CN115259900A - Very long (Ta)xHf1-x) C ultra-high temperature ceramic solid solution nanowire and preparation method thereof - Google Patents
Very long (Ta)xHf1-x) C ultra-high temperature ceramic solid solution nanowire and preparation method thereof Download PDFInfo
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- 239000006104 solid solution Substances 0.000 title claims abstract description 59
- 239000011215 ultra-high-temperature ceramic Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
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- 238000000034 method Methods 0.000 claims abstract description 21
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- 238000002791 soaking Methods 0.000 claims description 24
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- 238000005229 chemical vapour deposition Methods 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 17
- 229910004537 TaCl5 Inorganic materials 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 11
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 8
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
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Abstract
The invention relates to an extremely long (Ta)xHf1‑x) C ultra-high temperature ceramic solid solution nanowire and a preparation method thereof, the ultra-long solid solution nanowire with ultra-high melting point and more excellent toughness is developed, and the requirements of controlling the components and the morphology are met by adjusting process parameters, so that the controllable reinforcement of the composite material and the controllable toughening of the ultra-high temperature ceramic under the extreme environment are realized. (Ta)xHf1‑x) The ultra-high melting point, low thermal expansion coefficient and more excellent ablation resistance of the C solid solution are excellent choices of a reinforcing phase and a toughening phase. In addition, the preparation method is simple in preparation process, convenient to operate, suitable for various matrixes with simple shapes and complex shapes, and capable of preparing (Ta) with uniform and continuous product, high yield and high purityxHf1‑x) C ultra-high temperature ceramic solid solution nano-wire, (Ta)xHf1‑x) The C solid solution has excellent electrical conductivity, and therefore, the method is also advantageous for achieving further improvement in electromagnetic shielding properties of the material.
Description
Technical Field
The invention belongs to the field of ultra-high temperature ceramics, and relates to an ultra-long (Ta)xHf1-x) C ultra-high temperature ceramic solid solution nano-wire and a controllable preparation method.
Background
With the development of technology, one-dimensional nanomaterials, such as nanowires, whiskers and nanorods, have become the focus of people's attention due to their unique geometric shapes. In particular, ultrahigh temperature ceramic nanowires have the advantages of large specific surface area, high length-diameter ratio, good toughness, high temperature stability, good chemical inertness and excellent electrical conductivity, and are a research hotspot. In the existing ultra-high temperature ceramic, taC and HfC have the same NaCl structure, and Ta and Hf atoms in TaC and HfC crystal lattices can be mutually replaced by similar crystallographic characteristics, so that a solid solution is formed in the whole composition range. Wherein, the melting point of TaC is highest (3983 deg.C), hfC melting point (3938 deg.C) is second order, and (Ta)xHf1-x) C solid solution has a higher melting point; taC has the lowest coefficient of thermal expansion (6.3X 10)-6/° c), therefore, the solid solution of TaC and HfC may lower the thermal expansion coefficient of the material, such that (Ta)xHf1-x) C solid solution has a low coefficient of thermal expansion; (Ta)xHf1-x) Hf generated by C solid solution in high-temperature aerobic environment6Ta2O17The glassy oxide effectively blocks the penetration of oxygen, resulting in (Ta)xHf1-x) Compared with HfC and TaC, the C solid solution has more excellent ablation resistance; thus, (Ta)xHf1-x) The C solid solution nanowire can be used as a reinforcing phase of a composite material and a toughening phase of the ultrahigh-temperature ceramic, so that the mechanical property and the ablation resistance of the material are effectively improved. Furthermore, taC and HfC have good electromagnetic shielding properties, which means (Ta)xHf1-x) The C solid solution nanowire has wide development prospect in the field of electromagnetic shielding.
It is well known that the internal structure and morphology of a material are critical to its performance, however, at present for (Ta)xHf1-x) The reports on the preparation of the ultra-high temperature ceramic solid solution nanowire with controllable components and shapes are few.
To solve this problem, document 1, ren JC, zhang YL, hu H, et al.Oxidation resistance and mechanical properties of HfC nanowire-treated ultra-high temperature ceramic coating for SiC-coated C/C compositions, applied Surface science, 2016; 360-970-978, "reports HfC nanowire toughened ultra-high temperature ceramic coating, and researches show that the introduction of HfC nanowires can reduce the size of microcracks in the coating, avoid the formation of penetrating cracks, and effectively improve the mechanical property and the ablation resistance of the coating.
Document 2 Smith CJ, yu XX, guo Q, et al phase, hardness, and deformation slip behavor in mixed HfxTa1-xActa materialia.2018;145, 142-153. "reported (Ta)xHf1–x) The performance of C (x =0,0.13, 0.25,0.50,0.75,0.83 and 1.0) material, and research finds that the plasticity of the material is improved by introducing a small amount of Ta into HfC. Therefore, by introducing different contents of Ta, (Ta) having different excellent properties can be preparedxHf1-x) C solid solution.
Document 3"Ahlen N, johnsson M, larsson AK, et al, on the carbothermal vapour-liquid-solid (VLS) mechanism for TaC, tiC, and TaxTi1-xC whisker growth. Journal of the European Ceramic society.2000; 20-2607-2618, "Ta is reportedxTi1-xAnd C, preparing the crystal whisker, and analyzing a plurality of different shapes of the crystal whisker. The product prepared by the method has low yield and purity, and controllable preparation of the crystal whisker shape is difficult to realize.
Therefore, an extremely long and ultra-high Wen Taoci solid solution nanowire with high melting point, good high-temperature stability and excellent electromagnetic shielding performance and a controllable preparation method thereof are needed.
Disclosure of Invention
Technical problem to be solved
In order to avoid the defects of the prior art, the invention provides an extremely long (Ta)xHf1-x) The ultra-high temperature ceramic solid solution nano-wire with controllable shape and components, high yield and extremely long (Ta) continuously and uniformly distributed on the surface of a substrate and the preparation method thereofxHf1-x) C solid solution nanowires. Aims to realize the controllable preparation of the solid solution nanowire, lays a foundation for the controllable enhancement of the nanowire to the composite material and the controllable toughening of the ultrahigh-temperature ceramic, and provides a new idea for preparing the electromagnetic shielding material with light weight, good flexibility and continuous and uniform product.
Technical scheme
Very long (Ta)xHf1-x) C ultra-high temperature ceramic solid solution nano wire, its characterized in that: extremely long (Ta) of 70 μm in lengthxHf1-x) The C solid solution nanowires are continuously and uniformly distributed on the surface of the matrix and are face-centered cubic (Ta) with HfC and TaC performancesxHf1-x) C solid solution structure.
Preparation of said very long (Ta)xHf1-x) The method for preparing the ultra-high temperature ceramic solid solution nanowire is characterized by comprising the following steps of:
step 1: soaking the dried C/C composite material into Ni (NO)3)2Soaking in ethanol solution, oven drying,
step 2: hfCl with the molar ratio of 3:1-1:3 is added4And TaCl5Precursor powder is placed in a volatilization mould of a low-temperature volatilization area; suspending the C/C composite material in a deposition mould by using a molybdenum wire and placing the C/C composite material in a high-temperature deposition area of a chemical vapor deposition furnace;
and step 3: vacuumizing the deposition furnace to 2-4KPa, and introducing H with flow rate of 20-40ml/min2And are provided withHeating the deposition furnace at a heating rate of 8-12 ℃/min;
and 4, step 4: heating the deposition furnace to 1000-1100 ℃, introducing H with the flow ratio of 1:1-4:1 and the total flow of 100-500 ml/min2And CH4Keeping the temperature for 0.5 to 2.5 hours for chemical vapor deposition;
and 5: the heating program is closed, and CH introduction is stopped4Is prepared from H2Adjusting the flow to 30-50ml/min, waiting for the deposition furnace to naturally cool to room temperature, and obtaining the extremely long (Ta) material which uniformly grows on the surface of the C/C composite material and has controllable components and appearancexHf1-x) C ultra-high temperature ceramic solid solution nanowires.
The soaking time in the step 1 is 1-3h.
And drying in an oven at 80-100 ℃.
The deposition mold is provided with a plurality of air guide holes which are uniformly distributed.
The volatilization mold comprises an upper layer volatilization mold with adjustable space and a lower layer volatilization mold, namely TaCl5Placing the precursor powder in an upper layer volatilization mold, hfCl4The precursor powder is placed in the lower-layer volatilization mould.
The Ni (NO)3)2The concentration of the ethanol solution is 0.2-0.8mol/L.
H in said step 42Replaced by Ar.
The C/C composite material is replaced by graphite, carbon felt, graphite paper and ultrahigh-temperature ceramic.
Advantageous effects
The invention provides a very long (Ta)xHf1-x) The ultra-high temperature ceramic solid solution nanowire and the preparation method develop an ultra-long solid solution nanowire with ultra-high melting point and more excellent toughness performance, and the requirements of controlling the components and the appearance of the nanowire are met by adjusting process parameters, so that the controllable reinforcement of the composite material and the controllable toughening of the ultra-high temperature ceramic in an extreme environment are realized. (Ta)xHf1-x) The ultra-high melting point, low thermal expansion coefficient and more excellent ablation resistance of the C solid solution are excellent choices of a reinforcing phase and a toughening phase. In addition, the invention has simple preparation process and convenient operation, and is suitable for simple processVarious matrixes with shapes and complex shapes can be prepared to obtain (Ta) with uniform and continuous product, high yield and high purityxHf1-x) C ultra-high temperature ceramic solid solution nano-wire, (Ta)xHf1-x) The C solid solution has excellent electrical conductivity, and therefore, the method is also advantageous for achieving further improvement in electromagnetic shielding properties of the material.
The beneficial effects are as follows:
1) Since HfC and TaC have the same face-centered cubic structure, it is possible to form (Ta) over the entire composition rangexHf1-x) C solid solution, so that the nanowire prepared by the invention is a face-centered cubic (Ta) with both HfC and TaC excellent performancesxHf1-x) A C solid solution structure;
2) As the HfC and the TaC are simultaneously added into the components, the reaction mechanism is mutual solid solution of the HfC and the TaC, and the Hf atom and the Ta atom are mutually replaced to form a replacement solid solution, so that the components in the solid solution can be controlled, the ranges are all 0 & ltn & gt x & ltn 1, the solid solution with higher Hf content shows excellent ablation resistance, and the solid solution with higher Ta content shows lower thermal expansion coefficient and excellent plastic property;
3) Very long (Ta) prepared according to the inventionxHf1-x) The length of the C ultra-high temperature ceramic solid solution nanowire is 70 mu m, which is far larger than that of other ultra-high temperature ceramic nanowires, for example, the length of the HfC nanowire is 40 mu m, and the length of the TaC nanowire is 10 mu m;
4) The direction of airflow is not controlled when the nanowires are prepared by other chemical vapor deposition methods, and the airflow entering the deposition area is uniformly surrounded on each surface of the matrix by adding the uniformly distributed air guide holes in the deposition area, so that the uniform distribution and continuous growth of the nanowires on the surface of the matrix are realized;
5) The invention can prepare the extremely long (Ta) with different components, shapes and performances by adjusting the proportion of the precursor and the deposition parameters according to actual requirementsxHf1-x) The nano-wire has higher melting point and more excellent plasticity than the HfC nano-wire, and can realize controllable enhancement of the composite material and controllable toughening of the ultra-high temperature ceramic in an extreme environment;
6) The method has the advantages that continuous distribution of nanowire nucleation points is not provided when the ultrahigh-temperature ceramic nanowires are prepared by other methods, so that the yield of the nanowires is low, the controllable preparation and uniform and continuous distribution of the yield of the nanowires can be realized by controlling the content and distribution of the catalyst on the surface of the substrate, and the electromagnetic shielding performance of the material can be further improved;
7) The preparation method is simple in preparation process and convenient to operate, is suitable for matrixes made of various materials and having simple shapes and complex shapes, and widens the application range of the nanowires.
Drawings
FIG. 1 is an extremely long (Ta) film prepared by the present invention0.25Hf0.75) C, SEM picture of ultra-high temperature ceramic solid solution nano-wire;
FIG. 2 is a graph of very long (Ta) produced by the present invention0.25Hf0.75) A cross-sectional SEM image of the C ultrahigh-temperature ceramic solid solution nanowire on the surface of the C/C composite material;
FIG. 3 is an extremely long (Ta) film prepared in accordance with the present invention0.50Hf0.50) C, SEM image of the ultra-high temperature ceramic solid solution nanowire;
FIG. 4 is an extremely long (Ta) film prepared in accordance with the present invention0.50Hf0.50) C, TEM image of the superhigh temperature ceramic solid solution nanowire;
FIG. 5 is an extremely long (Ta) film prepared in accordance with the present invention0.75Hf0.25) C, SEM image of the ultra-high temperature ceramic solid solution nanowire;
FIG. 6 is an SEM image of nanowires prepared in example 1 of the present invention;
FIG. 7 is an SEM photograph of a product of example 2 of the present invention;
FIG. 8 is an SEM photograph of a product prepared according to example 3 of the present invention.
Detailed Description
The invention will now be further described with reference to the following examples and drawings:
in order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are some embodiments of the present invention, but not all embodiments. The components of embodiments of the present invention generally described and illustrated in the figures herein may be arranged and designed in a wide variety of different configurations.
Thus, the following detailed description of the embodiments of the present invention, presented in the figures, is not intended to limit the scope of the invention, as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, which can be obtained by a person skilled in the art based on the embodiments of the present invention without any creative effort, fall within the protection scope of the present invention.
Example 1:
cutting the C/C composite material into 6 × 6 × 6mm3The block sample is then polished by silicon carbide abrasive paper, ultrasonically cleaned by absolute ethyl alcohol and then dried in an oven at 70 ℃. Soaking the dried C/C composite material into Ni (NO) with the concentration of 0.2 mol/L3)2Soaking in ethanol solution for 3h; weighing HfCl with the molar ratio of 3:14And TaCl5Precursor powder, taCl5Placing the precursor powder in an upper layer die of a low-temperature volatilization region, and adding HfCl4Placing the precursor powder in a lower-layer mold of a low-temperature volatilization area; soaking Ni (NO)3)2Drying the C/C composite material subjected to ethanol solution in an oven at 80 ℃, hanging a molybdenum wire on a deposition mould, and placing the deposition mould in a high-temperature deposition area of a chemical vapor deposition furnace; then, the deposition furnace is vacuumized to 4KPa, the airtightness is checked to be good, and H with the flow rate of 40ml/min is introduced2Heating the deposition furnace to 1000 ℃ at a heating rate of 8 ℃/min, introducing H with a flow ratio of 4:1 and a total flow rate of 500ml/min2And CH4Airflow is uniformly dispersed and surrounds the periphery of the C/C composite material after passing through an air guide hole in the deposition mould, and the temperature is kept for 0.5h for chemical vapor deposition; after the deposition is finished, the heating program is closed, and the CH introduction is stopped4Is prepared from H2The flow is adjusted to 50ml/min, the deposition furnace is waited to naturally reduce to the room temperature, and the (Ta) uniformly growing on the surface of the C/C composite material is obtained0.25Hf0.75) C ultra-high temperature ceramic solid solution nanowires. FIG. 1 is an SEM image of nanowires showing uniform distribution of nanowires, high yield, and complete coverage of C/C complexSynthesizing a material matrix, wherein no obvious impurity exists in the product, so that the product has higher purity; from the enlarged view in the upper right corner, the diameter of the nanowire can be seen to be 150nm; from the EDS point scan of the nanowire at the lower left corner, the content ratio of the nanowire element is very close to 3:1, which shows that the nanowire composition is controlled, wherein a small amount of Ni element is derived from a catalyst essential for nanowire growth. FIG. 2 is a SEM image of the cross section of the nanowire vertically grown on the surface of the C/C composite material, the nanowire forms a uniform and continuous nanowire layer on the surface of the substrate, the thickness of the nanowire layer is as high as 70 μm, and the length of the nanowire is extremely large.
Example 2:
cutting the C/C composite material into 6X 6mm3The block sample is then polished by silicon carbide abrasive paper, ultrasonically cleaned by absolute ethyl alcohol and then dried in an oven at 70 ℃. Soaking the dried C/C composite material into Ni (NO) with the concentration of 0.5 mol/L3)2Soaking in ethanol solution for 2h; weighing HfCl with the molar ratio of 1:14And TaCl5Precursor powder, taCl5Placing the precursor powder in an upper layer die of a low-temperature volatilization region, and adding HfCl4Placing the precursor powder in a lower-layer mold of a low-temperature volatilization area; soaking Ni (NO)3)2Drying the C/C composite material subjected to the ethanol solution in a drying oven at 90 ℃, hanging the C/C composite material on a deposition mould by using a molybdenum wire, and placing the C/C composite material in a high-temperature deposition area of a chemical vapor deposition furnace; then, the deposition furnace is vacuumized to 3 KPa, the airtightness is checked to be good, and H with the flow rate of 30ml/min is introduced2Heating the deposition furnace to 1050 ℃ at a heating rate of 10 ℃/min, introducing H with a flow ratio of 2:1 and a total flow rate of 300ml/min2And CH4Airflow is uniformly dispersed and surrounds the periphery of the C/C composite material after passing through an air guide hole in the deposition mould, and the temperature is kept for 1.5h for chemical vapor deposition; after the deposition is finished, the heating program is closed, and the CH introduction is stopped4Is prepared from H2Adjusting the flow rate to 40ml/min, waiting for the deposition furnace to naturally reduce to the room temperature, and obtaining the (Ta) uniformly grown on the surface of the C/C composite material0.50Hf0.50) C ultra-high temperature ceramic solid solution nanowires. Figure 3 shows an SEM image of nanowires, where the nanowires are uniformly distributed, completely covering the substrate,the diameter was increased to 220nm compared to example 1; the EDS dot-plot at the bottom left shows the Hf/Ta atomic ratio in the product as 1/1. Fig. 4 is a TEM image of a nanowire, fig. 4 (a) is a typical low power TEM image of the nanowire, which shows that the nanowire grows linearly, fig. 4 (b) is an HRTEM image of the nanowire, in which only a clear parallel lattice fringe is observed, which shows that the solid solution nanowire prepared by the present invention is a single-phase solid solution structure, fig. 4 (C) is a SAED image of the nanowire, a significant diffraction spot shows that the nanowire is a single-crystal structure, and it can be seen from fig. 4 (d) - (g) that the elements of the nanowire are uniformly distributed in Hf, ta and C, and the enrichment of the top Ni element is an essential catalyst for growth.
Example 3:
cutting the C/C composite material into 6 × 6 × 6mm3The block sample is then polished by silicon carbide abrasive paper, ultrasonically cleaned by absolute ethyl alcohol and then dried in an oven at 70 ℃. Soaking the dried C/C composite material into Ni (NO) with the concentration of 0.8mol/L3)2Soaking in ethanol solution for 1h; weighing HfCl with the molar ratio of 1:34And TaCl5Precursor powder, taCl5Placing the precursor powder in an upper layer die of a low-temperature volatilization region, and adding HfCl4Placing the precursor powder in a lower-layer mold of a low-temperature volatilization area; soaking Ni (NO)3)2Drying the C/C composite material subjected to the ethanol solution in a drying oven at 100 ℃, and suspending the C/C composite material in a high-temperature deposition area of a chemical vapor deposition furnace by using a molybdenum wire; then, the deposition furnace was evacuated to 2KPa, and after checking that the gas tightness was good, H was introduced at a flow rate of 20ml/min2Heating the deposition furnace to 1100 deg.C at a heating rate of 12 deg.C/min, introducing H with a flow ratio of 1:1 and a total flow rate of 100ml/min2And CH4Airflow is uniformly dispersed and surrounds the periphery of the C/C composite material after passing through an air guide hole in the deposition mould, and the temperature is kept for 3 hours for chemical vapor deposition; after the deposition is finished, the heating program is closed, and the CH introduction is stopped4H is prepared by2Adjusting the flow rate to 30ml/min, waiting for the deposition furnace to naturally cool to room temperature, and obtaining the (Ta) uniformly growing on the surface of the C/C composite material0.75Hf0.25) C ultra-high temperature ceramic solid solution nanowires. FIG. 5 shows a graph of nanometersSEM picture of the wire, in which the nano wire is uniformly covered on the surface of the matrix, the diameter is further increased to 550nm, EDS picture shows that atomic ratio of Hf/Ta in the nano wire is 1/3.
From the above analysis, it can be seen that the very long (Ta) produced by the present inventionxHf1-x) The C ultra-high temperature ceramic solid solution nanowire is a single-phase solid solution with a single crystal structure, the yield and the purity of the nanowire are high, the components and the morphology are controllable, and the nanowires with different morphologies and yields can be obtained by adjusting process parameters so as to meet different application requirements. In addition, the applicable matrix of the invention comprises but is not limited to C/C composite material, and the corresponding matrix can be selected according to actual requirements, thereby effectively widening the application range of the nano wire.
The above description is only for the preferred embodiment of the present invention, and is not intended to limit the present invention in any way. Any simple modifications, alterations and equivalent changes of the above embodiments according to the technical essence of the invention are still within the protection scope of the technical solution of the invention.
In the following, several counter-examples are listed to assist in explaining the novelty and necessity of the present invention.
Example reverse example 1:
cutting the C/C composite material into 6X 6mm3The block sample is then polished by silicon carbide abrasive paper, and then is ultrasonically cleaned by absolute ethyl alcohol, and then is placed in a 70 ℃ oven for drying. Soaking the dried C/C composite material into Ni (NO) with the concentration of 0.2 mol/L3)2Soaking in ethanol solution for 3h; weighing HfCl with the molar ratio of 1:34And TaCl5Precursor powder, adding TaCl5Placing the precursor powder in an upper layer die of a low-temperature volatilization region, and adding HfCl4Placing the precursor powder in a lower-layer mold of a low-temperature volatilization area; soaking Ni (NO)3)2Drying the C/C composite material subjected to the ethanol solution in an oven at the temperature of 80 ℃, and suspending the C/C composite material in a high-temperature deposition area of a chemical vapor deposition furnace by using a molybdenum wire; then, the deposition furnace was evacuated to 4KPa, and after checking that the gas tightness was good, H having a flow rate of 40ml/min was introduced2Heating the deposition furnace to 1000 deg.C at a heating rate of 8 deg.C/min, introducing 4:1 at a flow rate of 500ml/minH2And CH4Keeping the temperature for 1h for chemical vapor deposition; after the deposition is finished, the heating program is closed, and the CH introduction is stopped4H is prepared by2The flow is adjusted to 50ml/min, and the deposition furnace is naturally cooled to the room temperature. FIG. 7 is a SEM image of the product, where it can be observed that the nanowires did not completely cover the substrate, the yield of nanowires was low, the product purity was low and the distribution was not uniform, there were more impurities, indicating that when the deposition area was not provided with uniformly distributed air holes to control the direction of the air flow, the (Ta) was preparedxHf1-x) The C solid solution nanowire is not uniform and discontinuous, and cannot meet the practical application.
Example comparative example 2:
cutting the C/C composite material into 6X 6mm3The block sample is then polished by silicon carbide abrasive paper, ultrasonically cleaned by absolute ethyl alcohol and then dried in an oven at 70 ℃. Soaking the dried C/C composite material into Ni (NO) with the concentration of 0.2 mol/L3)2Soaking in ethanol solution for 3h; weighing HfCl with the molar ratio of 3:14And TaCl5Precursor powder, adding TaCl5Placing the precursor powder in an upper layer die of a low-temperature volatilization region, and adding HfCl4Placing the precursor powder in a lower-layer mold of a low-temperature volatilization area; soaking Ni (NO)3)2Drying the C/C composite material subjected to the ethanol solution in an oven at the temperature of 80 ℃, and suspending the C/C composite material in a high-temperature deposition area of a chemical vapor deposition furnace by using a molybdenum wire; then, the deposition furnace was evacuated to 4KPa, and after checking that the gas tightness was good, H having a flow rate of 40ml/min was introduced2Heating the deposition furnace to 900 ℃ at a heating rate of 8 ℃/min, introducing H with a flow ratio of 4:1 and a total flow rate of 500ml/min2And CH4Keeping the temperature for 0.5h for chemical vapor deposition; after the deposition is finished, the heating program is closed, and the CH introduction is stopped4Is prepared from H2The flow rate is adjusted to 50ml/min, and the deposition furnace is naturally cooled to the room temperature. FIG. 8 is an SEM image of the product, where it can be seen that the product is an off-white floc with no apparent one-dimensional material features, indicating that it cannot be prepared at a deposition temperature of 900 deg.C (Ta)xHf1-x) C solid solution nanowires.
Example reverse 3:
mixing the C/C composite materialCutting into 6 × 6 × 6mm3The block sample is then polished by silicon carbide abrasive paper, ultrasonically cleaned by absolute ethyl alcohol and then dried in an oven at 70 ℃. Soaking the dried C/C composite material into Ni (NO) with the concentration of 0.2 mol/L3)2Soaking in ethanol solution for 3h; weighing HfCl with the molar ratio of 3:14And TaCl5Precursor powder, taCl5Placing the precursor powder in an upper layer die of a low-temperature volatilization region, and adding HfCl4Placing the precursor powder in a lower-layer mold of a low-temperature volatilization area; soaking Ni (NO)3)2Drying the C/C composite material subjected to the ethanol solution in an oven at the temperature of 80 ℃, and suspending the C/C composite material in a high-temperature deposition area of a chemical vapor deposition furnace by using a molybdenum wire; then, the deposition furnace was evacuated to 6KPa, and after checking that the gas tightness was good, H was introduced at a flow rate of 20ml/min2Heating the deposition furnace to 1250 ℃ at the heating rate of 12 ℃/min, introducing H with the flow ratio of 1:2 and the total flow of 300ml/min2And CH4Keeping the temperature for 3h for chemical vapor deposition; after the deposition is finished, the heating program is closed, and the CH introduction is stopped4Is prepared from H2The flow is adjusted to 50ml/min, and the deposition furnace is naturally cooled to the room temperature. FIG. 8 is a SEM image of the product, which shows that the product has one-dimensional material characteristics, but the diameter is as high as-6 μm, the surface is rough and has more pits, and the product has more ceramic particles, which indicates that the product prepared by using the parameters outside the scope of the invention is rod-shaped whisker with rough surface, the yield and the purity are not high, and more ceramic particles have impurities, thus the application requirements can not be met.
Claims (9)
1. Very long (Ta)xHf1-x) C ultra-high temperature ceramic solid solution nano wire, its characterized in that: extremely long (Ta) of 70 μm in lengthxHf1-x) The C solid solution nanowires are continuously and uniformly distributed on the surface of the matrix and are face-centered cubic (Ta) with HfC and TaC performancesxHf1-x) C solid solution structure.
2. Preparation of very long (Ta) as claimed in claim 1xHf1-x) The method of the C superhigh temperature ceramic solid solution nano line is characterized by comprising the following stepsThe method comprises the following steps:
step 1: soaking the dried C/C composite material into Ni (NO)3)2Soaking in ethanol solution, oven drying,
step 2: hfCl with the molar ratio of 3:1-1:3 is added4And TaCl5Precursor powder is placed in a volatilization mold of a low-temperature volatilization area; suspending the C/C composite material in a deposition mould by using a molybdenum wire and placing the C/C composite material in a high-temperature deposition area of a chemical vapor deposition furnace;
and step 3: vacuumizing the deposition furnace to 2-4KPa, and introducing H with flow rate of 20-40ml/min2Heating the deposition furnace at a heating rate of 8-12 ℃/min;
and 4, step 4: heating the deposition furnace to 1000-1100 ℃, introducing H with the flow ratio of 1:1-4:1 and the total flow of 100-500 ml/min2And CH4Keeping the temperature for 0.5 to 2.5 hours for chemical vapor deposition;
and 5: the heating program is closed, and CH introduction is stopped4Is prepared from H2Adjusting the flow to 30-50ml/min, waiting for the deposition furnace to naturally cool to room temperature, and obtaining the extremely long (Ta) material which uniformly grows on the surface of the C/C composite material and has controllable components and appearancexHf1-x) C ultra-high temperature ceramic solid solution nanowires.
3. The method of claim 2, wherein: the soaking time in the step 1 is 1-3h.
4. The method of claim 2, wherein: and drying in an oven at 80-100 ℃.
5. The method of claim 2, wherein: the deposition mould is provided with a plurality of air guide holes which are uniformly distributed.
6. The method of claim 2, wherein: the volatilization mould comprises an upper layer volatilization mould and a lower layer volatilization mould with adjustable intervals, and TaCl5Placing the precursor powder in an upper layer volatilization mold, hfCl4The precursor powder is placed in the lower-layer volatilization mould.
7. The method of claim 2, wherein: the Ni (NO)3)2The concentration of the ethanol solution is 0.2-0.8mol/L.
8. The method of claim 2, wherein: h in said step 42Replaced by Ar.
9. The method of claim 2, wherein: the C/C composite material is replaced by graphite, carbon felt, graphite paper and ultrahigh-temperature ceramic.
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