CN114751798A - Solvent suspension preparation method of fluorinated modified spherical micro/nano aluminum powder - Google Patents
Solvent suspension preparation method of fluorinated modified spherical micro/nano aluminum powder Download PDFInfo
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Abstract
The invention discloses a solvent suspension preparation method of fluorinated modified spherical micro/nano aluminum powder, which comprises the following steps: dispersing the micro/nano aluminum powder in an organic solvent to obtain micro/nano aluminum powder dispersion liquid; weighing the fluorine-rich oxidizing binder, suspending the fluorine-rich oxidizing binder in a dispersion solvent, adding the micro/nano aluminum powder dispersion, stirring, carrying out suction filtration, washing with absolute ethyl alcohol, and drying to obtain the fluorinated modified spherical micro/nano aluminum powder. The invention introduces the fluorine-rich oxidizing binder and amorphous inert shell Al into a micro/nano aluminum powder system2O3The fluorination reaction improves the participation degree of the micro/nano aluminum powder in the oxidation reaction stage, deepens the oxidation depth, promotes the reaction heat release and improves the combustion efficiency on the basis of reducing the ignition temperature of the aluminum powder; can realize complete cladding of a core-shell structure, has good density and is difficult to be coatedThe micro/nano aluminum powder falls off, so that the problems of easy agglomeration and difficult dispersion of the micro/nano aluminum powder in the using process are obviously improved; and the whole preparation method is simple, safe to operate and suitable for industrial production.
Description
Technical Field
The invention relates to the technical field of chemical materials, in particular to a solvent suspension preparation method of fluorinated modified spherical micro/nano aluminum powder.
Background
At present, a proper amount of metal combustible agent is added into the mixed explosive to promote the reaction, which is one of important ways for improving the performance of the mixed explosive. Aluminum powder is widely used as a common high-heat-value metal combustible agent in the fields of mixed explosives, propellants and the like. The combustion process of the micron-sized aluminum powder mainly passes through stages of thickening of an oxidation layer, melting of an aluminum core, melting of the oxidation layer, combustion of liquid aluminum, cracking of an oxidation layer shell, violent combustion of aluminum steam (vaporization of aluminum oxide) until aluminum particles are consumed and the like. However, a dense oxide film, typically a "core-shell" structure, exists on the surface of the micron aluminum powder, but Al2O3The melting point is as high as 2072 ℃, so that the micron-sized aluminum powder particles are difficult to ignite, thereby causing problems such as ignition delay, incomplete combustion, and the like. In order to overcome the above challenges of the micron aluminum powder particles in the combustion process, in addition to preparing high-performance modified nano aluminum powder and aluminum-based active composite materials, the development of aluminum fluoride powder research is also one of the most effective ways to solve the problems.
In the conventional combustion theory, Al is generated from aluminum powder through combustion reaction2O3A compact inert layer is formed to cover the surface of the aluminum powder, so that the diffusion of oxidizing gas in the aluminum powder is inhibited, and the oxidation depth of the aluminum powder is further influenced. But the fluorine-rich oxidizing binder can react with Al2O3Fluorination of inert shell to form beta-AlF3The phenomenon of pre-ignition reaction is generated, the ignition temperature of the aluminum powder can be reduced, and the content of high-activity aluminum and the high-energy release characteristic are kept; simultaneous beta-AlF3The sublimation temperature (1276 ℃) is lower than the combustion temperature of the aluminum powder, and the oxidation process of the aluminum powder can not be hindered. Secondly, the energy density of the fluorine aluminum oxide (56.10MJ/kg) is about 2 times higher than that of the aluminum oxide (30.98MJ/kg), and the spherical micro/nano aluminum powder is coated by the fluorine-rich oxidizing binder to deepen the oxidation depth and promote the reaction heat release.
The Polytetrafluoroethylene (PTFE) is obtained by free radical polymerization of monomer tetrafluoroethylene, the fluorine content is up to 76%, and the energy density is 21 kJ.cm-3And thus are often used as fluorine-rich oxidizing binders to coat micro/nano-aluminum powders. However, the PTFE-coated micro/nano aluminum powder is limited by operability and complexity, and then PTFE as a coating material is easy to be debonded, so that 'nuclear-nano aluminum powder' cannot be realizedThe shell structure is coated.
Disclosure of Invention
The invention aims to solve the problems of ignition delay and incomplete combustion of micro/nano aluminum powder in the combustion process in the prior art, and provides a solvent suspension preparation method of fluorinated modified spherical micro/nano aluminum powder.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows: a preparation method of fluorinated modified spherical micro/nano aluminum powder by solvent suspension comprises the following steps:
s1, dispersing the micro/nano aluminum powder in an organic solvent to obtain a micro/nano aluminum powder dispersion liquid;
s2, weighing the fluorine-rich oxidizing binder, suspending the fluorine-rich oxidizing binder in a dispersion solvent, adding the micro/nano aluminum powder dispersion liquid in the S1, stirring, performing suction filtration, washing with absolute ethyl alcohol, and drying to obtain the fluorinated modified micro/nano aluminum powder.
Preferably, the micron/nano aluminum powder in S1 is one of superfine spherical nano aluminum powder, FLQT2, FLQT3, FLQT4 and FLQT5 superfine spherical micron aluminum powder.
Preferably, the organic solvent in S1 is absolute ethanol or diethyl ether.
Preferably, the ratio of the micro/nano aluminum powder to the organic solvent in the S1 is 1 g: 3 mL-1 g: 6 mL.
Preferably, in the step S2, the weight of the fluorine-rich oxidizing binder is 2.5-10.0% of the weight of the micro/nano aluminum powder.
Preferably, the fluorine-rich oxidizing binder in S2 is one of perfluoropolyether, fluororubber, and polyvinylidene fluoride.
More preferably, the dispersing solvent in S2 is 1,1, 2-trifluorotrichloroethane or ethyl acetate.
Further preferably, the stirring time in the S2 is 45-60 min, and the rotating speed is 400-800 rpm.
Further preferably, the drying temperature in the S2 is 50-60 ℃.
The invention also provides the fluorinated modified spherical micro/nano aluminum powder prepared by the preparation method.
The invention has the following beneficial effects:
firstly), the invention introduces fluorine-rich oxidizing binder (perfluoropolyether, fluororubber or polyvinylidene fluoride) and amorphous inert shell Al into a micro/nano aluminum powder system2O3Fluorination reaction, namely improving the participation degree of the micro/nano aluminum powder in the oxidation reaction stage on the basis of reducing the ignition temperature of the aluminum powder; while maintaining high active aluminum content and high energy releasing characteristic, the pre-ignition reaction can deepen oxidation depth, promote reaction heat release and improve combustion efficiency.
Secondly), the preparation method can realize complete cladding of a core-shell structure, has good density and is not easy to fall off, thereby remarkably improving the problems of easy agglomeration and difficult dispersion of the micro/nano aluminum powder in the using process; and the whole preparation method is simple, safe to operate and suitable for industrial production.
Drawings
FIG. 1 shows perfluoropolyether (A), (B) of example 1
Y25 PFPE) before and after coating, TEM images of the ultra-fine spherical nano aluminum powder (1-a and 1-b are before coating; 1-c and 1-d are after coating);
FIG. 2 shows perfluoropolyether (A) of example 1
Y25 PFPE) coating the superfine spherical nano aluminum powder (2-e is the element distribution of aluminum element in a single PFPE coating nano aluminum powder particle; 2-f is the element distribution of oxygen in a single PFPE coated nano aluminum powder particle; 2-g is the element distribution of fluorine in a single PFPE coated nanometer aluminum powder particle; 2-h is the element distribution of aluminum, oxygen and fluorine elements in a single PFPE coated nano aluminum powder particle);
FIG. 3 shows perfluoropolyether (A) of example 1
Y25 PFPE) to coat the P-t curve chart of the superfine spherical nano aluminum powder;
FIG. 4 shows perfluoropolyether (A), (B) and (C) of example 1
Y25 PFPE) is coated on the superfine spherical nano aluminum powder.
Detailed Description
The invention is further described with reference to the following figures and specific embodiments.
Example 1
Dispersing 10g of superfine spherical nano aluminum powder in 30ml of absolute ethanol solvent, and performing ultrasonic dispersion for 30min to prepare superfine spherical nano aluminum powder dispersion liquid; 60mL of 1,1, 2-trifluorotrichloroethane as a fluorine-containing solvent was added to a beaker, and 0.25g of perfluoropolyether (f) (b)
Y25 PFPE) suspended in 1,1, 2-trifluorotrichloroethane, and adding the superfine spherical nano aluminum powder dispersion liquid; starting magnetic stirring, controlling the rotating speed at 600 +/-10 rpm, carrying out suction filtration after 45min, washing for 3 times by using absolute ethyl alcohol, and then placing in a 60 ℃ oven until the solvent is completely evaporated (about 24h) to prepare the perfluoropolyether fluorinated modified nano aluminum powder.
The TEM photograph of the perfluoropolyether fluorinated modified nano aluminum powder prepared in the embodiment is detailed in figure 1, and figure 1-b shows that the maximum shell thickness of the nano aluminum powder before coating is 3.82 mm; FIG. 1-d shows that the minimum shell thickness of the coated nano aluminum powder is 3.94 mm; and simultaneously, 1-a and 1-c show that compared with the nano aluminum powder before coating, the coated nano aluminum powder has no obvious agglomeration phenomenon and good density.
The EDS picture of the perfluoropolyether fluorinated modified nano aluminum powder prepared in the embodiment is shown in the attached figure 2 in detail; FIG. 2-e is the elemental distribution of aluminum in a single PFPE coated nano aluminum powder particle; FIG. 2-f is the element distribution of oxygen in a single PFPE coated nano aluminum powder particle; FIG. 2-g shows the elemental distribution of fluorine in a single PFPE coated nano aluminum powder particle; and fig. 2-h shows the element distribution of aluminum, oxygen and fluorine elements in a single PFPE coated nano aluminum powder particle. FIG. 2 shows that fluorine-rich oxidizing binder PFPE can be introduced into a nano aluminum powder system by a solvent suspension method, and complete coating of a core-shell structure can be realized.
The details of the P-t curve of the perfluoropolyether fluorinated modified nano aluminum powder prepared in the embodiment are shown in an attached figure 3; as can be seen from the attached figure 3, the maximum pressure of the nano aluminum powder coated by the PFPE in the constant volume combustion device is larger than that of the nano aluminum powder before coating, the PFPE can deepen the oxidation depth, promote the reaction to release heat and improve the combustion efficiency; and PFPE with different proportions is added to realize reaction regulation.
The comparative situation of the pressurization rate of the perfluoropolyether fluorinated modified nano aluminum powder prepared in the embodiment is shown in the attached figure 4 in detail; as can be seen from the attached figure 4, the maximum pressurizing rate of the PFPE-coated nano aluminum powder in the constant-volume combustion device is greater than that of the nano aluminum powder before coating, the PFPE can deepen the oxidation depth, promote the reaction heat release and improve the combustion efficiency, and meanwhile, the pressurizing rate is positively correlated with the addition of the PFPE.
Example 2
Dispersing 10g of FLQT2 superfine spherical micron aluminum powder in 30ml of absolute ethanol solvent, and ultrasonically dispersing for 30min to prepare FLQT2 superfine spherical micron aluminum powder dispersion liquid; adding 60mL of ethyl acetate into a beaker, weighing 0.5g of fluororubber F2603, and adding FLQT2 ultrafine spherical micron aluminum powder dispersion after the fluororubber F2603 is completely dissolved in the ethyl acetate; starting magnetic stirring, controlling the rotation speed at 600 +/-10 rpm, performing suction filtration after 60min, and washing for 3 times by using absolute ethyl alcohol; and then placing the mixture in an oven at 60 ℃ until the solvent is completely evaporated (about 24h), thus obtaining the fluorinated modified micron aluminum powder.
Example 3
Dispersing 10g of FLQT5 superfine spherical micron aluminum powder in 30ml of absolute ethanol solvent, and ultrasonically dispersing for 30min to prepare FLQT5 superfine spherical micron aluminum powder dispersion liquid; adding 60mL of ethyl acetate into a beaker, weighing 0.75g of polyvinylidene fluoride, and adding FLQT5 superfine spherical micron aluminum powder dispersion after the polyvinylidene fluoride is completely dissolved in the ethyl acetate; starting magnetic stirring, controlling the rotation speed at 800 +/-10 rpm, performing suction filtration after 45min, and washing for 3 times by using absolute ethyl alcohol; and then placing the mixture in an oven at 60 ℃ until the solvent is completely evaporated (about 24h), thus obtaining the fluorinated modified micron aluminum powder.
The present specification and figures are to be regarded in an illustrative rather than a restrictive sense, and it is intended that all such alterations and modifications that come within the spirit of the invention and the scope of the appended claims be embraced thereby by the appended claims.
Claims (10)
1. A solvent suspension preparation method of fluorinated modified spherical micro/nano aluminum powder is characterized by comprising the following steps:
s1, dispersing the micro/nano aluminum powder in an organic solvent to obtain a micro/nano aluminum powder dispersion liquid;
s2, weighing the fluorine-rich oxidizing binder, suspending the fluorine-rich oxidizing binder in a dispersion solvent, adding the micro/nano aluminum powder dispersion liquid in the S1, stirring, performing suction filtration, washing with absolute ethyl alcohol, and drying to obtain the fluorinated modified micro/nano aluminum powder.
2. The preparation method of claim 1, wherein the micro/nano aluminum powder in S1 is one of superfine spherical nano aluminum powder, FLQT2, FLQT3, FLQT4 and FLQT5 superfine spherical micron aluminum powder.
3. The method according to claim 1, wherein the organic solvent in S1 is absolute ethanol or diethyl ether.
4. The preparation method according to claim 1, wherein the ratio of micro/nano aluminum powder to organic solvent in S1 is 1 g: 3 mL-1 g: 6 mL.
5. The preparation method according to claim 1, wherein the weight of the fluorine-rich oxidizing binder weighed in the step S2 is 2.5-10.0% of the weight of the micro/nano aluminum powder.
6. The preparation method of claim 1, wherein the fluorine-rich oxidizing binder in S2 is one of perfluoropolyether, fluororubber, and polyvinylidene fluoride.
7. The method according to claim 1, wherein the dispersing solvent in S2 is 1,1, 2-trifluorotrichloroethane or ethyl acetate.
8. The method according to claim 1, wherein the stirring time in S2 is 45-60 min, and the rotation speed is 400-800 rpm.
9. The preparation method according to claim 1, wherein the drying temperature in S2 is 50-60 ℃.
10. A fluorinated modified spherical micro/nano aluminum powder, characterized in that the fluorinated modified spherical micro/nano aluminum powder obtained by the production method according to any one of claims 1 to 9.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115716129A (en) * | 2022-11-21 | 2023-02-28 | 北京理工大学 | Core-shell structure particle of fluoropolymer modified micro-nano aluminum powder and preparation method thereof |
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| CN109293463A (en) * | 2018-12-13 | 2019-02-01 | 中国工程物理研究院化工材料研究所 | A kind of method of aluminium powder surface self-activation |
| CN113683471A (en) * | 2021-08-17 | 2021-11-23 | 武汉理工大学 | Polyvinylidene fluoride coated micron aluminum composite powder and preparation method thereof |
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Patent Citations (3)
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| GB8811233D0 (en) * | 1987-05-19 | 1988-06-15 | Central Glass Co Ltd | Dispersion of fluororesin powder in organic liquid |
| CN109293463A (en) * | 2018-12-13 | 2019-02-01 | 中国工程物理研究院化工材料研究所 | A kind of method of aluminium powder surface self-activation |
| CN113683471A (en) * | 2021-08-17 | 2021-11-23 | 武汉理工大学 | Polyvinylidene fluoride coated micron aluminum composite powder and preparation method thereof |
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Cited By (1)
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| CN115716129A (en) * | 2022-11-21 | 2023-02-28 | 北京理工大学 | Core-shell structure particle of fluoropolymer modified micro-nano aluminum powder and preparation method thereof |
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