Nano composite burning rate catalyst of copper metal complex filled with carbon nano tube
阅读说明：本技术 碳纳米管填充铜金属配合物纳米复合燃速催化剂 (Nano composite burning rate catalyst of copper metal complex filled with carbon nano tube ) 是由 张国防 许锐哲 杨蕗菲 石晓玲 何倩 方海超 于 2021-07-27 设计创作，主要内容包括：本发明公开了一种碳纳米管填充铜金属配合物纳米复合燃速催化剂,将不同管径的多壁碳纳米管经混酸溶液超声处理,得到两端开口的氧化碳纳米管,将氧化碳纳米管加入Cu(NO-(3))-(2)·3H-(2)O、[Cu(TMEDA)-(2)](NO-(3))-(2)(TMEDA＝四甲基乙二胺)、[Cu(MIM)-(4)](DCA)-(2)(MIM＝1-甲基咪唑,DCA＝二氰胺负离子)或[Cu(NMIM)-(4)](DCA)-(2)(NMIM＝2-硝基-1-甲基咪唑,DCA＝二氰胺负离子)的饱和溶液中,超声处理,使氧化碳纳米管的官腔内填充这些铜金属配合物,从而获得碳纳米管填充铜金属配合物纳米复合燃速催化剂。本发明制备方法简单,所得纳米复合燃速催化剂催化效果好,易于放大制备。(The invention discloses a carbon nanotube-filled copper metal complex nano composite burning rate catalyst, which is characterized in that multi-wall carbon nanotubes with different tube diameters are subjected to ultrasonic treatment by mixed acid solution to obtain carbon oxide nanotubes with openings at two ends, and the carbon oxide nanotubes are added into Cu (NO) 3 ) 2 ·3H 2 O、[Cu(TMEDA) 2 ](NO 3 ) 2 (TMEDA ═ tetramethylethylenediamine), [ Cu (MIM) 4 ](DCA) 2 (MIM 1-methylimidazole, DCA dicyandiamide anion) or [ Cu (NMIM) 4 ](DCA) 2 And (NMIM ═ 2-nitro-1-methylimidazole, DCA ═ dicyandiamide negative ions) in a saturated solution, carrying out ultrasonic treatment, and filling the copper metal complexes in the lumen of the carbon oxide nanotube, thereby obtaining the carbon nanotube-filled copper metal complex nano composite burning rate catalyst. The preparation method is simple, and the obtained nano composite burning rate catalyst has good catalytic effect and is easy to be prepared in an enlarged way.)
1. A carbon nanotube filled copper metal complex nano composite burning rate catalyst is characterized in that: adding a carbon oxide nanotube into a saturated solution of a copper metal complex, performing ultrasonic treatment, washing with a solvent corresponding to the saturated solution of the copper metal complex until a filtrate is colorless, and performing vacuum drying on the obtained black precipitate to obtain the nano composite burning rate catalyst, wherein the filling rate of the copper metal complex is 5-25%;
the copper metal complex is Cu (NO)3)2·3H2O、[Cu(TMEDA)2](NO3)2、[Cu(MIM)4](DCA)2And [ Cu (NMIM) ]4](DCA)2Any one of them, wherein TMEDA represents tetramethylethylenediamine, MIM represents 1-methylimidazole, DCA represents dicyandiamide anion, and NMIM represents 2-nitro-1-methylimidazole.
2. The carbon nanotube-filled copper metal complex nanocomposite burn rate catalyst of claim 1, wherein: the carbon oxide nanotube is obtained by subjecting a multi-walled carbon nanotube to ultrasonic treatment by a mixed acid solution of concentrated sulfuric acid and concentrated nitric acid, and then settling, filtering, washing and drying.
3. The carbon nanotube-filled copper metal complex nanocomposite burn rate catalyst of claim 2, wherein: the pipe diameter of the multi-walled carbon nano-tube is 4-80 nm, and the volume ratio of concentrated sulfuric acid to concentrated nitric acid in the mixed acid solution is 1-4: 1.
4. The carbon nanotube-filled copper metal complex nanocomposite burn rate catalyst of claim 2, wherein: the temperature of ultrasonic treatment of the mixed acid solution is 20-50 ℃, the time is 2-6 h, the ultrasonic power is 200-400W, the settling time is 40-50 h, the drying temperature is 60-80 ℃, and the drying time is 10-20 h.
5. The carbon nanotube-filled copper metal complex nanocomposite burn rate catalyst of claim 1, wherein: the ratio of the carbon oxide nanotube to the saturated solution of the copper metal complex is 8-12 mg/mL.
6. The carbon nanotube-filled copper metal complex nanocomposite burn rate catalyst of claim 1, wherein: the solvent corresponding to the saturated solution of the copper metal complex is distilled water or absolute ethyl alcohol.
7. The carbon nanotube-filled copper metal complex nanocomposite burn rate catalyst of claim 1, wherein: the ultrasonic treatment is carried out at the temperature of 20-50 ℃ for 10-50 h, the ultrasonic power is 200-400W, and the vacuum drying is carried out at the temperature of 60-80 ℃ for 5-10 h.
Technical Field
The invention belongs to the technical field of solid propellants, and particularly relates to a carbon nanotube-filled copper metal complex nano composite burning rate catalyst.
Background
The solid propellant is a commonly used rocket engine power source, the combustion state of the solid propellant can directly influence the performance of an aviation rocket, and through long-term research, the current solid propellant has developed development trends with characteristics of high energy, high specific impulse and low signal. Ammonium Perchlorate (AP), a strong oxidant, is a common energetic material component in solid propellants, especially in the case of the dual-based propellants and modified propellants thereof. Because the ammonium perchlorate generally occupies a large proportion, the combustion speed, the thermal decomposition peak temperature and the heat release amount in the decomposition process have great influence on the combustion of the solid propellant. In the existing methods for improving the combustion performance of solid propellants, the combustion rate catalyst is widely applied to production and practice. The addition amount of the burning rate catalyst is generally 1-5% of the total mass fraction of the solid propellant, but the burning rate catalyst plays a vital role as an indispensable part in the solid propellant, and common burning rate catalysts in the solid propellant comprise: transition metal oxides, transition metal fluorides, cobaltates or chromites of copper and manganese, ferrocene and its derivatives, organometallic compounds, nano burn rate catalysts, and the like.
The carbon nano tube has a one-dimensional hollow structure with a nano scale close to an ideal structure, and the open carbon nano tube cavity can be used as a siphon, a nano reactor, an adsorbent, a catalyst carrier and the like. The filling of metal, oxide, carbide and other substances in the carbon nanotube can improve the electromagnetic performance, the conductivity, the mechanical performance, the catalytic performance and the like of the carbon nanotube, so that the tube filling of the carbon nanotube is concerned widely, and the filling of noble metal and oxide thereof in the tube cavity of the carbon nanotube as a catalytic material is widely applied to the field of catalysts.
The carbon nano tube surface loaded with nano metal oxide is widely researched in the field of burning rate catalysts, and the composite material has the advantages of large specific surface area, high surface energy, high surface activity and the like. In 2010, chinese researchers hong weiliang et al loaded nano CuO on the surface of carbon nanotubes and studied its catalytic action on combustion of bi-based propellants (hong weiliang, zhu xiying, zhao buhui, gao hong xu, tian de yu. preparation of CuO/CNTs and its catalytic action on combustion of bi-based propellants [ J ] fire and explosive science, 2010,33(06): 83-86.). Researches find that the combustion catalysis effect of the carbon nanotube loaded copper oxide on the double-base propellant is obviously superior to that of nano CuO, the CuO is highly dispersed on the surface of the carbon nanotube in the form of nano particles, and the carbon nanotube is used as a carrier to prevent the mutual agglomeration among nano CuO particles, so that the carbon nanotube loaded copper oxide composite material can be uniformly dispersed in the double-base propellant, the contact area of the nano CuO and the propellant is increased, and the catalysis effect of the nano CuO is enhanced. However, the particle size of the nanoparticles loaded on the surface of the carbon nanotube cannot be controlled, and after the nanoparticles are filled into the cavity of the carbon nanotube, the particle size of the nanoparticles filled into the carbon nanotube can be effectively controlled by utilizing the confinement effect of the carbon nanotube.
In recent years, the problem of carbon nanotube filling has been focused and studied in various fields, but the problem is rarely used in the field of burn rate catalysis. In 2009, wuqianqing adds carbon nanotubes and potassium nitrate into concentrated nitric acid, and the mixture is refluxed for 24h under the condition of oil bath to obtain carbon nanotubes embedded with potassium nitrate and test the combustion catalytic performance of the carbon nanotubes (wuqianqing, preparation and characterization of carbon nanotubes embedded with potassium nitrate [ D ]. nanjing university of physical engineering, 2009.). The test result shows that the combustion catalytic performance of the carbon nano tube embedded with potassium nitrate is obviously improved compared with the carbon nano tube. In 2012, Zhang rock et al filled nano CuO particles into carbon nanotubes to obtain a uniformly filled nano composite material (Zhang rock, Schujian. preparation and characterization of nano CuO particle filled multi-walled carbon nanotube composite material [ J ]. applied chemical industry, 2012,41(03):476- & 479.), but no study was made on the combustion catalytic performance of the composite material. At present, the preparation of novel composite catalytic materials by combining carbon nanotubes and metal oxides or complexes becomes a development trend in the field of catalytic materials.
Disclosure of Invention
The invention aims to provide the carbon nano tube filled copper metal complex nano composite burning rate catalyst which is simple to prepare, can be produced in large scale and has good catalytic action.
Aiming at the purposes, the technical scheme adopted by the invention is as follows: adding a carbon nanotube oxide into a saturated solution of a copper metal complex, performing ultrasonic treatment, washing with a solvent corresponding to the saturated solution of the copper metal complex until a filtrate is colorless, and performing vacuum drying on the obtained black precipitate to obtain the carbon nanotube-filled copper metal complex nanocomposite burning rate catalyst, wherein the filling rate of the copper metal complex is 5-25%.
The copper metal complex is Cu (NO)3)2·3H2O、[Cu(TMEDA)2](NO3)2、[Cu(MIM)4](DCA)2And [ Cu (NMIM) ]4](DCA)2Any one of them, wherein TMEDA represents tetramethylethylenediamine, MIM represents 1-methylimidazole, DCA represents dicyandiamide anion, and NMIM represents 2-nitro-1-methylimidazole.
The upper oxidized carbon nanotube is obtained by subjecting a multi-walled carbon nanotube to ultrasonic treatment by a mixed acid solution of concentrated sulfuric acid and concentrated nitric acid, and then settling, filtering, washing and drying. Wherein the temperature of the ultrasonic treatment of the mixed acid solution is 20-50 ℃, the time is 2-6 h, the ultrasonic power is 200-400W, the settling time is 40-50 h, the drying temperature is 60-80 ℃, and the drying time is 10-20 h.
The tube diameter of the multi-walled carbon nano tube is 4-80 nm, and the volume ratio of concentrated sulfuric acid to concentrated nitric acid in the mixed acid solution is 1-4: 1.
The ratio of the carbon oxide nanotube to the saturated solution of the copper metal complex is 8-12 mg/mL.
The solvent corresponding to the saturated solution of the copper metal complex is distilled water or absolute ethyl alcohol.
Adding the carbon oxide nanotube into a saturated solution of a copper metal complex, wherein the temperature of ultrasonic treatment is 20-50 ℃, the time is 10-50 h, the ultrasonic power is 200-400W, the temperature of vacuum drying is 60-80 ℃, and the time is 5-10 h.
The invention has the following beneficial effects:
the invention fills the copper metal complex into the inner part of the extremely fine cavity of the carbon nano tube, and utilizes the constraint effect of the nano-scale cavity to ensure that the complex is stably constrained in the tube cavity, the particle size of the complex can be further reduced from micron scale to nano scale, and the catalytic performances of the nano-copper metal complex and the carbon nano tube are complementary, thereby generating strong 'synergistic effect' and obviously improving the catalytic performance of the nano-copper metal complex and the carbon nano tube.
The novel nano composite burning rate catalyst obtained by combining the copper metal complex and the carbon nano tube directly and effectively greatly improves the combustion catalytic performance by a simple physical principle. The method has the advantages of simple operation, high yield, large-scale preparation, capability of obtaining the nano composite burning rate catalyst with high heat release and low heat release peak temperature under a simple treatment method, and large specific surface area and good catalytic effect, and the filling rate of the obtained nano composite burning rate catalyst is between 5 and 25 percent.
Drawings
FIG. 1 is a carbon nanotube-filled Cu (NO) prepared in example 43)2·3H2Transmission electron microscope picture of O nano composite burning rate catalyst.
FIG. 2 is a carbon nanotube-filled Cu (NO) prepared in example 53)2·3H2Transmission electron microscope picture of O nano composite burning rate catalyst.
FIG. 3 is a carbon nanotube-filled Cu (NO) prepared in example 63)2·3H2Transmission electron microscope picture of O nano composite burning rate catalyst.
FIG. 4 is a differential scanning calorimetry analysis curve of the nanocomposite burn rate catalysts prepared in examples 1 and 7-10 and pure AP.
FIG. 5 is an AP with 5% addition of Cu (NO) filled with carbon nanotubes prepared in examples 1 to 63)2·3H2Differential scanning calorimetry analysis curves of the O nano composite burning rate catalyst and pure AP.
FIG. 6 is AP addition of 5% carbon nanotube-filled Cu (NO) prepared in example 63)2·3H2O nano composite burning rate catalyst and AP with 5% of Cu (NO) loaded on surface prepared in comparative example 13)2·3H2Carbon nanotube of OAnd adding 5% pure Cu (NO) to AP3)2·3H2Differential scanning calorimetry curves for O and pure AP.
FIG. 7 is the addition of 5% of each of the carbon nanotube-filled Cu (NO) prepared in example 6 to AP3)2·3H2O nanocomposite burn rate catalyst, 5% carbon nanotube fill prepared in example 11 [ Cu (TMEDA) ]2](NO3)2Nanocomposite burn rate catalyst, 5% carbon nanotube fill [ Cu (MIM) prepared in example 124](DCA)2Nanocomposite burn rate catalyst, 5% carbon nanotube fill prepared in example 13 [ Cu (NMIM) ]4](DCA)2Differential scanning calorimetry analysis curves of the nanocomposite burn rate catalyst and pure AP.
Detailed Description
The invention will be further described in detail with reference to the following figures and examples, but the scope of the invention is not limited to these examples.
Example 1
Adding 150mg of multi-walled carbon nano-tubes with the tube diameters of 4-6 nm into 15mL of mixed acid solution of concentrated sulfuric acid and concentrated nitric acid in a volume ratio of 3:1, carrying out ultrasonic treatment at 30 ℃ and a power of 300W for 4h to obtain black viscous solution, adding deionized water into the solution, uniformly stirring by using a glass rod, standing at room temperature for settling for 12h to see that obvious layering exists in a beaker, pouring out the upper layer of transparent solution, adding deionized water again, and repeating the steps for multiple times to obtain black turbid liquid. And carrying out suction filtration and separation on the black suspension, repeatedly washing with deionized water until the pH value of the obtained black solid precipitate is neutral, transferring the black solid precipitate into a forced air drying oven, drying at 80 ℃ for 12h, and uniformly grinding to obtain the carbon oxide nanotube with openings at two ends. Adding 100mg of carbon nanotube oxide into 10mL of saturated aqueous solution of copper nitrate trihydrate, carrying out ultrasonic treatment for 50h at the temperature of 30 ℃ and the power of 300W, washing with distilled water until the obtained filtrate is colorless and transparent, placing the black solid precipitate in a sand core funnel into a vacuum drying oven, drying for 10h at the temperature of 80 ℃, taking out, and obtaining black powder which is carbon nanotube filled with Cu (NO)3)2·3H2O nano composite burning rate catalyst, wherein Cu: (NO3)2·3H2The O filling rate was 11.8%.
Example 2
In this example, multiwall carbon nanotubes with equal mass and tube diameters of 5-15 nm were used to replace multiwall carbon nanotubes with tube diameters of 4-6 nm in example 1, and the other steps were the same as in example 1, and the black powder obtained was carbon nanotubes filled with Cu (NO)3)2·3H2O-nanocomposite burn rate catalyst, Cu (NO)3)2·3H2The O filling rate was 8.2%.
Example 3
In this example, multiwall carbon nanotubes with equal mass and tube diameters of 10-20 nm were used to replace multiwall carbon nanotubes with tube diameters of 4-6 nm in example 1, and the other steps were the same as in example 1, and the black powder obtained was carbon nanotubes filled with Cu (NO)3)2·3H2O-nanocomposite burn rate catalyst, Cu (NO)3)2·3H2The O filling rate was 6.8%.
Example 4
In this example, multiwall carbon nanotubes with equal mass and tube diameters of 20-30 nm were used to replace multiwall carbon nanotubes with tube diameters of 4-6 nm in example 1, and the other steps were the same as in example 1, and the black powder obtained was carbon nanotubes filled with Cu (NO)3)2·3H2O-nanocomposite burn rate catalyst, Cu (NO)3)2·3H2The O filling rate was 10.5%.
Example 5
In this example, multiwall carbon nanotubes with equal mass and tube diameters of 30-50 nm were used to replace multiwall carbon nanotubes with tube diameters of 4-6 nm in example 1, and the other steps were the same as in example 1, and the black powder obtained was carbon nanotubes filled with Cu (NO)3)2·3H2O-nanocomposite burn rate catalyst, Cu (NO)3)2·3H2The O filling rate was 8.7%.
Example 6
In this example, multiwall carbon nanotubes with equal mass and tube diameter of 30-80 nm were used to replace multiwall carbon nanotubes with tube diameter of 4-6 nm in example 1, and the other steps were the same as in example 1The obtained black powder is carbon nanotube filled Cu (NO)3)2·3H2O-nanocomposite burn rate catalyst, Cu (NO)3)2·3H2The O filling rate was 13.2%.
Example 7
In this example, 100mg of carbon nanotubes was added to 10mL of a saturated aqueous solution of copper nitrate trihydrate, and after sonication was performed at 30 ℃ and 300W for 40 hours, the other steps were the same as in example 1, and the black powder obtained was Cu (NO) filled with carbon nanotubes3)2·3H2O-nanocomposite burn rate catalyst, Cu (NO)3)2·3H2The O filling rate was 11.5%.
Example 8
In this example, 100mg of carbon nanotubes was added to 10mL of a saturated aqueous solution of copper nitrate trihydrate, and after 30 hours of ultrasonic treatment at 30 ℃ and 300W, the other steps were the same as in example 1, and the black powder obtained was Cu (NO) filled with carbon nanotubes3)2·3H2O-nanocomposite burn rate catalyst, Cu (NO)3)2·3H2The O filling rate was 6.8%.
Example 9
In this example, 100mg of carbon nanotubes was added to 10mL of a saturated aqueous solution of copper nitrate trihydrate, and after sonication at 30 ℃ and 300W for 20 hours, the other steps were the same as in example 1, and the black powder obtained was Cu (NO) filled carbon nanotubes3)2·3H2O-nanocomposite burn rate catalyst, Cu (NO)3)2·3H2The O filling rate was 6.6%.
Example 10
In this example, 100mg of carbon nanotubes was added to 10mL of a saturated aqueous solution of copper nitrate trihydrate, and after sonication at 30 ℃ and 300W for 10 hours, the other steps were the same as in example 1, and the black powder obtained was Cu (NO) filled with carbon nanotubes3)2·3H2O-nanocomposite burn rate catalyst, Cu (NO)3)2·3H2The O filling rate was 6.2%.
Example 11
In this example, an equal volume of [ Cu (TMEDA) ]is used2](NO3)2The saturated aqueous solution of copper nitrate trihydrate of example 1 was replaced with the saturated aqueous solution of copper nitrate trihydrate of example 1, and the obtained black powder was carbon nanotube-filled [ Cu (TMEDA) ]2](NO3)2Nano composite burning rate catalyst, [ Cu (TMEDA) ]2](NO3)2The filling ratio of (A) was 22.6%.
Example 12
In this example, an equal volume of [ Cu (MIM) ]is used4](DCA)2Was used in place of the saturated aqueous solution of copper nitrate trihydrate in example 1, and the other steps were the same as in example 1, to obtain black powder filled with carbon nanotubes [ Cu (MIM) ]4](DCA)2Nano composite burning rate catalyst, [ Cu (MIM) ]4](DCA)2The filling ratio of (2) was 19.3%.
Example 13
In this example, an equal volume of [ Cu (NMIM) ]is used4](DCA)2Was used in place of the saturated aqueous solution of copper nitrate trihydrate in example 1, and the other steps were the same as in example 1, to obtain black powder filled with carbon nanotubes [ Cu (NMIM) ]4](DCA)2Nano composite burning rate catalyst, [ Cu (NMIM) ]4](DCA)2The filling ratio of (2) was 24.8%.
Comparative example 1
100mg of the oxidized carbon nanotube of example 6 was added to 20mL of a saturated aqueous solution of copper nitrate trihydrate, and then 20mg of sodium dodecylbenzenesulfonate was added as a surfactant, and after stirring for 24 hours with a magnetic stirrer, filtration, washing and drying were performed to obtain a carbon nanotube with copper nitrate trihydrate loaded on the surface.
The samples prepared in the above examples 4, 5 and 6 were subjected to transmission electron microscopy characterization, and the results are shown in fig. 1-3. As can be seen from FIGS. 1 to 3, the filling state of the complex depends on the tube diameter and the tube wall shape of the carbon nanotube, and a small amount of the complex is filled between the walls of the multi-walled carbon nanotube.
In order to prove the beneficial effects of the invention, the inventor adds 5% of the carbon nanotube-filled copper metal complex nanocomposite burning rate catalysts prepared in examples 1 to 13 into AP respectively to perform a combustion catalysis performance test, and simultaneously adds 5% of the carbon oxide nanotube loaded with copper nitrate trihydrate on the surface of comparative example 1 and 5% of pure copper nitrate trihydrate into AP respectively to perform a comparative experiment, and the results are shown in FIGS. 4 to 7.
As can be seen in FIG. 4, the heat evolution of the AP is not significant throughout the process. Under the same other conditions, the combustion catalytic performance of the combustion rate catalyst is obviously influenced by different ultrasonic time. When the ultrasonic time is 10, 20, 30, 40 and 50 hours respectively, the peak temperature of the AP pyrolysis stage is respectively reduced from 406.6 ℃ to 312.0 ℃, 312.7 ℃, 306.9 ℃, 305.3 ℃ and 307.8 ℃, the peak temperature is respectively reduced by 94.6 ℃, 93.9 ℃, 99.7 ℃, 101.3 ℃ and 98.8 ℃, and the peak temperature is obviously higher than the AP test result; in addition, the apparent decomposition heat of AP is respectively increased from 746.53J/g to 1908.48J/g, 1877.88J/g, 1976.35J/g, 1867.54J/g and 2019.87J/g, and 1161.95J/g, 1131.55J/g, 1229.82J/g, 1121.01J/g and 1273.34J/g are respectively increased, so that compared with pure AP in the pyrolysis stage, after 5 percent of carbon nano tube filling copper nitrate trihydrate nano composite burning rate catalyst prepared by example 1, example 7, example 8, example 9 and example 10 is added, the pyrolysis stage of AP presents a concentrated heat release phenomenon, the pyrolysis peak temperature of AP pyrolysis is obviously reduced, and the heat release quantity of the system is greatly increased compared with pure AP, which shows that the carbon nano tube filling copper nitrate trihydrate nano composite burning rate catalyst prepared by the invention has good combustion catalysis effect on AP, the carbon nanotube-filled copper nitrate trihydrate nanocomposite burning rate catalyst of example 1, in which the ultrasonic time was 50 hours, had the best catalytic effect on thermal decomposition of AP.
As can be seen in FIG. 5, the heat evolution of the AP is not significant throughout the process. Under the same condition, after 5% of the carbon nanotube filled copper nitrate trihydrate nanocomposite burn rate catalyst prepared in examples 1-6 is added into a solid propellant main component AP, the peak temperatures of AP pyrolysis stages are respectively reduced from 406.6 ℃ to 307.8 ℃, 319.3 ℃, 339.0 ℃, 330.9 ℃, 344.3 ℃ and 334.5 ℃, and are respectively reduced by 98.8 ℃, 87.3 ℃, 67.6 ℃, 75.7 ℃, 62.3 ℃ and 72.1 ℃, which are obviously higher than the AP test results, and the promotion effect of the carbon nanotube filled copper nitrate trihydrate nanocomposite burn rate catalyst prepared in examples 1-6 with 5% of addition on AP pyrolysis is more obvious; in addition, the apparent decomposition heat of AP is respectively increased from 746.53J/g to 2019.87J/g, 1830.52J/g, 1801.08J/g, 1728.42J/g, 1759.34J/g and 1769.49J/g, 1273.34J/g, 1083.99J/g, 1054.55J/g, 981.59J/g, 1012.81J/g and 1022.96J/g are respectively increased, so that compared with pure AP in the high-temperature decomposition stage, after 5% of the carbon nanotube filled copper nitrate trihydrate nano composite burning rate catalyst prepared in examples 1-6 is added, the high-temperature decomposition stage of the AP presents a concentrated heat release phenomenon, along with the reduction of the pipe diameter of the carbon nanotube, the high-temperature decomposition peak temperature of the AP thermal decomposition is obviously reduced, and the heat quantity released by the system is greatly increased compared with pure AP, which shows that the carbon nanotube filled copper nitrate trihydrate nano composite burning rate catalyst prepared by the invention has good combustion catalysis effect on the thermal decomposition of the AP, the carbon nanotube-filled copper nitrate trihydrate nanocomposite burning rate catalyst prepared in example 1 has the best catalytic effect on AP thermal decomposition. As can be seen from the graphs in FIGS. 4 and 5, the carbon nanotube has a diameter of 4-6 nm and the ultrasound time is 50h, the combustion catalysis performance of the copper nitrate trihydrate nanocomposite flame-retardant catalyst filled in the carbon nanotube is the best.
As can be seen from FIG. 6, the heat evolution of AP was not significant over the course of the process, nor was it increased upon addition of copper nitrate trihydrate. Under the same conditions, when 5% of the carbon nanotube loaded with copper nitrate trihydrate prepared in comparative example 1 was added as a catalyst to the solid propellant main component AP, the peak temperature in the AP pyrolysis stage was decreased from 406.6 ℃ to 311.3 ℃, and the apparent decomposition heat of AP was increased from 746.53J/g to 1032.3J/g, respectively. When 5% of the carbon nanotube-filled copper nitrate trihydrate nanocomposite burn rate catalyst prepared in example 6 was added to the solid propellant main component AP, the peak temperature in the AP pyrolysis stage was reduced from 406.6 ℃ to 334.5 ℃, and the apparent decomposition heat of AP was increased from 746.53J/g to 1769.49J/g, respectively. The combustion catalytic performance of the carbon nano tube filled with the copper nitrate trihydrate is obviously superior to that of the carbon nano tube loaded with the copper nitrate trihydrate on the surface.
As can be seen from FIG. 7, the heat evolution of the AP was not evident throughout the process. Under the same conditions, 5% of Cu (NO) filled with carbon nanotubes prepared in example 1 and examples 11 to 13 was added to AP as a main component of a solid propellant3)2·3H2O、[Cu(TMEDA)2](NO3)2、[Cu(MIM)4](DCA)2And [ Cu (NMIM) ]4](DCA)2After the nano composite burning rate catalyst is used, the peak temperatures of AP high-temperature decomposition stages are respectively reduced from 406.6 ℃ to 307.8 ℃, 308.1 ℃, 310.6 ℃ and 304.9 ℃, the peak temperatures are respectively reduced by 98.8 ℃, 98.5 ℃, 96 ℃ and 101.7 ℃, and the peak temperatures are obviously higher than the AP test results. In addition, the apparent decomposition heat of AP is respectively increased from 746.53J/g to 2019.87J/g, 1940.24J/g, 1886.94J/g and 1838.41J/g, and 1273.34J/g, 1193.71J/g, 1140.41J/g and 1091.88J/g are respectively increased, so that the pyrolysis stage of AP shows a concentrated heat release phenomenon after 5% of the burning rate catalysts prepared in example 1 and examples 11 to 13 are added compared with the pyrolysis stage of pure AP, and the heat released by the system is greatly increased compared with the pure AP, which shows that the carbon nanotube filled copper complex nano composite burning rate catalyst prepared by the invention has good combustion catalysis effect on the pyrolysis of AP, wherein the carbon nanotube filled Cu (NO) prepared in example 1 (NO) has good combustion catalysis effect on the pyrolysis of AP3)2·3H2The O nano composite burning rate catalyst has the best catalytic effect on the thermal decomposition of AP.
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