CN115215668A - High-temperature water-oxygen corrosion resistant fiber composite coating with sandwich structure and preparation method and application thereof - Google Patents
High-temperature water-oxygen corrosion resistant fiber composite coating with sandwich structure and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a preparation method of a coating deposited on the surface of a fiber and capable of greatly improving the water-oxygen corrosion resistance of the fiber, which comprises the following steps: sequentially depositing HfO on the surface of the fiber by a hydrothermal method 2 、YbPO 4 And HfO 2 To form a sandwich-structured coating, and densifying the coating by high-temperature heat treatment. HfO with sandwich structure prepared by the method of the invention 2 /YbPO 4 /HfO 2 The composite coating can obviously improve the water-oxygen corrosion resistance of the fiber (especially silicon-based fiber), and meanwhile, the hydrothermal method adopted by the invention is simple and reliable, the operability is strong, the thickness of the prepared coating is controllable, and the coating is deposited uniformly.
Description
Technical Field
The invention relates to the technical field of inorganic nonmetal surfaces, in particular to a high-temperature water-oxygen corrosion resistant fiber composite coating with a sandwich structure and a preparation method and application thereof.
Background
Reinforcing fibers represented by SiC fibers are designed and applied to ceramic matrix composite materials including hot end parts of aero-engines, the SiC fibers usually adopt Boron Nitride (BN) as an interface layer (high-temperature oxidation resistant coating), but the oxidation starting temperature point of the BN is about 800 ℃, the BN is particularly sensitive to water vapor, and the presence of trace water vapor at high temperature can cause the BN oxide to be rapidly volatilized, so that the BN cannot play a good water-oxygen corrosion protection role on the SiC fibers at high temperature (particularly 1000 ℃ and above).
Ytterbium phosphate (YbPO) 4 ) The melting point is more than 2000 ℃, and the product is stable in water-oxygen corrosion environment. However, ybPO in a high temperature reducing atmosphere 4 The coating can cause the degradation of silicon-based fibers such as SiC and the like, the performance is reduced, and LaPO 4 As a fiber protective coating, the porous structure is loose, and the porous structure cannot be used as an effective diffusion barrier for water vapor and oxygen. This limits YbPO 4 Use of a coating in a non-oxide ceramic matrix composite system.
In view of this, the invention is particularly proposed.
Disclosure of Invention
The invention aims to provide a preparation method of a high-temperature water-oxygen corrosion resistant fiber composite coating with a sandwich structure, which mainly improves the water-oxygen corrosion resistance of the fiber and solves the problem of YbPO 4 The coating reacts with fibers such as SiC.
The invention is realized by the following steps:
high-temperature water-oxygen corrosion resistant fiber composite coating with sandwich structure, wherein the sandwich structure is HfO 2 /YbPO 4 /HfO 2 Wherein the sandwich layer is YbPO 4 The other two layers are both HfO 2 。
The YbPO 4 The thickness of (A) is 200nm to 2 μm, preferably 300nm to 1 μm; the HfO 2 Each layer of (a) is 50 to 500nm, preferably 100 to 300nm. Two-layer HfO 2 The thickness of the two layers is required to be basically consistentThe difference is not more than 10%; the coating is required to uniformly cover the surface of the fiber, and the thickness is the thickness before heat treatment;
the total thickness of the high-temperature water and oxygen corrosion resistant fiber composite coating with the sandwich structure is 300 nm-3 mu m, preferably 500 nm-1.5 mu m, and more preferably 600 nm-1 mu m.
Optionally, a "sandwich" YbPO in a sandwich coating 4 Or other rare earth phosphates, e.g. CePO 4 、YPO 4 And the like.
Alternatively, the fibers may be of various types that may be used at high temperatures and require moisture or (and) oxidative corrosion protection, including but not limited to glass fibers, carbon (C) fibers, silicon carbide (SiC) fibers, silicon nitride (Si) 3 N 4 ) The fiber is one or more of silicon carbon nitrogen (SiCN) fiber, silicon boron carbon nitrogen (SiBCN) fiber, or the fiber is modified by doping other elements. Preferably, the fibers are SiC fibers having a diameter of 1 to 30 μm, more preferably, the SiC fibers have a diameter of 5 to 10 μm.
A method for preparing the high-temperature water-oxygen corrosion resistant fiber composite coating with the sandwich structure comprises the following steps:
s1: sequentially depositing HfO on the surface of the fiber by a hydrothermal method 2 、YbPO 4 And HfO 2 Obtaining a coating with a sandwich structure;
s2: and (4) densifying the deposited coating by high-temperature heat treatment to obtain the high-temperature water-oxygen corrosion resistant fiber composite coating with a sandwich structure.
Optionally, the hydrothermal method in step S1 is specifically: (1) Dipping the fiber into HfCl 4 Dispersing in the solution, then immersing in ammonia solution and standing; (2) The resulting fiber was dried and then dipped into Yb (NO) 3 ) 3 The solution and the mixed solution of triethylene tetramine and phosphoric acid are kept stand at 80-100 ℃.
Preferably, the HfCl 4 The concentration of the solution is 0.5-3 mol/L; the concentration of the ammonia water is 1-4 mol/L; the Na is 2 Si 2 O 3 The volume ratio of the solution to the nitric acid is 1-3.
Preferably, the Yb (NO) 3 ) 3 The concentration of the solution is0.5-3 mol/L; said H 3 PO 4 The concentration of (B) is 0.5-3 mol/L. Said Yb (NO) 3 ) 3 Solution, triethylene tetramine and H 3 PO 4 The volume ratio of (A) to (B) is 90-120: 3 to 8:90 to 120.
Preferably, the standing in the step (1) and the step (2) is 30 to 150s.
Preferably, the fiber in step (1) and step (2) also comprises the steps of washing with water after the fiber is completely placed, and then drying at 100-140 ℃.
Preferably, the step (1) or the step (2) is repeated for a plurality of times to obtain the coating with the required thickness.
Optionally, the temperature range of the high-temperature heat treatment of S2 is 900-1200 ℃, preferably 950-1000 ℃; the time of high-temperature heat treatment is 0.5 to 5 hours; the sintering treatment adopts gas for protection, and the oxygen partial pressure is not more than 0.1 standard atmospheric pressure, preferably not more than 0.05 standard atmospheric pressure; preferably, the gas to be protected is an inert gas.
The invention provides an application of the high-temperature water-oxygen corrosion resistant fiber composite coating with the sandwich structure in preparation of a fiber material reinforced ceramic matrix composite.
The invention has the following beneficial effects:
(1) the YbPO4 layer sandwiched in the composite material can be used as a mechanical functional layer of the composite interface layer with the sandwich structure, so that the composite interface can still play a role in deflecting cracks and transferring load; (2) YbPO 4 The layer may be in contact with HfO 2 React at the interface layer to form compact Yb 2 Hf 2 O 7 The protective layer is used for enhancing the interlayer combination of the coating and improving the water-oxygen corrosion protective performance of the interface layer; (3) HfO 2 Layer by layer YbPO 4 The layer is isolated from the SiC and other silicon-based fibers and the matrix of the ceramic matrix composite material, so that the reaction of the SiC and the matrix at high temperature is avoided; hfO in high temperature water oxygen environment 2 The layer can also form HfSiO on the surface of SiC fiber in situ 4 A protective layer; (4) the coating with the sandwich structure is particularly suitable for serving as a coating with the resistance to the water-oxygen corrosion of SiC fibers and SiC f The anti-oxyhydrogen corrosion interface layer of the/SiC composite material,the reason for this is HfO 2 Has a coefficient of thermal expansion between SiC and YbPO 4 HfSiO 2 4 Has a coefficient of thermal expansion equivalent to that of SiC, in which case HfO 2 The introduction of the layer also helps to improve the coefficient of thermal expansion matching of the interface layer with the SiC fiber and the matrix.
Drawings
FIG. 1 is a "sandwich structure" HfO 2 /YbPO 4 /HfO 2 Composite interface layer structure and interface function schematic diagram.
FIG. 2 shows (a, b) HfO deposited on the surface of SiC fibers in example 1 2 A single layer coating and (c, d) YbPO 4 /HfO 2 SEM image of composite coating.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions of the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The preparation method of the high-temperature water-oxygen corrosion resistant fiber composite coating with the sandwich structure provided by the invention is specifically explained below.
Some embodiments of the invention provide a preparation method of a high-temperature water-oxygen corrosion resistant fiber composite coating with a sandwich structure, which specifically comprises the following steps: sequentially depositing HfO on the surface of the fiber by a hydrothermal method 2 、YbPO 4 And HfO 2 Forming a coating layer with a sandwich structure; the coating is densified by high temperature heat treatment.
From the structure of the ceramic matrix composite, it is generally necessary to add an interface layer between the fiber and the ceramic matrix (because the interface layer is usually prefabricated on the fiber and then made into the composite, the interface layer of the ceramic matrix composite is actually a coating of the fiber), because: on one hand, the interface layer can form an effective diffusion barrier under the high-temperature oxidation and water vapor atmosphere to achieve the effect of protecting the fibers, and on the other hand, the interface layer also plays the roles of transferring load and deflecting cracks, so that the composite material can greatly improve the strength and the toughness through a fiber pull-out mechanism.
Based on this, the inventor proposes a sandwich structure HfO with excellent water and oxygen corrosion resistance 2 /YbPO 4 /HfO 2 A new idea of composite coating. To further illustrate the core idea of the present invention, take the most applied SiC/SiC composite material (SiC fiber reinforced SiC ceramic matrix composite material) as an example, hfO with "sandwich structure 2 /YbPO 4 /HfO 2 The structure and function of the composite interface layer are schematically shown in figure 1.
Wherein: hfO 2 Layer as YbPO 4 Barrier layer between the layer and SiC fiber and substrate, not only to avoid YbPO 4 The layer reacts with SiC and can also be on HfO 2 A water oxygen barrier layer is formed in situ at the/SiC interface, so that the water oxygen corrosion resistance of the composite material is improved; further, ybPO 4 Can also be mixed with HfO 2 In situ formation of a thin layer Yb at the interface 2 Hf 2 O 7 ，Yb 2 Hf 2 O 7 Is also a substance with better resistance to the corrosion of water and oxygen, and YbPO 4 And HfO 2 The interfacial bonding force of the two can be enhanced. Therefore, the sandwich structure coating designed by the invention can solve the problem of YbPO 4 The interface layer has insufficient high-temperature stability in the application process and can not become a bottleneck problem such as effective diffusion barrier of water vapor and oxygen.
Some embodiments of the present invention provide a method for preparing a sandwich structure high temperature water and oxygen corrosion resistant fiber composite coating, which may specifically include:
s1, sequentially depositing HfO on the surface of the fiber by adopting a hydrothermal method 2 Layer, ybPO 4 Layer and HfO 2 And (3) a layer.
In some preferred embodiments, the deposited coating structure is a "sandwich" structure, wherein the "sandwich" layer is YbPO 4 The other two layers are both HfO 2 (ii) a The sandwich structure coating needs to be uniformly covered on the surface of the fiber; the total thickness of the coating is 300nm to 3 μm, preferably 500nm to 1500nm.
Optionally, the thickness of the "sandwich" layer in the sandwich coating is from 200nm to 2 μm, preferably from 300nm to 1 μm. The other two layers in the sandwich structure coating have the thickness of 50-500 nm, preferably 100-300 nm.
And S2, performing densification sintering on the composite coating with the sandwich structure on the surface of the fiber at high temperature.
In some preferred embodiments, the temperature of the sintering process is in the range of 900 to 1200 ℃, preferably 950 to 1000 ℃; the sintering time is 0.5-5 h; the sintering treatment adopts gas for protection, and the oxygen partial pressure is not higher than 0.1 standard atmospheric pressure; the protective atmosphere is an inert atmosphere, preferably nitrogen.
The features and properties of the present invention are described in further detail below with reference to examples. The room temperature and the unspecified temperature are both 20-35 ℃.
Example 1
Preparing HfCl with the concentration of 1mol/L 4 Immersing SiC fiber in HfCl with a solution of 100mL and an ammonia solution of 100mL at a concentration of 1mol/L 4 And (3) putting the solution into an ultrasonic cleaning machine by using a container, fully dispersing the solution for 30 seconds, quickly putting the solution into an ammonia water solution, standing the solution for 1 minute, taking the solution out, washing the solution by using deionized water, and heating the solution in a 120 ℃ oven for 30 minutes to fully dry the solution. Repeat the above step 2 times. The resulting coating is shown in FIG. 2 (a, b).
(II) preparing Yb (NO) with the concentration of 1mol/L 3 ) 3 Adding 5mL of triethylene tetramine into 100mL of the solution, uniformly mixing, and then placing the solution in a refrigerator at 4 ℃ for refrigerating for 8h; will H 3 PO 4 100mL of the solution with the concentration of 1mol/L is prepared and placed in a refrigerator at 4 ℃ for refrigeration for 8h. After the two solutions were mixed uniformly, the SiC fiber was immersed in the mixed solution, and transferred to ultrasonic cleaning with a container to be sufficiently dispersed for 30 seconds. Then, the solution was quickly transferred to a water bath at 90 ℃ and left to stand for 1 minute, and then taken out. And taking the treated fibers out of the suspension, washing with deionized water, and heating in an oven at 120 ℃ for 30min for fully drying. Repeat the above step 2 times.
And (III) repeating the step (I).
And (IV) transferring the fiber with the coating (with the thickness of about 600 nm) obtained in the step (III) into an atmosphere furnace, treating the fiber at 1000 ℃ for 1h by taking nitrogen as protective gas, cooling the fiber along with the furnace, and taking out the fiber to obtain the fiber material (with the coating thickness of about 600 nm). The resulting coating is shown in FIG. 2 (c, d).
Example 2
Preparing HfCl with concentration of 1mol/L 4 Immersing the C fiber in HfCl with a solution of 100mL and an ammonia solution of 100mL at a concentration of 1mol/L 4 And (3) putting the solution into an ultrasonic cleaning machine by using a container, fully dispersing the solution for 30 seconds, quickly putting the solution into an ammonia solution, standing the solution for 1 minute, taking the solution out, washing the solution by using deionized water, and heating the solution in a 120 ℃ oven for 30 minutes to fully dry the solution. Repeat the above step 2 times.
(II) preparing Yb (NO) with concentration of 1mol/L 3 ) 3 Adding 5mL of triethylene tetramine into 100mL of the solution, uniformly mixing, and then placing the solution in a refrigerator at 4 ℃ for refrigerating for 8h; h is to be 3 PO 4 100mL of solution with the concentration of 1mol/L is prepared and placed in a refrigerator at 4 ℃ for cooling for 8h. After the two solutions were mixed well, the C fiber was immersed in the mixed solution and transferred to ultrasonic cleaning with a container to be sufficiently dispersed for 30 seconds. Then, the solution was quickly transferred to a water bath at 90 ℃ and left to stand for 1 minute, and then taken out. And taking the treated fibers out of the suspension, washing with deionized water, and heating in an oven at 120 ℃ for 30min for fully drying. Repeat the above step 2 times.
And (III) repeating the step (I).
And (IV) transferring the fiber with the coating (with the thickness of about 600 nm) obtained in the step (III) into an atmosphere furnace, treating the fiber at 1000 ℃ for 1h by taking nitrogen as protective gas, cooling the fiber along with the furnace, and taking out the fiber to obtain the fiber material (with the thickness of about 600 nm).
Comparative example 1
(I) preparing Yb (NO) with concentration of 1mol/L 3 ) 3 Adding 5mL of triethylene tetramine into 100mL of the solution, uniformly mixing, and then placing the solution in a refrigerator at 4 ℃ for refrigerating for 8h; h is to be 3 PO 4 100mL of the solution with the concentration of 1mol/L is prepared and placed in a refrigerator at 4 ℃ for refrigeration for 8h. After the two solutions are mixed evenly, siC fibers are immersed into the mixed solution and are moved into a super-high containerThe sonic cleaning was well dispersed for 30 seconds. Then, the solution was quickly transferred to a water bath at 90 ℃ and left to stand for 1 minute, and then taken out. And taking the treated fibers out of the suspension, washing with deionized water, and heating in an oven at 120 ℃ for 30min for fully drying. Repeat the above steps 3 times.
And (II) transferring the fiber with the coating (with the thickness of about 600 nm) obtained in the step (I) into an atmosphere furnace, treating the fiber at 1000 ℃ for 1h by taking nitrogen as protective gas, cooling the fiber along with the furnace, and taking out the fiber to obtain the fiber material (with the coating thickness of about 600 nm).
Comparative example 2
Preparing HfCl with concentration of 1mol/L 4 Immersing SiC fibers in HfCl in a solution of 100mL and an aqueous ammonia solution of 1mol/L of 100mL 4 And (3) putting the solution into an ultrasonic cleaning machine by using a container, fully dispersing the solution for 30 seconds, quickly putting the solution into an ammonia solution, standing the solution for 1 minute, taking the solution out, washing the solution by using deionized water, and heating the solution in a 120 ℃ oven for 30 minutes to fully dry the solution. Repeat the above steps 6 times.
And (II) transferring the fiber with the coating (with the thickness of about 600 nm) obtained in the step (I) into an atmosphere furnace, treating the fiber at 1000 ℃ for 1h by taking nitrogen as protective gas, cooling the fiber along with the furnace, and taking out the fiber to obtain the fiber material (with the coating thickness of about 600 nm).
Example 1 compares the performance with comparative examples 1 and 2:
(1) comparison of toughness and Effect
The SiC fiber material without the coating, the fiber material obtained in the step (IV) of the example 1, the fiber material obtained in the step (II) of the comparative example 1 and the fiber material obtained in the step (II) of the comparative example 2 are subjected to the same resin transfer molding and polymerization impregnation cracking method to obtain the corresponding ceramic matrix composite materials. The test shows that the tensile strength of the ceramic matrix composite material is 247MPa, 362MPa, 319MPa and 239MPa respectively, and the fracture toughness is 15.0 MPa.m 1/2 、21.4MPa·m 1/2 、22.1MPa·m 1/2 And 17.5MPa · m 1/2 . It can be seen that the fiber materials obtained in example 1, comparative example 1 and comparative example 2 all have a significant stiffening effect compared to the fiber material without a coating. However, the composite material of example 1 is comparable to that of the composite materialThe tensile strength is higher in comparative example 1 and comparative example 2, which shows that the fiber materials obtained in the examples have synergistic strengthening and toughening effects on the two interface layers formed on the interface layer of the ceramic matrix composite and the surface of the matrix.
(2) Comparison of resistance to Water sample Corrosion
The fiber material obtained in the step (four) of example 1, the fiber material obtained in the step (two) of comparative example 1, and the fiber material obtained in the step (two) of comparative example 2 were placed in a 1200 ℃ constant temperature tube furnace, and then 90vol.% H was fed into the tube furnace at a rate of 0.1L/min using an oxyhydrogen generator 2 O+10vol.％O 2 And (3) stopping introducing the steam after the steam is subjected to high-temperature water-oxygen corrosion for 5h, cooling the fiber material to room temperature along with the furnace, and taking out the fiber material. The tensile strength of the fiber before and after water-oxygen corrosion is measured, and the result shows that: the retention rate of the tensile strength of the fiber material obtained in the step (IV) of the example 2 is 62.4 percent, the retention rate of the tensile strength of the fiber material obtained in the step (II) of the comparative example 1 is 10.3 percent, and the retention rate of the tensile strength of the fiber material obtained in the step (II) of the comparative example 2 is 51.0 percent.
Example 1 differs from comparative example 1 in that example 1 constitutes a "sandwich" structured coating. It can be seen that the composite coating of example 1 has far better protection against SiC fibers than YbPO of comparative example 1 4 And (4) coating. Example 1 was more resistant to aqueous oxygen corrosion than comparative example 2 due to the formation of dense Yb in the interfacial layer 2 Hf 2 O 7 The protective layer can better enhance interlayer combination of the layers and improve the water oxygen corrosion resistance of the interface layer.
In conclusion, the overall performance of the coating of example 1 of the present invention is significantly better than that of comparative examples 1 and 2. The preparation method of the embodiment of the invention mainly comprises HfO 2 Layer, ybPO 4 Layer and HfO 2 The method has simple process and can solve YbPO 4 The interface layer has insufficient high-temperature stability in the application process and can not become a bottleneck problem such as an effective diffusion barrier of water vapor and oxygen.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The utility model provides a sandwich structure anti high temperature water oxygen corrosion fibre composite coating which characterized in that: the sandwich structure is HfO 2 /YbPO 4 /HfO 2 Wherein the sandwich layer is YbPO 4 The other two layers are both HfO 2 。
2. The sandwich structure high-temperature water-oxygen corrosion resistant fiber composite coating according to claim 1, characterized in that: the YbPO 4 Has a thickness of 200nm to 2 μm, the HfO 2 Each layer of the thickness of (A) is 50-500 nm; the total thickness of the high-temperature water-oxygen corrosion resistant fiber composite coating with the sandwich structure is 300 nm-3 mu m.
3. The sandwich structure high-temperature water-oxygen corrosion resistant fiber composite coating according to claim 1, characterized in that: ybPO 4 Can be replaced by CePO 4 Or YPO 4 。
4. The sandwich structure high-temperature water-oxygen corrosion resistant fiber composite coating according to claim 1, characterized in that: the matrix fiber is one or more of glass fiber, carbon fiber, silicon carbide fiber, silicon nitride fiber, silicon carbon nitrogen fiber and silicon boron carbon nitrogen fiber, or the fiber doped and modified by other elements.
5. A method for preparing the sandwich structure fiber composite coating resistant to high-temperature water-oxygen corrosion of any one of claims 1 to 4, which is characterized by comprising the following steps:
s1: sequentially depositing HfO on the surface of the substrate fiber by a hydrothermal method 2 、YbPO 4 And HfO 2 Obtaining a coating with a sandwich structure;
s2: and (4) densifying the deposited coating by high-temperature heat treatment to obtain the high-temperature water-oxygen corrosion resistant fiber composite coating with a sandwich structure.
6. The process according to claim 5, characterized in that the hydrothermal process of step S1 is in particular: (1) Dipping the fiber into HfCl 4 Dispersing in the solution, then immersing in ammonia solution and standing; (2) The resulting fiber was dried and then dipped into Yb (NO) 3 ) 3 The solution and the mixed solution of triethylene tetramine and phosphoric acid are kept stand at 80-100 ℃.
7. The method of claim 6, wherein the HfCl is present 4 The concentration of the solution is 0.5-3 mol/L; the concentration of the ammonia water is 1-4 mol/L; the Na is 2 Si 2 O 3 The volume ratio of the solution to the nitric acid is 1-3;
said Yb (NO) 3 ) 3 The concentration of the solution is 0.5-3 mol/L; said H 3 PO 4 The concentration of (A) is 0.5-3 mol/L; said Yb (NO) 3 ) 3 Solution, triethylene tetramine and H 3 PO 4 The volume ratio of (A) to (B) is 90-120: 3 to 8:90 to 120.
8. The method of claim 6, wherein the standing time in step (1) and step (2) is 30 to 150 seconds.
9. The preparation method according to claim 5, wherein the temperature of the high-temperature heat treatment of S2 is in the range of 900-1200 ℃; the time of high-temperature heat treatment is 0.5 to 5 hours.
10. Use of the sandwich structured high temperature water oxygen corrosion resistant fiber composite coating according to any one of claims 1 to 4 for preparing a fiber material reinforced ceramic matrix composite.
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