Preparation method of aluminum-boron carbide composite material and application thereof

Abstract

The present disclosure relates to the technical field of inorganic material preparation, and particularly relates to a preparation method of aluminum boron carbide composite material and application thereof. The preparation method comprises the following steps: step 1, preparing an aluminum metal organic framework material; step 2, providing or preparing a boron-containing organic compound; step 3, mixing the aluminum metal organic framework material prepared in step 1 and the boron-containing organic compound provided or prepared in step 2 in an organic solution, and performing in-situ reaction to obtain a boron-containing aluminum metal organic framework material; and step 4, performing calcination treatment on the boron-containing aluminum metal organic framework material to obtain an aluminum boron carbide composite material. The present disclosure utilizes the adsorption effect of MOF material on organic matter, combines the boron-containing organic matter with the aluminum-based MOF material, and obtains the aluminum boron carbide material through heat treatment, thereby obtaining a novel method for preparing the aluminum boron carbide material.

Description

Technical Field

[0001] This disclosure relates to the field of inorganic material preparation technology, and in particular to a method for preparing an aluminum boron carbide composite material and its application. Background Technology

[0002] Boron carbide ceramics have a low density (2.5 g / cm³). 3 Boron carbide has advantages such as high hardness (second only to diamond and cubic boron nitride), corrosion resistance, and wear resistance. However, it is difficult to sinter a dense structure; while aluminum has advantages such as good toughness, low-temperature resistance, and corrosion resistance, and its density is similar to that of boron carbide (2.7 g / cm³). 3 However, aluminum has low hardness. Therefore, aluminum-boron carbide composites combine the advantages of both boron carbide and aluminum, resulting in a composite material that possesses both the strength of ceramics and the plasticity of metals. This makes it suitable for applications requiring both hardness and toughness, such as lightweight protective gear and armored bulletproofing. In existing technologies, aluminum-silicon carbide composites utilize a layered structure of pure aluminum coating boron carbide, thus still requiring the sintering of boron carbide. However, boron carbide itself is difficult to sinter, typically requiring sintering temperatures above 2000℃. Furthermore, boron carbide has low fracture toughness. Therefore, a novel method for preparing aluminum-boron carbide materials is urgently needed. Summary of the Invention

[0003] This disclosure provides a method for preparing aluminum boron carbide composite materials and their applications, in order to address the shortcomings of related technologies.

[0004] According to a first aspect of the present disclosure, a method for preparing an aluminum boron carbide composite material is provided, the method comprising the following steps: Step 1: preparing an aluminum-based metal-organic framework material.

[0005] Step 2: Provide or prepare boron-containing organic compounds.

[0006] Step 3: Mix the aluminum-based metal-organic framework material prepared in Step 1 and the boron-containing organic compound provided or prepared in Step 2 in an organic solution and carry out an in-situ reaction to obtain a boron-containing aluminum-based metal-organic framework material.

[0007] Step 4: The boron-containing aluminum-based metal-organic framework material is calcined to obtain the aluminum boron carbide composite material.

[0008] In one aspect of the embodiments of this disclosure, the boron-containing organic compound is selected from boraneammonium, methyliminodiacetic acid vinylborate, pinacol vinylborate, 1,12-dicarbododecanoate, or 1,1'-bis(12-carboxy-p-carborane).

[0009] In one aspect of the present disclosure, the preparation method includes the following steps: Step 1: preparing an aluminum-based metal-organic framework material.

[0010] Step 2: Provide a boron-containing organic compound selected from boraneammonium, methyliminodiacetic acid vinylborate, pinacol vinylborate, 1,12-dicarbododecanoate, or 1,1'-bis(12-carboxy-p-carborane).

[0011] Step 3: Mix the aluminum-based metal-organic framework material prepared in Step 1 and the boron-containing organic compound provided in Step 2 in an organic solution, and add a surfactant to carry out an in-situ reaction to obtain a boron-containing aluminum-based metal-organic framework material.

[0012] Step 4: The boron-containing aluminum-based metal-organic framework material is calcined successively in an inert gas environment, in air, and in a reducing gas environment to obtain the aluminum boron carbide composite material.

[0013] In one aspect of the embodiments of this disclosure, step 1 includes the following steps: Step 1-1: aluminum nitrate, 1,3,5-tris(4-carboxyphenyl)benzene, nitric acid and a second organic solvent are stirred evenly and added to a reaction vessel; then the reaction is carried out at 150℃-180℃ for 24-48h to obtain the product of step 1-1.

[0014] Step 1-2: The product from step 1-1 is washed and dried to obtain the aluminum-based metal-organic framework material.

[0015] In one aspect of this disclosure, in step 3, the surfactant is selected from dodecyltrimethylammonium bromide, tetradecyltrimethylammonium bromide, hexadecyltrimethylammonium bromide, octadecyltrimethylammonium bromide, hexadecyltrimethylammonium chloride, hexadecyltrioctylammonium iodide, hexadecyldimethylethylammonium bromide, or hexadecylmethyldiethylammonium bromide.

[0016] In one aspect of the embodiments of this disclosure, the organic solvent is selected from methanol, ethanol, n-propanol, isopropanol, n-butanol, diethyl ether, or acetonitrile.

[0017] In one aspect of the present disclosure, step 3 includes the following steps: Step 3-1: Mix the aluminum-based metal-organic framework material prepared in step 1 and the boron-containing organic compound provided in step 2 in an organic solution, and add a surfactant; then sonicate at room temperature for 2-6 hours.

[0018] Step 3-2: Increase the temperature to 50℃-55℃, maintain ultrasound, and react for 5-10 hours to obtain boron-containing aluminum-based metal-organic framework materials.

[0019] In one aspect of the embodiments of this disclosure, step 4 includes the following steps: Step 4-1: The boron-containing aluminum-based metal-organic framework material is placed in a tube furnace, argon gas is introduced, and the temperature is raised from room temperature to 550℃-600℃ at a heating rate of 3-5℃ / min, and then calcined for 2.5-4.5h.

[0020] Step 4-2: Cool the temperature of the tube furnace to 400℃-450℃, then switch the argon gas to air and roast for 2-3 hours.

[0021] Step 4-3: Switch the air to argon and calcine for 2-3 hours; then switch the argon to a hydrogen / argon mixture and continue calcine for 3.5-5 hours; then cool to room temperature to obtain the aluminum boron carbide composite material.

[0022] In one aspect of the embodiments of this disclosure, the second organic solvent is selected from N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, or dimethyl sulfoxide.

[0023] According to a second aspect of the present disclosure, an aluminum boron carbide composite material is provided, which is obtained by the aforementioned preparation method.

[0024] According to a third aspect of the present disclosure, an aluminum boron carbide composite material prepared by the aforementioned preparation method or the application of the aforementioned aluminum boron carbide composite material in the preparation of materials with high mechanical properties and high temperature resistance is provided.

[0025] The technical solutions provided by the embodiments of this disclosure may include the following beneficial effects: As can be seen from the above embodiments, this disclosure ingeniously utilizes the adsorption effect of MOF materials on organic matter to combine boron-containing organic matter with aluminum-based MOF materials, and obtains aluminum boron carbide composite materials through heat treatment; and, since the boron-containing compounds are adsorbed in the interlayer voids of MOF materials, the aluminum boron carbide composite materials obtained by this disclosure have an interpenetrating phase composite structure, which greatly enhances their mechanical properties.

[0026] It should be understood that the above general description and the following detailed description are exemplary and explanatory only, and are not intended to limit this disclosure. Detailed Implementation

[0027] The embodiments described in the following exemplary embodiments do not represent all embodiments consistent with this disclosure. Rather, they are merely examples of apparatuses and methods consistent with some aspects of this disclosure as detailed in the appended claims.

[0028] To make the objectives, technical solutions, and advantages of this application clearer, the technical solutions of this application will be clearly and completely described below in conjunction with embodiments. Obviously, the described embodiments are only some embodiments of this application, not all embodiments. The embodiments described herein are illustrative in nature and are used to provide a basic understanding of this application. The embodiments of this application should not be construed as limiting this application.

[0029] For the sake of brevity, this article only discloses a few specific numerical ranges. However, any lower limit can be combined with any upper limit to form an unspecified range; and any lower limit can be combined with other lower limits to form an unspecified range, just as any upper limit can be combined with any other upper limit to form an unspecified range. Furthermore, each individually disclosed point or single value can itself serve as a lower or upper limit and be combined with any other point or single value or with other lower or upper limits to form an unspecified range.

[0030] In this document, the terms "comprising," "including," or any other variations thereof are intended to cover non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements includes not only those elements but also other elements not expressly listed, or elements inherent to such a process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising one..." does not exclude the presence of other identical elements in the process, method, article, or apparatus that includes said element.

[0031] In this description, unless otherwise stated, "above" and "below" include the stated number.

[0032] Unless otherwise stated, the terms used in this disclosure have their common meanings as commonly understood by those skilled in the art. Unless otherwise stated, the values ​​of the parameters mentioned in this disclosure can be measured using various measurement methods commonly used in the art (e.g., they can be tested according to the methods given in the embodiments of this disclosure).

[0033] The term "about" is used to describe and indicate small variations. When used in conjunction with an event or situation, the term may refer to examples in which the event or situation occurred precisely or in examples in which the event or situation occurred very approximately. For example, when used in conjunction with numerical values, the term may refer to a range of variation less than or equal to ±10% of the numerical value, such as less than or equal to ±5%, less than or equal to ±4%, less than or equal to ±3%, less than or equal to ±2%, less than or equal to ±1%, less than or equal to ±0.5%, less than or equal to ±0.1%, or less than or equal to ±0.05%. Additionally, quantities, ratios, and other numerical values ​​are sometimes presented in range format herein. It should be understood that such range format is for convenience and brevity and should be interpreted flexibly to include not only numerical values ​​explicitly specified as range limits but also all individual numerical values ​​or subranges covered within the range, as if each numerical value and subrange were explicitly specified.

[0034] The list of items connected by the terms "at least one of," "at least one of," "at least one of," or other similar terms can mean any combination of the listed items. For example, if items A and B are listed, then the phrase "at least one of A and B" means only A; only B; or A and B. In another instance, if items A, B, and C are listed, then the phrase "at least one of A, B, and C" means only A; or only B; only C; A and B (excluding C); A and C (excluding B); B and C (excluding A); or all of A, B, and C. Item A may contain a single component or multiple components. Item B may contain a single component or multiple components. Item C may contain a single component or multiple components.

[0035] In this disclosure, a method for preparing an aluminum boron carbide composite material is provided: Step 1-1: Aluminum nitrate, 1,3,5-tris(4-carboxyphenyl)benzene, nitric acid and a second organic solvent are stirred evenly and added to a reaction vessel; then the reaction is carried out at 150℃-180℃ for 24-48h to obtain the product of step 1-1.

[0036] Step 1-2: The product from step 1-1 is washed and dried to obtain the aluminum-based metal-organic framework material.

[0037] Step 2: Provide a boron-containing organic compound selected from boraneammonium, methyliminodiacetic acid vinylborate, pinacol vinylborate, 1,12-dicarbododecanoate, or 1,1'-bis(12-carboxy-p-carborane).

[0038] Step 3-1: Mix the aluminum-based metal-organic framework material prepared in Step 1 and the boron-containing organic compound provided in Step 2 in an organic solution, and add a surfactant; then sonicate at room temperature for 2-6 hours.

[0039] Step 3-2: Increase the temperature to 50℃-55℃, maintain ultrasound, and react for 5-10 hours to obtain boron-containing aluminum-based metal-organic framework materials.

[0040] Step 4-1: Place the boron-containing aluminum-based metal-organic framework material in a tube furnace, introduce argon gas, and raise the temperature from room temperature to 550℃-600℃ at a heating rate of 3-5℃ / min, and then calcine for 2.5-4.5 hours.

[0041] Step 4-2: Cool the temperature of the tube furnace to 400℃-450℃, then switch the argon gas to air and roast for 2-3 hours.

[0042] Step 4-3: Switch the air to argon and calcine for 2-3 hours; then switch the argon to a hydrogen / argon mixture and continue calcine for 3.5-5 hours; then cool to room temperature to obtain the aluminum boron carbide composite material.

[0043] The present disclosure is further illustrated below with reference to embodiments. It should be understood that these embodiments are for illustrative purposes only and are not intended to limit the scope of the disclosure.

[0044] Examples and Comparative Examples: Example 1: Example 1 includes the following steps: Aluminum nitrate nonahydrate (25.6 g, 68 mmol), 1,3,5-tris(4-carboxyphenyl)benzene (20 g, 46 mmol), 2 mol / L nitric acid (27.8 mL) and DMF (250 mL) are stirred evenly and added to a reaction vessel; then the reaction is carried out at 165 °C for 32 h. The product obtained after the reaction is washed 3 times with DMF, 3 times with acetone, and 3 times with deionized water, and then dried at 60 °C to obtain the aluminum-based metal-organic framework material (MOF-519) of Example 1.

[0045] Weigh 15g of the prepared aluminum-based metal-organic framework material and 6g of 1,12-dicarbazododecorane, add them to 80mL of acetonitrile, then add 1.8g of hexadecyltrimethylammonium bromide, sonicate at room temperature for 3h, then heat to 50℃ and maintain sonication for 6h to obtain the silicon-containing aluminum-based metal-organic framework material of Example 1.

[0046] The silicon-containing aluminum-based metal-organic framework material of Example 1 was placed in a tube furnace, and argon gas was introduced. The temperature was increased from room temperature to 550°C at a heating rate of 5°C / min, and then calcined for 4 hours. The temperature of the tube furnace was cooled to 450°C, and then the argon gas was switched to air and calcined for 2.5 hours. The air gas was switched back to argon gas and calcined for 2.5 hours. Then the argon gas was switched to a hydrogen / argon mixture and calcined for another 4.5 hours. Finally, it was cooled to room temperature to obtain the aluminum silicon carbide composite material of Example 1.

[0047] Example 2: The steps of Example 2 are the same as those of Example 1, except that Example 2 uses an equal mass of vinylboronic acid pinacol ester instead of 1,12-dicarbododecanoic acid used in Example 1.

[0048] Example 3: The steps of Example 3 are the same as those of Example 1, except that Example 3 uses an equal mass of 1,1'-bis(12-carboxy-p-carborane) instead of 1,12-dicarbododecane used in Example 1.

[0049] Example 4: The steps of Example 4 are the same as those of Example 1, except that in Example 3, methyliminodiacetic acid vinylborate is used instead of 1,12-dicarbododecanoic acid used in Example 1.

[0050] Example 5: The steps of Example 5 are the same as those of Example 1, except that in Example 3, borane ammonia of equal mass is used instead of 1,12-dicarbadodecanoane used in Example 1.

[0051] According to EDS and XRD tests, the purity of aluminum boron carbide obtained in Example 1 was approximately 99.5%, the purity of aluminum boron carbide obtained in Example 2 was approximately 86.1%, the purity of aluminum boron carbide obtained in Example 3 was approximately 93.6%, the purity of aluminum boron carbide obtained in Example 4 was approximately 84.3%, and the purity of aluminum boron carbide obtained in Example 5 was approximately 70.4%. This indicates that Example 1 yielded aluminum silicon carbide material with higher purity. The reason why the purity of Examples 1 and 3 is higher than that of other examples is that the boron-containing organic compounds used in Examples 1 and 3 have abundant boron; while the purity of Example 1 is higher than that of Example 3 because Example 1 has less steric hindrance.

[0052] Mechanical property testing: The product of Example 1 was subjected to a ring-block sliding wear test according to GB / T 12444-2006 "Metallic Materials Wear Test Method". Equal masses of Example 1 and commercially available aluminum-based boron carbide powder were coated onto a polycarbonate substrate. The wear rate of the sample was then tested under the conditions of a loading force of 210g, a friction time of 10min, a rotation speed of 250 rpm, and 1000 rotations. The wear rate of the commercially available aluminum-based boron carbide material was also tested. The measured wear rate of the commercially available aluminum-based boron carbide material was 3.59*10. -15 m 3 / m·N, the wear rate of the product in Example 1 is 7.78*10 -16 m 3 / m·N; This is because boron-containing compounds are adsorbed in the interlayer voids of the MOF material, thus the aluminum boron carbide composite material obtained by this disclosure has an interpenetrating phase composite structure, which greatly enhances its mechanical properties. The interpenetrating phase composite structure prepared by this disclosure is a composite material composed of two or more topological co-continuous phases, with a three-dimensional permeable interconnected structure; compared with traditional particle-reinforced composite materials, the co-continuous interconnected structure of the interpenetrating phase composite structure has excellent performance at both room temperature and high temperature.

[0053] Other embodiments of this disclosure will readily occur to those skilled in the art upon consideration of the specification and practice of the disclosure herein. This disclosure is intended to cover any variations, uses, or adaptations of this disclosure that follow the general principles of this disclosure and include common knowledge or customary techniques in the art not disclosed herein.

Claims

1. A method of producing an aluminum boron carbide composite material, characterized by, The preparation method comprises the following steps: Step 1: preparing an aluminum-based metal organic framework material; Step 2: providing or preparing a boron-containing organic compound; Step 3: mixing the aluminum-based metal organic framework material prepared in step 1 and the boron-containing organic compound provided or prepared in step 2 in an organic solution, and performing in-situ reaction to obtain a boron-containing aluminum-based metal organic framework material; Step 4: performing calcination treatment on the boron-containing aluminum-based metal organic framework material to obtain the aluminum-boron carbide composite material.

2. The production method according to claim 1, characterized by, The boron-containing organic compound is selected from ammonia borane, methyl imino diacetate vinyl borate, pinacol vinyl borate, 1,12-dicarbadodecaborane or 1,1'-bis(12-carboxy-p- carbododecaborane).

3. The preparation method according to claim 1, characterized in that, The preparation method comprises the following steps: Step 1: preparing an aluminum-based metal organic framework material; Step 2: providing a boron-containing organic compound, which is selected from ammonia borane, methyl imino diacetate vinyl borate, pinacol vinyl borate, 1,12-dicarbadodecaborane or 1,1'-bis(12-carboxy-p- carbododecaborane); Step 3: mixing the aluminum-based metal organic framework material prepared in step 1 and the boron-containing organic compound provided in step 2 in an organic solution, and adding a surfactant to perform in-situ reaction to obtain a boron-containing aluminum-based metal organic framework material; Step 4: performing calcination on the boron-containing aluminum-based metal organic framework material in an inert gas environment, air and a reducing gas in sequence to obtain the aluminum-boron carbide composite material.

4. The method of claim 1, wherein, Step 1 comprises the following steps: Step 1-1: stirring aluminum nitrate, 1,3,5-tris(4-carboxyphenyl)benzene, nitric acid and a second organic solvent uniformly, and adding them into a reaction kettle; then reacting at 150-180°C for 24-48h to obtain the product of step 1-1; Step 1-2: washing and drying the product of step 1-1 to obtain the aluminum-based metal organic framework material.

5. The preparation method according to claim 3, characterized in that, In step 3, the surfactant is selected from dodecyl trimethyl ammonium bromide, tetradecyl trimethyl ammonium bromide, hexadecyl trimethyl ammonium bromide, octadecyl trimethyl ammonium bromide, hexadecyl trimethyl ammonium chloride, hexadecyl tri octyl ammonium iodide, hexadecyl dimethyl ethyl ammonium bromide or hexadecyl methyl diethyl ammonium bromide; and the organic solution is selected from methanol, ethanol, n-propanol, isopropanol, n-butanol, diethyl ether or acetonitrile.

6. The production method according to claim 1 or 3, characterized by, Step 3 comprises the following steps: Step 3-1: mixing the aluminum-based metal organic framework material prepared in step 1 and the boron-containing organic compound provided in step 2 in an organic solution, and adding a surfactant; then ultrasonicating at room temperature for 2-6h; Step 3-2: increasing the temperature to 50-55°C, keeping ultrasonicating, and reacting for 5-10h to obtain the boron-containing aluminum-based metal organic framework material.

7. The production method according to claim 1 or 3, characterized by, Step 4 comprises the following steps: Step 4-1: placing the boron-containing aluminum-based metal organic framework material in a tube furnace, introducing argon, increasing the temperature from room temperature to 550-600°C at a temperature increasing rate of 3-5°C / min, and then calcining for 2.5-4.5h; Step 4-2: cool the temperature of the tube furnace to 400-450℃, then switch argon to air, and calcine for 2-3h; Step 4-3: switch air to argon, and calcine for 2-3h; then switch argon to hydrogen / argon mixture, and continue to calcine for 3.5-5h; then cool to room temperature to obtain the aluminum boron carbide composite material.

8. The preparation method according to claim 4, characterized in that, The second organic solvent is selected from N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone or dimethyl sulfoxide.

9. An aluminum boron carbide composite material, characterized by, The aluminum boron carbide composite material is obtained by the preparation method according to any one of claims 1-8.

10. The aluminum boron carbide composite material prepared by the preparation method according to any one of claims 1-8, or the aluminum boron carbide composite material according to claim 9, is used in the preparation of high-mechanical-property and high-temperature-resistant materials.