CN111331130B - Preparation method of flower-shaped nano manganese hydroxide coated aluminum composite material - Google Patents
Preparation method of flower-shaped nano manganese hydroxide coated aluminum composite material Download PDFInfo
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- CN111331130B CN111331130B CN202010166029.2A CN202010166029A CN111331130B CN 111331130 B CN111331130 B CN 111331130B CN 202010166029 A CN202010166029 A CN 202010166029A CN 111331130 B CN111331130 B CN 111331130B
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Abstract
The invention discloses a preparation method of a flower-shaped nano manganese hydroxide coated aluminum composite material. The method has the advantages of simple process, simple and convenient operation, low raw material price and low production cost, and is very suitable for large-scale production.
Description
Technical Field
The invention relates to a preparation method of a composite material, in particular to a preparation method of a flower-shaped nano manganese hydroxide coated aluminum composite material.
Background
With the continuous improvement of the requirements of modern wars on the performance of weaponry, in order to realize the purposes of accurate striking and efficient damage, higher requirements are put forward on the energy performance of a novel energetic material system, and the main direction of the development of modern energetic materials is to improve the energy of the energetic material system and increase the energy release rate.
At present, metal fuel is widely applied to modern energetic material systems, and the addition of the metal fuel is one of the main ways for improving the energy performance of the energetic material systems. Common metal fuels are aluminum, beryllium, boron, magnesium, lithium, and the like. The aluminum powder has obvious effect on improving the specific impulse due to high density, low oxygen consumption and high combustion heat, and is widely applied to the field of energetic materials such as propellant, explosive, thermite and the like as metal fuel due to rich raw materials and low cost.
In general, the surface of aluminum powder is wrapped by a layer of compact aluminum oxide film, and the oxide film on the surface of the aluminum powder needs to be cracked and evaporated when the aluminum powder is ignited and combusted, wherein the temperature is above 2000 ℃; in addition, the aluminum powder has a low melting point (about 660 ℃), and is very easy to sinter and agglomerate in the combustion process and agglomerate. Therefore, reducing sintering agglomeration in the aluminum powder heating process, reducing the ignition temperature of the aluminum powder and improving the combustion efficiency of the aluminum powder are important problems to be solved in the actual use process of the aluminum powder.
Surface coating design has proven to be an effective approach. Such as: phylling spring, et al (CN 103506621A) disclose a method for preparing fluororubber-coated aluminum powder composite particles, wherein the coating layer fluororubber can improve the high-temperature oxidation rate and heat release rate of nano aluminum powder. Zhao Fengji et al (CN 103611943A) disclose a method for preparing carbon-coated nano aluminum powder, which effectively prevents the nano aluminum from being oxidized after coating, keeps the activity of the nano aluminum and improves the heat release performance of the nano aluminum powder at high temperature. However, most of the coating materials involved in the research are inert substances, are not solid rocket propellant formula components, and have low combustion heat value.
The nanometer manganese hydroxide (manganese oxide) is proved to be an excellent solid rocket propellant burning rate catalyst (J. mater. chem. 22 (2012), 6536-6538, Nanomaterials 7 (2017) 450), and has a remarkable catalytic effect on thermal decomposition of an oxidant Ammonium Perchlorate (AP). At present, the research field of the nano-catalyst generally has a fatal problem that the agglomeration phenomenon of the nano-catalyst is very serious, the nano-catalyst is very difficult to uniformly disperse in an added system, and the full play of the performance of the nano-catalyst is seriously hindered.
In the existing literature, a preparation method of a flower-shaped nano manganese hydroxide coated aluminum composite material is not available.
Disclosure of Invention
The invention aims to: the flower-shaped nano manganese hydroxide coated aluminum composite material improves the oxidation reaction mechanism of aluminum powder at high temperature, improves the high-temperature oxidation efficiency of the aluminum powder, improves the dispersibility of a nano manganese hydroxide catalyst, fully exerts the excellent characteristics of the nano catalyst and provides technical support for the application of the flower-shaped nano manganese hydroxide coated aluminum composite material in a solid rocket propellant.
The technical solution of the invention is as follows: the preparation method of the flower-shaped nano manganese hydroxide coated aluminum composite material comprises the steps of mixing a water-phase suspension of aluminum powder with a manganese fluoride aqueous solution, and centrifugally separating a product obtained by reaction to obtain the flower-shaped nano manganese hydroxide coated aluminum composite material.
The preparation method comprises the following specific steps:
(1) adding aluminum powder into water for ultrasonic dispersion to obtain a water phase suspension of the aluminum powder;
(2) adding a certain amount of manganese fluoride into the aqueous suspension of the aluminum powder, and heating the mixed solution to the reaction temperature under the condition of stirring;
(3) after reacting for a certain time, centrifuging, washing and drying the product to obtain the flower-shaped nano manganese hydroxide coated aluminum composite material.
In the step (1), the particle size range of the aluminum powder is 100 nm-10 μm, and the ultrasonic dispersion power is 60-360W.
In the step (1), the concentration of the aqueous suspension of the aluminum powder is 3-10 g/L.
In the step (2), the mass of the manganese fluoride is 0.02-0.1 time of that of the aluminum powder; the mixed solution is heated to the reaction temperature by 2-5 ℃/min under the stirring condition of 250-500 rpm.
In the step (2), the reaction temperature is 30-60 ℃.
In the step (3), the reaction time is 10-30 minutes, and the drying temperature is 45 ℃.
The principle of the invention is as follows: after a certain amount of manganese fluoride is added into the aqueous suspension of the aluminum powder, the manganese fluoride firstly ionizes fluorine ions and manganese ions, and the fluorine ions are corrosive, so that the surface of the aluminum powder is etched, hydroxide ions are generated, and the pH value of the surface of the aluminum powder is increased; the formed hydroxide ions are captured by manganese ions, combined to form manganese hydroxide precipitate, and deposited on the surface of the aluminum powder; due to the lamellar structure of the manganese hydroxide, the flower-shaped nano manganese hydroxide coated aluminum composite material is obtained.
Compared with the prior art, the invention has the following beneficial effects:
1. the flower-shaped nano manganese hydroxide coated aluminum composite material is quickly prepared by only two reagents, namely aluminum powder and manganese fluoride.
2. Any surfactant and any organic solvent are not introduced in the preparation process, the required production equipment is simple, and the method is suitable for industrial production.
3. The flower-shaped nano manganese hydroxide is uniformly coated on the surface of the aluminum powder, the concentration of the manganese fluoride is regulated, and the content of the flower-shaped nano manganese hydroxide can be controlled.
Drawings
FIG. 1 is a scanning electron microscope photograph of a flower-like nano manganese hydroxide-coated aluminum composite material;
FIG. 2 is a thermal oxidation reaction performance diagram of the flower-like nano manganese hydroxide coated aluminum composite material;
FIG. 3 is a diagram of the catalytic performance of the flower-like nano-manganese hydroxide coated aluminum composite material on the thermal decomposition of ammonium perchlorate.
Detailed Description
The technical solution of the present invention is further illustrated below with reference to examples, but it should not be construed as being limited thereto.
Example 1: the flower-shaped nano manganese hydroxide coated aluminum composite material is prepared according to the following steps
(1) Adding aluminum powder with the particle size range of 100 nm into water to perform ultrasonic dispersion with the power of 60W to obtain a water phase suspension of the aluminum powder with the concentration of 3 g/L;
(2) adding manganese fluoride with the mass of 0.02 time of that of the aluminum powder into the aqueous suspension of the aluminum powder, and heating the mixed solution to the reaction temperature of 30 ℃ at the speed of 2 ℃/min under the stirring condition of 250 r/min;
(3) after reacting for 10 minutes, centrifuging and washing the product, and drying at 45 ℃ to obtain the flower-like nano manganese hydroxide coated aluminum composite material.
Example 2: the flower-shaped nano manganese hydroxide coated aluminum composite material is prepared according to the following steps
(1) Adding aluminum powder with the particle size range of 1 mu m into water to perform ultrasonic dispersion with the power of 210W to obtain a water phase suspension of the aluminum powder with the concentration of 6.5 g/L;
(2) adding manganese fluoride with the mass of 0.06 time of that of the aluminum powder into the aqueous suspension of the aluminum powder, and heating the mixed solution to the reaction temperature of 45 ℃ at 3 ℃/min under the stirring condition of 350 r/min;
(3) after reacting for 20 minutes, centrifuging and washing the product, and drying at 45 ℃ to obtain the flower-like nano manganese hydroxide coated aluminum composite material.
Example 3: the flower-shaped nano manganese hydroxide coated aluminum composite material is prepared according to the following steps
(1) Adding aluminum powder with the particle size range of 10 mu m into water to perform ultrasonic dispersion with the power of 360W to obtain a water phase suspension of the aluminum powder with the concentration of 10 g/L;
(2) adding manganese fluoride with the mass of 0.1 time of that of the aluminum powder into the aqueous suspension of the aluminum powder, and heating the mixed solution to the reaction temperature of 60 ℃ at the speed of 4 ℃/min under the stirring condition of 500 rpm;
(3) after reacting for 30 minutes, centrifuging and washing the product, and drying at 45 ℃ to obtain the flower-like nano manganese hydroxide coated aluminum composite material.
Example 4: the flower-shaped nano manganese hydroxide coated aluminum composite material is prepared according to the following steps
(1) Adding aluminum powder with the particle size range of 3 mu m into water to perform ultrasonic dispersion with the power of 300W to obtain aqueous suspension of the aluminum powder with the concentration of 6 g/L;
(2) adding manganese fluoride with the mass of 0.06 time of that of the aluminum powder into the aqueous suspension of the aluminum powder, and heating the mixed solution to the reaction temperature of 50 ℃ at the speed of 5 ℃/min under the stirring condition of 500 rpm;
(3) after reacting for 20 minutes, centrifuging and washing the product, and drying at 45 ℃ to obtain the flower-like nano manganese hydroxide coated aluminum composite material.
Claims (6)
1. A preparation method of a flower-shaped nano manganese hydroxide coated aluminum composite material comprises the steps of mixing a water-phase suspension of aluminum powder with a manganese fluoride aqueous solution, and centrifugally separating a product obtained by reaction to obtain the flower-shaped nano manganese hydroxide coated aluminum composite material; the preparation method is characterized by comprising the following specific steps:
(1) adding aluminum powder into water for ultrasonic dispersion to obtain a water phase suspension of the aluminum powder;
(2) adding a certain amount of manganese fluoride into the aqueous suspension of the aluminum powder, and heating the mixed solution to the reaction temperature under the condition of stirring;
(3) after reacting for a certain time, centrifuging, washing and drying the product to obtain the flower-shaped nano manganese hydroxide coated aluminum composite material.
2. The preparation method of the flower-like nano manganese hydroxide coated aluminum composite material as claimed in claim 1, which is characterized by comprising the following steps: in the step (1), the particle size range of the aluminum powder is 100 nm-10 μm, and the ultrasonic dispersion power is 60-360W.
3. The preparation method of the flower-like nano manganese hydroxide coated aluminum composite material as claimed in claim 1, which is characterized by comprising the following steps: in the step (1), the concentration of the aqueous suspension of the aluminum powder is 3-10 g/L.
4. The preparation method of the flower-like nano manganese hydroxide coated aluminum composite material as claimed in claim 1, which is characterized by comprising the following steps: in the step (2), the mass of the manganese fluoride is 0.02-0.1 time of that of the aluminum powder; the mixed solution is heated to the reaction temperature by 2-5 ℃/min under the stirring condition of 250-500 rpm.
5. The preparation method of the flower-like nano manganese hydroxide coated aluminum composite material as claimed in claim 2, which is characterized by comprising the following steps: in the step (2), the reaction temperature is 30-60 ℃.
6. The preparation method of the flower-like nano manganese hydroxide coated aluminum composite material as claimed in claim 2, which is characterized by comprising the following steps: in the step (3), the reaction time is 10-30 minutes, and the drying temperature is 45 ℃.
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| CN114853072B (en) * | 2022-03-18 | 2023-05-16 | 浙江帕瓦新能源股份有限公司 | Precursor material of nickel-cobalt-manganese ternary positive electrode material and preparation method thereof |
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