CN109834289B - Preparation method of nano aluminum powder - Google Patents
Preparation method of nano aluminum powder Download PDFInfo
- Publication number
- CN109834289B CN109834289B CN201711195123.5A CN201711195123A CN109834289B CN 109834289 B CN109834289 B CN 109834289B CN 201711195123 A CN201711195123 A CN 201711195123A CN 109834289 B CN109834289 B CN 109834289B
- Authority
- CN
- China
- Prior art keywords
- aluminum
- solvent
- aluminum powder
- nano aluminum
- nano
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Abstract
The invention provides a preparation method of nano aluminum powder, which is characterized in that raw material aluminum salt is uniformly mixed in a solvent, and the nano aluminum powder is prepared under the condition of a protective agent. By controlling the reaction conditions, nano aluminum powder with different particle sizes can be obtained, and the obtained nano aluminum powder is characterized by using methods such as an X-ray diffractometer (XRD), an infrared spectrum, a scanning electron microscope, thermogravimetric analysis and the like. The method provided by the invention has the advantages of simple operation, simple required raw materials, high yield and small particle size of the prepared nano aluminum powder.
Description
Technical Field
The invention relates to a separation technology of nano-powder, in particular to a preparation method of nano-aluminum powder.
Background
As a novel material, the nano-aluminum has three main application fields, including rocket propellant, explosive and solar cell aluminum back surface field. The three aspects have great significance for the development of national military and the development of economy. The nano aluminum material can enable missiles and torpedoes to attack at a very high speed before evasive measures are taken by targets, and can enable the combustion rate of propellant powder to reach 10 times of that of the current propellant powder, so that the bullet attack speed is higher.
At present, great progress is made on the application of the nano aluminum powder in the aspect of energetic materials at home and abroad. Compared with the common aluminum powder, the nano aluminum powder has the advantages of quick combustion and large heat release, and if 1% of ultrafine aluminum or nickel particles in mass ratio are added into the solid fuel propellant, the combustion heat of the fuel can be increased by 1 time. It has been reported in foreign countries that when 20% of alex (product of ARGON IDE company) is added into HTPB composite propellant, the combustion rate can be improved by 70% compared with the same content of delp aluminum powder. The addition of metal powder with high heat value into explosive is also one way to raise the work capacity of explosive. Aluminum-containing explosives which are high-density, high-explosive-heat and powerful explosives are widely applied to weapons in water and ammunitions of weapons for air force, and the preparation and application research of nano aluminum influences the further development of national defense construction and the gradual development of high-tech products in China.
From the research works in China and abroad, the research papers about the preparation method of the nano-aluminum are very few, and the used methods are mainly limited to physical methods, including an evaporation condensation method, a wire explosion method, a pulse laser ablation method and an arc discharge method, and the methods have the defects of high energy consumption, high equipment requirement, irregular particle size and the like. In recent years, the solution chemical method has the advantages of simple process, small equipment investment, uniform and controllable microstructure and the like, and has attracted extensive attention of researchers.
The common solution chemical method for preparing the nano aluminum has the defects that the product is easy to oxidize and agglomerate in the preparation process, and the byproduct LiCl impurity is easy to coat.
Therefore, the development of a novel preparation method of the nano-aluminum with low cost, high yield and small particle size, which is not easy to agglomerate, has extremely important significance.
Disclosure of Invention
In order to solve the above problems, the present inventors have conducted intensive studies and, as a result, have found that: adding raw material lithium aluminum hydride into anisole by using a solution chemical method for ultrasonic dissolution; adding raw material aluminum trichloride into anisole, performing ultrasonic dissolution, uniformly mixing the raw material aluminum trichloride in the anisole, and reacting under the condition of a protective agent to prepare the nano aluminum. By controlling the reaction conditions, nano aluminum powder with different particle sizes can be obtained, and the nano aluminum powder is characterized by methods such as an X-ray diffractometer (XRD), an infrared spectrum, a scanning electron microscope, thermogravimetric analysis and the like, so that the invention is completed.
The invention aims to provide a preparation method of nano aluminum powder, which comprises the following steps:
And 3, carrying out post-treatment to obtain the nano aluminum powder.
In the step 1, the method comprises the following steps of,
the aluminum salt is water or aluminum salt soluble in organic solvent, preferably single aluminum salt or aluminum and alkali metal composite salt, more preferably aluminum trichloride or lithium aluminum hydride;
the solvent I is a polar organic solvent, preferably an ether solvent such as anisole, phenetole, diphenyl ether, more preferably anisole.
A protecting agent is also added, said protecting agent being an organophosphine compound, such as an alkyl phosphine, an aryl phosphine, an alkyl aryl phosphine, preferably an aryl phosphine, more preferably triphenylphosphine.
The molar ratio of the aluminum salt to the auxiliary agent is lithium aluminum hydride to aluminum trichloride: and (2-6) 1 (3-25), preferably (3-5): 1: (5-20).
The mixing means includes stirring or ultrasonic oscillation, preferably ultrasonic oscillation, so that the mixing is uniform.
In the step 2, under the protection of inert gas, dropwise adding the mixed aluminum trichloride solution into the mixed solution of lithium aluminum hydride and triphenylphosphine, controlling the reaction temperature and the dropwise adding time during dropwise adding, continuing to react until the reaction is complete, stopping heating, cooling to room temperature, and/or
The reaction temperature during dripping is 140-160 ℃.
And 3, centrifuging the reaction solution, washing with a solvent II after the centrifugation is finished, adding a solvent III for centrifugation, washing with a solvent IV and centrifuging, drying, and crushing to obtain the nano aluminum powder.
In step 4, the solvent II is absolute methanol, the solvent III is absolute ethanol, and the solvent IV is acetone.
The nano aluminum powder prepared by the method has the particle size range of 50-200 nm, and the melting peak of the prepared nano aluminum powder is lower than that of the conventional aluminum material according to the TGA analysis result.
The method for separating the nano aluminum powder has the following beneficial effects:
(1) the operation is simple, and the byproducts are few;
(2) the loss of the nano aluminum powder is less in the preparation process;
(3) the preparation and separation effect is good, agglomeration is not easy to occur, and the particle size of the nano aluminum powder obtained by preparation and separation is small.
Drawings
FIGS. 1.1 and 1.2 show the XRD spectrum of the obtained nano aluminum powder and the standard XRD spectrum of the aluminum powder;
FIG. 2 shows an infrared spectrum of the obtained nano aluminum powder;
FIG. 3 shows an SEM image of the nano-aluminum powder obtained in example 1;
FIG. 4 shows an SEM image of the nano-aluminum powder obtained in example 2;
FIG. 5 shows an SEM image of the nano-aluminum powder obtained in example 3;
FIG. 6 shows an SEM image of the nano-aluminum powder obtained in example 4;
FIG. 7 shows an SEM image of the nano-aluminum powder obtained in example 5;
fig. 8 shows a thermogravimetric analysis spectrum of each of the obtained nano aluminum powder powders.
Detailed Description
The features and advantages of the present invention will become more apparent and appreciated from the following detailed description of the invention.
The word "exemplary" is used exclusively herein to mean "serving as an example, embodiment, or illustration. Any embodiment described herein as "exemplary" is not necessarily to be construed as preferred or advantageous over other embodiments.
The present invention is described in detail below.
According to the preparation method of the nano aluminum powder provided by the invention, the method comprises the following steps:
the aluminum salt is water or aluminum salt soluble in organic solvent, preferably single aluminum salt or aluminum and alkali metal composite salt, more preferably aluminum trichloride or lithium aluminum hydride;
the solvent I is a polar organic solvent, preferably an ether solvent such as anisole, phenetole, diphenyl ether, more preferably anisole.
In step 1, a protecting agent is also added, wherein the protecting agent is an organic phosphine compound, such as alkyl phosphine, aryl phosphine, alkyl aryl phosphine, preferably aryl phosphine, and more preferably triphenylphosphine.
The molar ratio of the aluminum salt to the auxiliary agent is lithium aluminum hydride to aluminum trichloride: and (2-6) 1 (3-25), preferably (3-5): 1: (5-20).
The preparation method of the nano aluminum is a solution chemical method. The basic principle of the solution chemical reaction method is to select one or more appropriate soluble metal salts, and prepare the solution according to the prepared material components, so that each element is in an ion or molecular state. Selecting proper solvent, carrying out a series of operations to precipitate metal ions uniformly, and finally producing the metal ionsWashing and separating the materials to prepare the nano powder. The solution chemical method for preparing the nano aluminum is to reduce aluminum salt in a solvent system to realize the synthesis of the nano aluminum, and the reaction equation is AlCl3+3LiAlH4＝4Al+3LiCl+6H2。
Lithium aluminum hydride (LiAlH)4) Can exist stably in dry air at normal temperature. Is vulnerable to moisture. React violently in the presence of water and alcohol. Solubility of lithium aluminum hydride: insoluble in hydrocarbons, soluble in diethyl ether, tetrahydrofuran, dimethylcellosolve, slightly soluble in n-butyl ether, insoluble or very slightly soluble in hydrocarbons and dioxane.
Aluminium trichloride (AlCl)3) I.e. aluminum chloride, which is a colorless transparent crystal or a white, slightly yellowish crystalline powder. The vapour of aluminium chloride, either dissolved in a non-polar solvent or in the molten state, is present as covalently dimerised molecules. Aluminum chloride is soluble in water and many organic solvents. The aqueous solution is acidic. In the presence of aromatic hydrocarbons, aluminum chloride and aluminum are mixed to synthesize bis (aromatic hydrocarbon) metal complexes.
Anisole, formula C7H8O, with the relative molecular weight of 108.13, is colorless liquid, has the melting point of-37 to-38 ℃, the boiling point of 155 ℃, the relative density of 0.9980 to 1.0010 and the refractive index of 1.5165 to 1.5175. For organic synthesis, and also as solvents, fragrances and insect repellents. Insoluble in water, and soluble in ethanol, diethyl ether, etc.
The inventor finds that the main raw materials of the reaction are anhydrous aluminum chloride and lithium aluminum hydride, and the melting points of the anhydrous aluminum chloride and the lithium aluminum hydride are 180 ℃ and 140 ℃ respectively, so that the organic solvent with the boiling point higher than 140 ℃ and low toxicity is selected as far as possible, and the anisole is selected as the reaction solvent, so that the anhydrous aluminum chloride and the lithium aluminum hydride have better solubility, the lithium aluminum hydride is in a liquid state during the reaction, and the full reaction with the anhydrous aluminum chloride is facilitated.
Triphenylphosphine (TPP), a common phosphorus-containing compound, is used in the fields of pharmaceutical industry, organic synthesis, analysis and the like, and can also be used as a brightener for dye technology, a high-molecular polymerization agent, an antioxidant for color film development, a polyepoxide stabilizer and the like.
The inventor finds that the nano aluminum is very active, so that oxygen in the air is easy to rapidly change into aluminum oxide. Therefore, the use of a suitable protective agent is very important for the chemical preparation of nano aluminum powder.
The inventor finds that P atoms are easy to be coordinately bound with metals, and the movement of nano aluminum particles is prevented or slowed down because the surface of Al atoms is bound with phosphorus in triphenylphosphine in a coordination bond form. Meanwhile, triphenylphosphine has the effects of preventing aluminum particles from aggregating and protecting nano aluminum from being oxidized, and the agglomeration of nano aluminum can be prevented due to the steric hindrance caused by triphenylphosphine molecules on the surface of Al, so that the generated Al has small particle size and high stability. The triphenylphosphine is used as a protective agent in the reaction process, so that the generated nano aluminum powder can be effectively prevented from being rapidly oxidized in the air, and the nano aluminum powder is favorably formed. In addition, the reaction raw materials are isolated from water and oxygen, so a protective gas must be used in the reaction process.
According to the reaction equation of the lithium aluminum hydride and the aluminum trichloride, the molar ratio of the lithium aluminum hydride to the aluminum trichloride is 2-6: 1.
The inventor finds that the dosage of the triphenylphosphine serving as a protective agent is crucial to the preparation process of the nano aluminum powder, and the dosage of the triphenylphosphine influences the particle size of the nano aluminum powder. The molar ratio of triphenylphosphine to aluminum trichloride in the invention is 3-25: 1.
in step 1, the mixing uniformly comprises stirring or ultrasonic oscillation, preferably ultrasonic oscillation, so that the mixing is uniform.
In the step 2, the mixing mode comprises stirring or ultrasonic oscillation, and the stirring can be electromagnetic stirring or mechanical stirring; and (3) ultrasonic oscillation mixing, namely placing the reaction container in the step (1) into an ultrasonic machine for ultrasonic oscillation, and using an ultrasonic oscillation method to assist aluminum salt to disperse, wherein the ultrasonic oscillation time is 10 min-1 h.
The inventor finds that the nano aluminum powder can be effectively broken up by using an ultrasonic oscillation method to assist the aluminum salt to disperse in the solvent, so that the nano aluminum powder is uniformly dispersed in the dispersing agent, the longer the ultrasonic oscillation time is, the better the dispersing effect is, but the longer the ultrasonic oscillation time is, the solvent is volatilized in a large amount, and the dispersing effect is reduced, so that the ultrasonic oscillation method is preferably used to assist the nano aluminum powder to disperse, and the ultrasonic oscillation time is 10min to 1 hour.
in the step 2, under the protection of inert gas, dropwise adding the mixed aluminum trichloride solution into the mixed solution of lithium aluminum hydride and triphenylphosphine, controlling the reaction temperature and the dropwise adding time during dropwise adding, continuing to react until the reaction is complete, stopping heating, and cooling to room temperature.
Due to LiAlH4And AlCl3The reaction is easy to occur in water and oxygen, so the water-free and oxygen-free environment is always kept in the weighing process, the dispersing process and the reaction process.
The reaction temperature during dripping is 140-160 ℃, the dripping time is 20 min-1 h, and the continuous reaction time is 5 min-30 min.
The inventor finds that at 140-160 ℃, the prepared nano aluminum particles are gradually reduced along with the increase of temperature. The reaction rate increases with increasing temperature, and higher reaction rates favor maintaining a higher degree of supersaturation during the nucleation phase, resulting in the formation of more nuclei, which results in a relatively smaller final growth size of the individual particles. As the boiling point of anisole is 155 ℃, the temperature is 154 ℃ at most when the solvent is anisole.
And 3, carrying out post-treatment to obtain the nano aluminum powder.
And 3, centrifuging the reaction solution, washing with a solvent II after the centrifugation is finished, adding a solvent III for centrifugation, washing with a solvent IV and centrifuging, drying, and crushing to obtain the nano aluminum powder.
In step 3, the solvent II is absolute methanol, the solvent III is absolute ethanol, and the solvent IV is acetone.
The present inventors have found that LiCl, which is a reaction by-product, can be removed well and Triphenylphosphine (TPP), which has not been reacted, can be removed well by washing with absolute methanol and absolute ethanol, respectively, and centrifuging.
The inventor also finds that the dried product is not easy to agglomerate when the product is washed by acetone and centrifuged during the post-treatment.
Wait for the final centrifuged product to dry. The drying method is not limited, and vacuum drying is preferable.
The nano aluminum powder prepared by the method has the particle size range of 50-200 nm, and the melting peak of the prepared nano aluminum powder is lower than that of the conventional aluminum material according to the TGA analysis result.
The method for separating the nano aluminum powder with different particle sizes, provided by the invention, has the following beneficial effects:
(1) the preparation and separation of the nano aluminum powder can be realized only by a conventional reaction device, a centrifugal machine and an ultrasonic machine without using large-scale equipment;
(2) the operation is simple, and the byproducts are few;
(3) the loss of the nano aluminum powder is less in the preparation process;
(4) the preparation and separation effect is good, agglomeration is not easy to occur, and the particle size distribution range of the nano aluminum powder obtained by preparation and separation is narrow.
Examples
Example 1
Taking a clean 250mL four-mouth flask, four glass stoppers, a stirrer and a 50mL constant-pressure dropping tube, then putting the flask into a vacuum glove box according to the correct operation steps, and weighing 0.23g of LiAlH on an electronic balance by using weighing paper 4And 2.63g of Triphenylphosphine (TPP) (triphenylphosphine with AlCl)3The molar ratio of the components is 5:1), 40mL of anisole is measured by a measuring cylinder, poured into a four-neck flask for mixing, simultaneously a stirrer is placed, and 0.27g of anhydrous AlCl is additionally taken3Simultaneously, measuring 10mL of anisole by using a measuring cylinder, pouring the anisole into a dropping liquid pipe for mixing, taking out the four-neck flask and the dropping liquid pipe from a vacuum glove box together, carrying out ultrasonic treatment for 10-15min, taking out the flask and the dropping liquid pipe after the anisole is completely dissolved, operating in a fume hood, opening the air exhaust function of the fume hood, firstly pulling out a glass plug, introducing argon, and then quickly connecting the flask with a condensing pipe and introducing argonHeating on an intelligent magnetic stirrer, stirring (the rotating speed is 650r/min), inserting a thermometer, heating to 154 ℃, opening a piston of a constant-pressure dropping liquid pipe, dropping liquid in the constant-pressure dropping liquid pipe into the four-neck flask drop by drop until the dropping is finished, continuing to react for a period of time until the solution is completely blackened, turning off the heating, and cooling to the room temperature. The laboratory instrument was turned off. The resulting solution was ready for use and ready for post-treatment.
And (II) pouring the solution in the four-neck flask into a centrifuge tube, putting the centrifuge tube into a centrifuge, centrifuging at the rotation speed of 5000r/min for 6min, washing and centrifuging respectively by using anhydrous methanol and anhydrous ethanol for 1 time, and washing once by using acetone. After complete drying, the product was collected. The obtained product nano aluminum powder is marked as No. 1.
Example 2
The procedure is as in example 1, except that 3.94g (AlCl) of triphenylphosphine are used3The molar ratio of the aluminum powder to the triphenylphosphine is 1:7.5), and the obtained product nano aluminum powder is marked as No. 2.
Example 3
The procedure is as in example 1, except that triphenylphosphine is used in an amount of 5.25g (AlCl)3The molar ratio of the aluminum powder to the triphenylphosphine is 1:10), and the obtained product nano aluminum powder is marked as No. 3.
Example 4
The procedure is as in example 1, except that 6.57g (AlCl) of triphenylphosphine are used3The molar ratio of the aluminum powder to the triphenylphosphine is 1:12.5), and the obtained product nano aluminum powder is marked as No. 4.
Example 5
The procedure is as in example 1, except that triphenylphosphine is used in an amount of 7.88g (AlCl)3The molar ratio of the aluminum powder to the triphenylphosphine is 1:15), and the obtained product nano aluminum powder is marked as No. 5.
Examples of the experiments
XRD spectrogram determination of nano aluminum powder prepared in Experimental example 1
And (3) tabletting the No. 1-5 nano aluminum powder sample, then measuring XRD, and comparing the obtained map with an aluminum powder standard map. The results are shown in FIGS. 1.1 and 1.2.
An X-ray diffractometer (XRD), an abbreviation of X-ray diffraction, is a means for obtaining information such as the composition of a material, the structure or morphology of atoms or molecules inside the material, and the like by performing X-ray diffraction on the material and analyzing the diffraction pattern thereof. XRD was used to analyze the phase structure of the target sample. FIG. 1.1 shows that product spectrograms with different triphenylphosphine dosages are combined together when the No. 1-5 nano aluminum powder samples are plotted by using origin software, FIG. 1.2 shows that when the triphenylphosphine dosage is 7.88g, the product spectrogram (A) and the standard spectrogram (B) are combined together by using JADE software, two nano aluminum powder pictures are obtained together, and the peak shape and the peak height map of each picture are basically similar.
In FIG. 1.2, A represents a spectrum of the product obtained with an amount of triphenylphosphine of 7.88 g; b represents a standard map of the aluminum powder.
The average particle size of the nano-aluminum is calculated by using the scherrer formula, and the result is detailed in table 1.1:
D＝Kγ/βcosθ
(K is the Scherrer constant, D is the average thickness of the crystal grain vertical to the crystal face direction, beta is the half-height width of the diffraction peak of the measured sample, theta is the diffraction angle, gamma is the X-ray wavelength)
TABLE 1.1 average particle diameter
| AlCl3Ratio to TPP | 1:5 | 1:7.5 | 1:10 | 1:12.5 | 1:15 |
| Average particle diameter/nm | 89.41 | 85.50 | 82.88 | 82.67 | 80.59 |
As can be seen from FIG. 1.1, FIG. 1.2 and Table 1.1, the obtained black powdery particles are aluminum powder prepared by comparing the peak shape and peak height of XRD at 5 different ratios with the standard spectrum3And LiAlH4The nano aluminum powder generated by the reaction has no impurity peak, and the sharp degree of the diffraction peak can indicate that the product has better crystallinity and higher purity. The average particle size of the prepared samples was calculated by the scherrer equation and was seen to decrease with increasing TPP to AlCl3 ratio.
Experimental example 2 Infrared Spectrometry of Nano-sized aluminum powder obtained
Carrying out infrared spectrum determination analysis on the sample No. 1-5, observing the absorption spectrum of the obtained nano aluminum powder, and judging whether the surface of the nano aluminum powder is wrapped by Triphenylphosphine (TPP); the results are shown in FIG. 2.
The Fourier infrared absorption spectrum is an absorption spectrum generated by vibrational energy level transition of bonding atoms in molecules, and infrared absorption can be generated only by vibration causing change of dipole moment of the molecules. Infrared absorption spectroscopy is mainly used for structural analysis, qualitative identification and quantitative analysis.
3350cm-1And 2981cm-1The peak at (A) is the stretching vibration mode of C-H stretching, 1178cm-1And 742cm-1The peak at (a) is associated with the ring deformation oscillation of the ring C-H wobble. 1800cm-1And 1660cm-1The weaker peak in between is the combined band of overtones and C-H deformation vibrations. At 1581cm-1Due to C-C elongationAnd (5) contracting and vibrating. At 916cm-1，852cm-1And 692cm-1The peak at (a) is the deformation vibration of the ring, which confirms the adsorption of the mono-substituted benzene. Due to sattler infrared spectroscopy handbook: it is believed that the low wavenumber motion is caused by coordination bonds between phosphorus and aluminum ions. The P ion shares a lone pair of electrons with the Al atom and forms a stable coordination compound. The movement of the nanoparticles may be prevented or slowed down due to the binding of the Al atom on the surface to the coordinate bond of phosphorus in triphenylphosphine. Meanwhile, triphenylphosphine will play a dual role in preventing nanoparticles from aggregating and protecting them from oxidation, since the steric hindrance caused by triphenylphosphine molecules on the Al surface prevents nanoparticles from aggregating, making the Al particle size small and stable.
SEM analysis of Nano aluminum powder obtained in Experimental example 3
And (4) carrying out scanning electron microscope analysis on the No. 1-5 sample to see whether the product is in a nanometer level. The results are shown in fig. 3, 4, 5, 6 and 7.
Scanning Electron Microscopy (SEM) is a microscopic imaging that directly exploits the material properties of surface materials. FIGS. 3 to 7 show the scanning electron micrographs of aluminum trichloride and triphenylphosphine at molar ratios of 1:5, 1:7.5, 1:10, 1:12.5 and 1:15, respectively. The morphology of the aluminum nanoparticles is spherical, and the phenomenon of "sticking" between particles is not the reason for preparation, but is caused by the overlapping of the particles in the direction of electron beams during SEM analysis, which is illustrated by the difference in contrast between particles in the figure. As can be seen from a scanning electron microscope image, the particle size distribution range of the prepared aluminum nanoparticles is narrow and is approximately distributed between 50 nm and 200 nm. The irregular floc existing among the aluminum nanoparticles may be amorphous substances formed by aggregation of some crystal nuclei and some atom clusters which are not long enough to grow during the preparation process, which is related to the properties of the metallic aluminum and the preparation conditions, and the amount of the floc can be reduced by adjusting the process parameters. From the above figure, it can be seen that the nano aluminum particles gradually decrease as the amount of TPP increases. When the molar ratio of the aluminum trichloride to the triphenylphosphine is 1:15, the aluminum nanoparticles are smallest, and the appearance and the dispersion degree are best
Prepared in Experimental example 4Thermogravimetric analysis of nano aluminum powder
And carrying out thermogravimetric analysis on the No. 1-5 samples, and observing the thermal stability and the difference between the melting point and the normal melting point of the prepared nano aluminum. The results are shown in FIG. 8.
J shows the spectrum of product No. 5 obtained;
h shows the spectrum of product No. 4 produced;
f shows the spectrum of the product No. 3;
d shows the spectrogram of the prepared product No. 2;
b shows the spectrum of the product No. 1 obtained.
Thermogravimetric Analysis (TG or TGA) refers to a thermal Analysis technique that measures the mass of a sample to be measured as a function of temperature at a programmed temperature to study the thermal stability and composition of the material. As can be seen from fig. 8, each curve is substantially identical. The molar ratio of the aluminum trichloride to the triphenylphosphine is 1:5, 1:7.5, 1:10, 1:12.5, 1:15 melting peaks at 657.78 deg.C, 657.78 deg.C, 657.03 deg.C, 659.36 deg.C, 656.93 deg.C, respectively. They are all about 3 ℃ lower than the melting point (660.4 ℃) of conventional aluminum materials. The experimental result shows the characteristic of low melting point of the nano aluminum metal material.
The preparation method of the nano aluminum powder provided by the invention adopts anhydrous AlCl3And LiAlH4Reacting, and preparing the nano aluminum by a solution chemical method and adding a protective agent triphenylphosphine. The phase structure, the surface structure and the phase property of the sample are characterized by a series of experiments such as X-ray diffraction (XRD), infrared spectrum (IR), thermogravimetric analysis, particle size analysis, Scanning Electron Microscope (SEM) and the like. When the ratio of the aluminum trichloride to the triphenylphosphine is 1:5, 1:7.5, 1:10, 1:12.5 and 1:15, the nano aluminum particles are gradually reduced along with the increase of the ratio. Therefore, when the ratio is 1:15, namely the dosage of triphenylphosphine is 7.88g, the nano aluminum particles are smallest, the morphology and the dispersion degree are best, and the effect of the nano aluminum powder prepared by the solution chemical method is best.
The invention has been described in detail with reference to specific embodiments and illustrative examples, but the description is not intended to be construed in a limiting sense. Those skilled in the art will appreciate that various equivalent substitutions, modifications or improvements may be made to the technical solution of the present invention and its embodiments without departing from the spirit and scope of the present invention, which fall within the scope of the present invention. The scope of the invention is defined by the appended claims.
Claims (1)
1. A preparation method of nano aluminum powder is characterized by comprising the following steps:
step 1, weighing aluminum salt and solvent
Mixing in a reaction vessel;
step 2, reacting the system in the step 1;
step 3, carrying out post-treatment to obtain nano aluminum powder;
in the step 1, the aluminum salt is aluminum trichloride and lithium aluminum hydride; the solvent is
Is anisole; adding triphenylphosphine serving as a protective agent;
the lithium aluminum hydride is aluminum trichloride: the molar ratio of the protective agent is (3-5): 1: (5-20);
the mixing mode is ultrasonic oscillation, the time of the ultrasonic oscillation is 10min to 15min,
in the step 2, dropwise adding the mixed aluminum trichloride solution into the mixed solution of lithium aluminum hydride and triphenylphosphine under the protection of inert gas, controlling the reaction temperature at 154 ℃ during dropwise adding, controlling the dropwise adding time to be 20 min-1 h, continuing to react until the reaction is complete, stopping heating, and cooling to room temperature;
In step 3, the post-treatment comprises centrifuging the reaction solution, and after the centrifugation is finished, using a solvent
Washing, adding solvent
Centrifuging, and finally using a solvent
Washing and centrifuging, then drying and crushing to obtain nano aluminum powder;
the solvent is
Is anhydrous methanol, the solvent
Is absolute ethyl alcohol, and the solvent is
Is acetone.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711195123.5A CN109834289B (en) | 2017-11-24 | 2017-11-24 | Preparation method of nano aluminum powder |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711195123.5A CN109834289B (en) | 2017-11-24 | 2017-11-24 | Preparation method of nano aluminum powder |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109834289A CN109834289A (en) | 2019-06-04 |
| CN109834289B true CN109834289B (en) | 2022-06-10 |
Family
ID=66878063
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711195123.5A Active CN109834289B (en) | 2017-11-24 | 2017-11-24 | Preparation method of nano aluminum powder |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109834289B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110860696A (en) * | 2018-08-27 | 2020-03-06 | 阜阳师范学院 | Method for preparing nano aluminum powder |
| CN110860697A (en) * | 2018-08-28 | 2020-03-06 | 阜阳师范学院 | Method for preparing nano aluminum powder by using protective agent |
| CN111203547B (en) * | 2020-03-01 | 2021-08-27 | 浙江大学 | Small-size aluminum nanocluster material and synthesis method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20110115916A (en) * | 2010-04-16 | 2011-10-24 | 서울대학교산학협력단 | Method of manufacturing a shperical nano powder of alumiun oxide |
| CN106984804A (en) * | 2017-05-10 | 2017-07-28 | 哈尔滨工程大学 | A kind of nanometer aluminium powder method for coating |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19734972A1 (en) * | 1997-08-13 | 1999-02-18 | Cerdec Ag | Gold-containing nanoporous alumina membranes, process for their preparation and their use |
| CN102218545B (en) * | 2011-05-30 | 2012-11-28 | 陶栋梁 | Method for preparing nano aluminum by utilizing chemical method |
| CN103058241B (en) * | 2012-12-21 | 2014-05-28 | 江苏大学 | High-efficiency synthetic method of nanometer aluminum particle |
| US20150307962A1 (en) * | 2014-04-23 | 2015-10-29 | Saint Louis University | Novel Hydrogen-Evolving Polymer-Capped Aluminum Nanoparticles, Composites, and Methods of Synthesis Using Lithium Aluminum Hydride |
| CN105348867A (en) * | 2015-12-16 | 2016-02-24 | 江南大学 | Modification method of nano aluminium oxide |
| CN107225254A (en) * | 2017-04-01 | 2017-10-03 | 北京化工大学 | A kind of aluminum nanoparticles and preparation method thereof |
-
2017
- 2017-11-24 CN CN201711195123.5A patent/CN109834289B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20110115916A (en) * | 2010-04-16 | 2011-10-24 | 서울대학교산학협력단 | Method of manufacturing a shperical nano powder of alumiun oxide |
| CN106984804A (en) * | 2017-05-10 | 2017-07-28 | 哈尔滨工程大学 | A kind of nanometer aluminium powder method for coating |
Non-Patent Citations (1)
| Title |
|---|
| 张坤.纳米铝的应用及其制备方法研究进展.《阜阳师范学院学报(自然科学版)》.2010,第27卷(第3期),第45-47+61页. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109834289A (en) | 2019-06-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109834289B (en) | Preparation method of nano aluminum powder | |
| US10131548B2 (en) | Modification of layered double hydroxides | |
| US7785392B2 (en) | Method for manufacturing metal nanoparticles | |
| Ghanta et al. | Chemical synthesis of aluminum nanoparticles | |
| Tang et al. | Controlled reactivity of metastable n-Al@ Bi (IO3) 3 by employment of tea polyphenols as an interfacial layer | |
| Cong et al. | Hybrid ZnO–Dye Hollow Spheres with New Optical Properties by a Self‐Assembly Process Based on Evans Blue Dye and Cetyltrimethylammonium Bromide | |
| Chakraborty et al. | Sunlight mediated synthesis and antibacterial properties of monolayer protected silver clusters | |
| Ghanta et al. | Single-pot synthesis of zinc nanoparticles, borane (BH 3) and closo-dodecaborate (B 12 H 12) 2− using LiBH 4 under mild conditions | |
| Qu et al. | Synthesis of octahedral ZnO mesoscale superstructures via thermal decomposing octahedral zinc hydroxide precursors | |
| CN109834288B (en) | Preparation method of nano aluminum powder with uniform particle size distribution | |
| Ashok et al. | Mgo nanoparticles prepared by microwave-irradiation technique and its seed germination application | |
| CN101607722B (en) | Method for synthesizing magnesium hydrate hexagonal nano-flake | |
| Yolchinyan et al. | Tailoring bismuth oxide flower-, bowtie-and brushwood-like structures through microfluidic synthesis | |
| CN110860696A (en) | Method for preparing nano aluminum powder | |
| Li et al. | Synthesis and characterization of fluorescent chitosan–ZnSe/ZnS nanoparticles for potential drug carriers | |
| CN109399678B (en) | Preparation method of nano-scale metal hydroxide | |
| Liu et al. | Synthesis and Structural Manipulation of a Polyanionic Zincoborate [Zn (H 2 O) 6](NO 3) 2·[Zn {B 3 O 3 (OH) 4} 2 (H 2 O) 4]· 2H 2 O by the Molten Salt Method and its Potential Application as a Flame Retardant | |
| Hippolyte et al. | N‐Heterocyclic Carbene Boranes: Dual Reagents for the Synthesis of Gold Nanoparticles | |
| CN108465821B (en) | Preparation method of nano aluminum sheet | |
| CN110860697A (en) | Method for preparing nano aluminum powder by using protective agent | |
| Pomogailo et al. | Controlled Thermolysis of Macromolecule‐Metal Complexes as a Way for Synthesis of Nanocomposites | |
| Pramanik et al. | Precursory Ag-bipyridine 2D coordination polymer: a new and efficient route for the synthesis of Ag nanoparticles | |
| Ranjbar et al. | Preparation of Zinc (II) Oxide Nanoparticles from a New Nano-Size Coordination Polymer Constructed from a Polypyridyl Amidic Ligand; Spectroscopic, Photoluminescence and Thermal Analysis Studies | |
| Shahid et al. | Isostructural cage complexes of copper with cadmium or zinc for single source deposition of composite materials | |
| Xiang et al. | Preparation of modified sodium lignosulfonate hydrogel–silver nanocomposites |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |