CN112195503B - Method for synthesizing hafnium carbide crystal whisker with large length-diameter ratio by carbothermic reduction method - Google Patents

Method for synthesizing hafnium carbide crystal whisker with large length-diameter ratio by carbothermic reduction method Download PDF

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CN112195503B
CN112195503B CN202011015062.1A CN202011015062A CN112195503B CN 112195503 B CN112195503 B CN 112195503B CN 202011015062 A CN202011015062 A CN 202011015062A CN 112195503 B CN112195503 B CN 112195503B
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hfc
diameter ratio
whiskers
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CN112195503A (en
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张守阳
郭瑶
张磊磊
宋强
何松
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Northwestern Polytechnical University
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    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B1/00—Single-crystal growth directly from the solid state
    • C30B1/10—Single-crystal growth directly from the solid state by solid state reactions or multi-phase diffusion
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
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    • C30B28/02—Production of homogeneous polycrystalline material with defined structure directly from the solid state
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/10—Inorganic compounds or compositions
    • C30B29/36—Carbides
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/60—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape characterised by shape
    • C30B29/62—Whiskers or needles

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Abstract

The invention relates to a method for synthesizing hafnium carbide whiskers with a large length-diameter ratio by a carbothermic method, wherein the carbothermic method is adopted, a catalyst is not used, no metal impurity is introduced, the obtained HfC whiskers have high purity and large length-diameter ratio, the length-diameter ratio of HfC whiskers reported in a literature is distributed in a range of 5-180, and the length-diameter ratio of the HfC whiskers prepared by the method is 50-500. Compared with HfC whiskers reported in the literature, the maximum length-diameter ratio of the HfC whiskers prepared by the method is improved by 178%. The HfC whisker can be used as a reinforcement material for preparing a porous HfC whisker preform, can also be used as a second reinforcement material for correspondingly being used for an ultrahigh-temperature ceramic matrix or a carbon-based composite material, can also be used as a functional material for a cathode field emitter, and has wide application prospect. The carbothermic method has the advantages of simple process, easily controlled parameters, low equipment requirement, low cost, good reliability and repeatability, and easy realization of large-scale production of HfC whiskers.

Description

Method for synthesizing hafnium carbide crystal whisker with large length-diameter ratio by carbothermic reduction method
Technical Field
The invention belongs to a whisker material preparation technology, and relates to a method for synthesizing hafnium carbide (HfC) whiskers with a large length-diameter ratio by a carbothermic method.
Background
The HfC serving as the ultrahigh-temperature ceramic has multiple excellent performances such as ultrahigh melting point, high hardness, good electric conductivity, heat conductivity, mechanical properties, high temperature resistance, corrosion resistance and the like, plays an effective role in the aspects of oxidation resistance, ablation resistance, matrix modified high-temperature structure composite materials and the like, and has good application prospects in the field of aerospace. The HfC whisker not only has the excellent performance of HfC ceramic, but also has the excellent mechanical property and unique geometric characteristic of one-dimensional materials. Due to the properties, the material can be used as a reinforcement material for preparing a porous HfC whisker preform, can also be used as a second reinforcement phase to be introduced into an ultrahigh-temperature ceramic matrix or carbon-based composite material for enhancing the mechanical property of the material, and can also be introduced into an anti-ablation coating for playing a toughening role, reducing the cracking of the coating and improving the anti-ablation property of the coating. In addition, HfC whiskers are used as functional materials, and have greater advantages and potential in a cathode field emitter.
At present, few reports are made about the preparation method of HfC whiskers, and the main preparation method is a chemical vapor deposition method.
"journal of Crystal Growth,1983,61:69-74 using Ni as a catalyst in HfCl", document 1 "M.Futamoto, I.Yuito and U.K. Kawabe. Hafnium carbide and nitride developers Growth by chemical vapor deposition 4 -CH 4 -H 2 The reaction system grows HfC whiskers by a chemical vapor deposition method in a relatively low temperature region (1000-1450 ℃). The HfC whiskers produced in this document have a maximum diameter of 25 μm, a maximum length of 4.5mm and a maximum aspect ratio of 180.
Document 2 "S.Motojima, Y.Kawashima.chemical vapor growth of HfC whitters and the same morphology. journal of Materials Science,1996,31:3697- 4 -CH 4 -H 2 -Ar reaction system HfC whiskers were prepared by chemical vapor deposition, the effect of different metal catalysts on whisker growth was investigated, and it was found that using cobalt as catalyst, HfC whiskers having a spherical tip were obtained at 1250 ℃, the spherical tip formation of which was due to the presence of cobalt. The diameter of the HfC whisker is distributed in the range of 3-5 μm, the length of the HfC whisker is distributed in the range of 60-170 μm, the length-diameter ratio of the HfC whisker is distributed in the range of 20-57, and the maximum length-diameter ratio of the HfC whisker is 57.
Reference 3 "Song Tian, Hejun Li, Yulei Zhang, et al. the effects of the element oxygen on hafnium carbide feeders synthesized by CVD. materials Chemistry and Physics,2013,140:323- 4 -C 3 H 6 -H 2 Ar reaction system by Ni (NO) 3 ) 2 -CH 3 CH 2 The HfC whiskers are obtained on a graphite substrate by an OH catalyst assisted vacuum chemical vapor deposition process. Obtained byThe diameter of the HfC whisker is 2-10 mu m, the length of the whisker is about 50 mu m, the length-diameter ratio is distributed in the range of 5-25, and the maximum length-diameter ratio is about 25.
Comprehensive analysis, the preparation of HfC whiskers by a chemical vapor deposition process requires a metal catalyst, and the introduction of the catalyst reduces the purity of the whiskers. Moreover, the process parameter is complex to regulate and control, has relatively high requirements on equipment and a long period, and is not beneficial to batch production. In addition, the length-diameter ratio distribution of HfC whiskers prepared by the chemical vapor deposition method is 5-180.
Disclosure of Invention
Technical problem to be solved
In order to avoid the defects of the prior art, the invention provides a method for synthesizing hafnium carbide whiskers with a large length-diameter ratio by a carbothermic method, the length-diameter ratio of the prepared HfC whiskers is distributed in a range of 50-500, no catalyst is introduced, and the whiskers have high purity. Meanwhile, the preparation process is simple, the reliability and the repeatability are good, and the period is short.
Technical scheme
A method for synthesizing hafnium carbide whiskers with a large length-diameter ratio by a carbothermic method is characterized by comprising the following steps:
step 1: activated carbon C and hafnium oxide HfO 2 Sodium fluoride NaF and ammonium chloride NH 4 Putting Cl powder into a ceramic mortar for grinding and mixing, and uniformly spreading sieved powder into a graphite crucible; HfO, C 2 ∶NaF∶NH 4 The mol ratio of Cl is 1: 0.5-1.5: 0.5-2: 0.4-1.2;
and 2, step: placing the graphite crucible in a horizontal tubular resistance furnace, introducing inert gas Ar as protective gas, raising the temperature to 1500-1700 ℃ at the heating rate of 3-5 ℃/min, and preserving the temperature for 1-4 h; and cooling to room temperature at the rate of 3-5 ℃/min, and taking out the graphite crucible to obtain the HfC whisker.
The mixed powder was sieved through a 100 mesh sieve.
Ammonium chloride NH of said step 1 4 Cl was replaced by NaCl.
Advantageous effects
The method for synthesizing the hafnium carbide whisker with the large length-diameter ratio by the carbothermic method has the advantages of simple process, easy parameter control, low equipment requirement, low cost, good reliability and repeatability, and easy realization of large-scale production of HfC whiskers. According to the method, a catalyst is not used, no metal impurity is introduced, the obtained HfC whisker has high purity and large length-diameter ratio, the length-diameter ratio of the HfC whisker reported in the literature is distributed in a range of 5-180, and the length-diameter ratio of the HfC whisker prepared by the method is 50-500. Compared with HfC whiskers reported in the literature, the maximum length-diameter ratio of the HfC whiskers prepared by the method is improved by 178%. The HfC whisker can be used as a reinforcement material for preparing a porous HfC whisker preform, can also be used as a second reinforcement material for correspondingly being used for an ultrahigh-temperature ceramic matrix or a carbon-based composite material, can also be used as a functional material for a cathode field emitter, and has wide application prospect.
Drawings
FIG. 1 is an X-ray diffraction pattern of HfC whiskers synthesized in example 1
FIG. 2 is a scanning electron micrograph of HfC whiskers synthesized in example 1
FIG. 3 is a high scanning electron microscope image of HfC whiskers synthesized in example 1
Detailed Description
The invention will now be further described with reference to the following examples and drawings:
example 1:
step 1: according to the molar ratio of C to HfO 2 :NaF:NH 4 Raw materials were prepared with Cl ═ 1:0.5:1:1.2, and ground in a ceramic mortar to mix well. The mixed powder is sieved by a 100-mesh sieve, and the sieved powder is uniformly paved into a graphite crucible.
Step 2: and (3) placing the graphite crucible containing the mixed powder in the step (2) in a horizontal tubular resistance furnace, introducing inert gas Ar as protective gas, raising the temperature to 1600 ℃ at the heating rate of 3 ℃/min, and preserving the temperature for 2 h. And cooling to room temperature at the cooling rate of 3 ℃/min, and taking out the graphite crucible to obtain the HfC whisker.
HfC whiskers were successfully prepared as described in example 1, and the X-ray diffraction pattern of the HfC whiskers is shown in FIG. 1, and the scanning electron microscope images are shown in FIGS. 2 and 3. The HfC whisker has the diameter of 1-2 mu m, the length of 200-500 mu m, the length-diameter ratio of 100-500 and high purity, and can be seen from figure 3 that the whisker has no metal spherical tip.
Example 2:
step 1: according to the molar ratio of C to HfO 2 :NaF:NH 4 Raw materials were prepared with Cl ═ 1:0.8:2:0.4, and the mixture was put into a ceramic mortar and ground to be mixed uniformly. The mixed powder is sieved by a 100-mesh sieve, and the sieved powder is uniformly laid in a graphite crucible.
Step 2: and (3) placing the graphite crucible containing the mixed powder in the step (2) in a horizontal tubular resistance furnace, introducing inert gas Ar as protective gas, raising the temperature to 1700 ℃ at the heating rate of 3 ℃/min, and preserving the temperature for 1 h. And cooling to room temperature at the cooling rate of 3 ℃/min, and taking out the graphite crucible to obtain the HfC whisker.
The length-diameter ratio of the HfC crystal whisker prepared in the example 2 is 75-400.
Example 3:
step 1: according to the molar ratio of C to HfO 2 NaF and NaCl in a ratio of 1:1.2:0.5:1 are prepared into raw materials, and the raw materials are put into a ceramic mortar and ground to be uniformly mixed. The mixed powder is sieved by a 100-mesh sieve, and the sieved powder is uniformly paved into a graphite crucible.
And 2, step: and (3) placing the graphite crucible containing the mixed powder in the step (2) in a horizontal tubular resistance furnace, introducing inert gas Ar as protective gas, raising the temperature to 1500 ℃ at the heating rate of 5 ℃/min, and preserving the temperature for 3 hours. And cooling to room temperature at the cooling rate of 4 ℃/min, and taking out the graphite crucible to obtain the HfC whisker.
The length-diameter ratio of the HfC crystal whisker prepared in the example 3 is 70-250.
Example 4:
step 1: according to the molar ratio of C to HfO 2 NaF and NaCl in a ratio of 1:1.5:1.5:0.8 are put into a ceramic mortar and ground to be uniformly mixed. The mixed powder is sieved by a 100-mesh sieve, and the sieved powder is uniformly laid in a graphite crucible.
Step 2: and (3) placing the graphite crucible containing the mixed powder in the step (2) in a horizontal tubular resistance furnace, introducing inert gas Ar as protective gas, raising the temperature to 1500 ℃ at the temperature rise rate of 5 ℃/min, and preserving the heat for 4 hours. And cooling to room temperature at the cooling rate of 4 ℃/min, and taking out the graphite crucible to obtain the HfC whisker.
The length-diameter ratio of the HfC whisker prepared in the example 4 is 50-200.

Claims (3)

1. A method for synthesizing hafnium carbide whiskers with a large length-diameter ratio by a carbothermic method is characterized by comprising the following steps:
step 1: activated carbon C and hafnium oxide HfO 2 Sodium fluoride NaF and ammonium chloride NH 4 Putting Cl powder into a ceramic mortar for grinding and mixing, and uniformly spreading sieved powder into a graphite crucible; HfO, C 2 ∶NaF∶NH 4 The mol ratio of Cl is 1: 0.5-1.5: 0.5-2: 0.4-1.2;
step 2: placing the graphite crucible in a horizontal tubular resistance furnace, introducing inert gas Ar as protective gas, raising the temperature to 1500-1700 ℃ at the heating rate of 3-5 ℃/min, and preserving the temperature for 1-4 h; and cooling to room temperature at a cooling rate of 3-5 ℃/min, and taking out the graphite crucible to obtain the HfC whisker with the length-diameter ratio of 50-500.
2. The method for synthesizing hafnium carbide whiskers with a large length-diameter ratio by the carbothermic reduction method according to claim 1, wherein the method comprises the following steps: the mixed powder was sieved through a 100 mesh sieve.
3. The method for synthesizing hafnium carbide whiskers with a large length-diameter ratio by the carbothermic method according to claim 1, wherein: ammonium chloride NH of the step 1 4 Cl was replaced by NaCl.
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CN106882977A (en) * 2017-02-22 2017-06-23 西北工业大学 The preparation method of the whisker modified carbon/carbon compound material of zirconium carbide
CN108298540A (en) * 2018-01-22 2018-07-20 浙江理工大学 A kind of preparation method of titanium carbide nano-wires
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