CN113862755A - Method for improving adhesion of electrophoretic deposition energetic film, improved energetic film and application - Google Patents
Method for improving adhesion of electrophoretic deposition energetic film, improved energetic film and application Download PDFInfo
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- CN113862755A CN113862755A CN202111149334.1A CN202111149334A CN113862755A CN 113862755 A CN113862755 A CN 113862755A CN 202111149334 A CN202111149334 A CN 202111149334A CN 113862755 A CN113862755 A CN 113862755A
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- 238000001652 electrophoretic deposition Methods 0.000 title claims abstract description 24
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- 238000000151 deposition Methods 0.000 claims abstract description 10
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- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 8
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 8
- 239000011259 mixed solution Substances 0.000 claims abstract description 8
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- 238000001132 ultrasonic dispersion Methods 0.000 claims abstract description 3
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical group [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 36
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 28
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 19
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 16
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- 239000010949 copper Substances 0.000 claims description 15
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- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- BPCXHCSZMTWUBW-UHFFFAOYSA-N triethoxy(1,1,2,2,3,3,4,4,5,5,8,8,8-tridecafluorooctyl)silane Chemical compound CCO[Si](OCC)(OCC)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)CCC(F)(F)F BPCXHCSZMTWUBW-UHFFFAOYSA-N 0.000 claims description 12
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- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 4
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(iii) oxide Chemical compound O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 claims description 4
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 claims description 4
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
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- 239000011347 resin Substances 0.000 claims description 3
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- KZUDODLIIRDHNH-UHFFFAOYSA-N C(CCCCCCCCCCCC)C(C)O[Si](OCC)(OCC)CCCCCCCC Chemical compound C(CCCCCCCCCCCC)C(C)O[Si](OCC)(OCC)CCCCCCCC KZUDODLIIRDHNH-UHFFFAOYSA-N 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical compound [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229910001220 stainless steel Inorganic materials 0.000 claims description 2
- 239000010935 stainless steel Substances 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 19
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- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
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- 239000003832 thermite Substances 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
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- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D13/00—Electrophoretic coating characterised by the process
- C25D13/02—Electrophoretic coating characterised by the process with inorganic material
-
- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B21/00—Apparatus or methods for working-up explosives, e.g. forming, cutting, drying
- C06B21/0033—Shaping the mixture
-
- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B33/00—Compositions containing particulate metal, alloy, boron, silicon, selenium or tellurium with at least one oxygen supplying material which is either a metal oxide or a salt, organic or inorganic, capable of yielding a metal oxide
-
- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B45/00—Compositions or products which are defined by structure or arrangement of component of product
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D13/00—Electrophoretic coating characterised by the process
- C25D13/04—Electrophoretic coating characterised by the process with organic material
Abstract
The invention discloses a method for improving the adhesive force of an electrophoretic deposition energetic film, which relates to the technical field of energetic materials and comprises the following steps: (1) adding Al or Mg and metal oxide into an organic solvent according to the mass ratio of 1:1-4, and performing ultrasonic dispersion to obtain a suspension; (2) adding an organic material into the mixed solution, and performing ultrasonic treatment to obtain a solution; (3) taking the suspension in the step (1) as an electrophoretic deposition solution, putting the electrophoretic deposition solution into a cathode and an anode, and depositing on the surface of the cathode after electrifying to obtain a film; (4) and (3) immersing the film in the solution obtained in the step (2), standing for 5-30s, and then drying in vacuum. The invention has the beneficial effects that: the invention adopts a solution soaking method to improve the adhesive force of the electrophoretic deposition energetic film on the surface of the base material, and has the advantages of simple operation flow, low cost, good film stability and strong adhesive force.
Description
Technical Field
The invention relates to the technical field of energetic materials, in particular to a method for improving the adhesion of an electrophoretic deposition energetic film, the improved energetic film and application.
Background
The thermite is an active reaction substance consisting of a reducing agent (Al, Mg, Si, B and the like) and an oxidizing agent (metal oxide or non-oxide), can generate violent redox reaction under the stimulation of external conditions, has high calorific value and high heat insulation temperature, can still generate self-propagation in an oxygen-free environment in the reaction process, and is widely applied to the fields of combustion agents, ignition charges, high-energy explosives, solid rocket propellants and the like. In recent years, as technologies of spacecraft, electric and mechanical products, and the like have been developed toward miniaturization and dexterity, attention has been paid to a thermite film forming technology.
The electrophoretic deposition technology is used as a film (or coating) preparation technology, has the advantages of rapid film formation, low requirements on electrode shape (the film can be formed on the surface and the inside of a deep hole or an electrode with a complex shape), low cost and the like, and has important application in the field of energetic materials. Unfortunately, thin film materials prepared by electrophoretic deposition often have the problems of uneven thickness, easy peeling, protrusion and the like, and the application range of the thin film materials is greatly limited. Therefore, the deep research on the solidification method of the electrophoretic deposition film material is very important to improve the adhesive force of the energy-containing film. For example, patent application with publication number CN111850655A discloses a method for preparing a high-adhesion nano thermite coating by electrophoretic deposition, but the method requires an oil phase synthesis method, i.e., synthesis of octadecylamine and nitrate to prepare MOx nanoparticles, and the preparation method is complex and the process is not easy to control.
Disclosure of Invention
The invention aims to solve the technical problems that the method for improving the electrodeposited thin film in the prior art is complex, the process is not easy to control, and provides a method for improving the adhesion of the electrophoretic deposition energetic thin film, the improved energetic thin film and application.
The invention solves the technical problems through the following technical means:
a method for improving the adhesion of an electrophoretically deposited energetic film, comprising the steps of:
(1) adding Al or Mg and metal oxide into an organic solvent according to the mass ratio of 1:1-4, and performing ultrasonic dispersion to obtain a suspension, wherein the metal oxide is CuO or MoO3、Fe2O3、Cr2O3、MnO2Or Bi2O3；
(2) Adding an organic material into the mixed solution, and performing ultrasonic treatment to obtain a solution, wherein the organic material is tridecyl octyl triethoxysilane, 1H,2H, 2H-perfluorodecyl triethoxysilane or Nafion perfluorinated resin;
(3) taking the suspension in the step (1) as an electrophoretic deposition solution, putting the electrophoretic deposition solution into a cathode and an anode, and depositing on the surface of the cathode after electrifying to obtain a film;
(4) and (3) immersing the film in the step (3) into the solution in the step (2), standing for 5-30s, and then drying in vacuum.
The energy-containing film with improved adhesive force prepared by the invention has no other substances except that tridecafluorooctyltriethoxysilane, 1H,2H, 2H-perfluorodecyltriethoxysilane or Nafion perfluorinated resin is loaded in the energy-containing film.
After vacuum drying, the organic solvent is volatilized, and the fluorine-containing organic material contains bifunctional groups and can generate chemical bonding with the inorganic particles and hydroxyl, carboxyl and oxygen-containing groups in the base material; in addition, the inert, low surface energy groups provide the treated substrate with very low surface energy and very poor wetting. Meanwhile, in the drying process, the particles which are isolated and loosely stacked in the cross-linked cured film effectively strengthen the compactness of the film and the adhesion force with the base material, and the organic matter is cross-linked to form a film and covers or fills the particles and the base material, so that the particles which are isolated and stacked are cured and form a whole with the base material, the physical stability and the weather resistance of the film are further improved, and the adhesion force and the hydrophobic capacity of the film on the surface of the base material are improved. It should be noted that the process membrane particles are only physically mixed with the organic matter and no chemical reaction occurs.
Has the advantages that: the invention adopts a solution soaking method to improve the adhesive force of the electrophoretic deposition energetic film on the surface of the base material, and has simple operation flow, low cost, good film stability and strong adhesive force;
the organic material adopted in the invention has the characteristics of combustibility, viscosity, hydrophobicity and the like, and the energy release effect of the energy-containing material is ensured while the adhesive force of the energy-containing film is improved.
The organic material contains C, H, O, F and other elements, has excellent combustion-supporting performance, and is loaded in an energy-containing film system, so that the adhesion of the energy-containing film is effectively improved, and the combustion and heat release performance of the energy-containing film is improved.
Preferably, the organic solvent in step (1) is isopropanol, acetone, methanol, ethanol, acetylacetone.
Preferably, the weight fraction of Al or Mg and the metal oxide in the organic solvent in the step (1) is 0.1-0.5%.
Preferably, in the step (1), aluminum and copper oxide powder are added into the organic solvent according to the mass ratio of 1: 2.
Preferably, the ultrasonic time in the step (1) is not less than 10min, and the ultrasonic temperature is not higher than 30 ℃.
Preferably, the mixed solution in the step (2) is deionized water and absolute ethyl alcohol.
Preferably, the tridecafluorooctyltriethoxysilane in the step (2) is dissolved in absolute ethyl alcohol and deionized water to prepare a solution, the concentration of the solution is between 0.1mol/L and 1.0mol/L, and the solution is uniformly mixed by ultrasonic treatment for 10 to 15 min.
Preferably, in the step (3), the anode and the cathode are polished to be smooth and flat by using 5000-mesh fine sand paper, and are ultrasonically washed by using acetone, ethanol and deionized water for 10min respectively, and then are dried for standby.
Preferably, the electrophoretic deposition voltage in the step (3) is 100-150V, and the deposition time is not less than 2 min.
Preferably, the deposition time is 2-10 min.
Preferably, the cathode and the anode in the step (3) are both pure copper sheets, pure titanium sheets, nickel sheets, iron sheets or stainless steel sheets.
Preferably, the vacuum drying temperature in the step (4) is 80-100 ℃, and the vacuum drying time is 3-5 h.
The energetic film obtained by the method.
Has the advantages that: the energetic film obtained by the invention has good stability and strong adhesive force, and can ensure the energy release effect of the energetic material.
The energetic film obtained by the method is applied to micro-nano energetic devices.
Preferably, the micro-nano energy-containing device comprises an electromechanical initiating explosive device and an energy-containing chip.
The invention has the advantages that: the invention adopts a solution soaking method to improve the adhesive force of the electrophoretic deposition energetic film on the surface of the base material, and has simple operation flow, low cost, good film stability and strong adhesive force;
the organic material adopted in the invention has the characteristics of combustibility, viscosity, hydrophobicity and the like, and the energy release effect of the energy-containing material is ensured while the adhesive force of the energy-containing film is improved.
The organic material contains C, H, O, F and other elements, has excellent combustion-supporting performance, and is loaded in an energy-containing film system, so that the adhesion of the energy-containing film is effectively improved, and the combustion and heat release performance of the energy-containing film is improved.
Drawings
FIG. 1 is a schematic illustration of an Al/TFs/CuO energetic film in an example of the present invention;
in the figure: 1 an organic network layer; a 2Al/CuO thin film layer; 3 copper sheet substrate.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Test materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
The specific techniques or conditions not specified in the examples can be performed according to the techniques or conditions described in the literature in the field or according to the product specification.
Comparative example 1
(1) Adding 100ml of isopropanol into the nano aluminum powder and the copper oxide powder according to the mass ratio of 1:2, and carrying out ultrasonic treatment at 40Hz and normal temperature for 10-15 min to prepare a uniform suspension B;
(2) mixing pure copper sheets (1 × 2 cm)2) Polishing with 5000-mesh fine sand paper until the surface is bright and flat, respectively performing ultrasonic treatment for 10min with acetone, ethanol and deionized water, and blow-drying;
(3) setting the voltage of an electrophoresis apparatus to 150V, setting the deposition time to 5min, and obtaining a uniform Al/CuO energetic film on a cathode copper sheet by using a copper sheet as a cathode and an anode and using a suspension B as an electrolyte;
(4) drying the obtained Al/CuO energy-containing film for 3h at the temperature of 60 ℃ in vacuum.
The adhesion of the dried Al/CuO film prepared according to the above procedure was evaluated by the scratch "X" test according to the film adhesion test standard ASTM D3359-02 approved by the department of defense. Marking an X symbol on the diagonal line of the film by using a sharp blade, and ensuring that the scratch penetrates through the film and reaches the bottom substrate; then, the 3M tape was tightly stuck to the film surface, and then pulled up quickly. As a result, it was found that the film was severely peeled off in an area exceeding 60%. From a film adhesion rating of 0-5, the unmodified Al/CuO film adhesion rating is about 0B, and the adhesion is extremely poor.
Example 1
A preparation method for improving the adhesive force of an electrophoretic deposition Al/CuO energetic film comprises the following steps:
(1) adding 100ml of isopropanol into the nano aluminum powder and the copper oxide powder according to the mass ratio of 1:2, and carrying out ultrasonic treatment at 40Hz and normal temperature for 10-15 min to prepare a uniform suspension A;
(2) polishing a pure copper sheet by using 5000-mesh fine sand paper until the surface is bright and flat, respectively performing ultrasonic treatment for 10min by using acetone, ethanol and deionized water, and drying for later use;
(3) adding 0.1ml of tridecafluorooctyl triethoxysilane into 100ml of anhydrous ethanol and deionized water mixed solution, and carrying out ultrasonic treatment for 10min to prepare a tridecafluorooctyl triethoxysilane solution A;
(4) setting the voltage of an electrophoresis apparatus to 150V, setting the deposition time to 5min, using a copper sheet as a cathode and an anode, using the suspension A as an electrolyte, obtaining a uniform Al/CuO energetic film on the cathode copper sheet, and drying for 30h in a vacuum environment at 60 ℃;
(5) immersing the dried copper sheet loaded with the Al/CuO film into the B solution for 10 s;
(6) and drying the soaked Al/CuO film for 3h at 70 ℃ in vacuum to obtain an energy-containing film, wherein a schematic diagram of the energy-containing film is shown in figure 1, an Al/CuO film layer 2 is attached to a copper sheet substrate 3, and a tridecafluorooctyltriethoxysilane organic network layer 1 is attached to the Al/CuO film layer 2.
(7) According to the film adhesion test standard ASTM D3359-02 approved by the department of defense, according to the procedure of comparative example 1, a small amount of powder was attached to the surface of the 3M tape, and the adhesion of the Al/CuO film was initially improved with an adhesion rating of about 2B.
Example 2
A preparation method for improving the adhesive force of an electrophoretic deposition Al/CuO energetic film comprises the following steps:
(1) adding 100ml of isopropanol into the nano aluminum powder and the copper oxide powder according to the mass ratio of 1:2, and carrying out ultrasonic treatment at 40Hz and normal temperature for 10-15 min to prepare a uniform suspension B;
(2) polishing a pure copper sheet by using 5000-mesh fine sand paper until the surface is bright and flat, respectively performing ultrasonic treatment for 10min by using acetone, ethanol and deionized water, and drying for later use;
(3) adding 0.5ml of tridecafluorooctyl triethoxysilane into 100ml of anhydrous ethanol and deionized water mixed solution, and carrying out ultrasonic treatment for 10min to prepare a tridecafluorooctyl triethoxysilane solution C;
(4) setting the voltage of an electrophoresis apparatus to 150V, setting the deposition time to 5min, using a copper sheet as a cathode and an anode, using the suspension A as an electrolyte, obtaining a uniform Al/CuO energetic film on the cathode copper sheet, and drying for 3h in a vacuum 60 ℃ environment;
(5) immersing the dried copper sheet loaded with the Al/CuO film into the C solution for 10 s;
(6) drying the Al/CuO film after soaking treatment for 3h at the temperature of 100 ℃ in vacuum;
according to the film adhesion test standard ASTM D3359-02 approved by the department of defense, according to the procedure of comparative example 1, the 3M adhesive tape has a cleaner surface, very little powder adhesion, and an Al/CuO film adhesion rating of about 3B, and the adhesion is significantly improved.
Example 3
A preparation method for improving the adhesive force of an electrophoretic deposition Al/CuO energetic film comprises the following steps:
(1) adding 100ml of isopropanol into the nano aluminum powder and the copper oxide powder according to the mass ratio of 1:2, and carrying out ultrasonic treatment at 40Hz and normal temperature for 10-15 min to prepare a uniform suspension B;
(2) polishing a pure copper sheet by using 5000-mesh fine sand paper until the surface is bright and flat, respectively performing ultrasonic treatment for 10min by using acetone, ethanol and deionized water, and drying for later use;
(3) adding 0.5ml of tridecafluorooctyl triethoxysilane into 100ml of anhydrous ethanol and deionized water mixed solution, and carrying out ultrasonic treatment for 10min to prepare a tridecafluorooctyl triethoxysilane solution D;
(4) setting the voltage of an electrophoresis apparatus to 150V, setting the deposition time to 5min, using a copper sheet as a cathode and an anode, using the suspension A as an electrolyte, obtaining a uniform Al/CuO film on the surface of the cathode copper sheet, and drying for 3h in a vacuum environment at 60 ℃;
(5) immersing the dried copper sheet loaded with the Al/CuO film into the D solution for 10 s;
(6) drying the soaked Al/CuO film for 3h at the temperature of 100 ℃ in vacuum;
according to the film adhesion test standard ASTM D3359-02 approved by the department of defense, according to the operation in comparative example 1, the test result shows that the surface of the 3M adhesive tape is clean, no other area of the film surface falls off, the adhesion grade of the Al/CuO film is about 4B, and the adhesion is greatly improved, except that a very small amount of powder is adhered to the position marked with the 'X'.
Example 4
The exothermic performance of the energetic films of examples 1-4 was tested by a differential scanning calorimeter, and the exothermic amounts of Al/CuO energetic films loaded with different contents of tridecafluorooctyltriethoxysilane were 1087J/g, 1817J/g, 1977J/g, and 2284J/g, respectively. The heat release of the composite film system is improved, and the heat release is increased along with the increase of the concentration of the tridecafluorooctyltriethoxysilane.
Table 1 shows the results of adhesion rating measurements for comparative examples and examples
| Examples | Al/CuO | Al/TFs(0.1mol/L)/CuO | Al/TFs(0.5mol/L)/CuO | Al/TFs(1.0mol/L)/CuO |
| Grade of adhesion | 0B | 2B | 3B | 4B |
Comparative example 1
The organic materials in the embodiments 1 to 3 are respectively replaced with PVDF or PTFE emulsion in equal amount, the prepared thin films can improve the heat release performance of the energetic materials, and experiments prove that the 6 groups of thin films have poor film forming property and no obvious improvement on the adhesive force, the special adhesive tape is used for pasting, the thin films still drop seriously, and the adhesive force reaches 1 grade at most. The main reasons are that PVDF or PTFE has poor film forming property and has poor effect of improving the adhesive force of the electrophoretic deposition energetic film.
The above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (10)
1. A method for improving the adhesion of an electrophoretically deposited energetic film, comprising: the method comprises the following steps:
(1) adding Al or Mg and metal oxide into an organic solvent according to the mass ratio of 1:1-4, and performing ultrasonic dispersion to obtain a suspension, wherein the metal oxide is CuO or MoO3、Fe2O3、Cr2O3、MnO2Or Bi2O3；
(2) Adding an organic material into the mixed solution, and performing ultrasonic treatment to obtain a solution, wherein the organic material is tridecyl octyl triethoxysilane, 1H,2H, 2H-perfluorodecyl triethoxysilane or Nafion perfluorinated resin;
(3) taking the suspension in the step (1) as an electrophoretic deposition solution, putting the electrophoretic deposition solution into a cathode and an anode, and depositing on the surface of the cathode after electrifying to obtain a film;
(4) and (3) immersing the film in the step (3) into the solution in the step (2), standing for 5-30s, and then drying in vacuum.
2. The method of improving the adhesion of an electrophoretically deposited energetic film of claim 1, wherein: the organic solvent in the step (1) is isopropanol, acetone, methanol, ethanol or acetylacetone.
3. The method of improving the adhesion of an electrophoretically deposited energetic film of claim 1, wherein: in the step (1), the weight fraction of Al or Mg and the metal oxide in the organic solvent is 0.1-0.5%.
4. The method of improving the adhesion of an electrophoretically deposited energetic film of claim 1, wherein: in the step (1), aluminum and copper oxide powder are added into an organic solvent according to the mass ratio of 1: 2.
5. The method of improving the adhesion of an electrophoretically deposited energetic film of claim 1, wherein: the mixed solution in the step (2) is deionized water and absolute ethyl alcohol.
6. The method of improving the adhesion of an electrophoretically deposited energetic film of claim 5, wherein: and (3) dissolving the tridecafluorooctyltriethoxysilane in the step (2) in absolute ethyl alcohol and deionized water to prepare a solution, wherein the concentration of the solution is between 0.1 and 1.0mol/L, and uniformly mixing by ultrasonic treatment for 10 to 15 min.
7. The method of improving the adhesion of an electrophoretically deposited energetic film of claim 1, wherein: and (4) in the step (3), the electrophoretic deposition voltage is 100-150V, and the deposition time is not less than 2 min.
8. The method of improving the adhesion of an electrophoretically deposited energetic film of claim 1, wherein: and (4) the cathode and the anode in the step (3) are both pure copper sheets, pure titanium sheets, nickel sheets, iron sheets or stainless steel sheets.
9. An energetic film produced by the process of any one of claims 1 to 8.
10. The application of the energetic film prepared by the method of any one of claims 1 to 8 in micro-nano energetic devices.
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| CN112899746A (en) * | 2021-02-05 | 2021-06-04 | 南京理工大学 | Method for reducing electrostatic sensitivity of cuprous azide film |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20130036930A1 (en) * | 2011-08-08 | 2013-02-14 | Lawrence Livermore National Security, Llc | Methods and systems for electrophoretic deposition of energetic materials and compositions thereof |
| CN105780089A (en) * | 2016-03-10 | 2016-07-20 | 南京理工大学 | Energy-containing film made of aluminum-copper oxide-graphene oxide ternary composite material and preparation method for energy-containing film |
| CN106467977A (en) * | 2016-10-13 | 2017-03-01 | 重庆大学 | One kind prepares Al/Bi2O3The method of Energetic Nanomaterials laminated film |
| CN111850655A (en) * | 2020-07-27 | 2020-10-30 | 重庆工商大学 | Method for preparing high-adhesion nano thermite coating by electrophoretic deposition and coating prepared by method |
-
2021
- 2021-09-29 CN CN202111149334.1A patent/CN113862755B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20130036930A1 (en) * | 2011-08-08 | 2013-02-14 | Lawrence Livermore National Security, Llc | Methods and systems for electrophoretic deposition of energetic materials and compositions thereof |
| CN105780089A (en) * | 2016-03-10 | 2016-07-20 | 南京理工大学 | Energy-containing film made of aluminum-copper oxide-graphene oxide ternary composite material and preparation method for energy-containing film |
| CN106467977A (en) * | 2016-10-13 | 2017-03-01 | 重庆大学 | One kind prepares Al/Bi2O3The method of Energetic Nanomaterials laminated film |
| CN111850655A (en) * | 2020-07-27 | 2020-10-30 | 重庆工商大学 | Method for preparing high-adhesion nano thermite coating by electrophoretic deposition and coating prepared by method |
Non-Patent Citations (3)
| Title |
|---|
| XIANG KE ET AL.: "Rapid fabrication of superhydrophobic Al/Fe 2 O 3 nanothermite film with excellent energy-release characteristics and long-term storage stability", 《APPLIED SURFACE SCIENCE》, vol. 407, pages 137 * |
| YANJUN YIN ET AL.: "Simultaneously Altering the Energy Release and Promoting the Adhesive Force of an Electrophoretic Energetic Film with a Fluoropolymer", 《LANGMUIR 》, vol. 38, pages 2569 * |
| 魏光平 等: "电泳沉积纳米铝热剂薄膜及在微点火器中的应用进展", 《化工新型材料》, vol. 48, no. 9, pages 38 - 42 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112899746A (en) * | 2021-02-05 | 2021-06-04 | 南京理工大学 | Method for reducing electrostatic sensitivity of cuprous azide film |
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