CN109576765B - Nano Mg/Fe2O3Low-pressure preparation method of energetic film - Google Patents
Nano Mg/Fe2O3Low-pressure preparation method of energetic film Download PDFInfo
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- CN109576765B CN109576765B CN201910029971.1A CN201910029971A CN109576765B CN 109576765 B CN109576765 B CN 109576765B CN 201910029971 A CN201910029971 A CN 201910029971A CN 109576765 B CN109576765 B CN 109576765B
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- C25D15/00—Electrolytic or electrophoretic production of coatings containing embedded materials, e.g. particles, whiskers, wires
Abstract
Nano Mg/Fe2O3A low pressure process for producing an energetic film comprising: preparation of nano Fe by using ferric chloride, hydrochloric acid, polyethylene glycol (PEG), water, ethanol and sodium hydroxide2O3(ii) a The obtained nano Fe2O3Adding the powder and Mg powder into water to formA dispersion liquid; then vinyl tri (beta-methoxyethoxy) silane and hexadecyl trimethyl ammonium bromide are used for forming stable suspension liquid from the dispersion liquid; finally, forming nano Mg/Fe on the cathode sheet substrate by using a low-voltage electrophoresis method2O3An energetic film. The invention has low preparation cost and high efficiency, and not only breaks through the nano Mg powder and Fe2O3The difficulty of co-directional efficient deposition and great reduction of voltage, thereby greatly improving the preparation safety. In addition, the super energetic material prepared by the invention has strong adhesive force and good stability, and has wide application prospect in the fields of national defense and military industry, MEMS, blasting and the like.
Description
Technical Field
The invention relates to a preparation method for preparing a nano energetic material, in particular to novel Mg/Fe2O3And (3) preparing the nano energetic material composite film at low pressure.
Background
Energetic Materials (Energetic Materials) as a reactive material are broadly a class of substances that can independently undergo rapid chemical reactions and release large amounts of energy under certain external triggering conditions. The energetic materials researched at present mainly comprise propellant powder, propellant, explosive and pyrotechnic agent, and have wide application prospect. Energetic materials such as nano thermite have attracted interest due to their high reactivity and high energy density.
At present, the methods for preparing the nano energetic material mainly comprise a magnetron sputtering method, a physical mixing method, a smearing method, a high-energy ball milling method, an evaporation method, an electrodeposition method and the like. Among them, the electrochemical assembly method is very attractive due to its convenient preparation process and fast film forming efficiency, but has operation risk and safety hazard caused by over high voltage (more than 100V); in addition, the resulting energetic film had insufficient adhesion.
Disclosure of Invention
It is an object of the present invention to provide a method for preparing a super energetic material by low pressure electrophoresis which is effective in overcoming some or all of the above disadvantages.
Nano Mg/Fe according to the invention2O3A method of making an energetic film comprising:
adding ferric chloride, hydrochloric acid and polyethylene glycol (PEG) into water and ethanol in an equal volume ratio to form a mixed solution, wherein the concentration of the ferric chloride is 0.02-0.1 mol/L, the concentration of the hydrochloric acid is 0.1-0.6 mol/L, the concentration of the PEG is 0.0001-0.001 mol/L,
heating the mixed solution in a constant-temperature water bath at the temperature of 55-75 ℃, and dripping sodium hydroxide into the mixed solution to react to generate Fe2O3Wherein the molar ratio of the sodium hydroxide to the ferric chloride is about 20: 1;
centrifuging the mixture to obtain Fe2O3Powder and vacuum drying;
the obtained Fe2O3Adding the powder and Mg powder into (dispersing agent) water, and ultrasonically dispersing for 10-30 min under a closed condition (air isolation) to form a dispersion liquid, wherein Fe2O3The molar ratio of Mg to Mg is 1: 1.5-1: 2.5, and the total concentration of the Mg and the Mg is 1.0-4.0 g/L;
adding vinyl tri (beta-methoxyethoxy) silane and hexadecyl trimethyl ammonium bromide with equal volume ratio into the dispersion liquid, and then continuing ultrasonic dispersion for about 20min to obtain a (stable) suspension liquid, wherein the volume ratio of the total volume of the vinyl tri (beta-methoxyethoxy) silane and the hexadecyl trimethyl ammonium bromide to the dispersion liquid is 2: 100-10: 100;
performing electrophoresis by inserting a sheet electrode pair comprising a cathode and an anode into the above suspension to form nano Mg/Fe on the cathode2O3An energy-containing film in which the electrode gap is 0.6 to 14cm, the electrophoresis voltage is 1-5V, and the temperature is 298 +/-2K.
In an alternative embodiment of the invention, octadecyl dimethyl benzyl quaternary ammonium chloride and 3-methacryloxypropyl trimethoxysilane may also be used in place of hexadecyl trimethyl quaternary ammonium bromide and vinyl tris (. beta. -methoxyethoxy) silane, respectively.
The method according to the invention may further comprise: carrying out vacuum drying and cooling on the obtained energy-containing film; preferably drying in a vacuum drying oven at 80 deg.C for 1h, and naturally cooling. Thereafter, the cathode as a substrate may also be peeled off or removed from the resulting energy-containing film.
According to the invention, the cathode may be formed from a sheet of titanium, copper or nickel, preferably titanium; the anode may be formed in the same manner.
According to the invention, the sheet electrode pairs are preferably inserted vertically into the suspension and are fixed at a spacing of 1 cm.
In the present invention, PEG4000 is preferably used.
According to a second aspect of the present invention, there is provided an energy-containing film prepared by the above method.
The invention has low preparation cost and high efficiency, and not only breaks through the nano Mg powder and Fe2O3The difficulty of co-directional efficient deposition and great reduction of voltage, thereby greatly improving the preparation safety. In addition, the super energetic material prepared by the invention has strong adhesive force and good stability, and has wide application prospect in the fields of national defense and military industry, MEMS, blasting and the like.
The sheet cathode substrate of the present invention is preferably further provided with a rupture line to form a suitable sheet region of a desired size to facilitate subsequent peeling. Furthermore, only the required number of panel sections may be peeled off (e.g., by performing a simple snapping action along the break line) as desired, thereby facilitating storage and carrying of the remaining energetic material.
In summary, the present invention has at least the following advantages:
1. the process adopted by the invention is simple to operate, has high efficiency, can reduce the pressure to about 1V, greatly improves the operation safety, saves a large amount of preparation cost, and is suitable for industrial production;
2. the novel Mg/Fe prepared by the invention2O3The super nanometer energetic film has novel structure and good heat release performance and combustion performance;
3. the novel Mg/Fe prepared by the invention2O3The super nano energetic material is uniformly distributed, and the agglomeration phenomenon hardly exists;
4. the suspension liquid in the invention has good stability;
5. the novel Mg/Fe of the present invention2O3The adhesive force of the super nano energetic material is greatly improved, and the harsh use requirements of military industry and other extreme environments can be met.
Drawings
FIG. 1(a) and FIG. 1(b) are respectively the novel nano Mg/Fe prepared according to the present invention2O3A scanning electron microscope image of low-magnification and high-magnification field emission of the energetic film;
FIG. 2 shows the novel nano Mg/Fe prepared according to the present invention2O3DSC exotherm for energetic film;
FIG. 3 shows the novel nano Mg/Fe prepared according to the present invention2O3A combustion flame pattern of an energetic film;
fig. 4 is a schematic view of a cathode substrate provided in accordance with the present invention.
Detailed Description
The invention is further illustrated by the following examples. It will be appreciated by those skilled in the art that the following examples are only for better understanding and realization of the present invention, and are not intended to limit the present invention.
As shown in fig. 4, the present invention first provides a suitably sized cathode sheet substrate 10, such as a titanium sheet. The substrate 10 is provided or formed with break lines 11 and 12 to facilitate subsequent peeling operations: for example, after the energy-containing film material is produced as follows, the upper right quarter shown in fig. 4 may be broken off along the breaking lines 11 and 12, and the substrate 10 attached thereto may be peeled off. The anode sheet size and material may be the same as the cathode sheet.
The invention uses a Field Emission Scanning Electron Microscope (FESEM), a Differential Scanning Calorimeter (DSC), a high-speed camera and the like to research, analyze, characterize and analyze the surface appearance and the performance of the composite film product.
Example 1
Accurately weighing 0.02mol/L ferric chloride, 2 drops of concentrated hydrochloric acid and 0.0005mol/L polyethylene glycol-4000, and dissolving in 200mL of a water and ethanol mixed solution, wherein the volume ratio of water to ethanol is 1:1, then ultrasonically mixing for 2 hours with the power of 200W; then heating in water bath for 0.5h, controlling the temperature at 70 deg.C, and attaching reflux device. Then 200mL of a solution of sodium hydroxide of a concentration of 0.4mol/L was added dropwise to the above cooled solution, followed by mixing with stirring thoroughly for 0.5 h. Then heating the mixed solution in water bath at constant temperature for 0.5h, and centrifuging for multiple times to obtain Fe2O3And putting the powder into a vacuum drying oven for fully processing for standby. Mixing the above Mg and Fe2O3The powder is weighed according to the molar ratio of 1:2 and then is sequentially added into 100mL of water, and ultrasonic treatment is carried out for 20min at room temperature after the sealing of a plastic packaging film. Then 2mL of vinyl tri (beta-methoxyethoxy) silane and hexadecyl trimethyl ammonium quaternary ammonium bromide are respectively weighed and added into the upper suspension, and then ultrasonic treatment is carried out for 20min at the same temperature, wherein the volumes of the vinyl tri (beta-methoxyethoxy) silane and the hexadecyl trimethyl ammonium quaternary ammonium bromide are equal. And vertically inserting the cathode and anode plates into the stable suspension at 2V, electrophoresis assembly time of 15min and deposition temperature of 298 +/-2K. Then the novel super energetic material obtained by deposition is transferred to a vacuum drying oven to be dried for 1h at the temperature of 80 ℃, and then is cooled to the room temperature. Obtaining the novel nano Mg/Fe2O3An energetic film.
As shown in FIGS. 1a and 1b, the super energetic film prepared by the method of the present invention is nano-scale and uniformly distributed. The novel nano Mg/Fe shown in figure 22O3The exothermic curve of the energetic film is as high as 4.5MJ Kg-1. As shown in FIG. 3, the obtained super energetic film has good combustion performance. The super energetic film still has high efficiency when the assembly voltage is 5V, and the standard test grade of the adhesive force by adopting a tape method is 4B.
Comparative example 2
In other same examples 1, the assembly voltage is reduced to 1V, the assembly efficiency is improved to a certain extent, and the energy output capacity is reduced by half through sediment mass rate calculationThe heat release amount under the condition is about 4.4MJ Kg after the corresponding DSC heat release curve is fitted-1. Furthermore, it was determined that the adhesion rating remained unchanged at 4B.
Comparative example 3
Otherwise, as in example 1, the bath temperature was controlled at 80 ℃ to obtain Fe2O3The powder particles mainly have micron particle size, so that the Fe content is greatly reduced2O3The contact area of the nano-particles and Al powder ensures that the novel nano-Mg/Fe obtained by final electrophoretic assembly2O3The exotherm for the energetic film was about 65% of that of example 1.
Comparative example 4
Otherwise, the same as example 1, except that cetyl trimethyl quaternary ammonium bromide is not added, the assembly efficiency is almost zero, i.e. the assembly of the super energetic material film cannot be realized.
Comparative example 5
Otherwise as in example 1, except that vinyltris (. beta. -methoxyethoxy) silicon was not added, assembly of the super energetic material film was successfully achieved, however, the adhesion rating was measured as low as 2B.
Comparative example 6
Otherwise as in example 1, except that cetyltrimethyl quaternary ammonium bromide was replaced with octadecyldimethylbenzyl quaternary ammonium chloride and vinyltris (. beta. -methoxyethoxy) silane was replaced with 3-methacryloxypropyltrimethoxysilane, the super energetic film was successfully prepared with an adhesion rating slightly above 4B and little exothermic heat.
Comparative example 7
Otherwise, the same as example 1, except that cetyltrimethyl ammonium bromide was replaced with octadecyldimethylbenzyl ammonium chloride, the super functional thin film was successfully prepared, but the adhesion was found to be greatly reduced, which was not favorable for practical use.
As described above, the invention adopts the low pressure method to obtain the novel portable practical Mg/Fe with excellent heat release performance and strong adhesive force by means of designing stable suspension composition and the like2O3A film of energetic material.
Claims (2)
1. Nano Mg/Fe2O3A method of making an energetic film comprising:
adding ferric chloride, hydrochloric acid and polyethylene glycol (PEG) into water and ethanol in an equal volume ratio to form a mixed solution, wherein the concentration of the ferric chloride is 0.02-0.1 mol/L, the concentration of the hydrochloric acid is 0.1-0.6 mol/L, the concentration of the PEG is 0.0001-0.001 mol/L,
heating the mixed solution in a constant-temperature water bath at the temperature of 55-75 ℃, and dripping sodium hydroxide into the mixed solution to react to generate Fe2O3Wherein the molar ratio of the sodium hydroxide to the ferric chloride is 20: 1;
centrifuging the mixture to obtain Fe2O3Powder and vacuum drying;
the obtained Fe2O3Adding the powder and Mg powder into water, and performing ultrasonic dispersion for 10-30 min under a closed condition to form a dispersion liquid, wherein Fe2O3The molar ratio of Mg to Mg is 1: 1.5-1: 2.5, and the total concentration of the Mg and the Mg is 1.0-4.0 g/L;
adding vinyl tri (beta-methoxyethoxy) silane and hexadecyl trimethyl ammonium bromide with equal volume ratio into the dispersion liquid, and then continuing ultrasonic dispersion for 20min to obtain a suspension, wherein the volume ratio of the total volume of the vinyl tri (beta-methoxyethoxy) silane and the hexadecyl trimethyl ammonium bromide to the dispersion liquid is 2: 100-10: 100;
performing electrophoresis by inserting a sheet electrode pair comprising a cathode and an anode into the above suspension to form nano Mg/Fe on the cathode2O3An energy-containing film, wherein the electrode spacing is 0.6-1.4 cm, the electrophoresis voltage is 1-2V, the temperature is 298 +/-2K, and the time is 15 minutes;
carrying out vacuum drying and cooling on the obtained energy-containing film;
the cathode as a substrate provided with a break line to form a suitable patch of the desired size is peeled or removed from the resulting energetic film.
2. The method of claim 1, wherein the cathode is formed from a titanium, copper or nickel sheet.
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| CN1257317C (en) * | 2004-01-14 | 2006-05-24 | 重庆大学 | Method for preparing thin film by electric field deposition |
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