PROTECTIVE LAYER AGAINST ENVIRONMENTAL INFLUENCES (ENVIRONMENTAL BARRIER LAYER) FOR Tl-AL MATERIAL
20230265564 · 2023-08-24
Inventors
- Beno Widrig (Bad Ragaz, CH)
- Oliver Jarry (Koln, DE)
- Bernhard Kohlhauser (Wien, AT)
- Jürgen Ramm (Maienfeld, CH)
Cpc classification
C23C28/3455
CHEMISTRY; METALLURGY
International classification
Abstract
A surface coating for protecting substrates with Ti—Al material, preferably comprising one or more of the materials from table 1, wherein the coating comprises a layer sequence with at least one layer which forms a diffusion barrier for Ti, preferably according to one or more of the layer sequences specified in table 1 in rows, and wherein the coating comprises an oxidation barrier which is in particular adjusted to the diffusion barrier and preferably adjusted according to table 2, and in particular wherein the surface coating comprises a thermal barrier which is preferably adjusted to the oxidation barrier according to table 3.
Claims
1. A surface coating for protecting substrates with Ti—Al material, comprising: one or more of the materials from Table 1, wherein the coating comprises a layer sequence with at least one layer which forms a diffusion barrier for Ti, and wherein the coating comprises an oxidation barrier adjusted to the diffusion barrier, and wherein the surface coating comprises a thermal barrier.
2. The surface coating according to claim 1, wherein the diffusion barrier is arranged between the oxidation barrier and the substrate.
3. The surface coating according to claim 1, wherein the thermal barrier is arranged directly on the oxidation barrier.
4. The surface coating according to claim 1, wherein the oxidation barrier and the thermal barrier are combined in one layer.
5. The surface coating according to claim 4, wherein the one layer is graded in the layer morphology, with the one layer in the vicinity of the substrate having a highest density of the one layer, and transitioning gradually and/or continuously into a columnar or different porous structure with increasing distance from the substrate.
6. The surface coating according to claim 1, wherein a metallic layer is deposited between the substrate and the diffusion barrier, directly on the substrate.
7. The surface coating according to claim 6, wherein the diffusion barrier is deposited on a gradient layer, and the gradient layer is deposited on the metallic layer.
8. The surface coating according to claim 1, wherein the diffusion barrier comprises at least one of the group consisting of Mo—Si, Ti—Si, Cr—Si, Ni—Si, Al—Si, Zr—Si, Nb—Si, Hf—Si, Y—Si, Ta—Si, and W—Si.
9. The surface coating according to claim 1, wherein the oxidation barrier comprises Si—O and/or Al—O and/or Al—Cr—O.
10. The surface coating according to claim 1, wherein the thermal barrier comprises Al—Cr—O and/or YSZ.
11. The surface coating according to claim 6, wherein the metallic layer comprises Cr and/or Al.
12. The surface coating according to claim 7, wherein the gradient layer is adapted to the diffusion barrier.
13. The surface coating according to claim 1, wherein a transition layer, in comprising oxide scaling, is arranged between the oxidation barrier and the diffusion barrier.
14. The surface coating according to claim 13, wherein the transition layer comprises Si—O.
15. A method for producing the surface coating according to claim 1, comprising applying the coating using a PVD method and a CVD method, and wherein the coating is preferably carried out in only one coating system.
16. The surface coating according to claim 1, wherein the coating comprises the layer sequence with at least one layer which forms the diffusion barrier for Ti according to one or more of the layer sequences specified in rows in Table 1.
17. The surface coating according to claim 1, wherein the oxidation barrier is adjusted to the diffusion barrier, which is adapted in accordance with Table 2.
18. The surface coating according to claim 1, wherein the thermal barrier is adjusted to the oxidation barrier according to Table 3.
Description
FIGURES
[0024]
[0025] Layer system according to the invention for an EBC on a Ti—Al substrate, consisting of substrate 101, diffusion barrier 102 and oxidation barrier 103.
[0026] In
[0033]
[0034] Layer system according to the invention for an EBC on a Ti—Al substrate, consisting of substrate 201, diffusion barrier 202, oxidation barrier 203 and a further thermal barrier layer 204.
[0035] That is,
[0036] In
[0041]
[0042] Layer system according to the invention for an EBC on a Ti—Al substrate, consisting of substrate 301, diffusion barrier 302, oxidation barrier 305 from 331 and 332, which has been expanded to a greater layer thickness and comprises the layer morphology in 332 which becomes more porous, as the layer thickness increases.
[0043] Accordingly, a further layer system is shown in
[0044] In
[0048]
[0049] XRD spectrum of a Mo—Si diffusion barrier layer according to the invention, which was produced with a silane flow of 90 sccm and which detects the coexistence of Mo and MoSi2 phases in the layer.
[0050]
[0051] XRD spectrum of a Mo—Si diffusion barrier layer according to the invention, which was produced with a silane flow of 180 sccm and which mainly has the MoSi2 phase.
[0052]
[0053] SEM layer cross section of an environmental barrier coating consisting of a 4.9 μm thick Mo—Si layer (diffusion barrier) and a 2.7 μm thick Al—Cr—O layer (oxidation barrier)
[0054]
[0055] SEM layer cross-section of the environmental barrier layer from
[0056]
[0057] SEM layer cross-section of a Mo—Si diffusion barrier without the oxidation barrier. Immediately after the coating which was again carried out at 450° C., this simplified variant showed no signs of diffusion processes in the interface in the SEM layer cross section. The layer was produced with a silane flow of 180 sccm and is characterized by the XRD spectrum shown in
[0058]
[0059] SEM layer cross-section of the Mo—Si diffusion barrier from
[0060]
[0061] SEM layer cross-section of the Mo—Si diffusion barrier from
PROCESS FOR MANUFACTURING LAYER SYSTEMS
[0062] The coating process can be carried out as a combination of physical vapor deposition (PVD) and plasma-assisted chemical vapor deposition (PECVD), i.e. both methods are used, if necessary, in particular simultaneously in order to realize the layer synthesis. For example, electron beam evaporation, sputtering and/or cathodic spark evaporation can be used as PVD methods. The CVD methods are essentially based on additional gas inlets, with which the various gaseous precursors can be introduced into the coating system used. The precursors are then decomposed and excited in the plasma. Advantageously, the same coating system is used for PVD methods and for CVD methods. The plasma required for the CVD methods can be generated by means of the plasma source that is present as a result of the PVD method, i.e. for example by the cathodic spark source. However, it can also be generated in other ways, for example by a separate low-voltage arc discharge. These methods are known to those skilled in this technological field.
[0063] An example is given below which explains and describes the production of a layer system according to the invention, without this description of the exemplary layer system being intended to restrict the more general idea of the invention.
[0064] First, the process during the production of the layer system according to the invention as shown in
[0065] The TiAl substrates are introduced into the coating system and fixed on the appropriate holders. The holders are mounted on a substrate holder system, which is stationary during the coating process and/or can be rotated one, two and/or three times. The coating system is pumped down to a pressure of about 10.sup.−5 mbar or less. Then the substrates are pretreated. They are heated to a desired temperature (200° C. to 600° C.), in the example by means of radiant heaters, and substrate pretreatment is carried out in the system, for example cleaning of the substrate surface by sputtering with Ar gas ions. For the cleaning step, a negative voltage (substrate bias) is usually applied to the substrates. After these pre-treatment steps, in the example this negative substrate bias is set to a value, for example −40 V, which is maintained during the coating. The synthesis of a Mo—Si layer in a combination of PVD and CVD process for the diffusion barrier layer is described here as an example. The coating starts with the ignition of the cathodic spark discharge on the Mo target, which is connected as the cathode of the spark discharge and is consequently vaporized by the cathodic spark. The reactive gas is admitted at the same time or, as described for the example below, briefly offset from one another. As a supporting measure, an inert gas or an inert gas mixture can be admitted, too. In the example, the spark discharge is operated with a source current of 220 A. A silane flow of 90 sccm is added with a time delay of 2 min. A bias voltage of −40 V is applied to the substrates. In this way, the substrates are coated with a Mo—Si layer, with the chemical composition of this layer being controllable over a wide range via the evaporation rate of the Mo target (spark current) and via the silane flow. As a result, the chemical composition of the layer can be set. As an example,
[0066] The following process step, namely the deposition of the oxidation barrier, takes place without interrupting the vacuum following the deposition of the Mo—Si layer. The transition between the deposition of the diffusion barrier and the oxidation barrier can be designed abruptly, i.e. switching off the spark discharge on the Mo target and switching off the silane flow and then starting the coating process for the oxidation barrier. However, it is also possible to choose a process transition in the coating to the oxidation barrier, in this example an Al—Cr—O layer, which is fluent and which is to be described here. For this purpose, the cathodic spark discharge is ignited on an Al—Cr target, preferably with a target composition of Al (70 at. %)-Cr (30 at %), in the last 3 minutes of the coating process for the diffusion barrier, i.e. during this process step (spark current 180 A). After a few minutes, that flow meter is also set to gas inlet, which supplies an oxygen flow of 400 sccm to the coating system. A few minutes can be understood to mean in particular about 0.5 minutes to about 15 minutes, preferably about 2 minutes to about 9 minutes, preferably about 2 minutes, preferably about 9 minutes, or in particular about 4 minutes to about 6 minutes. In a further embodiment of the invention, a few minutes can also be understood to mean other time specifications. After the oxygen flow has stabilized (approx. 1 minute), the Mo target is switched off and the silane flow meter is set to seal the silane gas inlet, i.e. the silane flow is switched off. The result is the formation of an Al—Cr—O layer on and slightly overlapping the Mo—Si diffusion barrier.
[0067] If a layer system according to the invention shown in
Examples of the Layers Produced According to the Invention
[0068] A layer system comprising and/or consisting of a Mo—Si diffusion barrier and an oxidation barrier is shown as an example in
[0069] The second requirement for an environmental barrier coating is also met with such a layer system. The Al—Cr—O layer prevents the penetration of oxygen and thus its diffusion to the interface between the substrate and the layer system.
[0070] The necessary conditions formulated to realize an environmental barrier coating on Ti—Al substrates are met by the above example. Si prevents diffusion in the interface to the substrate material during the coating. This applies to a pure Si layer, but also to Me-Si layers which guarantee better adhesion to the Ti—Al substrate and are mechanically much more stable than a pure ceramic-like Si layer.
[0071] A simplified variant of the environmental barrier coating described in
[0072] This process of oxide scaling is also significant in another context, namely if the transition from the Me-Si diffusion barrier layer to the oxidation barrier layer is problematic in the sense that the use of an oxygen plasma for depositing the oxidic oxidation barrier layer affects the diffusion barrier layer. In such a case, it is possible that Al—O scaling can be achieved without interrupting the vacuum by exposing the surface of the Me-Si diffusion barrier layer to non-plasma activated oxygen at elevated temperature.
[0073] The inventors tested a number of layer materials for the diffusion barrier properties for Ti—Al material and found that Me-Si layer materials are suitable for such a diffusion barrier. The selection of the specific Me-Si compounds must be made on the basis of the specific substrate materials and operating conditions and depends, for example, on the operating temperature and the choice of the oxidation barrier, which in turn depends on the corrosion conditions in the area of application. Corrosion resistance must be mentioned here as an important property of Me-Si. Me-Si layers on low alloy steel were examined in the salt spray test according to the standard ASTM B117. It turned out that these layers were stable for more than 1000 h and no corrosion occurred.
[0074] Table 1 lists many of these Me-Si compounds. According to the invention, these form a good diffusion barrier to the Ti—Al material and allow a further coating with an oxidation barrier layer in order to realize an environmental barrier coating according to
[0075]
Description of the Tests
[0076] The tests which were made here by way of example on the layers according to the invention were carried out at 800° C. in an ambient atmosphere, respectively for 20 h and 100 h. Ti50Al50 cast material was used as a demonstration substrate for the results presented here, which are not intended to be limiting. These materials contained no dopants to make them more sensitive to diffusion processes. An essential feature of an effective environmental barrier coating system is the prevention of Ti diffusion to the surface of the layer system after the annealing process in the atmosphere, with simultaneous evidence of good adhesion between the layer system and the substrate.
Tables
[0077]
TABLE-US-00001 TABLE 1 Coating of the diffusion barrier according to the invention according to FIG. 1 Layer sequence: ( . . . ) optional layers metallic Me—Si transition adhesive layer gradient layer layer oxidation barrier (Cr, Ni, Ti, Al, (Mo/Mo—Si) Mo—Si (Si—O) Nb, Zr) (Cr, Ni, Ti, Al, (Ti/Ti—Si) Ti—Si (Si—O) Nb, Zr) (Cr, Al) (Cr/Cr—Si) Cr—Si (Si—O, Cr—O) (Cr, Ni, Ti, Al) (Ni/Ni—Si) Ni—Si (Si—O) (Cr, Ti, Al) (Al/Al—Si) Al—Si (Si—O, Al—O) (Cr, Ti, Al, Zr) (Zr/Zr—Si) Zr—Si (Si—O, Zr—O) (Cr, Al, Nb) (Nb/Nb—Si) Nb—Si (Si—O, Nb—O) (Cr, Ti, Al, Hf) (Hf/Hf—Si) Hf—Si (Si—O, Hf—O) (Cr, Al, Zr) (Al—Zr—Y/ Y—Si (Si—O, Y—O) Y—Si) (Cr, Ti, Al, Ta) (Ta/Ta—Si) Ta—Si (Si—O, Ta—O) (Cr, Ti, Al, W) (W/W—Si) W—Si (Si—O)
TABLE-US-00002 TABLE 2 Oxidation barrier layers according to the invention for the various Me—Si diffusion barrier layers according to FIG. 1 transition Me—Si oxidation barrier oxidation barrier layers layer optional layers comma is to be understood as «and/or» Mo—Si (Si—O) Si—O, Al—O, Al—Cr—O, Cr—O Ti—Si (Si—O) Si—O, Al—O, Al—Cr—O, Cr—O Cr—Si (Si—O, Cr—O) Si—O, Al—O, Al—Cr—O, Cr—O Ni—Si (Si—O) Si—O, Al—O, Al—Cr—O, Cr—O Al—Si (Si—O, Al—O) Al—O, Al—Cr—O Zr—Si (Si—O, Zr—O) Si—O, Al—O, Al—Cr—O Nb—Si (Si—O, Nb—O) Si—O, Al—O, Al—Cr—O Hf—Si (Si—O, Hf—O) Si—O, Al—O, Al—Cr—O, Hf—O, Al—Hf—O Y—Si (Si—O, Y—O) Al—O, Al—Cr—O, Al—Y—O, Y—O Ta—Si (Si—O, Ta—O) Al—O, Al—Cr—O, Al—Ta—O, Ta—O W—Si (Si—O) Si—O, Al—O, Al—Cr—O
TABLE-US-00003 TABLE 3 Thermal barrier layers according to the invention for the various oxidation barrier layers oxidation barrier layers thermal barrier layer Me—Si comma is to be understood comma is to be layer as «and/or» understood as «and/or» Mo—Si Si—O, Al—O, Al—Cr—O, Cr—O Al—Cr—O, YSZ Ti—Si Si—O, Al—O, Al—Cr—O, Cr—O Al—Cr—O, YSZ Cr—Si Si—O, Al—O, Al—Cr—O, Cr—O Al—Cr—O, YSZ Ni—Si Si—O, Al—O, Al—Cr—O, Cr—O Al—Cr—O, YSZ Al—Si Al—O, Al—Cr—O Al—Cr—O, YSZ Zr—Si Si—O, Al—O, Al—Cr—O Al—Cr—O, YSZ Nb—Si Si—O, Al—O, Al—Cr—O Al—Cr—O, YSZ Hf—Si Si—O, Al—O, Al—Cr—O, Hf—O, Al—Cr—O, YSZ, Al—Hf—O Hf—O, Al—Hf—O Y—Si Al—O, Al—Cr—O, Al—Y—O, Al—Cr—O, YSZ Y—O Ta—Si Al—O, Al—Cr—O, Al—Ta—O, Al—Cr—O, YSZ Ta—O W—Si Si—O, Al—O, Al—Cr—O Al—Cr—O, YSZ
[0078] A surface coating for the protection of substrates with Ti—Al material has been disclosed, wherein the coating comprises a layer sequence with at least one layer, preferably according to one or more of the layer sequences given in table 2 in rows, and wherein the coating comprises an oxidation barrier which is adjusted to the diffusion barrier and preferably adjusted according to table 3, wherein the surface coating comprises a thermal barrier which is preferably adjusted to the oxidation barrier according to table 4.
[0079] A method for producing a surface coating has been disclosed, wherein the coating is applied by means of the PVD method and by means of the CVD method and the coating is preferably carried out in just one coating system.
[0080] Regardless of the claims, protection is also claimed for a surface coating for protecting substrates with Ti—Al material preferably comprising one or more of the materials from table 1, wherein the coating comprises a layer sequence with at least one layer which forms a diffusion barrier for Ti, preferably according to one or more of the layer sequences specified in table 1 in rows and wherein the coating comprises an oxidation barrier which is adjusted to the diffusion barrier and preferably adjusted according to table 2, wherein the surface coating comprises a thermal barrier which is preferably adjusted to the oxidation barrier according to table 3.
[0081] Regardless of the claims, protection is also claimed for a method for producing a surface coating according to the previous paragraph, characterized in that the coating is applied by means of the PVD method and by means of the CVD method and the coating is preferably carried out in just one coating system.
[0082] Within the scope of this disclosure, the layer system and the surface coating can—but do not have to—be used synonymously, i.e. they are in particular the same thing.