CN111850655B - Method for preparing high-adhesion nano thermite coating by electrophoretic deposition and coating thereof - Google Patents
Method for preparing high-adhesion nano thermite coating by electrophoretic deposition and coating thereof Download PDFInfo
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- 238000000576 coating method Methods 0.000 title claims abstract description 52
- 239000011248 coating agent Substances 0.000 title claims abstract description 44
- 238000000034 method Methods 0.000 title claims abstract description 40
- 238000001652 electrophoretic deposition Methods 0.000 title claims abstract description 38
- 239000003832 thermite Substances 0.000 title claims abstract description 27
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000002105 nanoparticle Substances 0.000 claims abstract description 27
- 239000000725 suspension Substances 0.000 claims abstract description 15
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims abstract description 8
- 229910002651 NO3 Inorganic materials 0.000 claims abstract description 7
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000002270 dispersing agent Substances 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 238000001308 synthesis method Methods 0.000 claims abstract description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 24
- 229910044991 metal oxide Inorganic materials 0.000 claims description 19
- 150000004706 metal oxides Chemical class 0.000 claims description 17
- 239000007788 liquid Substances 0.000 claims description 13
- 238000000151 deposition Methods 0.000 claims description 12
- 230000008021 deposition Effects 0.000 claims description 12
- 229920002873 Polyethylenimine Polymers 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 230000005684 electric field Effects 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 239000006185 dispersion Substances 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 238000005498 polishing Methods 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims 1
- 238000001132 ultrasonic dispersion Methods 0.000 claims 1
- 239000000853 adhesive Substances 0.000 abstract description 11
- 230000001070 adhesive effect Effects 0.000 abstract description 11
- 239000000758 substrate Substances 0.000 abstract description 9
- 238000003786 synthesis reaction Methods 0.000 abstract description 5
- 238000003860 storage Methods 0.000 abstract description 4
- 230000007123 defense Effects 0.000 abstract description 3
- 239000002360 explosive Substances 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract description 2
- 230000000977 initiatory effect Effects 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract 1
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- 239000002103 nanocoating Substances 0.000 description 24
- 238000012360 testing method Methods 0.000 description 13
- 238000003756 stirring Methods 0.000 description 12
- 239000002245 particle Substances 0.000 description 10
- 238000005303 weighing Methods 0.000 description 9
- 238000001816 cooling Methods 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- 229910020599 Co 3 O 4 Inorganic materials 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 239000010936 titanium Substances 0.000 description 5
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 4
- 239000010405 anode material Substances 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000010406 cathode material Substances 0.000 description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 4
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 4
- 238000009210 therapy by ultrasound Methods 0.000 description 4
- 229910052719 titanium Inorganic materials 0.000 description 4
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 238000000634 powder X-ray diffraction Methods 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 206010063385 Intellectualisation Diseases 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004200 deflagration Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001017 electron-beam sputter deposition Methods 0.000 description 1
- 238000001523 electrospinning Methods 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- -1 metal oxide MO Chemical class 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000002207 thermal evaporation Methods 0.000 description 1
- 230000001960 triggered effect Effects 0.000 description 1
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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
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G3/00—Compounds of copper
- C01G3/02—Oxides; Hydroxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/02—Oxides; Hydroxides
- C01G49/06—Ferric oxide [Fe2O3]
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G51/00—Compounds of cobalt
- C01G51/04—Oxides; Hydroxides
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/04—Oxides; Hydroxides
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
- Powder Metallurgy (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
Abstract
The invention provides a method for preparing a high-adhesion nano thermite coating by electrophoretic deposition and a coating thereof, wherein an oil phase synthesis method, namely synthesizing octadecylamine and nitrate to prepare MO x Nanoparticles, MO x Mixing the nano particles with nano aluminum powder, dispersing the mixture in an organic solution, adding a dispersing agent to form a suspension, and obtaining a nano thermite Al-MO by an electrophoretic deposition method x And (4) coating. The invention constructs the nano thermite Al-MO with good adhesive force x The coating solves the problem of Al-MO prepared by the current EPD method x The problems of poor adhesion between the energetic coating and the substrate, easy large-area shedding and environmental failure are solved, and a universal strategy is provided for developing and rapidly preparing a practical initiating explosive device which is suitable for a complex storage and transportation environment and has high energy output. The nano-synthesis process has simple conditions and high coating assembling speed, is suitable for industrial production, can be widely applied to various fields such as national defense and military industry, micromotor systems and the like, and has good market application prospect.
Description
Technical Field
The invention relates to the technical field of coatings, in particular to a method for preparing a high-adhesion nano thermite coating by electrophoretic deposition and a coating prepared by the method.
Background
Thermite (Al-MO) x ) Is a mixture of aluminum (Al) and Metal Oxide (MO) x Such as Fe 2 O 3 、CuO、Co 3 O 4 NiO, etc.) can be triggered by external energy to generate thermite reaction (2x Al + 3MO) x ＝x Al 2 O 3 +3M + Q) releases a large amount of heat, and has unique and important application value in the field of national defense and military industry due to excellent heat release performance and deflagration performance. With the increasing demand of miniaturization and intellectualization of weaponry in the 21 st century, the assembly of energetic materials on Micro-Electro-mechanical systems (MEMS) devices is realized in the form of coatingIt is an urgent demand for improving the energy output of the igniter and the propeller. Al-MO compared to organic energetic materials x The higher triggering temperature leads the storage, transportation and use safety of the coating to be higher, and the assembly and preparation of the coating become the focus of attention of scholars at home and abroad.
Nano thermite (Al-MO) x ) The coating has good adhesive force with the device substrate, is not easy to fall off in complex storage, transportation and use environments, and is one of the prerequisites that the energy-containing device can meet the practical application. Commonly used energetic material coating techniques include magnetron sputtering, electron beam sputtering, thermal evaporation, electrospinning, etc., which generally result in energetic coatings with good adhesion to device substrates, but also suffer from expensive equipment, complex operation, poor assembly adaptability to substrates of complex shape, etc.
In addition to the above method, the 2012 foreign scholars Sullivan first prepared nano Al/CuO coating by Electrophoretic deposition (EPD), and since EPD has the advantages of simple equipment, convenient method, low cost, and capability of adapting to substrates with complex and various shapes, it is used for preparing Al-MO-containing coating x Various strategies for energetic coatings have received attention from researchers. Of these, most exciting is that second-order (seconds or tens of seconds) preparation of the coating is expected to be achieved when the electrophoretic suspension nanoparticle concentration is significantly increased. Zhang successfully realizes Al/Fe 2 O 3 、Al/Co 3 O 4 The method is used for preparing EPD of various energetic coatings such as Al/NiO, B/Ti and the like, and verifies the advantages and feasibility of rapidly assembling the energetic coatings on micro-ignition bridges of the MEMS system in a device mode for the first time. Guo and Yin et al, achieve the preparation of energetic materials on substrates of different micro-morphologies, and disclose that the feasibility of EPD preparation of energetic coatings is not affected by the micro-morphology of the substrate.
However, due to the nano thermite (Al-MO) x ) The contradiction between the thermite reaction triggering temperature and the sintering temperature of the coating (fig. 5) does not allow the use of post-sintering treatment to convert the nano thermite (Al-MO) into a nano thermite x ) The microscopic morphology of the coating is transformed from a simple accumulation of nanoparticles to a continuous, solidified state. Thus, EPD produced energetic coatings and device substratesThe poor adhesion between the two materials causes large-area cracking and falling easily, and still becomes a key bottleneck which cannot be solved so far.
Disclosure of Invention
The invention aims to provide a method for preparing a high-adhesion nano thermite coating by electrophoretic deposition and a coating prepared by the method, which can effectively overcome some or all of the defects.
A method for preparing a high-adhesion nano thermite coating by electrophoretic deposition adopts an oil phase synthesis method to prepare metal oxide MO x Nanoparticles, MO x Mixing the nano particles with nano aluminum powder, dispersing the mixture in an organic solution, adding a dispersing agent to form a suspension, and obtaining the nano thermite coating by using an electrophoretic deposition method.
The method specifically comprises the following steps:
(1) Heating octadecylamine to melt and heating to 120-250 ℃, and adding MO x Nitrate corresponding to the nano particles is stirred at high temperature to prepare MO x Centrifugally collecting the nano particles for later use;
(2) Polishing and washing the cathode and anode electrode plates, and then placing the cathode and anode electrode plates in a vacuum drying oven for drying for later use;
(3) Mixing nano aluminum powder and MO obtained in step (1) x The nano particles are sequentially added into the dispersion liquid according to the weight ratio of 10;
(4) Fixing cathode and anode plates, vertically inserting into uniformly dispersed suspension, performing electrophoretic deposition with an external electric field of 50-200Vcm -1 After 5 to 30 minutes, a deposition film is obtained on the cathode plate;
(5) And drying the deposition film obtained by electrophoretic deposition.
The MO x M is one of Fe, co, ni, cu and Zn.
In the step (1), the mass ratio of the octadecylamine to the nitrate is 40-10, the synthesis reaction temperature is 120-250 ℃, and the synthesis reaction time is 10-180 minutes.
The dispersion liquid in the step (3) is selected from isopropanol, ethanol or a mixture of ethanol and acetylacetone according to the volume ratio of 1:1; the dispersant is polyethyleneimine, nitric acid or hydrochloric acid.
The prepared nano thermite Al-MO x The adhesion of the coating (above 4B) is significantly better than with commercially available MO x Nano thermite Al-MO prepared from nano particles x The coating (2B) has uniform film surface distribution and good heat release performance and thermal stability.
The preparation method adopts an oil phase synthesis method, namely' octadecylamine (C1) 8 H 37 NH 2 ODA) -nitrate "synthesis, referred to herein as the ODA method, for the preparation of nano-MOs x MO prepared x The coating and the substrate have extremely strong adhesion effect, and the reasons are that: octadecylamine is used as a solvent and a surfactant, and a long-chain oleophylic group of octadecylamine can be adsorbed on nano MO prepared from a nitrate metal precursor x Surface, long chain lipophilic group is expected to endow MO x Strong adhesion performance. In contrast, commercially available nanoparticles for EPD production of energetic coatings have been reported to have "clean" surfaces and no adhesion-forming elements. Therefore, the method utilizes the ODA oil phase synthesis method to prepare MO x Nanoparticle replacement for commercially purchased MO x Used as EPD powder raw material to prepare novel nano thermite Al-MO x Coating of MO x The Al nano-particles and the MO are effectively improved by taking the Al nano-particles as a reactant in the energy-containing coating and simultaneously playing the role of a binder x The tendency of easy falling off provides a brand new and effective technical scheme for constructing the energy-containing device with good adhesive force.
The invention constructs the nano thermite Al-MO with good adhesive force x The coating (M = Fe, co, ni, cu) solves the problem of Al-MO prepared by the current EPD method x The problems of poor adhesion between the energetic coating and the substrate, easy large-area falling off and failure due to environment are solved, and a universal strategy is provided for developing a practical initiating explosive device which is suitable for a complex storage and transportation environment and has high energy output. The method has simple nano synthesis process condition and high coating assembling speed, is suitable for industrial production, and can be widely applied to national defense military industry and micromotor systemsAnd the like, and has good market application prospect.
Drawings
FIG. 1 (a) is a schematic diagram showing comparative example 1 using commercially available Co 3 O 4 Al/Co by electrophoretic deposition 3 O 4 A nano-coating;
FIG. 1 (b) shows the preparation of Co by ODA method in example 1 of the present invention 3 O 4 Al/Co by electrophoretic deposition 3 O 4 A nano-coating;
FIG. 2 shows Al/Co ratios of example 1 of the present invention 3 O 4 Characteristic XRD diffractogram of the nanocoating;
FIG. 3 shows Al/Co of example 1 of the present invention 3 O 4 The exotherm for the nanocoating;
FIG. 4 shows Al/Co photographed by the high-speed camera in embodiment 1 of the present invention 3 O 4 A burning picture of the nano-coating;
FIG. 5 is Al-MO prepared by prior art EPD x The inherent contradiction between improving adhesion by coating sintering and triggering thermite reaction.
Detailed Description
The specific technical scheme of the invention is described by combining the embodiment.
Example 1
Accurately weighing 20 g of octadecylamine, placing the octadecylamine in a round-bottom flask, heating to melt and stirring to 120 ℃, accurately weighing 2 g of cobalt nitrate, putting the cobalt nitrate into the octadecylamine, keeping the reaction temperature at 120 ℃, continuing stirring for 10 minutes, stopping stirring, standing, cooling to 80 ℃, pouring out the upper liquid octadecylamine, collecting the bottom product of the flask, and using ethanol and cyclohexane at the rotating speed of 10000 r.m.min -1 Centrifugally washing for three times to obtain nano Co 3 O 4 Particles.
0.03g of nano-aluminum particles and 0.07g of synthetic Co were weighed 3 O 4 Adding the nano particles into an ethanol solution, adding 1 mg of polyethyleneimine (1% of polyethyleneimine aqueous solution can be prepared according to the mass ratio), and carrying out ultrasonic treatment for 30 minutes under the condition of 298 +/-1K to form a stable suspension. Immediately, the pretreated cathode and anode materials of the titanium sheet are vertically inserted into the stable suspension liquid, and the external electric field is 200Vcm -1 Electrophoretic deposition 20And the deposition temperature is controlled at 298 +/-1K in minutes. Then Al/Co obtained by deposition 3 O 4 And transferring the nano coating to a vacuum drying oven, drying for 1 hour at 333-373 +/-1K, and cooling to room temperature. Namely, al/Co is obtained 3 O 4 And (4) nano coating.
The surface appearance and performance of the composite film product are researched, analyzed and characterized by a Zeta potentiometer, X-ray powder diffraction (XRD), a Field Emission Scanning Electron Microscope (FESEM), X-ray energy dispersion spectroscopy (EDX), a Differential Scanning Calorimeter (DSC), a high-speed camera and the like.
As shown in FIG. 1 (b), al/Co prepared by the method of the present invention 3 O 4 The nanocoating was smooth, evenly distributed, and had little agglomeration, relative to commercially available Co as shown in FIG. 1 (a) of comparative example 1 below 3 O 4 Prepared Al/Co 3 O 4 The nano coating (a large amount of shedding occurs after the cutting by the knife) does not obviously shed after the cutting by the knife.
As shown in FIG. 2, al/Co was prepared 3 O 4 Characteristic XRD diffraction peak of nano coating and Al and Co in standard JCPDS 3 O 4 The standard map cards are matched.
As shown in FIG. 3, al/Co obtained 3 O 4 The nano coating has an exothermic curve with an exothermic amount up to 1890 J.g -1 。
As shown in FIG. 4, al/Co was obtained 3 O 4 The combustion performance of the nano coating is good.
The obtained Al/Co 3 O 4 The nano coating adopts a standard test (ASTM D3359-2009) for testing the adhesive force of the coating by a tape method to test the adhesive force grade to be 4B.
Comparative example 1
Similar to example 1, except that Co was used in the electrophoretic deposition 3 O 4 Nanoparticles are commercially available. The adhesion rating was 2B using a standard tape method.
Example 2
Accurately weighing 20 g of octadecylamine, placing the octadecylamine in a round bottom flask, heating, melting and stirring the octadecylamine to 180 ℃, accurately weighing 0.5 g of ferric nitrate, putting the ferric nitrate into the octadecylamine,keeping the reaction temperature at 180 ℃, continuing stirring for 30 minutes, stopping stirring, standing, cooling to 80 ℃, pouring the upper liquid octadecylamine, collecting the bottom product of the flask, and using ethanol and cyclohexane at the rotating speed of 10000 r.m. -1 Centrifugally washing for three times to obtain the nano Fe 2 O 3 And (3) particles.
0.04g of nano-aluminum particles and 0.06g of synthesized Fe were weighed 2 O 3 Adding the nano particles into an ethanol solution, adding 1 mg of polyethyleneimine (1% of polyethyleneimine aqueous solution can be prepared according to the mass ratio), and carrying out ultrasonic treatment for 30 minutes under the condition of 298 +/-1K to form a stable suspension. Immediately, the pretreated cathode and anode materials of the titanium sheet are vertically inserted into the stable suspension liquid, and the external electric field is 200Vcm -1 Electrophoretic deposition is carried out for 20 minutes, and the deposition temperature is controlled at 298 +/-1K. Al/Fe obtained by the subsequent deposition 2 O 3 And transferring the nano coating to a vacuum drying oven, drying for 1 hour at 333-373 +/-1K, and cooling to room temperature. Thus obtaining Al/Fe 2 O 3 And (4) nano coating.
The Al/Fe obtained 2 O 3 The nano coating adopts a standard test (ASTM D3359-2009) for testing the adhesive force of the coating by a tape method to test the adhesive force grade to be 4B.
Comparative example 2
Similar to example 2, except that Fe was used in the electrophoretic deposition 2 O 3 Nanoparticles are commercially available. The adhesion rating was 2B using a standard tape method.
Example 3
Accurately weighing 20 g of octadecylamine, placing the octadecylamine in a round bottom flask, heating, melting and stirring the octadecylamine to 180 ℃, accurately weighing 2 g of nickel nitrate, putting the nickel nitrate into the octadecylamine, keeping the reaction temperature at 180 ℃, continuously stirring the nickel nitrate for 10 minutes, stopping stirring, standing, cooling the nickel nitrate to 80 ℃, pouring out the upper liquid octadecylamine, collecting a bottom product of the flask, and using ethanol and cyclohexane to rotate at the rotating speed of 10000 r.m.min -1 And centrifuging and washing for three times to obtain the nano NiO particles.
Weighing 0.04g of nano aluminum particles and 0.06g of synthesized NiO nanoparticles, adding into ethanol solution, adding 1 mg of polyethyleneimine (1% by mass)Preparing a polyethyleneimine aqueous solution), and carrying out ultrasonic treatment for 30 minutes under the condition of 298 +/-1K to form a stable suspension. Immediately, the pretreated cathode and anode materials of the titanium sheet are vertically inserted into the stable suspension liquid, and the external electric field is 200Vcm -1 Electrophoretic deposition is carried out for 20 minutes, and the deposition temperature is controlled at 298 +/-1K. Then transferring the Al/NiO nano coating obtained by the deposition to a vacuum drying oven, drying for 1 hour at 333-373 +/-1K, and then cooling to room temperature. Thus obtaining the Al/NiO nano coating.
The obtained Al/NiO nano coating adopts a standard test (ASTM D3359-2009) for testing the adhesive force of the coating by using a tape method to test the adhesive force grade to be 4B.
Comparative example 3
Similar to example 3, except that NiO nanoparticles used in electrophoretic deposition were commercially available. The adhesion rating was 2B using a standard tape method.
Example 4
Accurately weighing 20 g of octadecylamine, placing the octadecylamine in a round bottom flask, heating, melting and stirring the octadecylamine to 230 ℃, accurately weighing 0.5 g of copper nitrate, putting the copper nitrate into the octadecylamine, keeping the reaction temperature at 230 ℃, continuously stirring the mixture for 30 minutes, stopping stirring, standing, cooling the mixture to 80 ℃, pouring the upper liquid octadecylamine, collecting a bottom product of the flask, and using ethanol and cyclohexane at the rotation speed of 10000 r.min -1 And centrifuging and washing for three times to obtain the nano CuO particles.
0.04g of nano aluminum particles and 0.06g of synthesized CuO nanoparticles are weighed and added into an ethanol solution, 1 mg of polyethyleneimine (1% of polyethyleneimine aqueous solution can be prepared according to the mass ratio) is added, and ultrasonic treatment is carried out for 30 minutes under the condition of 298 +/-1K to form a stable suspension. Immediately, the pretreated cathode and anode materials of the titanium sheet are vertically inserted into the stable suspension liquid, and the external electric field is 200Vcm -1 Electrophoretic deposition is carried out for 20 minutes, and the deposition temperature is controlled at 298 +/-1K. Then transferring the Al/CuO nano coating obtained by the deposition to a vacuum drying oven, drying for 1 hour at 333-373 +/-1K, and then cooling to room temperature. Thus obtaining the Al/CuO nano coating.
The obtained Al/CuO nano coating adopts a standard test (ASTM D3359-2009) for testing the adhesion of the coating by a tape method to test the adhesion grade to be 4B.
Comparative example 4
Similar to example 4, except that CuO nanoparticles used in electrophoretic deposition were commercially available. The adhesion rating was 2B using a standard tape method.
Through comparison of a plurality of examples, the nano MO synthesized by using ODA x Particles instead of commercially purchased nano-MOs x Particles, al-MO prepared by electrophoretic deposition x The standard test of the adhesive force of the nano coating determines that the level reaches the standards of 4B and above 4B, and the nano coating has uniform surface distribution, good heat release performance and good thermal stability.
Claims (5)
1. The method for preparing the high-adhesion nano thermite coating by electrophoretic deposition is characterized in that an oil phase synthesis method is adopted to prepare metal oxide MO x Nanoparticles, MO x Mixing the nano particles with nano aluminum powder, dispersing the mixture in an organic solution, adding a dispersing agent to form a suspension, and obtaining a nano thermite coating by using an electrophoretic deposition method;
the method specifically comprises the following steps:
(1) Heating octadecylamine to melt, heating to 120 to 250 ℃, and adding MO x Nitrate corresponding to nano particles is stirred at high temperature to prepare MO x Centrifugally collecting the nano particles for later use;
(2) Polishing and washing the cathode and anode electrode plates, and then placing the cathode and anode electrode plates in a vacuum drying oven for drying for later use;
(3) Mixing nano aluminum powder and MO obtained in step (1) x The nano particles are sequentially added into the dispersion liquid according to the weight ratio of 10 to 1 to 10, the total concentration range of the solid powder is 1.0 g/L-20.0 g/L, a proper amount of dispersing agent is added, and stable suspension liquid is formed after ultrasonic dispersion;
(4) Fixing cathode and anode plates, vertically inserting into uniformly dispersed suspension, performing electrophoretic deposition with an external electric field of 50-200Vcm -1 Obtaining a deposition film on the cathode plate after 5 to 30 minutes;
(5) And drying the deposition film obtained by electrophoretic deposition.
2. The method of claim 1, wherein the MO is a high adhesion nano thermite coating x M is one of Fe, co, ni, cu and Zn.
3. The method for preparing the high-adhesion nano thermite coating through electrophoretic deposition according to claim 1, wherein in the step (1), the mass ratio of the octadecylamine to the nitrate is (40) - (10).
4. The method for preparing the high-adhesion nano thermite coating by electrophoretic deposition according to claim 1, wherein the dispersion liquid in the step (3) is selected from isopropanol, ethanol, or a mixture of ethanol and acetylacetone according to a volume ratio of 1:1; the dispersant is polyethyleneimine, nitric acid or hydrochloric acid.
5. A nano thermite coating obtained by the method of any one of claims 1 to 4.
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