CN112408984A - High-temperature-resistant near-infrared-absorption high-entropy ceramic and preparation method thereof - Google Patents
High-temperature-resistant near-infrared-absorption high-entropy ceramic and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a high-temperature-resistant near-infrared absorption high-entropy ceramic and a preparation method thereof, wherein the high-entropy ceramic is prepared from the following raw materials in an equal molar ratio: 1 part of yttrium oxide, 1 part of neodymium oxide, 1 part of samarium oxide, 1 part of europium oxide, 1 part of ytterbium oxide, 1 part of erbium oxide, 1 part of niobium oxide and 1 part of tantalum oxide. The high-temperature-resistant near-infrared-absorption high-entropy ceramic has the purity of not less than 99 wt%, the relative density of not less than 98% and the near-infrared band absorption rate of not less than 0.9 in the range of 0.25-2.5 microns. The invention utilizes the high-entropy technology, simultaneously introduces no less than 6 rare earth metal elements into niobium tantalate, adjusts the absorption energy level of forbidden bandwidth to match with the near-infrared wavelength, and obtains the high-temperature-resistant near-infrared absorption high-entropy ceramic, and the process is simple, rapid, flexible and controllable.
Description
Technical Field
The invention belongs to the field of high-temperature thermal protection ceramics, relates to high-temperature-resistant near-infrared-absorption high-entropy ceramics and a preparation method thereof, and particularly relates to high-purity, high-relative-density and high-near-infrared-absorption high-entropy ceramics and a preparation method thereof.
Background
The surface of the thermal protection material of the new generation hypersonic aircraft needs to be coated with a layer of material with high infrared emissivity (i.e. absorptivity) to improve the thermal protection capability of the thermal protection material at high temperature and ultrahigh temperature. However, the emissivity of the existing material with high infrared emissivity is not sufficient in an infrared band, and simultaneously, the existing material also faces the problems of unstable structure and oxidation at high temperature, so that the infrared emissivity of the existing material at high temperature and ultrahigh temperature can be further reduced, the thermal protection capability of the thermal protection material is reduced, and the service reliability of an aircraft is influenced.
At present, infrared protection materials widely applied at home and abroad are mainly non-oxide ceramics, such as silicon carbide or silicon boride, the infrared emissivity of the infrared protection materials can reach about 0.8 to 0.9, however, the non-oxide ceramics have the problem of poor oxidation resistance, and cannot be kept stable for a long time in a high-temperature oxidation atmosphere, so that the thermal protection capability of the thermal protection materials is reduced, and the service reliability of an aircraft is influenced.
On the other hand, in the development of high-temperature oxide system infrared radiation materials, materials represented by cordierite ceramics, ferrite amorphous ceramics, magnetoplumbite hexaaluminate ceramics and the like have attracted much attention, and the infrared emissivity of the materials is generally between 0.7 and 0.84. However, in general, compared with non-oxide ceramics such as silicon carbide and silicon boride, the current oxide ceramics have a significant gap in infrared emissivity.
Disclosure of Invention
The invention aims to overcome the defects and provide a high-temperature-resistant near-infrared absorption high-entropy ceramic material which has the characteristics of high purity, high relative density and high near-infrared absorption.
The invention also aims to provide a preparation method of the high-temperature-resistant near-infrared absorption high-entropy ceramic, which is characterized in that a high-entropy technology is utilized, and no less than 6 rare earth metal elements are simultaneously introduced into niobium tantalate, so that the absorption energy level of the forbidden bandwidth is adjusted to be matched with the near-infrared wavelength, and the high-temperature-resistant near-infrared absorption high-entropy ceramic is obtained.
In order to achieve the above purpose, the invention provides the following technical scheme:
the high-temperature-resistant near-infrared absorption high-entropy ceramic is prepared from the following raw materials in molar ratio:
the types of the cations or metal ions in the high-temperature-resistant near-infrared absorption high-entropy ceramic compound are more than or equal to 5.
The high-temperature-resistant near-infrared absorption high-entropy ceramic compound has the service temperature of more than or equal to 1000 ℃.
In the high-temperature-resistant near-infrared absorption high-entropy ceramic, yttrium oxide, neodymium oxide, samarium oxide, europium oxide, ytterbium oxide, erbium oxide, niobium oxide and tantalum oxide in raw material components are powder materials.
In the high-temperature-resistant near-infrared absorption high-entropy ceramic, the particle sizes of yttrium oxide, neodymium oxide, samarium oxide, europium oxide, ytterbium oxide, erbium oxide, niobium oxide and tantalum oxide in the raw material components are less than or equal to 2 micrometers.
The purity of the high-temperature-resistant near-infrared-absorption high-entropy ceramic is not less than 99 wt%, the relative density is not less than 98%, and the absorption rate in a near-infrared band of 0.25-2.5 microns is not less than 0.9.
The preparation method of the high-temperature-resistant near-infrared absorption high-entropy ceramic comprises the following steps:
(1) mixing the raw material powder with absolute ethyl alcohol in a ball milling tank to obtain uniformly mixed slurry;
(2) drying the obtained slurry to obtain mixed powder, and then putting the mixed powder into a high-temperature furnace for calcining to obtain ceramic powder;
(3) the obtained ceramic powder is put into a discharge plasma sintering furnace for high-temperature sintering, and the atmosphere is vacuum.
In the preparation method of the high-temperature-resistant near-infrared-absorption high-entropy ceramic, in the step (1), the mixing time is 6-12 hours.
In the preparation method of the high-temperature-resistant near-infrared absorption high-entropy ceramic, in the step (2), the calcining temperature is more than or equal to 1450 ℃, and the calcining time is 1-3 h.
In the preparation method of the high-temperature-resistant near-infrared-absorption high-entropy ceramic, in the step (3), the sintering temperature is not lower than the calcination temperature in the step (2).
In the preparation method of the high-temperature-resistant near-infrared absorption high-entropy ceramic, in the step (3), the sintering temperature is 1600-1700 ℃.
In the preparation method of the high-temperature-resistant near-infrared absorption high-entropy ceramic, in the step (3), the sintering time is less than or equal to 30min, and the sintering pressure is 20-40 MPa.
In the preparation method of the high-temperature-resistant near-infrared-absorption high-entropy ceramic, in the step (3), the sintering time is 3-10 min.
In the preparation method of the high-temperature-resistant near-infrared absorption high-entropy ceramic, in the step (3), the sintering temperature rise rate is 50-120 ℃/min.
Compared with the prior art, the invention has the following beneficial effects:
(1) the invention firstly uses Y2O3、Nd2O3、Sm2O3、Eu2O3、Yb2O3、Er2O3、Nb2O5And Ta2O5As a starting material, a novel compound (Y) was obtained1/6Nd1/6Sm1/6Eu1/6Yb1/6Er1/6)3(Nb1/2Ta1/2)O7The high-entropy ceramic has the characteristics of high purity, high relative density and high near-infrared absorption, wherein the purity is over 99 wt%, the relative density is over 98%, and the near-infrared band absorption rate of 0.25-2.5 microns is over 0.9.
(2) The high-entropy ceramic prepared by the invention has good adjustability in purity, relative density and particle size, and can be adjusted by a vacuum high-temperature sintering process.
(3) The high-entropy technology is utilized to carry out discharge plasma sintering under the vacuum condition, not less than 6 rare earth metal elements are simultaneously introduced into niobium tantalate by controlling the sintering temperature and the sintering time, and the absorption energy level of the forbidden bandwidth is adjusted to be matched with the near-infrared wavelength, so that the high-temperature-resistant near-infrared absorption high-entropy ceramic is obtained.
(4) The process for preparing the high-entropy ceramic is simple, rapid, flexible and controllable. From Y2O3、Nd2O3、Sm2O3、Eu2O3、Yb2O3、Er2O3、Nb2O5And Ta2O5The high-entropy ceramic powder is directly obtained from the raw materials, a high-temperature sintering aid is not required to be added in the process, and the high-entropy ceramic is quickly obtained in a short time by a discharge plasma sintering method.
Drawings
FIG. 1 is an X-ray diffraction spectrum of the high-temperature-resistant near-infrared absorption high-entropy ceramic powder prepared in example 1 of the present invention;
FIG. 2 is a near-infrared absorption spectrum of the high-temperature-resistant near-infrared-absorption high-entropy ceramic component prepared in example 1 of the present invention.
Detailed Description
The features and advantages of the present invention will become more apparent and appreciated from the following detailed description of the invention.
The word "exemplary" is used exclusively herein to mean "serving as an example, embodiment, or illustration. Any embodiment described herein as "exemplary" is not necessarily to be construed as preferred or advantageous over other embodiments. While the various aspects of the embodiments are presented in drawings, the drawings are not necessarily drawn to scale unless specifically indicated.
The invention provides a high-temperature-resistant near-infrared absorption high-entropy ceramic which is prepared from the following raw materials in molar ratio:
the types of the cations or metal ions in the high-temperature-resistant near-infrared absorption high-entropy ceramic compound are more than or equal to 5.
The high-temperature-resistant near-infrared absorption high-entropy ceramic compound has the service temperature of more than or equal to 1000 ℃.
Further, Y in the raw material component2O3、Nd2O3、Sm2O3、Eu2O3、Yb2O3、Er2O3、Nb2O5And Ta2O5Is a powder material, and the particle size is preferably not more than 2 microns.
In the present invention, the high-entropy ceramic has a composition of (Y)1/6Nd1/6Sm1/6Eu1/6Yb1/6Er1/6)3(Nb1/2Ta1/2)O7The purity is not less than 99 wt%, the relative density is not less than 98%, and the absorption rate in the near-infrared band of 0.25-2.5 microns is not less than 0.9; wherein, the relative density refers to the theoretical density of the high-entropy ceramics relative to 100% purity.
The invention provides a preparation method of high-temperature-resistant near-infrared absorption high-entropy ceramic, which is used for preparing the high-temperature-resistant near-infrared absorption high-entropy ceramic and comprises the following steps:
(1) mixing the raw material powder of the high-entropy ceramic with absolute ethyl alcohol in a ball milling tank to obtain uniformly mixed slurry;
(2) drying the obtained slurry to obtain mixed powder, and calcining the dried powder in a high-temperature furnace to obtain ceramic powder;
(3) and (3) putting the obtained ceramic powder into a discharge plasma sintering furnace for high-temperature sintering, wherein the atmosphere is vacuum, the sintering temperature is not lower than the calcining temperature in the step (2), the sintering time is not longer than 30min, and the sintering pressure is controlled to be 20-40 MPa, so that the high-entropy ceramic block is obtained.
In a preferred embodiment, in step (2), the calcination temperature is not less than 1450 ℃ and the calcination time is 1-3 h. In the present invention, the purpose of calcination is to synthesize high-entropy ceramic powder.
In a preferred embodiment, in the step (3), the sintering temperature is 1600-1800 ℃ and the sintering time is 3-10 min; preferably, the sintering temperature is 1650-1700 ℃, and the sintering time is 3-5 min.
In the present invention, the sintering is performed to obtain a high-entropy ceramic block having high density and high near-infrared absorption. Research shows that the sintering temperature and the sintering time are closely related to the density and near infrared absorption of a final product, the sintering temperature and the sintering time mainly affect the density of the ceramic material, and if the sintering temperature is too low and is lower than the minimum value of the range, the powder cannot be diffused to obtain a high-entropy niobium tantalate ceramic block with the density higher than 98%; if the sintering temperature is too high and is higher than the maximum value of the range, the powder diffusion speed is too high, pores which cannot be eliminated are formed inside the block, and then the high-entropy ceramic block with the density higher than 98% cannot be obtained. If the sintering time is too short and is lower than the minimum value of the range, the powder is not sufficiently diffused, and a high-entropy niobium tantalate ceramic block with the density higher than 98% cannot be obtained; if the sintering time is too long and is higher than the maximum value of the above range, the energy consumption level is significantly increased but the density of the block cannot be further increased. Meanwhile, the reduction of the density can cause the infrared absorptivity, namely the emissivity, to be reduced. Therefore, in order to achieve the infrared absorption rate of 0.90, the sintering temperature and time of the product need to be controlled, the optimal sintering temperature is 1600-1700 ℃, and the sintering time is 3-10 min.
In a preferred embodiment, in the step (3), the sintering pressure is controlled to be 30-40 MPa.
In a preferred embodiment, in the step (3), the temperature rise rate is 50-120 ℃/min; preferably, the temperature is 80-100 ℃/min. The heating rate is important for the density and near infrared absorption of the final product, and if the heating rate is smaller and lower than the minimum value of the range, the ceramic sintering process is prolonged, the energy consumption is increased, and the density of the block cannot be increased; if the temperature rise rate is larger than the maximum value of the range, the density of the final product is too low.
In the invention, the preparation method also comprises a high-entropy ceramic crushing treatment process, and the high-entropy ceramic is pulverized by a ball milling mode.
The raw material sources of the examples and the comparative examples in the invention are as follows: y is2O3(Beijing Huawei Ruiko chemical Co., Ltd., purity 99.9%); nd (neodymium)2O3(Beijing Huawei Ruiko chemical Co., Ltd., purity 99.9%); sm2O3(Beijing Huawei Ruiko chemical Co., Ltd., purity 99.9%); eu (Eu)2O3(Beijing Huawei Ruiko chemical Co., Ltd., purity 99.9%); yb of2O3(Beijing Huawei Ruiko chemical Co., Ltd., purity 99.9%); er2O3(Beijing Huawei Ruiko chemical Co., Ltd., purity 99.9%); nb2O5(ii) a (Beijing Huawei Rui Ke chemical Co., Ltd., purity 99.9%) Ta2O5(Beijing Huawei Ruiko chemical Co., Ltd., purity 99.9%); high temperature furnace (Tianjin Zhonghuan electric furnace Co., Ltd., sx-G01163); spark plasma sintering furnaces (Shanghai Chenghua electric furnace Co., Ltd., SPS-20T-6-IV).
Example 1
Will Y2O3、Nd2O3、Sm2O3、Eu2O3、Yb2O3、Er2O3、Nb2O5And Ta2O5According to Y2O3∶Nd2O3∶Sm2O3∶Eu2O3∶Yb2O3∶Er2O3∶Nb2O5∶Ta2O5Weighing according to the molar ratio of 1: 1, mixing in a ball milling tank for 6 hours, and obtaining slurry by using anhydrous ethyl alcohol as a mixing medium; filtering the obtained slurry, drying to obtain mixture powder, calcining the dried powder in a high temperature furnace at 1450 deg.C for 2 hr to obtain high entropy (Y)1/6Nd1/6Sm1/6Eu1/6Yb1/6Er1/6)3(Nb1/2Ta1/2)O7Ceramic powder. Putting high-entropy ceramic powder into a discharge plasma sintering furnaceThe high-temperature sintering is carried out in vacuum, the sintering temperature is 1650 ℃, the sintering time is 4min, the sintering pressure is controlled to be 40MPa, the vacuum degree is 8Pa, the heating rate is 100 ℃/min, the purity of the obtained high-temperature-resistant near-infrared absorption high-entropy ceramic is 100 wt%, the relative density is 98%, and the absorption rate in the near-infrared band of 0.25-2.5 microns is 0.91. The obtained high-entropy ceramic component is shown in an X-ray diffraction pattern of figure 1, and the absorption performance of the high-entropy ceramic in a near infrared band of 0.25-2.5 microns is shown in an absorption pattern method of figure 2. Shows that near infrared absorption high-entropy ceramic with the purity not less than 99 wt% can be prepared when the high-temperature reaction temperature is 1450 ℃.
Example 2
Will Y2O3、Nd2O3、Sm2O3、Eu2O3、Yb2O3、Er2O3、Nb2O5And Ta2O5According to Y2O3∶Nd2O3∶Sm2O3∶Eu2O3∶Yb2O3∶Er2O3∶Nb2O5∶Ta2O5Weighing according to the molar ratio of 1: 1, mixing in a ball milling tank for 6 hours, and obtaining slurry by using anhydrous ethyl alcohol as a mixing medium; filtering the obtained slurry, drying to obtain mixture powder, calcining the dried powder in a high temperature furnace at 1450 deg.C for 2 hr to obtain high entropy (Y)1/6Nd1/6Sm1/6Eu1/6Yb1/6Er1/6)3(Nb1/2Ta1/2)O7Ceramic powder. The high-entropy ceramic powder is put into a discharge plasma sintering furnace for high-temperature sintering, the atmosphere is vacuum, the sintering temperature is 1600 ℃, the sintering time is 10min, the sintering pressure is controlled to be 40MPa, the vacuum degree is 8Pa, the heating rate is 120 ℃/min, the purity of the obtained high-temperature-resistant near-infrared absorption high-entropy ceramic is 100 wt%, the relative density is 98%, and the absorption rate in a near-infrared band of 0.25-2.5 microns is 0.90.
Comparative example 1
Will Y2O3、Nd2O3、Sm2O3、Eu2O3、Yb2O3、Er2O3、Nb2O5And Ta2O5According to Y2O3∶Nd2O3∶Sm2O3∶Eu2O3∶Yb2O3∶Er2O3∶Nb2O5∶Ta2O5Weighing according to the molar ratio of 1: 1, mixing in a ball milling tank for 6 hours, and obtaining slurry by using anhydrous ethyl alcohol as a mixing medium; filtering the obtained slurry, drying to obtain mixture powder, calcining the dried powder in a high temperature furnace at 1450 deg.C for 2 hr to obtain high entropy (Y)1/6Nd1/6Sm1/6Eu1/6Yb1/6Er1/6)3(Nb1/2Ta1/2)O7Ceramic powder. The high-entropy ceramic powder is placed into a discharge plasma sintering furnace for high-temperature sintering, the atmosphere is vacuum, the sintering temperature is 1400 ℃, the sintering time is 15min, the sintering pressure is controlled to be 40MPa, the vacuum degree is 8Pa, the heating rate is 100 ℃/min, the purity of the obtained high-temperature-resistant near-infrared absorption high-entropy ceramic is 100 wt%, the relative density is 95%, and the absorption rate in a near-infrared band of 0.25-2.5 microns is 0.88. It can be seen that sintering temperatures below the desired range are not conducive to obtaining high-entropy ceramics with high density.
Comparative example 2
Will Y2O3、Nd2O3、Sm2O3、Eu2O3、Yb2O3、Er2O3、Nb2O5And Ta2O5According to Y2O3∶Nd2O3∶Sm2O3∶Eu2O3∶Yb2O3∶Er2O3∶Nb2O5∶Ta2O5Weighing according to the molar ratio of 1: 1, mixing in a ball milling tank for 6 hours, and obtaining slurry by using anhydrous ethyl alcohol as a mixing medium; filtering the obtained slurry, drying to obtain mixture powder, calcining the dried powder in a high temperature furnace at 1450 deg.C for 2 hr to obtain high entropy (Y)1/6Nd1/6Sm1/6Eu1/6Yb1/6Er1/6)3(Nb1/2Ta1/2)O7Ceramic powder. The high-entropy ceramic powder is put into a discharge plasma sintering furnace for high-temperature sintering, the atmosphere is vacuum, the sintering temperature is 1950 ℃, the sintering time is 15min, the sintering pressure is controlled to be 40MPa, the vacuum degree is 8Pa, the heating rate is 100 ℃/min, the purity of the obtained high-temperature-resistant near-infrared absorption high-entropy ceramic is 100 wt%, the relative density is 98%, and the absorption rate in a near-infrared band of 0.25-2.5 microns is 0.91. Therefore, the density and the near infrared absorption performance of the high-entropy ceramic cannot be improved when the sintering temperature is higher than the required range.
The invention has been described in detail with reference to specific embodiments and illustrative examples, but the description is not intended to be construed in a limiting sense. Those skilled in the art will appreciate that various equivalent substitutions, modifications or improvements may be made to the technical solution of the present invention and its embodiments without departing from the spirit and scope of the present invention, which fall within the scope of the present invention. The scope of the invention is defined by the appended claims.
Those skilled in the art will appreciate that those matters not described in detail in the present specification are well known in the art.
Claims (12)
1. The high-temperature-resistant near-infrared absorption high-entropy ceramic is characterized by being prepared from the following raw materials in molar ratio:
2. the high-temperature-resistant near-infrared-absorbing high-entropy ceramic of claim 1, wherein yttrium oxide, neodymium oxide, samarium oxide, europium oxide, ytterbium oxide, erbium oxide, niobium oxide, and tantalum oxide in the raw material components are powder materials.
3. The high-temperature-resistant near-infrared-absorbing high-entropy ceramic of claim 1, wherein the grain sizes of yttrium oxide, neodymium oxide, samarium oxide, europium oxide, ytterbium oxide, erbium oxide, niobium oxide and tantalum oxide in the raw material components are less than or equal to 2 microns.
4. The high-temperature-resistant near-infrared-absorption high-entropy ceramic according to claim 1, wherein the purity of the high-temperature-resistant near-infrared-absorption high-entropy ceramic is not less than 99 wt%, the relative density is not less than 98%, and the absorptivity of the high-temperature-resistant near-infrared-absorption high-entropy ceramic in a near-infrared band of 0.25-2.5 micrometers is not less than 0.9.
5. The preparation method of the high-temperature-resistant near-infrared-absorption high-entropy ceramic according to any one of claims 1 to 3, characterized by comprising the following steps:
(1) mixing the raw material powder with absolute ethyl alcohol in a ball milling tank to obtain uniformly mixed slurry;
(2) drying the obtained slurry to obtain mixed powder, and then calcining to obtain ceramic powder;
(3) the obtained ceramic powder is put into a discharge plasma sintering furnace for high-temperature sintering, and the atmosphere is vacuum.
6. The preparation method of the high-temperature-resistant near-infrared-absorption high-entropy ceramic according to claim 5, wherein in the step (1), the mixing time is 6-12 h.
7. The preparation method of the high-temperature-resistant near-infrared-absorption high-entropy ceramic as claimed in claim 5, wherein in the step (2), the calcination temperature is not less than 1450 ℃, and the calcination time is 1-3 h.
8. The method for preparing high-temperature-resistant near-infrared-absorption high-entropy ceramics according to claim 5, wherein in the step (3), the sintering temperature is not lower than the calcination temperature in the step (2).
9. The method for preparing high-temperature-resistant near-infrared absorption high-entropy ceramics according to any one of claims 5 or 8, wherein in the step (3), the sintering temperature is 1600-1700 ℃.
10. The preparation method of the high-temperature-resistant near-infrared-absorption high-entropy ceramic as claimed in claim 5, wherein in the step (3), the sintering time is less than or equal to 30min, and the sintering pressure is 20-40 MPa.
11. The preparation method of the high-temperature-resistant near-infrared-absorption high-entropy ceramic according to claim 10, wherein in the step (3), the sintering time is 3-10 min.
12. The preparation method of the high-temperature-resistant near-infrared-absorption high-entropy ceramic according to claim 5, wherein in the step (3), the sintering temperature rise rate is 50-120 ℃/min.
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