference lot.
  • the sagging behavior of heating coils at the application temperature is investigated in a sagging test.
  • the sagging of heating coils from the horizontal is determined after a certain period of time. The less sagging there is, the greater the dimensional stability or creep resistance of the material.
  • soft annealed wire having a diameter of 1.29 mm is wound into spirals that have an interior diameter of 14 mm.
  • a total of 6 heating coils are produced, each coil having 31 windings. All heating coils are brought to a uniform starting temperature of 1000° C. at the beginning of the test. The temperature is measured with a pyrometer. The test is performed at constant voltage with a switching cycle of 30 s “On”/30 s “Off”. The test concludes after 4 hours. After the heating coils have cooled, the sagging of the individual windings from the horizontal is measured and the mean of the 6 readings for the heating coils is found.
  • FIG. 1 depicts the relative burn time as a function of La content, adjusted for the effects of Ni, Cr, and Si content. It can be seen that the relative burn time increases sharply as La content increases. An La content of 0.04 to 0.15% is particularly advantageous.
  • FIG. 2 depicts how sagging is a function of N content, adjusted for the effects of Ni, Cr, Si and C content. It is already evident that sagging drops sharply as N content increases. An N content of 0.05 to 0.09% is especially advantageous.
  • FIG. 3 indicates how sagging is a function of C content, adjusted for the effects of Ni, Cr, Si and N content. It is evident that sagging drops sharply as C content increases. C content of 0.04 to 0.10% is especially advantageous.
  • Alloys having a low nickel content are particularly cost-effective. Therefore the alloys in the range from 19% to 34% Ni are of great interest, despite the worse temperature coefficients and lower specific electrical resistances in comparison to alloys with higher nickel content.
  • the upper limit for the alloys having a low nickel content should be 34% (variant 1).
  • the temperature coefficient increasingly improves with greater than 42% Ni.
  • the specific electrical resistance is higher, as well.
  • the nickel portion compared to alloys having high nickel content is relatively low, approx. 80%. Therefore 42% is a reasonable lower limit for the alloys having a higher nickel content (variant 2).
  • Alloys with more than 87% no longer include enough Cr and Si to have adequate oxidation resistance.
  • the upper limit for nickel content is therefore 87%.
  • Cr content that is too low means that the Cr concentration drops below the critical limit too rapidly.
  • the lower limit for chromium is therefore 12%.
  • Cr content that is too high has a negative impact on the alloy's processability.
  • the upper limit for Cr should therefore be 26%.
  • a minimum content of 0.01% La is necessary to retain the effect La has of increasing oxidation resistance.
  • the upper limit is set at 0.26%, which equals a PwE of 0.38. Greater values for PwE do not make sense in this case.
  • Al is required for improving the processability of the alloy. A minimum content of 0.05% is therefore necessary. A content that is too high again has a negative effect on processability. Al content is therefore limited to 1%.
  • a minimum content of 0.04% 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 0.02% N is necessary for good dimensional stability and low sagging. N is limited to 0.14% because this element reduces oxidation resistance and processability.
  • a minimum content of 0.0005% Mg is necessary; it improves the processability of the material.
  • the limit is set at 0.05% because too much Mg has proved to have a negative effect.
  • a minimum content of 0.0005% Ca is necessary because it enhances the processability of the material.
  • the limit is established at 0.07% because too much CA has proved to have a negative effect.
  • the sulfur and boron contents should be kept as low as possible because these surfactant elements have a negative effect on oxidation resistance. Therefore max. 0.01% S and max. 0.005% B are established.
  • Copper is limited to max. 1% because this element reduces oxidation resistance.
  • Pb is limited to max. 0.002% because this element reduces oxidation resistance. The same applies to Sn.
  • a minimum content of 0.01% Mn is necessary for enhancing processability.
  • Manganese is limited to 1% because this element also reduces oxidation resistance.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
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  • Soft Magnetic Materials (AREA)
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US12/646,756 2007-06-26 2009-12-23 Iron-nickel-chromium-silicon alloy Abandoned US20100172790A1 (en)

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

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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)
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WO2015038406A1 (en) * 2013-09-13 2015-03-19 Eaton Corporation Wear resistant alloy
US20200396803A1 (en) * 2019-06-12 2020-12-17 Lg Electronics Inc. Surface type heating element and manufacturing method thereof

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JP2022049630A (ja) * 2020-09-16 2022-03-29 優章 荒井 発熱体
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JP5447864B2 (ja) 2014-03-19
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US20130200068A1 (en) 2013-08-08
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EP2162558B1 (de) 2017-08-09
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MX2009013253A (es) 2010-01-25
DE102007029400A1 (de) 2009-01-02
SI2162558T1 (sl) 2017-11-30
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BRPI0813917A8 (pt) 2016-05-03
JP2013177691A (ja) 2013-09-09

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