Preparation method and application of aluminum boron carbide composite material

Abstract

The invention relates to the technical field of inorganic material preparation, in particular to a preparation method and application of an aluminum boron carbide composite material. The preparation method comprises the following steps: step 1, preparing an aluminum-based metal organic framework material; 2, providing or preparing a boron-containing organic compound; 3, mixing the aluminum-based metal organic framework material prepared in the step 1 and the boron-containing organic compound provided or prepared in the step 2 in an organic solution, and carrying out an in-situ reaction to obtain a boron-containing aluminum-based metal organic framework material; and 4, roasting the boron-containing aluminum-based metal organic framework material to obtain the aluminum boron carbide composite material. The boron-containing organic matter and the aluminum-based MOF material are combined by utilizing the adsorption effect of the MOF material on the organic matter, the aluminum boron carbide material is obtained through heat treatment, and the novel method for preparing the aluminum boron carbide material is obtained.

Description

Technical Field

[0001] The present disclosure relates to the technical field of inorganic material preparation, and in particular to a preparation method and application of an aluminum boron carbide composite material. Background Art

[0002] Boron carbide ceramics have a low density (2.5g / cm 3 ), high hardness (second only to diamond and cubic boron nitride), corrosion resistance and wear resistance. However, boron carbide is difficult to sinter densely; while aluminum has the advantages of good toughness, low temperature resistance and corrosion resistance, and its density is similar to that of boron carbide (2.7g / cm 3 ), but the hardness of aluminum is low. Therefore, aluminum boron carbide composite materials combine the advantages of boron carbide and aluminum. They are composite materials that have both the strength of ceramics and the plasticity of metals. They are used in applications such as lightweight protection and armor bulletproofing that require both material hardness and toughness. In the existing technology, aluminum silicon carbide composite materials use a layered structure of pure aluminum coated with boron carbide, so boron carbide still needs to be sintered. However, boron carbide itself is difficult to sinter, and the sintering temperature is usually above 2000°C. In addition, boron carbide has low fracture toughness. Therefore, a new method for preparing aluminum boron carbide materials is urgently needed. Summary of the Invention

[0003] The present disclosure provides a preparation method of an aluminum boron carbide composite material and its application to address the deficiencies in the related art.

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

[0005] Step 2: providing or preparing a boron-containing organic compound.

[0006] Step 3: The aluminum-based metal-organic framework material prepared in step 1 and the boron-containing organic compound provided or prepared in step 2 are mixed in an organic solution, and an in-situ reaction is carried out to obtain a boron-containing aluminum-based metal-organic framework material.

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

[0008] In one aspect of the embodiments of the present disclosure, the boron-containing organic compound is selected from borane, vinylboronic acid methyliminodiacetate, vinylboronic acid pinacol ester, 1,12-dicarbadodecaborane or 1,1′-bis(12-carboxy-p-carborane).

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

[0010] Step 2: providing a boron-containing organic compound, wherein the boron-containing organic compound is selected from borane ammonia, vinylboronic acid methyliminodiacetate, vinylboronic acid pinacol ester, 1,12-dicarbadodecaborane or 1,1'-bis(12-carboxyl-p-carborane).

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

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

[0013] In one aspect of the embodiments of the present disclosure, step 1 includes the following steps: Step 1-1: Stir aluminum nitrate, 1,3,5-tris(4-carboxyphenyl)benzene, nitric acid and a second organic solvent evenly, and add them to a reactor; then react at 150°C-180°C for 24-48h to obtain the product of step 1-1.

[0014] Step 1-2: Wash and dry the product of step 1-1 to obtain the aluminum-based metal-organic framework material.

[0015] In one aspect of the embodiments of the present 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 the present disclosure, the organic solvent is selected from methanol, ethanol, n-propanol, isopropanol, n-butanol, diethyl ether or acetonitrile.

[0017] In one aspect of the embodiments of the present disclosure, step 3 includes 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 2-6 hours.

[0018] Step 3-2: Raise the temperature to 50° C.-55° C., maintain ultrasonication, and react for 5-10 hours to obtain a boron-containing aluminum-based metal-organic framework material.

[0019] In one aspect of the embodiments of the present disclosure, step 4 includes the following steps: Step 4-1: placing the boron-containing aluminum-based metal-organic framework material in a tubular furnace, introducing argon gas, raising the temperature from room temperature to 550°C-600°C at a heating rate of 3-5°C / min, and then calcining for 2.5-4.5h.

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

[0021] Step 4-3: switching the air to argon and baking for 2-3 hours; then switching the argon to a hydrogen / argon mixed gas and continuing baking for 3.5-5 hours; then cooling to room temperature to obtain the aluminum boron carbide composite material.

[0022] In one aspect of the embodiments of the present 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 an embodiment of the present disclosure, there is provided an aluminum boron carbide composite material, which is obtained by the aforementioned preparation method.

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

[0025] The technical solutions provided by the embodiments of the present disclosure may include the following beneficial effects: As can be seen from the above embodiments, the present disclosure cleverly utilizes the adsorption effect of MOF materials on organic matter, combines boron-containing organic matter with aluminum-based MOF materials, and obtains aluminum boron carbide composite materials through heat treatment; and, since the boron-containing compound is adsorbed in the interlayer gaps of the MOF material, the aluminum boron carbide composite material obtained by the present disclosure has an interpenetrating phase composite structure, which greatly enhances its mechanical properties.

[0026] It is to be understood that the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the disclosure. DETAILED DESCRIPTION

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

[0028] To make the purpose, technical solutions, and advantages of this application more clear, the technical solutions of this application will be clearly and completely described below in conjunction with the embodiments. Obviously, the described embodiments are part of the embodiments of this application, rather than all the embodiments. The relevant embodiments described herein are illustrative and are used to provide a basic understanding of this application. The embodiments of this application should not be interpreted as limiting this application.

[0029] For the sake of clarity, only some numerical ranges are specifically disclosed herein. However, any lower limit may be combined with any upper limit to form an unspecified range; and any lower limit may be combined with other lower limits to form an unspecified range, and similarly, any upper limit may be combined with any other upper limit to form an unspecified range. In addition, each individually disclosed point or single value may itself serve as a lower limit or upper limit and be combined with any other point or single value, or with other lower limits or upper limits, to form an unspecified range.

[0030] As used herein, the terms "comprises," "comprising," or any other variations thereof are intended to encompass non-exclusive inclusion, such that a process, method, article, or apparatus that includes a list of elements includes not only those elements but also other elements not expressly listed, or elements inherent to such process, method, article, or apparatus. In the absence of further limitations, an element defined by the phrase "comprising a ..." does not preclude the presence of additional identical elements in the process, method, article, or apparatus that includes the element.

[0031] In the description herein, unless otherwise specified, “above” and “below” include the number itself.

[0032] Unless otherwise specified, the terms used in this disclosure have the commonly understood meanings commonly understood by those skilled in the art. Unless otherwise specified, the numerical values ​​of the various parameters mentioned in this disclosure can be measured using various measurement methods commonly used in the art (for example, they can be tested according to the methods given in the examples of this disclosure).

[0033] The term "about" is used to describe and illustrate small changes. When used in conjunction with an event or situation, the term may refer to an example in which the event or situation occurs precisely and an example in which the event or situation occurs very approximately. For example, when used in conjunction with a numerical value, the term may refer to a variation range of 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%. In addition, amounts, ratios, and other numerical values ​​are sometimes presented in this article in a range format. It should be understood that such range formats are for convenience and brevity, and should be flexibly understood to include not only numerical values ​​explicitly designated as range limits, but also all individual numerical values ​​or subranges encompassed within the range, as if each numerical value and subrange were explicitly designated.

[0034] A 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, the phrase "at least one of A and B" means only A; only B; or A and B. In another example, if items A, B, and C are listed, 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 can contain a single component or multiple components. Item B can contain a single component or multiple components. Item C can contain a single component or multiple components.

[0035] In the present 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 reactor; then the mixture is reacted at 150°C-180°C for 24-48 hours to obtain the product of step 1-1.

[0036] Step 1-2: Wash and dry the product of step 1-1 to obtain the aluminum-based metal-organic framework material.

[0037] Step 2: providing a boron-containing organic compound, wherein the boron-containing organic compound is selected from borane ammonia, vinylboronic acid methyliminodiacetate, vinylboronic acid pinacol ester, 1,12-dicarbadodecaborane or 1,1'-bis(12-carboxyl-p-carborane).

[0038] Step 3-1: The aluminum-based metal organic framework material prepared in step 1 and the boron-containing organic compound provided in step 2 are mixed in an organic solution, and a surfactant is added; and then ultrasonicated at room temperature for 2-6 hours.

[0039] Step 3-2: Raise the temperature to 50° C.-55° C., maintain ultrasonication, and react for 5-10 hours to obtain a boron-containing aluminum-based metal-organic framework material.

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

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

[0042] Step 4-3: switching the air to argon and baking for 2-3 hours; then switching the argon to a hydrogen / argon mixed gas and continuing baking for 3.5-5 hours; then cooling to room temperature to obtain the aluminum boron carbide composite material.

[0043] The present disclosure is further described below with reference to the following examples. It should be understood that these examples are only used to illustrate the present disclosure and are not intended to limit the scope of the present 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 reactor; then the mixture is reacted at 165°C for 32 hours, and 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] 15 g of the prepared aluminum-based metal-organic framework material and 6 g of 1,12-dicarbonadodecaborane were weighed and added to 80 mL of acetonitrile, and then 1.8 g of hexadecyltrimethylammonium bromide was added. After ultrasonication at room temperature for 3 h, the mixture was heated to 50°C and maintained for 6 h 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, argon was introduced, and the temperature was increased from room temperature to 550°C at a heating rate of 5°C / min, and then baked for 4 hours; the temperature of the tube furnace was cooled to 450°C, and then the argon was switched to air, and baked for 2.5 hours; the air was switched to argon, and baked for 2.5 hours; then the argon was switched to a hydrogen / argon mixture, and the baking was continued for 4.5 hours; and then 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 the 1,12-dicarbonadodecaborane 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-carboxyl-p-carborane) instead of the 1,12-dicarbadodecaborane used in Example 1.

[0049] Example 4: The steps of Example 4 are the same as those of Example 1, except that an equal mass of vinylboronic acid methyliminodiacetate is used in Example 3 instead of 1,12-dicarbadodecaborane used in Example 1.

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

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

[0052] Mechanical properties test: The product of Example 1 was subjected to a ring-test block sliding wear test according to GBT12444-2006 "Metallic Material Wear Test Methods". Equal masses of Example 1 and commercially available aluminum-based boron carbide powder were coated on a polycarbonate substrate. The wear rate of the sample was then tested under the conditions of a loading force of 210 g, a friction time of 10 min, a rotation speed of 250 rpm, and a rotation number of 1000 times. The wear rate of the commercially available aluminum-based boron carbide material was also tested. The wear rate of the commercially available aluminum-based boron carbide material was found to be 3.59*10 -15 m 3 / m·N, the wear rate of the product of Example 1 is 7.78*10 -16 m 3 / m·N; This is due to the boron-containing compound being adsorbed in the interlayer voids of the MOF material. Therefore, the aluminum boron carbide composite material obtained by the present disclosure has an interpenetrating phase composite structure, which greatly enhances its mechanical properties. The interpenetrating phase composite structure prepared by the present disclosure is a composite material composed of two or more topological co-continuous phases, with a three-dimensional percolating interconnection structure. Compared with traditional particle-reinforced composite materials, the co-continuous interconnection structure of the interpenetrating phase composite structure has excellent performance at both room temperature and high temperature.

[0053] Those skilled in the art will readily appreciate other embodiments of the present disclosure after considering the specification and practicing the disclosure disclosed herein. This disclosure is intended to cover any variations, uses, or adaptations of the present disclosure that follow the general principles of the present disclosure and include common knowledge or customary techniques in the art not disclosed herein.

Claims

1. A method for preparing an aluminum boron carbide composite material, characterized in that: 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 an in-situ reaction to obtain a boron-containing aluminum-based metal-organic framework material; and step 4: calcining the boron-containing aluminum-based metal-organic framework material to obtain the aluminum boron carbide composite material.

2. The preparation method according to claim 1, characterized in that The boron-containing organic compound is selected from ammonia borane, vinyl boronic acid methyliminodiacetate, vinyl boronic acid pinacol ester, 1,12-dicarbadodecaborane or 1,1'-bis(12-carboxyl-p-carborane).

3. The preparation method according to claim 1, characterized in that The preparation method The invention comprises the following steps: step 1: preparing an aluminum-based metal-organic framework material; step 2: providing a boron-containing organic compound, wherein the boron-containing organic compound is selected from borane ammonia, vinylboronic acid methyliminodiacetate, vinylboronic acid pinacol ester, 1,12-dicarbonadodecaborane or 1,1'-bis(12-carboxyl-p-carborane); 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, adding a surfactant, and performing an in-situ reaction to obtain a boron-containing aluminum-based metal-organic framework material; and step 4: calcining the boron-containing aluminum-based metal-organic framework material in an inert gas environment, in air, and in a reducing gas in sequence to obtain the aluminum boron carbide composite material.

4. The preparation method according to claim 1, characterized in that Step 1 includes the following steps: Step 1-1: stirring aluminum nitrate, 1,3,5-tris(4-carboxyphenyl)benzene, nitric acid and a second organic solvent evenly and adding them to a reactor; then reacting at 150°C-180°C for 24-48 hours 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 1 or 3, characterized in that 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; and the organic solvent is selected from methanol, ethanol, n-propanol, isopropanol, n-butanol, ether or acetonitrile.

6. The preparation method according to claim 1 or 3, characterized in that Step 3 includes 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 2-6 hours; Step 3-2: raising the temperature to 50°C-55°C, maintaining ultrasonication, and reacting for 5-10 hours to obtain a boron-containing aluminum-based metal-organic framework material.

7. The preparation method according to claim 1 or 3, characterized in that Step 4 includes the following steps: Step 4-1: placing the boron-containing aluminum-based metal-organic framework material in a tube furnace, introducing argon, heating the temperature from room temperature to 550°C-600°C at a heating rate of 3-5°C / min, and then roasting for 2.5-4.5 hours; Step 4-2: cooling the temperature of the tube furnace to 400°C-450°C, then switching the argon to air, and roasting for 2-3 hours; Step 4-3: switching the air to argon, and roasting for 2-3 hours; then switching the argon to a hydrogen / argon mixture, and continuing to roast for 3.5-5 hours; and then cooling 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 in that: The aluminum boron carbide composite material is obtained by the preparation method according to any one of claims 1 to 8.

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