CA3020420A1 - Ferritic alloy - Google Patents

Ferritic alloy Download PDF

Info

Publication number
CA3020420A1
CA3020420A1 CA3020420A CA3020420A CA3020420A1 CA 3020420 A1 CA3020420 A1 CA 3020420A1 CA 3020420 A CA3020420 A CA 3020420A CA 3020420 A CA3020420 A CA 3020420A CA 3020420 A1 CA3020420 A1 CA 3020420A1
Authority
CA
Canada
Prior art keywords
ferritic alloy
alloy according
alloy
weight
ferritic
Prior art date
Legal status (The legal status 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 status listed.)
Granted
Application number
CA3020420A
Other languages
French (fr)
Other versions
CA3020420C (en
Inventor
Bo Jonsson
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Kanthal AB
Original Assignee
Sandvik Intellectual Property AB
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
Application filed by Sandvik Intellectual Property AB filed Critical Sandvik Intellectual Property AB
Publication of CA3020420A1 publication Critical patent/CA3020420A1/en
Application granted granted Critical
Publication of CA3020420C publication Critical patent/CA3020420C/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/06Ferrous alloys, e.g. steel alloys containing aluminium
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C1/00Making non-ferrous alloys
    • C22C1/02Making non-ferrous alloys by melting
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/001Ferrous alloys, e.g. steel alloys containing N
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/005Ferrous alloys, e.g. steel alloys containing rare earths, i.e. Sc, Y, Lanthanides
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/02Ferrous alloys, e.g. steel alloys containing silicon
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/04Ferrous alloys, e.g. steel alloys containing manganese
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/18Ferrous alloys, e.g. steel alloys containing chromium
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/18Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/22Ferrous alloys, e.g. steel alloys containing chromium with molybdenum or tungsten
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/18Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/28Ferrous alloys, e.g. steel alloys containing chromium with titanium or zirconium
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/18Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/34Ferrous alloys, e.g. steel alloys containing chromium with more than 1.5% by weight of silicon
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/18Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/44Ferrous alloys, e.g. steel alloys containing chromium with nickel with molybdenum or tungsten
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/18Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/50Ferrous alloys, e.g. steel alloys containing chromium with nickel with titanium or zirconium
    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C30/00Coating with metallic material characterised only by the composition of the metallic material, i.e. not characterised by the coating process
    • CCHEMISTRY; METALLURGY
    • C21METALLURGY OF IRON
    • C21DMODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D2211/00Microstructure comprising significant phases
    • C21D2211/005Ferrite

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Heat Treatment Of Sheet Steel (AREA)
  • Powder Metallurgy (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Fuel Cell (AREA)
  • Catalysts (AREA)

Abstract

A ferritic alloy comprising the following elements in weight% [wt%] C 0.01 to 0.1; N: 0.001 to 0.1; O: = 0.2; Cr 4 to 15; Al 2 to 6; Si 0.5 to 3; Mn: = 0.4; Mo + W = 4; Y = 1.0; Sc, Ce, and/or La = 0.2; Zr = 0.40; RE = 0.4; balance Fe and normal occurring impurities and also fulfilling the following equation has to be fulfilled: 0.014 = (Al + 0.5SQ (Cr + 10Si + 0.1) = 0.022.

Description

Ferritic alloy Technical field The present disclosure relates to a ferritic alloy according to the preamble of claim 1. The present disclosure further relates to use of the ferritic alloy and to objects or coatings manufactured thereof.
Background and introduction Ferritic alloys, such as FeCrAl-alloys comprising chromium (Cr) levels of 15 to 25 wt%
and aluminium (Al) levels from 3 to 6 wt% are well known for their ability to form protective a-alumina (A1203), aluminium oxide, scales when exposed to temperatures between 900 and 1300 C. The lower limit of Al content to form and maintain the alumina scale varies with exposure conditions. However, the effect of a too low Al level at higher temperatures is that the selective oxidation of Al will fail and less stable and less protective scales based on chromium and iron will be formed.
It is commonly agreed that FeCrAl alloys will normally not form the protective a-alumina layer if exposed to temperatures below about 900 C. There have been attempts to optimize the compositions of FeCrAl alloys so that they will form the protective a-alumina at temperature below about 900 C. However, in general, these attempts have not been very successful because the diffusion of oxygen and aluminium to the oxide-metal interface will be relatively slow at lower temperatures and thereby the rate of formation of the alumina scale will be low, which means that there will be a risk of severe corrosion attacks and formation of less stable oxides.
Another problem arising at lower temperature, i.e. temperatures below 900 C, is a long term embrittlement phenomena arising from a low temperature miscibility gap for Cr in the FeCrAl alloy system. The miscibility gap exists for Cr levels above approximately 12 wt% at 550 C. Recently, alloys with lower Cr levels of about 10 to 12 wt% Cr have been developed in order to avoid this phenomenon. This group of alloys has been found to work very well in molten lead at controlled and low pressure 02.
2 EP 0 475 420 relates to a rapidly solidified ferritic alloy foil essentially consisting of Cr, Al, Si, about 1.5 to 3 wt % and REM (Y, Ce, La, Pr, Nd, the balance being Fe and impurities. The foil may further contain about 0.001 to 0.5 wt % of at least one element selected from the group consisting of Ti, Nb, Zr and V. The foil has a grain size of not more than about 10 gm. EP 075 420 discusses Si additions in order to improve the flow properties of the alloy melt but the success was limited due to reduced ductility.
EP 0091 526 relates to thermal cyclic oxidation resistant and hot workable alloys, more particularly, to iron-chromium-aluminium alloys with rare earth additions. In oxidation, the alloys will produce a whisker-textured oxide that is desirable on catalytic converter surfaces. However, the obtained alloys did not provide a high temperature resistance.
Hence, there is still a need to further improve the corrosion resistance of ferritic alloys so that they can be used in corrosive environments during high temperature conditions. The aspects of the present disclosure are to solve or at least reduce the above-mentioned problems.
Summary of the disclosure The present disclosure therefore relates to a ferritic alloy, which will provide a combination of good oxidation resistance and an excellent ductility, comprising the following composition in weight% (wt%):
C 0.01 to 0.1;
N: 0.001 - 0.1;
0: 0.2;
Cr 4 to 15;
Al 2 to 6;
Si 0.5 to 3;
Mn: <0.4;
Mo + W < 4.
_ , Y <1.0;
3 Sc, Ce, and/or La < 0.2;
Zr < 0.40;
RE <1.0;
balance Fe and normal occurring impurities and also fulfilling the following equation has to be fulfilled:
0.014 < (Al + 0.5Si)(Cr + 10Si + 0.1) < 0.022.
Thus, there exists a relationship between the content of Cr and Si and Al in the alloy according to the present disclosure, which if fulfilled will provide an alloy having excellent oxidation resistance and ductility and also a reduced brittleness in combination with increased high temperature corrosion resistance.
The present disclosure also relates to an object and/or a coating comprising the ferritic alloy according to the present disclosure. Additionally, the present disclosure also relates to the use of the ferritic alloy as defined hereinabove or hereinafter for manufacturing an object and/or a coating.
Brief description of the figures Figure la and Figure lb disclose the phases in Fe-10%Cr-5%Al vs. Si level (figure la) and Fe-20%Cr-5%Al vs. Si level (figure lb). The diagram has been made by using Database TCFE7 and Thermocalc software.
Figures 2a to e disclose polished sections of two alloys according to the present disclosure compared to three reference alloys after exposure to 50 times 1 hour cycles at 850 C exposed to biomass (wood pellets) ash containing large amounts of potassium.
Detailed description of the disclosure As already stated above, the present disclosure provides a ferritic alloy comprising in weight% (wt%):
4 C 0.01 to 0.1;
N: 0.001 - 0.1;
0: 0.2;
Cr 4 to 15;
Al 2 to 6;
Si 0.5 to 3;
Mn: <0.4;
Mo + W < 4;
Y <1.0;
Sc, Ce, and/or La < 0.2;
Zr <0.40;
RE <1.0;
balance Fe and normal occurring impurities and also fulfilling the following equation has to be fulfilled:
0.014 < (Al + 0.5Si)(Cr +10Si + 0.1) < 0.022.
It has surprisingly been found that an alloy as defined hereinabove or hereinafter, i.e.
containing the alloying elements and in the ranges mentioned herein, unexpectedly will form a protective surface layer containing aluminium rich oxide even at chromium levels as low as 4 wt%. This is very important both for the workability and for the long term phase stability of the alloy as the undesirable brittle G-phase, after exposure for long time in the herein mentioned temperature range, will be reduced or even avoided.
Thus, the interaction between Si and Al and Cr will enhance the formation of a stable and continuous protective surface layer containing aluminium rich oxide, and by using the above equation, it will be possible to add Si and still obtain a ferritic alloy which will be possible both to produce and to form into different objects. The inventor has surprisingly found that if the amounts of Si and Al and Cr are balanced so that the following condition is fulfilled (all the numbers of the elements are in weight fractions):
0.014 < (Al + 0.5Si)(Cr +10Si + 0.1) < 0.022, the obtained alloy will have a combination of excellent oxidation resistance and workability and formability within the Cr range of the present disclosure.
According to one embodiment, 0.015< (Al + 0.5Si)(Cr +10Si + 0.1) <0.021, such as 0.016<

(Al + 0.5SO(Cr + 10Si + 0.1) 0.020, such as 0.017 (Al + 0.5Si)(Cr + 10Si +
0.1) < 0.019.
The ferritic alloy of the present disclosure is especially useful at temperatures below
5 about 900 C since a protective surface layer containing aluminium rich oxide will be formed on an object and/or a coating made of said alloy, which will prevent corrosion, oxidation and embrittlement of the object and/or the coating. Furthermore, the present ferritic alloy may provide protection against corrosion, oxidation and embrittlement at temperatures as low as 400 C as a protective surface layer containing aluminium rich oxide will be formed on the surface of the object and/or coating manufactured thereof Additionally, the alloy according to the present disclosure will also work excellent at temperatures up to about 1100 C and it will show a reduced tendency for long-term embrittlement in the temperature range of 400 to 600 C.
The present alloy may be used in the form of a coating. Additionally, an object may also comprise the present alloy. According to the present disclosure, the term "coating" is intended to refer to embodiments in which the ferritic alloy according to the present disclosure is present in form of a layer exposed to a corrosive environment that is in contact with a base material, regardless of the means and methods to accomplish it, and regardless of the relative thickness relation between the layer and the base material.
Hence, examples of this but not limited to is a PVD coating, a cladding or a compound or composite material. The aim of the alloy is that is should protect the material underneath from both corrosion and oxidation. Examples, but not limited to, of suitable objects is a compound tube, a tube, a boiler, a gas turbine component and a steam turbine component.
Other examples include a superheater, a water wall in a power plant, a component in a vessel or a heat exchanger (for example for reforming or other processing of hydrocarbons or gases containing CO/CO2), a component used in connection with industrial heat treatment of steel and aluminium, powder metallurgy processes, gas and electric heating elements.
6 Furthermore, the alloy according to the disclosure is suitable to be used in environments having corrosive conditions. Examples of such environments include but are not limited exposure to salts, liquid lead and other metals, exposures to ash or high carbon content deposits, combustion atmospheres, atmospheres with low p02 and/or high N2 and/or high carbon activity environments.
Additionally, the present ferritic alloy may be manufactured by using normally occurring solidification rates ranging from conventional metallurgy to rapid solidification. The present alloy will also be suitable for manufacturing all types of objects both forged and extruded, such as a wire, a strip, a bar and a plate. The amount of hot and cold plastic deformation as well as grain structure and grain size will, as the person skilled in the art know vary between the forms of the objects and the production route.
The functions and effects of essential alloying elements of the alloy defined hereinabove and hereinafter will be presented in the following paragraphs. The listing of functions and effects of the respective alloying elements is not to be seen as complete as there may be further functions and effects of said alloying elements.
Carbon (C) Carbon may be present as an unavoidable impurity resulting from the production process.
Carbon may also be included in the ferritic alloy as defined hereinabove or hereinafter to increase strength by precipitation hardening. To have a noticeable effect on the strength in the alloy, carbon should be present in an amount of at least 0.01 wt%. At too high levels, carbon may result in difficulties to form the material and also a negative effect on the corrosion resistance. Therefore, the maximum amount of carbon is 0.1 wt%.
For example, the content of carbon is 0.02 ¨ 0.09 wt%, such as 0.02 ¨ 0.08 wt%, such as 0.02 ¨ 0.07 wt% such as 0.02 ¨ 0.06 wt% such as 0.02 ¨ 0.05 wt%, such as 0.01 ¨
0.04 wt%.
Nitrogen (N) Nitrogen may be present as an unavoidable impurity resulting from the production process. Nitrogen may also be included in the ferritic alloy as defined hereinabove or
7 hereinafter to increase strength by precipitation hardening, in particular when a powder metallurgical process route is applied. At too high levels, nitrogen may result in difficulties to form the alloy and also have a negative effect on the corrosion resistance.
Therefore, the maximum amount of nitrogen is 0.1 wt%. Suitable ranges of nitrogen are for example 0.001 ¨ 0.08 wt%, such as 0.001 ¨ 0.05 wt%, such as 0.001 ¨ 0.04 wt%, such as 0.001 ¨ 0.03 wt%, such as 0.001 ¨ 0.02 wt%.
Oxygen (0) Oxygen may exist in the alloy as defined hereinabove or hereinafter as an impurity resulting from the production process. In that case, the amount of oxygen may be up to 0.02 wt%, such as up to 0.005 wt%. If oxygen is added deliberately to provide strength by dispersion strengthening, as when manufacturing the alloy through a powder metallurgical process route, the alloy as defined hereinabove or hereinafter, comprises up to or equal to 0.2 wt% oxygen.
Chromium (Cr) Chromium is present in the present alloy primarily as a matrix solid solution element.
Chromium promotes the formation of the aluminium oxide layer on the alloy through the so-called third element effect, i.e. by formation of chromium oxide in the transient oxidation stage. Chromium shall be present in the alloy as defined hereinabove or hereinafter in an amount of at least 4 wt% to fulfill this purpose. In the present inventive alloy, Cr also enhances the susceptibility to form brittle 05 phase and Cr3Si.
This effect emerges at around 12 wt% and is enhanced at levels above 15 wt%, therefore the limit of Cr is 15 wt%. Also from oxidation point of view, higher levels than 15 wt%
will result in an undesirable contribution of Cr into the protective oxide scales. According to one embodiment, the content of Cr is 5 to 13 wt%, such as 5 to 12 wt%, such as 6 to 12 wt%, such as 7 to 11 wt%, such as 8 to 10 wt%.
Aluminium (Al) Aluminium is an important element in the alloy as defined hereinabove or hereinafter.
Aluminium, when exposed to oxygen at high temperature, will form the dense and thin
8 oxide, A1203, through selective oxidation, which will protect the underlying alloy surface from further oxidation. The amount of aluminium should be at least 2 wt% to ensure that a protective surface layer containing aluminium rich oxide is formed and also to ensure that sufficient aluminium is present to heal the protective surface layer when damaged.
However, aluminium has a negative impact on the formability and high amounts of aluminium may result in the formation of cracks in the alloy during mechanical working thereof Consequently, the amount of aluminium should not exceed 6 wt%. For example, aluminium may be 3 ¨ 5 wt%, such as 2.5 ¨4.5 wt%, such as 3 to 4 wt%.
Silicon (Si) In commercial FeCrAl alloys, silicon is often present in levels of up to 0.4 wt%. In ferritic alloys as defined hereinabove or hereinafter, Si will play a very important role as it has been found to have a great effect on improving the oxidation and corrosion resistance. The upper limit of Si is set by the loss of workability in hot and cold condition and increasing susceptibility to formation of brittle Cr3Si and G phase during long term exposure. Additions of Si therefore have to be performed in relation to the content of Al and Cr. The amount of Si is therefore between 0.5 to 3 wt%, such as 1 to 3 wt%, such as 1 to 2.5 wt%, such as 1.5 to 2.5 wt%.
Manganese (Mn) Manganese may be present as an impurity in the alloy as defined hereinabove or hereinafter up to 0.4 wt%, such as from 0 to 0.3 wt%.
Yttrium (Y) In melt metallurgy, yttrium may be added in an amount up to 0.3 wt% to improve the adherence of the protective surface layer. Furthermore, in powder metallurgy, if yttrium is added to create a dispersion of together with oxygen and/or nitrogen, the yttrium content is in an amount of at least 0.04 wt%, in order to accomplish the desired dispersion hardening effect by oxides and/or nitrides. The maximum amount of yttrium in dispersion hardened alloys in the form of oxygen containing Y compounds may be up to 1.0 wt%.
9 Scandium (Sc), Cerium (Ce) and Lanthanum (La) Scandium, Cerium, and Lanthanum are interchangeable elements and may be added individually or in combination in a total amount of up to 0.2 wt% to improve oxidation properties, self-healing of the aluminium oxide (A1203) layer or the adhesion between the alloy and the A1203 layer.
Molybdenum (Mo) and Tungsten (W) Both molybdenum and tungsten have positive effects on the hot-strength of the alloy as defined hereinabove or hereinafter. Mo has also a positive effect on the wet corrosion properties. They may be added individually or in combination in an amount up to 4.0 wt%, such as from 0 to 2.0 wt%.
Reactive elements (RE) Per definition, the reactive elements are highly reactive with carbon, nitrogen and oxygen. Titanium (Ti), Niobium (Nb), Vanadium (V), Hafnium (Hf), Tantalum (Ta) and Thorium (Th) are reactive elements in the sense that they have high affinity to carbon, thus being strong carbide formers. These elements are added in order to improve the oxidation properties of the alloy. The total amount of the elements is up to 1.0 wt% such as 0.4 wt%, such as up to 0.15.
The maximum amounts of respective reactive element will depend mainly on tendency of the element to form adverse intermetallic phases.
Zirconium (Zr) Zirconium is often referred to as a reactive element as since it is very reactive towards oxygen, nitrogen and carbon. In the present alloy, it has been found that Zr has a double role as it will be present in the protective surface layer containing aluminium rich oxide thereby improving the oxidation resistance and it will also form carbides and nitrides.
Thus, in order to achieve the best properties of the protective surface layer containing aluminium rich oxide, it is advantageous to include Zr in the alloy.

However, Zr-levels above 0.40 wt% will have an effect on the oxidation due to the formation of Zr rich intermetallic inclusions and levels below 0.05 wt% will be too small to fulfill the dual purpose, regardless of the C and N content. Thus, if Zr is present, the range is between 0.05 to 0.40 wt%, such as 0.10 to 0.35.

Furthermore, it has also been found that the relationship between Zr and N and C may be important in order to achieve even better oxidation resistance of the protective surface layer, i.e. the alumina scale. Thus, the inventor has surprisingly found that if Zr is added to the alloy and the alloy also comprises N and C and if the following condition (the
10 element content given in weight%) is fulfilled:
4,7C+4N 47C+4N
-0.15 < Zr < 0.15, such as -0.15 < Zr ,< 0.10, such as -0.05<
0,62 - 0,62 -4,7C+4N
Zr 062 __ < 0.10, the obtained alloy will achieve a good oxidation resistance.
, The balance in the ferritic alloy as defined hereinabove or hereinafter is Fe and unavoidable impurities. Examples of unavoidable impurities are elements and compounds which have not been added on purpose, but cannot be fully avoided as they normally occur as impurities in e.g. the material used for manufacturing the ferritic alloy.
Figure la and Figure lb shows that higher Cr in a Si-containing ferritic alloy is prone to form Si3Cr inclusions and at 20% Cr also to promote undesirable brittle G-phase after exposure for long time in the focus temperature area. Although diagrams are only shown for two Cr levels, 10 and 20%, the trend of embrittling phases increasing with higher Cr is clearly demonstrated Note the absence of G-phase at 10% Cr and the increasing amount of Cr3Si phase at higher Si content at both Cr levels. Hence, these figures show that there will be problems when using Cr levels around 20%.
When the terms "<" or "less than or equal to" are used in the following context: "element < number", the skilled person knows that the lower limit of the range is 0 wt%
unless another number is specifically stated. Further, the undefined article "a" does not exclude a plurality.
11 The present disclosure is further illustrated by the following non-limiting examples.
Examples Test melts were produced in a vacuum melting furnace. The compositions of the test melts are shown in table 1.
The obtained samples were hot rolled and machined to flat rods with a cross section of 2 x 10 mm. They were then cut into 20 mm long coupons and ground with SiC paper to 800 mesh for exposure to air and combustion conditions. Some of the rods were cut to 200 mm long x 3 x12 mm rods for tensile testing at room temperature in a Zwick/Roell Z100 tensile test apparatus.
The results from exposure and tensile tests are shown in table 1.
The samples were tested for yield and rupture stress as well as elongation to rupture in a standard tensile test machine and the result giving >3% elongation to rupture is designated "x" in "Workable" column of the table. The "x" therefore designates an alloy that is easily hot rolled and that shows ductile behavior at room temperature.
In the "Oxidation" column, the "x" designates that the alloy forms a protective alumina rich oxide scale at 950 C in air and at 850 C with biomass ash deposit.
Table 1 ¨ Composition of the melts and the results of testing workability and oxidation an (x) designates a value between 3 and 6% elongation.
Composition/ Cr Al Si C N Zr Workable Oxidation Melt-number 4785 5.2 4.0 0.03 0.020 0.012 0.296 x No Comparative 4784 5.2 6.0 0.02 0.025 0.012 0.297 x No Comparative 4783 5.2 3.9 1.96 0.021 0.010 0.292 x X
12 (disclosure) 4782 10.0 2.0 0.02 0.025 0.014 0.273 x No Comparative 4781 10.0 3.0 0.03 0.025 0.021 0.296 x No Comparative 4780 10.1 4.0 0.02 0.021 0.015 0.296 x No Comparative 4779 10.1 4.0 1.91 0.022 0.013 0.296 x X
(disclosure) 4778 10.2 5.9 0.11 0.018 0.012 0.294 x No Comparative 4777 20.0 4.0 0.02 0.018 0.020 0.295 Failed in No Comparative rolling 4776 20.1 4.0 0.04 0.014 0.296 x No Comparative 4774 20.2 5.1 0.05 0.014 0.009 <0.01 x No Comparative 4773 19.7 4.8 0.02 0.004 <0.01 <0.01 x No Comparative 4772 12.2 3.6 2.5 0.003 <0.01 0.237 Failed in No comparative rolling 4799 20.0 2.8 1.87 0.023 0.017 0.281 x No Comparative 4800 14.9 3.0 1.9 0.022 0.013 0.296 x x (disclosure) 4855 10.1 3.8 1.96 0.019 0.012 0.279 x x (disclosure) 4856 10.0 5.0 2.0 0.015 0.012 0.285 Failed in No Comparative rolling 4857 10.0 3.1 1.97 0.025 0.015 0.297 x x
13 (disclosure) 4858 14.7 3.9 2.01 0.022 0.015 0.292 x x (disclosure) 4859 12.1 4.0 2 0.024 0.014 0.289 X x (disclosure) 4860 12.0 3.1 1.98 0.016 0.014 0.284 X x (disclosure) 4861 10.0 4.0 1.99 0.015 0.015 0.29 X x (disclosure) Thus, as can be seen from the table above, the alloys of the present disclosure shows good workability and good oxidation performance.
Figures 2 a) to e) disclose samples which are polished sections of of the present disclosure (figures 2a) 4783 and 2b) 4779) compared to three comparative alloys after exposure to 50 times 1 hour cycles at 850 C exposed to biomass (wood pellets) ash containing large amounts of potassium. The micrographs are taken in a JEOL FEG
SEM
at 1000 times magnification and show a clear advantage in behavior between the alloys of the present disclosure and reference materials. As can be seen, on the alloys of present disclosure, a 3-4 gm thin and protective alumina scale (aluminium oxide layer) has been formed, whereas a thicker and less protective chromia (chromium oxide) rich scale is formed on the stainless steel (2c - 11Ni, 21Cr, N, Ce, Fe bal.) and Ni-base alloy (2e -Inconel 625: 58Ni, 21Cr, 0.4A1, 0.5Si, Mo, Nb, Fe), and a relatively porous and not as protective alumina scale forms on the comparative FeCrAl alloy (alloy 4776) (figure 2d -20Cr, 5A1, 0.04 Si, Fe bal).
As can be seen from figures 2a - e, the addition of Si, Al and Cr according to the ranges according to the present disclosure will promote alumina scale formation at Al levels as low as about 2 wt% and at chromium levels as low as 5 wt%.

Claims (17)

14
1. A ferritic alloy comprising the following elements in weight% [wt%]
C 0.01 to 0.1;
N: 0.001 to 0.1;
O: 0.2;
Cr 4 to 15;
Al 2 to 6;
Si 0.5 to 3;
Mn: <= 0.4;
Mo+W<4;
Y
Sc, Ce, and/or La < 0.2;
Zr <= 0.40;
RE <= 1.0;
balance Fe and normal occurring impurities and also fulfilling the following equation has to be fulfilled (elements in weight fraction):
0.014 <= (Al + 0.5Si)(Cr +10Si + 0.1) <=0.022.
2. The ferritic alloy according to claim 1, wherein (elements in weight fractions) 0.015 <= (Al + 0.5Si)(Cr +10Si + 0.1) <=0.021
3. The ferritic alloy according to claim 1 or claim 2, wherein Zr is of from 0.05 to 0.40 weight%.
4. The ferritic alloy according to any one of claims 1 to 3, wherein Cr is of from 5 to 13 weight%.
5. The ferritic alloy according to any of claim 1 to 4, wherein Cr is of from 6 to 12 weight%.
6. The ferritic alloy according to any preceding claims, wherein Al is of from 2.5 to 4.5 weight% or from 3 to 5 weight%.
7. The ferritic alloy according to any preceding claims, wherein Al is of from 3 to 4 weight%.
8. The ferritic alloy according to any preceding claims, wherein Si is of from 1.0 to 3 weight%.
9. The ferritic alloy according to any preceding claims, wherein Si is of from 1.5 to 2.5 weight%.
10. The ferritic alloy according to any preceding claims, wherein Zr is of from 0.10 to 0.35 weight%.
11. The ferritic alloy according to any preceding claims, wherein the amount of C, N
and Zr fulfills the following equation:
12. A coating comprising the ferritic alloy according to any preceding claims.
13. An object comprising the ferritic alloy according to any preceding claims.
14. Use of the the ferritic alloy according to anyone of claims 1 to 11 for manufacturing a coating and/or a cladding and/or an object.
15. Use of the ferritic alloy according to anyone of claims 1 to 11 for manufacturing an object or a coating to be used in corrosive environments.
16. Use of the ferritic alloy according to anyone of claims 1 to 11 for manufacturing an object or a coating to be used in a furnace or as a heating element.
17. Use of the ferritic alloy according to anyone of claims 1 to 11 in environments wherein the ferritic alloy is exposed to salts, liquid lead and other metals, exposed to ash or high carbon content deposits, combustion atmospheres, atmospheres with low pO2 and/or high N2 and/or high carbon activity.
CA3020420A 2016-04-22 2017-03-06 Ferritic alloy Active CA3020420C (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP16166661 2016-04-22
EP16166661.5 2016-04-22
PCT/EP2017/055143 WO2017182188A1 (en) 2016-04-22 2017-03-06 Ferritic alloy

Publications (2)

Publication Number Publication Date
CA3020420A1 true CA3020420A1 (en) 2017-10-26
CA3020420C CA3020420C (en) 2023-08-29

Family

ID=56072196

Family Applications (1)

Application Number Title Priority Date Filing Date
CA3020420A Active CA3020420C (en) 2016-04-22 2017-03-06 Ferritic alloy

Country Status (10)

Country Link
US (1) US20190106774A1 (en)
EP (1) EP3445884B1 (en)
JP (3) JP7059198B2 (en)
CN (2) CN109072384A (en)
BR (1) BR112018071646B1 (en)
CA (1) CA3020420C (en)
DK (1) DK3445884T3 (en)
ES (1) ES2842424T3 (en)
PL (1) PL3445884T3 (en)
WO (1) WO2017182188A1 (en)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20200181745A1 (en) * 2017-05-24 2020-06-11 Sandvik Intellectual Property Ab Ferritic alloy
WO2021043913A1 (en) * 2019-09-03 2021-03-11 Kanthal Ab A new welding material
CN110760760B (en) * 2019-12-05 2020-12-04 中国核动力研究设计院 Preparation method of FeCrAl-based alloy for nuclear reactor structural material
CN116970873B (en) * 2023-09-25 2023-12-15 上海核工程研究设计院股份有限公司 Beryllium-containing ferrite heat-resistant steel and manufacturing method thereof

Family Cites Families (43)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1850953A (en) * 1925-06-19 1932-03-22 Percy A E Armstrong Heat, rust, and acid resisting ferrous alloy
US2210308A (en) * 1936-06-08 1940-08-06 Kemet Lab Co Inc Iron alloy suitable for electrical resistances
CA928537A (en) * 1968-06-28 1973-06-19 Allegheny Ludlum Corporation Oxidation resistant stainless steel
DE2161954A1 (en) * 1971-12-14 1973-06-20 Deutsche Edelstahlwerke Gmbh FERRITIC HEAT RESISTANT STEEL
JPS5541290B2 (en) * 1973-11-02 1980-10-23
US4261739A (en) * 1979-08-06 1981-04-14 Armco Inc. Ferritic steel alloy with improved high temperature properties
JPS5911660B2 (en) * 1979-10-31 1984-03-16 日新製鋼株式会社 Stainless steel for combustion equipment heat absorption radiator
GB2070642A (en) * 1980-02-28 1981-09-09 Firth Brown Ltd Ferritic iron-aluminium- chromium alloys
JPS5915974B2 (en) * 1980-04-18 1984-04-12 住友金属工業株式会社 Ferrite steel for petroleum and coal chemical plants
JPS5919984B2 (en) * 1980-09-19 1984-05-10 大同特殊鋼株式会社 Corrosion-resistant material for molten sodium polysulfide
CA1178084A (en) 1981-09-14 1984-11-20 Daniel W. Yankovich, Jr. Apparatus and method for detecting fouled cooling circuits in a blast furnace or the like
US4414023A (en) * 1982-04-12 1983-11-08 Allegheny Ludlum Steel Corporation Iron-chromium-aluminum alloy and article and method therefor
JPH02217443A (en) * 1989-02-16 1990-08-30 Sumitomo Metal Ind Ltd High chromium steel for trash incineration waste heat boiler tube
US5160390A (en) 1990-09-12 1992-11-03 Kawasaki Steel Corporation Rapidly solidified fe-cr-al alloy foil having excellent anti-oxidation properties
EP0674015A1 (en) * 1992-12-11 1995-09-27 Nippon Steel Corporation Steel of high corrosion resistance and high processability
JPH0741905A (en) * 1993-07-27 1995-02-10 Nippon Steel Corp Steel for automotive exhaust system
JPH0741917A (en) * 1993-07-27 1995-02-10 Nippon Steel Corp Steel for automotive exhaust system
JP3541458B2 (en) * 1993-10-15 2004-07-14 Jfeスチール株式会社 Ferritic stainless steel with excellent high-temperature salt damage characteristics
CN1122841A (en) * 1994-11-11 1996-05-22 冶金工业部包头稀土研究院 Non-brittle Cr-Al-rare earth metal-Fe alloy
SE504797C2 (en) * 1995-08-11 1997-04-28 Kanthal Ab Metallic, high temperature resistant material and ways of making it
JPH108214A (en) * 1996-06-14 1998-01-13 Sumitomo Metal Ind Ltd Iron-chromium-aluminum cast steel product
SE508595C2 (en) * 1997-08-12 1998-10-19 Sandvik Ab Use of a ferritic Fe-Cr-Al alloy in the manufacture of compound tubes, as well as compound tubes and the use of the tubes
JP2000273592A (en) * 1999-03-19 2000-10-03 Sanyo Special Steel Co Ltd Electrical stainless steel for cold forging and its production
JP2001164317A (en) * 1999-12-09 2001-06-19 Nippon Steel Corp Method for producing automotive exhaust system steel pipe excellent in oxidation resistance
SE513989C2 (en) * 2000-01-01 2000-12-11 Sandvik Ab Process for manufacturing a FeCrAl material and such a mortar
DE10002933C1 (en) * 2000-01-25 2001-07-05 Krupp Vdm Gmbh Iron-chromium-aluminum foil production, used e.g. as support material for exhaust gas treatment catalysts, comprises coating one or both sides of supporting strip with aluminum or aluminum alloys, and carrying out homogenizing treatment
FR2806940B1 (en) * 2000-03-29 2002-08-16 Usinor STAINLESS STEEL FERRITIC STRIP ALUMINUM-CONTAINING, ESPECIALLY USEFUL FOR A MOTOR VEHICLE EXHAUST CATALYST SUPPORT AND METHOD FOR MANUFACTURING SAID STRIP
SE517894C2 (en) * 2000-09-04 2002-07-30 Sandvik Ab FeCrAl alloy
AU2002302575A1 (en) * 2001-04-26 2002-11-11 Thyssenkrupp Vdm Gmbh Iron-chrome-aluminium-alloy
SE520617C2 (en) * 2001-10-02 2003-07-29 Sandvik Ab Ferritic stainless steel, foil made of steel, use of steel and foil, and method of making steel
JP2004269915A (en) * 2003-03-05 2004-09-30 Jfe Steel Kk Al-CONTAINING HIGHLY OXIDATION RESISTANT STAINLESS STEEL FOIL HAVING NO WRINKLING ON JOINING, AND CATALYST CARRIER
SE528027C2 (en) * 2004-04-16 2006-08-08 Sandvik Intellectual Property Use of a ferritic steel in catalysts for diesel engines
CN101090986A (en) * 2004-04-28 2007-12-19 蒂森克鲁普德国联合金属制造有限公司 Iron-chrome-aluminum alloy
JP5401039B2 (en) * 2008-01-11 2014-01-29 日新製鋼株式会社 Ferritic stainless steel and manufacturing method thereof
CN102168226B (en) * 2011-04-02 2013-04-10 裘德鑫 Martensite antibacterial stainless steel and manufacturing method thereof
DE102012004488A1 (en) * 2011-06-21 2012-12-27 Thyssenkrupp Vdm Gmbh Heat-resistant iron-chromium-aluminum alloy with low chromium evaporation rate and increased heat resistance
WO2013178629A1 (en) * 2012-05-29 2013-12-05 Thyssenkrupp Steel Europe Ag Heat-resistant fe-al-cr steel
EP2902523B1 (en) * 2012-09-25 2018-09-05 JFE Steel Corporation Ferritic stainless steel
CN103060700B (en) * 2013-01-07 2014-12-31 北京工业大学 Boride particle reinforced Fe-Cr-Al composite material and its preparation method
JP6392501B2 (en) 2013-05-10 2018-09-19 新日鐵住金ステンレス株式会社 Stainless steel substrate for solar cell with excellent insulation and small thermal expansion coefficient and method for producing the same
EP3064606B1 (en) * 2013-11-01 2022-03-02 NIPPON STEEL Stainless Steel Corporation Ferritic stainless steel for use in fuel reformer and method of manufacturing ferritic stainless steel
ES2726676T3 (en) * 2014-12-11 2019-10-08 Sandvik Intellectual Property A ferritic alloy
CN104726778A (en) * 2015-03-25 2015-06-24 上海大学兴化特种不锈钢研究院 Rare-earth La containing electrothermal alloy material having excellent high-temperature oxidation resistance

Also Published As

Publication number Publication date
CN113088830B (en) 2023-09-01
BR112018071646A2 (en) 2019-02-19
CA3020420C (en) 2023-08-29
JP2022046521A (en) 2022-03-23
DK3445884T3 (en) 2020-11-30
CN113088830A (en) 2021-07-09
WO2017182188A1 (en) 2017-10-26
JP2024079699A (en) 2024-06-11
BR112018071646B1 (en) 2022-03-22
EP3445884B1 (en) 2020-10-07
JP7059198B2 (en) 2022-04-25
JP2019516015A (en) 2019-06-13
PL3445884T3 (en) 2021-04-19
EP3445884A1 (en) 2019-02-27
US20190106774A1 (en) 2019-04-11
ES2842424T3 (en) 2021-07-14
CN109072384A (en) 2018-12-21

Similar Documents

Publication Publication Date Title
EP2781612B1 (en) Seamless austenite heat-resistant alloy tube
JP5177330B1 (en) Carburization-resistant metal material
TWI645049B (en) FABRICABLE, HIGH STRENGTH, OXIDATION RESISTANT Ni-Cr-Co-Mo-Al ALLOYS
CA3020420C (en) Ferritic alloy
EP2479302B1 (en) Ni-based heat resistant alloy, gas turbine component and gas turbine
JP5600012B2 (en) Ferritic stainless steel with excellent oxidation resistance and secondary work brittleness resistance, as well as steel and secondary work products
KR20120137520A (en) Austenitic stainless steel
KR20090020701A (en) Austenitic stainless steel welded joint and austenitic stainless steel welding material
EP3318653B1 (en) Ferritic stainless steel
EP3118341B1 (en) Ferritic stainless steel
US20200181745A1 (en) Ferritic alloy
US5296054A (en) Austenitic steel
JPWO2018066573A1 (en) Austenitic heat-resistant alloy and welded joint using the same
JP2003171745A (en) Austenitic stainless steel sheet for heat exchanger
JP5554180B2 (en) Austenitic stainless steel
JP2005144488A (en) Build-up welding material for continuous casting roll and roll using it
WO2021043913A1 (en) A new welding material
JPH0577739B2 (en)
WO2004087980A1 (en) Stainless steel for use in high temperature applications
JPH068482B2 (en) Cr-Mo heat resistant steel with excellent toughness for chromizing
JP2001220635A (en) Nickel aluminide series superalloy

Legal Events

Date Code Title Description
EEER Examination request

Effective date: 20210601

EEER Examination request

Effective date: 20210601

EEER Examination request

Effective date: 20210601

EEER Examination request

Effective date: 20210601

EEER Examination request

Effective date: 20210601

EEER Examination request

Effective date: 20210601

EEER Examination request

Effective date: 20210601