# US 6,720,088 B2 · Materials for protection of substrates at high temperature, articles made therefrom, and method for protecting substrates

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- Number: US 6,720,088 B2
- Document ID: US6720088B2
- Status: Granted
- Kind: B2
- Application number: 09/683,700
- Filed: 2002-02-05
- Published: 2003-08-07
- Granted: 2004-04-13
- Earliest claimed: 2002-02-05
- Assignees: General Electric Company
- Inventors: Ji-Cheng Zhao; Melvin Robert Jackson; Richard John Grylls; Ramgopal Darolia
- Web page: https://patentgrep.com/patent/US6720088B2

## CPC

- C22C 5/04: Alloys based on a platinum group metal
- B32B 15/01: all layers being exclusively metallic {(making layered metal workpieces by pressure cladding B23K20/22; making coatings with a metallic material characterised by its composition C23C30/00)}
- C22C 30/00: Alloys containing less than 50% by weight of each constituent
- C23C 10/30: using a layer of powder or paste on the surface (using liquid suspensions of solids C23C10/18)
- C23C 26/00: Coating not provided for in groups C23C2/00 - C23C24/00
- C23C 28/321: {with at least one metal alloy layer}
- C23C 28/3215: {at least one MCrAlX layer}
- C23C 28/325: {with layers graded in composition or in physical properties}
- C23C 28/3455: {with a refractory ceramic layer, e.g. refractory metal oxide, ZrO2, rare earth oxides or a thermal barrier system comprising at least one refractory oxide layer}
- Y02T 50/60: Efficient propulsion technologies, e.g. for aircraft
- Y10S 428/926: Thickness of individual layer specified
- Y10S 428/937: Sprayed metal
- Y10S 428/938: Vapor deposition or gas diffusion
- Y10S 428/941: Solid state alloying, e.g. diffusion, to disappearance of an original layer
- Y10T 428/12493: Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
- Y10T 428/12535: with additional, spatially distinct nonmetal component
- Y10T 428/12542: More than one such component
- Y10T 428/12576: Boride, carbide or nitride component
- Y10T 428/12611: Oxide-containing component
- Y10T 428/12806: Refractory [Group IVB, VB, or VIB] metal-base component
- Y10T 428/12861: Group VIII or IB metal-base component
- Y10T 428/12875: Platinum group metal-base component
- Y10T 428/12931: Co-, Fe-, or Ni-base components, alternative to each other
- Y10T 428/12944: Ni-base component
- Y10T 428/12986: Adjacent functionally defined components
- C22C: ALLOYS (treatment of alloys C21D, C22F)
- B32B: LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- 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 (making metal-coated products by extrusion B21C23/22; covering with metal by connecting pre-existing layers to articles, see the relevant places, e.g. B21D39/00, B23K; metallising of glass C03C; metallising mortars, concrete, artificial stone, ceramics or natural stone C04B41/00; enamelling of, or applying a vitreous layer to, metals C23D; treating metal surfaces or coating of metals by electrolysis or electrophoresis C25D; single-crystal film growth C30B; by metallising textiles D06M11/83; decorating textiles by locally metallising D06Q1/04)
- Y02T: CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y10S: TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10T: TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION

## Abstract

A group of alloys suitable for use in a high-temperature, oxidative environment, a protective coating system comprising a diffusion barrier that comprises an alloy selected from the group, an article comprising the diffusion barrier layer, and a method for protecting an article from a high-temperature oxidative environment comprising disposing the diffusion barrier layer onto a substrate are presented.

## Claims

### Claim 1

An alloy for use in a high-temperature, oxidative environment, comprising, in atomic percent:
from about 20% to about 80% ruthenium (Ru);
from about 2% to about 15% aluminum (Al);
up to about 15% chromium (Cr); and
the balance comprising at least one of nickel (Ni), cobalt (Co), and mixtures thereof.

### Claim 2 (depends on 1)

The alloy of claim 1, wherein said alloy comprises, in atomic percent:
from about 30% to about 80% Ru;
from about 4% to about 10% Al;
from about 2% to about 12% Cr; and the balance comprising at least one of nickel (Ni), cobalt (Co), and mixtures thereof.

### Claim 3 (depends on 2)

The alloy of claim 2, comprising, in atomic percent:
from about 40% to about 60% Ru;
from about 4% to about 80% Al;
from about 5% to about 12% Cr; and the balance comprising at least one of nickel (Ni), cobalt (Co), and mixtures thereof.

### Claim 4

An alloy for use in a high-temperature, oxidative environment, comprising, in atomic percent:
at least about 80% ruthenium (Ru);
from about 20% to about 20% aluminum (Al);
up to about 20% chromium (Cr); and
the balance comprising at least one of nickel (Ni), cobalt (Co), and mixtures thereof.

### Claim 5 (depends on 4)

The alloy of claim 4, comprising, in atomic percent:
at least about 80% ruthenium (Ru);
from about 2% to about 15% aluminum (Al);
from about 2% to about 10% chromium (Cr); and
the balance comprising at least one of nickel (Ni), cobalt (Co), and mixtures thereof.

### Claim 6 (depends on 5)

The alloy of claim 5, comprising, in atomic percent:
at least about 80% ruthenium (Ru);
from about 3% to about 8% aluminum (Al);
from about 3% to about 8% chromium (Cr); and
the balance comprising at least one of nickel (Ni), cobalt (Co), and mixtures thereof.

### Claim 7

An alloy for use in a high-temperature, oxidative environment, comprising, in atomic percent:
from about 60% to about 85% ruthenium (Ru);
from about 15% to about 40% aluminum (Al);
up to about 25% chromium (Cr); and
up to about 25% of at least one of nickel (Ni), cobalt (Co), and mixtures thereof.

### Claim 8 (depends on 7)

The alloy of claim 7, comprising, in atomic percent:
from about 60% to about 85% ruthenium (Ru);
from about 18% to about 35% aluminum (Al);
from about 5% to about 15% chromium (Cr); and
up to about 17% of at least one of nickel (Ni), cobalt (Co), and mixtures thereof.

### Claim 9 (depends on 8)

The alloy of claim 8, comprising, in atomic percent:
from about 60% to about 80% ruthenium (Ru);
from about 20% to about 30% aluminum (Al);
from about 8% to about 10% chromium (Cr); and
up to about 12% of at least one of nickel (Ni), cobalt (Co), and mixtures thereof.

### Claim 10

A protective coating system for protecting an article from a high-temperature, oxidative environment, said protective coating system comprising:
a diffusion barrier layer comprising an alloy selected from the group consisting of
a. an alloy comprising, in atomic percent, from about 20% to about 80% ruthenium (Ru), from about 2% to about 15% aluminum (Al), up to about 15% chromium (Cr), and the balance comprising at least one of nickel (Ni), cobalt (Co), and mixtures thereof;
b. an alloy comprising, in atomic percent, at least about 80% Ru, from about 2% to about 20% Al, up to about 20% Cr, and the balance comprising at least one of Ni, Co, and mixtures thereof; and
c. an alloy comprising, in atomic percent, from about 60% to about 85% Ru, from about 15% to about 40% Al, up to about 25% Cr, and up to about 25% of at least one of Ni, Co, and mixtures thereof.

### Claim 11 (depends on 10)

The protective coating system of claim 10, further comprising a thermal barrier coating disposed over said diffusion barrier layer.

### Claim 12 (depends on 10)

The protective coating system of claim 10, said protective coating system further comprising a layer of oxidation-resistant material disposed over said diffusion barrier layer.

### Claim 13 (depends on 12)

The protective coating system of claim 12, wherein said oxidation-resistant material comprises aluminum.

### Claim 14 (depends on 13)

The protective coating system of claim 13, wherein said oxidation-resistant material comprises an aluminide.

### Claim 15 (depends on 14)

The protective coating system of claim 14, wherein said oxidation-resistant material further comprises platinum (Pt).

### Claim 16 (depends on 12)

The protective coating system of claim 12, wherein said oxidation-resistant material comprises a material of general formula MCrAl(X), wherein M is at least one of nickel, cobalt, and iron, and wherein X is at least one of yttrium (Y), tantalum (Ta), silicon (Si), hafnium (Hf), titanium (Ti), zirconium (Zr), boron (B), carbon (C).

### Claim 17 (depends on 12)

The protective coating system of claim 12, further comprising a thermal barrier coating, wherein said layer of oxidation-resistant material is disposed between said diffusion barrier layer and said thermal barrier coating.

### Claim 18

A protective coating system for protecting an article from a high-temperature, oxidative environment, said protective coating system comprising:
a diffusion barrier layer comprising, in atomic percent, from about 20% to about 45% Ru, from about 15% to about 40% Cr, from about 20% to about 50% Al, and the balance comprising at least one of Ni, Co, and mixtures thereof;
a layer of oxidation-resistant material, said material comprising an alumiide, disposed over said diffusion barrier layer; and
a thermal barrier coating disposed over said layer of oxidation-resistant material.

### Claim 19

An article for use in a high-temperature, oxidative environment, comprising:
a substrate; and
a diffusion barrier layer disposed on said substrate, said diffusion barrier layer comprising an alloy selected from the group consisting of
a. an alloy comprising, in atomic percent, from about 20% to about 80% ruthenium (Ru), from about 2% to about 15% aluminum (Al), up to about 15% chromium (Cr), and the balance comprising at least one of nickel (Ni), cobalt (Co), and mixtures thereof;
b. an alloy comprising, in atomic percent, at least about 80% Ru, from about 20% to about 20% Al, up to about 20% Cr, and the balance comprising at least one of Ni, Co, and mixtures thereof; and
c. an alloy comprising, in atomic percent, from about 60% to about 85% Ru, from about 15% to about 40% Al, up to about 25% Cr, and up to about 25% of at least one of Ni, Co, and mixtures thereof.

### Claim 20 (depends on 19)

The article of claim 19, further comprising a layer of oxidation-resistant material disposed over said diffusion barrier layer.

### Claim 21 (depends on 20)

The article of claim 20, wherein said oxidation-resistant material comprises aluminum.

### Claim 22 (depends on 20)

The article of claim 20, further comprising a thermal barrier coating disposed over said layer of oxidation-resistant material.

### Claim 23 (depends on 19)

The article of claim 19, wherein said substrate comprises a superalloy.

### Claim 24 (depends on 23)

The article of claim 23, wherein said superalloy is a nickel-based superalloy comprising at least one refractory metal selected from the group consisting of tungsten, rhenium, tantalum, hafnium, molybdenum, niobium, and zirconium.

### Claim 25 (depends on 23)

The article of claim 23, wherein said substrate further comprises a gas turbine engine component.

### Claim 26 (depends on 25)

The article of claim 25, wherein said gas turbine engine component is a component selected from the group consisting of a turbine blade, a vane, a transition piece, and a combustor.

### Claim 27

A gas turbine engine component comprising:
a substrate comprising a gas turbine engine component, said component comprising a nickel-based superalloy;
a diffusion barrier layer disposed over said substrate, said diffusion barrier layer comprising an alloy comprising, in atomic percent, from about 20% to about 45% Ru, from about 15% to about 40% Cr, from about 2% to about 50% Al, and the balance comprising at least one of Ni, Co, and mixtures thereof,
a layer of oxidation-resistant material, said material comprising an aluminide, disposed over said diffusion barrier layer; and
a thermal barrier coating disposed over said layer of oxidation-resistant material.

### Claim 28

A method for protecting an article from exposure to a high-temperature, oxidative environment, said method comprising:
providing a substrate; and
disposing a diffusion barrier layer on said substrate, said diffusion barrier layer comprising an alloy selected from the group consisting of
a. an alloy comprising, in atomic percent, from about 20% to about 80% ruthenium (Ru), from about 2% to about 15% aluminum (Al), up to about 15% chromium (Cr), and the balance comprising at least one of nickel (Ni), cobalt (Co), and mixtures thereof,
b. an alloy comprising, in atomic percent, at least about 80% Ru, from about 20% to about 20% Al, up to about 20% Cr, and the balance comprising at least one of Ni, Co, and mixtures thereof, and
c. an alloy comprising, in atomic percent, from about 60% to about 85% Ru, from about 15% to about 40% Al, up to about 25% Cr, and up to about 25% of at least one of Ni, Co, and mixtures thereof.

### Claim 29 (depends on 28)

The method of claim 28, wherein providing a substrate comprises providing a nickel-based superalloy substrate, said superalloy substrate comprising at least one refractory metal selected from the group consisting of tungsten, rhenium, tantalum, hafnium, molybdenum, niobium, and zirconium.

### Claim 30 (depends on 28)

The method of claim 28, further comprising disposing a layer of oxidation-resistant material over said diffusion barrier layer.

### Claim 31 (depends on 30)

The method of claim 30, wherein disposing said layer of oxidation-resistant material comprises disposing a layer comprising aluminum.

### Claim 32 (depends on 31)

The method of claim 31, wherein disposing said diffusion barrier layer comprises disposing a layer of ruthenium (Ru) on said substrate prior to the disposition of said layer of oxidation-resistant material, and heating said substrate after disposition of said layer of oxidation-resistant material to react said Ru with said substrate and said layer of oxidation-resistant material to form said diffusion barrier layer.

### Claim 33 (depends on 30)

The method of claim 30, further comprising disposing a thermal barrier coating over said layer of oxidation-resistant material.

### Claim 34 (depends on 28)

The method of claim 28, wherein providing said substrate comprises providing a gas turbine engine component.

### Claim 35 (depends on 34)

The method of claim 34, wherein said gas turbine engine component is a component selected from the group consisting of a turbine blade, a vane, a transition piece, and a combustor.

### Claim 36

A method for protecting a gas turbine engine component, said method comprising:
providing a gas turbine engine component;
disposing a diffusion barrier layer on said component, said diffusion barrier layer comprising an alloy comprising, in atomic percent, from about 20% to about 45% Ru, from about 15% to about 40% Cr, from about 2% to about 50% Al, and the balance comprising at least one of Ni, Co, and mixtures thereof;
disposing a layer of oxidation-resistant material over said diffusion barrier layer, said oxidation-resistant material comprising an aluminide; and
disposing a thermal barrier coating over said layer of oxidation-resistant material.

### Claim 37

A protective coating system for protecting an article from a high-temperature, oxidative environment, said protective coating system comprising:
a diffusion barrier layer comprising an alloy, said alloy comprising, in atomic percent, from about 20% to about 45% Ru, from about 15% to about 40% Cr, from about 2% to about 50% Al, and the balance comprising at least one of Ni, Co, and mixtures thereof; and
at least one additional layer disposed over said diffusion barrier layer, said at least one additional layer comprising at least one of a layer of oxidation-resistant material and a thermal barrier coating.

### Claim 38 (depends on 37)

The protective coating system of claim 37, wherein said alloy of said diffusion barrier layer comprises, in atomic percent, from about 25% to about 45% Ru, from about 15% to about 35% Cr, from about 50% to about 40% Al, and the balance comprising at least one of Ni, Co, and mixtures thereof.

### Claim 39 (depends on 38)

The protective coating system of claim 38, wherein said alloy of said diffusion barrier layer comprises, in atomic percent, from about 30% to about 45% Ru, from about 20% to about 35% Cr, from about 5% to about 35% Al, and the balance comprising at least one of Ni, Co, and mixtures thereof.

### Claim 40 (depends on 37)

The protective coating system of claim 37, whereln said oxidation-resistant material comprises aluminum.

### Claim 41 (depends on 40)

The protective coating system of claim 40, wherein said oxidation-resistant material comprises an aluminide.

### Claim 42 (depends on 41)

The protective coating system of claim 41, wherein said oxidation-resistant material further comprises platinum (Pt).

### Claim 43 (depends on 40)

The protective coating system of claim 40, wherein said oxidation-resistant material comprises a material of general formula MCrAl(X), wherein M is at least one of nickel, cobalt, and iron, and wherein X is at least one of yttrium (Y), tantalum (Ta), silicon (Si), hafnium (Hf), titanium (Ti), zirconium (Zr), boron (B), carbon (C).

### Claim 44

An article for use in a high-temperature, oxidative environment, comprising:
a substrate; and
a diffusion barrier layer disposed on said substrate, said diffusion barrier layer comprising an alloy, said alloy comprising, in atomic percent, from about 20% to about 45% Ru, from about 15% to about 40% Cr, from about 2% to about 50% Al, and the balance comprising at least one of Ni, Co, and mixtures thereof; and
a layer of oxidation-resistant material disposed over said diffusion barrier layer.

### Claim 45 (depends on 44)

The article of claim 44, wherein said oxidation resistant material comprises at least one of
a. an aluminide, and
b. a material of general formula MCrAI(X), wherein M is at least one of nickel, cobalt, and iron, and wherein X is at least one of yttrium (Y), tantalum (Ta), silicon (Si), hafnium (Hf), titanium (Ti), zirconium (Zr), boron (B), carbon (C).

### Claim 46 (depends on 45)

The article of claim 45, further comprising a thermal barrier coating disposed over said layer of oxidation-resistant material.

### Claim 47 (depends on 44)

The article of claim 44, wherein said substrate comprises a superalloy.

### Claim 48

A method for protecting an article from exposure to a high-temperature, oxidative environment, said method comprising:
providing a substrate; and
disposing a diffusion barrier layer on said substrate, said diffusion barrier layer comprising an alloy, said alloy comprising, in atomic percent, from about 20% to about 45% Ru, from about 15% to about 40% Cr, from about 2% to about 50% Al, and the balance comprising at least one of Ni, Co, and mixtures thereof; and
disposing a layer of oxidation-resistant material over said diffusion barrier layer.

### Claim 49 (depends on 48)

The method of claim 48, wherein said oxidation resistant material comprises at least one of
a. an aluminide, and
b. a material of general formula MCrAl(X), wherein M is at least one of nickel, cobalt, and iron, and wherein X is at least one of yttrium (Y), tantalum (Ta), silicon (Si), hafnium (Hf), titanium (Ti), zirconium (Zr), boron (B), carbon (C).