CN116063135A - High-activity composite aluminum powder capable of catalyzing ammonium perchlorate and preparation method thereof - Google Patents
High-activity composite aluminum powder capable of catalyzing ammonium perchlorate and preparation method thereof Download PDFInfo
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- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 111
- 230000000694 effects Effects 0.000 title claims abstract description 32
- GDDNTTHUKVNJRA-UHFFFAOYSA-N 3-bromo-3,3-difluoroprop-1-ene Chemical compound FC(F)(Br)C=C GDDNTTHUKVNJRA-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 239000002131 composite material Substances 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims abstract description 66
- 239000005751 Copper oxide Substances 0.000 claims abstract description 63
- 229910000431 copper oxide Inorganic materials 0.000 claims abstract description 63
- 238000000034 method Methods 0.000 claims abstract description 29
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 26
- 239000011737 fluorine Substances 0.000 claims abstract description 26
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229920000642 polymer Polymers 0.000 claims abstract description 23
- 238000007590 electrostatic spraying Methods 0.000 claims abstract description 16
- 239000002243 precursor Substances 0.000 claims abstract description 14
- 230000032683 aging Effects 0.000 claims abstract description 9
- 239000007788 liquid Substances 0.000 claims abstract description 9
- 239000003960 organic solvent Substances 0.000 claims abstract description 5
- 229920001973 fluoroelastomer Polymers 0.000 claims description 39
- 239000002033 PVDF binder Substances 0.000 claims description 33
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 33
- 230000008569 process Effects 0.000 claims description 14
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- 238000007787 electrohydrodynamic spraying Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 229910052782 aluminium Inorganic materials 0.000 abstract description 62
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical group [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 abstract description 5
- 239000010410 layer Substances 0.000 abstract description 5
- 230000009257 reactivity Effects 0.000 abstract description 4
- 239000002344 surface layer Substances 0.000 abstract description 4
- 230000003647 oxidation Effects 0.000 abstract description 2
- 238000007254 oxidation reaction Methods 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 29
- 238000005979 thermal decomposition reaction Methods 0.000 description 20
- 230000004580 weight loss Effects 0.000 description 16
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 14
- 239000000243 solution Substances 0.000 description 14
- 239000000523 sample Substances 0.000 description 9
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 8
- 238000001938 differential scanning calorimetry curve Methods 0.000 description 8
- 239000011888 foil Substances 0.000 description 8
- IRPGOXJVTQTAAN-UHFFFAOYSA-N 2,2,3,3,3-pentafluoropropanal Chemical compound FC(F)(F)C(F)(F)C=O IRPGOXJVTQTAAN-UHFFFAOYSA-N 0.000 description 7
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminum fluoride Inorganic materials F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 7
- 229910052802 copper Inorganic materials 0.000 description 7
- 239000010949 copper Substances 0.000 description 7
- 238000000354 decomposition reaction Methods 0.000 description 7
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 7
- 239000004810 polytetrafluoroethylene Substances 0.000 description 7
- 229910021594 Copper(II) fluoride Inorganic materials 0.000 description 6
- GWFAVIIMQDUCRA-UHFFFAOYSA-L copper(ii) fluoride Chemical compound [F-].[F-].[Cu+2] GWFAVIIMQDUCRA-UHFFFAOYSA-L 0.000 description 6
- 230000007246 mechanism Effects 0.000 description 6
- 239000003380 propellant Substances 0.000 description 6
- 238000009210 therapy by ultrasound Methods 0.000 description 6
- 239000003832 thermite Substances 0.000 description 6
- 238000010586 diagram Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 4
- -1 polytetrafluoroethylene Polymers 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000003682 fluorination reaction Methods 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- XAGFODPZIPBFFR-BJUDXGSMSA-N Aluminum-26 Chemical compound [26Al] XAGFODPZIPBFFR-BJUDXGSMSA-N 0.000 description 2
- 229910021593 Copper(I) fluoride Inorganic materials 0.000 description 2
- 239000012300 argon atmosphere Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000012496 blank sample Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 229920002313 fluoropolymer Polymers 0.000 description 2
- 239000004811 fluoropolymer Substances 0.000 description 2
- 230000002431 foraging effect Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000003746 solid phase reaction Methods 0.000 description 2
- 238000000859 sublimation Methods 0.000 description 2
- 230000008022 sublimation Effects 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000002076 thermal analysis method Methods 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- 229910016569 AlF 3 Inorganic materials 0.000 description 1
- 235000017060 Arachis glabrata Nutrition 0.000 description 1
- 235000010777 Arachis hypogaea Nutrition 0.000 description 1
- 244000105624 Arachis hypogaea Species 0.000 description 1
- 235000018262 Arachis monticola Nutrition 0.000 description 1
- 229920002449 FKM Polymers 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- JVNBHJHFCSAISC-UHFFFAOYSA-N aluminum lead(2+) oxygen(2-) Chemical compound [Pb+2].[O-2].[Al+3] JVNBHJHFCSAISC-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000007707 calorimetry Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical group FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000002073 nanorod Substances 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 238000007557 optical granulometry Methods 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 235000020232 peanut Nutrition 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
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- 229920002379 silicone rubber Polymers 0.000 description 1
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- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Images
Classifications
-
- 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
- C06B33/06—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 the material being an inorganic oxygen-halogen salt
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/125—Halogens; Compounds thereof with scandium, yttrium, aluminium, gallium, indium or thallium
-
- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B23/00—Compositions characterised by non-explosive or non-thermic constituents
- C06B23/005—Desensitisers, phlegmatisers
-
- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06D—MEANS FOR GENERATING SMOKE OR MIST; GAS-ATTACK COMPOSITIONS; GENERATION OF GAS FOR BLASTING OR PROPULSION (CHEMICAL PART)
- C06D5/00—Generation of pressure gas, e.g. for blasting cartridges, starting cartridges, rockets
- C06D5/06—Generation of pressure gas, e.g. for blasting cartridges, starting cartridges, rockets by reaction of two or more solids
Abstract
The invention discloses high-activity composite aluminum powder capable of catalyzing ammonium perchlorate and a preparation method thereof. The method comprises the steps of firstly dissolving fluorine-containing high polymer in an organic solvent, then sequentially adding aluminum powder and copper oxide, fully and uniformly mixing to prepare electrostatic spraying precursor liquid, then collecting active aluminum powder by adopting an electrostatic spraying method, and aging to prepare the high-activity composite aluminum powder. According to the invention, the fluorine-containing high polymer is introduced to weaken the oxidation layer on the surface layer of insensitive aluminum powder and expose the aluminum core, so that the reactivity of aluminum is improved, and meanwhile, a small amount of copper oxide is uniformly added, so that the copper oxide can be uniformly dispersed into ammonium perchlorate when the high-activity composite aluminum powder is mixed with the ammonium perchlorate.
Description
Technical Field
The invention belongs to the field of propellants, and relates to high-activity composite aluminum powder capable of catalyzing ammonium perchlorate and a preparation method thereof.
Background
Aluminum powder as a high-activity metal has wide application in the field of energetic materials. For aluminum/ammonium perchlorate systems, aluminum powder activity has a great influence on the combustion performance of the propellant when used as a major component of the propellant. At present, the method for increasing the activity of the aluminum powder is mainly cladding. The mechanism of the activity improvement of the coating material is different from that of the coating material. The main coating material is fluorine-containing high polymer. Although much research has been done on aluminum/fluorine-containing polymers, there is still a relatively preliminary understanding of the mechanism by which they increase activity, i.e., fluorine is more oxidizing than oxygen, reacts with and de-coats the alumina shells of the aluminum spheres. However, the relationship between the decomposition initiation temperature of the fluorine-containing polymer and the activity of promoting the aluminum powder has not been further studied.
As a common fluorine-containing high polymer, the polyvinylidene fluoride has the characteristics of strongest toughness, low friction coefficient, strong corrosion resistance, ageing resistance, weather resistance and good irradiation resistance. The 26-type fluororubber (VITON) is a copolymer of vinylidene fluoride and hexafluoropropylene, has high chemical stability as high as that of silicone rubber, is the best in the prior elastomer, has excellent physical and mechanical properties with excellent vacuum performance, and is applied to the industrial fields of modern aviation, missile, rocket, space navigation, naval vessels, atomic energy and the like in the tip technologies of automobiles, shipbuilding, chemistry, petroleum, telecommunication, instruments, machinery and the like.
Ammonium perchlorate is often used as an oxidizing agent in various types of propellants, the combustion properties of which are mainly related to its thermal decomposition. Studies have shown that oxides of transition metals are capable of catalyzing the thermal decomposition of ammonium perchlorate, with copper oxide having the most pronounced catalytic effect on ammonium perchlorate. However, the main research direction of the existing copper oxide catalysis ammonium perchlorate is how to control the morphology of nano copper oxide and how to uniformly mix with ammonium perchlorate ([ 1]C.Yang,J.Wang,F.Xiao,X.Su,Microwave hydrothermal disassembly for evolution from CuO dendrites to nanosheets and their applications in catalysis and photo-analysis, powder Technology 264 (2014) 36-42.[2]J.Yin,Z.Sheng,W.Zhang,Y.Zhang,H.Zhong,R.Li,Z.Jiang,X.Wang,Synthesis and catalytic properties of novel peanut shaped CuO hollow architectures,Materials Letters 131 (2014) 317-320.[3]L.Chen,L.Li,G.Li,Synthesis of CuO nanorods and their catalytic activity in the thermal decomposition of ammonium perchlorate,Journal of Alloys and Compounds 464 (2008) 532-536 ]).
Disclosure of Invention
The invention aims to provide high-activity composite aluminum powder capable of catalyzing ammonium perchlorate and a preparation method thereof. According to the invention, the fluorine-containing high polymer is introduced to weaken the oxidation layer on the surface layer of insensitive aluminum powder and expose the aluminum core, so that the reactivity of aluminum is improved, and meanwhile, a small amount of copper oxide is uniformly added, so that the copper oxide can be uniformly dispersed into ammonium perchlorate when the high-activity composite aluminum powder is mixed with the ammonium perchlorate.
The technical scheme for realizing the purpose of the invention is as follows:
the preparation method of the high-activity composite aluminum powder capable of catalyzing ammonium perchlorate comprises the following steps:
and 2, collecting active aluminum powder on the negative plate by adopting an electrostatic spraying method, and aging to obtain the high-activity composite aluminum powder.
Preferably, in step 1, the concentration of the fluorine-containing polymer in the electrospraying precursor solution is 0.9 to 1.1mg/mL.
Preferably, in step 1, the organic solvent is N, N-dimethylformamide or acetone.
Preferably, in step 1, the concentration of the aluminum powder is 47-48 mg/mL.
Preferably, in step 1, the concentration of copper oxide is 2 to 3mg/mL.
Preferably, in the step 1, the mass ratio of the aluminum powder to the copper oxide to the fluorine-containing polymer is 95:5:20.
Preferably, in step 1, the ultrasonic dispersion time is 8 to 12 minutes.
Preferably, in step 1, the final stirring time is 10 to 14 hours.
Preferably, in step 2, the parameters of the electrostatic spraying are: the diameter of the nozzle is 0.4-1 mm, the distance from the nozzle to the negative plate is 5-10 cm, and the voltage is 24-28 kilovolts.
Preferably, in the step 2, the aging temperature is 68-72 ℃ and the aging time is 2 hours.
Compared with the prior art, the invention has the following beneficial results:
the invention utilizes the extremely high electronegativity of fluorine element in fluorine-containing polymer to react with the oxide layer of the outer layer of aluminum powder, weakens the passivation effect on the aluminum powder, exposes the high-activity aluminum powder core, and improves the reactivity. Secondly, the addition of copper oxide further improves the decomposition of the active aluminum powder in the propellant system to catalyze the decomposition of ammonium perchlorate, so that the reaction between the active aluminum powder and the ammonium perchlorate is further activated. In addition, the ultrasonic dispersion method can fully lead the fluorine-containing high polymer and the copper oxide to be in close contact with the aluminum powder. The electrostatic spraying method can change the particle morphology obtained by volatilizing the solvent in the conventional method, so that the electrostatic spraying method is easier to apply in the field of propellants.
Drawings
FIG. 1 is a diagram showing a thermal decomposition process of type 26 fluororubber and polyvinylidene fluoride in an argon atmosphere.
FIG. 2 is a thermal decomposition process diagram of aluminum/copper oxide, aluminum/copper oxide/polyvinylidene fluoride, and aluminum/copper oxide/26 type fluororubber.
FIG. 3 is a thermal decomposition process diagram of aluminum/26 type fluororubber, aluminum oxide/26 type fluororubber, copper oxide/26 type fluororubber, aluminum/polyvinylidene fluoride, aluminum oxide/vinylidene fluoride, copper oxide/vinylidene fluoride.
FIG. 4 shows the results of X-ray diffraction analysis of the calcined residues of aluminum/copper oxide/26 type fluororubber at 400℃and 450℃and 500℃and of copper oxide/26 type fluororubber at 500℃and c.
FIG. 5 shows the results of X-ray diffraction analysis of the calcined residues of aluminum/copper oxide/polyvinylidene fluoride, aluminum/polyvinylidene fluoride, and copper oxide/polyvinylidene fluoride at 400 (a) and 500℃ (b).
FIG. 6 is a graph of the reaction mechanism of aluminum/copper oxide/polyvinylidene fluoride.
FIG. 7 is a reaction mechanism diagram of aluminum/copper oxide/26 type fluororubber.
FIG. 8 is a thermal decomposition process diagram of aluminum/copper oxide/polytetrafluoroethylene.
Detailed Description
The invention will now be described in further detail with reference to the drawings and to specific embodiments.
In the following examples and comparative examples, the reactivity of each sample was analyzed by thermal analysis, and the specific method was: 1mg of the sample was placed in an 80mL perforated alumina crucible with a lid and heated from 30℃to 1200℃under an argon atmosphere at a heating rate of 15K/min and at a heating rate of 20 mL/min.
Example 1
(1) Preparing an aluminum/copper oxide/polyvinylidene fluoride precursor liquid: 10mg of polyvinylidene fluoride is dissolved in 10mL of N, N-dimethylformamide solution, the solution is magnetically stirred for 0.5 hour and then is subjected to ultrasonic treatment for 10 minutes, 47.5mg of aluminum powder is added, the solution is magnetically stirred for 0.5 hour and then is subjected to ultrasonic treatment for 10 minutes, 2.5mg of copper oxide is added, the solution is magnetically stirred for 0.5 hour and then is subjected to ultrasonic treatment for 10 minutes, and finally, the solution is stirred for 12 hours to prepare the precursor solution.
(2) Preparing high-activity composite aluminum powder by electrostatic spraying: the precursor liquid is sucked by a needle tube and then placed on an injection pump, and the propulsion speed is regulated to be 1mL/min. And (3) clamping the negative electrode on an aluminum foil, clamping the positive electrode on a needle with the inner diameter of 0.51mm, turning on a high-voltage power supply, adjusting the power supply voltage to 26 kilovolts, adjusting the polar distance to 5cm, starting electrostatic spraying, collecting high-activity composite aluminum powder on the aluminum foil after the spraying is finished, and placing the aluminum foil in a baking oven at 70 ℃ for aging for 2 hours to obtain the high-activity composite aluminum powder capable of catalyzing ammonium perchlorate.
FIG. 1 (a) shows a thermal decomposition process of 26-type fluororubber, which is thermally decomposed into one-step weightlessness and ends at 700 ℃. As is clear from the DSC curve, the first endothermic peak (a) peak temperature of the 26-type fluororubber is 455℃and corresponds to the initial temperature of the weight loss thereof. This result indicates that it absorbs heat (0.46J/g) at the onset of weight loss. The peak temperature of the endothermic peak (b) immediately after the peak (a) was 465℃and the peak area thereof was 10.77J/g. The peak temperature of the peak (c) corresponds to the peak temperature of the DTG curve. This indicates that the DSC curve is shifted due to the exothermic reaction, and peak (c) is observed.
As a blank sample, the thermal decomposition process of aluminum/copper oxide is shown in fig. 2. No significant weight loss was observed on the thermogravimetric curve due to the solid-solid phase reaction between aluminum and copper oxide. As is clear from the DSC curve, the reaction zone of the thermite reaction between aluminum and copper oxide is 500-600 ℃, and the peak area of the main exothermic peak is 101J/g. And the endothermic peaks at 660 c and 1100 c are due to melting of aluminum and copper. And after the addition of polyvinylidene fluoride, the initial reaction temperature of the main exothermic peak was reduced by 120 ℃. In the main exothermic reaction zone, the corresponding weight loss of the sample was 20%. At the same time, the endothermic peak intensity of the sample at 660℃was significantly reduced, indicating a decrease in the residual aluminum content after the end of the main reaction. It should be noted that at 880 c, a 6% loss in weight was observed on the thermal weight curve of aluminum/copper oxide/polyvinylidene fluoride, corresponding to an endothermic peak observed on the DSC curve. This is due to the presence of aluminum fluoride. In summary, the addition of polyvinylidene fluoride greatly advances the initial reaction temperature of the thermite system and greatly increases the heat release.
Example 2
(1) Preparation of aluminum/copper oxide/26-type fluororubber precursor liquid: 10mg of 26-type fluororubber is dissolved in 10mL of acetone solution, stirred magnetically for 0.5 hour, then sonicated for 10 minutes, added with 47.5mg of aluminum powder, stirred magnetically for 0.5 hour, then sonicated for 10 minutes, added with 2.5mg of copper oxide, stirred magnetically for 0.5 hour, then sonicated for 10 minutes, and finally stirred for 12 hours to prepare the precursor solution.
(2) Preparing high-activity composite aluminum powder by electrostatic spraying: the precursor liquid is sucked by a needle tube and then placed on an injection pump, and the propulsion speed is regulated to be 1mL/min. And (3) clamping the negative electrode on an aluminum foil, clamping the positive electrode on a needle with the inner diameter of 0.51mm, turning on a high-voltage power supply, adjusting the power supply voltage to 26 kilovolts, adjusting the polar distance to 5cm, starting electrostatic spraying, collecting high-activity composite aluminum powder on the aluminum foil after the spraying is finished, and placing the aluminum foil in a baking oven at 70 ℃ for aging for 2 hours to obtain the high-activity composite aluminum powder capable of catalyzing ammonium perchlorate.
The thermal decomposition process of polyvinylidene fluoride is significantly different from that of type 26 fluororubber. As shown in FIG. 1 (b), the weight loss of polyvinylidene fluoride was from 400℃to 530℃and the total weight loss was 62% less than that of fluororubber by 38%. The polyvinylidene fluoride reached the fastest decomposition rate at 469 ℃ and no endothermic peak was associated with it. Two endothermic peaks (d & e) were observed at the beginning of their thermal decomposition. At the end of peak d, the corresponding weight loss curve is only slightly weight-lost, as known from literature [ W Ma, X Wang, J Zhang (2011) Journal of Thermal Analysis and Calorimetry 103:319.Doi:10.1007/s10973-010-0961 ], when there is a seeding of PVDF. At the end of the weight loss, a small exothermic peak (f) was observed on the DSC curve of polyvinylidene fluoride, which suggests that PVDF may give off some heat upon thermal decomposition.
As a blank sample, the thermal decomposition process of aluminum/copper oxide is shown in fig. 2. No significant weight loss was observed on the thermogravimetric curve due to the solid-solid phase reaction between aluminum and copper oxide. As is clear from the DSC curve, the reaction zone of the thermite reaction between aluminum and copper oxide is 500-600 ℃, and the peak area of the main exothermic peak is 101J/g. And the endothermic peaks at 660 c and 1100 c are due to melting of aluminum and copper. And after the addition of the 26-type fluororubber, the initial reaction temperature of the main exothermic peak was reduced by 70 ℃. In the main exothermic reaction zone, the corresponding weight loss of the sample was 9.34%. At the same time, the endothermic peak intensity of the sample at 660℃was significantly reduced, indicating a decrease in the residual aluminum content after the end of the main reaction. It should be noted that at 880 ℃, the corresponding weight loss on the thermal weight curve of the aluminum/copper oxide/26 type fluororubber was 3%, and an endothermic peak was observed on the corresponding DSC curve. This is due to the presence of aluminum fluoride. In summary, the addition of 26 fluororubber greatly advances the initial reaction temperature of the thermite system and greatly increases the heat release.
Example 3
To investigate the reason why the type 26 fluororubber and polyvinylidene fluoride have improved the activity of aluminum powder, a series of test samples were prepared in the same manner as in example 1, and the composition and mass fraction of each sample are shown in table 1.
TABLE 1 sample types and sample compositions
The thermal decomposition process of aluminum/26 type fluororubber, aluminum oxide/26 type fluororubber, copper oxide/26 type fluororubber, aluminum/polyvinylidene fluoride, aluminum oxide/vinylidene fluoride, copper oxide/vinylidene fluoride is shown in FIG. 3. The initial reaction temperature of the alumina/26 type fluororubber is 365 ℃, and the initial reaction temperature of the alumina/vinylidene fluoride is 306 ℃, which are all less than the initial decomposition temperature of the fluorine-containing high polymer. This means that the alumina can react with the fluoropolymer before it is decomposed. While a small peak at 500℃of alumina/vinylidene fluoride indicates the presence of beta-AlF at this time 3 To alpha-AlF 3 Is a crystal transformation process. However, in the alumina/26 type fluororubber, no significant crystal transformation process could be observed. 18% weight loss was observed on both the thermal weight curves at 1100 c for alumina/vinylidene fluoride and alumina/26 type fluororubber, probably due to sublimation of aluminum fluoride.
For thermal decomposition of aluminum/polyvinylidene fluoride, a weak exothermic peak was observed at 350 ℃; on the DSC curve of aluminum/26 type fluororubber, a weak exothermic peak was also observed at 365 ℃. These two exothermic peaks are due to the reaction of alumina with the fluoropolymer. And then, the main exothermic peak of the aluminum/polyvinylidene fluoride is between 430 and 500 ℃, which is the fluorination reaction of aluminum. For aluminum/26 type fluororubber, the main heat release zone is consistent with aluminum/polyvinylidene fluoride. Notably, the reaction between aluminum and the fluorine-containing polymer all began before the thermal decomposition of the fluorine-containing polymer, indicating that the decomposition of the fluorine-containing polymer had a significant effect on the fluorination of aluminum.
For the reaction of copper oxide/26 type fluororubber, the main heat release interval is between 410 and 500 ℃, which shows that copper oxide can react with 26 type fluororubber. Similarly, for copper oxide/polyvinylidene fluoride, copper oxide may also react with polyvinylidene fluoride. However, the thermal decomposition of the 26-type fluororubber is simultaneously present in the reaction zone, which indicates that copper oxide can simultaneously react with the cracking products of the 26-type fluororubber. An endothermic peak at 1070 ℃ indicates the presence of elemental copper in the reaction product; meanwhile, no melting peak of copper fluoride was observed at 950 ℃; this means that copper oxide is reduced to elemental copper only by fluorine and cannot continue to be oxidized to copper fluoride.
XRD analysis of the phases of aluminum/copper oxide/26 fluororubber at different temperatures (FIG. 4) revealed that the products of aluminum, copper oxide, aluminum/copper oxide and 26 fluororubber were aluminum fluoride, copper fluoride, cuprous fluoride, and copper. This means that aluminum is fluorinated by the 26-type fluororubber to aluminum fluoride, copper oxide is substituted for copper fluoride, and then stepwise reduction of copper fluoride is performed to produce cuprous fluoride and copper, respectively.
As is clear from XRD analysis of phases of aluminum/copper oxide/polyvinylidene fluoride at different temperatures (fig. 5), the aluminum-free fluorination was the same as before, and it was different from aluminum/copper oxide/26-type fluororubber in that the reduction process of copper oxide was to reduce copper oxide to copper. It should be noted that no copper fluoride was found in the bulk phase, and that the weight loss at 900 ℃ was a sublimation of aluminum fluoride.
From the above analysis, the reaction mechanism of aluminum/copper oxide/polyvinylidene fluoride is shown in FIG. 6. First, polyvinylidene fluoride is decomposed in advance and free HF is generated due to the presence of hydroxyl groups on the surface layer of alumina. HF then reacts first with the alumina to impair the inhibition of the activity of the inner aluminum core by the alumina layer, and subsequently the alumina shell breaks away from the aluminum core and exposes the inner highly active aluminum core. At this point, the polyvinylidene fluoride is further cleaved to produce more free HF, which reacts with the highly active aluminum nuclei to produce aluminum fluoride. The reaction mechanism of aluminum/copper oxide/26 type fluororubber (fig. 7) is similar to that of aluminum/copper oxide/polyvinylidene fluoride, and the hydroxyl groups on the surface layer of aluminum oxide lead to the advanced decomposition of 26 type fluororubber.
Comparative example 1
(1) Preparing an aluminum/copper oxide/polytetrafluoroethylene precursor liquid: 10mg of polytetrafluoroethylene is dissolved in 10mL of n-hexane, the solution is magnetically stirred for 0.5 hour and then is subjected to ultrasonic treatment for 10 minutes, 47.5mg of aluminum powder is added, the solution is magnetically stirred for 0.5 hour and then is subjected to ultrasonic treatment for 10 minutes, 2.5mg of copper oxide is added, the solution is magnetically stirred for 0.5 hour and then is subjected to ultrasonic treatment for 10 minutes, and finally, the solution is stirred for 12 hours, so that the precursor solution is prepared.
(2) Preparing high-activity composite aluminum powder by electrostatic spraying: the precursor liquid is sucked by a needle tube and then placed on an injection pump, and the propulsion speed is regulated to be 1mL/min. And (3) clamping the negative electrode on an aluminum foil, clamping the positive electrode on a needle with the inner diameter of 0.51mm, turning on a high-voltage power supply, adjusting the power supply voltage to 26 kilovolts, adjusting the polar distance to 5cm, starting electrostatic spraying, collecting the composite aluminum powder on the aluminum foil after the spraying is finished, and aging in a baking oven at 70 ℃ for 2 hours to obtain the composite aluminum powder capable of catalyzing ammonium perchlorate.
As is clear from FIG. 8, the main reaction zone in the thermal decomposition process of polytetrafluoroethylene is 500 to 620℃and the weight loss is 100%. At the same time of weight loss, the thermal decomposition reaction absorbs heat. As is clear from the comparison of the thermite reaction between aluminum and copper oxide, the exothermic interval of the thermite reaction is 500-600 ℃, and the peak area of the main exothermic peak is 101J/g. The thermal decomposition process of aluminum/copper oxide/polytetrafluoroethylene shows that the main heat release interval is 500-620 ℃ and the area is 702.6J/g. Meanwhile, no obvious weight loss is observed in the main heat release zone, that is, the initial temperature of the thermit reaction cannot be observed in advance, and no reaction between polytetrafluoroethylene and aluminum is observed, which means that the polytetrafluoroethylene has very limited improvement on the activity of aluminum powder.
Claims (10)
1. The preparation method of the high-activity composite aluminum powder capable of catalyzing ammonium perchlorate is characterized by comprising the following steps of:
step 1, dissolving fluorine-containing high polymer in an organic solvent, after the fluorine-containing high polymer is fully dissolved, performing ultrasonic dispersion, adding aluminum powder, uniformly stirring, performing ultrasonic dispersion, adding copper oxide, after the stirring is fully performed, performing ultrasonic dispersion, and stirring to obtain an electrostatic spraying precursor liquid, wherein the fluorine-containing high polymer is polyvinylidene fluoride or 26-type fluororubber;
and 2, collecting active aluminum powder on the negative plate by adopting an electrostatic spraying method, and aging to obtain the high-activity composite aluminum powder.
2. The method according to claim 1, wherein in step 1, the concentration of the fluorine-containing polymer in the electrospraying precursor is 0.9 to 1.1mg/mL.
3. The method according to claim 1, wherein in step 1, the organic solvent is N, N-dimethylformamide or acetone.
4. The method according to claim 1, wherein in step 1, the concentration of the aluminum powder is 47 to 48mg/mL and the concentration of the copper oxide is 2 to 3mg/mL.
5. The preparation method according to claim 1, wherein in the step 1, the mass ratio of the aluminum powder, the copper oxide and the fluorine-containing polymer is 95:5:20.
6. The method according to claim 1, wherein in step 1, the ultrasonic dispersion time is 8 to 12 minutes.
7. The method according to claim 1, wherein in step 1, the final stirring time is 10 to 14 hours.
8. The method according to claim 1, wherein in step 2, parameters of the electrostatic spraying are: the diameter of the nozzle is 0.4-1 mm, the distance from the nozzle to the negative plate is 5-10 cm, and the voltage is 24-28 kilovolts.
9. The process according to claim 1, wherein in step 2, the aging temperature is 68 to 72℃and the aging time is 2 hours.
10. The high-activity composite aluminum powder produced by the production method according to any one of claims 1 to 9.
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