CN116478001A - Preparation and combustion performance adjusting method of calcium iodate-based energetic microsphere with bactericidal effect - Google Patents
Preparation and combustion performance adjusting method of calcium iodate-based energetic microsphere with bactericidal effect Download PDFInfo
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- 239000004005 microsphere Substances 0.000 title claims abstract description 71
- 238000002485 combustion reaction Methods 0.000 title claims abstract description 69
- 238000000034 method Methods 0.000 title claims abstract description 65
- 239000004151 Calcium iodate Substances 0.000 title claims abstract description 25
- UHWJJLGTKIWIJO-UHFFFAOYSA-L calcium iodate Chemical compound [Ca+2].[O-]I(=O)=O.[O-]I(=O)=O UHWJJLGTKIWIJO-UHFFFAOYSA-L 0.000 title claims abstract description 25
- 235000019390 calcium iodate Nutrition 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 15
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 50
- 239000000243 solution Substances 0.000 claims abstract description 36
- 239000002243 precursor Substances 0.000 claims abstract description 35
- 239000002033 PVDF binder Substances 0.000 claims abstract description 32
- 239000000446 fuel Substances 0.000 claims abstract description 32
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims abstract description 32
- 239000000843 powder Substances 0.000 claims abstract description 30
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 28
- 239000002245 particle Substances 0.000 claims abstract description 27
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000011575 calcium Substances 0.000 claims description 72
- 239000011521 glass Substances 0.000 claims description 20
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 14
- 239000011888 foil Substances 0.000 claims description 12
- 238000009210 therapy by ultrasound Methods 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 11
- 230000009977 dual effect Effects 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 7
- 239000003517 fume Substances 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 230000000694 effects Effects 0.000 claims description 6
- 230000005686 electrostatic field Effects 0.000 claims description 6
- 238000002347 injection Methods 0.000 claims description 6
- 239000007924 injection Substances 0.000 claims description 6
- 238000000520 microinjection Methods 0.000 claims description 6
- 229910052791 calcium Inorganic materials 0.000 claims description 4
- 239000012046 mixed solvent Substances 0.000 claims description 4
- 239000005543 nano-size silicon particle Substances 0.000 claims description 3
- 238000000875 high-speed ball milling Methods 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 239000003832 thermite Substances 0.000 abstract description 13
- 239000000463 material Substances 0.000 abstract description 8
- 238000007590 electrostatic spraying Methods 0.000 abstract description 7
- 239000011259 mixed solution Substances 0.000 abstract description 5
- 230000005684 electric field Effects 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 15
- 239000011863 silicon-based powder Substances 0.000 description 15
- 230000001954 sterilising effect Effects 0.000 description 14
- 238000004659 sterilization and disinfection Methods 0.000 description 12
- 230000001965 increasing effect Effects 0.000 description 6
- 238000000151 deposition Methods 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 230000002708 enhancing effect Effects 0.000 description 4
- 239000007800 oxidant agent Substances 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 3
- ICIWUVCWSCSTAQ-UHFFFAOYSA-M iodate Chemical compound [O-]I(=O)=O ICIWUVCWSCSTAQ-UHFFFAOYSA-M 0.000 description 3
- 229910052740 iodine Inorganic materials 0.000 description 3
- 239000011630 iodine Substances 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000003760 magnetic stirring Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- -1 and thus Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
Classifications
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- 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
-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
The invention discloses a preparation method and a combustion performance adjusting method of calcium iodate-based energetic microspheres with bactericidal effect. Based on the electrostatic spraying principle, polyvinylidene fluoride, nano Al powder, calcium iodate and a combustion performance regulator are dispersed in a mixed solution of N, N-dimethylformamide and acetone step by step to prepare a precursor solution, and the precursor solution is sprayed and dried in a high-voltage electric field to obtain the calcium iodate-based energetic microsphere. The combustion performance of the calcium iodate-based energetic microsphere can be adjusted by adjusting the stoichiometric ratio of Al to calcium iodate, or constructing a dual-fuel system by using another fuel except Al, or adjusting the content of nano Si by using Al and Si as fuels, or adjusting the particle size of nano Si by using Al and Si as fuels. The energetic microsphere obtained by the invention has uniform particle size, so that all components of the energetic microsphere are tightly combined, and meanwhile, the invention provides a plurality of methods for adjusting the combustion characteristics of the energetic microsphere, which can be widely applied to energy regulation and control of a plurality of thermite materials.
Description
Technical Field
The invention relates to the field of energetic materials, in particular to a preparation method and a combustion performance adjusting method of calcium iodate-based energetic microspheres with a bactericidal effect.
Background
Bacteria in the environment bring more and more serious threat to human health, and the traditional sterilization methods, such as a heating sterilization method, an ultraviolet sterilization method and the like, have the defects of long time required for sterilization, low sterilization efficiency and the like. When the nano thermite is combusted, the flame temperature can reach 3000K, and a high-temperature and high-pressure environment can be formed in a short time, so that the nano thermite has good application prospect in the field of biological sterilization. Iodate or iodate can act as both a sterilant and an oxidant in the thermite system, e.g. I 2 、AgIO 3 、I 2 O 5 、Bi(IO 3 ) 2 And the like, and the sterilizing gas is released at the same time of generating high temperature and high pressure, thereby enhancing the sterilizing effect. Iodate-based thermites are also more excellent in energy characteristics than metal oxide-based thermites, and thus, iodine-containing nanothermites have received great attention.
In recent years, researchers have been working on how to increase the iodine content of thermite having bactericidal properties, thereby enhancing the bactericidal effect. Haiyang Wang et Al added I to Al/CuO 2 To realize sterilization effect I 2 Up to 40 wt.%, then I 2 Added into an Al/PVDF energetic film, I 2 The content can be up to 67wt%, but with I 2 The content is increased, and the combustion performance of the thermite is greatly reduced (Combustion and Flame,162 (2015): 2823-2829;Combustion and Flame,197 (2018): 120-126). And by enhancing the combination compactness between the fuel and the oxidant in the thermite, the heat and mass transfer distance in the reaction is shortened, and the energy characteristic of the thermite can be improved. The electrostatic spraying technology is adopted, iodized salt or oxide is used as oxidant, and a small amount of binder is added into the thermite system to formThe components are combined closely and uniformly distributed with the thermite microspheres, and the gas generated by the decomposition of the binder is utilized to reduce the reaction sintering degree of the aluminum powder, improve the energy release rate and flame temperature of the system and reduce the ignition temperature. Thus, there is a need to develop methods for improving the combustion performance of energetic microspheres having bactericidal properties, particularly methods for enhancing the combustion performance of energetic microspheres, using electrostatic spraying. Therefore, we propose a method for preparing calcium iodate-based energetic microspheres with bactericidal effect and adjusting combustion performance.
Disclosure of Invention
In order to solve the problems, the invention provides a preparation method of calcium iodate-based energetic microspheres with bactericidal effect and a combustion performance adjusting method, so as to solve the problems in the background art.
The invention uses calcium iodate (Ca (IO) 3 ) 2 ) Is an oxidant in the energetic microsphere, which is used to release I-containing material when burned 2 The steam achieves the sterilization effect. The object of the present invention is to provide Ca (IO) having a bactericidal effect 3 ) 2 Preparation and combustion performance adjusting method of base energetic microsphere, and Ca (IO) is realized by adopting electrostatic spraying process 3 ) 2 The preparation of the base energetic microsphere realizes Ca (IO) by using 4 methods of adjusting the stoichiometric ratio (phi), constructing a dual-fuel system and adjusting the content and the grain diameter of nano Si 3 ) 2 And (3) adjusting the combustion performance of the base energetic microsphere.
The preparation and combustion performance adjusting method of calcium iodate-based energetic microsphere with bactericidal effect in the invention has Ca (IO) with bactericidal effect 3 ) 2 Preparation of base energetic microsphere and combustion performance adjusting method, wherein Ca (IO 3 ) 2 The preparation method of the base energetic microsphere comprises the following specific steps:
the first step: 20mg of PVDF is added to a 5mL glass bottle and to the mixed solvent and placed in a 35℃oven;
and a second step of: adding submicron Ca (IO) after PVDF is completely dissolved 3 ) 2 Washing the inner wall of the glass bottle with acetone, magnetically stirring at 700rpm for 10min, ultrasonic treating for 30min, adding nanometer Al powder, washing the inner wall of the glass bottle with acetone, and mixingAnd then, the precursor solution is magnetically stirred at 700rpm for 10min for preliminary mixing, then, ultrasonic treatment is carried out for 1h, and finally, the precursor solution is magnetically stirred at 700rpm for 18h for standby.
And a third step of: the precursor solution was sucked into a 5mL syringe and placed on a syringe pump, and a needle (inner diameter 0.43 mm) was attached. Using clean aluminum foil as a receiving plate, setting the distance between the needle and the receiving plate to be 10cm, setting the voltage to be 15kV, starting a micro injection pump, setting the injection speed to be 1.5mL/h, moving the precursor solution in a high-voltage electrostatic field, depositing the precursor solution on the aluminum foil, and drying in a fume hood for 12h to obtain Ca (IO) 3 ) 2 And (3) base energetic microspheres.
The Ca (IO) 3 ) 2 The combustion performance adjusting method of the base energetic microsphere can be realized by improving the second step, and the specific method is that Al and Ca (IO) are adjusted in the second step 3 ) 2 Or using another fuel except Al to construct a dual-fuel system, or using Al and Si as fuel and adjusting the nano Si content, or using Al and Si as fuel and adjusting the nano Si particle size.
Preferably, in the first step, the mixed solvent is N, N-Dimethylformamide (DMF) and acetone, and the volume ratio of DMF to acetone is 3:1;
preferably, in the second step, the submicron Ca (IO 3 ) 2 The nanometer aluminum powder is prepared by a mechanochemical method or a high-speed ball milling method, the particle size is 0.5-2.0 mu m, the particle size of the nanometer aluminum powder is 50nm, and the activity content is 80%;
preferably, in the second step, the precursor solution is prepared from PVDF, ca (IO 3 ) 2 Al and other fuels, the total mass of solids used in the precursor solution formulation being 400mg;
preferably, in the first step and the second step, the total volume of DMF and acetone in the precursor solution is 1.2mL and the volume ratio of DMF to acetone is 1:3;
preferably, the Ca (IO 3 ) 2 In the method for adjusting the combustion performance of the base energetic microsphere, one of the methods is to adjust the content of Al and Ca (IO) 3 ) 2 Except the stoichiometric ratio of (2), each component phi of the rest methods is 1 and is calculated according to the formulas 1-5;
10B+3Ca(IO 3 ) 2 →5B 2 O 3 +3CaO+3I 2 (1)
5Si+2Ca(IO 3 ) 2 →5SiO 2 +2CaO+2I 2 (2)
5Ti+2Ca(IO 3 ) 2 →5TiO 2 +2CaO+2I 2 (3)
2Ta+Ca(IO 3 ) 2 →Ta 2 O 5 +CaO+I 2 (4)
2Al+3C 2 H 2 F 2 →2AlF 3 +6C+3H 2 (5)
preferably, the Ca (IO 3 ) 2 In the method for adjusting the combustion performance of the base energetic microsphere, one of the methods adjusts the content of Al and Ca (IO) 3 ) 2 In the stoichiometric ratio of Al to Ca (IO 3 ) 2 Phi in the range of 1.0-3.0;
preferably, the Ca (IO 3 ) 2 In the method for adjusting the combustion performance of the base energetic microsphere, one fuel of the method is constructed into a dual-fuel system, the other fuel is B, ti, ta or Si except Al powder, and the mass ratio of the B, ti, ta or Si to the Al powder is 1:9; the average particle size of the powder B is 500nm, the average particle size of Ti is 50nm, the average particle size of Ta is 50nm, and the average particle size of Si is 6nm;
preferably, the Ca (IO 3 ) 2 In the method for adjusting the combustion performance of the base energetic microsphere, one of the methods takes Al and Si as fuel and adjusts the content of nano Si, wherein the average grain diameter of the nano Si is 6nm, the activity content is 65%, and the mass fraction of the nano Si in an Al/Si system is 1.5-15%;
preferably, the Ca (IO 3 ) 2 In the method for adjusting the combustion performance of the base energetic microsphere, one of the methods takes Al and Si as fuel and adjusts the particle size of nano Si, wherein the average particle size of the nano Si is 5-500nm.
The invention has the advantages and beneficial effects that: the invention provides a preparation method and a combustion performance adjusting method of calcium iodate-based energetic microspheres with bactericidal effect, which have the following advantages:
1. the invention is based on the electrostatic spraying technology, the particle size of the obtained energetic microsphere is uniform, the dispersibility is good, the components of the energetic microsphere are tightly combined, the mass transfer and heat transfer distances among the components are reduced, the reaction rate among the components is enhanced, and therefore Ca (IO) is improved 3 ) 2 Combustion characteristics of the base energetic microspheres;
2. the method for adjusting the combustion characteristics of the energetic microsphere provided by the invention is based on an electrostatic spraying technology, does not need to additionally increase equipment, has easily available raw materials, is simple and convenient to operate, and realizes high temperature, high pressure and I while improving the combustion characteristics 2 The multiple sterilization effect of steam overcomes the defects of long time, low sterilization efficiency and the like of the prior sterilization technology;
3. the invention provides a method for adjusting the combustion characteristics of various energetic microspheres, which has wide energy adjustment range and strong applicability and can be widely applied to energy adjustment and control of various thermite materials.
Drawings
In order to more clearly illustrate the embodiments of the invention or the technical solutions of the prior art, the drawings which are used in the description of the embodiments or the prior art will be briefly described, it being obvious that the drawings in the description below are only some embodiments of the invention, and that other drawings can be obtained according to these drawings without inventive faculty for a person skilled in the art.
FIG. 1 is a graph showing the Al/Ca (IO) 3 ) 2 SEM images of (a).
FIG. 2 is a graph showing the Al/Ca (IO) 3 ) 2 SEM image of PVDF microspheres.
FIG. 3 shows the Al/Ca (IO) prepared in example 1 3 ) 2 SEM image of PVDF microspheres.
FIG. 4 shows Ca (IO) prepared in examples 5-8 3 ) 2 Combustion performance of the base microspheres.
FIG. 5 shows the Al/Si/Ca (IO) prepared in example 9 3 ) 2 SEM image of PVDF microspheres.
FIG. 6 is a sample of Al/Si/Ca (IO) 3 ) 2 TEM image of PVDF microspheres.
FIG. 7 shows the Al/Si/Ca (IO) prepared in examples 9-12 3 ) 2 Combustion diagram of PVDF microspheres.
Fig. 8 is a graph of the corresponding combustion performance of each material.
Detailed Description
The following describes the embodiments of the present invention further with reference to the drawings and examples. The following examples are only for more clearly illustrating the technical aspects of the present invention, and are not intended to limit the scope of the present invention.
As shown in figures 1-7, the invention relates to a preparation method of calcium iodate-based energetic microsphere with bactericidal effect and a combustion performance adjusting method, as shown in figure 8 (table 1-table 4), which is a combustion performance diagram of corresponding materials, wherein:
table 1 shows the combustion performance of the prepared Ca (IO 3) 2-based material obtained in comparative examples 1-2;
table 2 shows the combustion performance of the Al/Ca (IO 3) 2/PVDF microspheres obtained in examples 1 to 4;
table 3 shows the combustion performance of the Al/Si/Ca (IO 3) 2/PVDF microspheres obtained in examples 9-12;
table 4 shows the combustion performance of the Al/Si/Ca (IO 3) 2/PVDF microspheres obtained in examples 13 to 16.
Comparative example 1
Preparation of Al/Ca (IO) by physical ultrasonic mixing method 3 ) 2 The compound comprises the following specific steps:
the first step: 77.6mg Ca (IO) was weighed out separately 3 ) 2 And 22.4mg of nano Al powder are placed in a 20mL glass bottle;
and a second step of: adding 10mL of n-hexane into the glass, and carrying out ultrasonic treatment for 1h;
and a third step of: drying the mixture in a fume hood for 24 hr, and lightly crushing the powder to obtain Al/Ca (IO) 3 ) 2 A complex.
For the prepared Al/Ca (IO 3 ) 2 When the composite is observed under a Scanning Electron Microscope (SEM), as shown in FIG. 1, the combustion characteristics are shown in Table 1, and it is comprehensively known that the nano-meter can be improved despite the ultrasonic actionThe dispersibility of the material, but the presence of agglomerates in the form of blocks on the order of microns, which would allow Al to Ca (IO 3 ) 2 The contact area is drastically reduced and the reaction diffusion distance is increased, thereby suppressing the combustion characteristics thereof.
Comparative example 2
Preparation of Al/Ca (IO) by electrostatic spraying 3 ) 2 PVDF energetic microsphere comprises the following specific steps:
the first step: 20mg of PVDF is added to a 5mL glass bottle and to a mixed solution containing 0.3mL DMF and 0.1mL acetone and placed in an oven at 35 ℃;
and a second step of: 284.3mg Ca (IO) was weighed out separately at a phi of 1 3 ) 2 And 95.7mg of nano Al powder, and Ca (IO) is added after PVDF is completely dissolved 3 ) 2 Washing the inner wall of the glass bottle with 0.3mL of acetone, magnetically stirring at 700rpm for 10min, performing ultrasonic treatment for 30min, adding nano Al powder, washing the inner wall of the glass bottle with 0.5mL of acetone, magnetically stirring the precursor solution at 700rpm for 10min for preliminary mixing, performing ultrasonic treatment for 1h, and magnetically stirring the precursor solution at 700rpm for 18h for later use.
And a third step of: the precursor solution was sucked into a 5mL syringe and placed on a syringe pump, and a needle (inner diameter 0.43 mm) was attached. Using clean aluminum foil as a receiving plate, setting the distance between the needle and the receiving plate to be 10cm, setting the voltage to be 15kV, starting a micro injection pump, setting the injection speed to be 1.5mL/h, moving the precursor solution in a high-voltage electrostatic field, depositing the precursor solution on the aluminum foil, and drying in a fume hood for 12h to obtain Al/Ca (IO) 3 ) 2 PVDF energetic microspheres.
For the prepared Al/Ca (IO 3 ) 2 When the PVDF energetic microsphere is observed under SEM, as shown in FIG. 2, the combustion characteristics are shown in Table 1 in FIG. 8, and the result shows that the obtained particle is spherical or spheroid, the dispersibility is good, and the combustion performance is improved compared with that of comparative example 1 due to the tighter structure.
Examples 1-4 are examples of the use of adjusting the stoichiometry to adjust the combustion characteristics of calcium iodate based energetic microspheres.
Example 1
The first step: 20mg of PVDF is added to a 5mL glass bottle and to a mixed solution containing 0.3mL DMF and 0.1mL acetone and placed in an oven at 35 ℃;
and a second step of: 260.4mg Ca (IO) are weighed according to phi of 1.5 3 ) 2 And 119.6mg of nano Al powder, and adding Ca (IO) after PVDF is completely dissolved 3 ) 2 Washing the inner wall of a glass bottle with 0.3mL of acetone, magnetically stirring at 700rpm for 10min, performing ultrasonic treatment for 30min, adding nano Al powder, washing the inner wall of the glass bottle with 0.5mL of acetone, magnetically stirring the precursor solution at 700rpm for 10min for preliminary mixing, performing ultrasonic treatment for 1h, and magnetically stirring the precursor solution at 700rpm for 18h for later use;
and a third step of: the precursor solution was sucked into a 5mL syringe and placed on a syringe pump, and a needle (inner diameter 0.43 mm) was attached. Using clean aluminum foil as a receiving plate, setting the distance between the needle and the receiving plate to be 10cm, setting the voltage to be 15kV, starting a micro injection pump, setting the injection speed to be 1.5mL/h, moving the precursor solution in a high-voltage electrostatic field, depositing the precursor solution on the aluminum foil, and drying in a fume hood for 12h to obtain Al/Ca (IO) 3 ) 2 PVDF energetic microspheres.
For the prepared Al/Ca (IO 3 ) 2 The PVDF energetic microspheres were observed under SEM as shown in FIG. 3, and the results showed that the particles obtained were similar to comparative example 2, and had a spherical or spheroid shape and good dispersibility.
Example 2
Except that in the second step, 236.5mg Ca (IO) was weighed according to phi of 2.0 3 ) 2 And 143.5mg of nano Al powder, the rest of the procedure is the same as in example 1.
Example 3
Except that in the second step, 216.7mg Ca (IO) was weighed according to phi of 2.5 3 ) 2 And 163.3mg of nano Al powder, the rest of the procedure was as in example 1.
Example 4
200.0mg Ca (IO) was weighed separately except for the second step at a ratio of 3.0 3 ) 2 And 180.0mg of nano Al powder, the rest of the procedure is the same as in example 1.
The combustion performance of the samples obtained in examples 1-4 is shown in Table 2 of FIG. 8, and when 2.0> Φ >1.0, the combustion pressure and the pressure increase rate gradually increase; when Φ >2.0, the combustion pressure and the pressure-increasing rate gradually decrease, and the combustion performance (energy release rate) tends to be enhanced and then weakened. The combustion time shows a trend of increasing and then decreasing with increasing phi, and also shows a trend of increasing and then decreasing combustion performance. Flame temperature has no obvious relation with phi, and temperature is stabilized to be about 2600 ℃. In conclusion, by adjusting the stoichiometric ratio, not only can the combustion performance of the calcium iodate-based energetic microsphere be adjusted, but also the iodine content can be adjusted, so that the biological sterilization requirements under different environments can be met.
Examples 5-8 are the use of a dual flame system constructed to adjust the combustion characteristics of calcium iodate based energetic microspheres.
Example 5
The first step: 20mg of PVDF is added to a 5mL glass bottle and to a mixed solution containing 0.3mL DMF and 0.1mL acetone and placed in an oven at 35 ℃;
and a second step of: 295.2mg Ca (IO) was weighed out separately at a phi of 1 3 ) 2 77.1mg of nano Al powder and 7.7mg of nano Si powder, and adding Ca (IO) after PVDF is completely dissolved 3 ) 2 Washing the inner wall of a glass bottle with 0.3mL of acetone, magnetically stirring at 700rpm for 10min, performing ultrasonic treatment for 30min, adding nano Al and Si powder, washing the inner wall of the glass bottle with 0.5mL of acetone, magnetically stirring the precursor solution at 700rpm for 10min for preliminary mixing, performing ultrasonic treatment for 1h, and magnetically stirring the precursor solution at 700rpm for 18h for later use;
and a third step of: the precursor solution was sucked into a 5mL syringe and placed on a syringe pump, and a needle (inner diameter 0.43 mm) was attached. Using clean aluminum foil as a receiving plate, setting the distance between the needle and the receiving plate to be 10cm, setting the voltage to be 15kV, starting a micro injection pump, setting the injection speed to be 1.5mL/h, moving the precursor solution in a high-voltage electrostatic field, depositing the precursor solution on the aluminum foil, and drying in a fume hood for 12h to obtain Al/Ca (IO) 3 ) 2 PVDF energetic microspheres.
Example 6
Except that in the second step, 299.8mg Ca (IO) are respectively weighed according to phi of 1 3 ) 2 72.9mg of nanometerThe procedure of example 5 was followed except that Al powder and 7.3mg of nano B powder were used.
Example 7
Except that in the second step, 293.1mg Ca (IO) are respectively weighed according to phi of 1 3 ) 2 The procedure of example 5 was followed except that 79.0mg of nano Al powder and 7.9mg of nano B powder were used.
Example 8
Except that in the second step, 290.1mg Ca (IO) was weighed according to phi 1 3 ) 2 The procedure of example 5 was followed except that 81.7mg of nano Al powder and 8.2mg of nano B powder were used.
The samples obtained in examples 5-8 have combustion performance as shown in FIG. 4, and the dual fuel electrospray microspheres have combustion pressures of Al/Si, al/Ti and Al/Ta dual fuel systems which are 2.2, 2.5 and 2.7 times that of comparative example 1, respectively, except that the combustion pressure of the Al/B system is slightly lower than that of the Al system alone; and are 1.2, 1.4 and 1.6 times that of comparative example 2, respectively. The dual fuel systems Al/Si, al/Ti and Al/Ta all had higher boost rates than the Al system alone, 8.0, 10.6 and 13.5 times that of comparative example 1, and 2.7, 3.9 and 5.2 times that of comparative example 2, respectively. The burn times for the Al/Si, al/Ti and Al/Ta dual fuel systems were all less than the individual fuel systems, 43% and 32% for comparative example 1, and 57%, 57% and 43% for comparative example 2, respectively. As for the combustion temperature, the flame temperature of the Al/Si system was comparable to that of comparative example 2, while the flame temperatures of the Al/B, al/Ta and Al/Ti systems were slightly lower than that of comparative example 2. In conclusion, the combustion performance of the calcium iodate-based energetic microsphere can be adjusted by constructing a double-combustion system.
Examples 9-12 are the use of nano Si content adjustment to adjust the combustion characteristics of calcium iodate based energetic microspheres.
Example 9
The first step: 20mg of PVDF is added to a 5mL glass bottle and to a mixed solution containing 0.3mL DMF and 0.1mL acetone and placed in an oven at 35 ℃;
and a second step of: 294.9mg Ca (IO) are weighed according to phi 1 3 ) 2 83.8mg of nano Al powder and 1.3mg of nano Si powder, and adding Ca (IO) after PVDF is completely dissolved 3 ) 2 And the inner wall of the glass bottle was rinsed with 0.3mL of acetone at 700Magnetic stirring at rpm for 10min, ultrasonic treatment for 30min, adding nano Al and Si powder, washing the inner wall of a glass bottle with 0.5mL of acetone, magnetic stirring at 700rpm for 10min for preliminary mixing, ultrasonic treatment for 1h, and magnetic stirring at 700rpm for 18h for later use;
and a third step of: the precursor solution was sucked into a 5mL syringe and placed on a syringe pump, and a needle (inner diameter 0.43 mm) was attached. Using clean aluminum foil as a receiving plate, setting the distance between the needle and the receiving plate to be 10cm, setting the voltage to be 15kV, starting a micro injection pump, setting the injection speed to be 1.5mL/h, moving the precursor solution in a high-voltage electrostatic field, depositing the precursor solution on the aluminum foil, and drying in a fume hood for 12h to obtain Al/Si/Ca (IO) 3 ) 2 PVDF energetic microspheres.
For the prepared Al/Si/Ca (IO 3 ) 2 When the PVDF energetic microsphere is observed under SEM and a Transmission Electron Microscope (TEM), the result is shown in figures 5 and 6, and the 6nm Si powder and the Al powder are observed to be fully mixed, and part of Si powder can fill the gaps of the microsphere to form a compact spherical structure.
Example 10
295.0mg Ca (IO) was weighed separately in the second step 3 ) 2 The procedure of example 9 was followed except that 80.9mg of nano Al powder and 4.1mg of nano Si powder were used.
Example 11
295.1mg Ca (IO) was weighed separately in the second step 3 ) 2 The procedure of example 9 was followed except that 79.0mg of nano Al powder and 5.9mg of nano Si powder were used.
Example 12
295.3mg Ca (IO) was weighed separately in the second step 3 ) 2 The procedure of example 9 was followed except that 73.7mg of nano Al powder and 11.0mg of nano Si powder were used.
The combustion performance of the samples obtained in examples 9-12 is shown in table 3 in fig. 7 and 8, from which it is seen that the Al/Si dual fuel energetic microspheres all showed a tendency to increase and decrease with increasing nano Si content, both reaching a maximum at Si content of 7.5%, with a maximum pressure of 382.7kPa, which is 2.1 times that of comparative example 2; the maximum boost rate was 402.4kPa/ms, 7.4 times that of comparative example 2. After nano Si powder is added, the burning time is shortened, which indicates that the burning of the energetic microsphere is more severe after nano Si is added. In summary, the combustion performance of the calcium iodate-based energetic microsphere can be adjusted by adjusting the content of the nano Si powder.
Examples 13-16 are the use of nano-Si particle size adjustment to adjust the combustion characteristics of calcium iodate based energetic microspheres.
Example 13
The procedure of example 9 was followed except that the nano Si powder used in the second step had a particle size of 20 nm.
Example 14
The procedure of example 9 was followed except that the nano Si powder used in the second step had a particle size of 50 nm.
Example 15
The procedure of example 9 was followed except that the nano Si powder used in the second step had a particle size of 100 nm.
Example 16
The procedure of example 9 was followed except that the nano Si powder used in the second step had a particle size of 500nm.
The samples obtained in examples 13-16 have combustion properties as shown in Table 4 of FIG. 8, which shows that the addition of nano Si of different particle sizes can adjust the combustion properties of calcium iodate-based energetic microspheres to some extent.
Therefore, the invention provides the method for adjusting the combustion performance of the calcium iodate-based energetic microsphere in 4 steps of adjusting the stoichiometric ratio (phi), constructing a dual-fuel system, adjusting the content of nano Si and the particle size, and the experimental data are combined to prove that the method provided by the invention has wide adjustment range of the combustion performance of the energetic microsphere, high universality and strong applicability.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the invention.
Claims (10)
1. The preparation and combustion performance adjusting method of calcium iodate-based energetic microspheres with bactericidal effect is characterized by comprising the following steps:
the specific preparation method of the calcium iodate Ca (IO 3) 2-based energetic microsphere comprises the following steps:
the first step: 20mg of PVDF is added to a 5mL glass bottle and to the mixed solvent and placed in a 35℃oven;
and a second step of: adding submicron Ca (IO 3) 2 after PVDF is completely dissolved, washing the inner wall of a glass bottle with acetone, magnetically stirring at 700rpm for 10min, performing ultrasonic treatment for 30min, adding nano Al powder, washing the inner wall of the glass bottle with acetone, magnetically stirring the precursor solution at 700rpm for 10min for preliminary mixing, performing ultrasonic treatment for 1h, and magnetically stirring the precursor solution at 700rpm for 18h for later use.
And a third step of: the precursor solution was sucked into a 5mL syringe and placed on a syringe pump, and a needle (inner diameter 0.43 mm) was attached. Clean aluminum foil is used as a receiving plate, the distance between a needle head and the receiving plate is 10cm, the voltage is 15kV, a microinjection pump is started, the injection speed is 1.5mL/h, a precursor solution moves in a high-voltage electrostatic field and is deposited on the aluminum foil, and the Ca (IO 3) 2-based energetic microsphere is obtained after drying in a fume hood for 12 hours.
Secondly, the invention is characterized in that the combustion performance adjusting method of the Ca (IO 3) 2-based energetic microsphere can be realized by improving the second step, and the specific method is that the phi of the Al and Ca (IO 3) 2 is adjusted in the second step, or another fuel except the Al is used for constructing a dual-fuel system, or the Al and the Si are used as the fuel and the nano Si content is adjusted, or the Al and the Si are used as the fuel and the grain size of the nano Si is adjusted.
2. The preparation method according to claim 1, wherein in the first step, the mixed solvent is N, N-Dimethylformamide (DMF) and acetone, and the volume ratio of DMF to acetone is 3:1.
3. The preparation method according to claim 1, wherein in the second step, submicron Ca (IO 3) 2 is prepared by a mechanochemical method or a high-speed ball milling method, the particle size is 0.5-2.0 μm, the particle size of the nano aluminum powder is 50nm, and the activity content is 80%.
4. The method of claim 1, wherein in the second step, the precursor solution is composed of PVDF, ca (IO 3) 2, al and other fuels, and the total mass of solids used in the precursor solution preparation is 400mg.
5. The method according to claim 1, wherein in the first and second steps, the total volume of DMF and acetone in the precursor solution is 1.2mL and the volume ratio of DMF to acetone is 1:3.
6. The method for adjusting combustion performance of claim 1, wherein the method for adjusting combustion performance of Ca (IO 3) 2-based energetic microspheres is one of 4 methods of adjusting stoichiometric ratio (phi), constructing a dual fuel system and adjusting nano Si content and particle size, and the method comprises the steps of adjusting stoichiometric ratio of Al to Ca (IO 3) 2 and each component phi of the rest methods is 1.
7. The adjusted stoichiometry of claim 6 wherein the stoichiometry is a stoichiometric ratio of Al to Ca (IO 3) 2 and Φ of the Al to Ca (IO 3) 2 is in the range of 1.0-3.0.
8. The build dual fuel system of claim 6, wherein in the dual fuel system, the other fuel is one of B, ti, ta, or Si, in addition to the ai powder, and the mass ratio of B, ti, ta, or Si to ai powder is 1:9; the average particle diameter of the powder B is 500nm, the average particle diameter of Ti is 50nm, the average particle diameter of Ta is 50nm, and the average particle diameter of Si is 6nm.
9. The method for adjusting nano Si content according to claim 6, wherein the average grain size of the nano Si is 6nm, the active content is 65%, and the mass fraction of the nano Si in the Al/Si system is 1.5-15%.
10. The nano-Si particle size of claim 6, wherein said nano-Si has an average particle size in the range of 5-500nm.
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