Title of Invention | HIGH TEMPERATURE MATERIAL OF A METALLURGICAL FeCrAI ALLOY |
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Abstract | A method of producing an FeCrAl material by gas atomisation, wherein in addition to containing iron (Fe), chromium (Cr) and aluminium (Al) the material also contains minor fractions of one or more of the materials molybdenum (Mo), hafnium (Hf), zirconium (Zr), yttrium (Y), nitrogen (N), carbon (C) and oxygen (O). The invention is characterised by causing the smelt to be atomised to contain 0.05-0.50 percent by weight tantalum (Ta) and, at the same time, less than 0.10 percent by weight titanium (Ti). According to one highly preferred embodiment, nitrogen gas (N¿2?) is used as an atomising gas to which a given amount of oxygen gas (O¿2?) is added, said amount of oxygen gas being such as to cause the atomised powder to contain 0.02-0.10 percent by weight oxygen (0) at the same time as the nitrogen content of the powder is 0.01-0.06 percent by weight. The invention also relates to a high temperature material. |
Full Text | FORM 2 THE PATENTS ACT 1970 [39 OF 1970] & THE PATENTS RULES, 2003 COMPLETE SPECIFICATION [See Section 10; rule 13] "A METHOD OF MAKING A FeCraL MATERIAL, AND SUCH MATERIAL" SANDVIK AB, a Swedish company of S-811 81 Sandviken, Sweden, The following specification particularly describes the invention and the manner in which it is to be performed: 2002-05-29 13:00 Fran-Norens Patent by ra AB +46 8 54587429 T-744 S.005/033 F WO 01/49441 PCT/SE00/02571 A METHOD OF MAKING A FeCrAl MATERIAL, AND SUCH MATERIAL The present invention relates to a method of producing an FeCrAl material, and also to such material. 5 Conventional iron based alloys containing typically Fe and 12-25% Cr and 3-7% Al,. so-called FeCrAl-alloys, have been found highly useful in various high temperature applications, due to their good oxidation resistance. Thus, such materials have been used in the production of electrical resistance elements and as carrier materials in motor vehicle 10 catalysts. As a result of its aluminium content, the alloy is able to form at high temperatures and in the majority,of atmospheres an impervious and adhesive surface oxide consisting substantially of Al2O3. This oxide protects the-metal against further oxidation. and also against many other forms of corrosion, such as carburization, sulphuration, etc.. . 15 A pure FeCrAl alloy is characterised by a relatively low mechanical strength at elevated temperatures. Such alloys are relatively weak at high temperatures and tend to become brittle at low temperatures subsequent to having been. subjected to-elevated temperatures for a relatively long period of time, due to grain growth. One way of improving the high temperature strength of such alloys is to include non-metallic inclusions in the alloy and 20 therewith obtain a precipitation hardening effect. One known way of adding said inclusions is by a so-called mechanical alloying process in which the components are mixed in solid phase. In this regard, a mixture of fine oxide powder, conventionally Y203, and metal powder having an FeCrAl composition is ground 25 in high energy mills over a long period of time until an homogenous structure is obtained. Grinding results in a powder that can later be. consolidated, for instance by hot extrusion or hot isostatic pressing to form a completely tight product. 2002-05-29 13:01 Fran-Norens Patent by AB +4B 8 54587429 T-744 S.006/033 F-B30 WO 01/49441 PCT/SE00/02571 2 Although YA can be considered to be a highly stable oxide from a thermodynamical aspect, small particles of yttrium can be transformed or dissolved in a metal matrix under different circumstances. 5 It is known that in a mechanical alloy process yttrium particles react with aluminium, and oxygen, therewith, forming different kinds of Y-Al-oxides. The composition of these mixed oxide inclusions will change, and their stability lowered during long-term use of .the material, due to changes in the surrounding matrix. 10 It has also been reported that an addition of a strongly oxide-forming element in the form of titamiumi to a mechanically alloyed material that contains Y203 and 12% Cr can cause the separation of complex (Y+Ti) oxides, resulting in a material that has "greater mechanical strength than a material that contains no titamiumi. The strength at elevated temperatures: can be further improved, by adding molybdenum. 15 Thus. a.-material, that. f has-good strength properties: .can. b& obtained- by means-.of a-, mechanical alloying process. Mechanical alloying, however, is encumbered with several drawbacks. Mechanical 20 alloying is carried out batch-wise in high energy mills, in which the components are mixed to obtain an homogenous mixture. The batches are relatively limited in size, and the grinding process requires a relatively long period of time to complete. The grinding process is also energy demanding. The decisive drawback with mechanical alloying resides in the high product costs entailed. 25 A process in which an FeCrAl material alloyed with fine particles could be produced (i without needing to apply high energy grinding would be highly beneficial from the aspect of cost P. 06 WO 01/49441 PCT/SE00/02571 3 It would be to advantage if the material could be produced by gas atomisation, i.e. the .production of a fine powder that is later compressed. This process is less expensive than when the powder is produced by grinding- Very small carbides and nitrides are precipitated. in conjunction with the rapid solidification process, such carbides and nitrides being 5 desirable. However, the titanium, constitutes a serious problem when atomising an FeCrAl material. The problem is that small particles of mainly TiN and TiC are formed in the smelt prior to atomisation. These particles tend to fasten on the refractory material. Since the smelt 10 passes through a relatively fine ceramic nozzle prior-to atomisation, these particles will fasten to the nozzle and gradually accumulate. This causes clogging of the nozzle, therewith making :it necessary to disrupt the atomisation process. Such stoppages in production are expensive and troublesome. Consequently, FeCrAl materials that contain titanium are not produced by atomisation in practice 15 The present invention solves this problem and relates to a method in which an FeCrAl . material can be produced by means of atomisation The present invention thus relates to a method of producing^ an FeCrAl material by gas atomisation, wherein said material in addition to iron (Fe), chromium (Cr) and aluminium 20 (Al) also contains minor fractions of one or more of the materials molybdenum (Mo), hafnium.(Hf), zirconium (Zr), yttrium (Y), nitrogen (N), carbon (C) and oxygen (O), and wherein the method is characterised by causing the smelt to be atomised to contain 6.05-0.50 percent by weight tantalum (Ta) and, at the same time, less than 0.10 percent by weight titanium (Ti). 25 The invention also relates to a material of the kind defined in Claim 6 and having the essential features set forth in said Claim. P.07 WO 01/49441 PCT/SE00/02S71 ' 4 The present invention relates to a method of producing an FeCrAl material by gas atomisation In addition to iron (Fe), chromium (Cr) and aluminium (AT), the FeCrAl material also includes minor fractions of one or more of the materials molybdenum (Mo), hafnium (Hf), zirconium (Zr), yttrium (Y), nitrogen (N), carbon (C) and oxygen (O). 5 According to the present invention, the smelt to be atomised is caused, to contain 0.05-0.50 percent by weight tantalum (Ta) and also less than 0.10 percent by weight titanium (Ti). It has been found that tantalum imparts strength properties that are comparable with those 10 obtained when using titanium at the same time as TiC and TiN are not formed in quantities that cause clogging of the nozzle. -This applies even when the smelt contains 0.10 percent by weight titanium. Thus, it is possible to produce the material in question by gas atomisation, by using 15 tantalum instead of at least a part of the titanium quantity. It is usual, and also possible, to use argon (Ar) as the atomising gas. However, argon is adsorbed partly on accessible and available surfaces and partly in pores in the powder grains. In conjunction with subsequent heat consolidation and heat processing of the 20 product, the argon will collect under high pressure in microdefects. These defects swell to form pores in later use at low pressure and high temperature, thereby impairing the strength of the product Powder that is atomised by means of nitrogen gas does not behave in the same mariner as 25 argon, since nitrogen has greater solubility in the metal than argon and since nitrogen is able to form nitrides. When gas atomising with pure nitrogen gas, the aluminium will react with the gas and marked nitration of the surfaces of the powder grains can occur. This nitration makes it difficult to create bonds between the powder grains in conjunction with '; P.08 WO 01/49441 PCT/SE00/02571 5. hot isostatic pressing (HIP),, causing difficulties in the heat processing or the heat treatment of the resultant blank, ha addition, individual powder grains may be so significantly nitrated as to cause the major part of the aluminium to hind as nitrides. Such particles are unable to form a protective oxide. Consequently, they can disturb the formation of oxide if 5 they are present close to the surface of the end product It has been found that some oxidation of the powder surfaces is obtained when a controlled amount of gaseous oxygen is supplied to the nitrogen gas, while considerably reducing nitration at the same time. The risk of oxide disturbances is also greatly reduced. 10 Consequently, in accordance' with one highly preferred embodiment, nitrogen gas (N2) is used as an atomising gas to which a given quantity of oxygen gas (O2) is added, said . amount of oxygen gas being such as to cause the atomised powder 'to contain; 0.02-13:10 percent by weight oxygen (O) at the same time as the nitrogen content of the powder is 15 0.01-0.06 percent by weight According to one preferred embodiment, the smelt is caused to have a composition in which the powder obtained has the following composition in percent by weight, subsequent to atomisation: 20 Fe balance Cr 15-25 percent by weight Al 3-7 Mo 0-5 Y 0.05-0.60 25 Zr 0.01-030 Hf 0.05-0.50 P. 09 2002-05-29 ,3:02 Fran-Norans Patent by ra AB +46 8 54587429 \ T-744 S.010/033 F-B30 WO 01/49441 ~ PCT/SE00/02S71 6 Ta 0.0543.50 Ti 0-0.10 C 0.01-0.05 N 0.01-0.06 O 0.02-0.10 . Si 0.10-0.70. MO 0.05-0.50 P 0-0.08 S 0-0.005 10 According to one particularly preferred embodiment, the smelt is caused to have a composition such, that subsequent to atomisation the resultant powder will have roughly the following composition in percent by weight: Fe balance 15 Cr 21 percent by weight Al 4.7 Mo 3 Y 0.2 - Zr 0.1 20 Hf 0.2 Ta 0.2 Ti P. 10 +46 8 54587429 ' T-744 S,011/033 F-630 PCT/SE00/02571 2002-05-29 13:02' Fran-Norans Patent by r a AB WO 01/49441 C 0.03 N 0.04 0 0.06 Si 0.4 5 Mn 0.15 P . S Subsequent to heat treatment, the creep strength, or creep resistance of the material is 10 influenced to a great extent by the presence of oxides of yttrium and tantalum and by carbides of hafnium, arid zirconium. Avoiding to one preferred embodiment, the value of the formula ((3xY + Ta)xO) + ((2xZr + Hr)x(N + C)), "where elements in the formula shall be replaced by the content in weight 15 percent of respective elements in the smelt, is greater than 0.04 but-smaller than 0.35". Although the invention has been described above with reference to a number of exemplifying embodiments, it will be understood that the composition of the material can be modified to some extent while still obtaining a satisfactory material. 20 The present invention is therefore, not restricted to said embodiments, since variations can be made within the scope of the accompanying Claims. P.11 WE CLAIM: 1. A gas atomisation method for producing a FeCrAI material, said material also containing in addition to iron (Fe), chromium (Cr) and aluminium (Al) minor fractions of one or more of the materials molybdenum (Mo), hafnium (Hf), zirconium (Zr), ytterium (Y), nitrogen (N), carbon (C) and oxygen, the method being characterized in that the smelt to be atomised is caused to contain 0,05 -0,50 percent by weight tantalum (Ta) and, at the same time less than 0,10 percent by weight titanium (Ti). 2. A method as claimed in claim 1, wherein by using nitrogen gas (N2) as an atomising gas and by adding a given amount of oxygen gas (O2) to the atomising gas, wherein said amount of oxygen gas is caused to be such that the atomised powder will contain 0.02-0.10 percent by weight oxygen (O) at the same time as the nib:ogen content of the powder is 0.01-0.06 percent by weight. 3. A method as claimed in claim 1 or 2, wherein by causing the smelt to have a composition such that the powder obtained after atomisation will have the following composition in percent by weight Fe balance Cr 15-25 percent by weight Al 3-7 9 Mo 0-5 Y 0.05-0.60 Zr 0.01-0.30 Hf 0.05-0.50 Ta 0.05-0.50 Ti 0-0.10 C 0.01-0.05 N 0.01-0.06 O 0.02-0.10 Si 0.10-0.70 Mn 0.05-0.50 P 0-0.8 S 0-0.005 4. A method as claimed in claim 3, wherein by causing the smelt to have a composition such that the powder obtained after 10 atomisation has the following approximate composition in percent by weight Fe balance Cr 21 percent by weight Al 4.7 ' Mo 3 Y 0.2 Zr 0.1 Hf 0.2 Ta 0.2 Ti C 0.03 N 0.04 O 0.06 Si 0.4 11 Mn 0.15 P S 5. A method as claimed in claims 1, 2, 3 or 4, wherein the value of the formula ((3xY + Ta)xO) + J(2xZr + Hf)x(N + C)) in which the elements are given in percent by weight in the smelt, shall exceed 0.04 but be less than 0.35. 6 6. High temperature material of a powder metallurgical FeCrAl alloy produced by gas atomisation, wherein the material in addition to containing iron (Fe), chromium (Cr) and aluminium (Al) also includes minor fractions of one or more of the materials molybdenum (Mo) hafnium (Hf) zirconium (Zr) yttrium (Y) nitrogen (N), carbon (C) and oxygen (O), wherein the material includes 0.05-0.50 percent by weight tantalum (Ta) and, at the same, time less than 0.10 percent by weight titanium. (Ti). 7. High temperature material as claimed in Claim 6, wherein the powder obtained by gas atomisation has the following composition in percent by weight: Fe balance Cr 15-25 percent by weight 12 Al 3-7 Mo 0-5 Y 0.05-0.60 Zr 0.01-0.30 Hf 0.05-0.50 Ta 0.05-0.50 Ti 0-0.10 C 0.01-0.05 N 0.01-0.06 O 0.02-0.10 Si 0.10-0.70 Mn 0.05-0.50 P 0-0.08 S 0-0.005 13 8. High temperature material as claimed in claim 7, the powder obtained has the following approximate composition in percent by weight: Fe balance Cr 21 percent by weight Al 4.7 Mo 3 Y 0.2 Zr 0.1 Hf 0.2 Ta 0.2 Ti C 0.03 N 0.04 O 0.06 14 Si 0.4. Mn 0.15 P S 9. High temperature material as claimed in claim 6, 7 or 8, wherein the value of the formula ((3xY + Ta)xO) + ((2xZr + Hf)x(N + C)), in which the elements are given in percent by weight in the smelt, shall exceed 0.04 but be less than 0.35. Dated this June 3, 15 |
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342-MUMNP-2005-ABSTRACT 30-6-2008.tif
342-MUMNP-2005-ABSTRACT(30-6-2008).pdf
342-mumnp-2005-assignement(23-12-2005).pdf
342-MUMNP-2005-ASSIGNMENT 30-6-2008.pdf
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342-MUMNP-2005-CERTIFIED COPY OF PRIORITY DOCUMENT 30-6-2008.pdf
342-MUMNP-2005-CLAIMS 30-6-2008.pdf
342-MUMNP-2005-CLAIMS(30-6-2008).pdf
342-mumnp-2005-claims(complete)-(28-4-2005).pdf
342-MUMNP-2005-COPY EP(1257375 B1)30-6-2008.tif
342-MUMNP-2005-CORRESPONDENCE 30-6-2008.pdf
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342-mumnp-2005-correspondence(ipo)-(8-8-2008).pdf
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342-mumnp-2005-correspondence-received.pdf
342-mumnp-2005-deed of assignment(23-12-2005).pdf
342-mumnp-2005-description (complete).pdf
342-MUMNP-2005-DESCRIPTION(COMPLETE) 30-6-2008.pdf
342-mumnp-2005-description(complete)-(28-4-2005).pdf
342-MUMNP-2005-DESCRIPTION(COMPLETE)-(30-6-2008).pdf
342-MUMNP-2005-FORM 1 30-6-2008.pdf
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342-MUMNP-2005-FORM 2(TITLE PAGE) 30-6-2008.pdf
342-MUMNP-2005-FORM 2(TITLE PAGE)-(30-6-2008).pdf
342-mumnp-2005-form 2(title page)-(complete)-(28-4-2005).pdf
342-MUMNP-2005-FORM 3 30-6-2008.pdf
342-MUMNP-2005-FORM 5 30-6-2008.pdf
342-mumnp-2005-form-pct-ipea-401.pdf
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342-MUMNP-2005-OTHER DOCUMENT 30-6-2008.pdf
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342-MUMNP-2005-POWER OF ATTORNEY 30-6-2008.pdf
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342-mumnp-2005-power of authority(30-6-2008).pdf
342-mumnp-2005-specification(amended)-(30-6-2008).pdf
342-mumnp-2005-wo international publication report(28-4-2005).pdf
Patent Number | 253724 | ||||||||||||
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Indian Patent Application Number | 342/MUMNP/2005 | ||||||||||||
PG Journal Number | 34/2012 | ||||||||||||
Publication Date | 24-Aug-2012 | ||||||||||||
Grant Date | 17-Aug-2012 | ||||||||||||
Date of Filing | 28-Apr-2005 | ||||||||||||
Name of Patentee | SANDVIK AB | ||||||||||||
Applicant Address | S-811 81 SANDVIKEN. | ||||||||||||
Inventors:
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PCT International Classification Number | B22F9/08 | ||||||||||||
PCT International Application Number | PCT/SE00/02571 | ||||||||||||
PCT International Filing date | 2000-12-18 | ||||||||||||
PCT Conventions:
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