CN119912276A - A method for preparing a C/C composite material high entropy ceramic coating - Google Patents
A method for preparing a C/C composite material high entropy ceramic coating Download PDFInfo
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- CN119912276A CN119912276A CN202510161541.0A CN202510161541A CN119912276A CN 119912276 A CN119912276 A CN 119912276A CN 202510161541 A CN202510161541 A CN 202510161541A CN 119912276 A CN119912276 A CN 119912276A
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Abstract
本发明提供了一种C/C复合材料高熵陶瓷涂层的制备方法，采用放电等离子烧结方法，通过短时间内烧结等原子比的难熔碳化物混合粉末，实现了在C/C复合材料表面制备高熵陶瓷涂层，减少了对于基体的热损伤，拓展了C/C复合材料陶瓷涂层的制备方法。解决了现有C/C复合材料抗氧化涂层制备工艺复杂、热损伤较大、涂层防护温度有限的问题，提高了难熔陶瓷涂层的制备效率。
The present invention provides a method for preparing a high-entropy ceramic coating of a C/C composite material, which adopts a spark plasma sintering method, and realizes the preparation of a high-entropy ceramic coating on the surface of a C/C composite material by sintering a mixed powder of refractory carbides with an equal atomic ratio in a short time, thereby reducing the thermal damage to the substrate and expanding the preparation method of the C/C composite material ceramic coating. The problems of the existing C/C composite material anti-oxidation coating having a complex preparation process, large thermal damage, and limited coating protection temperature are solved, and the preparation efficiency of the refractory ceramic coating is improved.
Description
Technical Field
The invention relates to the field of preparation of high-temperature thermal protection structures, in particular to a preparation method of a high-entropy ceramic coating of a C/C composite material. The invention can improve the preparation efficiency of the C/C composite material thermal protection ceramic coating and reduce the thermal damage to the C/C composite material.
Background
With the rapid development of aerospace technology, higher requirements are put on rocket propulsion technology. The jet pipe is used as a key component of a thrust chamber on a rocket engine, and the used material has the characteristics of light weight, high strength, high temperature resistance, ablation resistance and the like. The carbon fiber reinforced carbon-based composite material (C/C composite material) is a high-performance material which is rapidly developed and applied in the aerospace field in recent years, has the characteristics of light specific gravity, strong heat conduction capacity, excellent thermal shock resistance, friction and abrasion resistance, good high-temperature performance and the like, and is one of the best choices for producing and preparing the jet pipe material of the aerospace engine at present. However, the C/C composite material oxidizes above 350 ℃ resulting in a dramatic decrease in its properties. The anti-oxidation coating technology can isolate the direct contact between the C/C composite material and the aerobic atmosphere, and realize the anti-oxidation protection at a longer time and a higher temperature, thereby improving the anti-oxidation, high temperature resistance and ablation resistance of the C/C composite material, and being the most widely and most mature anti-oxidation protection technology at present.
The ceramic coating is the most deeply studied antioxidation coating of the C/C composite material at present, and the silicon-based ceramic coating is used as the most widely used ceramic coating at present, but the effective protection temperature is below 1500 ℃, and the effective protection is difficult to form for the ultra-high temperature environment above 1800 ℃. In order to meet the more severe high Wen Fuyi requirements of the jet pipe material of the space engine, chemical vapor deposition technology and plasma spraying technology are mainly adopted at home and abroad to prepare HfC, zrC, taC and other single-component refractory metal carbide ceramic coatings on the surface of the C/C composite material. The chemical vapor deposition technology has the defects of long preparation period, low deposition rate, complex process and the like, while the coating prepared by the plasma spraying technology has higher porosity, weaker interface combination of the coating and a matrix, and the coating is easy to peel off, crack and the like during high-temperature thermal cycle. In addition, most of the prior refractory metal carbide ceramic coatings are single components, and researches and reports on multi-component refractory high-entropy ceramic coatings with more excellent mechanical properties and high-temperature stability are very few.
Chinese patent CN 108530110A discloses an ultra-high temperature ceramic coating of C/C composite material and a method for preparing the same. The method comprises the steps of firstly preparing a layer of SiC coating on the surface of a C/C composite material in a high-temperature furnace through a chemical gas phase reaction method, and then spraying ultra-high temperature ceramic powder (one or more of SiC, zrC, hfC, taC, tiC, zrB, hfB2, taB2 and TiB 2) on the surface of the SiC coating by adopting a plasma spraying machine, so as to form a composite coating with an inner layer of SiC and an outer layer of ultra-high temperature ceramic. The method has complex preparation process, and the inner protective coating and the outer protective coating are prepared by adopting two different processes successively. When the SiC inner coating is prepared, the SiC inner coating is heated for 2 hours at the temperature of more than 2000 ℃, then the plasma is adopted for repeatedly spraying to prepare the outer superhigh temperature ceramic coating, and a heat source with long-time heating and high energy density easily causes larger thermal damage to the C/C composite material. In addition, the effective protection temperature of the prepared SiC inner coating is low (below 1500 ℃), and effective ultra-high temperature protection is difficult to form.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides a preparation method of a C/C composite material high-entropy ceramic coating. The invention provides a novel preparation method of a ceramic coating and a high-entropy ceramic coating prepared from a C/C composite material. The invention aims to solve the problems of complex preparation process, long heating time, easiness in thermal damage and the like of the conventional C/C composite material antioxidation coating, and provides a novel ceramic coating preparation method. The carbide mixed powder is sintered in a spark plasma sintering furnace, so that the high-entropy ceramic coating is prepared on the surface of the C/C composite material in situ.
The invention provides a method for preparing a high-entropy ceramic coating on the surface of a C/C composite material in a short time, which solves the problems of complex preparation process, large thermal damage and limited coating protection temperature of the traditional C/C composite material oxidation-resistant coating, and improves the preparation efficiency of a refractory ceramic coating. According to the invention, a spark plasma sintering method is adopted, and the refractory carbide mixed powder with equal atomic ratio is sintered in a short time, so that the preparation of the high-entropy ceramic coating on the surface of the C/C composite material is realized, the thermal damage to a matrix is reduced, and the preparation method of the C/C composite material ceramic coating is expanded.
The technical scheme adopted by the invention for solving the technical problems comprises the following steps:
1) Weighing carbide powder according to the proportion of each component in the high-entropy ceramic, and ball-milling the weighed powder uniformly;
2) Weighing the required carbide mixed powder, and uniformly spreading the carbide mixed powder on the surface of the C/C composite material;
3) C/C composite material of the spread carbide mixed powder is put into a graphite mould and is put into a discharge plasma sintering furnace for prepressing;
4) After prepressing, heating, heat preservation and cooling are continuously carried out in a discharge plasma sintering furnace, and sintering molding of carbide mixed powder is completed;
5) And (3) carrying out surface grinding, polishing and drying on the sintered and molded C/C composite material high-entropy ceramic coating obtained in the step (4) to obtain the final C/C composite material high-entropy ceramic coating.
Further, in the step 1), the proportion of each component in the (ZrHfNbTa) C high-entropy ceramic coating is Zr to Hf to Nb to Ta=1 to 1, the carbide powder is weighed according to the equal molar ratio, the carbide powder comprises ZrC powder, hfC powder, nbC powder and TaC powder, the carbide powder weighed according to the equal molar ratio is mixed, the mixed carbide powder is placed in a ball milling tank, and the ball milling is carried out in a planetary ball mill for 12-24 hours, so that the mixed powder is uniformly ball milled.
In the step 2), 0.4-0.6 g of carbide mixed powder is weighed from the ball-milling powder by an electronic balance, the carbide mixed powder is sieved, the mesh number of the sieve is 200-400, and the carbide mixed powder is uniformly spread on the surface of the C/C composite material with the specification of 10mm multiplied by 5 mm.
Further, in the step 3), the specification of the graphite mold is phi 20mm, the graphite mold is pre-pressed in a discharge plasma sintering furnace, the pre-pressing pressure is 5-10 kN, the time is 10-20 min, and the graphite mold is performed at room temperature;
further, the specific steps of the step 4) are as follows:
And (3) sintering the carbide mixed powder in a spark plasma sintering furnace, wherein the sintering pressure is 5-10 kN, the heating rate is 50-100 ℃ per minute, the sintering temperature is 1500-2000 ℃, the sintering time is 10-30 min, and the cooling rate is 50-100 ℃ per minute, so that the C/C composite material (ZrHfNbTa) C high-entropy ceramic coating is obtained.
Further, in the step 5), the prepared C/C composite material high-entropy ceramic coating is ground and polished by adopting sand paper with the mesh number of 200# and the surface of the coating is dried by using a blower.
Meanwhile, the invention also provides a C/C composite material high-entropy ceramic coating which is manufactured by adopting the method.
The C/C composite material high-entropy ceramic coating prepared by the method comprises (ZrHfNbTa) C, any four of refractory metal elements Ti, V, cr, zr, nb, mo, hf, ta, W and high-entropy ceramic coating formed by any more than four elements and C element.
The invention has the beneficial effects that:
1. The prior ceramic coating is mostly a SiC coating, which is difficult to protect the C/C composite material in an ultra-high temperature environment of more than 1800 ℃, while the prior refractory metal carbide ceramic coating is mostly a single component, so that researches on the preparation of the high-entropy ceramic coating with more excellent mechanical properties and high-temperature stability are carried out.
2. The preparation method of the ultra-high temperature ceramic coating, namely the spark plasma sintering process, can promote the rapid sintering and forming of the coating under the auxiliary effect of pulse direct current, has short heating time and smaller thermal damage to the C/C composite material.
3. The invention also has reference significance for preparing the single-component refractory carbide ceramic coating of the C/C composite material.
Drawings
FIG. 1 is a schematic diagram of the graphite mold assembly of the present invention;
FIG. 2 is a spark plasma sintering heating curve of the present invention;
FIG. 3 is a back-scattered electron image of a C/C composite material high-entropy ceramic coating prepared by the invention under a scanning electron microscope, wherein (a) is the overall morphology of the coating, (b) is the morphology of the bonding interface between the coating and a substrate, and (C) is the enlarged morphology of the bonding interface between the coating and the substrate;
FIG. 4 is an EDS element plane distribution image of the C/C composite material high-entropy ceramic coating prepared by the invention under a scanning electron microscope.
Detailed Description
The invention will be further described with reference to the drawings and examples.
A preparation method of a C/C composite material high-entropy ceramic coating comprises the following steps:
1) Weighing carbide mixed powder of ZrC powder, hfC powder, nbC powder and TaC powder according to the proportion of each component in the (ZrHfNbTa) C high-entropy ceramic coating which is finally required to be prepared, wherein the components are Zr to Hf to Nb to Ta=1:1:1:1 in an equimolar ratio, the total weight of the carbide mixed powder is 100g, and putting the mixed carbide mixed powder into a ball milling tank, and putting the ball milling tank into a planetary ball mill for ball milling for 12 hours to ensure that the ball milling is uniform;
2) Weighing 0.5g of carbide mixed powder from the ball-milling powder by using an electronic balance, wherein the mesh number of the sieve is 200 meshes, and uniformly spreading the carbide mixed powder on the surface of a C/C composite material with the specification of 10mm multiplied by 5 mm;
3) Placing the C/C composite material of the spread carbide mixed powder into a graphite mold, wherein the specification of the graphite mold is phi 20mm, an assembly schematic diagram is shown in figure 1, pre-pressing the assembled graphite mold in a discharge plasma sintering furnace, the pre-pressing pressure is 5kN, the time is 10min, and the process is carried out at room temperature;
4) Sintering mixed carbide powder in a spark plasma sintering furnace, wherein the sintering pressure is 5kN, the heating rate is 100 ℃ per minute, the sintering temperature is 2000 ℃, the sintering time is 30 minutes, the cooling rate is 100 ℃ per minute, and a spark plasma sintering heating curve is shown in fig. 2, so that a C/C composite material (ZrHfNbTa) C high-entropy ceramic coating is obtained;
5) And (3) grinding and polishing the prepared C/C composite material high-entropy ceramic coating by adopting sand paper with the mesh number of 200# and drying the surface of the coating by using a blower.
In order to test the quality of the C/C composite material high-entropy ceramic coating prepared by the preparation method, the prepared C/C composite material high-entropy ceramic coating is cut along the direction perpendicular to the interface bonding direction to prepare a metallographic specimen. The structure of the coating in the joint was observed under a scanning electron microscope, as shown in FIG. 3, the thickness of the coating was about 500. Mu.m, the whole was continuous and dense, no pores and cracks were observed, and the interface bonding of the coating and the substrate was tight. EDS point analysis was performed on different locations of the coated tissue and the results are shown in table 1:
TABLE 1 EDS analysis results for each location/region in FIG. 3 (b)
Table 1 shows EDS analysis results of each position/region in the high-entropy ceramic coating of the C/C composite material in (b) of FIG. 3, and it can be seen that the atomic ratio of Zr, hf, nb, ta elements in each position/region is basically close to 1:1:1:1, which indicates that a (ZrHfNbTa) C high-entropy ceramic coating structure with relatively uniform composition is prepared on the surface of the C/C composite material, and a high-entropy ceramic coating with uniform composition can be prepared on the surface of the C/C composite material by adopting a spark plasma sintering technology. EDS characterization was performed on the surface distribution of each element of the coating, as shown in fig. 4, with a very uniform distribution of Zr, hf, nb, ta elements.
The method can prepare the high-entropy ceramic coating on the surface of the C/C composite material in a short time, reduces the thermal damage of the preparation process to the C/C composite material, can also play a reference role in preparing single-component refractory metal carbide ceramic coatings and multi-component high-entropy ceramic coatings of other types of the C/C composite material, and realizes the ultra-high temperature application of the C/C composite material oxidation-resistant coating above 1800 ℃.
Claims (8)
1. The preparation method of the C/C composite material high-entropy ceramic coating is characterized by comprising the following steps of:
1) Weighing carbide powder according to the proportion of each component in the high-entropy ceramic, and ball-milling the weighed powder uniformly;
2) Weighing the required carbide mixed powder, and uniformly spreading the carbide mixed powder on the surface of the C/C composite material;
3) C/C composite material of the spread carbide mixed powder is put into a graphite mould and is put into a discharge plasma sintering furnace for prepressing;
4) After prepressing, heating, heat preservation and cooling are continuously carried out in a discharge plasma sintering furnace, and sintering molding of carbide mixed powder is completed;
5) And (3) carrying out surface grinding, polishing and drying on the sintered and molded C/C composite material high-entropy ceramic coating obtained in the step (4) to obtain the final C/C composite material high-entropy ceramic coating.
2. The method for preparing the high-entropy ceramic coating of the C/C composite material according to claim 1, which is characterized in that:
in the step 1), the proportion of each component in the (ZrHfNbTa) C high-entropy ceramic coating is Zr, hf and Nb:
Ta=1:1:1:1, weighing carbide powder in an equimolar ratio, wherein the carbide powder comprises ZrC powder, hfC powder, nbC powder and TaC powder, mixing the carbide powder weighed in the equimolar ratio, putting the mixed carbide powder into a ball milling tank, and putting the mixed carbide powder into a planetary ball mill for ball milling for 12-24 hours to ensure that the mixed powder is uniformly ball milled.
3. The method for preparing the high-entropy ceramic coating of the C/C composite material according to claim 1, which is characterized in that:
In the step 2), 0.4-0.6 g of carbide mixed powder is weighed from ball milling powder by an electronic balance, the carbide mixed powder is sieved, the mesh number of the sieve is 200-400, and the carbide mixed powder is uniformly spread on the surface of the C/C composite material with the specification of 10mm multiplied by 5 mm.
4. The method for preparing the high-entropy ceramic coating of the C/C composite material according to claim 1, which is characterized in that:
In the step 3), the specification of the graphite mold is phi 20mm, the graphite mold is pre-pressed in a spark plasma sintering furnace, the pre-pressing pressure is 5-10 kN, the time is 10-20 min, and the graphite mold is performed at room temperature.
5. The method for preparing the high-entropy ceramic coating of the C/C composite material according to claim 1, which is characterized in that:
the specific steps of the step 4) are as follows:
And (3) sintering the carbide mixed powder in a spark plasma sintering furnace, wherein the sintering pressure is 5-10 kN, the heating rate is 50-100 ℃ per minute, the sintering temperature is 1500-2000 ℃, the sintering time is 10-30 min, and the cooling rate is 50-100 ℃ per minute, so that the C/C composite material (ZrHfNbTa) C high-entropy ceramic coating is obtained.
6. The method for preparing the high-entropy ceramic coating of the C/C composite material according to claim 1, which is characterized in that:
in the step 5), the prepared C/C composite material high-entropy ceramic coating is ground and polished by adopting sand paper with the mesh number of 200# and the surface of the coating is dried by using a blower.
7. A C/C composite material high-entropy ceramic coating is characterized in that the C/C composite material high-entropy ceramic coating is manufactured by the method of claims 1-6.
8. The C/C composite high entropy ceramic coating according to claim 7, wherein:
the C/C composite material high-entropy ceramic coating comprises (ZrHfNbTa) C, any four of refractory metal elements Ti, V, cr, zr, nb, mo, hf, ta, W and high-entropy ceramic coating consisting of more than any four elements and C element.
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