DE2530197A1 - COATING ALLOYS OF THE MCRALY TYPE - Google Patents
COATING ALLOYS OF THE MCRALY TYPEInfo
- Publication number
- DE2530197A1 DE2530197A1 DE19752530197 DE2530197A DE2530197A1 DE 2530197 A1 DE2530197 A1 DE 2530197A1 DE 19752530197 DE19752530197 DE 19752530197 DE 2530197 A DE2530197 A DE 2530197A DE 2530197 A1 DE2530197 A1 DE 2530197A1
- Authority
- DE
- Germany
- Prior art keywords
- alloy
- weight
- coating
- platinum
- group
- 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
Links
- 229910045601 alloy Inorganic materials 0.000 title claims description 63
- 239000000956 alloy Substances 0.000 title claims description 63
- 238000000576 coating method Methods 0.000 title claims description 40
- 239000011248 coating agent Substances 0.000 title claims description 27
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 46
- 229910052697 platinum Inorganic materials 0.000 claims description 22
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 18
- 238000005260 corrosion Methods 0.000 claims description 17
- 230000007797 corrosion Effects 0.000 claims description 17
- 229910052703 rhodium Inorganic materials 0.000 claims description 17
- 239000010948 rhodium Substances 0.000 claims description 17
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 16
- 229910052751 metal Inorganic materials 0.000 claims description 13
- 239000002184 metal Substances 0.000 claims description 13
- 229910052727 yttrium Inorganic materials 0.000 claims description 10
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 9
- 229910052782 aluminium Inorganic materials 0.000 claims description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 8
- 229910017052 cobalt Inorganic materials 0.000 claims description 8
- 239000010941 cobalt Substances 0.000 claims description 8
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 8
- 229910052759 nickel Inorganic materials 0.000 claims description 8
- 229910000510 noble metal Inorganic materials 0.000 claims description 8
- 229910052706 scandium Inorganic materials 0.000 claims description 6
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 5
- 240000002989 Euphorbia neriifolia Species 0.000 claims description 5
- 229910052804 chromium Inorganic materials 0.000 claims description 5
- 239000011651 chromium Substances 0.000 claims description 5
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 claims description 5
- 150000002910 rare earth metals Chemical class 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 3
- 229910000967 As alloy Inorganic materials 0.000 claims description 2
- 229910000531 Co alloy Inorganic materials 0.000 claims 1
- 229910000990 Ni alloy Inorganic materials 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 229910052761 rare earth metal Inorganic materials 0.000 claims 1
- 239000000203 mixture Substances 0.000 description 16
- 239000000758 substrate Substances 0.000 description 6
- 229910000951 Aluminide Inorganic materials 0.000 description 5
- 238000009792 diffusion process Methods 0.000 description 5
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 description 4
- 239000008199 coating composition Substances 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 229910052746 lanthanum Inorganic materials 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 230000001681 protective effect Effects 0.000 description 3
- 229910000601 superalloy Inorganic materials 0.000 description 3
- 238000007740 vapor deposition Methods 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000003628 erosive effect Effects 0.000 description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 2
- 235000002639 sodium chloride Nutrition 0.000 description 2
- 229910002543 FeCrAlY Inorganic materials 0.000 description 1
- 108010013381 Porins Proteins 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 229910052776 Thorium Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000007750 plasma spraying Methods 0.000 description 1
- 102000007739 porin activity proteins Human genes 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000005486 sulfidation Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01D—NON-POSITIVE DISPLACEMENT MACHINES OR ENGINES, e.g. STEAM TURBINES
- F01D5/00—Blades; Blade-carrying members; Heating, heat-insulating, cooling or antivibration means on the blades or the members
- F01D5/12—Blades
- F01D5/28—Selecting particular materials; Particular measures relating thereto; Measures against erosion or corrosion
- F01D5/288—Protective coatings for blades
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C19/00—Alloys based on nickel or cobalt
- C22C19/03—Alloys based on nickel or cobalt based on nickel
- C22C19/05—Alloys based on nickel or cobalt based on nickel with chromium
- C22C19/058—Alloys based on nickel or cobalt based on nickel with chromium without Mo and W
-
- C—CHEMISTRY; METALLURGY
- C23—COATING 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
- C23C—COATING 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
- C23C30/00—Coating with metallic material characterised only by the composition of the metallic material, i.e. not characterised by the coating process
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T50/00—Aeronautics or air transport
- Y02T50/60—Efficient propulsion technologies, e.g. for aircraft
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/12—All metal or with adjacent metals
- Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
- Y10T428/12771—Transition metal-base component
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/12—All metal or with adjacent metals
- Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
- Y10T428/12771—Transition metal-base component
- Y10T428/12778—Alternative base metals from diverse categories
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/12—All metal or with adjacent metals
- Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
- Y10T428/12771—Transition metal-base component
- Y10T428/12861—Group VIII or IB metal-base component
- Y10T428/12875—Platinum group metal-base component
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/12—All metal or with adjacent metals
- Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
- Y10T428/12771—Transition metal-base component
- Y10T428/12861—Group VIII or IB metal-base component
- Y10T428/12944—Ni-base component
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Metallurgy (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Engineering & Computer Science (AREA)
- Coating By Spraying Or Casting (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
- Solid-Phase Diffusion Into Metallic Material Surfaces (AREA)
- Physical Vapour Deposition (AREA)
- Turbine Rotor Nozzle Sealing (AREA)
Description
ft±rtarvdt„ft ± rtarvdt "
Diplrkj M MengDiplrkj M Meng
UNITED TECHNOLOGIES CORPORATIONUNITED TECHNOLOGIES CORPORATION
1 Financial Plaza 8011 Porin9 /München, Hjbertusstrasse 2· 1 Financial Plaza 8011 Porin 9 / Munich, Hjbertusstrasse 2
' Telefon (0 81 00) 21 76'' Telephone (0 81 00) 21 76
Hartford, Connecticut 06101 Telegramme PATENTMENGES Zorneding Hartford, Connecticut 06101 Telegrams PATENTMENGES Zorneding
. Juli 1975. July 1975
ÜEBERZUGSLEGIERUNGEN DES MCrAlY TYPS.COATING ALLOYS OF THE MCrAlY TYPE.
Die vorliegende Erfindung bezieht sich auf Legierungen und im beisonderen auf Nickel, Kobalt oder Nickel-Kobalt-Ueberzugslegierungen mit verbessertem Korrosionswiderstand in der Wärme.The present invention relates to alloys and in particular to nickel, cobalt or nickel-cobalt coating alloys with improved corrosion resistance in heat.
Es ist bekannt, dass die Superlegierungen von Strahltriebwerken einer Oxydation-Erosion und Wärmekorrosion bei sehr hohen Temperaturen ausgesetzt sind und dass diese Superlegierungen normalerweise mit einer von der Legierung verschiedenen Zusammensetzung überzogen werden welche mit Bezug auf die Legierung einen höheren Widerstand gegen die Oxydationserosion und Korrosion aufweist.It is known that the superalloys of jet engines are susceptible to oxidation-erosion and thermal corrosion at very high levels Temperatures and that these superalloys usually have a composition different from the alloy which, with respect to the alloy, have a higher resistance to oxidative erosion and corrosion having.
!Sei Arten von Üeberzugslegierungen sind bekannt:! There are known types of coating alloys:
(1) Aluminidüberzüge wie z.B. in den US Patenten 3 102 044,(1) aluminide coatings such as in U.S. Patents 3,102,044,
3 677 789 und 3 692 554 beschrieben gemäss welchen die Aluminide öurch Reaktion mit oder Diffusion eines Ueberzuges auf die Substratoberfläche der Legierungen erhalten werden und,3,677,789 and 3,692,554, according to which the aluminides By reaction with or diffusion of a coating on the Substrate surface of the alloys are obtained and,
(2) Ueberzüge des MCrAlY Typs, z.B. NiCrAlY aus dem US Patent 3 754 903, CoCrAlY aus dem US Patent 3 676 085, NiCoCrAlY aus der US Patentanmeldung 469 186 vom 13. Mai 1974 und FeCrAlY(2) Coatings of the MCrAlY type, e.g. NiCrAlY from the US patent 3,754,903, CoCrAlY from U.S. Patent 3,676,085, NiCoCrAlY from U.S. Patent Application 469,186 dated May 13, 1974, and FeCrAlY
509885/1232509885/1232
25 3019?25 3019?
aus dem US Patent 3 542 530. Besonders wirkungsvoll sind MCrAlY Ueberzüge welche aus ungefähr 8 bis 30 Gew.% Chrom, 5 bis 15 Gew.% Aluminium, bis zu 1 Gew.% eines reaktiven Metalles ausgewählt aus Yttrium, Scandium, Thor und Lanthan und anderen Elementen der Gruppe der seltenen Erden ausgewählt werden, wobei der Rest von Nickel, Kobalt und Nickel-Kobalt gebildet wird. Solche Ueberzüge werden in einer Schichtdicke um 0,12 bis 0,15 mm aufgetragen.from US Pat. No. 3,542,530. MCrAlY coatings which consist of approximately 8 to 30% by weight of chromium and 5 to 15% by weight are particularly effective Aluminum, up to 1% by weight of a reactive metal selected from yttrium, scandium, thor and lanthanum and other elements of the Rare earth group, with the remainder made up of nickel, cobalt and nickel-cobalt. Such coatings are applied in a layer thickness of 0.12 to 0.15 mm.
Im Gegensatz zu diesen Ueberzügen werden die Diffusionsaluminidueberzüge durch Reaktion von Aluminium mit der entoxydierten Oberfläche der zu schützenden Legierung erhalten wobei die Aluminidschicht durch Diffusion mit den Substratbestandteilen erhalten wird und somit verschiedene Komponentenverteilungen aufweist. Die Aluminidschicht oxydiert wobei ein inertes Schutzoxyd entsteht. Gemäss den US Patenten 3 677 789 und 3 692 554 wird eine separate Schicht eines Metalles aus der Platingruppe vor der Aluminiumdiffusionsbehandlung aufgebracht. Da die meisten eingesetzten Substratlegierungen jedoch sehr komplex sind und da die Ueberzugszusammensetzung teilweise aus Bestandteilen der Substratlegierungen aufgebaut wird ist es schwierig die Ueberzugszusammensetzung sowie die Ausbildung eines geeigneten Schutzoxydes zu regeln. Desweiteren sind die durch Diffusion hergestellten Ueberzüge nicht homogen und, mit Bezug auf den Gehalt an Metall der platingruppe, tritt eine hohe Konzentration dieses Metalles an der Oberfläche des Ueberzuges auf. Das Vorherrschen eines solchen Konzentrationsgradienten ist unvorteilhaft da die Wirksamkeit des Ueberzuges von der Zusammensetzung desselben abhängt.In contrast to these coatings, the diffusion aluminide coatings are used obtained by reaction of aluminum with the deoxidized surface of the alloy to be protected, the Aluminide layer is obtained by diffusion with the substrate components and thus has different component distributions. The aluminide layer oxidizes and an inert protective oxide is formed. According to U.S. Patents 3,677,789 and 3,692,554, a separate layer of a metal from the platinum group applied before the aluminum diffusion treatment. As most of the used However, substrate alloys are very complex and because the coating composition is partly made up of constituents of the substrate alloys It is difficult to determine the coating composition and the formation of a suitable protective oxide rules. Furthermore, the coatings produced by diffusion are not homogeneous and, with regard to the metal content, the platinum group, a high concentration of this metal occurs at the Surface of the coating. The prevalence of such a concentration gradient is disadvantageous because of the effectiveness the coating depends on its composition.
Obschon die Ueberzugszusammensetzungen der Technik verschiedene Vorteile mit Bezug auf die älteren Ueberzugszusammensetzungen aufwiesen waren diese ueberzüge noch nicht befriedigend und Anstrengungen wurden unternommen um bessere Ueberzüge, insbesondere mit Bezug auf Wärmekorrosion, zu erhalten.Although the coating compositions of the technology differ These coatings were not yet satisfactory and had advantages with respect to the older coating compositions Efforts have been made to obtain better coatings, particularly with regard to thermal corrosion.
Die vorliegende Erfindung bezieht sich auf Ueberzugslegierungszusammensetzungen insbesondere auf Nickel, Kobalt und Nickel-Kobalt Ueberzugslegierungen mit verbessertem Widerstand gegen Wärmekorrosion. Insbesondere bezieht sich die vorliegende Erfindung auf verbesserte Ueberzugslegierungszusammensetzungen desThe present invention relates to coating alloy compositions especially on nickel, cobalt and nickel-cobalt coating alloys with improved resistance to Heat corrosion. In particular, the present invention relates to improved coating alloy compositions
B0988 5/1232B0988 5/1232
25301372530137
MCrAlY Typs welche hauptsächlich aus ungefähr 8 bis 30 Gew.% Chrom, 5 bis 15 Gew.% Aluminium, bis zu 1% eines reaktiven Metalles, ausgewählt aus der Gruppe bestehend aus Yttrium, Scandium, Thor und weiteren Elementen der Gruppe der seltenen Erden, und 3 bis 12 % eines Edelmetalles,ausgewählt aus der Gruppe bestehend aus Platin oder Rhodium, bestehen wobei der Rest von Metallen der Gruppe bestehend aus Nickel, Kobalt und Nickel-Kobalt gebildet wird. Die Verwendung eines Edelmetalles als Legierungsbestandteil führt zu einer gleichmässigen Verteilung desselben in der Zusammensetzung wodurch eine hohe Homogenität der Legierung, welche ein Charakteristikum der Ueberzugslegierungen des MCrAlY Typs ist, erhalten wird.MCrAlY type which mainly consists of about 8 to 30% by weight of chromium, 5 to 15% by weight of aluminum, up to 1% of a reactive metal selected from the group consisting of yttrium, scandium, Thor and other elements of the rare earth group, and 3 to 12% of a precious metal selected from the group Consists of platinum or rhodium, with the remainder being made up of metals from the group consisting of nickel, cobalt and nickel-cobalt is formed. The use of a noble metal as an alloy component leads to an even distribution the same in the composition resulting in a high homogeneity of the alloy, which is a characteristic of the coating alloys of the MCrAlY type is obtained.
Gemäss einem bevorzugten Aspekt der Erfindung wird als reaktives Metall Yttrium und als Edelmetall 5 bis 10 Gew.% Platin eingesetzt. Gemäss einem weiteren Aspekt der Erfindung wird als reaktives Metall Yttrium und als Edelmetall 5 % Rhodium eingesetzt.According to a preferred aspect of the invention, yttrium is used as the reactive metal and 5 to 10% by weight of platinum is used as the noble metal. According to a further aspect of the invention, yttrium is used as the reactive metal and 5% rhodium is used as the noble metal.
Zum besseren Verständnis der Erfindung wird Bezug genommen auf die nachfolgende Beschreibung und die beiliegenden Figuren in welchenFor a better understanding of the invention, reference is made to FIG the following description and the accompanying figures in which
Figur 1 eine graphische Darstellung des Sulfidierungsverhaltens verschiedener NiCrAl Legierungen bei 10000C ist, ;Figure 1 is a graphical representation of the various Sulfidierungsverhaltens NiCrAl alloys at 1000 0 C;
die Figuren 2 und 3 graphische Darstellungen des Oxydationsverhaltens verschiedener NiCrAl Legierungen bei HOO0C bzw. 12000C in der Luft sind;Figures 2 and 3 are graphic representations of the oxidation behavior of various NiCrAl alloys at HOO 0 C and 1200 0 C in the air;
FigurVeine graphische Darstellung des Warmekorrosionsverhaltens verschiedener CoCrAlY und NiCrAlY Legierungen bei 955°C und 2,0Figure: A graphic representation of the hot corrosion behavior of various CoCrAlY and NiCrAlY alloys at 955 ° C and 2.0
2
mg/cm Na.SO, ist? und2
mg / cm Na.SO, is? and
Figur 5 eine graphische Darstellung des Warmekorrosionsverhaltens von NiCrAlY Legierungen bei 955°C und 0,5 mg/cm Na3SO4 ist.Figure 5 is a graph of the hot corrosion behavior of NiCrAlY alloys at 955 ° C and 0.5 mg / cm Na 3 SO 4 .
Die Ueberzugslegierungen der vorliegenden Erfindung weisen ; einen wesentlich verbesserten Widerstand gegen Wärmekorrosion auf und eignen sich besonders als Ueberzüge auf den modernen Superlegierungen. Die Ueberzugslegierungen der Erfindung sind widerstandsfähig gegen Korrosion und die Wirksamkeit ist nicht abhängig von einer Reaktion der Ueberzugslegierung mit dem The coating alloys of the present invention have ; have a significantly improved resistance to heat corrosion and are particularly suitable as coatings on modern superalloys. The coating alloys of the invention are resistant to corrosion and the effectiveness is not dependent on a reaction of the coating alloy with the
509885/1232509885/1232
Substratmaterial. Die Ueberzugslegierungen der Erfindung weisen eine gleichmässige Konzentration durch die ganze Schicht auf und können so ihre Schutzeigenschaften gbichmässiger und beständiger ausführen als die Aluminüüberzüge.Substrate material. The coating alloys of the invention have a uniform concentration through the entire layer and can thus carry out their protective properties more consistently and consistently than the aluminum coatings.
Die gewünschten Resultate werden mit einer Grundlegierung bestehend aus ungefähr 8 bis 30 Gev.% Chrom, 5 bis 15 Gew.% Aluminium, 5 bis 10 Gew.% Platin oder Rhodium bis zu 1 Gew.% eines reaktiven Metalles ausgewählt aus der Gruppe bestehend aus Yttrium, Scandium, Thor und Lanthan sowie weiteren Elementen der Gruppe der seltenen Erden, wobei der Rest aus Nickel und/oder Kobalt besteht erhalten. Eine bevorzugte Legierungszusammensetzung enthält 0,5% Yttrium und 5 bis 10 Gew.% Platin.The desired results are made up of a base alloy from about 8 to 30% by weight of chromium, 5 to 15% by weight of aluminum, 5 to 10% by weight of platinum or rhodium up to 1% by weight of a reactive Metals selected from the group consisting of yttrium, scandium, thor and lanthanum as well as other elements of the group of rare Earths, with the remainder consisting of nickel and / or cobalt. A preferred alloy composition contains 0.5% yttrium and 5 to 10 wt% platinum.
üeberraschend war dass ein Zusatz von geringen spezifischen Mengen Platin oder Rhodium als Legierungsbestandteile zu Ueberzügen des MCrAlY Typs nicht nur zu einer Verbesserung des Sulfidierungswiderstandes beiträgt sondern dass dadurch auch eine Verbesserung der Oxydhaftung, selbst in Abwesenheit der reaktiven Metalle ι(Y, Sc, Th, La und anderen Elementen der Gruppe der seltenen Erden), welche normalerweise die Oxydhaftung zu dem Substrat bilden, erhalten wird. · ! It was surprising that the addition of small specific amounts of platinum or rhodium as alloy components to coatings of the MCrAlY type not only contributes to an improvement in the sulfidation resistance but also improves the oxide adhesion, even in the absence of the reactive metals ι (Y, Sc, Th, La and other rare earth group elements) which normally form the oxide bond to the substrate. · !
Das Vorliegen von Platin oder Rhodium in der Ueberzugslegierung verhindert, durch die niedrigen Dampfdrucke von Platin oder
Rhodium, ein Auftragen der Legierung durch Dampf niederschlag. Die
Legierungen können jedoch durch weitere bekannte Verfahren aufgetragen
werden. So können die Legierungen z.B. durch Aufdampfen yon MCrAlY und Bedampfen von Platin oder Rhodium aufgebracht
werden. Die üeberzüge können auch durch Plasmaspühverfahren aufgetragen
werden.
IThe presence of platinum or rhodium in the coating alloy prevents, due to the low vapor pressures of platinum or rhodium, an application of the alloy by vapor deposition. However, the alloys can be applied by other known methods. For example, the alloys can be applied by vapor deposition of MCrAlY and vapor deposition of platinum or rhodium. The coatings can also be applied by plasma spraying.
I.
Zum besseren Verständnis der Erfindung wird Bezug genommen auf die nachfolgenden Beispiele: iFor a better understanding of the invention, reference is made to the following examples: i
Beispiel 1 ίExample 1 ί
Legierungen aus Ni-8Cr-6Al mit Zusatz von Platin und Rhodium wurden durch das bekannte Lichtbogenschmelze-Tropf-Verfahren hergestellt. Muster der Zusammensetzungen zur Bestimmung der Daten aus Figur 1 hatten folgende Dimensionen 1 cm χ 1 cm χ 0,2 cm und wurden Korrosionstestversuchen wie folgt unterworfen. Die Muster derAlloys of Ni-8Cr-6Al with the addition of platinum and rhodium were made produced by the well-known melt-arc drip process. Sample of the compositions for determining the data from FIG. 1 had the following dimensions 1 cm 1 cm 0.2 cm and were Subjected to corrosion tests as follows. The pattern of the
509885/1232509885/1232
Legierungen wurden mit wässrigen Na-SO^ Lösungen besprüht, getrocknet und gewogen. Nach dem Aufbringen eines Ueberzuges von 0,5 mg/cm Na3SO. wurden sie während 20 Stunden bei lOOO C in einer Sauerstoffatmosphäre im thermischen Gleichgewicht oxydiert. Das Gewicht der Muster wurde kontinuierlich als Funktion der Zeit gemessen und die Gewichtsveränderungen als Gewichtszunahme pro Oberflächeneinheit wie in Figur 1 dargestellt aufgetragen.Alloys were sprayed with aqueous Na-SO4 solutions, dried and weighed. After applying a coating of 0.5 mg / cm Na 3 SO. they were oxidized for 20 hours at 100 ° C. in an oxygen atmosphere in thermal equilibrium. The weight of the samples was measured continuously as a function of time, and the changes in weight were plotted as weight increase per unit surface area, as shown in FIG.
Wie aus der Figur hervorgeht wurde durch Zusatz von 2,5 Gew.% Platin keine nennenswerte Verbesserung der Eigenschaften der Ni-8Cr-6Al Legierung in diesem Versuch erhalten. Wesentliche Verbesserungen des Verhaltens der Legierung wurde jedoch mit einem Zusatz von 5 oder 10 Gew.% Platin erhalten. Muster einer Ni-8Cr-6Al-5Rh Legierung waren den Legierungen mit einem Zusatz von 10 Gew.% Platin ungefähr gleichwertig.As can be seen from the figure, the addition of 2.5% by weight Platinum did not get any significant improvement in the properties of the Ni-8Cr-6Al alloy in this experiment. Essential Improvements in the behavior of the alloy, however, were obtained with the addition of 5 or 10% by weight of platinum. Pattern one Ni-8Cr-6Al-5Rh alloys were approximately equivalent to the alloys with an addition of 10% by weight of platinum.
Muster wurden wie in Beispiel 1 beschrieben mit den Zusammensetzungen
der Figuren 2 und 3 hergestellt. Die Muster wurden zyklischen Oxydationsversuchen bei hoher Temperatur unterworfen
und es wurde überraschenderweise gefunden, dass durch Zusatz von Rhodium oder Platin die Oxydhaftung des ausgebildeten Al3O3
auf den Legierungen verbessert wurde. Aus den Figuren geht hervor, dass Legierungen mit einem Zusatz an 5 oder 10 Gew.%
Platin Legierungen mit einem Zusatz an 2,5 Gew.% Pt überlegen sind und letztere Legierung wesentlich bessere Eigenschaften aufweist
als unmodifizierte Legierungen, i.e. ohne Platinzusatz. Es wurde gefunden, dass die Oxydhaftung einer Ni-8Cr-6Al-5Rh Legierung bei
1200°C der Oxydhaftung einer Ni-81
selben Temperatur ebenbürtig war.Samples were produced as described in Example 1 with the compositions of FIGS. 2 and 3. The samples were subjected to cyclic oxidation tests at high temperature and it was surprisingly found that the oxide adhesion of the Al 3 O 3 formed on the alloys was improved by adding rhodium or platinum. The figures show that alloys with an addition of 5 or 10% by weight of platinum are superior to alloys with an addition of 2.5% by weight of Pt and the latter alloy has significantly better properties than unmodified alloys, ie without the addition of platinum. It was found that the oxide adhesion of a Ni-8Cr-6Al-5Rh alloy at 1200 ° C compared to the oxide adhesion of a Ni-81
was equal to the same temperature.
1200°C der Oxydhaftung einer Ni-8Cr-6Al-10Pt Legierung bei der-1200 ° C of the oxide adhesion of a Ni-8Cr-6Al-10Pt alloy in the
Legierungsmuster von 1 cm χ 0,8 cm χ 0,1 bis 0,2 cm der Zusammensetzungen Ni-17Cr-12Al-O,5Y, Ni-17Cr-12Al-5Rh-O,5Y, Ni-17Cr-12Al-10Pt-0,5Y, Co-17Cr-llAl-0,5Y, Co-17Cr-llAl-5Rh-0,5Y und Co-17Cr-llAl-lOPt-0,5Y wurden hergestellt, gewogen, gemessen und mit 0,5-2,0 mg/cm Na3SO- überzogen. Sie wurden alsdann 14 Oxydationszyklen unterworfen wobei ein jeder Zyklus aus Oxydation in Luft während 20 Stunden bei 955°C, Abkühlen aufAlloy samples from 1 cm χ 0.8 cm χ 0.1 to 0.2 cm of the compositions Ni-17Cr-12Al-O, 5Y, Ni-17Cr-12Al-5Rh-O, 5Y, Ni-17Cr-12Al-10Pt- 0.5Y, Co-17Cr-IIAl-0.5Y, Co-17Cr-IIAl-5Rh-0.5Y, and Co-17Cr-IIAl-IOPt-0.5Y were prepared, weighed, measured and found to be 0.5-2 , 0 mg / cm Na 3 SO-coated. They were then subjected to 14 oxidation cycles, each cycle consisting of oxidation in air for 20 hours at 955 ° C. and cooling
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Raumtemperatur, Waschen und Wägen bestand unterworfen. Die Sequenz wurde wiederholt bis ein Abfall der Legierungseigenschaften festgestellt werden konnte. Die Resultate einer Versuchsreihe bei 955°C mit einem Salzüberzug von 2 mg/cm sind in Figur 4 dargestellt. Obschon eine CoCrAlY Legierung einen höheren Widerstand gegen Wärmekorrosion als eine NiCrAlY Legierung aufweist kann so festgestellt werden, dass durch einen Zusatz von Pt oder Rh zu einer CoCrAlY oder einer NiCrAlY Legierung der Widerstand gegen Wärmekorrosion stark verbessert werden kann.Room temperature, washing and weighing were subjected. The sequence was repeated until there was a drop in alloy properties could be determined. The results of a series of tests at 955 ° C. with a salt coating of 2 mg / cm are shown in FIG shown. Although a CoCrAlY alloy has a higher resistance against heat corrosion as a NiCrAlY alloy can thus be determined that by adding Pt or Rh to a CoCrAlY or a NiCrAlY alloy, the resistance against thermal corrosion can be greatly improved.
In einem Brenner wurden Muster von Ni-17Cr-12Al-O,5Y, Ni-17Cr-12Al-5Rh-O,5Y, Ni-17Cr-12Al-5Pt-O,5Y und Ni-17Cr-12Al-lOPt-O,5Y Legierungen einer zyklischen Wärmekorrosion bei 955°C unterworfen wobei dem Brennstoff 35 ppm Seesalz vor der Verbrennung zugesetzt wurden. Eine wesentliche Erosion der Spitzen Ser beiden NiCrAlY Zusammensetzungen und der mit Rhodium modifizierten Zusammensetzung wurde nach 110 Stunden festgestellt. Versagen in der Hitze für diese Muster nacß 300 und 400 Stunden festgestellt, wobei das mit Rhodium modifizierte Muster eine leicht längere Lebensdauer als die Grundzusammensetzung aufwies. Obschon die mit Rhodium modifizierte Zusammensetzung eine geringe Verbesserung mit Bezug auf die Grundzusammensetzung in diesem Versuch, aufwies war die Natur dieses Versagens unerwartet und die Resultate welche erhalten wurden sollten nicht zu voreiligen Schlussfolgerungen herangezogen werden. Die mit Platin modifizierten Zusammensetzungen wiesen nämlich einen weit höheren Widerstand gegen Wärmekorrosion auf als die Grundzusanimensetzungen. Diese Zusammensetzungen wiesen noch kein Versagen nach 675 Stunden auf als die Versuchsreihe abgebrochen wurde.Samples of Ni-17Cr-12Al-O, 5Y, Ni-17Cr-12Al-5Rh-O, 5Y, Ni-17Cr-12Al-5Pt-O, 5Y and Ni-17Cr-12Al-IOPt-O, 5Y alloys of cyclic heat corrosion at 955 ° C, with 35 ppm sea salt added to the fuel before combustion. An essential one Erosion of the tips of both NiCrAlY compositions and the rhodium modified composition was observed after 110 hours established. Heat failure for these specimens was noted after 300 and 400 hours, the rhodium modified Pattern had a slightly longer lifespan than the basic composition. Although the composition modified with rhodium exhibited little improvement with respect to the base composition in this trial, the nature of this was this Failure unexpectedly and the results which have been obtained should not be used to jump to conclusions will. This is because the compositions modified with platinum exhibited a much higher resistance to thermal corrosion than the basic arrangements. These compositions still showed no failure after 675 hours when the series of tests was terminated became.
Aus der vorliegenden Beschreibung und den beiliegenden Beispielen und Figuren geht hervor, dass die Erfindung üeberzugslegierungen beschreibt welche eine wesentliche Verbesserung des Widerstandes gegen Wärmekorrosion mit Bezug auf bekannte üeberzugslegierungen aufweisen.From the present description and the accompanying examples and figures it can be seen that the invention covers alloys describes a substantial improvement in the resistance to thermal corrosion with respect to known coating alloys exhibit.
509885/1232509885/1232
Claims (7)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US487074A US3918139A (en) | 1974-07-10 | 1974-07-10 | MCrAlY type coating alloy |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| DE2530197A1 true DE2530197A1 (en) | 1976-01-29 |
| DE2530197C2 DE2530197C2 (en) | 1983-02-03 |
Family
ID=23934299
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE2530197A Expired DE2530197C2 (en) | 1974-07-10 | 1975-07-05 | Coating alloy |
Country Status (13)
| Country | Link |
|---|---|
| US (1) | US3918139A (en) |
| JP (1) | JPS5842255B2 (en) |
| BR (1) | BR7504327A (en) |
| CA (1) | CA1158075A (en) |
| CH (1) | CH606455A5 (en) |
| DE (1) | DE2530197C2 (en) |
| FR (1) | FR2277902A1 (en) |
| GB (1) | GB1500780A (en) |
| IL (1) | IL47407A (en) |
| IN (1) | IN144076B (en) |
| IT (1) | IT1039467B (en) |
| NO (1) | NO141371C (en) |
| SE (1) | SE410477B (en) |
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| US3399058A (en) * | 1963-11-07 | 1968-08-27 | Garrett Corp | Sulfidation and oxidation resistant cobalt-base alloy |
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-
1974
- 1974-07-10 US US487074A patent/US3918139A/en not_active Expired - Lifetime
-
1975
- 1975-05-23 GB GB23056/75A patent/GB1500780A/en not_active Expired
- 1975-05-28 IN IN1079/CAL/1975A patent/IN144076B/en unknown
- 1975-06-03 IL IL47407A patent/IL47407A/en unknown
- 1975-06-04 CH CH721275A patent/CH606455A5/xx not_active IP Right Cessation
- 1975-06-19 SE SE7507095A patent/SE410477B/en unknown
- 1975-06-26 CA CA000230272A patent/CA1158075A/en not_active Expired
- 1975-06-27 IT IT24839/75A patent/IT1039467B/en active
- 1975-06-30 NO NO75752355A patent/NO141371C/en unknown
- 1975-07-03 FR FR7520876A patent/FR2277902A1/en active Granted
- 1975-07-05 DE DE2530197A patent/DE2530197C2/en not_active Expired
- 1975-07-09 BR BR7504327*A patent/BR7504327A/en unknown
- 1975-07-09 JP JP50084341A patent/JPS5842255B2/en not_active Expired
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3754903A (en) * | 1970-09-15 | 1973-08-28 | United Aircraft Corp | High temperature oxidation resistant coating alloy |
Also Published As
| Publication number | Publication date |
|---|---|
| IL47407A0 (en) | 1975-08-31 |
| NO141371C (en) | 1980-02-27 |
| JPS5130530A (en) | 1976-03-15 |
| GB1500780A (en) | 1978-02-08 |
| CA1158075A (en) | 1983-12-06 |
| AU8156075A (en) | 1976-12-02 |
| SE410477B (en) | 1979-10-15 |
| NO752355L (en) | 1976-01-13 |
| IN144076B (en) | 1978-03-18 |
| FR2277902B1 (en) | 1978-07-28 |
| US3918139A (en) | 1975-11-11 |
| FR2277902A1 (en) | 1976-02-06 |
| DE2530197C2 (en) | 1983-02-03 |
| SE7507095L (en) | 1976-01-12 |
| JPS5842255B2 (en) | 1983-09-19 |
| CH606455A5 (en) | 1978-10-31 |
| NO141371B (en) | 1979-11-19 |
| IL47407A (en) | 1977-08-31 |
| IT1039467B (en) | 1979-12-10 |
| BR7504327A (en) | 1976-07-06 |
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