EP3842556B1 - Impfverfahren zur kornfeinerung einer nickelbasislegierung - Google Patents
Impfverfahren zur kornfeinerung einer nickelbasislegierung Download PDFInfo
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- EP3842556B1 EP3842556B1 EP19383203.7A EP19383203A EP3842556B1 EP 3842556 B1 EP3842556 B1 EP 3842556B1 EP 19383203 A EP19383203 A EP 19383203A EP 3842556 B1 EP3842556 B1 EP 3842556B1
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- fenb
- crfenb
- inoculant
- base alloy
- nickel base
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims description 194
- 229910045601 alloy Inorganic materials 0.000 title claims description 92
- 239000000956 alloy Substances 0.000 title claims description 92
- 238000000034 method Methods 0.000 title claims description 79
- 229910052759 nickel Inorganic materials 0.000 title claims description 68
- 230000008569 process Effects 0.000 title claims description 58
- 238000011081 inoculation Methods 0.000 title claims description 46
- 239000002054 inoculum Substances 0.000 claims description 93
- 239000000843 powder Substances 0.000 claims description 48
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 47
- 239000000155 melt Substances 0.000 claims description 42
- 239000000203 mixture Substances 0.000 claims description 26
- 229910052742 iron Inorganic materials 0.000 claims description 24
- 239000002245 particle Substances 0.000 claims description 19
- 239000000463 material Substances 0.000 claims description 14
- 238000004519 manufacturing process Methods 0.000 claims description 10
- 229910052799 carbon Inorganic materials 0.000 claims description 9
- 229910052796 boron Inorganic materials 0.000 claims description 5
- 229910052804 chromium Inorganic materials 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 229910052758 niobium Inorganic materials 0.000 claims description 5
- 238000005275 alloying Methods 0.000 claims description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims description 3
- 238000007789 sealing Methods 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 229910052717 sulfur Inorganic materials 0.000 claims description 3
- 238000003466 welding Methods 0.000 claims description 3
- 239000012803 melt mixture Substances 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims 2
- 229910052748 manganese Inorganic materials 0.000 claims 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 14
- 229910000601 superalloy Inorganic materials 0.000 description 14
- 238000005266 casting Methods 0.000 description 11
- 239000002994 raw material Substances 0.000 description 11
- 239000000126 substance Substances 0.000 description 11
- 238000004458 analytical method Methods 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 10
- 238000002844 melting Methods 0.000 description 10
- 230000008018 melting Effects 0.000 description 10
- 238000005259 measurement Methods 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 229910000831 Steel Inorganic materials 0.000 description 7
- 239000010959 steel Substances 0.000 description 7
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 6
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 6
- 229910052791 calcium Inorganic materials 0.000 description 6
- 239000011575 calcium Substances 0.000 description 6
- 239000011651 chromium Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 229910052749 magnesium Inorganic materials 0.000 description 6
- 239000011777 magnesium Substances 0.000 description 6
- 239000007787 solid Substances 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 238000011049 filling Methods 0.000 description 4
- 229910001092 metal group alloy Inorganic materials 0.000 description 4
- 238000007670 refining Methods 0.000 description 4
- 229910000990 Ni alloy Inorganic materials 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000005498 polishing Methods 0.000 description 3
- 230000000750 progressive effect Effects 0.000 description 3
- 238000005086 pumping Methods 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 239000011343 solid material Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 238000004876 x-ray fluorescence Methods 0.000 description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000003486 chemical etching Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 230000003009 desulfurizing effect Effects 0.000 description 2
- 230000001627 detrimental effect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000000265 homogenisation Methods 0.000 description 2
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 2
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 230000006698 induction Effects 0.000 description 2
- 238000005495 investment casting Methods 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- 229910001018 Cast iron Inorganic materials 0.000 description 1
- 229910019114 CoAl2O4 Inorganic materials 0.000 description 1
- 229910005347 FeSi Inorganic materials 0.000 description 1
- 206010037660 Pyrexia Diseases 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 239000000788 chromium alloy Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000005562 fading Methods 0.000 description 1
- RLQJEEJISHYWON-UHFFFAOYSA-N flonicamid Chemical compound FC(F)(F)C1=CC=NC=C1C(=O)NCC#N RLQJEEJISHYWON-UHFFFAOYSA-N 0.000 description 1
- 239000003517 fume Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910000816 inconels 718 Inorganic materials 0.000 description 1
- 238000010297 mechanical methods and process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 238000005088 metallography Methods 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910000623 nickel–chromium alloy Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- -1 preferably Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000011819 refractory material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
- C22C1/023—Alloys based on nickel
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/06—Making non-ferrous alloys with the use of special agents for refining or deoxidising
-
- 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
-
- 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
- C22C3/00—Removing material from alloys to produce alloys of different constitution separation of the constituents of alloys
Definitions
- the present invention is encompassed within the sector of metallurgical industry. Particularly it is related to an inoculation process for a nickel base alloy to achieve grain refinement.
- the process of the present invention comprises using a mixture of Co 3 FeNb 2 and CrFeNb(Ni) as inoculant, where such compounds are introduced inside the melt nickel base alloy encapsulated, and the inoculation step is carried out at a temperature from 1450 to 1500 °C for a period from 5 to 30 seconds.
- the inoculant process described in this document can produce a fine and equiaxial grain size, which promotes high mechanical properties such as tensile stress, yield stress and elongation and, at the same time, this process can provide a complete filling of the mold.
- the invention further comprises the manufacture of the encapsulated inoculant and adaption for its introduction inside the melt nickel base alloy.
- Nickel base alloys and, in particular, the so-called nickel base superalloys are frequently used for elevated mechanical strength and high temperature performance applications, mainly for aeronautics and energy sectors ( G. Marahleh, A. R. I. Kheder, H. F. Hamad, CREEP-LIFE PREDICTION OF SERVICE-EXPOSED TURBINE BLADES, Materials Science, Vol. 42, No. 4, 2006 ).
- Some components for engines are manufactured by conventional casting in an open-air furnace but most of them by investment casting process using a Vacuum Induction Melting (VIM) furnace as equipment for the melting, casting and pouring of the melt.
- VIP Vacuum Induction Melting
- Common problems associated to the investment casting are high pouring temperature ( ⁇ 1450°C) of the melt and the use of preheated mold, both practices assure a good filling of the components but result in long solidification time and thus coarse and columnar grain sizes.
- Inoculation process is a well-known technology for the modification of internal microstructure of metallic alloys.
- Addition of FeSi to cast iron, and Titanium and Boron to AlSi7Mg alloys are some traditional examples of inoculation processes for grain refinement performed in metallic alloys with great mechanical properties improvement and reduction of porosity.
- the demands of better performance have led to the development of methods to obtain fine and uniform grain sizes in the microstructure.
- WO2015108599 A2 describes a method of preparing superalloy metals having a crystallographic texture controlled micro structure by electron beam melting.
- the method therein described comprises the steps of providing a metal alloy powder composition, providing a seed crystal, and processing the metal alloy powder composition in the presence of the seed crystal to provide a superalloy metal having a textured or single crystal micro structure.
- the process further comprises providing an inoculant prior to the processing step.
- Said inoculant may be an oxide or iron-based inoculant, in particular, the inoculant may be Co 3 FeNb 2 , CrFeNb, CoAl 2 O 4 or combinations thereof.
- GB414053 A describes a high vacuum furnace that can be used in the production and refining of Ni based alloys.
- US3343828 A describes improvements in vacuum furnaces used in the production of Ni based alloys.
- US4094666 A relates to a method for refining molten iron, steel, nickel alloy or chromium alloy by adding a compressed and deformed composite clad containing deoxidizing agent or desulfurizing agent. More particularly, this patent document refers to a method for refining molten iron and steels by adding the composition clads containing calcium, calcium base alloys, magnesium or magnesium base alloy having a low vaporizing temperature as the core at a high feeding rate (column 1, lines 5-14).
- the method for refining molten iron and steel bath therein described comprises feeding a compressed and deformed composite clad material of a solidified core encased in a sheath in wire and rod form having a sufficient rigidity obtained by clading a core consisting essentially of at least one element of metallic calcium, metallic magnesium, calcium base alloys and magnesium base alloys, with a sheath of iron and mechanically compressing and deforming the resulting clad, into the molten iron and steel bath at a feeding rate of 20-500 m/min, a rate of feeding fast enough to avoid forming a fume or a flame of calcium or magnesium, whereby substantially 100% of the added calcium or magnesium is effectively reacted with said molten iron and steel bath, while deoxidizing, desulfurizing, spherodizing of graphite and inoculating said molten iron and steel bath are effectively carried out.
- the present invention provides an improved inoculation process, which is able to achieve successful grain refinement of castings at industrial pouring temperatures, preferable from 1450°C to 1500°C.
- the chemical composition of the encapsulated inoculant used in this process does not introduce strange elements or modify seriously the chemical composition of the nickel base alloy.
- the invention disclosed in this patent application refers to an inoculation process of a nickel base alloy, wherein the process is carried out in a vacuum furnace and comprises:
- the inoculation process of the present invention can successfully achieve grain refinement of the nickel base alloy, more specifically the inoculated nickel base alloy, obtained by such process.
- the ratio between the mean length (L) and the mean width (W) has been evaluated for the definition of the columnar or equiaxial morphology of the grain.
- the approach taken for the grain refinement measurement is defined by two parameters: the grain size value and the grain morphology, which should correspond to mean grain length (L) below 2 mm and L/W ratio equal or below 1.5 for equiaxial grain, respectively.
- the pouring of the inoculated nickel base alloy takes place immediately after the inoculation period has finished, this means that steps b) and c) shall be done consecutively, without any delay between them.
- the inoculation process described herein is carried out in a vacuum furnace, preferably a Vacuum Induction Melting (VIM) furnace.
- VIM Vacuum Induction Melting
- this process can be carried out by introduction of the encapsulated inoculant inside a melt of a nickel base alloy in a VIM furnace, which comprises internally communicated two chambers (charging and main chamber) with vacuum pressure, which can be measured by Pirani and Penning gauges.
- the encapsulated inoculant can be placed in the charging chamber and the main chamber is used for the melting and inoculation process of the nickel base alloy.
- the vacuum furnace (in particular, VIM furnace) wherein the inoculation process is to be carried out has been modified, so that it further comprises means for introducing the encapsulated inoculant inside the melt of nickel base alloy, such as, for example a pulley system.
- the melt of nickel base alloy to be inoculated in the process of the invention comprises Ni, Cr, Co, Nb and Fe. These elements are present in the inoculant mixture used in the process herein described and, therefore, such process can provide the desired grain refinement without introducing strange elements or significantly modifying the chemical composition of the alloy.
- the melt of nickel base alloy provided in step a) of the inoculation process more preferably comprises:
- the melt of nickel base alloy to be inoculated in the process described is an alloy, commonly known as IN718, which comprises:
- the melt of a nickel base alloy of step a) can be obtained by any suitable means known by the skilled person in the art.
- such melt can be obtained by melting one or more nickel base alloy ingots or, alternatively, the melt of a nickel base alloy can be obtained from raw materials of the elements comprised such alloy, preferably, raw materials with purity between 99-100 wt. %.
- step a) of the inoculation process can comprise progressively heating either the nickel base alloy ingots or raw materials of the alloying elements in vacuum conditions, for example, at a pressure from 5 ⁇ 10 -3 to 5 ⁇ 10 -4 mbar, until the melt of nickel base alloy is obtained.
- the temperature of the alloy can be continuously measured by a Spectropyrometer (FAR Associates FMP2 multi-wavelength pyrometer) instead of a conventional two-color optical pyrometer or immersion thermocouple.
- Spectropyrometer FAR Associates FMP2 multi-wavelength pyrometer
- the advantage of the Spectropyrometer is that the emissivity behavior is determined from data collected every measurement by means of the use of hundreds of narrow wavebands which allows accurate temperature control.
- the encapsulated inoculant preferably comprises a mixture of
- the Co 3 FeNb 2 and CrFeNb(Ni) contained in the encapsulated inoculant are powders with a particle size from 1 to 80 ⁇ m.
- the encapsulated inoculant comprises a mixture of:
- the above-mentioned particle size distribution provided is particularly advantageous because an improved grain refinement effect can be achieved. More specifically, the combination of the powder size of the inoculants, time used for inoculation and temperature of the molten metal during inoculation are relevant to achieve a better effectiveness of the inoculation process. The control of these features results in the repeatability of the process.
- Inoculants used in the process of the invention i.e., Co 3 FeNb 2 and CrFeNb(Ni), preferably have an amount of C lower than 0.05 %wt. Carbon is an impurity that might be present on the raw materials used to manufacture these inoculant. A higher amount of C in the inoculant could give rise to carbide formation, which could negatively affect mechanical properties of the inoculated nickel base alloy.
- the powders of Co 3 FeNb 2 and CrFeNb(Ni) are introduced inside the melt nickel base alloy encapsulated in a sealed container of a material compatible with the nickel base alloy, i.e., a material not comprising significant amounts of any elements strange to the nickel base alloy.
- a material compatible with the nickel base alloy i.e., a material not comprising significant amounts of any elements strange to the nickel base alloy.
- such material is iron based and, more preferably, the sealed container of the encapsulated inoculant is made of an iron base alloy comprising
- the container where the inoculants are encapsulated may have different dimensions and different forms such as tubular form. In the process of the invention, however, it is preferable that such container will be as small as possible, with the proviso that the inoculant powders can be stored into the container. Additionally, the thickness of the container's walls are lower than 2 mm, so that the minimum amount of the container's material is incorporated at the nickel base alloy in the inoculation process.
- the container of the encapsulated inoculant has to be sealed, so that the inoculant powders cannot left the container prior to the introduction of said encapsulated inoculant inside the melt nickel base alloy.
- Any conventional sealing means can be used, for example, pressure and/or spot welding.
- the total content of Co 3 FeNb 2 and CrFeNb(Ni) contained in the encapsulated inoculant introduced inside the melt nickel base alloy is from 0.1 wt. % to 0.8 wt. %, preferably from 0.4 wt. % to 0.6 wt. %, of the weight of the melt nickel base alloy weight in step a).
- the total content of Co 3 FeNb 2 and CrFeNb(Ni) in the encapsulated inoculant is 0.6 wt. % of the weight of the nickel base alloy weight in step a), both Co 3 FeNb 2 and CrFeNb(Ni) are powders with a particle size from 1 to 80 ⁇ m, and the encapsulated inoculant is introduced, preferably for a period of 10 seconds, inside the melt mixture of alloying elements at a temperature of 1485 °C.
- a power supply of the vacuum furnace is reduced or, preferably, switched off to avoid electromagnetic stirring.
- the inventors have found that a high electromagnetic stirring during the inoculation step can jeopardize grain refinement, among other things due to quick dissolution of the inoculants.
- a reduced power supply in the heating process to obtain the melt of nickel base alloy can be used or, preferably, the power supply required to achieve a melt in a suitable time can be reduced or even switched off, once the melt is obtained.
- An important advantage of the inoculation process of the present invention is that the mixture of inoculant powders with the required particle size of between 1 ⁇ m and 80 ⁇ m are contained in the encapsulated inoculant within a sealed container and, therefore, they can be properly introduced inside the melt of nickel base alloy, preferably in the central part of said melt, without electromagnetic stirring. If such powders would be left (un-encapsulated) on the surface of the melt, they would be mixed with the slag and, therefore, the inoculant compounds could not disperse thought the melt alloy.
- Another important advantage of using encapsulated inoculants is that the dissolution rate of the inoculant powder can be reduced, so that a greatest grain refinement effect is achieved with the process of the present invention.
- An alumina crucible can be used to obtain the melt of nickel base alloy.
- such crucible is preferably a high alumina crucible with a content of alumina higher than 60 wt. %, because this material avoids the formation of impurities during the procedure.
- the mold can be positioned close to the alumina crucible, in particular, the distance between the mold and the alumina crucible containing the melt inoculated nickel base alloy is about 300 mm, so that turbulence when pouring can be avoided.
- the encapsulated inoculant is manufactured by the following method:
- the encapsulated inoculant comprises a handling system, which can be used for introducing it inside the melt of nickel base alloy, for example, using any suitable means incorporated to the vacuum furnace such as a pulley system.
- the handling system can be a wire of similar material than the container.
- a material compatible with the nickel base alloy as defined in this document in relation with the material of the container is particularly preferred.
- the method for manufacturing it further comprises attaching the handling system to the container.
- Co 3 FeNb 2 and CrFeNb(Ni) powders to be used as inoculant can be separately manufactured using conventional methods.
- these inoculants can be manufactured, for example in the 20 kg single chamber Consarc VIM furnace, by a method comprising the following steps:
- the cast inoculated can be sectioned and specimen can be prepared by conventional grinding and polishing methods. Then, ADLER chemical etching (40-60% hydrogen chloride, 5-25% iron trichloride, 2-5% diammonium tetrachlorocuprate) for nickel alloys can be used to reveal grain structure.
- the average grain length and width size can be obtained according to the length and the width of 10-25 grain measurement performed in two 11 mm ⁇ 8 mm regions of the central area of the cast part (metallic sample of 30 mm ⁇ 30 mm ⁇ 35 mm) with 10X magnification in a Olympus SZH binocular magnifier.
- the ratio between the mean length (L) and the mean width (W) has been also evaluated for the definition of the columnar or equiaxial morphology of the grain.
- the approach taken for the grain refinement method is defined by two parameters: the grain size and the grain morphology which should correspond to mean grain length below 2 mm and L/W ratio equal or below 1.5 for equiaxial grain, respectively.
- Table 4 Amount and powder size range of the inoculant compounds Amount (g) from 1 ⁇ m to 20 ⁇ m of Co 3 FeNb 2 4.5 from above 20 ⁇ m to 80 ⁇ m of Co 3 FeNb 2 4.5 from 1 ⁇ m to 20 ⁇ m of CrFeNb(Ni) 4.5 from above 20 ⁇ m to 80 ⁇ m of CrFeNb(Ni) 4.5
- the encapsulated inoculant prepared in Example 4 has been placed in the charging chamber of the VIM furnace.
- a defined mold for the 30 ⁇ 30 ⁇ 35 mm part has been positioned close to the crucible (in particular, at the distance of 300 mm) to avoid the turbulence when pouring the mold, as shown in Figure 4 .
- the VIM furnace has been vacuum pumped to 5 ⁇ 10 -4 mbar pressure and then the melt of the alloy has been obtained by manual control of the power settings to allow slow heating of the crucible following this sequence: 5 KW for 20 minutes, 10 KW for 10 minutes and 15 KW for 10 minutes.
- the power has been slightly increased to 18 KW to reach the preferred temperature range for industrial process (1480-1490 °C).
- the temperature of the nickel base alloy during the heating process has been continuously measured by a Spectropyrometer (FAR Associates FMP2 multi-wavelength pyrometer), showing the temperature at the end of the heating process in Figure 5 .
- the solid materials have been progressively melted until reaching 1484 °C, at this moment the power of the furnace has been switched off and the encapsulated inoculant (obtained as described in Example 4) has been introduced into the molten alloy.
- the container of the encapsulated inoculant has been melted in approximately 10 seconds and then the inoculant powders have been left for 5-10 seconds inside the metal.
- the inoculated alloy has been poured into the mold and left for natural cooling inside the furnace.
- the cast inoculated 30 ⁇ 30 ⁇ 35 mm part has been sectioned as presented in Figure 6 and specimen has been prepared by conventional grinding and polishing methods.
- grinding has been carried out according to the use of SiC papers in this order: P80, P220, P1200 and P2400 and polishing with diamond paste of 3, 0.25 and 0.04 ⁇ m.
- ADLER chemical etching 40-60% hydrogen chloride, 5-25% iron trichloride, 2-5% diammonium tetrachlorocuprate
- the average grain size has been obtained according to the length and the width of 10-25 grains.
- Grain size measurements have been carried out in two 11mm ⁇ 8mm regions ( Figure 7 and Figure 8 ) of 0.6 wt. % inoculated cast part. Images have been taken with 10X magnification by a Olympus SHZ binocular magnifier. The ratio between the mean length (L) and the mean width (W) has been also measured for the definition of the morphology (columnar or equiaxial) of the grain. Mean values of length and width and the morphology of the grains from both regions are detailed in Table 6. It is demonstrated that the requirements of grain size below 2 mm and ratio morphology equal or below 1.5 are fulfilled and therefore grain refinement has been successfully achieved.
- Figure 9 shows an image of a non inoculated cast part with large grains up to 4 mm length and columnar grain microstructure with approximate ratio of 3 between the length and the width.
- Table 6 Mean grain size measurements from Zone 1 and Zone 2 of 0.6 wt. % inoculated cast part Mean length ( ⁇ m) Mean width ( ⁇ m) Grain morphology (Length/Width) Zone 1 915 625 Equiaxial 1.46 Zone 2 1010 680 Equiaxial 1.49
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- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Refinement Of Pig-Iron, Manufacture Of Cast Iron, And Steel Manufacture Other Than In Revolving Furnaces (AREA)
Claims (13)
- Impfverfahren für eine Nickelbasislegierung, wobei das Verfahren in einem Vakuumofen durchgeführt wird und aufweist:a) Bereitstellen einer Schmelze aus einer Nickelbasislegierung unter Vakuumbedingungen, dadurch gekennzeichnet, dass das Impfverfahren ferner aufweist:b) Einbringen eines gekapselten Impfmittels, das eine Mischung aus Co3FeNb2 und CrFeNb(Ni) aufweist, in die Schmelze der Nickelbasislegierung bei einer Temperatur von 1450 bis 1500 °C für einen Zeitraum von 5 bis 30 Sekunden,c) sofortiges Gießen der geimpften Nickelbasislegierung aus Schritt b) in eine Form, vorzugsweise bei einer Temperatur von 1450 bis 1500 °C, undd) Abkühlen der geimpften Nickelbasislegierung,wobei die Mischung aus Co3FeNb2 und CrFeNb(Ni) in einem auf Eisenbasis versiegelten Behälter eingekapselt ist, wobei der Behälter Wände mit einer Dicke von weniger als 2 mm aufweist,wobei der Gesamtgehalt an Co3FeNb2 und CrFeNb(Ni) von 0,1 Gew.-% bis 0,8 Gew.-% der geschmolzenen Nickelbasislegierung beträgt, undwobei das Co3FeNb2 und CrFeNb(Ni), die in dem eingekapselten Impfstoff enthalten sind, Pulver mit einer Teilchengröße von 1 bis 80 µm sind.
- Das Impfverfahren nach Anspruch 1, wobei die schmelzflüssige Nickelbasislegierung Ni, Cr, Co, Nb und Fe aufweist.
- Das Impfverfahren nach einem der Ansprüche 1 bis 2, wobei die schmelzflüssige Nickelbasislegierung aufweist:Ni: 50 Gew.-% bis 65 Gew.-%,Cr: 10 Gew.-% bis 25 Gew.-%,Mo: 2 Gew.-% bis 5 Gew.-%,Co: 0,01 Gew.-% bis 1 Gew.-%,Nb: 0,04 Gew.-% bis 5,5 Gew.-%, undFe: 1 Gew.-% bis 24 Gew.-%,wobei die Prozentangaben in Gewichtsprozent in Bezug auf das Gesamtgewicht der Nickelbasislegierung angegeben sind.
- Das Impfverfahren nach einem der Ansprüche 1 bis 3, wobei die Schmelze der Nickelbasislegierung aufweist:Ni: 50 Gew.-% bis 55 Gew.-%,Cr: 17 Gew.-% bis 21 Gew.-%,Mo: 2,8 Gew.-% bis 3,3 Gew.-%,Co: 0,01 Gew.-% bis 1 Gew.-%,Nb: 4,75 Gew.-% bis 5,5 Gew.-%,Fe: 12 Gew.-% bis 22 Gew.-%,Ti: 0,65 Gew.-% bis 1,15 Gew.-%,Al: 0,2 Gew.-% bis 0,8 Gew.-%,C: nicht mehr als 0,08 Gew.-%,Si: nicht mehr als 0,35 Gew.-%,Mn: nicht mehr als 0,35 Gew.-%,P: nicht mehr als 0,015 Gew.-%,S: nicht mehr als 0,015 Gew.-% undB: nicht mehr als 0,006 Gew.-%,wobei die Prozentsätze in Gewichtsprozent in Bezug auf das Gesamtgewicht der Nickelbasislegierung angegeben sind.
- Impfverfahren nach einem der Ansprüche 1 bis 4, wobei das eingekapselte Impfmittel eine Mischung aufweist ausvon 45 bis 55 Gew.-% Co3FeNb2, und55 bis 45 Gew.-% CrFeNb(Ni),wobei die Prozentsätze in Gewichtsprozent angegeben sind, bezogen auf das Gesamtgewicht der Mischung aus Co3FeNb2 und CrFeNb(Ni).
- Impfverfahren nach Anspruch 1, wobei das eingekapselte Impfmittel eine Mischung aus:20 Gew.-% bis 30 Gew.-% Co3FeNb2-Pulver mit einer Teilchengröße von 1 bis 20 µm, und20 Gew.-% bis 30 Gew.-% Co3FeNb2-Pulver mit einer Teilchengröße von über 20 bis 80 µm, mit der Maßgabe, dass das Gesamtgewicht der Co3FeNb2-Pulver 45 bis 55 Gew.-% des Gesamtgewichts von Co3FeNb2 und CrFeNb(Ni) beträgt;20 Gew.-% bis 30 Gew.-% CrFeNb(Ni)-Pulver mit einer Teilchengröße von 1 bis 20 µm, und20 Gew.-% bis 30 Gew.-% CrFeNb(Ni)-Pulver mit einer Teilchengröße von über 20 bis 80 µm; vorausgesetzt, dass das Gesamtgewicht der CrFeNb(Ni)-Pulver 55 bis 45 Gew.-% des Gesamtgewichts von Co3FeNb2 und CrFeNb(Ni) beträgt.
- Das Impfverfahren nach einem der Ansprüche 1 bis 6, wobei sowohl Co3FeNb2 als auch CrFeNb(Ni) eine Menge an C von weniger als 0,05 Gew.-% aufweisen.
- Das Impfverfahren nach einem der Ansprüche 1 bis 7, wobei der versiegelte Behälter auf Eisenbasis aufweist:C: 0 bis 0,08 Gew.-%,S: 0 bis 0,03 Gew.-%,P: 0 bis 0,045 Gew.-%,B: 0 bis 0,045 Gew.-%, undSi: 0 bis 0,075 Gew.-%,wobei die Prozentangaben in Gewichtsprozent in Bezug auf das Gesamtgewicht des Eisenbasismaterials des Behälters angegeben sind.
- Das Impfverfahren nach einem der Ansprüche 1 bis 8, wobei der Gesamtgehalt an Co3FeNb2 und CrFeNb(Ni) von 0,4 Gew.-% bis 0,6 Gew.-% der geschmolzenen Nickelbasislegierung beträgt.
- Das Impfverfahren nach Anspruch 9, wobei der Gesamtgehalt an Co3FeNb2 und CrFeNb(Ni) in dem eingekapselten Impfmittel 0,6 Gew.-% der geschmolzenen Nickelbasislegierung beträgt, sowohl Co3FeNb2 als auch CrFeNb(Ni) Pulver mit einer Teilchengröße von 1 bis 80 µm sind und das eingekapselte Impfmittel vorzugsweise für einen Zeitraum von 10 Sekunden in die Schmelzmischung der Legierungselemente bei einer Temperatur von 1485 °C eingebracht wird.
- Das Impfverfahren nach einem der Ansprüche 1 bis 10, wobei die Energieversorgung des Vakuumofens reduziert oder vorzugsweise abgeschaltet wird, bevor das eingekapselte Impfmittel in die Schmelze der Nickelbasislegierung eingebracht wird.
- Das Impfverfahren nach einem der Ansprüche 1 bis 11, wobei das eingekapselte Impfmittel nach dem folgenden Verfahren hergestellt wird:i) Bereitstellen von Co3FeNb2-Pulvern mit einer Teilchengröße von 1 bis 80 µm;ii) Bereitstellen von CrFeNb(Ni)-Pulvern mit einer Teilchengröße von 1 bis 80 µm;iii) Herstellen einer Mischung, die 45 bis 55 Gew.-% der Co3FeNb2-Pulver aus Schritt i) und 55 bis 45 Gew.-% der CrFeNb(Ni)-Pulver aus Schritt ii) aufweist;iv) Einbringen der in Schritt iii) hergestellten Mischung in einen Behälter auf Eisenbasis, vorzugsweise ein Rohr, undv) Versiegeln des Behälters, vorzugsweise durch Druck- und Punktschweißen.
- Das Impfverfahren nach Anspruch 12, wobei das eingekapselte Impfmittel ein Handhabungssystem aufweist und, vorzugsweise, das Verfahren zur Herstellung eines solchen eingekapselten Impfmittels ferner das Anbringen des Handhabungssystems an dem Behälter umfasst.
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