EP2964808A1 - Thermo-mechanical fatigue resistant aluminum abradable coating - Google Patents

Thermo-mechanical fatigue resistant aluminum abradable coating

Info

Publication number
EP2964808A1
EP2964808A1 EP13877283.5A EP13877283A EP2964808A1 EP 2964808 A1 EP2964808 A1 EP 2964808A1 EP 13877283 A EP13877283 A EP 13877283A EP 2964808 A1 EP2964808 A1 EP 2964808A1
Authority
EP
European Patent Office
Prior art keywords
particles
aluminum
powder
boride
coating
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP13877283.5A
Other languages
German (de)
French (fr)
Other versions
EP2964808A4 (en
EP2964808B1 (en
Inventor
Christopher W. Strock
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
RTX Corp
Original Assignee
United Technologies Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by United Technologies Corp filed Critical United Technologies Corp
Publication of EP2964808A1 publication Critical patent/EP2964808A1/en
Publication of EP2964808A4 publication Critical patent/EP2964808A4/en
Application granted granted Critical
Publication of EP2964808B1 publication Critical patent/EP2964808B1/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C21/00—Alloys based on aluminium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/02—Making metallic powder or suspensions thereof using physical processes
    • B22F9/06—Making metallic powder or suspensions thereof using physical processes starting from liquid material
    • B22F9/08—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying
    • B22F9/082—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying atomising using a fluid
    • 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
    • C22C1/04—Making non-ferrous alloys by powder metallurgy
    • C22C1/0408—Light metal alloys
    • C22C1/0416—Aluminium-based alloys
    • 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
    • C22C1/10—Alloys containing non-metals
    • C22C1/1036—Alloys containing non-metals starting from a melt
    • C22C1/1042—Alloys containing non-metals starting from a melt by atomising
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C32/00—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ
    • C22C32/0047—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with carbides, nitrides, borides or silicides as the main non-metallic constituents
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C32/00—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ
    • C22C32/0047—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with carbides, nitrides, borides or silicides as the main non-metallic constituents
    • C22C32/0073—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with carbides, nitrides, borides or silicides as the main non-metallic constituents only borides
    • 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
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
    • C23C4/06—Metallic material
    • 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
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/18—After-treatment

Definitions

  • thermo- mechanical fatigue (TMF) resistant aluminum abradable coating which has particular utility as an outer air seal .
  • Compressor efficiency is related to blade tip clearance and outer air seal roughness. Coatings for the fan and the low pressure compressor are typically applied on titanium or iron based parts. The coefficient of thermal expansion (CTE) mismatch between the aluminum coating and the base metal (the titanium or iron) is almost a factor of two. This may lead to high
  • thermo- mechanical fatigue cracking and coating spallation With many thermal cycles from room temperature and back, the result is thermo- mechanical fatigue cracking and coating spallation.
  • Blades that mate with an aluminum seal may be titanium- or iron-based. During rub interaction, under certain conditions, metal is transferred to the blade tips. This may cause localized wear of the seal in what is known as record groove patterns. The result is increased average tip clearance and increased roughness in the air flow direction.
  • an aluminum coating having a
  • an aluminum coating to be deposited on a substrate having a first coefficient of thermal expansion which aluminum coating broadly comprises an aluminum matrix, particles of a material having a low thermal expansion coefficient incorporated into the matrix; and the particles bonding sufficiently we 11 to the aluminum matrix to carry a portion of the mechanical load .
  • the particles are selected from the group consisting of carbides, borides, oxides , and combinations thereof .
  • the particles are aluminum boride particles .
  • the particles are titanium boride particles .
  • the titanium boride particles have a ratio of titanium to boron in the range of 1:1 to 1:4.
  • the particles are present in an amount from 1.0 to 33 vol% .
  • the particles are present in an amount of from 10 to 25 vol%
  • the particles are present in an amount of 15 to 20 vo 1% .
  • the aluminum coating further comprises a pore making
  • the pore making material is selected from the group consisting of hexagonal boron nitride, polyester and Lucite .
  • the part providing step comprises providing a part formed from a titanium based alloy or an iron based alloy.
  • the powder forming step comprises forming a powder containing particles selected from the group consisting of oxide material, a carbide, a boride, and combinations thereof.
  • the powder forming step comprises forming the powder to have from 1.0 to 33 vol% of the particles.
  • the powder forming step comprises forming the powder to have from 10 to 25 vol% of the particles.
  • the powder forming step comprises forming the powder to have from 15 to 20 vol% of the particles.
  • the powder forming step comprises using titanium boride particles .
  • the powder forming step comprises using aluminum boride particles .
  • the process further comprises adding a pore making material to the powder .
  • the process further comprises melt atomization of a boride containing aluminum alloy and quenching the boride containing aluminum alloy during atomization to form particles of a metastable solid solution.
  • the process further comprises subjecting the aluminum coating to a heat treatment in the range of from 1100 to 1200 degrees Centigrade for 2.0 hours.
  • a process for forming an aluminum alloy matrix containing fine particles which broadly comprises the steps of: melt atomizing a boride containing aluminum alloy; and quenching the boride containing aluminum alloy during atomization to form particles of a metastable solid solution.
  • thermo-mechanical fatigue resistant aluminum abradable coating are set forth in the following detailed description.
  • the substrate to which the aluminum coating described herein may be applied may be formed from a titanium alloy or from an iron based alloy.
  • the substrate may be a fan casing or a casing for a compressor section of gas turbine engine.
  • the aluminum coating has an aluminum matrix formed from an aluminum alloy such as an aluminum-silicon alloy.
  • the aluminum coating further includes fine particles in the range of 20 nm to 5 microns mean particle diameter of a low coefficient of thermal expansion (cte) material, which is defined as having a cte that is lower than that of the aluminum matrix, which are incorporated into the aluminum matrix.
  • the fine particles may be in the range of from 20 nm to 2 microns in mean particle size.
  • the inclusion of the fine particles of a low coefficient of thermal expansion material results in hardening, strengthening and coefficient of thermal expansion reduction.
  • the fine particles to be incorporated into the aluminum coating may be fine particles selected from the group consisting of an oxide material, a boride, a carbide, and combinations thereof. Only those particles which bond sufficiently well to the aluminum matrix material and are capable of carrying a portion of the mechanical load and which act as a composite material are used in the aluminum coating described herein.
  • the fine particles may be boride particles, such as aluminum boride particles and titanium boride
  • Aluminum boride particles form high aspect ratio platelets when precipitated at a temperature of below about 650 degrees Centigrade. When aluminum boride particles are used, the technique used to manufacture the aluminum coatings must contain sufficient heating of the alloy constituents to fully dissolve any A1B12 which tends to form at temperatures between 650 degrees
  • A1B12 Centigrade and 1550 degrees Centigrade depending on boron concentration.
  • the formation of A1B12 during cooling may be suppressed by quenching to below 650 degrees
  • Centigrade This can bed one by rapid cooling of the melt or passively as one of the characteristics of thermal spray coating in which molten particles are quench cooled upon impact with a surface. If desired, the thermal spray coating may be subsequently heat treated to a temperature of up to 650 degrees Centigrade.
  • Aluminum boride is a desirable candidate due to its low cost, high thermal conductivity, low coefficient of thermal expansion, and good adhesion to the matrix.
  • Aluminum boride at 20 vol% has been shown to increase the strength of aluminum by 80%.
  • Titanium boride is also a desirable candidate for the aluminum coating.
  • the titanium boride particles may be incorporated into the aluminum matrix by precipitation from a quenched metastable solid solution.
  • the titanium boride may have a ratio of titanium to boron which ranges from 1:1 to 1:4. It is also possible to include the titanium boride particles by mechanical alloying, agglomeration with the matrix alloy in a thermal spray feed stock powder, pressed and sintered.
  • borides such as titanium boride or aluminum boride
  • they may be present in a range of from 1.0 vol% to 33 vol%, balance aluminum matrix.
  • the boride particles may be present in an amount from 10 to 25 vol% .
  • the boride particles may be present in an amount from 15 to 20 vol% .
  • the borides may be dissolved in melt
  • melt atomization of a boride containing aluminum alloy that quenches during
  • precipitation of undesirable phases may be suppressed as a result of rapid cooling rates.
  • other powder manufacturing routes that result in powder with undesirable phases may be melted and solutionized during the spray coating operation. Either way, molten or softened particles may then be quench cooled during deposition.
  • titanium boride precipitates from a metastable quenched structure to form precipitates in the 20nm to 2.0 micron size range, depending on subsequent heat treat temperature. The heat treatment could be heating the aluminum coating at 625 to 650 degrees Centigrade for 2.0 hours .
  • Carbides which may be used include those in the covalent and interstitial carbide groups with prime candidates being silicon carbide and titanium carbide.
  • the aluminum matrix with fine particles is formed into a powder with the fine particles is formed into a powder so that it can be applied on the substrate by a spray process such as thermal spraying.
  • the fine particles may be included in the particles forming the aluminum matrix material by agglomeration, alloying and precipitation, or ball milling and cold working.
  • the amount of fine particles is a function of the desired coefficient of thermal expansion for the aluminum coating. Also, considerations of through thickness thermal gradient may be taken into account.
  • the aluminum coating may be applied to the substrate by thermally spraying the matrix material with the incorporated fine particles. If desired, a pore making fugitive or soft filler material may also be added to the matrix material while it is being sprayed.
  • the fugitive or soft filler material do not affect the coefficient of thermal expansion of the aluminum coating. To affect the coefficient of thermal expansion, the filler material would have to both bond with the aluminum matrix and have sufficient elastic modulus to at least partially elastically constrain the aluminum matrix.
  • the elastic modulus of the filler material may be higher than that of aluminum.
  • Fugitives and fillers like hexagonal boron nitride, polyester, and Lucite are candidates for affecting the abradability of the aluminum coating and may be used to offset the strengthening of the matrix material by the fine particles.
  • Fugitives and soft fillers may be used at up to about 70 volume percent of the coating.
  • the fugitives and soft fillers may be present in an amount from 40 to 65 volume percent.
  • the coating may be made from an aluminum alloy containing 70.4 wt% aluminum, 13.8 wt% titanium, 9.6 wt% silicon, and 6.2 wt% boron and hexagon boron nitride to produce a coating of 40 volume % metal alloy, 50 volume % hBN and 10% porosity.
  • the titanium boride particles may be precipitated from a quenched metal alloy with heat treatment at 625 to 650 degrees Centigrade for 2.0 hours. [ 0041 ] While the aluminum coating particles are sprayed onto the substrate, the sprayed particles may be quenced by conduction of heat to the coating and
  • the substrate with the sprayed particles may be subjected to a heat treatment in the range of from 625 to 650 degrees Centigrade for 2.0 hours.
  • the benefits of the abradable coating described herein include reduced coefficient of thermal expansion and thermo-mechanical fatigue. This results in a more stable part shape with temperature change and improved coating durability.
  • the filler material also helps to reduce metal transfer to blades during low interaction rate sliding contact wear and result in tighter tip clearance and a smoother coating. As compared to choosing a conventional alloy that has a lower
  • the technique described herein does not increase the incipient melting point of the coating.
  • this is because the titanium and boride constituents fully precipitate as a high melting point phase.
  • the blade tip temperature, particularly of a titanium blade tip, during rub is still limited to the melting point of aluminum. This helps reduce the risk of a titanium fire .
  • thermo- mechanical fatigue resistant aluminum abradable coating There has been described herein a thermo- mechanical fatigue resistant aluminum abradable coating. While the coating has been described in the context of specific embodiments thereof, other unforeseeable alternatives, modifications, and variations may become apparent to those skilled in the art having read the foregoing description. Accordingly, it is intended to embrace those alternatives, modifications, and variations as fall within the broad scope of the appended claims.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Plasma & Fusion (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Coating By Spraying Or Casting (AREA)
  • Structures Of Non-Positive Displacement Pumps (AREA)

Abstract

An aluminum coating to be deposited on a substrate having a first coefficient of thermal expansion has an aluminum matrix, and particles of a material having a low coefficient of thermal expansion incorporated into the matrix. The particles bond sufficiently well to the aluminum matrix to carry a portion of the mechanical load.

Description

THERMO-MECHA ICAL FATIGUE RESISTANT ALUMINUM ABRADABLE
COATING
BACKGROUND
[ 0001 ] The present disclosure relates to a thermo- mechanical fatigue (TMF) resistant aluminum abradable coating which has particular utility as an outer air seal .
[ 0002 ] Compressor efficiency is related to blade tip clearance and outer air seal roughness. Coatings for the fan and the low pressure compressor are typically applied on titanium or iron based parts. The coefficient of thermal expansion (CTE) mismatch between the aluminum coating and the base metal (the titanium or iron) is almost a factor of two. This may lead to high
compressive stresses in the coating during elevated temperature operation. With many thermal cycles from room temperature and back, the result is thermo- mechanical fatigue cracking and coating spallation.
[ 0003 ] Blades that mate with an aluminum seal may be titanium- or iron-based. During rub interaction, under certain conditions, metal is transferred to the blade tips. This may cause localized wear of the seal in what is known as record groove patterns. The result is increased average tip clearance and increased roughness in the air flow direction.
[ 0004 ] It is known in the art to form an aluminum based abradable coating made with hexagonal boron nitride. The problem with this type of coating however is that the hexagonal boron nitride is weak and does not bond well to the matrix.
[ 0005 ] It is desirable to control the coefficient of thermal expansion of the aluminum coating to be closer to the coefficient of thermal expansion of the base metal and thereby prevent thermo-mechanical fatigue related coating failure .
SUMMARY
[ 0006 ] In accordance with the present disclosure, there is provided an aluminum coating having a
coefficient of thermal expansion which better matches the coefficient of thermal expansion of the substrate to which the aluminum coating is applied.
[ 0007 ] In accordance with the present disclosure, there is provided an aluminum coating to be deposited on a substrate having a first coefficient of thermal expansion , which aluminum coating broadly comprises an aluminum matrix, particles of a material having a low thermal expansion coefficient incorporated into the matrix; and the particles bonding sufficiently we 11 to the aluminum matrix to carry a portion of the mechanical load .
[ 0008 ] In another and alternative embodiment, the particles are selected from the group consisting of carbides, borides, oxides , and combinations thereof .
[ 0009 ] In another and alternative embodiment, the particles are aluminum boride particles .
[ 0010 ] In another and alternative embodiment, the particles are titanium boride particles .
[ 0011 ] In another and alternative embodiment, the titanium boride particles have a ratio of titanium to boron in the range of 1:1 to 1:4.
[ 0012 ] In another and alternative embodiment, the particles are present in an amount from 1.0 to 33 vol% .
[ 0013 ] In another and alternative embodiment, the particles are present in an amount of from 10 to 25 vol%
[ 0014 ] In another and alternative embodiment, the particles are present in an amount of 15 to 20 vo 1% . [ 0015 ] In another and alternative embodiment, the aluminum coating further comprises a pore making
material .
[ 0016 ] In another and alternative embodiment, the pore making material is selected from the group consisting of hexagonal boron nitride, polyester and Lucite .
[ 0017 ] Further in accordance with the present
disclosure, there is provided a process for applying an aluminum coating to a part comprising the steps of:
providing a part; forming a powder containing an aluminum matrix and particles having a low thermal coefficient of thermal expansion bonded to the aluminum matrix; and thermally spraying the powder onto the part.
[ 0018 ] In another and alternative embodiment, the part providing step comprises providing a part formed from a titanium based alloy or an iron based alloy.
[ 0019 ] In another and alternative embodiment, the powder forming step comprises forming a powder containing particles selected from the group consisting of oxide material, a carbide, a boride, and combinations thereof.
[ 0020 ] In another and alternative embodiment, the powder forming step comprises forming the powder to have from 1.0 to 33 vol% of the particles.
[ 0021 ] In another and alternative embodiment, the powder forming step comprises forming the powder to have from 10 to 25 vol% of the particles.
[ 0022 ] In another and alternative embodiment, the powder forming step comprises forming the powder to have from 15 to 20 vol% of the particles.
[ 0023 ] In another and alternative embodiment, the powder forming step comprises using titanium boride particles . [ 0024 ] In another and alternative embodiment, the powder forming step comprises using aluminum boride particles .
[ 0025 ] In another and alternative embodiment, the process further comprises adding a pore making material to the powder .
[ 0026 ] In another and alternative embodiment, the process further comprises melt atomization of a boride containing aluminum alloy and quenching the boride containing aluminum alloy during atomization to form particles of a metastable solid solution.
[ 0027 ] In another and alternative embodiment, the process further comprises subjecting the aluminum coating to a heat treatment in the range of from 1100 to 1200 degrees Centigrade for 2.0 hours.
[ 0028 ] Further in accordance with the present
disclosure, there is provided a process for forming an aluminum alloy matrix containing fine particles which broadly comprises the steps of: melt atomizing a boride containing aluminum alloy; and quenching the boride containing aluminum alloy during atomization to form particles of a metastable solid solution.
[ 0029 ] Other details of the thermo-mechanical fatigue resistant aluminum abradable coating are set forth in the following detailed description.
DETAILED DESCRIPTION
[ 0030 ] As discussed above, there is disclosed an aluminum coating which has a coefficient of thermal expansion which more closely matches the coefficient of thermal expansion of the substrate to which the aluminum coating is applied.
[ 0031 ] The substrate to which the aluminum coating described herein may be applied may be formed from a titanium alloy or from an iron based alloy. For example, the substrate may be a fan casing or a casing for a compressor section of gas turbine engine.
[ 0032 ] The aluminum coating has an aluminum matrix formed from an aluminum alloy such as an aluminum-silicon alloy. The aluminum coating further includes fine particles in the range of 20 nm to 5 microns mean particle diameter of a low coefficient of thermal expansion (cte) material, which is defined as having a cte that is lower than that of the aluminum matrix, which are incorporated into the aluminum matrix. In a non- limiting embodiment, the fine particles may be in the range of from 20 nm to 2 microns in mean particle size. The inclusion of the fine particles of a low coefficient of thermal expansion material results in hardening, strengthening and coefficient of thermal expansion reduction. By controlling the amount of fine particles incorporated into the coating, one can control the coefficient of thermal expansion so as to reduce the coefficient of thermal expansion mismatch with the substrate to which the aluminum coating is applied. The amount of fine particles may also be controlled to provide other desirable coating properties.
[ 0033 ] The fine particles to be incorporated into the aluminum coating may be fine particles selected from the group consisting of an oxide material, a boride, a carbide, and combinations thereof. Only those particles which bond sufficiently well to the aluminum matrix material and are capable of carrying a portion of the mechanical load and which act as a composite material are used in the aluminum coating described herein. For example, the fine particles may be boride particles, such as aluminum boride particles and titanium boride
particles . [ 0034 ] Aluminum boride particles form high aspect ratio platelets when precipitated at a temperature of below about 650 degrees Centigrade. When aluminum boride particles are used, the technique used to manufacture the aluminum coatings must contain sufficient heating of the alloy constituents to fully dissolve any A1B12 which tends to form at temperatures between 650 degrees
Centigrade and 1550 degrees Centigrade depending on boron concentration. The formation of A1B12 during cooling may be suppressed by quenching to below 650 degrees
Centigrade. This can bed one by rapid cooling of the melt or passively as one of the characteristics of thermal spray coating in which molten particles are quench cooled upon impact with a surface. If desired, the thermal spray coating may be subsequently heat treated to a temperature of up to 650 degrees Centigrade. Aluminum boride is a desirable candidate due to its low cost, high thermal conductivity, low coefficient of thermal expansion, and good adhesion to the matrix.
Aluminum boride at 20 vol% has been shown to increase the strength of aluminum by 80%.
[ 0035 ] Titanium boride is also a desirable candidate for the aluminum coating. When using titanium boride, the titanium boride particles may be incorporated into the aluminum matrix by precipitation from a quenched metastable solid solution. The titanium boride may have a ratio of titanium to boron which ranges from 1:1 to 1:4. It is also possible to include the titanium boride particles by mechanical alloying, agglomeration with the matrix alloy in a thermal spray feed stock powder, pressed and sintered.
[ 0036 ] When borides, such as titanium boride or aluminum boride, are used as the fine particles, they may be present in a range of from 1.0 vol% to 33 vol%, balance aluminum matrix. In another non-limiting embodiment, the boride particles may be present in an amount from 10 to 25 vol% . In still another non-limiting embodiment, the boride particles may be present in an amount from 15 to 20 vol% .
[ 0037 ] The borides may be dissolved in melt
processing, such as melt atomization, to form a spray powder. For example, melt atomization of a boride containing aluminum alloy that quenches during
atomization forms particles of a metastable solid solution. This allows deposition of solid or semi-solid particles and subsequent precipitation. The
precipitation of undesirable phases may be suppressed as a result of rapid cooling rates. Alternatively, other powder manufacturing routes that result in powder with undesirable phases may be melted and solutionized during the spray coating operation. Either way, molten or softened particles may then be quench cooled during deposition. When an aluminum - titanium - boron alloy is used, titanium boride precipitates from a metastable quenched structure to form precipitates in the 20nm to 2.0 micron size range, depending on subsequent heat treat temperature. The heat treatment could be heating the aluminum coating at 625 to 650 degrees Centigrade for 2.0 hours .
[ 0038 ] Carbides which may be used include those in the covalent and interstitial carbide groups with prime candidates being silicon carbide and titanium carbide.
[ 0039 ] The aluminum matrix with fine particles is formed into a powder with the fine particles is formed into a powder so that it can be applied on the substrate by a spray process such as thermal spraying. The fine particles may be included in the particles forming the aluminum matrix material by agglomeration, alloying and precipitation, or ball milling and cold working. The amount of fine particles is a function of the desired coefficient of thermal expansion for the aluminum coating. Also, considerations of through thickness thermal gradient may be taken into account.
[ 0040 ] The aluminum coating may be applied to the substrate by thermally spraying the matrix material with the incorporated fine particles. If desired, a pore making fugitive or soft filler material may also be added to the matrix material while it is being sprayed. The fugitive or soft filler material do not affect the coefficient of thermal expansion of the aluminum coating. To affect the coefficient of thermal expansion, the filler material would have to both bond with the aluminum matrix and have sufficient elastic modulus to at least partially elastically constrain the aluminum matrix. The elastic modulus of the filler material may be higher than that of aluminum. Fugitives and fillers like hexagonal boron nitride, polyester, and Lucite are candidates for affecting the abradability of the aluminum coating and may be used to offset the strengthening of the matrix material by the fine particles. Fugitives and soft fillers may be used at up to about 70 volume percent of the coating. In a non-limiting embodiment, the fugitives and soft fillers may be present in an amount from 40 to 65 volume percent. In one example, the coating may be made from an aluminum alloy containing 70.4 wt% aluminum, 13.8 wt% titanium, 9.6 wt% silicon, and 6.2 wt% boron and hexagon boron nitride to produce a coating of 40 volume % metal alloy, 50 volume % hBN and 10% porosity. The titanium boride particles may be precipitated from a quenched metal alloy with heat treatment at 625 to 650 degrees Centigrade for 2.0 hours. [ 0041 ] While the aluminum coating particles are sprayed onto the substrate, the sprayed particles may be quenced by conduction of heat to the coating and
substrate cooling the particles. After quenching, the substrate with the sprayed particles may be subjected to a heat treatment in the range of from 625 to 650 degrees Centigrade for 2.0 hours.
[ 0042 ] The benefits of the abradable coating described herein include reduced coefficient of thermal expansion and thermo-mechanical fatigue. This results in a more stable part shape with temperature change and improved coating durability. The filler material also helps to reduce metal transfer to blades during low interaction rate sliding contact wear and result in tighter tip clearance and a smoother coating. As compared to choosing a conventional alloy that has a lower
coefficient of thermal expansion, the technique described herein does not increase the incipient melting point of the coating. With regard to the alloy mentioned above, this is because the titanium and boride constituents fully precipitate as a high melting point phase. As a result, the blade tip temperature, particularly of a titanium blade tip, during rub is still limited to the melting point of aluminum. This helps reduce the risk of a titanium fire .
[ 0043 ] The coatings described herein have good adhesion between the fine particles and the matrix.
[ 0044 ] There has been described herein a thermo- mechanical fatigue resistant aluminum abradable coating. While the coating has been described in the context of specific embodiments thereof, other unforeseeable alternatives, modifications, and variations may become apparent to those skilled in the art having read the foregoing description. Accordingly, it is intended to embrace those alternatives, modifications, and variations as fall within the broad scope of the appended claims.

Claims

WHAT IS CLAIMED
1. An aluminum coating to be deposited on a substrate having a first coefficient of thermal expansion, said aluminum coating comprising:
an aluminum matrix;
particles of a material having a low coefficient of thermal expansion incorporated into said matrix; and
said particles bonding sufficiently well to the aluminum matrix to carry a portion of a mechanical load.
2. The aluminum coating of claim 1, wherein said particles are selected from the group consisting of carbides, borides, oxides, and combinations thereof.
3. The aluminum coating of claim 1, wherein said particles are aluminum boride particles .
4. The aluminum coating of claim 1, wherein said particles are titanium boride particles.
5. The aluminum coating of claim 4, wherein said titanium boride particles have a ratio of titanium boron in the range of 1:1 to 1:4.
6. The aluminum coating of claim 1, wherein said particles are present in an amount from 1.0 to 33 vol%.
7. The aluminum coating of claim 1, wherein said particles are present in an amount of from 10 to 25 vol%.
8. The aluminum coating of claim 1, wherein said particles are present in an amount of 15 to 20 vol% .
9. The aluminum coating of claim 1, further comprising a pore making material.
10. The aluminum coating of claim 9, wherein said pore making material is selected from the group consisting of hexagonal boron nitride, polyester and Lucite .
11. A process for applying an aluminum coating to a part comprising the steps of: providing a part; forming a powder containing an aluminum matrix and particles having a low coefficient of thermal expansion bonded to said aluminum matrix; and thermally spraying said powder onto said part.
12. The process of claim 11, wherein said part providing step comprises providing a part formed from a titanium based alloy or an iron based alloy.
13. The process of claim 11, wherein said powder forming step comprises forming a powder containing particles selected from the group consisting of oxide material, a carbide, a boride, and combinations thereof.
14. The process of claim 13, wherein said powder forming step comprises forming said powder to have from 1.0 to 33 vol% of said particles.
15. The process of claim 13, wherein said powder forming step comprises forming said powder to have from 10 to 25 vol% of said particles.
16. The process of claim 13, wherein said powder forming step comprises forming said powder to have from 15 to 20 vol% of said particles.
17. The process of claim 13, wherein said powder forming step comprises using titanium boride particles.
18. The process of claim 13, wherein said powder forming step comprises using aluminum boride particles.
19. The process of claim 11, further comprises adding a pore making material to said powder.
20. The process of claim 11, wherein said powder forming step comprises melt atomization of a boride containing aluminum alloy and quenching the boride containing aluminum alloy during atomization to form particles of a metastable solid solution.
21. The process of claim 11, further comprising
subjecting said aluminum coating to a heat treatment in the range of from 625 to 650 degrees Centigrade for 2.0 hours .
22. A process for forming an aluminum alloy matrix containing fine particles comprising the steps of: melt atomizing a boride containing aluminum alloy; and quenching the boride containing aluminum alloy during atomization to form particles of a metastable solid solution.
EP13877283.5A 2013-03-06 2013-12-30 Thermo-mechanical fatigue resistant aluminum abradable coating Active EP2964808B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US201361773344P 2013-03-06 2013-03-06
PCT/US2013/078183 WO2014137464A1 (en) 2013-03-06 2013-12-30 Thermo-mechanical fatigue resistant aluminum abradable coating

Publications (3)

Publication Number Publication Date
EP2964808A1 true EP2964808A1 (en) 2016-01-13
EP2964808A4 EP2964808A4 (en) 2016-10-26
EP2964808B1 EP2964808B1 (en) 2019-05-01

Family

ID=51491755

Family Applications (1)

Application Number Title Priority Date Filing Date
EP13877283.5A Active EP2964808B1 (en) 2013-03-06 2013-12-30 Thermo-mechanical fatigue resistant aluminum abradable coating

Country Status (3)

Country Link
US (1) US20160017474A1 (en)
EP (1) EP2964808B1 (en)
WO (1) WO2014137464A1 (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10697464B2 (en) 2016-07-29 2020-06-30 Raytheon Technologies Corporation Abradable material
US20190186281A1 (en) * 2017-12-20 2019-06-20 United Technologies Corporation Compressor abradable seal with improved solid lubricant retention

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4836982A (en) * 1984-10-19 1989-06-06 Martin Marietta Corporation Rapid solidification of metal-second phase composites
US5196471A (en) * 1990-11-19 1993-03-23 Sulzer Plasma Technik, Inc. Thermal spray powders for abradable coatings, abradable coatings containing solid lubricants and methods of fabricating abradable coatings
EP1247941A1 (en) * 2001-04-03 2002-10-09 Siemens Aktiengesellschaft Gas turbine blade
US8187720B2 (en) * 2005-11-14 2012-05-29 Lawrence Livermore National Security, Llc Corrosion resistant neutron absorbing coatings
US7754342B2 (en) * 2005-12-19 2010-07-13 General Electric Company Strain tolerant corrosion protecting coating and spray method of application
US8034153B2 (en) * 2005-12-22 2011-10-11 Momentive Performances Materials, Inc. Wear resistant low friction coating composition, coated components, and method for coating thereof
US8790789B2 (en) * 2008-05-29 2014-07-29 General Electric Company Erosion and corrosion resistant coatings, methods and articles

Also Published As

Publication number Publication date
US20160017474A1 (en) 2016-01-21
EP2964808A4 (en) 2016-10-26
EP2964808B1 (en) 2019-05-01
WO2014137464A1 (en) 2014-09-12

Similar Documents

Publication Publication Date Title
EP1583850B1 (en) Thermal spray composition and method of deposition for abradable seals
WO2020173151A1 (en) Method for preparing amorphous oxide ceramic composite coating simultaneously having toughness, thermal conductivity and high-temperature structural stability
JP2008538385A (en) Method for forming metal matrix composite and coating layer and bulk produced using the same
PT1322794E (en) Thermally applied coating for piston rings, consisting of mechanically alloyed powders
Nejati et al. Microstructural analysis and thermal shock behavior of plasma sprayed ceria-stabilized zirconia thermal barrier coatings with micro and nano Al2O3 as a third layer
CN102296289A (en) Preparation method of metal ceramic coating with intermetallic compound as binding phase
EP2591136B1 (en) Thermally sprayed completely amorphic oxide coating
CN109396453B (en) Preparation method of dispersion-strengthened aluminum bronze spherical powder
CN102605230A (en) Bi-phase nano particle reinforced titanium alloy protective coating and preparation method of bi-phase nano particle reinforced titanium alloy protective coating
Zhang et al. Microstructure and properties of Al2O3-13% TiO2 coatings sprayed using nanostructured powders
CN109402564A (en) A kind of AlCrSiN and AlCrSiON double-layer nanometer composite coating and preparation method thereof
Liu et al. Effects of temperature and atmosphere on microstructure and tribological properties of plasma sprayed FeCrBSi coatings
Xu et al. Improved the elevated temperature mechanical properties of Al-Si alloy deposited with Al-Si coating by magnetron sputtering
Pradeep et al. Review on tribological and mechanical behavior in HVOF thermal-sprayed composite coatings
Liu et al. The anisotropic wear and friction property of Inconel 718 superalloy fabricated by laser directed energy deposition
EP2964808B1 (en) Thermo-mechanical fatigue resistant aluminum abradable coating
Weitong et al. Influence of Al2O3 mass fractions on microstructure, oxidation resistance and friction–wear behaviors of CoCrAlYTaSi coatings
CN113186483B (en) Amorphous functional protective coating suitable for complex working conditions and preparation method thereof
CN110923610A (en) Preparation method of cobalt-based alloy composite powder and cladding coating for plasma spraying
JP4731645B2 (en) Cemented carbide and coated cemented carbide and method for producing the same
Yang et al. Microstructure and high PV wear behavior of novel amorphous Al 2 O 3-YAG ceramic coating fabricated by atmospheric plasma spraying
CN107460476A (en) A kind of titanium alloy surface TiC enhancings titanium-based composite coat and preparation method thereof
Kumar¹ et al. A review on mechanical and tribological behaviors of nickel matrix composites
CN108611588B (en) High-temperature oxidation resistant and sulfur and chlorine corrosion resistant alloy coating and preparation method thereof
Pavan et al. Review of ceramic coating on mild steel methods, applications and opportunities

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20151006

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

AX Request for extension of the european patent

Extension state: BA ME

DAX Request for extension of the european patent (deleted)
A4 Supplementary search report drawn up and despatched

Effective date: 20160922

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: UNITED TECHNOLOGIES CORPORATION

RIC1 Information provided on ipc code assigned before grant

Ipc: C23C 4/06 20060101AFI20160916BHEP

Ipc: C23C 4/18 20060101ALI20160916BHEP

Ipc: B22F 9/08 20060101ALI20160916BHEP

REG Reference to a national code

Ref country code: DE

Ref legal event code: R079

Ref document number: 602013054837

Country of ref document: DE

Free format text: PREVIOUS MAIN CLASS: C23C0030000000

Ipc: C23C0004060000

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: GRANT OF PATENT IS INTENDED

RIC1 Information provided on ipc code assigned before grant

Ipc: C23C 4/18 20060101ALI20181012BHEP

Ipc: C23C 4/06 20160101AFI20181012BHEP

Ipc: C22C 21/00 20060101ALI20181012BHEP

Ipc: C22C 1/10 20060101ALI20181012BHEP

Ipc: C22C 1/04 20060101ALI20181012BHEP

Ipc: B22F 9/08 20060101ALI20181012BHEP

INTG Intention to grant announced

Effective date: 20181115

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE PATENT HAS BEEN GRANTED

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

Ref country code: AT

Ref legal event code: REF

Ref document number: 1126976

Country of ref document: AT

Kind code of ref document: T

Effective date: 20190515

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 602013054837

Country of ref document: DE

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: NL

Ref legal event code: MP

Effective date: 20190501

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG4D

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190501

Ref country code: HR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190501

Ref country code: NO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190801

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190501

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190901

Ref country code: AL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190501

Ref country code: ES

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190501

Ref country code: LT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190501

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190501

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190802

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190801

Ref country code: RS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190501

Ref country code: LV

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190501

REG Reference to a national code

Ref country code: AT

Ref legal event code: MK05

Ref document number: 1126976

Country of ref document: AT

Kind code of ref document: T

Effective date: 20190501

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190901

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190501

Ref country code: AT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190501

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190501

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190501

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190501

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190501

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 602013054837

Country of ref document: DE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SM

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190501

Ref country code: IT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190501

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: TR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190501

26N No opposition filed

Effective date: 20200204

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: PL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190501

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190501

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

REG Reference to a national code

Ref country code: BE

Ref legal event code: MM

Effective date: 20191231

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MC

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190501

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20191230

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20191230

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20191231

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20191231

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20191231

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190501

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190501

Ref country code: HU

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT; INVALID AB INITIO

Effective date: 20131230

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190501

REG Reference to a national code

Ref country code: DE

Ref legal event code: R081

Ref document number: 602013054837

Country of ref document: DE

Owner name: RAYTHEON TECHNOLOGIES CORPORATION (N.D.GES.D.S, US

Free format text: FORMER OWNER: UNITED TECHNOLOGIES CORPORATION, FARMINGTON, CONN., US

P01 Opt-out of the competence of the unified patent court (upc) registered

Effective date: 20230520

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20231124

Year of fee payment: 11

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20231122

Year of fee payment: 11

Ref country code: DE

Payment date: 20231121

Year of fee payment: 11