CN116815113B - Yttrium modified refractory high-entropy silicide coating and preparation method thereof - Google Patents
Yttrium modified refractory high-entropy silicide coating and preparation method thereof Download PDFInfo
- Publication number
- CN116815113B CN116815113B CN202310798653.8A CN202310798653A CN116815113B CN 116815113 B CN116815113 B CN 116815113B CN 202310798653 A CN202310798653 A CN 202310798653A CN 116815113 B CN116815113 B CN 116815113B
- Authority
- CN
- China
- Prior art keywords
- entropy
- refractory high
- nbmotaw
- powder
- yttrium
- 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.)
- Active
Links
- 238000000576 coating method Methods 0.000 title claims abstract description 100
- 239000011248 coating agent Substances 0.000 title claims abstract description 96
- 229910021332 silicide Inorganic materials 0.000 title claims abstract description 81
- FVBUAEGBCNSCDD-UHFFFAOYSA-N silicide(4-) Chemical compound [Si-4] FVBUAEGBCNSCDD-UHFFFAOYSA-N 0.000 title claims abstract description 81
- 229910052727 yttrium Inorganic materials 0.000 title claims abstract description 69
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 99
- 239000000956 alloy Substances 0.000 claims abstract description 99
- 239000000843 powder Substances 0.000 claims abstract description 64
- 239000011159 matrix material Substances 0.000 claims abstract description 45
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 42
- 230000000149 penetrating effect Effects 0.000 claims abstract description 42
- 230000003647 oxidation Effects 0.000 claims abstract description 41
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 41
- 238000005475 siliconizing Methods 0.000 claims abstract description 24
- 238000002679 ablation Methods 0.000 claims abstract description 22
- 239000011863 silicon-based powder Substances 0.000 claims abstract description 19
- 238000007789 sealing Methods 0.000 claims abstract description 10
- 239000012298 atmosphere Substances 0.000 claims abstract description 9
- 229910052758 niobium Inorganic materials 0.000 claims description 27
- 229910052721 tungsten Inorganic materials 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 25
- 239000003870 refractory metal Substances 0.000 claims description 20
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 18
- 238000001816 cooling Methods 0.000 claims description 17
- 238000004140 cleaning Methods 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 16
- 239000002002 slurry Substances 0.000 claims description 13
- 239000000126 substance Substances 0.000 claims description 12
- 238000002844 melting Methods 0.000 claims description 11
- 230000008018 melting Effects 0.000 claims description 11
- 229910052751 metal Inorganic materials 0.000 claims description 11
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 10
- 229910052786 argon Inorganic materials 0.000 claims description 9
- 238000000498 ball milling Methods 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 238000005520 cutting process Methods 0.000 claims description 9
- 238000005238 degreasing Methods 0.000 claims description 9
- 238000000227 grinding Methods 0.000 claims description 9
- 239000004615 ingredient Substances 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- 238000005498 polishing Methods 0.000 claims description 9
- 238000011065 in-situ storage Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 230000004584 weight gain Effects 0.000 claims description 4
- 235000019786 weight gain Nutrition 0.000 claims description 4
- 239000013078 crystal Substances 0.000 claims description 2
- 238000004321 preservation Methods 0.000 description 14
- 229910004298 SiO 2 Inorganic materials 0.000 description 12
- 229910052782 aluminium Inorganic materials 0.000 description 9
- 239000007789 gas Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 238000009792 diffusion process Methods 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 229910052710 silicon Inorganic materials 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000007745 plasma electrolytic oxidation reaction Methods 0.000 description 3
- 230000003068 static effect Effects 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 239000012190 activator Substances 0.000 description 2
- 230000003064 anti-oxidating effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229910004016 SiF2 Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- MGNHOGAVECORPT-UHFFFAOYSA-N difluorosilicon Chemical compound F[Si]F MGNHOGAVECORPT-UHFFFAOYSA-N 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010301 surface-oxidation reaction Methods 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
- ATVLVRVBCRICNU-UHFFFAOYSA-N trifluorosilicon Chemical compound F[Si](F)F ATVLVRVBCRICNU-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
Classifications
-
- 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
- C23C10/00—Solid state diffusion of only metal elements or silicon into metallic material surfaces
- C23C10/28—Solid state diffusion of only metal elements or silicon into metallic material surfaces using solids, e.g. powders, pastes
- C23C10/34—Embedding in a powder mixture, i.e. pack cementation
- C23C10/52—Embedding in a powder mixture, i.e. pack cementation more than one element being diffused in one step
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Solid-Phase Diffusion Into Metallic Material Surfaces (AREA)
Abstract
The invention discloses an yttrium modified refractory high-entropy silicide coating and a preparation method thereof, wherein the yttrium modified refractory high-entropy silicide coating has excellent oxidation resistance at 1450 ℃ and ultra-high temperature ablation resistance at 2100 ℃, and the preparation method comprises the following steps: (1) preparing a penetrating agent: the penetrating agent consists of the following components in percentage by mass: 25-35% of Si powder, 2-8%Y 2O3% of NaF powder, 3-5% of Al 2O3 powder and the balance; (2) Embedding and compacting a NbMoTaW refractory high-entropy alloy matrix into a crucible filled with a penetrating agent, covering and sealing the crucible, and carrying out embedding and siliconizing treatment on the NbMoTaW refractory high-entropy alloy matrix in an inert atmosphere at 900-1200 ℃ for 3-24 h; and (3) obtaining the yttrium modified refractory high-entropy silicide (NbMoTaW) Si 2 coating on the surface of the NbMoTaW refractory high-entropy alloy.
Description
Technical Field
The invention relates to an yttrium modified refractory high-entropy silicide coating and a preparation method thereof.
Background
The high-entropy alloy is an alloy composed of a plurality of metal elements in equimolar or near equimolar ratio. The high-entropy alloy has excellent mechanical, friction and wear resistance, corrosion resistance and high temperature resistance and is one of the most potential novel materials. The refractory high-entropy alloy composed of refractory metal elements Nb, mo, ta, W, V, hf and the like has stable structure and excellent high-temperature mechanical properties, for example, the compressive yield strength of the NbMoTaW refractory high-entropy alloy can still reach 405MPa at 1600 ℃.
However, refractory high-entropy alloys have poor oxidation resistance at medium and high temperatures, greatly restricting their engineering applications in high-temperature aerobic environments. Therefore, for refractory high-entropy alloys used in the high-temperature field, modification is needed to improve the high-temperature oxidation resistance. Currently, the main approaches for improving the high-temperature performance of materials are divided into two types, including alloy component design and surface oxidation-resistant coating. Liu et Al (J.alloy.Compd., 2014, 583:162-169) have found that NbCrMoTiAl 0.5,NbCrMoTiVAl0.5,NbCrMoTiVAl0.5Si0.3 and NbCrMoVAl 0.5 refractory high-entropy alloys both have single-phase BCC solid solution structures, oxidation kinetics in 1300 ℃ air follow a linear rule, and addition of Ti and Al can effectively improve the oxidation resistance of the refractory high-entropy alloy. However, when antioxidant elements such as silicon (Si), aluminum (Al), chromium (Cr) and the like are added into the refractory metal alloy, a hard and brittle phase (NbCr 2、TaCr2、Nb3 Al) is easily formed, and when the doping element ratio exceeds a threshold value, the alloy processing performance is rapidly reduced, so that the alloy has a certain limitation; in addition, the melting point of the added element is lower, so that the high-temperature mechanical property of the refractory high-entropy alloy is often reduced.
The surface coating method can maintain the room temperature and high temperature mechanical properties of the alloy matrix and simultaneously remarkably improve the high temperature oxidation resistance of the material. Shi et al (int.J. Refract.Met.H.,2021, 98:105562) prepared micro-arc oxidation (MAO) films on AlTiCrVZr refractory high-entropy alloy surfaces. Oxides such as Al 2O3、Cr2O3 and SiO 2 in the MAO coating can inhibit the diffusion of oxygen to the matrix and inhibit the volatilization of V element, but the oxidation temperature studied in the work is only 800 ℃. Han et al (Materials, 2020, 13:3592) prepared a Si-20Cr-20Fe coating on MoNbTaTiW refractory high-entropy alloys by slurry sintering, which silicide coating was effective in improving oxidation of the alloys at 1000℃ and 1300℃. However, the silicide coating prepared by the slurry melting method has a large number of pores, which affect the antioxidation effect of the coating. In the existing research on the surface antioxidation coating of the refractory high-entropy alloy, the oxidation temperature is low and the research on the oxidation behavior is not long-term.
Disclosure of Invention
The invention aims to: the invention aims to provide an yttrium modified refractory high-entropy silicide coating and a preparation method thereof, and the method can form the yttrium modified refractory high-entropy silicide coating on the surface of an NbMoTaW refractory high-entropy alloy, so that the high-temperature oxidation resistance and the ultrahigh-temperature ablation resistance of the NbMoTaW refractory high-entropy alloy can be effectively improved.
The technical scheme is as follows: the chemical composition of the yttrium modified refractory high-entropy silicide coating is [ NbMoTaW (Y) ] Si 2; the Nb, mo, ta, W atomic percent of a is more than or equal to 5 percent and less than or equal to 10 percent, the Y atomic percent of b is more than or equal to 0.2 percent and less than or equal to 4.5 percent, the Si atomic percent of c is more than or equal to 64 percent and less than or equal to 69 percent; the yttrium modified refractory high-entropy silicide coating has a hexagonal C40 crystal structure and is formed by in-situ reaction on the surface of the NbMoTaW refractory high-entropy alloy; the high-temperature oxidation at 1450 ℃ for 24h is less than 3.5mg/cm 2, the mass ablation rate is only 0.014-0.1mg/s after 180s ablation at 2100 ℃, and the limit ablation temperature reaches 2200 ℃.
The preparation method of the yttrium modified refractory high-entropy silicide coating comprises the following steps:
(1) Preparing a penetrating agent: the penetrating agent consists of the following components in percentage by mass: 25-35% of Si powder, 2-8%Y 2O3% of NaF powder, 3-5% of Al 2O3 powder and the balance;
(2) Embedding and compacting a NbMoTaW refractory high-entropy alloy matrix into a crucible filled with a penetrating agent, covering and sealing the crucible, and carrying out embedding and siliconizing treatment on the NbMoTaW refractory high-entropy alloy matrix in an inert atmosphere at 900-1200 ℃ for 3-24 h; and (3) obtaining the yttrium modified refractory high-entropy silicide (NbMoTaW) Si 2 coating on the surface of the NbMoTaW refractory high-entropy alloy.
In the step (1), si powder, Y 2O3 powder, naF powder, al 2O3 powder and grinding balls are placed in a ball mill, and ball milling is carried out for 6-8 hours and uniformly mixed.
In the step (2), refractory metal simple substances Nb, mo, ta, W with equal molar ratio are taken as ingredients, and oxide films on the metal surfaces are removed firstly; then preparing NbMoTaW refractory high-entropy alloy cast ingots by adopting a vacuum arc melting method; and sequentially carrying out linear cutting, degreasing, polishing and cleaning on the high-entropy alloy cast ingot to obtain the NbMoTaW refractory high-entropy alloy matrix. The purity of the refractory metal element Nb, mo, ta, W feedstock was 99.9wt.%.
In the step (2), the NbMoTaW refractory high-entropy alloy matrix is buried in a crucible filled with the penetrating agent and compacted, so that the thickness of the penetrating agent covered on each surface of the alloy matrix is not less than 10mm.
Wherein in the step (2), al 2O3 powder and silica sol are mixed according to the mass volume ratio of 1.5g:1mL of the mixture is mixed and prepared into slurry, and the crucible cover is sealed by adopting the slurry.
In the step (2), the inert atmosphere is an argon protection atmosphere.
Wherein, in the step (2), the heating rate is 10 ℃/min.
In the step (2), the NbMoTaW refractory high-entropy alloy matrix is subjected to embedding siliconizing treatment in an inert atmosphere at 1000 ℃ for 12 hours. The optimal embedding siliconizing temperature of the yttrium modified (NbMoTaW) Si 2 coating is 1000 ℃ and the time is 12h.
In the step (2), the cooling rate in the process of cooling to room temperature after embedding siliconizing treatment is 5 ℃/min.
In the embedding siliconizing process, si reacts with an activator (NaF) to form a large amount of gas fluoride SiF x (x is more than or equal to 1 and less than or equal to 4) in the reaction formula 1, such as SiF 4、SiF3、SiF2 and SiF; y 2O3 reacts with an activator (NaF) to form a gaseous fluoride YF 3 (equation 2); these SiF x and YF 3 diffuse to the substrate surface through the interstices between the infiltrant powder particles driven by the chemical potential gradient. The SiF x and the YF 3 respectively undergo disproportionation reaction to form an activity [ Si ] and an activity [ Y ] at an atomic scale (reaction formulas 3 and 4), a part of the activity [ Y ] and SiF x undergo substitution reaction to promote the formation of the activity [ Si ] (reaction formula 5), and in addition, active Y atoms are adsorbed on the surface of the refractory high-entropy alloy matrix and diffuse inwards, and because the size of the Y atoms is slightly larger than that of the NbMoTaW refractory high-entropy alloy, the Y forms a substitutional solid solution with the matrix alloy, so that lattice distortion is increased, a larger channel is provided for Si to diffuse inwards, and the active Si atoms are adsorbed on the surface of the refractory high-entropy alloy matrix and diffuse inwards to react with the high-entropy alloy to form the refractory high-entropy silicide coating (reaction formula 7).
Si(s) +xNaF (l) →SiF x (g) +xNa (g) equation 1
Y 2O3(s)+6NaF(l)→2YF3(g)+3Na2 O(s) reaction 2
(X+1) SiF x(g)→xSiFx-1 (g) + [ Si ](s) equation 3
2YF 3(g)→2[Y](s)+3F2 (g) reaction 4
X < Y >(s) +3SiF x(g)→xYF3 (g) +3 < Si >(s) equation 5
NbMoTaW+ [ Y ] →NbMoTaW (Y) equation 6
NbMoTaW (Y) +2Si→ [ NbMoTaW (Y) ] Si 2 equation 7.
The yttrium modified refractory high-entropy silicide (NbMoTaW) Si 2 coating grows on the surface of the refractory high-entropy alloy matrix in situ, yttrium can effectively promote Si diffusion and permeation, increases the diffusion rate of Si in the matrix alloy, and forms the refractory high-entropy silicide coating with fine and uniform grains. The refractory high-entropy silicide has the advantages that due to the hysteresis diffusion and the selective oxidation, yttrium can improve the adhesiveness of an oxide film and the anti-stripping capability. The yttrium modified refractory high-entropy silicide coating has excellent high-temperature stability at 1450 ℃, si is preferentially oxidized in the refractory high-entropy silicide coating, a continuous compact SiO 2 film is formed on the surface, meanwhile, Y 2O3,Y2O3 is formed to react with SiO 2 in an oxide film to form a Y 2Si2O7 stable oxide film structure, and the NbMoTaW refractory high-entropy alloy substrate is protected from being oxidized for more than 24 hours at 1450 ℃.
The beneficial effects are that: compared with the prior art, the invention has the following remarkable advantages: (1) The yttrium modified refractory high-entropy silicide (NbMoTaW) Si 2 coating prepared by the method grows in situ on the surface of the NbMoTaW refractory high-entropy alloy, and the coating is tightly combined with a matrix and is not easy to crack and fall off; (2) The yttrium in the penetrating agent can provide more diffusion channels for silicon in the embedding and siliconizing process, so that the diffusion growth of Si and NbMoTaW refractory high-entropy alloy matrix is accelerated; the yttrium modified refractory high-entropy silicide (NbMoTaW) Si 2 coating can obviously improve the high-temperature oxidation resistance of the NbMoTaW refractory high-entropy alloy at a temperature of more than 1450 ℃, and the surface SiO 2 oxide film of the yttrium modified refractory high-entropy silicide (NbMoTaW) Si 2 coating at a high temperature is continuous and compact and can be self-repaired; the coating has stable structure at high temperature, and the surface oxide film is continuous and compact, so that the oxidation resistance of the coating can be maintained for a long time (more than 24 h); (3) The yttrium modified refractory high-entropy silicide (NbMoTaW) Si 2 coating can obviously improve the ablation resistance of the NbMoTaW refractory high-entropy alloy above 2000 ℃, the coating remains intact after 180s ablation at 2100 ℃, a sample appears a pit after 100s ablation at 2200 ℃, and yttrium in the coating can promote the formation of an SiO 2 oxide film and delay the oxidation of oxygen to the refractory high-entropy silicide layer.
Drawings
FIG. 1 is an XRD pattern for yttrium-modified refractory high entropy silicide coatings obtained in examples 1-4;
FIG. 2 is a surface SEM image of the yttrium modified refractory high entropy silicide coating obtained in example 3 after 24 hours of oxidation at 1450 ℃;
FIG. 3 is a surface XRD pattern of the yttrium modified refractory high entropy silicide coating obtained in example 3 after 24 hours of oxidation at 1450 ℃;
FIG. 4 is a cross-sectional SEM elemental profile of the yttrium modified refractory high entropy silicide coating obtained in example 3 after 24h oxidation at 1450 ℃;
FIG. 5 is a surface SEM image of the refractory high entropy silicide coating obtained in comparative example 3 after 24 hours of oxidation at 1450 ℃;
FIG. 6 is a plot of ablated surface temperature versus ablation time at 2100℃and 2200℃for the yttrium-modified refractory high entropy silicide coating obtained in example 3;
FIG. 7 is a macroscopic photograph of the surface of the yttrium-modified refractory high entropy silicide coating obtained in example 3 after ablation at 2100℃and 2200 ℃.
Detailed Description
Example 1
The preparation method of the yttrium modified refractory high-entropy silicide coating comprises the following steps:
(1) Taking refractory metal simple substances Nb, mo, ta, W with equal molar ratio as ingredients, and firstly removing an oxide film on the metal surface; then preparing NbMoTaW refractory high-entropy alloy cast ingots by adopting a vacuum arc melting method; sequentially performing linear cutting, degreasing, polishing and cleaning on the high-entropy alloy cast ingot to obtain a NbMoTaW refractory high-entropy alloy matrix; the purity of the refractory metal element Nb, mo, ta, W raw material is 99.9wt.%;
(2) Preparing a penetrating agent: the penetrating agent consists of the following components in percentage by mass: 30% Si powder, 2%Y 2O3 powder, 5% NaF powder and 63% Al 2O3 powder; placing the Si powder, the Y 2O3 powder, the NaF powder, the Al 2O3 powder and the grinding balls with the formula amount into a ball mill, and uniformly mixing after ball milling for 6 hours;
(3) Embedding an NbMoTaW refractory high-entropy alloy matrix into an Al 2O3 crucible filled with a penetrating agent, compacting the crucible to ensure that the thickness of the penetrating agent covered on each surface of the NbMoTaW refractory high-entropy alloy matrix is not less than 10mm, covering the crucible, sealing the crucible by adopting slurry prepared by silica sol and Al 2O3 powder, placing the sealed crucible into a high-temperature tubular furnace for embedding and siliconizing treatment, heating the crucible along with the furnace under the protection of argon gas, wherein the heating rate is 10 ℃/min, the heat preservation temperature is 1200 ℃, and then cooling the crucible along with the furnace after heat preservation for 3h, and the cooling rate is 5 ℃/min;
(4) Taking out the sample after embedding siliconizing cooled to room temperature, and cleaning by ultrasonic to obtain the product which is the NbMoTaW refractory high-entropy alloy surface with yttrium modified refractory high-entropy silicide (NbMoTaW) Si 2 coating.
The yttrium modified refractory high-entropy silicide (NbMoTaW) Si 2 coating contains Nb, mo, ta, W atom percent of 6.92, 6.95, 7.57 and 9.65 percent of 6.92, 0.74 percent of Y and 68.18 percent of Si.
Example 2
The preparation method of the yttrium modified refractory high-entropy silicide coating comprises the following steps:
(1) Taking refractory metal simple substances Nb, mo, ta, W with equal molar ratio as ingredients, and firstly removing an oxide film on the metal surface; then preparing NbMoTaW refractory high-entropy alloy cast ingots by adopting a vacuum arc melting method; sequentially performing linear cutting, degreasing, polishing and cleaning on the high-entropy alloy cast ingot to obtain a NbMoTaW refractory high-entropy alloy matrix; the purity of the refractory metal element Nb, mo, ta, W raw material is 99.9wt.%;
(2) Preparing a penetrating agent: the penetrating agent consists of the following components in percentage by mass: 25% Si powder, 8%Y 2O3 powder, 3% NaF powder and 64% Al 2O3 powder; placing the Si powder, the Y 2O3 powder, the NaF powder, the Al 2O3 powder and the grinding balls with the formula amount into a ball mill, and uniformly mixing after ball milling for 6 hours;
(3) Embedding an NbMoTaW refractory high-entropy alloy matrix into an Al 2O3 crucible filled with a penetrating agent, compacting the crucible to ensure that the thickness of the penetrating agent covered on each surface of the NbMoTaW refractory high-entropy alloy matrix is not less than 10mm, covering the crucible, sealing the crucible by adopting slurry prepared by silica sol and Al 2O3 powder, placing the sealed crucible into a high-temperature tubular furnace for embedding and siliconizing treatment, heating the crucible along with the furnace under the protection of argon gas, wherein the heating rate is 10 ℃/min, the heat preservation temperature is 900 ℃, and then cooling the crucible along with the furnace after heat preservation for 24 hours, and the cooling rate is 5 ℃/min;
(4) Taking out the sample after embedding siliconizing cooled to room temperature, and cleaning by ultrasonic to obtain the product which is the NbMoTaW refractory high-entropy alloy surface with yttrium modified refractory high-entropy silicide (NbMoTaW) Si 2 coating.
The yttrium modified refractory high-entropy silicide (NbMoTaW) Si 2 coating contains Nb, mo, ta, W atom percent of 6.82 percent, 6.65 percent, 7.10 percent and 8.75 percent of Y atom percent of 4.11 percent and 66.57 percent of Si atom percent respectively.
Example 3
The preparation method of the yttrium modified refractory high-entropy silicide coating comprises the following steps:
(1) Taking refractory metal simple substances Nb, mo, ta, W with equal molar ratio as ingredients, and firstly removing an oxide film on the metal surface; then preparing NbMoTaW refractory high-entropy alloy cast ingots by adopting a vacuum arc melting method; sequentially performing linear cutting, degreasing, polishing and cleaning on the high-entropy alloy cast ingot to obtain a NbMoTaW refractory high-entropy alloy matrix; the purity of the refractory metal element Nb, mo, ta, W raw material is 99.9wt.%;
(2) Preparing a penetrating agent: the penetrating agent consists of the following components in percentage by mass: 30% Si powder, 4%Y 2O3 powder, 5% NaF powder and 61% Al 2O3 powder; placing the Si powder, the Y 2O3 powder, the NaF powder, the Al 2O3 powder and the grinding balls with the formula amount into a ball mill, and uniformly mixing after ball milling for 6 hours;
(3) Embedding an NbMoTaW refractory high-entropy alloy matrix into an Al 2O3 crucible filled with a penetrating agent, compacting the crucible to ensure that the thickness of the penetrating agent covered on each surface of the NbMoTaW refractory high-entropy alloy matrix is not less than 10mm, covering the crucible, sealing the crucible by adopting slurry prepared by silica sol and Al 2O3 powder, placing the sealed crucible into a high-temperature tubular furnace for embedding and siliconizing treatment, heating the crucible along with the furnace under the protection of argon gas, wherein the heating rate is 10 ℃/min, the heat preservation temperature is 1000 ℃, and then cooling the crucible along with the furnace after heat preservation for 12h, and the cooling rate is 5 ℃/min;
(4) Taking out the sample after embedding siliconizing cooled to room temperature, and cleaning by ultrasonic to obtain the product which is the NbMoTaW refractory high-entropy alloy surface with yttrium modified refractory high-entropy silicide (NbMoTaW) Si 2 coating.
The yttrium modified refractory high-entropy silicide (NbMoTaW) Si 2 coating contains Nb, mo, ta, W atom percent of 7.33%, 7.54%, 7.69%, 8.65%, Y atom percent of 2.03% and Si atom percent of 66.76%.
Example 4
The preparation method of the yttrium modified refractory high-entropy silicide coating comprises the following steps:
(1) Taking refractory metal simple substances Nb, mo, ta, W with equal molar ratio as ingredients, and firstly removing an oxide film on the metal surface; then preparing NbMoTaW refractory high-entropy alloy cast ingots by adopting a vacuum arc melting method; sequentially performing linear cutting, degreasing, polishing and cleaning on the high-entropy alloy cast ingot to obtain a NbMoTaW refractory high-entropy alloy matrix; the purity of the refractory metal element Nb, mo, ta, W raw material is 99.9wt.%;
(2) Preparing a penetrating agent: the penetrating agent consists of the following components in percentage by mass: 35% Si powder, 6%Y 2O3% NaF powder, 54% Al 2O3 powder; placing the Si powder, the Y 2O3 powder, the NaF powder, the Al 2O3 powder and the grinding balls with the formula amount into a ball mill, and uniformly mixing the materials after ball milling for 8 hours;
(3) Embedding an NbMoTaW refractory high-entropy alloy matrix into an Al 2O3 crucible filled with a penetrating agent, compacting the crucible to ensure that the thickness of the penetrating agent covered on each surface of the NbMoTaW refractory high-entropy alloy matrix is not less than 10mm, covering the crucible, sealing the crucible by adopting slurry prepared by silica sol and Al 2O3 powder, placing the sealed crucible into a high-temperature tubular furnace for embedding and siliconizing treatment, heating the crucible along with the furnace under the protection of argon gas, wherein the heating rate is 10 ℃/min, the heat preservation temperature is 1000 ℃, and then cooling the crucible along with the furnace after heat preservation for 12h, and the cooling rate is 5 ℃/min;
(4) Taking out the sample after embedding siliconizing cooled to room temperature, and cleaning by ultrasonic to obtain the product which is the NbMoTaW refractory high-entropy alloy surface with yttrium modified refractory high-entropy silicide (NbMoTaW) Si 2 coating.
The yttrium modified refractory high-entropy silicide (NbMoTaW) Si 2 coating contains Nb, mo, ta, W atom percent of 5.96 percent, 7.14 percent, 6.25 percent and 8.24 percent of Y atom percent of 3.41 percent and 69.00 percent of Si atom percent.
Comparative example 1
A preparation method of an yttrium modified refractory high-entropy silicide coating comprises the following steps:
(1) Taking refractory metal simple substances Nb, mo, ta, W with equal molar ratio as ingredients, and firstly removing an oxide film on the metal surface; then preparing NbMoTaW refractory high-entropy alloy cast ingots by adopting a vacuum arc melting method; sequentially performing linear cutting, degreasing, polishing and cleaning on the high-entropy alloy cast ingot to obtain a NbMoTaW refractory high-entropy alloy matrix; the purity of the refractory metal element Nb, mo, ta, W raw material is 99.9wt.%;
(2) Preparing a penetrating agent: the penetrating agent consists of the following components in percentage by mass: 30% Si powder, 4%Y 2O3 powder, 5% NaF powder and 61% Al 2O3 powder; placing the Si powder, the Y 2O3 powder, the NaF powder, the Al 2O3 powder and the grinding balls with the formula amount into a ball mill, and uniformly mixing after ball milling for 6 hours;
(3) Embedding an NbMoTaW refractory high-entropy alloy matrix into an Al 2O3 crucible filled with a penetrating agent, compacting the crucible to ensure that the thickness of the penetrating agent covered on each surface of the NbMoTaW refractory high-entropy alloy matrix is not less than 10mm, covering the crucible, sealing the crucible by adopting slurry prepared by silica sol and Al 2O3 powder, placing the sealed crucible into a high-temperature tubular furnace for embedding and siliconizing treatment, heating the crucible along with the furnace under the protection of argon gas, wherein the heating rate is 10 ℃/min, the heat preservation temperature is 1500 ℃, and then cooling the crucible along with the furnace after heat preservation for 12h, and the cooling rate is 5 ℃/min;
(4) Taking out the sample after embedding siliconizing cooled to room temperature, and cleaning by ultrasonic to obtain the product which is the NbMoTaW refractory high-entropy alloy surface with yttrium modified refractory high-entropy silicide (NbMoTaW) Si 2 coating.
Nb, mo, ta, W atomic percent of the yttrium modified refractory high-entropy silicide (NbMoTaW) Si 2 coating is 6.01 percent, 5.14 percent, 5.71 percent and 9.21 percent respectively, Y atomic percent is 2.51 percent and Si atomic percent is 71.42 percent.
Comparative example 2
A preparation method of an yttrium modified refractory high-entropy silicide coating comprises the following steps:
(1) Taking refractory metal simple substances Nb, mo, ta, W with equal molar ratio as ingredients, and firstly removing an oxide film on the metal surface; then preparing NbMoTaW refractory high-entropy alloy cast ingots by adopting a vacuum arc melting method; sequentially performing linear cutting, degreasing, polishing and cleaning on the high-entropy alloy cast ingot to obtain a NbMoTaW refractory high-entropy alloy matrix; the purity of the refractory metal element Nb, mo, ta, W raw material is 99.9wt.%;
(2) Preparing a penetrating agent: the penetrating agent consists of the following components in percentage by mass: 30% Si powder, 10% Y 2O3 powder, 5% NaF powder and 61% Al 2O3 powder; placing the Si powder, the Y 2O3 powder, the NaF powder, the Al 2O3 powder and the grinding balls with the formula amount into a ball mill, and uniformly mixing after ball milling for 6 hours;
(3) Embedding an NbMoTaW refractory high-entropy alloy matrix into an Al 2O3 crucible filled with a penetrating agent, compacting the crucible to ensure that the thickness of the penetrating agent covered on each surface of the NbMoTaW refractory high-entropy alloy matrix is not less than 10mm, covering the crucible, sealing the crucible by adopting slurry prepared by silica sol and Al 2O3 powder, placing the sealed crucible into a high-temperature tubular furnace for embedding and siliconizing treatment, heating the crucible along with the furnace under the protection of argon gas, wherein the heating rate is 10 ℃/min, the heat preservation temperature is 1000 ℃, and then cooling the crucible along with the furnace after heat preservation for 12h, and the cooling rate is 5 ℃/min;
(4) Taking out the sample after embedding siliconizing cooled to room temperature, and cleaning by ultrasonic to obtain the product which is the NbMoTaW refractory high-entropy alloy surface with yttrium modified refractory high-entropy silicide (NbMoTaW) Si 2 coating.
Nb, mo, ta, W atomic percent of the yttrium modified refractory high-entropy silicide (NbMoTaW) Si 2 coating is 6.94 percent, 6.51 percent, 8.24 percent and 8.25 percent respectively, Y atomic percent is 4.64 percent and Si atomic percent is 65.42 percent.
Comparative example 3
A method for preparing a refractory high entropy silicide coating, comprising the steps of:
(1) Taking refractory metal simple substances Nb, mo, ta, W with equal molar ratio as ingredients, and firstly removing an oxide film on the metal surface; then preparing NbMoTaW refractory high-entropy alloy cast ingots by adopting a vacuum arc melting method; sequentially performing linear cutting, degreasing, polishing and cleaning on the high-entropy alloy cast ingot to obtain a NbMoTaW refractory high-entropy alloy matrix; the purity of the refractory metal element Nb, mo, ta, W raw material is 99.9wt.%;
(2) Preparing a penetrating agent: the penetrating agent consists of the following components in percentage by mass: 30% Si powder, 5% NaF powder and 65% Al 2O3 powder; placing Si powder, naF powder, al 2O3 powder and grinding balls with the formula amount into a ball mill, and uniformly mixing after ball milling for 6 hours;
(3) Embedding an NbMoTaW refractory high-entropy alloy matrix into an Al 2O3 crucible filled with a penetrating agent, compacting the crucible to ensure that the thickness of the penetrating agent covered on each surface of the NbMoTaW refractory high-entropy alloy matrix is not less than 10mm, covering the crucible, sealing the crucible by adopting slurry prepared by silica sol and Al 2O3 powder, placing the sealed crucible into a high-temperature tubular furnace for embedding and siliconizing treatment, heating the crucible along with the furnace under the protection of argon gas, wherein the heating rate is 10 ℃/min, the heat preservation temperature is 1000 ℃, and then cooling the crucible along with the furnace after heat preservation for 12h, and the cooling rate is 5 ℃/min;
(4) Taking out the sample after embedding siliconizing cooled to room temperature, and cleaning by ultrasonic to obtain the product, wherein the surface of the NbMoTaW refractory high-entropy alloy has a refractory high-entropy silicide (NbMoTaW) Si 2 coating.
Nb, mo, ta, W atomic percent of the refractory high-entropy silicide (NbMoTaW) Si 2 coating is 5.74 percent, 6.24 percent, 9.91 percent and 11.35 percent of the refractory high-entropy silicide (NbMoTaW) Si 2 coating is 0 percent, and the atomic percent of Y is 66.76 percent.
The structures of the yttrium-modified refractory high-entropy silicide coatings prepared in examples 1 to 4 were tested by an X-ray diffractometer, and the results are shown in fig. 1, and all the prepared yttrium-modified refractory high-entropy silicide coating samples have a single-phase structure, corresponding to (NbMoTaW) Si 2.
The yttrium modified refractory high-entropy silicide coatings prepared in examples 1-4 were subjected to static oxidation at 1450 ℃ by a high-temperature box furnace, the oxidation weight increase per unit area after 24 hours of oxidation is shown in Table 1, and the minimum oxidation weight increase of the yttrium modified refractory high-entropy silicide coating in example 3 is only 1.92mg/cm 2, and the yttrium modified refractory high-entropy silicide coating has optimal oxidation resistance.
TABLE 1
The yttrium-modified refractory high entropy silicide coating in example 3 was up to 58 μm thick. The surface of the sample oxidized for 24 hours at 1450 ℃ is provided with a morphology as shown in figure 2, and the surface is a continuous and compact SiO 2 film. Example 3 XRD analysis of the sample surface after 24h oxidation at 1450 c as shown in fig. 3, the oxidized surface of the yttrium-modified refractory high entropy silicide coating has Y 2Si2O7 formed by the reaction of Y 2O3 and SiO 2 in the oxide film, in addition to SiO 2, which can play a role in stabilizing the structure of the SiO 2 oxide film. The morphology analysis is carried out on the section of the sample oxidized for 24 hours at 1450 ℃ in the example 3, and the result is shown in figure 4, the yttrium modified refractory high-entropy silicide coating has thermal growth cracks after high-temperature oxidation, the SiO 2 oxide film on the surface has self-repairing capability, and the cracks are filled to block oxygen diffusion, so that the coating has excellent oxidation resistance.
The yttrium modified refractory high-entropy silicide coating in comparative example 1 has the thickness of 500 mu m, a large number of cracks exist due to overlarge thermal stress generated by the coating due to overhigh preparation temperature, the unit oxidation weight of the coating reaches 54.48mg/cm 2 after static oxidation for 10 hours at 1450 ℃, the coating has no protection effect, and the substrate starts to be oxidized.
The thickness of the yttrium modified refractory high-entropy silicide coating in comparative example 2 is 46 mu m, and when the addition amount of Y 2O3 powder is excessive, excessive active yttrium atoms are accumulated on the surface of the matrix, so that Si is blocked from diffusing into the NbMoTaW refractory high-entropy alloy, and the growth of the coating is inhibited. The weight per unit area of oxidation increased by about 1.85mg/cm 2 after static oxidation at 1450℃for 2 h. The yttrium on the surface of the coating reacts with oxygen rapidly, so that the oxidation weight gain is obvious, the continuous and compact SiO 2 oxidation film is not formed, and the oxidation weight gain reaches 4.94mg/cm 2 after 24 hours of oxidation.
The refractory high entropy silicide coating of comparative example 3 had a thickness of only 31 μm and was about half that of the yttrium-modified refractory high entropy silicide coating of example 3. Insufficient coating thickness will not provide longer protection to the substrate. The unit area oxidation weight gain of the refractory high-entropy silicide coating after 24h oxidation at 1450 ℃ is obviously increased to 3.7mg/cm 2, the surface morphology of the sample after 24h oxidation is shown in figure 5, and the surface of the oxidized surface is more refractory metal oxide, so that the SiO 2 film is destroyed, and the long-term oxidation at 1450 ℃ is seriously influenced.
An ablation experiment is carried out on the yttrium modified refractory high-entropy silicide coating prepared in the embodiment 3 by adopting a plasma ablation method, a change curve of the surface temperature of a sample along with ablation time is shown in figure 6, a macroscopic photograph of the surface of the sample after ablation is shown in figure 7, the coating remains intact after ablation for 180s at 2100 ℃, the mass ablation rate is only 0.014mg/s, the sample has ablation pits after ablation for 100s at 2200 ℃, and the mass ablation rate is-2.075 mg/s. Illustrating that the yttrium-modified refractory high-entropy silicide coating prepared in example 3 has ultra-high temperature ablation resistance.
Claims (9)
1. The preparation method of the yttrium modified refractory high-entropy silicide coating is characterized by comprising the following steps of:
(1) Preparing a penetrating agent: the penetrating agent consists of the following components in percentage by mass: 25-35% of Si powder, 2-8% of Y 2O3 powder, 3-5% of NaF powder and the balance of Al 2O3 powder;
(2) Embedding a NbMoTaW refractory high-entropy alloy matrix into a crucible filled with a penetrating agent, compacting, covering and sealing the crucible, and carrying out embedding siliconizing treatment on the NbMoTaW refractory high-entropy alloy matrix in an inert atmosphere at 900-1200 ℃ for 3-24 hours; obtaining an yttrium modified refractory high entropy silicide (NbMoTaW) Si 2 coating on the surface of the NbMoTaW refractory high entropy alloy;
The chemical composition of the yttrium modified refractory high-entropy silicide coating is [ NbMoTaW (Y) ] Si 2; the Nb, mo, ta, W atomic percent of a is more than or equal to 5 percent and less than or equal to 10 percent, the Y atomic percent of b is more than or equal to 0.2 percent and less than or equal to 4.5 percent, the Si atomic percent of c is more than or equal to 65 percent and less than or equal to 69 percent; the yttrium modified refractory high-entropy silicide coating has a hexagonal C40 crystal structure and is formed by in-situ reaction on the surface of the NbMoTaW refractory high-entropy alloy;
The weight gain is 1.92mg/cm 2 after the high-temperature oxidation at 1450 ℃ for 24 hours; the coating remained intact after 180s ablation at 2100 c, with a mass ablation rate of only 0.014mg/s.
2. The method of preparing a yttrium-modified refractory high entropy silicide coating as claimed in claim 1, wherein: in the step (1), si powder, Y 2O3 powder, naF powder, al 2O3 powder and grinding balls are placed in a ball mill, and ball milling is carried out for 6-8 hours and uniformly mixed.
3. The method of preparing a yttrium-modified refractory high entropy silicide coating as claimed in claim 1, wherein: in the step (2), refractory metal simple substances Nb, mo, ta, W with equal molar ratio are taken as ingredients, and oxide films on the metal surfaces are removed firstly; then preparing NbMoTaW refractory high-entropy alloy cast ingots by adopting a vacuum arc melting method; and sequentially carrying out linear cutting, degreasing, polishing and cleaning on the high-entropy alloy cast ingot to obtain the NbMoTaW refractory high-entropy alloy matrix.
4. The method of preparing a yttrium-modified refractory high entropy silicide coating as claimed in claim 1, wherein: in the step (2), the NbMoTaW refractory high-entropy alloy matrix is buried in a crucible filled with the penetrating agent and compacted, so that the thickness of the penetrating agent covered on each surface of the alloy matrix is not less than 10mm.
5. The method of preparing a yttrium-modified refractory high entropy silicide coating as claimed in claim 1, wherein: in the step (2), the crucible cover is sealed by adopting slurry prepared by silica sol and Al 2O3 powder.
6. The method of preparing a yttrium-modified refractory high entropy silicide coating as recited in claim 5, wherein: al 2O3 powder and silica sol according to the mass volume ratio of 1.5g:1mL of the mixture was mixed to prepare a slurry.
7. The method of preparing a yttrium-modified refractory high entropy silicide coating as claimed in claim 1, wherein: in the step (2), the inert atmosphere is an argon protection atmosphere.
8. The method of preparing a yttrium-modified refractory high entropy silicide coating as claimed in claim 1, wherein: in the step (2), the heating rate of the embedding siliconizing treatment is not higher than 10 ℃/min, and the cooling rate is not higher than 5 ℃/min.
9. The method of preparing a yttrium-modified refractory high entropy silicide coating as claimed in claim 2, wherein: in the step (2), the NbMoTaW refractory high-entropy alloy matrix is subjected to embedding siliconizing treatment in an inert atmosphere at 1000 ℃ for 12 hours.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2023104495322 | 2023-04-24 | ||
| CN202310449532 | 2023-04-24 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN116815113A CN116815113A (en) | 2023-09-29 |
| CN116815113B true CN116815113B (en) | 2024-05-07 |
Family
ID=88121792
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310798653.8A Active CN116815113B (en) | 2023-04-24 | 2023-06-30 | Yttrium modified refractory high-entropy silicide coating and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116815113B (en) |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103993259A (en) * | 2014-04-25 | 2014-08-20 | 西北工业大学 | Two-step preparation method for Y and Al modified silicide infiltrated layer on surface of Nb-Si-based alloy |
| CN104313541A (en) * | 2014-09-25 | 2015-01-28 | 西北工业大学 | Method for preparing antioxidant Zr-Y modified silicide infiltrated layer on Nb-based superhigh-temperature alloy surface by two-step method |
| CN104911537A (en) * | 2015-06-09 | 2015-09-16 | 西北工业大学 | Nb-Ti-Si-base alloy surface B-Y modified silicide coating and preparation method thereof |
| CN107267914A (en) * | 2017-06-19 | 2017-10-20 | 西北工业大学 | A kind of Ti2The method that AlNb alloy surface two-step methods prepare Si Al Y compisite seeping layers |
| AU2020100541A4 (en) * | 2019-04-16 | 2020-05-21 | Hefei University Of Technology | Method for preparing oxidation-resistant coating for pure tungsten by modifying with rare earth element yttrium and aluminizing by embedding |
| CN112941459A (en) * | 2021-01-29 | 2021-06-11 | 中国人民解放军军事科学院国防科技创新研究院 | Refractory high-entropy alloy surface oxidation-resistant coating and preparation method thereof |
| CN113789464A (en) * | 2021-08-16 | 2021-12-14 | 东南大学 | Ceramic phase reinforced refractory high-entropy alloy composite material and preparation method thereof |
-
2023
- 2023-06-30 CN CN202310798653.8A patent/CN116815113B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103993259A (en) * | 2014-04-25 | 2014-08-20 | 西北工业大学 | Two-step preparation method for Y and Al modified silicide infiltrated layer on surface of Nb-Si-based alloy |
| CN104313541A (en) * | 2014-09-25 | 2015-01-28 | 西北工业大学 | Method for preparing antioxidant Zr-Y modified silicide infiltrated layer on Nb-based superhigh-temperature alloy surface by two-step method |
| CN104911537A (en) * | 2015-06-09 | 2015-09-16 | 西北工业大学 | Nb-Ti-Si-base alloy surface B-Y modified silicide coating and preparation method thereof |
| CN107267914A (en) * | 2017-06-19 | 2017-10-20 | 西北工业大学 | A kind of Ti2The method that AlNb alloy surface two-step methods prepare Si Al Y compisite seeping layers |
| AU2020100541A4 (en) * | 2019-04-16 | 2020-05-21 | Hefei University Of Technology | Method for preparing oxidation-resistant coating for pure tungsten by modifying with rare earth element yttrium and aluminizing by embedding |
| CN112941459A (en) * | 2021-01-29 | 2021-06-11 | 中国人民解放军军事科学院国防科技创新研究院 | Refractory high-entropy alloy surface oxidation-resistant coating and preparation method thereof |
| CN113789464A (en) * | 2021-08-16 | 2021-12-14 | 东南大学 | Ceramic phase reinforced refractory high-entropy alloy composite material and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| Kuang Juan et al..Formation and oxidation behavior of refractory high-entropy silicide (NbMoTaW)Si2 coating.Corrosion Science.2022,第2节. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN116815113A (en) | 2023-09-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Vojtěch et al. | High temperature oxidation of titanium–silicon alloys | |
| Pan et al. | Oxidation behavior of Mo-Si-B alloys at medium-to-high temperatures | |
| Maître et al. | Effect of silica on the reactive sintering of polycrystalline Nd: YAG ceramics | |
| Bahrami et al. | Wetting and reaction characteristics of crystalline and amorphous SiO2 derived rice-husk ash and SiO2/SiC substrates with Al–Si–Mg alloys | |
| Qian-Gang et al. | Microstructure and anti-oxidation property of CrSi2–SiC coating for carbon/carbon composites | |
| Paswan et al. | Isothermal oxidation behaviour of Mo–Si–B and Mo–Si–B–Al alloys in the temperature range of 400–800 C | |
| Astapov et al. | Kinetics and mechanism of high-temperature oxidation of the heterophase ZrSi2-MoSi2-ZrB2 ceramics | |
| Shao et al. | Oxidation behavior of the B-modified silicide coating on Nb-Si based alloy at intermediate temperatures | |
| Kuang et al. | Formation and oxidation behavior of refractory high-entropy silicide (NbMoTaW) Si2 coating | |
| Li et al. | Improved thermal conductivity of sintered reaction-bonded silicon nitride using a BN/graphite powder bed | |
| KR100454715B1 (en) | MoSi2-Si3N4 COMPOSITE COATING AND MANUFACTURING METHOD THEREOF | |
| Xie et al. | Experimental and theoretical study on the effect of different rare-earth oxides on the high-temperature stability of SiO2 glass at 1973K | |
| Zhang et al. | Nb doping in Ti3AlC2: effects on phase stability, high-temperature compressive properties, and oxidation resistance | |
| Liu et al. | Oxidation behavior of Ni–Mo–Si alloy coatings fabricated on carbon steel by laser cladding | |
| Lu et al. | High-temperature oxidation behavior of TiAl-based alloys fabricated by spark plasma sintering | |
| Wu et al. | Oxidation behavior of Si-rich Mo-Si-B coating doped with La by spark plasma sintering | |
| CN109536883B (en) | Method for improving high-temperature oxidation resistance of Ti-45Al-8.5Nb alloy | |
| Li et al. | The morphology of oxides and oxidation behavior of Ti3SiC2-based composite at high-temperature | |
| Shao et al. | Effects of boron and carbon on the oxidation behavior of a NbMoTaW refractory high entropy alloy | |
| Vojtěch et al. | Influence of silicon on high-temperature cyclic oxidation behaviour of titanium | |
| CN116815113B (en) | Yttrium modified refractory high-entropy silicide coating and preparation method thereof | |
| EP1015134A4 (en) | Surface treatment of 312 ternary ceramic materials and products thereof | |
| Lee et al. | The oxidation of TiB2 particle-reinforced TiAl intermetallic composites | |
| Son et al. | Microstructure of NbSi2/SiC nanocomposite coating formed on Nb substrate | |
| Kun et al. | Isothermal oxidation behavior of TiAl intermetallics with different oxygen contents |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |