DE102016100587A1 - Improved adhesion of coatings using bonding compositions - Google Patents

Abstract

A multilayer article (1) disclosed herein includes a metallic substrate (2), a protective layer (6), and an adhesive bonding layer (14) that includes an oxygen-containing compound that bonds the adhesive bonding layer to the metallic substrate, the protective layer, or both. A method of forming the multilayer article includes the steps of heating a protective bonding composition (20) to form a melt (24) in contact with a metal-containing surface (2), allowing the melt to cool and solidify to the adhesive bond layer (14) attached to the metal-containing surface ), Applying a ceramic material (26) to the adhesive bonding layer, and heating the ceramic material to form the protective layer (6) attached to the adhesive bonding layer.

Description

FIELD OF THE INVENTION

This invention relates generally to the field of materials science, and more particularly to the fabrication and repair of multilayer metallic articles containing adhesive coatings.

BACKGROUND OF THE INVENTION

Components of hot areas of modern gas turbine engines are often made of high temperature alloys including superalloys based on nickel, iron and cobalt. Cast superalloys (eg, 247, 738, CMSX4, Rene 5, etc.) and high performance forgings (eg, X, 625, 617, etc.) are often used in such high temperature applications (eg, turbine blades , Wings, combustion liners). These superalloys have been developed to withstand ever higher operating temperatures as well as the presence of corrosive and oxidative conditions. To withstand these extreme conditions, protective coating systems are often applied to the surface of superalloy components to form multilayer articles. These coating systems include an environmental coating which may also serve as a metallic primer layer and typically as a thermal barrier ceramic coating (TBC) overlying the ambient or primer layer.

Such environmental coatings (or coupling agents) are typically metallic overlay coatings of the formula "MCrAlX" (wherein M is a Group VIIIB element such as Co, Ni or a mixture thereof, and X is a rare earth element such as Y, Hf, W, Zr, La or a mixture thereof) or diffusion aluminide coatings, such as NiAl or a modified NiAl, including an element such as Pt, Rh or Pd. In thermal barrier coating (TBC) systems that include both a metallic adhesive and a ceramic TBC layer, the TBC layer is often formed from metal oxides such as yttria-stabilized zirconia (YSZs). One of the purposes of the primer layer in a TBC system is to improve the adhesion between the outer TBC layer and the underlying substrate to be protected.

In such multilayer coating systems, the adhesion of the outer protective layer to the underlying metallic substrate is an important consideration that can greatly affect the effectiveness and longevity of a component of the hot zone. Protective coatings are subject to degradation as a function of performance. Elevated temperatures, high loads (both sustained and cyclical), reactions with process gas, and the action of foreign bodies can cause a variety of chemical and physical property changes that result in a loss of coating (eg, cracking and spalling), resulting in a loss of coating Exposure of the underlying substrate and further damage to components leads.

1 illustrates a non-limiting example in which a superalloy substrate 2 through a multi-layered TBC system 8th which is an inner MCrAlY adhesion promoter layer 4 and an outer ceramic TBC layer 6 includes, by the degradation of the outer ceramic TBC layer 6 is impaired, causing erosion 12 both the primer layer 4 as well as the underlying superalloy substrate 2 leads. In this illustration, the missing part 10 the TBC layer due to relatively poor adhesion between the outer ceramic TBC layer 6 and the MCrAlY inner tie layer 4 have occurred.

There is a need, somehow, for the adhesion between these outer protective layers 4 . 6 and the underlying substrate 2 to improve the longevity and efficiency of the components or components.

BRIEF DESCRIPTION OF THE DRAWINGS

The invention will be elucidated in the following description with reference to the drawings, which show:

1 illustrates damage that can occur to an underlying metallic substrate when a protective coating is damaged or degraded.

2 FIG. 10 is a cross-sectional view of a multilayer article including a metallic substrate, an adhesive bonding layer, and a ceramic protective layer according to an embodiment. FIG.

3 FIG. 12 is a cross-sectional view of a multilayer article including a metallic substrate, a primer layer, an adhesive bonding layer, and a ceramic protective layer, according to one embodiment. FIG.

4 FIG. 12 is a cross-sectional view of a multilayer article comprising a metallic substrate, a ceramic protective layer, and a plurality of chemical anchors associated with both the metallic substrate as well as the protective layer are glued, contains, according to one embodiment.

5 FIG. 12 is a cross-sectional view of a multilayer article including a metallic substrate, a primer layer, a ceramic protective layer, and a plurality of chemical anchors bonded to both the primer layer and the ceramic protective layer, according to one embodiment.

6 is a photograph illustrating a spear-like cuspid crystal, according to one embodiment.

7 illustrates process steps of a method of forming a multilayer article, according to an embodiment.

8th illustrates process steps of a method of forming a multilayer article, according to an embodiment.

9 illustrates process steps of a method of forming a multilayer article, according to an embodiment.

DETAILED DESCRIPTION OF THE INVENTION

The inventors were aware that certain weld and liner flux formulations produce slag deposits that are difficult to remove. This adhesion is generally considered problematic in the welding industry - especially in multi-pass welds, where it becomes both laborious to remove the deposits and where incomplete removal can lead to the formation of inclusions and inferior weld metal. For this reason, welding compositions (e.g., flux compositions) are generally formulated to improve the removability of the resulting slag deposits; see, for. B. Oladipupo, AO, "Slag Detachability from Submerged Arc Welds," Doctoral Thesis (Massachusetts Institute of Technology) February 1987 and US 2006/0266799 ,

Although inconsistent with the art-recognized wisdom, the inventors recognized a potential benefit of weld composites capable of forming such low-releasability deposits as a way to improve the adhesion between protective coating systems and underlying metallic substrates , It is also envisaged that certain deposits could also be formulated to provide protective features that either complement or completely replace the outer protective layer (eg, TBC / primer). Based on this finding, the inventors have developed protective bonding compositions and methods for the use of such compositions in the manufacture and repair of multi-layered articles having improved adhesion between protective outer layer (s) and underlying metallic substrates.

2 is a cross-sectional view of a multilayer article 1 according to one embodiment. In this non-limiting example, the multilayer article comprises 1 a metallic substrate 2 that with a Klebbondierschicht 14 is glued, that of a protective layer 6 is covered. Unlike previously reported coating systems, the multilayer article contains 1 In this embodiment, there is no intervening primer layer, but instead relies on the adhesive bonding layer 14 , which is a non-MCrAlY deposit with low removability, as briefly outlined above and described in more detail below.

The metallic substrate 2 from 2 (as well as in other embodiments described and implied below) may be an iron-containing substrate (eg, stainless steel) or a non-ferrous substrate such as a superalloy. The term "superalloy" is used herein as it is commonly used in the art, ie, a highly corrosion and oxidation resistant alloy that exhibits excellent mechanical strength and creep resistance at high temperatures. Superalloys typically include a high nickel or cobalt content. Examples of superalloys include alloys sold under the trademarks and trade names Hastelloy, Inconel alloys (e.g., IN 100, IN 700, IN 713, IN 738, IN 792, IN 939), Rene alloys (e.g. Rene N5, Rene 41, Rene 80, Rene 108, Rene 142, Rene 220), Haynes alloys (282), Mar M, CM 247, CM 247 LC, C263, 718, X-750, 25 ECY 768, 282, X45, PWA 1480, PWA 1483, PWA 1484, CMSX single crystal alloys (eg CMSX-4, CMSX-8, CMSX-10), GTD 111, GTD 222, MGA 1400, MGA 2400, PSM 116, M-200, Udimet 600, Udimet 500 and Titanaluminid be marketed. The terms "metal", "metallic material", "alloy" and "metal alloy" are used herein in a general sense to describe pure metals, semi-pure metals and metal alloys.

The protective layer 6 from 2 (as well as in other embodiments described and implied below) may be a ceramic layer suitable for use as a thermal barrier coating (TBC), including TBCs well known in the art. Such ceramic coatings have generally low thermal conductivity and include metal oxides such as zirconia (ZrO ₂ ) partially or fully stabilized by yttria (Y ₂ O ₃ ), magnesia (MgO) or other oxides. In some embodiments, the protective layer 6 a yttria-stabilized zirconia (YSZ).

The Klebbondierschicht 14 from 2 (and in other embodiments described and implied below) contains one or more inorganic compounds which may include metal oxides, metal halides, metal oxometalates, metal carbonates, as well as elemental metals and metalloids of Groups IIA, IIIB, IVB, VB, VIB, VIIB, VIIIB, IB, IIB, IIIA, IVA, VA of the periodic table, lanthanides and nonmetals such as boron and carbon. As explained in more detail below, the Klebbondierschicht 14 by heating a protective bonding composition to a melt in contact with a metal-containing surface, and thereafter the melt is allowed to cool and solidify to a deposit having a low releasability from the metal-containing surface.

To the desired low removability of Klebbondierschicht 14 To achieve this, the protective bonding composition is formulated to contain certain mixtures of compounds (described in more detail below) that will react in the heated environment of the melt to form at least one oxygen-containing compound which will adhere the adhesive bonding layer 14 with the metallic substrate 2 , the protective layer 6 or both supported.

In some embodiments, the oxygen-containing compound is selected from a spinel compound, a perovskite compound, a cuspidin compound, and mixtures thereof. In some embodiments, the oxygen-containing compound is selected from MgAlCrO ₄ , FeCrO ₄ , CaTiO ₃ , Ca ₄ (Si ₂ O ₇ ) (F, OH) ₂ and mixtures thereof.

The term "spinel compound" is used herein in a general sense to describe an inorganic compound or mineral of the general formula MgAlMO ₄ wherein the element "M" refers to a metallic element such as Al, or a transition metal such as Cr. The term "spinel compound" is also used herein in the same manner as that term is commonly understood in the relevant art. The term "perovskite compound" is used herein in a general sense to describe an inorganic compound or a mineral of the general formula CaTiO ₃ . The term "perovskite compound" is also used herein in the same manner as that term is commonly understood in the relevant art. The term "cuspidin compound" is used herein in a general sense to describe an inorganic compound or a mineral of the general formula Ca ₄ (Si ₂ O ₇ ) (F, OH) ₂ . The term "cuspidin compound" is also used herein in the same manner as that term is commonly understood in the relevant art.

In some embodiments, the oxygen-containing compound is to adhere between the adhesive bonding layer 14 and the metallic substrate 2 , the protective layer 6 or reinforcing both by forming rigid crystalline structures which serve as hooks or anchors to which the respective materials can stick together. 6 is a photograph showing such rigid crystalline structures in the form of spear-like cuspidin crystals 52 exemplified chemically on a surface of a metallic substrate 50 are anchored. The spear-like protrusions of the cuspidin crystals 52 can then be rigidly bonded to an upper layer (eg, a Klebbondierschicht 14 or a protective layer 6 ), which is formed subsequently or simultaneously, to produce a multi-layered article in which the outer protective layer has a low releasability.

Like also in 2 In some embodiments, for example, the multilayer article may 1 a variety of chemical anchors 16 that with the Klebbondierschicht 14 and at least one of the metallic substrate 2 and the protective layer 6 are glued, included. In the embodiment of 2 forms the variety of chemical anchors 16 Bonding bonds between the layers, leaving part of the chemical anchor 16 with the Klebbondierschicht 14 is glued and another part of the chemical anchor with the metallic substrate 2 is glued.

3 is a cross-sectional view of a multilayer article 3 , which is a metallic substrate 2 , a primer layer 4 , a Klebbondierschicht 14 and a protective layer 6 contains, according to one embodiment. The primer layer 4 may be in the form of a metallic coating of the general formula MCrAlX wherein "M" is a Group VIIIB element such as Co, Ni or a mixture thereof, and "X" is a rare earth element such as Y, Hf, W, Zr, La or or a mixture of them. In other embodiments, the primer layer 4 in the form of a diffusion aluminide coating, such as NiAl or modified NiAl, including an element such as Cr, Pt, Rh or Pd. 3 also illustrates the possible presence of a variety of chemical anchors 16 that with the Klebbondierschicht 14 and with the primer layer 4 by forming bonding connections between the Layers are glued, leaving a part of the chemical anchor 16 with the Klebbondierschicht 14 is glued and another part of the chemical anchor 16 with the primer layer 4 is glued.

For example, in some embodiments, the metallic substrate 2 from 2 in the form of a superalloy substrate, the primer layer 4 may be in the form of an MCrAlY primer layer, and the protective layer 6 may be in the form of a ceramic TBC layer.

The 4 and 5 illustrate other embodiments in which the plurality of chemical anchors 16 the adhesion of the multilayered objects 5 . 7 reinforced by forming bonding bonds between the layers, leaving a first portion of the chemical anchors 16 with the metallic substrate 2 glued, a second part of the chemical anchor 16 with a remaining part 18 a Klebbondierschicht is glued and a third part of the chemical anchor 16 with the protective layer 6 is glued.

4 is a cross-sectional view of a multilayer article 5 , which is a metallic substrate 2 , a protective layer 6 and a variety of chemical anchors 16 , with each other both with the metallic substrate 2 as well as with the protective layer 6 are glued contains. In some embodiments, the multilayer article 5 also a remaining part 18 a Klebbondierschicht included, so that the chemical anchor 16 with each other with all three of the metallic substrate 2 , the protective layer 6 and the rest 18 glued to a Klebbondierschicht.

5 is a cross-sectional view of a multilayer article 7 , which is a metallic substrate 2 , a primer layer 4 , a protective layer 6 and a variety of chemical anchors 16 , the one below the other with both the primer layer 4 as well as with the protective layer 6 are glued contains. In some embodiments, the multilayer article 7 also a remaining part 18 a Klebbondierschicht included, so that the chemical anchor 16 with each other with all three from the adhesive layer 4 , the protective layer 6 and the rest 18 glued to a Klebbondierschicht.

7 illustrates process steps of a method of forming the multilayer article 1 from 2 according to one embodiment. In step 1 from 7 becomes a protective bonding composition 20 on a surface of a metallic substrate 2 applied, and an energy ray 22 ' becomes across the surface of the protective bonding composition 20 to form a melt pool 24 run, then cool and to one on the metallic substrate 2 attached Klebbondierschicht 14 is allowed to freeze. In some embodiments, the resulting article may vary depending on the content of the protective bonding composition 20 also a variety of chemical anchors 16 , with each other both with the metallic substrate 2 as well as with the Klebbondierschicht 14 are glued, included. In step 2 from 7 becomes a ceramic powder 26 thereafter on a surface of the adhesive bonding layer 14 applied, and an energy ray 22 '' becomes across the surface of the ceramic powder 26 to form a region 28 run by sintered ceramic powder, which after cooling a protective ceramic layer 6 forms.

8th illustrates process steps of a method of forming the multilayer article 3 from 3 according to an embodiment. In step 1 from 8th becomes an MCrAlY powder 30 on a surface of a metallic substrate 2 applied, and a protective bonding composition 20 (such as a powder) is applied to the layer of MCrAlY powder 30 upset, and an energy ray 22 ' becomes across the surface of the resulting multipulver layer to form a melt pool 32 run, then cool and to one with the metallic substrate 2 bonded MCrAlY adhesion promoter layer 4 solidified and one at the adhesive layer 4 attached Klebbondierschicht 14 is covered. In some embodiments, the resulting article may vary depending on the content of the protective bonding composition 20 also a variety of chemical anchors 16 , the one below the other with both the primer layer 4 as well as with the Klebbondierschicht 14 are glued, included. In other embodiments, the MCrAlY powder 30 and the protective bonding composition 20 on the surface of the metallic substrate 2 are applied as a mixture of powders (unlike those in the 8th illustrated separate multilayers). In step 2 from 8th becomes a ceramic powder 26 thereafter on a surface of the adhesive bonding layer 14 applied, and an energy ray 22 '' becomes across the surface of the ceramic powder 26 to form a region 28 run by sintered ceramic powder, which after cooling a protective ceramic layer 6 forms.

9 illustrates process steps of a method of forming the multilayer article 7 from 5 according to one embodiment. In step 1 from 9 becomes an MCrAlY powder 30 on a surface of a metallic substrate 2 applied, and a protective bonding composition 20 (such as a powder) is applied to the layer of MCrAlY powder 30 applied, and an energy ray 22 ' becomes across the surface of the resulting multipulver layer to form a melt pool 32 run, then cool and to one with the metallic substrate 2 bonded MCrAlY adhesion promoter layer 4 solidified and one at the adhesive layer 4 attached Klebbondierschicht 14 is covered. In some embodiments, the resulting article may vary depending on the content of the protective bonding composition 20 also a variety of chemical anchors 16 , the one below the other with both the primer layer 4 as well as with the Klebbondierschicht 14 are glued, included. In other embodiments, the MCrAlY powder 30 and the protective bonding composition 20 on the surface of the metallic substrate 2 are applied as a mixture of powders (unlike those in the 8th illustrated separate multilayers).

step 2 from 9 involves the removal of a portion of the Klebbondierschicht 14 to form a remaining part 18 the Klebbondierschicht 14 , leaving some parts of the chemical anchor 16 are exposed in an upward direction. Chemical and / or mechanical processes known in the relevant art for the removal of slag layers may be used to effect the removal of a portion of the adhesive bonding layer 14 in step 2 be used.

In step 3 from 9 becomes a ceramic powder 26 then on a surface of the in step 2 formed article, and an energy beam 22 '' becomes across the surface of the ceramic powder 26 run, to form a region 28 of sintered ceramic powder, which after cooling a protective ceramic layer 6 forms. Because the removal step 2 Parts of the chemical anchor 16 exposed in an upward direction, the application of step 3 the protective ceramic layer 6 done so, so that the chemical anchor 16 Bonding connections between layers form, in which a first part of the chemical anchor 16 with the metallic substrate 2 glued, a second part of the chemical anchor 16 with the remaining part 18 the Klebbondierschicht 14 is glued and a third part of the chemical anchor 16 with the protective ceramic layer 6 is glued.

Protective bonding compositions 20 may include inorganic compounds such as metal oxides, metal halides, metal oxometalates, metal carbonates, a mixture thereof - as well as elemental metals, lanthanides and metalloids. Protective bonding compositions 20 Also organic compounds such as high molecular weight hydrocarbons (eg beeswax, paraffin), carbohydrates (eg cellulose), natural and synthetic oils (eg palm oil), organic reducing agents (eg charcoal or activated carbon , Coke), carboxylic acids and dicarboxylic acids (eg abietic acid, isopimaric acid, neoabienoic acid, dehydroabietic acid, rosin resins), carboxylic acid salts (eg rosin salts), carboxylic acid derivatives (eg dehydroabietylamine), amines (eg triethanolamine), Alcohols (eg, high polyglycols, glycerols), natural and synthetic resins (eg, polyol esters of fatty acids), and other organic compounds, as well as a mixture thereof.

The term "metal oxides" is used herein in a general sense to describe compounds having the general formula M _a O _b wherein the variable "M" represents a metal atom and the variables "a" and "b" are integers greater than to stand as zero. Non-limiting examples of metal oxides include compounds such as Li ₂ O, BeO, B ₂ O ₃ , B ₆ O, MgO, Al ₂ O ₃ , SiO ₂ , CaO, Sc ₂ O ₃ , TiO, TiO ₂ , Ti ₂ O ₃ , VO, V ₂ O ₃ , V ₂ O ₄ , V ₂ O ₅ , Cr ₂ O ₃ , CrO ₃ , MnO, MnO ₂ , Mn ₂ O ₃ , Mn ₃ O ₄ , FeO, Fe ₂ O ₃ , Fe ₃ O ₄ , CoO, Co ₃ O ₄ , NiO, Ni ₂ O ₃ , Cu ₂ O, CuO, ZnO, Ga ₂ O ₃ , GeO ₂ , As ₂ O ₃ , Rb ₂ O, SrO, Y ₂ O ₃ , ZrO ₂ , NiO, NiO ₂ , Ni ₂ O ₅ , MoO ₃ , MoO ₂ , RuO ₂ , Rh ₂ O ₃ , RhO ₂ , PdO, Ag ₂ O, CdO, In ₂ O ₃ , SnO, SnO ₂ , Sb ₂ O ₃ , TeO ₂ , TeO ₃ , Cs ₂ O, BaO, HfO ₂ , Ta ₂ O ₅ , WO ₂ , WO ₃ , ReO ₃ , Re ₂ O ₇ , PtO ₂ , Au ₂ O ₃ , La ₂ O ₃ , CeO ₂ , Ce ₂ O ₃ and mixtures thereof, to name a few. The term "metal oxides" is also used herein in the same manner as this term is commonly understood in the relevant art.

The term "metal halides" is used herein in a general sense to describe compounds containing a metal atom and at least one halogen atom. Non-limiting examples of metal halides include compounds such as LiF, LiCl, LiBr, LiI, Li ₂ NiBr 4, Li ₂ CuCl ₄ , LiAsF ₆ , LiPF ₆ , LiAlCl ₄ , LiGaCl ₄ , Li ₂ PdCl ₄ , NaF, NaCl, NaBr, Na ₃ AlF ₆ , NaSbF ₆ , NaAsF ₆ , NaAuBr ₄ , NaAlCl ₄ , Na ₂ PdCl ₄ , Na ₂ PtCl ₄ , MgF ₂ , MgCl ₂ , MgBr ₂ , AlF ₃ , KCl, KF, KBr, K ₂ RuCl ₅ , K ₂ IrCl ₆ , K ₂ PtCl ₆ , K ₂ PtCl ₆ , K ₂ ReCl ₆ , K ₃ RhCl ₆ , KSbF ₆ , KAsF ₆ , K ₂ NiF ₆ , K ₂ TiF ₆ , K ₂ ZrF ₆ , K ₂ PtI ₆ , KAuBr ₄ , K ₂ PdBr ₄ , K ₂ PdCl ₄ , CaF ₂ , CaF, CaBr ₂ , CaCl ₂ , CaI ₂ , ScBr ₃ , ScCl ₃ , ScF ₃ , ScI ₃ , TiF ₃ , VCl ₂ , VCl ₃ , CrCl ₃ , CrBr ₃ , CrCl ₂ , CrF ₂ , MnCl ₂ , MnBr ₂ , MnF ₂ , MnF ₃ , MnI ₂ , FeBr ₂ , FeBr ₃ , FeCl ₂ , FeCl ₃ , FeI ₂ , CoBr ₂ , CoCl ₂ , CoF ₃ , CoF ₂ , CoI ₂ , NiBr ₂ , NiCl ₂ , NiF ₂ , NiI ₂ , CuBr, CuBr ₂ , CuCl, CuCl ₂ , CuF ₂ , CuI, ZnF ₂ , ZnBr ₂ , ZnCl ₂ , ZnI ₂ , GaBr ₃ , Ga ₂ Cl ₄ , GaCl ₃ , GaF ₃ , GaI ₃ , GaBr ₂ , GeBr ₂ , GeI ₂ , GeI ₄ , RbBr, RbCl, RbF, RbI, SrBr ₂ , SrCl ₂ , SrF ₂ , SrI ₂ , YCl ₃ , YF ₃ , YI ₃ , YBr ₃ , ZrBr ₄ , ZrCl ₄ , ZrI ₂ , YBr, ZrBr ₄ , ZrCl ₄ , ZrF ₄ , ZrI ₄ , NbCl ₅ , NbF ₅ , MoCl ₃ , MoCl ₅ , RuI ₃ , RhCl ₃ , PdBr ₂ , PdCl ₂ , PdI ₂ , AgCl, AgF, AgF ₂ , AgSbF ₆ , AgI, CdBr ₂ , CdCl ₂ , CdI ₂ , InBr, InBr ₃ , InCl, InCl ₂ , InCl ₃ , InF ₃ , InI, InI ₃ , SnBr ₂ , SnCl ₂ , SnI ₂ , SnI ₄ , SnCl ₃ , SbF ₃ , SbI ₃ , CsBr, CsCl, CsF, CsI, BaCl ₂ , BaF ₂ , BaI ₂ , BaCoF ₄ , BaNiF ₄ , HfCl ₄ , HfF ₄ , TaCl ₅ , TaF ₅ , WCl ₄ , WCl ₆ , ReCl ₃ , ReCl ₅ , IrCl ₃ , PtBr ₂ , PtCl ₂ , AuBr ₃ , AuCl, AuCl ₃ , AuI, KAuCl ₄ , LaBr ₃ , LaCl ₃ , LaF ₃ , LaI ₃ , CeBr ₃ , CeCl ₃ , CeF ₃ , CeF ₄ , CeI _3, and mixtures thereof, to name a few. The term "metal halides" is also used herein in the same manner as that term is commonly understood in the relevant art.

The term "metal oxometalates" is used herein in a general sense to describe compounds having the general formula M _a X _b O _c wherein the variable "M" represents a metal atom, the variable "X" represents a metal or non-metal atom and the variables "a""b" and "c" are integers greater than zero. Non-limiting examples of metal oxometallates include compounds such as LiIO ₃ , LiBO ₂ , Li ₂ SiO ₃ , LiClO ₄ , Na ₂ B ₄ O ₇ , NaBO ₃ , Na ₂ SiO ₃ , NaVO ₃ , Na ₂ MoO ₄ , Na ₂ SeO ₄ , Na ₂ SeO ₃ , Na ₂ TeO ₃ , K ₂ SiO ₃ , K ₂ CrO ₄ , K ₂ Cr ₂ O ₇ , CaSiO ₃ , BaMnO _4, and mixtures thereof, to name a few. The term "metal oxometalates" is also used herein in the same way as this term is commonly understood in the relevant art.

The term "metal carbonates" is used herein in a general sense to describe compounds containing a metal atom and at least one carbonate group. Non-limiting examples of metal carbonates include compounds such as Li ₂ CO ₃ , Na ₂ CO ₃ , NaHCO ₃ , MgCO ₃ , K ₂ CO ₃ , CaCO ₃ , Cr ₂ (CO ₃ ) 3 , MnCO ₃ , CoCO ₃ , NiCO ₃ , CuCO ₃ , Rb ₂ CO ₃ , SrCO ₃ , Y ₂ (CO ₃ ) 3 , Ag ₂ CO ₃ , CdCO ₃ , In ₂ (CO ₃ ) ₃ , Sb ₂ (CO ₃ ) ₃ , C ₂ CO ₃ , BaCO ₃ , La ₂ (CO ₃ ) ₃ , Ce ₂ (CO ₃ ) ₃ , NaAl (CO ₃ ) (OH) ₂ and mixtures thereof, to name a few. The term "metal carbonates" is also used herein in the same way as this term is commonly understood in the relevant art.

In some embodiments, TBC-6 adhesion to an MCrAlY primer sublayer 4 (such as in the 3 and 5 ) by using a protective bonding composition 20 , which contains MgO and Al ₂ O ₃ , improved. It is known in the welding industry that slag is particularly difficult to remove from chromium-bearing substrates or deposits formed with a chromium-bearing filler or from deposits using chromium oxide in the flux. See, for example, B. Oladipupo, AO, "Slag Detachability from Submerged Arc Welds," Doctoral Thesis (Massachusetts Institute of Technology) February 1987 , Magnesium oxide and alumina fluxes are particularly problematic due to the formation of chromium spinels such as iron chromate and magnesium aluminum chromate by reactions such as: MgO + Al ₂ O ₃ → MgAlCrO ₄

These spinels represent solid reaction products that embed and adhere to the underlying metallic substrate and therefore as chemical anchors 16 which can greatly enhance the ability to bond (bonding integrity) in multilayer articles of the present disclosure.

Protective bonding compositions 20 In some embodiments, MgO and Al ₂ O ₃ in respective proportions, such that a melt mixture containing the composition 20 and Cr, MgAlCrO ₄ forms. In some embodiments, the molar ratio of the MgO to the Al ₂ O _{3 is} in the protective bonding composition 20 ranging from about 1.5: 1 to about 1: 1.5 or from about 1.3: 1 to about 1: 1.3, or from about 1.1: 1 to about 1: 1.1. In other embodiments, the molar ratio of the MgO to the Al ₂ O _{3 is} about 1: 1.

Some MgO / Al ₂ O ₃ -containing compositions 20 include at least one of: (1) more than about 25 weight percent MgO; and (2) greater than about 25 weight percent Al ₂ O ₃ , based on the total weight of the protective bonding composition 20 , In other embodiments, the compositions include 20 at least one of: (1) more than about 35 weight percent MgO; and (2) greater than about 35 weight percent Al ₂ O ₃ , based on the total weight of the protective bonding composition 20 , In some embodiments, the MgO / Al ₂ O ₃ -containing compositions 20 further comprise Cr, such as greater than about 10 weight percent Cr or greater than about 15 weight percent Cr. In other embodiments, the MgO / Al ₂ O ₃ -containing compositions 20 further at least one selected from the group consisting of Cr, CrO ₂ , Cr ₂ O ₃ and CrO ₃ .

Some MgO / Al ₂ O ₃ -containing compositions 20 Further, TiO ₂ , SiO ₂ and ZrO ₂ contain such that the sum of the weights of Al ₂ O ₃ , TiO ₂ , SiO ₂ and ZrO _{2 is} less than about 6.5 weight percent or more than about 12 weight percent based on the total weight the protective bonding composition 20 , In still further embodiments, the MgO / Al ₂ O ₃ -containing compositions 20 further comprises at least one of: (1) CaO and TiO ₂ in respective proportions so that a melt blend, the composition of the 20 also forms CaTiO ₃ ; and (2) CaF ₂ and SiO ₂ in respective proportions, such that a melt mixture containing the composition 20 also forms Ca ₄ (Si ₂ O ₇ ) (F, OH) ₂ forms.

Flux compositions containing calcium oxide and rutile are also known in the relevant art to be problematic (in terms of peelability) Slag from a weld) and calcium titanate perovskites by reactions such as: CaO + TiO ₂ → CaTiO ₃ form.

These perovskites can also act as chemical anchors 16 act, which reduce the detachability. The inventors have recognized that protective bonding compositions 20 containing mixtures of compounds selected from MgO, Al ₂ O ₃ , CaO and TiO ₂ , TBC-6 adhesion to chromium-containing MCrAlY coupling agents 4 can increase.

Some protective bonding compositions 20 contain CaO and TiO ₂ in respective proportions, leaving a melt mixture containing the composition 20 contains CaTiO ₃ forms. In some embodiments, the molar ratio of the CaO to the TiO ₂ ranges from about 1.5: 1 to about 1: 1.5, or from about 1.3: 1 to about 1: 1.3, and from about 1.1: 1, respectively to about 1: 1.1. In other embodiments, the molar ratio of the CaO to the TiO _{2 is} about 1: 1.

Some CaO / TiO ₂ -containing compositions 20 include at least one of: (1) greater than about 5 percent by weight of the CaO; and (2) greater than about 5 weight percent of the TiO ₂ , based on the total weight of the protective bonding composition 20 , In other embodiments, the compositions include 20 at least one of: (1) more than about 10% by weight of the CaO; and (2) greater than about 10 weight percent of the TiO ₂ based on the total weight of the protective bonding composition 20 ,

Some CaO / TiO ₂ -containing compositions 20 Further, SiO ₂ , Al ₂ O ₃ and ZrO ₂ such that the sum of the weights of Al ₂ O ₃ , TiO ₂ , SiO ₂ and ZrO _{2 are} less than about 6.5% by weight or more than about 12% by weight on the total weight of the protective bonding composition 20 , In yet other embodiments, the CaO / TiO ₂ -containing compositions include 20 further at least one of: (1) CaF ₂ and SiO ₂ in respective proportions such that a melt mixture containing the composition 20 also forms Ca ₄ (Si ₂ O ₇ ) (F, OH) ₂ forms; and (2) MgO and Al ₂ O ₃ in respective proportions, such that a melt mixture containing the composition 20 and Cr, MgAlCrO ₄ forms.

Flux compositions containing calcium fluoride and silica are also known in the relevant art to be problematic and form cuspidin [Ca ₄ (Si ₂ O ₇ ) (F, OH) ₂ ], which also hinders slag removal. Cuspis is Greek and means "spear", which refers to the shape of crystalline cuspidin (see 6 ), which is probably responsible for its anchoring effect when contained in slags.

Some protective bonding compositions 20 of the present disclosure contain CaF ₂ and SiO ₂ in respective proportions, so that a melt mixture containing the composition 20 contains, Ca ₄ (Si ₂ O ₇ ) (F, OH) ₂ forms. 1 to about 2.5: 1 to about 2.3: In some embodiments, a molar ratio of CaF ₂ to the SiO ₂ ranges from about 1.5 or from about 1.7 1 1 or from about 1.9: 1 to about 2.1: 1. In other embodiments, the molar ratio of CaF ₂ to SiO _{2 is} about 2: 1, respectively.

Some CaF ₂ / SiO ₂ -containing compositions 20 include at least one of: (1) more than about 25 weight percent CaF ₂ ; and (2) more than about 25 weight percent SiO ₂ . In other embodiments, CaF ₂ / SiO ₂ -containing compositions include 20 at least one of: (1) more than about 35% by weight CaF ₂ ; and (2) more than about 35 weight percent SiO ₂ .

Some CaF ₂ / SiO ₂ -containing compositions 20 Further, Al ₂ O ₃ , TiO ₂ and ZrO ₂ contain such that the sum of the weights of Al ₂ O ₃ , TiO ₂ , SiO ₂ and ZrO _{2 is} less than about 6.5 weight percent or more than about 12 weight percent on the total weight of the protective bonding composition 20 , In still other embodiments, the CaF ₂ / SiO ₂ containing compositions 20 further at least one of: (1) CaO and TiO ₂ in respective proportions so that the melt mixture also forms CaTiO ₃ ; and (2) MgO and Al ₂ O ₃ in respective proportions, such that a melt mixture containing the composition 20 and Cr, MgAlCrO ₄ forms.

While various embodiments of the present invention have been shown and described herein, it will be apparent that such embodiments are merely exemplary in nature. Numerous variations, changes and substitutions may be made without departing from the invention described herein.

Embodiments:

• 1. Multilayer article comprising: a metallic substrate; a protective layer; and an adhesive bonding layer comprising an oxygen-containing compound that bonds the adhesive bonding layer to the metallic substrate, the protective layer, or both.
• 2. The article according to embodiment 1, further comprising a plurality of with the Klebbondierschicht and at least one of the metallic substrate and the protective layer bonded anchors, wherein: the anchors include the oxygen-containing compound; and a structure of the anchors is effective to adhere the metallic substrate, the protective layer or both to the Klebbondierschicht by forming links between the layers, so that a part of the anchors is attached to the Klebbondierschicht and another part of the anchors on the metallic substrate or attached to the protective layer.
• 3. article according to embodiment 1, comprising: a superalloy substrate; an MCrAlY primer layer bonded to a surface of the superalloy substrate; the adhesive bond layer bonded to a surface of the MCrAlY primer layer; and a ceramic thermal barrier layer bonded to a surface of the adhesive bonding layer.
• 4. article according to embodiment 1, comprising: a superalloy substrate; the adhesive bonding layer adhered to a surface of the superalloy substrate; and a ceramic thermal barrier layer bonded to a surface of the adhesive bonding layer.
• 5. The article according to Embodiment 1, wherein the oxygen-containing compound is at least one selected from the group consisting of a spinel compound, a perovskite compound and a cuspidin compound.
• 6. The article of embodiment 1 wherein the oxygen-containing compound is at least one that is selected from the group consisting of MgAlCrO _4, FeCrO _4, CaTiO _3, and Ca ₄ (Si ₂ O ₇₎ (F, OH) ₂ is comprised.
• 7. The article according to embodiment 1, wherein the adhesive bonding layer is formed of a protective bonding composition comprising at least one of: a mixture of MgO and Al ₂ O ₃ in respective proportions so that an adhesive bonding layer comprising Cr further comprises MgAlCrO ₄ ; a mixture of CaO and TiO ₂ in respective proportions such that the adhesive bonding layer comprises CaTiO ₃ ; and a mixture of CaF ₂ and SiO ₂ in respective proportions such that the adhesive bonding layer comprises Ca ₄ (Si ₂ O ₇ ) (F, OH) ₂ .
• 8. The article of embodiment 7 that satisfies at least one of the following conditions: (i) the protective bonding composition comprises at least one of greater than about 25 weight percent MgO and greater than about 25 weight percent Al ₂ O ₃ ; (ii) the protective Bondierzusammensetzung comprises at least one of more than about 5 percent by weight of CaO and more than about 5 percent by weight of TiO _2; and (iii) the protective bonding composition comprises at least one of greater than about 25 weight percent of the CaF ₂ and greater than about 20 weight percent of the SiO ₂ , based on the total weight of the protective bonding composition.
• 9. Multilayer article comprising: a metallic layer; a protective layer; and a plurality of anchors bonded to both the metallic layer and the protective layer, in which: the anchors comprise an oxygen-containing inorganic compound; and a structure of the anchors is effective to adhere the metallic layer to the protective layer by forming interconnections between the layers such that a part of the anchors is attached to the metallic layer and another part of the anchors is attached to the protective layer.
• The article of embodiment 9, further comprising an adhesive bonding layer disposed between the metallic layer and the protective layer and in direct contact with the anchors, the anchors forming the interconnections between the layers such that a first portion of the anchors the metallic layer is connected, a second part of the armature is connected to the Klebbondierschicht and a third part of the armature is connected to the protective layer.
• 11. The article according to Embodiment 9, wherein the oxygen-containing inorganic compound is at least one selected from the group consisting of a spinel compound, a perovskite compound and a cuspidin compound.
• The article according to embodiment 9, wherein the oxygen-containing inorganic compound is at least one selected from the group consisting of MgAlCrO ₄ , FeCrO ₄ , CaTiO ₃ and Ca ₄ (Si ₂ O ₇ ) (F, OH) ₂ .
• 13. A method of forming a multilayer article according to embodiment 1, the method comprising: heating a protective bonding composition to form a melt in contact with a metal-containing surface; Allowing the melt to solidify and solidify to the adhesive bonding layer attached to the metal-containing surface; Applying a ceramic material to the adhesive bonding layer; and Heating the ceramic material to form the protective layer attached to the adhesive bonding layer, to form the multilayer article.
• 14. The method of embodiment 13, wherein the protective bonding composition comprises at least two selected from the group consisting of MgO, Al ₂ O ₃ , CaO, TiO ₂ , CaF ₂ and SiO ₂ .
• 15. The method of embodiment 13, wherein the protective bonding composition comprises MgO and Al ₂ O ₃ in respective proportions such that the melt contains MgAlCrO ₄ in the presence of Cr.
• 16. The method of embodiment 15, wherein the molar ratio of the MgO to the Al ₂ O ₃ ranges from about 1.5: 1 to about 1: 1.5.
• 17. The method of embodiment 15, wherein the protective bonding composition comprises at least one of: greater than about 25 weight percent of the MgO; and greater than about 25 weight percent of the Al ₂ O ₃ , based on the total weight of the protective bonding composition.
• 18. The method of embodiment 13, wherein the protective bonding composition comprises CaO and TiO ₂ in respective proportions such that the melt contains CaTiO ₃ .
• 19. The method of embodiment 18, wherein the molar ratio of the CaO to the TiO ₂ ranges from about 1.5: 1 to about 1: 1.5.
• 20. The method of embodiment 18, wherein the protective bonding composition comprises at least one of: greater than about 5 weight percent of the CaO; and more than about 5 weight percent of the TiO ₂ , based on the total weight of the protective bonding composition.
• 21. The method of embodiment 13, wherein the protective bonding composition comprises CaF ₂ and SiO ₂ in respective proportions such that the melt contains Ca ₄ (Si ₂ O ₇ ) (F, OH) ₂ .
• 22. The method of embodiment 21, wherein the molar ratio of the CaF ₂ to the SiO ₂ ranges from about 1.5: 1 to about 2.5: 1.
• 23. The method of embodiment 21, wherein the protective bonding composition comprises at least one of: greater than about 25 weight percent of the CaF ₂ ; and more than about 20 weight percent of the SiO ₂ , based on the total weight of the protective bonding composition.
• 24. The method according to embodiment 13, wherein the metal-containing surface is a metallic substrate or a primer layer attached to the surface of the metallic substrate.
• 25. The method according to embodiment 13, further comprising removing a portion of the adhesive bonding layer prior to applying the ceramic material, such that: Anchors contained in the Klebbondierschicht not be removed and remain attached to the metal-containing surface; and exposed parts of the anchors during the heating of the ceramic material to the protective layer undergo attachment.

QUOTES INCLUDE IN THE DESCRIPTION

This list of the documents listed by the applicant has been generated automatically and is included solely for the better information of the reader. The list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions.

Cited patent literature

• US 2006/0266799 [0017]

Cited non-patent literature

• Oladipupo, AO, "Slag Detachability from Submerged Arc Welds," Doctoral Thesis (Massachusetts Institute of Technology) February 1987 [0043]

Claims (10)

Multilayer article comprising: a metallic substrate; a protective layer; and an adhesive bonding layer comprising an oxygen-containing compound that bonds the adhesive bonding layer to the metallic substrate, the protective layer, or both. The article of claim 1, further comprising a plurality of anchors bonded to the adhesive bonding layer and at least one of the metallic substrate and the protective layer; in which: the anchors comprise the oxygen-containing compound; and a structure of the anchors is effective to adhere the metallic substrate, the protective layer or both to the Klebbondierschicht by forming links between the layers, so that a part of the anchors is attached to the Klebbondierschicht and another part of the anchors to the metallic Substrate or attached to the protective layer. The article of claim 1, comprising: a superalloy substrate; an MCrAlY primer layer bonded to a surface of the superalloy substrate; the adhesive bond layer bonded to a surface of the MCrAlY primer layer; and a ceramic thermal barrier layer bonded to a surface of the adhesive bonding layer. The article of claim 1, comprising: a superalloy substrate; the adhesive bonding layer adhered to a surface of the superalloy substrate; and a ceramic thermal barrier layer bonded to a surface of the adhesive bonding layer. The article according to claim 1, wherein the oxygen-containing compound is at least one selected from the group consisting of a spinel compound, a perovskite compound and a cuspidin compound. The article of claim 1, wherein the adhesive bonding layer is formed of a protective bonding composition comprising at least one of: a mixture of MgO and Al ₂ O ₃ in respective proportions such that an adhesive bonding layer comprising Cr further comprises MgAlCrO ₄ ; a mixture of CaO and TiO ₂ in respective proportions such that the adhesive bonding layer comprises CaTiO ₃ ; and a mixture of CaF ₂ and SiO ₂ in respective proportions such that the adhesive bonding layer comprises Ca ₄ (Si ₂ O ₇ ) (F, OH) ₂ . The article of claim 6, which satisfies at least one of the following conditions: (i) the protective Bondierzusammensetzung comprises at least one of more than about 25 percent by weight of MgO and more than about 25 percent by weight of Al ₂ O _3; (ii) the protective bonding composition comprises at least one of greater than about 5 weight percent of the CaO and greater than about 5 weight percent of the TiO ₂ ; and (iii) the protective bonding composition comprises at least one of greater than about 25 weight percent of the CaF ₂ and greater than about 20 weight percent of the SiO ₂ , based on the total weight of the protective bonding composition. Multilayer article comprising: a metallic layer; a protective layer; and a plurality of anchors bonded to both the metallic layer and the protective layer, in which: the anchors comprise an oxygen-containing inorganic compound; and a structure of the anchors is effective to adhere the metallic layer to the protective layer by forming interconnections between the layers such that a part of the anchors is attached to the metallic layer and another part of the anchors is attached to the protective layer. The article of claim 1 or 8, wherein the oxygen-containing inorganic compound is at least one from the group consisting of from MgAlCrO _4, FeCrO _4, CaTiO _3, and Ca ₄ (Si ₂ O ₇₎ (F, OH) ₂ is selected. A method of forming a multilayer article according to claim 1, said method comprising: Heating a protective bonding composition to form a melt in contact with a metal-containing surface; Allowing the melt to cool and solidify to the adhesive bonding layer attached to the metal-containing surface; Applying a ceramic material to the adhesive bonding layer; and Heating the ceramic material to form the protective layer attached to the adhesive bonding layer to form the multilayer article.

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