Rapid preparation method of high-solid-solubility multi-element ultra-high-temperature ceramic powder

Abstract

The invention belongs to the technical field of ultrahigh-temperature ceramic powder preparation, and particularly discloses a rapid preparation method of high-solid-solubility multi-element ultrahigh-temperature ceramic powder, which comprises the following steps: S1, taking metal element powder and nano carbon powder as raw materials, and weighing the powder according to a molar ratio for later use; s2, mixing the raw materials in the step 1 by utilizing planetary ball milling and stirring; s3, putting the ball-milled powder mixture into a blast drying oven, and drying at 40-50 DEG C for 24-48 hours; and S4, a vacuum induction furnace is used for preparing solid solution powder under the vacuum condition, the heating rate ranges from 100 DEG C / min to 500 DEG C / min, and the sintering time ranges from 10 min to 30 min. According to the rapid preparation method of the high-solid-solubility multi-element ultra-high-temperature ceramic powder, the prepared solid solution ceramic powder is uniform in element distribution and uniform in phase, required equipment is simple, the speed is high, the cost is low, and large-scale preparation can be achieved.

Description

TECHNICAL FIELD

[0001] The application relates to the technical field of ultrahigh-temperature ceramic powder preparation, in particular to a high-solubility multi-element ultrahigh-temperature ceramic powder rapid preparation method. BACKGROUND

[0002] MeC (Me=Hf, Zr) ultrahigh-temperature ceramics with a melting point of more than 3500 DEG C have been widely studied in the fields of aviation, aerospace and thermal protection due to their good high-temperature stability, high-temperature oxidation resistance and ablation resistance. However, the melting point, hardness and ablation resistance of single HfC or ZrC ceramics prepared by a traditional solid-phase method have been difficult to meet the increasingly extreme performance requirements of thermal protection materials for next-generation ultrahigh-speed aircraft.

[0003] By constructing a multi-element carbide solid solution, the high-temperature mechanical properties, thermal stability and oxidation / ablation resistance of the material can be significantly improved by using the solid solution strengthening effect, which is an important breakthrough direction at present. Raw materials that can be applied to multi-element carbide solid solutions usually include solid solution powders, but existing preparation technologies usually have problems such as complex process flow, high reaction temperature, long cycle, limited solid solubility of products, easy segregation of components and the like, which restrict the efficient preparation and application of the raw materials. Therefore, developing a rapid preparation method for high-solubility multi-element ultrahigh-temperature ceramic powder with uniform composition is of great significance for promoting the practical application of such advanced materials in the fields of aviation and aerospace. SUMMARY

[0004] The application aims to provide a high-solubility multi-element ultrahigh-temperature ceramic powder rapid preparation method, which can prepare solid solution ceramic powder with uniform element distribution and uniform phase, and has the advantages of simple required equipment, fast speed, low cost and large-batch preparation.

[0005] To achieve the above-mentioned purpose, the application provides a high-solubility multi-element ultrahigh-temperature ceramic powder rapid preparation method, which comprises the following steps: S1, using metal element powder and nano carbon powder as raw materials, the powders are weighed according to the molar ratio for standby; S2, the raw materials in step 1 are mixed by using a planetary ball mill; S3, the powder mixture after ball milling is placed in a blast drying oven and dried at 40-50 DEG C for 24-48 h; S4, a solid solution powder is prepared by using a vacuum induction furnace under vacuum conditions, wherein the heating rate is 100-500 DEG C / min, and the sintering time is 10-30 min.

[0006] Preferably, in step S1, the molar ratio of the metal element powder to the nano carbon powder is 1:1, and the metal elements include Zr, Hf, Ti and Ta.

[0007] Preferably, the molar ratio of Zr:Hf:Ti:Ta:nanocarbon powder is 8:6:1:3:18; the molar ratio of Zr:Hf:Ti:nanocarbon powder is 9:6:3:18; the molar ratio of Zr:Hf:Ti:nanocarbon powder is 10:6:2:18.

[0008] Preferably, in step S2, the mixing is performed by planetary ball milling at 150-300 rpm for 6-24 hours, wherein the ball milling tank and the ball milling medium are both zirconium oxide, and the ball-to-material ratio is 5-10:1.

[0009] Preferably, in step S2, alcohol is added as a wet milling medium during the ball milling.

[0010] Preferably, in step S4, the solid solution powder is prepared by a vacuum induction furnace at 2000℃ under vacuum conditions.

[0011] The advantages and beneficial effects of the above-mentioned method for rapidly preparing a high-solid-solution multi-element ultra-high-temperature ceramic powder are: 1. The present application utilizes the active chemical properties of metal powder and nanocarbon powder to cause rapid reaction and diffusion at high temperatures, so that various metal atoms can form compounds with carbon atoms and mutually solid-solve in a short time, and then form multi-element single-phase carbides. Compared with traditional carbothermic reduction and high-temperature solid solution of carbide powder, the multi-element solid solution powder formed has uniform chemical composition and distribution, high solid solution degree, and small powder particle size, due to the rapid and intense reaction.

[0012] 2. The high-temperature vacuum induction furnace can achieve very rapid heating and cooling, and by virtue of this characteristic, the crystallinity of the solid solution powder can be effectively improved, and the phase separation phenomenon during the cooling process can be prevented.

[0013] The technical solutions of the present application will be further described in detail below through the accompanying drawings and examples. BRIEF DESCRIPTION OF DRAWINGS

[0014] Figure 1 The experimental process flowchart of the present application is shown in the following table: Figure 2 The XRD diffraction pattern of Zr8Hf6Ti1Ta3C powder in Example 1 of the present application is shown in the following table: 18 Figure 3 The XRD diffraction pattern of Zr8Hf6Ti1Ta3C powder in Comparative Example 1 of the present application is shown in the following table: 18 Figure 4 The XRD diffraction pattern of Zr9Hf6Ti3C powder in Example 2 of the present application is shown in the following table: 18 Figure 5 ​​​Zr9Hf6Ti3C in Comparative Example 2 of this invention 18 XRD diffraction pattern of the powder; Figure 6 Zr in Embodiment 3 of the present invention 10 Hf6Ti2C 18 XRD diffraction pattern of the powder; Figure 7 Zr in Comparative Example 3 of this invention 10 Hf6Ti2C 18 XRD diffraction pattern of the powder. Detailed Implementation

[0015] The technical solution of the present invention will be further described below with reference to the accompanying drawings and embodiments.

[0016] Unless otherwise defined, the technical or scientific terms used in this invention shall have the ordinary meaning as understood by one of ordinary skill in the art to which this invention pertains.

[0017] The following examples are not intended to limit the invention, but are only for illustration. Unless otherwise specified, the experimental methods used in the following examples are generally performed under conventional conditions. Unless otherwise specified, the materials and reagents used in the following examples are commercially available.

[0018] Example 1 A rapid preparation method for multi-component ultra-high temperature ceramic powder with high solid solubility, such as Figure 1 As shown, it includes the following steps: S1. Using metal element powders Zr, Hf, Ti, Ta and nano carbon powder as raw materials, weigh the powders according to the set molar ratio, wherein the molar ratio of Zr, Hf, Ti, Ta and nano carbon powder is 8:6:1:3:18, and set aside.

[0019] S2. The mixture is stirred at 150 rpm for 24 hours using a planetary ball mill, wherein the ball mill jar and the ball milling media are both zirconium oxide, and the ball-to-material ratio is 10:1.

[0020] S3. Place the ball-milled powder mixture into a forced-air drying oven and dry it at 40°C for 48 hours.

[0021] S4. Solid solution powder was prepared using a vacuum induction furnace under vacuum conditions at 2000℃. The heating rate was 200℃ / min, the sintering time was 20min, and after sintering, the power was turned off and the powder was naturally cooled using an industrial circulating water system, ultimately obtaining a multi-element ultra-high temperature ceramic solid solution powder Zr8Hf6Ti1Ta3C. 18 .

[0022] Comparative Example 1 A method for preparing a high-solubility multi-element ultra-high-temperature ceramic powder, comprising the following steps: S1, using element powders Zr, Hf, Ti, Ta and nano-carbon powder as raw materials, weighing the powders according to the set molar ratio, wherein the molar ratio of Zr, Hf, Ti, Ta and nano-carbon powder is 8:6:1:3:18, and standby.

[0023] S2, mixing by planetary ball milling at 150 rpm for 24 hours, wherein the ball milling tank and the ball milling medium are both zirconia, and the ball-to-material ratio is 10:1.

[0024] S3, placing the ball-milled powder mixture into a blast oven and drying at 40°C for 48h.

[0025] S4, preparing a solid solution powder under vacuum conditions at 2000°C using a vacuum carbon tube furnace, wherein the heating rate is 10°C / min, the sintering time is 60min, the power is turned off after sintering is completed, and the final multi-element ultra-high-temperature ceramic solid solution powder Zr8Hf6Ti1Ta3C 18 .

[0026] Example 2 A method for rapidly preparing a high-solubility multi-element ultra-high-temperature ceramic powder, comprising the following steps: S1, using element powders Zr, Hf, Ti and nano-carbon powder as raw materials, weighing the powders according to the set molar ratio, wherein the molar ratio of Zr, Hf, Ti and nano-carbon powder is 9:6:3:18, and standby.

[0027] S2, mixing by planetary ball milling at 150 rpm for 24 hours, wherein the ball milling tank and the ball milling medium are both zirconia, and the ball-to-material ratio is 10:1.

[0028] S3, placing the ball-milled powder mixture into a blast oven and drying at 40°C for 48h; S4, preparing a solid solution powder under vacuum conditions at 2000°C using a vacuum induction furnace, wherein the heating rate is 200°C / min, the sintering time is 20min, the power is turned off after sintering is completed, and the final multi-element ultra-high-temperature ceramic solid solution powder Zr9Hf6Ti3C 18 .

[0029] Comparative Example 2 A method for preparing a high-solubility multi-element ultra-high-temperature ceramic powder, comprising the following steps: S1, using element powders Zr, Hf, Ti and nano-carbon powder as raw materials, weighing the powders according to the set molar ratio, wherein the molar ratio of Zr, Hf, Ti and nano-carbon powder is 9:6:3:18, and standby.

[0030] S2, mixing by planetary ball milling at 150 rpm for 24 hours, wherein the ball milling tank and the ball milling medium are both zirconium oxide, and the ball-to-material ratio is 10:1.

[0031] S3, placing the powder mixture after ball milling into a blast drying oven, drying at 40℃ for 48h.

[0032] S4, preparing a solid solution powder under vacuum conditions at 2000℃ by using a vacuum induction furnace, wherein the temperature rising rate is 200℃ / min, the sintering time is 20min, and after sintering, the power is turned off and the system is naturally cooled by using an industrial circulating water system, finally obtaining a multi-element ultra-high-temperature ceramic solid solution powder Zr 18 .

[0033] Example 3 A method for rapidly preparing a multi-element ultra-high-temperature ceramic powder with high solid solubility, comprising the following steps: S1, using element powders Zr, Hf, Ti and nano carbon powder as raw materials, weighing the powders according to the set molar ratio, wherein the molar ratio of Zr, Hf, Ti and nano carbon powder is 10:6:2:18, and reserving.

[0034] S2, mixing by planetary ball milling at 150 rpm for 24 hours, wherein the ball milling tank and the ball milling medium are both zirconium oxide, and the ball-to-material ratio is 10:1.

[0035] S3, placing the powder mixture after ball milling into a blast drying oven, drying at 40℃ for 48h.

[0036] S4, preparing a solid solution powder under vacuum conditions at 2000℃ by using a vacuum induction furnace, wherein the temperature rising rate is 200℃ / min, the sintering time is 20min, and after sintering, the power is turned off and the system is naturally cooled by using an industrial circulating water system, finally obtaining a multi-element ultra-high-temperature ceramic solid solution powder Zr 10 Hf6Ti2C 18 .

[0037] Comparative Example 3 A method for preparing a multi-element ultra-high-temperature ceramic powder with high solid solubility, comprising the following steps: S1, using element powders Zr, Hf, Ti and nano carbon powder as raw materials, weighing the powders according to the set molar ratio, wherein the molar ratio of Zr, Hf, Ti and nano carbon powder is 10:6:2:18, and reserving.

[0038] S2, mixing by planetary ball milling at 150 rpm for 24 hours, wherein the ball milling tank and the ball milling medium are both zirconium oxide, and the ball-to-material ratio is 10:1.

[0039] S3, placing the powder mixture after ball milling into a blast drying oven, drying at 40℃ for 48h.

[0040] S4, preparing solid solution powder under 2000℃ vacuum condition by using vacuum carbon tube furnace. The heating rate is 10℃ / min, the sintering time is 60min, and the power is turned off after sintering to cool naturally. Finally, the multi-element ultra-high temperature ceramic solid solution powder Zr 10 Hf6Ti2C 18 .

[0041] Example 4 A method for rapidly preparing a multi-element ultra-high temperature ceramic powder with high solid solubility, comprising the following steps: S1, using metal element powders Zr, Hf, Ti, Ta and nano carbon powder as raw materials, weighing the powders according to the set molar ratio, wherein the molar ratio of Zr, Hf, Ti, Ta and nano carbon powder is 8:6:1:3:18, and standby.

[0042] S2, mixing by using planetary ball milling at 200rpm for 20 hours, wherein the ball milling tank and ball milling medium are both zirconia, and the ball-to-material ratio is 8:1.

[0043] S3, placing the ball-milled powder mixture into a blast drying oven and drying at 45℃ for 40h.

[0044] S4, preparing solid solution powder under 2100℃ vacuum condition by using vacuum induction furnace. The heating rate is 150℃ / min, the sintering time is 25min, and the power is turned off after sintering to cool naturally using industrial circulating water system. Finally, the multi-element ultra-high temperature ceramic solid solution powder is obtained.

[0045] Example 5 A method for rapidly preparing a multi-element ultra-high temperature ceramic powder with high solid solubility, comprising the following steps: S1, using metal element powders Zr, Hf, Ti and nano carbon powder as raw materials, weighing the powders according to the set molar ratio, wherein the molar ratio of Zr, Hf, Ti and nano carbon powder is 9:6:3:18, and standby.

[0046] S2, mixing by using planetary ball milling at 250rpm for 18 hours, wherein the ball milling tank and ball milling medium are both zirconia, and the ball-to-material ratio is 5:1.

[0047] S3, placing the ball-milled powder mixture into a blast drying oven and drying at 48℃ for 36h.

[0048] S4, preparing solid solution powder under 1900℃ vacuum condition by using vacuum induction furnace. The heating rate is 300℃ / min, the sintering time is 15min, and the power is turned off after sintering to cool naturally using industrial circulating water system. Finally, the multi-element ultra-high temperature ceramic solid solution powder is obtained.

[0049] Example 6 A rapid preparation method for multi-element ultra-high temperature ceramic powder with high solid solubility includes the following steps: S1. Using metal element powders Zr, Hf, Ti and nano carbon powder as raw materials, weigh the powders according to the set molar ratio, wherein the molar ratio of Zr, Hf, Ti and nano carbon powder is 10:6:2:18, and set aside.

[0050] S2. The mixture was stirred at 250 rpm for 10 hours using a planetary ball mill, wherein the ball mill jar and the ball milling media were both zirconium oxide, and the ball-to-material ratio was 6:1.

[0051] S3. Place the ball-milled powder mixture into a forced-air drying oven and dry it at 42°C for 30 hours.

[0052] S4. Solid solution powder was prepared using a vacuum induction furnace under vacuum conditions of 1800℃. The heating rate was 300℃ / min, the sintering time was 10min, and after sintering, the power was turned off and the powder was naturally cooled using an industrial circulating water system to finally obtain multi-element ultra-high temperature ceramic solid solution powder.

[0053] X-ray diffraction analysis was performed on the samples obtained in Example 1 and Comparative Example 1, Example 2 and Comparative Example 2, Example 3 and Comparative Example 3 to determine their solid solution degree and phase distribution.

[0054] Table 1 shows the sintering parameters corresponding to Example 1 and Comparative Example 1, Example 2 and Comparative Example 2, Example 3 and Comparative Example 3.

[0055] Table 1 Sintering parameters

[0056] Figures 2-7 The XRD diffraction patterns are shown for Examples 1 and 1, Examples 2 and 2, and Examples 3 and 3, respectively. As can be seen from the figures, the multi-element ultra-high temperature ceramic solid solution powders obtained in Examples 1, 2, and 3 under rapid heating and cooling conditions in a vacuum induction furnace exhibited single crystallization peaks without significant diffraction peak segmentation. Meanwhile, in Comparative Example 1, under slow heating conditions in a vacuum carbon tube furnace, multiple sets of diffraction peaks were clearly observed. Verification confirmed that the excess peaks were TaC, indicating poor solid solution properties. Furthermore, a comprehensive comparison of the main peak widths of the diffraction peaks in Examples 1 and 1, Examples 2 and 2, and Examples 3 and 3 reveals that the solid solution powder prepared using the vacuum induction furnace has a smaller main peak width, indicating higher crystallinity.

[0057] Figure 2 Zr8Hf6Ti1Ta3C in Example 1 18 The XRD diffraction pattern of the powder shows no impurity peaks, indicating a single-phase rock salt structure with uniform distribution of Zr, Hf, Ti, Ta, and C elements.

[0058] Figure 3 Zr8Hf6Ti1Ta3C in Comparative Example 1 18 XRD diffraction pattern of the powder; TaC impurity peak appeared, Ta element was locally enriched, and composition segregation was obvious.

[0059] Figure 4 Zr9Hf6Ti3C in Example 2 18 XRD diffraction pattern of the powder; no impurity peak, single-phase rock salt structure; and element distribution was uniform.

[0060] Figure 5 Zr9Hf6Ti3C in Comparative Example 2 18 XRD diffraction pattern of the powder; weak TiC impurity peak appeared, and composition had slight segregation.

[0061] Figure 6 Zr9Hf6Ti3C in Example 3 10 Hf6Ti2C 18 XRD diffraction pattern of the powder; no impurity peak, single-phase rock salt structure; and element distribution was uniform.

[0062] Figure 7 Zr9Hf6Ti3C in Comparative Example 3 10 Hf6Ti2C 18 XRD diffraction pattern of the powder; weak HfC impurity peak appeared, and composition had slight segregation.

[0063] Therefore, the present application adopts the above-mentioned rapid preparation method of a high-solubility multi-element ultrahigh-temperature ceramic powder, utilizes the active chemical properties of metal powder and nano-carbon powder, makes them rapidly react and diffuse at high temperature, so that various metal atoms can form compounds with carbon atoms and mutually solid-solve in a short time, and then form multi-element single-phase carbide. The prepared solid-solution ceramic powder has uniform element distribution and uniform phase, and the required equipment is simple, fast, low in cost, and can be mass-produced.

[0064] Finally, it should be noted that: the above examples are only used to illustrate the technical solutions of the present application rather than limiting them, although the present application has been described in detail with reference to the preferred embodiments, those skilled in the art should understand that the technical solutions of the present application can still be modified or equivalently replaced, and these modifications or equivalent replacements cannot make the modified technical solutions deviate from the spirit and scope of the technical solutions of the present application.

Claims

1. A method for rapidly preparing a high solid solubility multi-element ultra-high temperature ceramic powder, characterized by, The method comprises the following steps: S1, taking metal element powder and nano-carbon powder as raw materials, and weighing the powders according to a molar ratio; S2, mixing the raw materials of step 1 by using a planetary ball mill; S3, placing the mixed powder after ball milling into a blast drying oven, and drying at 40-50 DEG C for 24-48 h; S4, preparing a solid solution powder under vacuum conditions by using a vacuum induction furnace, wherein the heating rate is 100-500 DEG C / min, and the sintering time is 10-30 min.

2. The method according to claim 1, wherein the method is characterized by: In step S1, the molar ratio of the metal element powder to the nano-carbon powder is 1:1, and the metal elements include Zr, Hf, Ti and Ta.

3. The method according to claim 2, wherein the method is characterized by: The molar ratio of Zr:Hf:Ti:Ta: nano-carbon powder is 8:6:1:3:18; the molar ratio of Zr:Hf:Ti: nano-carbon powder is 9:6:3:18; and the molar ratio of Zr:Hf:Ti: nano-carbon powder is 10:6:2:

18.

4. The method of claim 1, wherein the method is characterized by: In step S2, the mixing is performed by using a planetary ball mill at 150-300 rpm for 6-24 hours, wherein the ball mill tank and the ball mill medium are both zirconia, and the ball-to-material ratio is 5-10:

1.

5. The method of claim 1, wherein the method is characterized by: In step S2, alcohol is added as a wet grinding medium during the ball milling process.

6. The method of claim 1, wherein the method is characterized by: In step S4, the solid solution powder is prepared under vacuum conditions by using a vacuum induction furnace at 1800-2200 DEG C.

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