阅读说明：本技术 一种碳化硼纳米线的制备方法 (Preparation method of boron carbide nanowires ) 是由 王志江 于 2021-01-18 设计创作，主要内容包括：一种碳化硼纳米线的制备方法,本发明涉及碳化硼材料制备领域,具体涉及碳化硼纳米线的制备技术,具体涉及B-4C纳米线的制备技术。本发明要解决现有方法制备B-4C纳米线的纯度低,形貌不均的技术问题。方法：一、原料的混合；二、高温加热生长B-4C纳米线。本发明制备的碳化硼纳米线纯度高、长径比高、形貌均一。本发明制备的碳化硼纳米线用于提高陶瓷、金属、树脂等材料的强度。(The invention discloses a preparation method of a boron carbide nanowire, relates to the field of preparation of boron carbide materials, particularly relates to a preparation technology of the boron carbide nanowire, and particularly relates to B 4 C preparation technology of the nano wire. The invention aims to solve the problem of preparing B by the existing method 4 The purity of the C nanowire is low, and the morphology is uneven. The method comprises the following steps: firstly, mixing raw materials; secondly, high-temperature heating growth B 4 And C, nano wires. The boron carbide nanowire prepared by the method has high purity, high length-diameter ratio and uniform appearance. The boron carbide nanowire prepared by the method is used for improving the strength of materials such as ceramics, metals, resins and the like.)

1. The preparation method of the boron carbide nanowire is characterized by comprising the following steps:

firstly, drying boron oxide and boron powder, and uniformly mixing to obtain mixed powder;

and secondly, placing the mixed powder obtained in the first step into a crucible, heating the mixed powder by adopting a high-temperature furnace under the condition of inert atmosphere, controlling the heating rate to be 1-50 ℃/min, heating the mixed powder to the temperature of 1200-1800 ℃, stopping introducing inert gas, introducing reducing gas, and carrying out gas-phase reaction to obtain the boron carbide nanowire, thus completing the method.

2. The method for preparing boron carbide nanowires according to claim 1, wherein the molar ratio of the boron oxide to the boron powder in the first step is (1-10): 1.

3. The method according to claim 1, wherein the drying temperature in the first step is 50 ℃ to 150 ℃ and the boron carbide nanowires are dried to a constant weight.

4. The method according to claim 1, wherein the boron oxide in step one is boric acid, metaboric acid, pyroboric acid, or boron oxide.

5. The method for preparing boron carbide nanowires of claim 1, wherein the mixing manner in the step one is planetary ball milling mixing, and the milling ball material is SiC, WC, B₄C or ZrO, the mass ratio of the ball material is (3-10) to 1, and the ball milling time is 0.5-4 h.

6. The method for preparing boron carbide nanowires according to claim 1, wherein the crucible in the second step is an alumina crucible or a graphite crucible.

7. The method according to claim 1, wherein the inert gas in step two is nitrogen or argon.

8. The method for preparing boron carbide nanowires according to claim 1, wherein when the high temperature furnace in the second step is heated, the temperature rise rate is 1-5 ℃/min when the temperature is lower than 1000 ℃; when the temperature is higher than 1000 ℃, the heating rate is 20-30 ℃/min.

9. The method for preparing boron carbide nanowires of claim 1, wherein the reducing gas in step two is CO or CH₄The flow rate of the gas is controlled to be 1-200 mL/min.

10. The method for preparing boron carbide nanowires according to claim 1, wherein the gas phase reaction time in the second step is controlled to be 0.5-6 h.

Technical Field

The invention relates to the field of preparation of boron carbide materials, in particular to a preparation technology of boron carbide nanowires.

Background

B₄C was first discovered in 1858 and had a stoichiometric formula of B₄Compounds of C were not recognized until 1934. B is₄The C has higher melting point, higher hardness, good wear resistance, acid and alkali corrosion resistance, small density and very high thermal neutron absorption capacity due to the property of covalent bonds. The hardness of the material is second to that of diamond and cubic boron nitride, and the material belongs to a non-metallic material and has important physicochemical properties. B is₄C has the performance of high-temperature extraordinary hardness and is widely applied to the fields of body armor, grinding tools and the like. B is₄C is the lightest ceramic material, can be used as a jet plane blade due to the low density, and is widely applied in the field of aerospace. Can be used as control rod of nuclear reactor due to its strong neutron absorption capacityAnd materials that prevent leakage of radioactive materials.

Typical nanowires have aspect ratios above 1000 and are often referred to as one-dimensional materials. Generally, as the size is reduced, the nanowires show better mechanical properties, higher strength and better toughness. It is believed that some one-dimensional nanomaterials are ideal reinforcement for brittle ceramics due to their extremely high strength and toughness. The introduction of one-dimensional nano materials such as fibers, whiskers, nanowires, nanotubes and the like into the carbide ceramic matrix composite can improve the mechanical properties of the carbide ceramic matrix composite, optimize the structure of the composite and achieve the toughening effect. The defect of low toughness of the traditional ceramic composite material is overcome to a certain extent, the length-diameter ratio of the nanowire can also play roles of bridging, crack turning and the like, and the mechanical properties of the material, such as strength, toughness and the like, are further enhanced. In addition, B₄C nanowires are also widely used to increase the structural strength of resin-based and metal-based materials.

Are currently related to B₄The preparation and development of the C nanowire are few, the specific methods mainly comprise a carbothermic method, a chemical deposition method, an organic precursor method and the like, transition metal such as iron, cobalt, nickel and the like or metal salt thereof is used as a catalyst, and the nanowire is formed at high temperature in a mode of controlling the growth direction by the catalyst. These methods have disadvantages of low purity, non-uniform morphology, and difficult removal of the metal catalyst present at the head of the nanowire.

Disclosure of Invention

The invention aims to solve the problem of preparing B by the existing method₄The C nanowire has low length-diameter ratio and uneven appearance, and provides a preparation method of the boron carbide nanowire.

A preparation method of boron carbide nanowires specifically comprises the following steps:

firstly, drying boron oxide and boron powder, and uniformly mixing to obtain mixed powder;

and secondly, placing the mixed powder obtained in the first step into a crucible, heating the mixed powder by adopting a high-temperature furnace under the condition of inert atmosphere, controlling the heating rate to be 1-50 ℃/min, heating the mixed powder to the temperature of 1200-1800 ℃, stopping introducing inert gas, introducing reducing gas, and carrying out gas-phase reaction to obtain the boron carbide nanowire, thus completing the method.

Wherein, in the second step, an empty crucible is placed at the lower end of the airflow of the crucible in the high-temperature furnace.

The main reaction equation of the invention is as follows:

2B+2B₂O₃＝3B₂O₂ (1)

2B₂O₂+6CO＝B₄C+5CO₂ (2)

the invention has the beneficial effects that:

the invention adopts pure gas phase reaction to prepare boron carbide nano-wire, and the core step is 2B₂O₂(g)+6CO(g)＝B₄C(s)+5CO₂(g) In that respect It is now generally accepted that controlling supersaturation is the primary consideration in obtaining one-dimensional nanostructures, and evidence suggests that the degree of supersaturation determines the predominant growth morphology. According to the VS mechanism, gaseous CO and B₂O₂CO and B being the main reactants and thus participating in the reaction₂O₂Has a gas supersaturation degree of B₄And C, important influence factors of the morphology of the final product. When CO and B are in the system₂O₂When the gas partial pressure is large, the nucleation reaction is dominant. When in the system, the participating gases CO and B₂O₂When the degree of supersaturation is low, B₄C will grow along the one surface with the lowest energy, forming a nanowire-like structure.

Reacting boron oxide with carbon source to generate B₂O₂The reaction temperature required is relatively high, at which B is₂O₂And the supersaturation degree of CO is high, resulting in difficulty in controlling the morphology. The invention adds simple substance boron with higher reaction activity to ensure that boron and boron oxide generate B at lower temperature₂O₂And further control B₄And C growing. At the reaction temperature, B in the reaction system₂O₂And a low degree of supersaturation of CO, B₄The growth of C grows along the lowest energy crystal plane, thereby generating B₄The reaction of C tends to form a nanowire-like structure, which is obtainedSimple form B₄And C, nano wires. The invention adjusts CO and B in the reaction system by controlling parameters such as reaction temperature, heating rate, raw material ratio, flow rate of protective gas and the like₂O₂The supersaturation degree of the gas can be regulated and controlled to obtain B with different diameters and different length-diameter ratios₄And C, nano wires.

Thus, the process of the invention and conventional B₄Compared with the preparation method of the C nanowire, the preparation method has the following specific effects:

1. compared with the precursor method. The preparation method has simple process and low equipment requirement, and is easy for industrial production.

2. The nanowire with the specific morphology can be controllably prepared by changing the air flow speed to control the process parameters such as the reaction temperature and the like.

3. The used raw materials are cheap and easy to obtain, and the production cost is low.

4. The product has high aspect ratio and uniform appearance, the diameters of the nanowires are mainly distributed in the range of 50-200 nm, and the aspect ratio can reach 100-1000.

5. The main peak in the product is B by XRD test analysis₄And C, the obtained product has high purity, no metal catalyst and other residues, and complex treatment such as subsequent separation and impurity removal is not needed.

The boron carbide nanowire prepared by the method is used for improving the strength of materials such as ceramics, metals, resins and the like.

Drawings

FIG. 1 is an XRD spectrum of boron carbide nanowires prepared in the first example;

FIG. 2 is an SEM micrograph of boron carbide nanowires prepared according to the first example.

Detailed Description

The technical solution of the present invention is not limited to the specific embodiments listed below, and includes any combination of the specific embodiments.

The first embodiment is as follows: the preparation method of the boron carbide nanowire provided by the embodiment specifically comprises the following steps:

firstly, drying boron oxide and boron powder, and uniformly mixing to obtain mixed powder;

and secondly, placing the mixed powder obtained in the first step into a crucible, heating the mixed powder by adopting a high-temperature furnace under the condition of inert atmosphere, controlling the heating rate to be 1-50 ℃/min, heating the mixed powder to the temperature of 1200-1800 ℃, stopping introducing inert gas, introducing reducing gas, and carrying out gas-phase reaction to obtain the boron carbide nanowire, thus completing the method.

The second embodiment is as follows: the first difference between the present embodiment and the specific embodiment is: in the first step, the molar ratio of the boron oxide to the boron powder is (1-10): 1. The rest is the same as the first embodiment.

The third concrete implementation mode: the present embodiment differs from the first or second embodiment in that: in the first step, the drying temperature is 50-150 ℃ and the mixture is dried to constant weight. The other is the same as in the first or second embodiment.

The fourth concrete implementation mode: the difference between this embodiment mode and one of the first to third embodiment modes is: the oxide of boron in the first step is boric acid, metaboric acid, pyroboric acid or boron oxide. The others are the same as in one of the first to third embodiments.

The fifth concrete implementation mode: the difference between this embodiment and one of the first to fourth embodiments is: step one, the mixing mode is planetary ball milling mixing, and the grinding ball material is SiC, WC and B₄C or ZrO, the mass ratio of the ball material is (3-10) to 1, and the ball milling time is 0.5-4 h. The other is the same as one of the first to fourth embodiments.

The sixth specific implementation mode: the difference between this embodiment and one of the first to fifth embodiments is: and step two, the crucible is an alumina crucible or a graphite crucible. The other is the same as one of the first to fifth embodiments.

The seventh embodiment: the difference between this embodiment and one of the first to sixth embodiments is: and step two, the inert gas is nitrogen or argon. The other is the same as one of the first to sixth embodiments.

The specific implementation mode is eight: the present embodiment differs from one of the first to seventh embodiments in that: when the high-temperature furnace is used for heating, when the temperature is lower than 1000 ℃, the heating rate is 1-5 ℃/min; when the temperature is higher than 1000 ℃, the heating rate is 20-30 ℃/min. The other is the same as one of the first to seventh embodiments.

The specific implementation method nine: the present embodiment differs from the first to eighth embodiments in that: step two, the reducing gas is CO or CH₄The flow rate of the gas is controlled to be 1-200 mL/min. The rest is the same as the first to eighth embodiments.

The detailed implementation mode is ten: the present embodiment differs from one of the first to ninth embodiments in that: and in the second step, the gas phase reaction time is controlled to be 0.5-6 h. The other is the same as one of the first to ninth embodiments.

The following examples were used to demonstrate the beneficial effects of the present invention:

the first embodiment is as follows:

the preparation method of the boron carbide nanowire provided by the embodiment specifically comprises the following steps:

firstly, putting boron oxide and amorphous boron powder into an oven, drying at 105 ℃ to constant weight, then weighing the boron oxide and amorphous boron powder with a molar ratio of 1:1, mixing by adopting a planetary ball mill, wherein a grinding ball material is B₄C, ball-milling the mixture at a ball-milling speed of 120r/min for 120min in a mass ratio of 5: 1, and uniformly mixing to obtain mixed powder;

secondly, placing the mixed powder obtained in the first step into an alumina crucible, then placing the alumina crucible into a tubular furnace, placing an empty alumina crucible at the lower end of the airflow of the alumina crucible, heating the alumina crucible by adopting the tubular furnace under the condition of argon atmosphere, and controlling the heating rate to be 5 ℃/min when the temperature is lower than 1000 ℃; and when the temperature is higher than 1000 ℃, the heating rate is 20 ℃/min, the temperature is increased to 1450 ℃, the introduction of argon is stopped, reducing gas CO is introduced, the flow rate of the gas is controlled to be 50mL/min, and gas phase reaction is carried out for 4h to obtain the boron carbide nanowire, thus completing the method.

FIG. 1 is an XRD spectrum of boron carbide nanowires prepared in the first example; wherein · represents B₄C, the figure proves that the method prepares the B₄C, and B₄The content of C is high.

FIG. 2 is an SEM microscopic morphology of the boron carbide nanowires prepared in the first embodiment, and it can be seen that the nanowire-shaped material with uniform morphology, i.e., the boron carbide nanowires, is prepared by the method of the present invention, wherein the nanowires mainly have diameters of 50-200 nm, lengths of more than 80 μm, and aspect ratios of 100-1200.