This application is a § 371 National Stage Application of PCT International Application No. PCT/EP2016/065334 filed Jun. 30, 2016 claiming priority to EP 15174789.6 filed Jul. 1, 2015.
The present disclosure relates to a method which uses welding in order to join a FeCrAl alloy to a FeNiCr alloy by using a specific filler metal. The present disclosure also relates to a product obtained thereof. Further, the present disclosure relates to the use of products obtained by said method, especially in high temperature applications.
In many industrial processes, there are high temperatures and adverse atmospheres. In this environment, materials may oxidize or corrode rapidly and/or creep. One example of such an environment is the process of thermal cracking for obtaining ethylene for polymer manufacturing. This requires great demands on corrosion resistance and high-temperature strength of the materials used. In this process, it is a goal to increase the service life of the material in order to decrease the number of maintenance shutdowns and expensive repairs. It is also a goal to raise the temperature in the manufacturing process in order to increase productivity.
One material used for high-temperature applications is ferritic iron-chromium-aluminum (FeCrAl) alloys. In many cases when a FeCrAl alloy is used as construction material, it has to be joined to another high-temperature material, which is often an austenitic stainless steel, such as a FeNiCr alloy. However, there are challenges joining these two materials by welding because of the differences in the material chemistry which causes difficulties formation of intermetallic phases, which will impair the mechanical properties of the weld.
WO 2014/204388 A1 discloses a filler for welding comprising (in % by weight): C: ≮0.036, Ni: 15.0-20.0, Cr: 15.0-22.0, Mn: 0.75-2.0, Zr: 0.1-1.45, Si: 0-1.5, Al: 0-2, N: <0.06 and a balance of Fe and inevitable impurities.
US 2006/163231 A1 discloses ferritic stainless steel welding wire consisting essentially of, by mass, 0.03% or less C, 3% or less Si, 3% or less Mn, 2% or less Ni, 11 to 20% Cr, 3% or less Mo, 1% or less Co, 2% or less Cu, 0.02 to 2.0% Al, 0.2 to 1.0% Ti, 0.02% or less O, 0.04% or less N, and at least one of Nb and Ta, the mass % thereof being eight times the total mass percent of said C and said N to 1.0 mass %, the balance being Fe and unavoidable impurities.
It is therefore of great importance to minimize and/or eliminate the formation of brittle intermediate phases formed during welding, especially when the objects to be joined are used in high temperature applications. It is also important to avoid the formation of a continuous film of brittle precipitations in the weld as this also will reduce the mechanical properties of the weld.
Thus, one aspect of the present disclosure is to provide a method of joining a FeCrAl alloy to FeNiCr alloy by welding in which at least one of the above problems is reduced or avoided.
In the present disclosure, the term “FeCrAl”, is intended to mean FeCrAl alloys having chromium content of above 11 wt %, an aluminum content of more than 4 wt % and the balance is Fe (and unavoidable impurities). These stainless steels have a ferritic microstructure and will also form a protective layer of aluminum oxide on the surface of an object comprising said alloys. These alloys may also contain a large content of molybdenum.
In the present disclosure, the term “FeNiCr” is intended to mean FeNiCr alloys having a chromium content of above 11 wt %, a nickel content of between 20-60 wt % and a balance of Fe (and unavoidable impurities). These FeNiCr stainless steel alloys, including iron-base and nickel-base alloys always have austenitic microstructure and will form a protective layer of chromium oxide on the surface of objects comprising said alloys.
In the present disclosure, the terms “wt %”, “weight %” or “%” are used interchangeably and means weight percent.
The present disclosure provides a method of joining two different alloys by using a specific kind of filler metal. The present disclosure therefore provides a method of joining a FeCrAl alloy to a FeNiCr alloy by welding using a filler metal, wherein the filler metal comprises (wt %):
Hence, the method as defined hereinabove or hereinafter is based on the finding that it is possible to join two or more alloys having different material chemistry by welding using filler metal as defined hereinabove or hereinafter, said filler metal comprises controlled amounts of N, Al, and Ni in combination with controlled amounts of C, Nb, Ti and/or Zr.
The different alloys, i.e. the FeCrAl alloy and the FeNiCr alloy, may be in the form of a tube and or a strip and the filler metal may, for example, be provided in a form of strip or wire, which strip or wire are suitable for be used in welding applications.
In particular, the method as defined hereinabove or hereinafter is suitable for joining a FeCrAl alloy to a FeNiCr alloy and the obtained product (the terms object and product will be interchangeably used herein) will have good creep strength as well as good corrosion resistance at high temperatures. Thus, the obtained product is suitable to use in high temperature applications, i.e. at temperatures which are 650° C. or higher. However, the product may also be used for other applications wherein good creep strength and good corrosion resistance is required.
This, the present method will provide a weld wherein the effect of the initially mentioned brittle phases is avoided or at least minimized. Also, the product obtained by the method as defined hereinabove or hereinafter no continuous film of brittle precipitations, which means that the if said product is use in plants which are run at high temperatures, the service life of the parts made of said product will be increased, thus decreasing the number of maintenance shutdowns.
Also, the method as defined hereinabove and hereinafter will provide a product having sufficient mechanical strength, such as tensile strength, ultimate tensile elongation and ductility over time, which is especially useful when said product is used in high temperature applications, i.e. a temperatures above 650° C. The present disclosure therefore relates to an object comprising at least one FeCrAl alloy and at least FeNiCr alloy which are joined together with a filler metal having the composition as defined hereinabove or hereinafter. Furthermore, the present disclosure also provides for parts made of said objects which are to be used in plants or parts of plants which are run at high temperatures.
The alloying elements of the filler metal according to the present disclosure will now be described.
Carbon (C): 0.01 to 0.10 wt %
C has a positive effect of increasing the creep strength as it will form carbides with Ti, Zr and Nb. However, too high concentration of carbon may reduce the corrosion and oxidation properties. Accordingly, the carbon content is of from 0.01-0.10 wt %, such as of from 0.01-0.08 wt %.
Silicon (Si): Less or Equal to 1.5 wt %
Si reduces the oxygen content and has a positive effect on the fluidity of the weld pool. Silicon has also a positive effect against carburization. However, too high content of Si will increase the tendency for precipitation of intermetallic phases. Accordingly, the Si content is less than or equal to 1.5 wt %, such as of from 0.01 to 1.5 wt %.
Manganese (Mn): Less or Equal to 2.0 wt %
Mn has a positive impact on the hot ductility by fixing sulphur. However, too high content of Mn may cause embrittlement of the obtained weld. Accordingly, the Mn content is set to be at less than or equal to 2 wt %.
Chromium (Cr): 14.0-27.0 wt %
Cr improves corrosion and oxidation properties of the weld. However, too high content of Cr will stabilize the sigma phase, which result in a brittle material. The Cr content should therefore be limited to 27.0% by weight. A too low Cr content will reduce the corrosion resistance. Hence, the content of Cr is of from 14.0 to 27.0 wt %, such as of from 18.0-23.0 wt % in the filler metal.
Nickel (Ni): Less than or Equal to 2.0 wt %
The Ni content is kept as low as possible in the filler metal since Ni may increase the formation of brittle phases, such as nickel-aluminides. The brittle phases will weaken the strength of weld as a continuous film of nickel-aluminides will be formed. However, a low amount of nickel-aluminides will have a positive effect on the creep strength of the weld. Hence, the content of Ni is less than or equal to 2.0 wt %, such as less than or equal to 1.0 wt %, such as less than or equal to 0.5 wt %, such as less than or equal to 0.25 wt %, such as less than or equal to 0.1 wt %, such as 0 wt %.
Molybdenum (Mo): Less than or Equal to 1.5 wt %
Mo improves the creep properties and also stabilizes the brittle sigma phase. However, too high content of Mo will increase the formation of intermetallic phases. Hence, Mo content is set to be at less than or equal to 1.5 wt %, such as less than or equal to 0.3 wt %.
Vanadium (V): Less than or Equal to 0.35 wt %
Vanadium forms carbides that improve the creep properties and reduce the risk of forming chromium carbides. However, too high content of V may cause coarse carbide precipitates to be formed which will reduce the mechanical strength of the weld. Accordingly, the V content is set to be at less than or equal to 0.35 wt %, such as less than or equal to 0.25 wt % in the filler metal.
Aluminum (Al): Less than or Equal to 0.7 wt %
Aluminum is kept low in order to reduce the formation of nickel aluminides and aluminum nitrides in the weld as but high concentration of these precipitates may result in brittle failure of the weld. However, a small concentration of nickel aluminides or aluminum nitrides may have a positive effect on the creep strength. Therefore, the Al content is set to be at 0.7 wt %, such as less than 0.5 wt %, such as less than 0.25 wt % in the filler metal.
Titanium and/or Zirconium (Ti and/or Zr): 0.4 to 1.0 wt %
Ti and Zr may be used equivalently and will form carbides that improve the creep properties and reduce the risk of forming chromium carbides. However, too high content of Ti and/or Zr will cause the formation of coarse precipitates which will reduce the mechanical properties of the weld. Hence, the content of Ti and/or Zr is of from 0.4 to 1.0 wt %, such as of from 0.5 to 1.0 wt %.
Niobium (Nb): 0.3 to 1.5 wt %
Niobium forms carbides that improve the creep properties and reduce the risk of forming chromium carbides. However, too high content of Nb will cause the formation of coarse precipitates which will reduce the mechanical properties of the weld. Accordingly, the content of Nb is of from 0.3 to 1.5 wt %, such as of from 0.3 to 1.0 wt %.
Nitrogen (N): less than or equal to 0.02 wt % Nitrogen should be kept as low as possible in the filler metal, since it gives rise to brittle phases such as aluminum nitrides. The content of nitrogen is therefore less than or equal to 0.02 wt %, such as less than or equal to 0.015 wt %.
The balance is iron (Fe) and unavoidable impurities.
The minimization of Ni, Al and N in the filler metal will result in that the presence of aluminium nitrides (AlN) as well as nickel aluminide (NixAl) in the obtained weld i minimized or even eliminated. Furthermore, there will be no continuous film of precipitates formed in the weld. The minimization of the formation of intermetallic phases will have a positive impact on the mechanical properties of the welded joint. The lack or low presence of both AlN and NixAl in the weld is, without being bound to any theory, assumed to depend on the composition of filler metal wherein the content of Ni, Al and N is minimized.
The present disclosure is further illustrated by the following non-limiting example.
A FeCrAl-alloy was joined to a FeNiCr-alloy using a filler metal. TIG (tungsten inert gas) was used as a welding method.
The FeCrAl-alloy used in this example was Kanthal® APMT, the FeNiCr-alloy used was an Alloy 800HT obtained from Sandvik Materials Technology AB (hereinafter referred to as Sandvik steel grade Sanicro™ 31HT) and the filler metal used was the Sandvik® 19.LNbTi welding wire. The FeCrAl-alloy and the FeNiCr-alloy were in the form of tubes. The compositions of the different materials are found in table 1 (the compositions have been obtained from the product sheets of respective alloy):
The alloys were joined using TIG method according to the welding parameters shown in table 2.
The tubes were pre-heated to a temperature of between 250-300° C. and TIG welded at a temperature between 250-300° C. with argon (99.99%) as both shield and backing gas. After welding, the obtained weld was subjected to a post-weld heat treatment at a temperature of 850° C.±20° C. for 30 minutes, before being slowly cooled down to an ambient temperature at a rate of at least 100° C./h.
Samples of the weld were aged at 750° C. for 5000 h, before being characterized microstructural and evaluated mechanically.
The microstructural characterization after ageing showed that both Kanthal® APMT and Sanicro™ 31HT had no continuous film of precipitations along their fusion line to the metal filler, see
Mechanical Properties
As can be seen from the figures, the ageing affected the tensile strength of the weld; however as can be seen the mechanical strength of the weld is still sufficient for high temperature application (over time). Furthermore, as both the as-welded and aged samples had an elongation between 20-25% at 750° C., this means that both welds had good ductility.
Thus, the results show that the selection of the composition of filler metal is of fundamental importance and that the weld obtained had very good mechanical properties, i.e. very good tensile strength, very good ductility and very good creep rupture time at high temperatures.
Number | Date | Country | Kind |
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15174789 | Jul 2015 | EP | regional |
Filing Document | Filing Date | Country | Kind |
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PCT/EP2016/065334 | 6/30/2016 | WO | 00 |
Publishing Document | Publishing Date | Country | Kind |
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WO2017/001575 | 1/5/2017 | WO | A |
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