CN113307709A - Core-shell aluminum @ perchlorate/catalyst composite microsphere and solid propellant based on same - Google Patents

Core-shell aluminum @ perchlorate/catalyst composite microsphere and solid propellant based on same Download PDF

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Publication number
CN113307709A
CN113307709A CN202110656079.3A CN202110656079A CN113307709A CN 113307709 A CN113307709 A CN 113307709A CN 202110656079 A CN202110656079 A CN 202110656079A CN 113307709 A CN113307709 A CN 113307709A
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perchlorate
catalyst
core
composite
aluminum
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严启龙
吕杰尧
孙德民
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Jiangsu Yongchuang Pharmaceutical Technology Co ltd
Northwestern Polytechnical University
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Jiangsu Yongchuang Pharmaceutical Technology Co ltd
Northwestern Polytechnical University
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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
    • C06B21/0008—Compounding the ingredient
    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B45/00—Compositions or products which are defined by structure or arrangement of component of product
    • C06B45/18—Compositions or products which are defined by structure or arrangement of component of product comprising a coated component
    • C06B45/30—Compositions or products which are defined by structure or arrangement of component of product comprising a coated component the component base containing an inorganic explosive or an inorganic thermic component
    • 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 provides a core-shell type aluminum @ perchlorate/catalyst composite microsphere and a solid propellant based on the microsphere, which are used for reducing the pressure index of the conventional Al-based composite solid propellant and improving the catalytic efficiency of a catalyst. The core-shell type aluminum @ perchlorate/catalyst composite microsphere comprises the following components in percentage by mass: 25-80% of perchlorate oxidant, 5-75% of aluminum powder and 0-20% of catalyst, wherein the perchlorate oxidant is tightly coated on the aluminum powder to form a core-shell composite microsphere with the particle size of 1.0-400 mu m; when the composite microsphere contains the catalyst, the catalyst is embedded between perchlorate oxidant crystals, and the components are in close contact.

Description

Core-shell aluminum @ perchlorate/catalyst composite microsphere and solid propellant based on same
Technical Field
The invention belongs to the technical field of composite solid propellants, and particularly relates to a core-shell type aluminum @ perchlorate/catalyst composite microsphere and a solid propellant based on the microsphere.
Background
The Solid propellant is used as an energy source and a working medium source of a Solid Rocket engine (SRM), is widely applied to various carrier rockets and weaponry, and the combustion performance of the Solid propellant determines the performance of the SRM to a great extent. In addition to solid propellants for variable thrust SRM, designers often desire propellants having lower firing rate pressure indexes. The high pressure index means that small pressure disturbances during the operation of the SRM cause a large change in the combustion rate, resulting in pressure oscillations in the SRM combustion chamber. This not only presents a significant challenge to the structural design of the SRM, but can also cause significant safety concerns.
Researchers have traditionally used methods of adding Combustion catalysts to adjust the burn rate pressure index of propellants, but numerous experimental results have shown that existing Combustion catalysts can negatively affect the energy level, mechanical properties, storage stability, and process performance of propellants to varying degrees (inert S, Groven L J, Lucht R P, et al. the effect of encapsulated nanosized catalysts on the Combustion of composite solid catalysts [ J ]. Combustion and Flame 2015,162(5): 1821-1828.). Therefore, in order to improve the catalytic efficiency of combustion catalysts and reduce the amount of the combustion catalysts used in propellant formulations, researchers have conducted extensive studies on the catalytic combustion mechanism of the catalysts, but the results are not ideal.
In view of the above, another method is needed to reduce the combustion pressure index of the existing composite solid propellant and improve the catalytic efficiency of the catalyst.
Disclosure of Invention
In order to solve the defects of the prior art, the invention provides a core-shell type aluminum @ perchlorate/catalyst composite microsphere and a solid propellant based on the microsphere, so that the pressure index of the existing Al-based composite solid propellant is reduced, and the catalytic efficiency of a catalyst is improved.
In order to achieve the purpose, the technical solution provided by the invention is as follows:
the core-shell type aluminum @ perchlorate/catalyst composite microsphere is characterized by comprising the following components in percentage by mass:
perchlorate oxidizer 25-80%
5 to 75 percent of aluminum powder
0 to 20 percent of catalyst
Wherein the perchlorate oxidant is tightly coated with aluminum powder to form a core-shell composite microsphere with the particle size of 1.0-400 mu m;
when the composite microsphere contains the catalyst, the catalyst is embedded between perchlorate oxidant crystals, and the components are in close contact.
Further, the composition comprises the following components in percentage by mass:
40 to 65 percent of perchlorate oxidizer
35 to 60 percent of aluminum powder
0 to 5 percent of catalyst.
Further, the perchlorate oxidant is one or a combination of ammonium perchlorate, potassium perchlorate, lithium perchlorate and nitroxyl perchlorate;
the particle size of the aluminum powder is 0.030-700 mu m;
the catalyst is one or the combination of any more of metal oxide, metal composite oxide, inorganic metal salt and metal organic compound.
Further, the metal oxide is PbO or Pb3O4、CuO、Cu2O、Cr2O3、Fe2O3、Fe3O4、Co2O3、Al2O3、ZrO2、Bi2O3、MgO、La2O3、TiO2、CeO2、SiO2、Ni2O3、SnO2Or CaO;
the metal composite oxide is PbSnO3、CuCO3、PbTiO3、CuCrO4、CuCr2O4、CuFeO3、PbO·CuO、PbO·SnO2、CuO·Bi2O3、CuO·Fe2O3Or CuO. NiO;
the inorganic metal salt is PbCO3、CuCO3、CaCO3、MgCO3、BaC2O4、MgC2O4Or CuC2O4；
The metal organic compound is cyclopentene ferrocene and its derivatives, bismuth copper gallate, bismuth zirconium gallate, copper zirconium tartrate, beta-copper lead resilicate or copper lead methylene disalicylate.
The invention also provides a preparation method of the core-shell type aluminum @ perchlorate/catalyst composite microsphere, which is characterized by comprising the following steps of:
s1, adding aluminum powder and a catalyst into a perchlorate oxidant aqueous solution, and stirring the components uniformly by ultrasonic and magnetic force to prepare a precursor solution;
s2, adding a water-soluble thickening agent into the precursor solution prepared in the step S1, and adjusting the viscosity of the precursor solution to be 5.0-250 mPa & S;
s3, treating the thickened precursor solution obtained in the step 2) by adopting a spray drying process, and collecting the obtained compound;
s4, placing the compound obtained in the step S3 in a perchlorate antisolvent, fully stirring to completely dissolve the thickening agent, filtering, collecting solid materials, and freeze-drying to obtain the composite microsphere.
Further, in S2, the thickener is a crosslinked polymer of methyl cellulose, carboxymethyl cellulose, ethyl cellulose, hydroxyethyl cellulose, carboxymethyl hydroxyethyl cellulose, hydroxypropyl methyl cellulose, polyoxyethylene, polyacrylate, alginate, polyvinylpyrrolidone, or decadiene;
further, in S3, the process parameters specifically include:
the sample introduction rate is 3-30 ml/min-1The air inlet temperature is 100-180 ℃, and the fan is 15-45 m3·min-1。
Further, in S4, the perchlorate antisolvent is ethyl acetate, tert-butanol, or dichloromethane.
The application of the core-shell type aluminum @ perchlorate/catalyst composite microsphere in preparing a solid propellant.
A solid propellant, characterized in that: the core-shell aluminum @ perchlorate/catalyst composite microspheres replace metal fuel, a main oxidant and a catalyst in the traditional composite solid propellant. The perchlorate oxidizer (as a main oxidizer) is coated on the aluminum powder, and the catalyst is doped into the main oxidizer to form the composite microsphere with a compact core-shell structure, so that the composite microsphere replaces corresponding components in the traditional propellant formula, and the novel composite solid propellant is prepared.
The method adopts the perchlorate oxidant (propellant main oxidant) to coat aluminum powder (metal fuel), and the catalyst is embedded into the perchlorate crystal, so that the problem of difficult coating is encountered, and the method mainly comprises the following steps: in the spray drying process, compared with the large-size composite microspheres formed by coating aluminum powder crystals, perchlorate tends to be crystallized alone, so that close contact between perchlorate and metal fuel cannot be realized. In order to solve the problem, the invention introduces a thickening agent into a precursor solution, adjusts the viscosity of the precursor solution to a specific range, and removes the thickening agent by using a perchlorate antisolvent after obtaining the composite microsphere, thereby realizing the preparation of the core-shell type aluminum @ perchlorate/catalyst composite microsphere.
The mechanism of the invention is as follows:
according to the invention, the core-shell type composite microspheres are prepared by finely compounding aluminum powder, perchlorate oxidant and catalyst in a micro-nano scale, and replace corresponding components in the traditional solid propellant, so that the high-efficiency regulation and control of the pressure index of the solid propellant are realized, and the catalytic efficiency of the catalyst is further improved. Meanwhile, the perchlorate oxidizer is used as a main oxidizer of the solid propellant, the content of the perchlorate oxidizer in the propellant formula is usually higher than 50 wt%, and all aluminum powder used in the propellant can be coated in the perchlorate oxidizer without changing any components; in addition, the main oxidant has strong oxidizing ability, and the coating of the main oxidant can enhance the heat and mass transfer process among the components (such as between the oxidant and the metal fuel) in the enhanced combustion process, thereby achieving the effect of adjusting the pressure index of the propellant. Meanwhile, the invention also finds that if the components contain the catalyst, the catalyst is embedded into the perchlorate crystal by adopting the coating mode of the invention, so that the mixing mode between the catalyst and the main oxidant can be changed, the distributability and the contact area between the catalyst and a catalyzed object are further optimized, and the catalytic efficiency of the catalyst is greatly improved.
The invention has the advantages that:
1. the core-shell aluminum @ perchlorate/catalyst composite microsphere provided by the invention can be used for preparing a solid propellant, can coat all aluminum powder surfaces with an oxidant under the condition of not introducing excessive nitramine explosive (namely, under the condition of not reducing the energy level of the propellant), and can further improve the regulation capacity of the propellant pressure index due to the comprehensive action of stronger oxidation capacity of a main oxidant than that of a nitramine oxidant.
2. According to the invention, through the close contact between aluminum powder and perchlorate oxidizer, the heat and mass transfer process between components can be obviously enhanced, the burning rate of the propellant under low pressure is improved by 67.8%, so that the burning rate pressure index of the propellant is reduced from 0.42 to 0.07; meanwhile, the close contact action between the perchlorate oxidizer and the catalyst can improve the catalytic efficiency of the catalyst from 1.11 to 1.63, further reduce the burning rate pressure index of the propellant and improve the platformization effect of the propellant from 1.92 to 2.37. By the technical means, the burning rate pressure index of the existing Al-based composite solid propellant is comprehensively reduced, and the catalytic efficiency of the catalyst is improved.
3. According to the invention, the catalyst with irregular shape is coated by the perchlorate oxidant to form the composite microsphere with high sphericity, so that the friction between the catalyst and the oxidant (main oxidant and secondary oxidant) in the preparation process of the propellant can be avoided, and the safety of the preparation process of the propellant is improved. Furthermore, the increased catalyst efficiency means that less catalyst can be used to achieve the desired regulatory goals, while reducing the amount of catalyst can increase the overall energy level of the propellant, increasing the specific impulse of the solid rocket engine.
4. The preparation method and the process of the composite microsphere and the solid propellant provided by the invention are simple and reliable, the content of each component can be accurately controlled, the process for preparing the component integrated composite microsphere by spray drying is convenient and mature, and the industrial production is easy to realize.
Drawings
FIG. 1 is a SEM-EDS chart and an idealized model of example 1 of the present invention;
FIG. 2 is an SEM photograph of comparative example 1 of the present invention;
FIG. 3 is a DSC curve of example 1 of the present invention and comparative example 1;
FIG. 4 is a SEM-EDS chart and an idealized model of example 2 of the present invention;
FIG. 5 is a DSC curve of example 1, example 2 and comparative example 2 of the present invention;
FIG. 6 is a SEM-EDS view of a cross-section of a comparative example 3 propellant of the present invention and an idealized model thereof;
FIG. 7 is an SEM-EDS view of a section of a propellant of example 4 of the present invention and an idealized model thereof;
FIG. 8 is an SEM-EDS picture of a section of a propellant of example 5 of the present invention and an idealized model thereof;
FIG. 9 is a SEM-EDS view of propellant cross-sections of examples 6 and 7 of the present invention and an idealized model thereof;
fig. 10 is SEM images of examples 8, 9, and 10 of the present invention.
Detailed Description
The invention is described in further detail below with reference to the following figures and specific examples:
example 1
The preparation process can be divided into the following three steps:
s1: adding 2.5g of AP (ammonium perchlorate) into 15ml of distilled water, adding 2.5g of Al powder, carrying out ultrasonic treatment for 10min, and carrying out magnetic stirring for 2h to obtain a precursor solution;
s2: adding 0.1g of polyvinylpyrrolidone (PVP) into the precursor solution to adjust the viscosity of the precursor solution;
s3: processing the precursor solution obtained in step S2 with a spray drying device at 150 deg.C and 9 ml/min-1The fan is 35m3·min-1HarvestingCollecting the obtained compound;
s4: and (4) placing the compound obtained in the step S3 in a dichloromethane solvent, stirring for 12h, filtering, collecting a solid material, and freeze-drying for 24h to obtain the composite microsphere Al @ AP.
The results of the particle size distribution of example 1 are shown in Table 1, D50It was 5.09 μm. FIG. 1 is a SEM-EDS diagram of example 1 and an idealized model thereof, and it can be seen that the Al @ AP composite microspheres are structurally complete, highly spherical (a and b in FIG. 1), and have multiple Al particles embedded in a single microsphere (c in FIG. 1); compared with the AP spray drying alone, the addition of Al powder provides nucleation sites for AP crystallization (d in fig. 1), and the AP uniformly coats the Al powder to form a spherical composite, an ideal model of which is shown as e in fig. 1.
Comparative example 1
Comparative example 1 has the same component contents as example 1 except that Al and AP were sufficiently mixed by milling to obtain an Al + AP mixture, which was dried to obtain comparative example 1.
FIG. 2 is a SEM photograph of comparative example 1 in which there is no close contact between the AP and Al particles. Fig. 3 is DSC curves of example 1 and comparative example 1, and it can be seen that coating AP on the surface of Al powder can greatly advance the decomposition process of AP, and advance the peak temperature of AP pyrolysis from 415.2 ℃ to 389.5 ℃.
Example 2
Otherwise, as in example 1, 0.28g of CuO was added to the precursor solution in step S1 to obtain composite microspheres Al @ AP/CuO.
The particle size distribution results of example 2 are shown in Table 1, D50It was 5.21. mu.m. FIG. 4 is a SEM-EDS diagram of example 2 and an ideal model thereof, and it can be seen that the Al @ AP/CuO composite microsphere has a complete structure and a high sphericity (a and b of FIG. 4), and CuO is uniformly embedded in the interior of AP crystals (c of FIG. 4), and the ideal model thereof is shown as e of FIG. 4.
Comparative example 2
Comparative example 2 has the same contents of components as example 2 except that 5.0g of CuO of example 1 and 0.28g of CuO were sufficiently mixed by milling to obtain Al @ AP + CuO mixture, which was dried to obtain comparative example 2.
Fig. 5 is a DSC plot for example 1, example 2 and comparative example 2. comparative example 1 and comparative example 2 can find that adding CuO to catalyze the thermal decomposition of AP in Al @ AP composite microspheres advances the AP low and pyrolysis peak temperatures from 297.9 ℃ and 389.5 ℃ to 271.5 ℃ and 334.1 ℃, respectively. The design of the core-shell composite microspheres can further improve the catalytic effect of CuO, and the comparison of example 2 and comparative example 2 shows that the peak area of low-temperature decomposition of AP is significantly increased, the energy release is more sufficient, and therefore, the thermal decomposition efficiency can be significantly improved by coating aluminum powder and a catalyst in a main oxidant.
Example 3
Otherwise, as in example 1, 0.28g of Fe was further added to the feed forward solution in step S12O3Obtaining the core-shell composite microsphere Al @ AP/Fe2O3. The particle size distribution results of example 3 are shown in Table 1, D50It was 5.15 μm.
Comparative example 3
A common composite solid propellant is prepared from hydroxy-terminated polybutadiene (HTPB), diisooctyl sebacate (DOS) as plasticizer, isophorone diisocyanate (IPDI) as solidifying agent, Al (18 wt%) and AP (67 wt%). The specific formula is shown in Table 2, and the theoretical specific impulse of the formula is 2598.7 m.s-1。
The preparation method of the specific propellant comprises the following steps:
1) raw material treatment: drying the required solid material in an oven at 60 ℃ for 120 h;
2) weighing and mixing: weighing 100g of each component according to the formula, and stirring and kneading for 120min under the condition of oil bath at 60 ℃ to prepare composite propellant slurry;
3) vacuum pouring: pouring the slurry into a customized mould in vacuum, wherein the vacuum pouring time is not less than 2 h;
4) curing the pharmaceutical strip: heating and curing the propellant slurry at 70 ℃ for 120h, demolding after complete curing, and processing the propellant into a drug strip to be tested.
As can be seen from fig. 6, the AP and Al particles in comparative example 3 are randomly distributed in the binder system with no interfacial contact between the particles. Comparative example 3 the propellant has a burning rate coefficient of 3.83, a pressure index of 0.42 (see table 3) and a plateau effect of 1.74 (see table 4) in the range of 1-4 MPa.
Example 4
The other procedure is the same as that of comparative example 3, wherein 9.0 wt% of Al powder and 9.0 wt% of AP in the formulation are replaced by 18.0 wt% of Al @ AP composite microspheres. The specific formulation is shown in table 2, and the theoretical specific impulse of this formulation is the same as that of comparative example 3.
As can be seen in fig. 7, both Al @ AP composite microspheres and randomly dispersed AP and Al particles are present in the binder matrix of example 4. Example 4 the propellant has a burning rate coefficient of 5.12 in the range of 1-4MPa, a pressure index of 0.24 (see table 3), a significant reduction compared to comparative example 3, and an increase in the plateau effect from 1.74 to 2.28 (see table 4).
Example 5
The other procedure was the same as in comparative example 3 except that 18.0 wt% of Al powder and 18.0 wt% of AP in the formulation were replaced with 36.0 wt% of Al @ AP composite microspheres. The specific formulation is shown in table 2, and the theoretical specific impulse of this formulation is the same as that of comparative example 3.
As can be seen in FIG. 8, only the Al @ AP composite microspheres were present in the binder matrix of example 5, and the amount of Al @ AP composite microspheres was doubled compared to example 4. Example 5 the propellant has a burning rate coefficient of 6.40 in the range of 1-4MPa, a pressure index of only 0.07 (see table 3), a further reduction compared to example 4, and a plateau effect of 2.79 (see table 4).
Comparing examples 4-5 with comparative example 3, it can be found that the pressure index of the propellant can be significantly reduced by refined compounding of common components of the traditional solid propellant, namely, Al @ AP composite microspheres are adopted to replace Al powder and AP which are separately dispersed in a binder matrix.
Comparative example 4
In the same manner as in comparative example 3, AP in an amount of 1.0 wt% based on the formulation was replaced with CuO and added directly to the propellant slurry. The specific formula is shown in Table 2, and the theoretical specific impulse of the formula is 2584.7 m.s-1。
Compared with comparative example 3, the burning rate coefficient of comparative example 4 was increased from 3.83 to 4.25, the pressure index was decreased from 0.42 to 0.36 (see table 3), and the catalytic efficiency of CuO at 1MPa was only 1.11 (see table 4).
This indicates that the addition of conventional composite propellants is frequently catalyzedThe CuO oxidizer can reduce the pressure index of the propellant to a certain extent. But the theoretical specific impulse is reduced by 14.0 m.s compared with the comparative example 3-1This suggests that the use of a catalyst can have a significant negative impact on the propellant energy level.
Example 6
Otherwise, as in example 5, AP in an amount of 1.0 wt% based on the formulation was replaced with CuO and added directly to the propellant slurry. The specific formula is shown in Table 2, and the theoretical specific impulse of the formula is 2584.7 m.s-1。
Comparing example 5 and example 6, it can be seen that, when CuO, a conventional catalyst, is added to the propellant formulation, the pressure index rises from 0.24 to 0.27 (see table 3), although the firing rate coefficient of the propellant rises from 5.13 to 5.67. This illustrates that the addition of a conventional catalyst alone does not provide a catalytic effect on the novel propellants proposed by the present invention, probably because the effective contact area of the catalyst with AP in example 6 is much smaller than that in comparative example 4.
Example 7
Otherwise, as in example 6, the formulation content of 9.0 wt% Al powder, 9.0 wt% AP and 1.0 wt% CuO was replaced with 19.0 wt% Al @ AP/CuO composite microspheres. The specific formulation is shown in Table 2, and the theoretical specific impulse of this formulation is the same as that of comparative example 6.
Comparing example 6 and example 7, it can be seen that the burning rate coefficient of the propellant is increased from 5.67 to 6.26 after the CuO is embedded into the Al @ AP composite microspheres, but the pressure index is decreased from 0.27 to 0.21 (see Table 3), and the catalytic efficiency of the CuO at 1MPa is increased to 1.63, which shows that the catalytic efficiency of the catalyst can be increased by embedding the catalyst into the oxidant crystal.
Example 8
The preparation process can be divided into the following three steps:
s1: adding 2.0g of AP (ammonium perchlorate) into 10ml of distilled water, adding 8.0g of Al powder, performing ultrasonic treatment for 10min, and magnetically stirring for 2h to obtain a precursor solution;
s2: adding 0.1g of polyvinylpyrrolidone (PVP) into the precursor solution to adjust the viscosity of the precursor solution;
s3: treating the precursor solution obtained in step S2 with a spray-drying apparatusThe air inlet temperature is 150 ℃, and the sample injection rate is 9 ml/min-1The fan is 35m3·min-1Collecting the resulting complex;
s4: and (4) placing the compound obtained in the step S3 in a dichloromethane solvent, stirring for 12h, filtering, collecting the obtained solid material, and freeze-drying for 24h to obtain the composite microspheres.
The particle size distribution results of example 8 are shown in Table 1, D502.11 μm, SEM picture as shown in FIG. 10.
Example 9
The preparation process can be divided into the following three steps:
s1: adding 7.5g of perchloric acid nitroxyl into 20ml of distilled water, adding 2.5g of Al powder, performing ultrasonic treatment for 10min, and performing magnetic stirring for 2h to obtain a precursor solution;
s2: adding 0.15g of polyoxyethylene into the precursor solution, and adjusting the viscosity of the precursor solution;
s3: treating the precursor solution obtained in S2 with spray drying device at air inlet temperature of 100 deg.C and sample injection rate of 3 ml/min-1The fan is 45m3·min-1Collecting the resulting complex;
s4: and (4) placing the compound obtained in the step S3 in a tert-butyl alcohol solvent, stirring for 12h, filtering, collecting the obtained solid material, and freeze-drying for 24h to obtain the composite microspheres.
The particle size distribution results of example 9 are shown in Table 1, D502.65 μm, SEM picture as shown in FIG. 10.
Example 10
The preparation process can be divided into the following three steps:
s1: adding 6g of potassium perchlorate into 15ml of distilled water, adding 4g of Al powder, performing ultrasonic treatment for 10min, and magnetically stirring for 2h to obtain a precursor solution;
s2: adding 0.11g of carboxymethyl cellulose into the precursor solution, and adjusting the viscosity of the precursor solution;
s3: treating the precursor solution obtained in S2 with a spray drying device at air inlet temperature of 180 deg.C and sample injection rate of 30 ml/min-1The fan is 15m3·min-1Collecting the resulting complex;
s4: and (4) placing the compound obtained in the step S3 in an ethyl acetate solvent, stirring for 12h, filtering, collecting the obtained solid material, and freeze-drying for 24h to obtain the composite microspheres.
The particle size distribution results of example 10 are shown in Table 1, D50It was 4.18 μm, and the SEM image is shown in FIG. 10.
Table 1 laser particle size test results
Name (R) D10 D50 D90
Example 1 2.29 5.09 11.8
Example 2 1.32 5.21 13.8
Example 3 2.39 5.15 14.6
Example 8 0.98 2.11 4.82
Example 9 0.88 2.65 3.74
Example 10 1.93 4.18 11.1
Table 2 propellant formulations and theoretical specific impacts for comparative and example
Figure BDA0003113677550000151
Note: a. the mass ratio of Al powder to main oxidant in the composite microspheres is 1: 1; b. the mass fractions of HTPB, DOS and IPDI in the formula are respectively 11.5 wt%, 2.5 wt% and 1.0 wt%; c. the theoretical specific impulse was calculated over CEA and according to the aerospace industry Standard QJ 1953-90.
TABLE 3 ignition rate and pressure index of comparative and example propellants at 1-4MPa
Figure BDA0003113677550000152
Figure BDA0003113677550000161
Note: r-burning rate (mm. s)-1) A-burning rate coefficient, p is pressure intensity (MPa), and n-pressure intensity index.
TABLE 4 catalytic efficiency (Z) and planarization effect (p) of comparative and example propellants at 1-4MPat)
Figure BDA0003113677550000162
Note: the ratio of the burning rate of the propellant containing the catalyst to the burning rate of the propellant without the catalyst is used for measuring the catalytic effect of the catalyst; platformization effect (1-4 MPa) ptDefined as (1-n). times.3, is used to measure the propellant plateau effect.
Therefore, the common Al powder of the propellant is coated by the perchlorate serving as the main oxidant of the propellant, and the common catalyst is embedded into the oxidant crystal, so that the burning rate pressure index can be reduced, the catalytic efficiency is improved, and the preparation method is simple and reliable in both the preparation process of the composite microsphere and the preparation process of the composite solid propellant, and is easy to realize industrial production.
While the invention has been described with reference to specific embodiments, the invention is not limited thereto, and various equivalent modifications or substitutions can be easily made by those skilled in the art within the technical scope of the present disclosure.

Claims (10)

1. The core-shell type aluminum @ perchlorate/catalyst composite microsphere is characterized by comprising the following components in percentage by mass:
perchlorate oxidizer 25-80%
5 to 75 percent of aluminum powder
0 to 20 percent of catalyst
Wherein the perchlorate oxidant is tightly coated with aluminum powder to form a core-shell composite microsphere with the particle size of 1.0-400 mu m;
when the composite microsphere contains the catalyst, the catalyst is embedded between perchlorate oxidant crystals, and the components are in close contact.
2. The core-shell aluminum @ perchlorate/catalyst composite microsphere of claim 1, which is composed of, in mass percent:
40 to 65 percent of perchlorate oxidizer
35 to 60 percent of aluminum powder
0 to 5 percent of catalyst.
3. The core-shell aluminum @ perchlorate/catalyst composite microsphere according to claims 1 to 2, characterized in that:
the perchlorate oxidant is one or a combination of more of ammonium perchlorate, potassium perchlorate, lithium perchlorate and nitroxyl perchlorate;
the particle size of the aluminum powder is 0.030-700 mu m;
the catalyst is one or the combination of any more of metal oxide, metal composite oxide, inorganic metal salt and metal organic compound.
4. The core-shell aluminum @ perchlorate/catalyst composite microsphere of claim 3, wherein:
the metal oxide is PbO or Pb3O4、CuO、Cu2O、Cr2O3、Fe2O3、Fe3O4、Co2O3、Al2O3、ZrO2、Bi2O3、MgO、La2O3、TiO2、CeO2、SiO2、Ni2O3、SnO2Or CaO;
the metal composite oxide is PbSnO3、CuCO3、PbTiO3、CuCrO4、CuCr2O4、CuFeO3、PbO·CuO、PbO·SnO2、CuO·Bi2O3、CuO·Fe2O3Or CuO. NiO;
the inorganic metal salt is PbCO3、CuCO3、CaCO3、MgCO3、BaC2O4、MgC2O4Or CuC2O4；
The metal organic compound is cyclopentene ferrocene and its derivatives, bismuth copper gallate, bismuth zirconium gallate, copper zirconium tartrate, beta-copper lead resilicate or copper lead methylene disalicylate.
5. The preparation method of the core-shell type aluminum @ perchlorate/catalyst composite microsphere as claimed in any one of claims 1 to 4, which is characterized by comprising the following steps:
s1, adding aluminum powder and a catalyst into a perchlorate oxidant aqueous solution, and stirring the components uniformly by ultrasonic and magnetic force to prepare a precursor solution;
s2, adding a water-soluble thickening agent into the precursor solution prepared in the step S1, and adjusting the viscosity of the precursor solution to be 5.0-250 mPa & S;
s3, treating the thickened precursor solution obtained in the step 2) by adopting a spray drying process, and collecting the obtained compound;
s4, placing the compound obtained in the step S3 in a perchlorate antisolvent, fully stirring to completely dissolve the thickening agent, filtering, collecting solid materials, and freeze-drying to obtain the composite microsphere.
6. The method according to claim 5, wherein:
in the step S2, the thickener is a crosslinked polymer of methyl cellulose, carboxymethyl cellulose, ethyl cellulose, hydroxyethyl cellulose, carboxymethyl hydroxyethyl cellulose, hydroxypropyl methyl cellulose, polyoxyethylene, polyacrylate, alginate, polyvinylpyrrolidone, or decadiene.
7. The method according to claim 6, wherein:
in S3, the process parameters specifically include:
the sample introduction rate is 3-30 ml/min-1The air inlet temperature is 100-180 ℃, and the fan is 15-45 m3·min-1。
8. The method according to claim 7, wherein:
in S4, the perchlorate antisolvent is ethyl acetate, tert-butyl alcohol or dichloromethane.
9. Use of the core shell aluminum @ perchlorate/catalyst composite microspheres as claimed in any one of claims 1 to 4 for the preparation of a solid propellant.
10. A solid propellant characterized by: the core-shell type aluminum @ perchlorate/catalyst composite microspheres as claimed in any one of claims 1 to 4 are used to replace metal fuel, main oxidant and catalyst in the traditional composite solid propellant.
CN202110656079.3A 2021-06-11 2021-06-11 Core-shell aluminum @ perchlorate/catalyst composite microsphere and solid propellant based on same Pending CN113307709A (en)

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