CN115215711B - Yang Meizhuang core-shell structure Al/Ti/CuO micro-nano composite energetic material and preparation method thereof - Google Patents

Yang Meizhuang core-shell structure Al/Ti/CuO micro-nano composite energetic material and preparation method thereof Download PDF

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CN115215711B
CN115215711B CN202210843785.3A CN202210843785A CN115215711B CN 115215711 B CN115215711 B CN 115215711B CN 202210843785 A CN202210843785 A CN 202210843785A CN 115215711 B CN115215711 B CN 115215711B
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cuo
fuel
mass
energetic material
ball milling
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CN115215711A (en
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陈永进
任慧
焦清介
闫石
张咪
吴鑫洲
赵婉君
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Beijing Institute of Technology BIT
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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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/06—Metallic powder characterised by the shape of the particles
    • B22F1/065—Spherical particles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/16—Metallic particles coated with a non-metal
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/17—Metallic particles coated with metal
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/02—Making metallic powder or suspensions thereof using physical processes
    • B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/02—Making metallic powder or suspensions thereof using physical processes
    • B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
    • B22F2009/043—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling by ball milling

Abstract

The invention relates to an Al/Ti/CuO micro-nano composite energetic material with a waxberry-shaped core-shell structure and a preparation method thereof, belonging to the technical field of energetic composite materials. The composite energetic material has novel structure and consists of fuel and oxidant, wherein the fuel is Al and Ti, the oxidant is copper oxide, and the mass ratio of the fuel to the oxidant is 0.5-4.0; the composite material is prepared by adopting a high-energy ball milling method, so that the assembly of fuel and oxidant on the molecular level is realized, new impurities are not introduced, the original structures of Al, ti and CuO particles are not damaged, and conditions are provided for uniform distribution and full contact of the particles of each component, so that the reaction heat conduction distance can be reduced, the mass transfer efficiency is improved, the combustion heat of the composite energetic material is obviously improved, the composite material releases heat more severely, the heat release efficiency is higher, the energy release is more complete, and the composite material is added into the explosive and is favorable for improving the actual energy level and the energy release efficiency of the explosive.

Description

Yang Meizhuang core-shell structure Al/Ti/CuO micro-nano composite energetic material and preparation method thereof
Technical Field
The invention relates to an Al/Ti/CuO micro-nano composite energetic material with a waxberry-shaped core-shell structure and a preparation method thereof, belonging to the technical field of energetic composite materials.
Background
In recent years, under the traction of high energy density materials in countries such as America and Russia,the global search for new energetic materials is being pursued, and the composite energetic material (Energetic materials) is one of the high-activity and high-energy energetic materials. The composite energetic material is prepared from Al, ti, mg and other fuels, cuO and Fe 2 O 3 、MoO 3 The energetic material composed of the oxygen-containing compounds can be subjected to quick chemical reaction under a certain triggering condition and release a large amount of heat, has the advantages of high heat value, low ignition initiation energy, high energy release rate and the like, can control and change the combustion performance of the composite energetic material by adjusting components, equivalent ratio or particle size, is often used as an energy additive of a combustion agent, an ignition charge, a high-energy explosive and a solid rocket propellant, and has wide application prospect in the fields of military and the like.
The performance of the composite energetic material is mainly influenced by the mass transfer and heat conduction distance between the fuel and the oxidant, at present, researchers regulate and control the mass transfer distance between reactant components mainly by reducing the particle sizes of the fuel and the oxide, but when the particle sizes of the fuel and the oxide are reduced to a certain degree, agglomeration phenomenon can occur among particles, and the surface of the fuel is easily oxidized to form an oxide layer, so that the reactivity of the fuel is reduced, and the performance of the composite energetic material is greatly influenced. Meanwhile, researchers increase the contact area between each component by manufacturing composite energetic materials with different structures to reduce the heat and mass transfer distance, thereby improving and adjusting the performance of the materials.
Al/CuO two-phase composite material is a typical composite energetic material, however, the physical and chemical properties of the material and the preparation method limit the application development to a certain extent. The Al/CuO two-phase composite material prepared by a mechanical mixing method by Yu.Ananev et Al (Ananev, S.Yu, et Al, "block-Wave Initiation of a Thermite Mixture of Al +CuO." Combustion, explosion, and block Waves 56.2 (2020): 220-230) has the defect of poor mixing uniformity of each component; jiaxing Song et Al (Song, jiaxing, et Al, "A comparative study of thermal kinetics and combustion performance of Al/CuO, al/Fe) 2 O 3 and Al/MnO 2 nanothermites, "Vacuum 176 (2020): 109339.) an Al/CuO nanothermite was prepared by ultrasonic dispersion, but it was prone to partial agglomeration and dispersibilityPoor defects; the Al/CuO core-shell structured composite material was prepared by electrostatic spraying by Haiyang Wang et Al (Wang, haiyang, et Al, "Assembly and reactive properties of Al/CuO based nanothermite microparticalles." Combustion and Flame 161.8.161.8 (2014): 2203-2208.), but because inert substances irrelevant to raw materials are introduced as binders, the overall reactivity and energy density of the system are reduced, and the Al/CuO yield prepared by the electrostatic spraying method is low, and large-scale production cannot be realized.
In the prior art, a small amount of titanium energetic composite materials are reported, but the materials are generally simply and physically mixed, the components are unevenly distributed, and the agglomeration phenomenon exists; or inert components such as nitrated fiber (NC) and the like are required to be added into the composite energetic material to be used as a binder in the preparation process of the composite energetic material, so that the performance of a composite system is affected; in addition, a small amount of Ti/CuO composite materials are reported to be of a film structure, and the mass transfer distance and the diffusion distance between the components are large, so that the reactivity and the heat release performance are influenced.
At present, no report of an Al/Ti/CuO ternary energetic composite material is yet seen in the prior art; the energy of the whole system is not necessarily improved by adding the three-phase system composite energetic material consisting of the third phase fuel into the two-phase composite energetic material, because the heat value of the Al/CuO system is mainly derived from the heat value of metal aluminum combustion, the heat value of Al is far greater than that of Ti, and the strict calculation of the ratio of adding the third phase substance into the two-phase composite material is required to realize that the performance of jointly using Al and Ti as fuel is higher than that of using single-phase Al as fuel.
Disclosure of Invention
In order to overcome the defects in the prior art, one of the purposes of the invention is to provide an Al/Ti/CuO micro-nano composite energetic material with a waxberry-shaped core-shell structure; the composite energetic material is introduced with a Ti metal composition Al/Ti/CuO ternary composite system with higher density and activity, has a waxberry-shaped core-shell structure with rough surface and fine internal structure, is not easy to agglomerate, and has high reaction activity and energy density.
The second purpose of the invention is to provide a preparation method of the waxberry-shaped core-shell structure Al/Ti/CuO micro-nano composite energetic material; the method has the advantages of good mixing uniformity, simple process, safety, reliability, mild conditions, strong applicability, easy control of the preparation process and realization of large-scale preparation production.
In order to achieve the purpose of the invention, the following technical scheme is provided.
An Yang Meizhuang core-shell structure Al/Ti/CuO micro-nano composite energetic material comprises fuel and an oxidant, wherein the fuel is metal Al and Ti, and the oxidant is CuO;
the Al is particles with the particle size of 1-5 mu m, the Ti is particles with the particle size of 100-1000 nm, and the CuO is particles with the particle size of 20-100 nm; the waxberry-shaped core-shell structure takes Al particles as cores, ti particles and CuO particles are uniformly adsorbed, wrapped and inlaid on the surfaces or subsurface of the Al particles as shells, so that composite particles with complete shell-coated cores are formed, and granular protrusions exist on the surfaces of the composite particles, so that a Yang Meizhuang core-shell structure is formed.
Oxygen-fuel equivalent ratio of the micro-nano composite energetic materialThe value is 0.5 to 4.0; preferably, a +>The value is 1 to 3.5;
preferably, the waxberry-shaped core-shell structure is spherical or spheroidic, the grain diameter of Al is 1-3 mu m, the grain diameter of Ti is 200-500 nm, and the grain diameter of CuO is 20-40 nm;
preferably, the mass fraction of Al is 10-90% and the mass fraction of Ti is 10-90% based on 100% of the total mass of the fuel; further preferably, the mass fraction of Al is 70% and the mass fraction of Ti is 30%.
The invention discloses a preparation method of an Al/Ti/CuO micro-nano composite energetic material with a waxberry-shaped core-shell structure, which comprises the following steps:
(1) Determination of the equivalent ratio of oxygen to fuelAnd mass fraction of each component in the fuel, binding substanceThe mass ratio of the Al/Ti/CuO ternary micro-nano composite energetic material can be determined according to the law of conservation of quantity, each component fuel and oxidant are weighed according to the mass ratio, then a solvent is added, and preliminary mechanical dispersion is carried out uniformly to obtain a mixed dispersion liquid;
specifically, the oxygen equivalent ratioIs the actual value of the combustion-oxygen ratio (phi) Actual value ) And a fuel-to-oxygen ratio stoichiometric value (phi) Stoichiometric value ) Ratio of (2), namely: />
Wherein the actual value of the fuel-oxygen ratio (phi Actual value ) The mass ratio of the total mass of the fuel actually added to the oxidant actually added;
stoichiometric value of fuel-oxygen ratio (phi) Stoichiometric value ) The weighted sum of stoichiometric values of the fuel-oxygen ratio of each component in the fuel is as follows: phi Stoichiometric value ＝∑k i Φ i, stoichiometric value ；
Wherein i is a component in the fuel; weight k i Is the mass percentage of the component i in the fuel; phi i, The stoichiometric value of the fuel-oxygen ratio of a certain component in the fuel is the mass ratio of the component and the oxidant consumed by complete reaction according to the stoichiometric coefficient;
the component Al in the fuel reacts with copper oxide according to chemical equation (1):
2Al+3CuO→Al 2 O 3 +Cu(1)；Φ al, stoichiometric value ＝0.226；
The component Ti in the fuel reacts with copper oxide according to chemical equation (2):
Ti+2CuO→TiO 2 +2Cu(2)；Φ stoichiometric value of Ti ＝0.301；
After determining the oxygen equivalent ratio and the mass fraction of Al and Ti in the fuel, according to phi Stoichiometric value ＝∑k i Φ i, a stoichiometric value, can calculate phi Stoichiometric value The method comprises the steps of carrying out a first treatment on the surface of the According toCan calculate phi Actual value The mass ratio of the total mass of the actually added fuel to the mass of the actually added oxidant is 1, and according to the mass conservation law, the mass ratio of the actually added fuel to the mass ratio of the actually added oxidant is calculated, and the mass ratio of the actually added oxidant to the mass ratio of the actually added fuel is calculated, and the mass ratio of Al to Ti to CuO in the known fuel is combined, so that the mass ratio of the actually added Al to the mass ratio of the actually added Ti to the mass ratio of the actually added Cu to the known fuel can be determined; the solvent is n-hexane, cyclohexane, n-heptane, benzene, toluene or xylene, and the solvent also has the functions of a coolant and a process control agent;
the ratio of the volume (mL) of the solvent to the sum (g) of the mass of the fuel and the oxidant is (0.3-1.0): 1;
preferably, the mechanical dispersion is carried out by stirring for 10min by magnetic force and then ultrasonic dispersion for 5min;
(2) Pouring the mixed dispersion liquid obtained in the step (1) into a ball milling tank by adopting a high-energy ball milling method, adding grinding balls with diameters of 5, 8, 10, 12 and 15mm respectively as ball milling media, wherein the mass ratio of the 5 grinding balls is 1:11:25:50:100, the mass ratio of the grinding balls to raw materials consisting of Al, ti and CuO is (10-30): 1, filling protective gas into the grinding tank for sealing, and putting into a planetary ball mill;
the protective gas is inert gas or nitrogen, and the purity is more than 99.999%;
(3) Setting parameters of a planetary ball mill, wherein the rotating speed is 150-500 r/min, and the ball milling time is 1-4 h; suspending for 10min after ball milling for 30min, and exchanging the ball milling rotation direction when the ball mill is started automatically next time; the rotation direction is clockwise or anticlockwise;
preferably, the rotating speed is 180-300 r/min, and the ball milling time is 1-3 h;
(4) And after ball milling is finished, cooling for 10min, taking out a ball milling tank, vacuum drying the obtained composite metal powder until the solvent is completely volatilized, and picking out grinding balls to obtain the Al/Ti/CuO micro-nano composite energetic material with the waxberry-shaped core-shell structure.
Preferably, the vacuum drying temperature is 50-70 ℃ and the vacuum drying time is 3-6 h.
Advantageous effects
(1) The invention provides an Al/Ti/CuO micro-nano composite energetic material with a Yang Meizhuang core-shell structure, wherein a Ti metal with higher density and activity is introduced into a composite energetic material system to form an Al/Ti/CuO ternary composite system, and the oxygen-fuel equivalent ratio in the composite energetic material is determinedThe mass proportion of each component in the Al/Ti/CuO ternary system energetic composite material is limited to 0.5-4.0, and further, the combustion thermal performance of the ternary energetic composite material obtained by adding Ti in the proportion range is obviously superior to that of the Al/CuO or Ti/CuO binary system energetic composite material; when->The combustion heat of the Al/Ti/CuO micro-nano composite energetic material is 6161J/g, which is obviously higher than the combustion heat value of the Al/CuO or Ti/CuO composite energetic material when the value is 3, the mass fraction of Al in the fuel is 70% and the mass fraction of Ti is 30%.
(2) The invention provides an Al/Ti/CuO micro-nano composite energetic material with a Yang Meizhuang core-shell structure, which has novel structure, nano Ti and nano CuO particles with smaller particle diameters are uniformly adsorbed, coated and even embedded on the surfaces or subsurface layers of micro Al particles with larger particle diameters to form a Yang Meizhuang core-shell structure, and the Al/Ti/CuO micro-nano composite energetic material is uniformly coated, monodisperse and free of agglomeration, so that the contact between the particles is more compact and sufficient, the mass transfer distance and the diffusion distance are shorter, the reaction strength is higher, and the combustion rate is higher.
(3) The invention provides a preparation method of an Al/Ti/CuO micro-nano composite energetic material with a Yang Meizhuang core-shell structure, which realizes the assembly of metal fuel Al, ti and oxidant CuO on a molecular level by a high-energy ball milling method after optimizing parameters, does not introduce new impurities or damage the original structures of Al, ti and CuO particles, and provides conditions for uniform distribution and full contact of each component particle, thereby being capable of reducing the reaction heat conduction distance, improving the mass transfer efficiency, obviously improving the combustion heat of the composite energetic material, leading the composite material to release heat more severely, leading the heat release efficiency to be higher, leading the energy release to be more complete, and being added into the explosive, and being beneficial to improving the actual energy level and the energy release efficiency of the explosive.
(4) The invention provides a preparation method of an Al/Ti/CuO micro-nano composite energetic material with a Yang Meizhuang core-shell structure, which has the advantages of simple process, safety, reliability, mild condition, strong applicability, easily controlled preparation process, realization of large-scale preparation and production, low economic cost and strong environmental protection.
Drawings
FIG. 1 is a Scanning Electron Microscope (SEM) image of a sample prepared according to example 1;
FIG. 2 is a Transmission Electron Microscope (TEM) image of the sample prepared in example 1;
FIG. 3 is a scanning electron microscope (SEM-EDSMxing) elemental profile of a sample prepared in example 1; wherein, the graph (f) is an SEM image of the sample, and the graphs (i) - (j) respectively correspond to Al, ti, cu and O oxygen elements;
FIG. 4 is an X-ray diffraction pattern (XRD) of the sample (Al/Ti/CuO) prepared in example 1 and raw materials Al, ti and CuO;
FIG. 5 is an X-ray photoelectron spectrum (XPS) of the sample (Al/Ti/CuO) prepared in example 1 and O1s, al2p, ti2p and Cu2 p;
FIG. 6 is a thermal weight loss curve (DSC) under an air atmosphere of the sample prepared in example 1, the sample prepared in comparative example 1 (Al/CuO) and the sample prepared in comparative example 2 (Ti/CuO);
FIG. 7 is a high-speed image of the combustion state of the sample (Al/Ti/CuO) prepared in example 1 and the sample (Al/CuO) prepared in comparative example 1;
FIG. 8 is a Transmission Electron Microscope (TEM) image of the sample prepared in comparative example 6.
Detailed Description
The invention will now be described in detail with reference to the drawings and specific examples, but is not intended to limit the scope of the patent.
The metal aluminum (Al) has a particle size of 1-5 μm and a purity of 99.5%, and is purchased from Shanghai Ala Biochemical technology Co., ltd.
The grain size of the metallic titanium (Ti) is 100 nm-1000 nm, the purity is 99.5%, and the metallic titanium is purchased from Shanghai Michlin Biochemical technology Co.
Copper oxide (CuO) having a particle size of 40nm and a purity of 99.5% was purchased from Shanghai Yi En chemical technology Co., ltd
N-hexane (GC) was 99.5% pure, analytically pure, purchased from Shanghai Ala Biotechnology Co., ltd.
JX-4G planetary ball mill, model: JX-4GL, shanghai Jingzhi practical development Co., ltd.
Combustion heat testing instrument: oxygen bomb instrument, model: TRHW-7000C, tianrun electronic technologies Co., ltd. The test conditions were: air is at normal pressure, the mass of the sample is 200+/-10 mg, and the volume of ultrapure water in a calorimeter bomb is 10+/-0.5 mL.
High-speed image pickup instrument: thousand-eye wolf high-speed camera, model: x213, hefeihuang Junzhen Gaokao information technology Co. Test conditions: open system, air normal pressure, sample mass 50+ -5 mg, sample state as powder, ignition mode as CO 2 And (5) igniting the laser.
Example 1
A preparation method of a Yang Meizhuang core-shell structure Al/Ti/CuO micro-nano composite energetic material comprises the following steps:
(1) Determination of the equivalent ratio of oxygen to fuel3, wherein the mass fraction of Al is 70% and the mass fraction of Ti is 30% based on 100% of the total mass of the fuel; according to phi Stoichiometric value ＝∑k i Φ i, a stoichiometric value, can calculate phi Stoichiometric value =0.226×0.7+0.301×0.3= 0.2485; according to->Can calculate phi Actual value = 0.7455, i.e. the mass ratio of the total mass of the actually added fuel to the mass of the actually added oxidant is 0.7455, and according to the law of conservation of mass, the sum of the mass fractions of the actually added fuel and the actually added oxidant is 1, it can be calculated that the mass fraction of the actually added oxidant is 57.3%, the mass fraction of the actually added fuel is 42.7%, the mass fraction of Al in the fuel is 70%, and the mass fraction of Ti is 30%, so as to determine that the mass fractions of the actually added Al, ti and CuO in the composite energetic material are 29.89%, 12.81% and 57.30%, respectively, i.e. the mass ratio of each component of the composite energetic material is 29.89:12.81:57.30;
2.989g of Al powder, 1.281g of Ti powder and 5.730g of CuO powder are weighed according to the mass ratio respectively, put into a beaker, 8mL of normal hexane is added, and the ratio of the volume (mL) of the normal hexane to the sum (g) of the mass of fuel and oxidant is 0.8:1, sealing a beaker by using a sealing film, magnetically stirring for 10min, and ultrasonically dispersing for 5min to obtain a mixed dispersion liquid;
(2) Pouring the mixed dispersion liquid obtained in the step (1) into a clean agate ball milling tank by adopting a high-energy ball milling method, adding agate balls with diameters of 5, 8, 10, 12 and 15mm respectively as ball milling media, wherein the mass ratio of the 5 grinding balls is 1:11:25:50:100, the mass ratio of the grinding balls to raw materials consisting of Al powder, ti powder and CuO powder is 20:1, filling Ar with the purity of 99.999%, sealing, and putting into a planetary ball mill;
(3) Setting parameters of a planetary ball mill, wherein the rotating speed is 200r/min, the ball milling time is 2h, and starting ball milling; suspending for 10min after ball milling for 30min, and exchanging the ball milling rotation direction when the ball mill is started automatically next time; the rotation direction is clockwise rotation or anticlockwise rotation;
(4) And after the ball milling is finished, continuing to cool for 10min, opening a ball mill cover, taking out a ball mill tank, rapidly pouring the composite metal powder obtained by ball milling into a quartz culture dish, putting the culture dish into a vacuum drying oven at 60 ℃ for drying treatment for 4h, and picking out agate balls after n-hexane volatilizes to obtain a powdery sample.
Example 2
A preparation method of a Yang Meizhuang core-shell structure Al/Ti/CuO micro-nano composite energetic material comprises the following steps:
(1) Determination of the equivalent ratio of oxygen to fuel2, wherein the mass fraction of Al is 70% and the mass fraction of Ti is 30% based on 100% of the total mass of the fuel; according to phi Stoichiometric value ＝∑k i Φ i, a stoichiometric value, can calculate phi Stoichiometric value ＝0.226×0.7+0.301×0.3＝0.2485；
According toCan calculate phi Actual value =0.497, i.e. the mass ratio of the total mass of the actually added fuel to the mass of the actually added oxidant is 0.497, and according to the law of conservation of mass, the sum of the mass fractions of the actually added fuel and the actually added oxidant is 1, it can be calculated that the mass fraction of the actually added oxidant is 66.8%, the mass fraction of the actually added fuel is 33.2%, the mass fraction of Al in the fuel is 70%, and the mass fraction of Ti is 30%, so as to determine that the mass fractions of Al, ti and CuO actually added in the composite energetic material are 23.24%, 9.96% and 66.8%, respectively, i.e. the mass ratio of each component of the composite energetic material is 23.24:9.96:66.8;
4.648g of Al powder, 1.992g of Ti powder and 13.36g of CuO powder are respectively weighed according to the mass ratio, put into a beaker, 20mL of normal hexane is added, and the ratio of the volume (mL) of the normal hexane to the sum (g) of the mass of fuel and oxidant is 1:1, sealing a beaker by using a sealing film, magnetically stirring for 10min, and ultrasonically dispersing for 5min to obtain a mixed dispersion liquid;
(2) Pouring the mixed dispersion liquid obtained in the step (1) into a clean agate ball milling tank by adopting a high-energy ball milling method, adding agate balls with diameters of 5, 8, 10, 12 and 15mm respectively as ball milling media, wherein the mass ratio of the 5 grinding balls is 1:11:25:50:100, the mass ratio of the grinding balls to raw materials consisting of Al powder, ti powder and CuO powder is 30:1, filling Ar with the purity of 99.999%, sealing, and putting into a planetary ball mill;
(3) Setting parameters of a planetary ball mill, wherein the rotating speed is 300r/min, the ball milling time is 3h, and starting ball milling; suspending for 10min after ball milling for 30min, and exchanging the ball milling rotation direction when the ball mill is started automatically next time; the rotation direction is clockwise rotation or anticlockwise rotation;
(4) And after the ball milling is finished, continuing to cool for 10min, opening a ball mill cover, taking out a ball mill tank, rapidly pouring the composite metal powder obtained by ball milling into a quartz culture dish, putting the culture dish into a vacuum drying oven at 70 ℃ for drying treatment for 6h, and picking out agate balls after n-hexane volatilizes to obtain a powdery sample.
Example 3
A preparation method of a Yang Meizhuang core-shell structure Al/Ti/CuO micro-nano composite energetic material comprises the following steps:
(1) Determination of the equivalent ratio of oxygen to fuel3.5, wherein the mass fraction of Al is 70% and the mass fraction of Ti is 30% based on 100% of the total mass of the fuel; according to phi Stoichiometric value ＝∑k i Φ i, a stoichiometric value, can calculate phi Stoichiometric value ＝0.226×0.7+0.301×0.3＝0.2485；
Can calculate phi Actual value = 0.8698, i.e. the mass ratio of the total mass of the actually added fuel to the mass of the actually added oxidant is 0.8698, and according to the law of conservation of mass, the sum of the mass fractions of the actually added fuel and the actually added oxidant is 1, it can be calculated that the mass fraction of the actually added oxidant is 53.5%, the mass fraction of the actually added fuel is 46.5%, the mass fraction of Al in the fuel is 32.55%, and the mass fraction of Ti is 13.95%, so as to determine that the mass fractions of actually added Al, ti and CuO in the composite energetic material are 32.55%, 13.95% and 53.5%, respectively, i.e. to determine the mass ratio of each component of the composite energetic material is 32.55:13.95:53.5；
1.628g of Al powder, 0.697g of Ti powder and 2.675g of CuO powder are respectively weighed according to the mass ratio, put into a beaker, 2.5mL of normal hexane is added, and the ratio of the volume (mL) of the normal hexane to the sum (g) of the mass of fuel and oxidant is 0.5:1, sealing a beaker by using a sealing film, magnetically stirring for 10min, and ultrasonically dispersing for 5min to obtain a mixed dispersion liquid;
(2) Pouring the mixed dispersion liquid obtained in the step (1) into a clean agate ball milling tank by adopting a high-energy ball milling method, adding agate balls with diameters of 5, 8, 10, 12 and 15mm respectively as ball milling media, wherein the mass ratio of the 5 grinding balls is 1:11:25:50:100, the mass ratio of the grinding balls to raw materials consisting of Al powder, ti powder and CuO powder is 10:1, filling Ar with the purity of 99.999%, sealing, and putting into a planetary ball mill;
(3) Setting parameters of a planetary ball mill, wherein the rotating speed is 180r/min, the ball milling time is 1h, and starting ball milling; suspending for 10min after ball milling for 30min, and exchanging the ball milling rotation direction when the ball mill is started automatically next time; the rotation direction is clockwise rotation or anticlockwise rotation;
(4) And after ball milling is finished, cooling for 10min, opening a ball mill cover, taking out a ball mill tank, rapidly pouring the composite metal powder into a quartz culture dish, putting the culture dish into a vacuum drying oven at 65 ℃ for drying treatment for 3h, and picking out agate balls after n-hexane volatilizes to obtain a powdery sample.
Example 4
A preparation method of a Yang Meizhuang core-shell structure Al/Ti/CuO micro-nano composite energetic material comprises the following steps:
(1) Determination of the equivalent ratio of oxygen to fuel1, wherein the mass fraction of Al is 70% and the mass fraction of Ti is 30% based on 100% of the total mass of the fuel; according to phi Stoichiometric value ＝∑k i Φ i, a stoichiometric value, can calculate phi Stoichiometric value ＝0.226×0.7+0.301×0.3＝0.2485；
Can calculate phi Actual value = 0.2485, i.e. the mass ratio of the total mass of the actually added fuel to the mass of the actually added oxidant is 0.2485, and according to the law of conservation of mass, the sum of the mass fractions of the actually added fuel and the actually added oxidant is 1, which can be calculated to be 80.1% by mass of the actually added oxidant, 19.9% by mass of the actually added fuel, 13.93% by mass of Al in the fuel, and 5.97% by mass of Ti, so as to determine that the mass fractions of the actually added Al, ti and CuO in the composite energetic material are 13.93%, 5.97% and 80.1%, respectively, i.e. the mass ratio of each component of the composite energetic material is determined to be 13.93:5.97:80.1;
6.965g of Al powder, 2.985g of Ti powder and 40.05g of CuO powder are respectively weighed according to the mass ratio, put into a beaker, 35mL of normal hexane is added, and the ratio of the volume (mL) of the normal hexane to the sum (g) of the mass of fuel and oxidant is 0.7:1, sealing a beaker by using a sealing film, magnetically stirring for 10min, and ultrasonically dispersing for 5min to obtain a mixed dispersion liquid;
(2) Pouring the mixed dispersion liquid obtained in the step (1) into a clean agate ball milling tank by adopting a high-energy ball milling method, adding agate balls with diameters of 5, 8, 10, 12 and 15mm respectively as ball milling media, wherein the mass ratio of the 5 grinding balls is 1:11:25:50:100, the mass ratio of the grinding balls to raw materials consisting of Al powder, ti powder and CuO powder is 25:1, filling Ar with the purity of 99.999%, sealing, and putting into a planetary ball mill;
(3) Setting parameters of a planetary ball mill, wherein the rotating speed is 290r/min, the ball milling time is 2.5h, and starting ball milling; suspending for 10min after ball milling for 30min, and exchanging the ball milling rotation direction when the ball mill is started automatically next time; the rotation direction is clockwise rotation or anticlockwise rotation;
(4) And after ball milling is finished, cooling for 10min, opening a ball mill cover, taking out a ball mill tank, rapidly pouring the composite metal powder into a quartz culture dish, putting the culture dish into a vacuum drying oven at 70 ℃ for drying treatment for 6h, and picking out agate balls after n-hexane volatilizes to obtain a powdery sample.
Comparative example 1
Comparative example 1 an Al/CuO composite material was prepared on the basis of example 1 only, without adding metallic titanium.
Comparative example 2
Comparative example 2 a Ti/CuO composite material was prepared on the basis of example 1 only, without adding metallic aluminum.
Comparative example 3
Comparative example 3 an Al/CuO composite material was prepared on the basis of example 2 only, without adding metallic titanium.
Comparative example 4
Comparative example 4 an Al/CuO composite material was prepared on the basis of example 3 only, without adding metallic titanium.
Comparative example 5
Comparative example 5 an Al/CuO composite material was prepared on the basis of example 4 only, without adding metallic titanium.
Comparative example 6
Comparative example 6 the "high energy ball milling" in step (2) was replaced by "simple physical mixing", i.e. "2.989 g Al powder, 1.281g Ti powder and 5.730g CuO powder were weighed into a beaker respectively, stirred with a spatula for 10min and then shaken for 3min", to prepare Al/Ti/CuO composite material.
Characterization of the morphology of the samples prepared in example 1 and comparative example 6 shows that the sample of the Al/Ti/CuO composite material prepared in comparative example 6 by a simple physical mixing method is shown in FIG. 8, the uniformity of distribution among the particles in the sample is poor, a more obvious self-agglomeration phenomenon exists, and the surface of the micrometer Al particles is smooth; the Al/Ti/CuO micro-nano composite energetic material sample prepared by the high-energy ball milling method in the embodiment 1 is shown in figures 1-2, the sample is spherical, and the nano particles with smaller particle size are uniformly adsorbed, wrapped and even embedded on the surface or the subsurface of the particles with larger particle size to form a core-shell structure; the surface of the composite particle is slightly rough and has small granular protrusions, similar to a waxberry shape, and the particles are in a monodisperse state and do not agglomerate.
The morphology characterization results of the samples prepared in examples 2-4 are similar to those of example 1.
The analysis of the types and structures of the sample elements prepared in the embodiment 1 shows that the results are shown in figures 3-5, and as can be seen from figure 3, the elements of O, ti and Cu are uniformly distributed on the surface of the Al core, so that Ti and CuO are uniformly adsorbed, coated and even embedded on the surface or subsurface of the micron Al particles to form a waxberry-shaped core-shell structure; as can be seen from fig. 4, in the JCPDS card of the control raw materials Al, ti and CuO, the XRD characteristic peak of the sample prepared in example 1 is a superposition of Al, ti, cuO characteristic peaks, and no new other diffraction peak characteristics appear, which indicates that the sample prepared in example 1 is an Al/Ti/CuO micro-nano composite energetic material, which is a three-phase system, that is, an aluminum powder phase, a titanium powder phase and a copper oxide particle phase, al, cuO and Ti are in a purely physical "coating" or "embedding" effect, no chemical reaction or alloying effect occurs between each component in the whole high-energy ball milling process, and no energy is lost in advance in the whole system during the ball milling process. As can be seen from fig. 5, the sample prepared in example 1 contains four elements of Al, ti, cu and O. The elemental and structural characterization results for the samples prepared in examples 2-4 were similar to example 1.
In summary, the samples prepared in examples 1 to 4 were Yang Meizhuang core-shell Al/Ti/CuO micro-nano composite energetic materials.
Fig. 6 shows, in order from bottom to top, thermal weight loss curves of the sample (Al/Ti/CuO) prepared in example 1, the sample (Ti/CuO) prepared in comparative example 2, and the sample (Al/CuO) prepared in comparative example 1 in an air atmosphere. As can be seen from fig. 6, compared with the Al/CuO binary system, with the addition of Ti, both the initial reaction temperature and the peak temperature of the two exothermic peaks of the Al/Ti/CuO ternary system are advanced, the heat release is also greatly improved, the peak temperatures of the two stages are advanced by 3.2 ℃ and 47 ℃ respectively, and the duration of the second exothermic reaction is longer. It can be seen that the addition of Ti enhances the exothermic reaction of the Al/CuO system, so that the Al/Ti/CuO reaction activity and the heat generation increase are improved, which has positive significance for the application. The thermogravimetric characterization of the samples prepared in examples 2-4 was similar to that of example 1.
The samples prepared in examples 1 to 4 and comparative examples 1 to 5 were burnedThe heat was tested and the results are shown in Table 1 whenUnder the condition of the same values, the combustion heat value of the sample (Al/Ti/CuO) prepared in the example 1 is obviously higher than that of the composite energetic material prepared in the comparative example 1 (Al/CuO) and the comparative example 2 (Ti/CuO), which shows that the combustion heat performance of the Al/Ti/CuO three-phase composite energetic material is obviously higher than that of the binary composite energetic material only containing titanium or aluminum; compared with comparative examples 1, 4 and 5, the combustion heat of the samples (Al/Ti/CuO) prepared in examples 1-3 is obviously improved, which shows that the addition of metallic titanium can obviously improve the combustion heat of the composite energetic material; oxygen equivalent ratio->The mass ratio of fuel and oxidant in the composite energetic material is reacted, when +.>When the value is lower than 3, with +.>The value is increased, the specific gravity of fuel in the composite energetic material is increased, the specific gravity of oxidant is reduced, and the combustion heat of the composite energetic material is correspondingly increased; when->When the value is greater than 3, the specific gravity of the fuel is continuously increased, and the combustion heat is not continuously increased any more. Thus->At a value equal to 3, the heat of combustion of the composite energetic material is greatest. According to the combustion heat test results of the embodiment 1 and the comparative example 6, compared with the simple physical mixing method, the high-energy ball milling method has the advantages that the uniformity of distribution among the component particles in the Al/Ti/CuO composite material is good, the composite particles are in a monodisperse state, no agglomeration phenomenon exists, and the combustion heat performance of the sample is better.
Table 1 examples 1 to 4 and comparative example 1, comparative examples 3 to 5 were prepared to obtain the sample combustion heat value
The high-speed imaging of the combustion state of the sample (Al/Ti/CuO) prepared in example 1 and the sample (Al/CuO) prepared in comparative example 1 is shown in FIG. 7, compared with the Al/CuO, the Al/Ti/CuO micro-nano composite energetic material has larger fireball diameter and brightness generated during combustion, the time for reaching the maximum fireball area is shorter, the ignition delay time of particles is shorter, and the combustion reaction of the Al/Ti/CuO micro-nano composite energetic material prepared in example 1 is quicker and more severe and the reaction is more sufficient compared with comparative example 1; the high-speed image of the combustion state of the samples prepared in examples 2 to 4 was similar to that in example 1. The Yang Meizhuang core-shell structure Al/Ti/CuO micro-nano composite energetic material prepared by the method is more compact and sufficient in contact among particles, so that the mass transfer distance and the diffusion distance are shorter, the reaction intensity is higher, and the combustion rate is higher. Therefore, the high-energy ball milling method has positive effect on improving the reactivity of the composite particles.
The above examples merely illustrate embodiments of the present invention and are not to be construed as limiting the scope of the invention, it being understood that variations and modifications can be made by those skilled in the art without departing from the spirit of the invention.

Claims (5)

1. An Yang Meizhuang core-shell structure Al/Ti/CuO micro-nano composite energetic material is characterized in that: the material consists of fuel and oxidant, wherein the fuel is metal Al and Ti, and the oxidant is CuO;
the Al is particles with the particle size of 1-5 mu m, the Ti is particles with the particle size of 100-1000 nm, and the CuO is particles with the particle size of 20-100 nm;
the waxberry-shaped core-shell structure takes Al particles as cores, ti particles and CuO particles are uniformly adsorbed, wrapped and embedded on the surfaces or subsurface of the Al particles as shells, so that composite particles with the cores completely covered by the shells are formed, and granular bulges exist on the surfaces of the composite particles, so that a Yang Meizhuang core-shell structure is formed;
the fuel-oxygen equivalent ratio of the composite energetic material is 1-3.5;
the mass fraction of Al is 70% and the mass fraction of Ti is 30% based on 100% of the total mass of the fuel.
2. The Yang Meizhuang core-shell structured Al/Ti/CuO micro-nano composite energetic material according to claim 1, wherein the material is characterized in that: the waxberry-shaped core-shell structure is spherical or spheroidic, the grain diameter of Al is 1-3 mu m, the grain diameter of Ti is 200-500 nm, and the grain diameter of CuO is 20-40 nm.
3. A method for preparing the waxberry-shaped core-shell structure Al/Ti/CuO micro-nano composite energetic material according to claim 1 or 2, which is characterized in that: the method comprises the following steps:
(1) Determining the oxygen equivalent ratio and the mass fraction of each component in the fuel, combining with the law of mass conservation, determining the mass ratio of the Al/Ti/CuO ternary micro-nano composite energetic material, weighing and adding each component fuel and oxidant according to the mass ratio, then adding a solvent, and carrying out preliminary mechanical dispersion to obtain a mixed dispersion liquid;
the solvent is n-hexane, cyclohexane, n-heptane, benzene, toluene or xylene;
the ratio of the volume of the solvent to the sum of the mass of the fuel and the mass of the oxidant is (0.3-1.0) mL 1g;
(2) Pouring the mixed dispersion liquid into a ball milling tank by adopting a high-energy ball milling method, adding grinding balls with diameters of 5, 8, 10, 12 and 15mm respectively, wherein the mass ratio of the 5 grinding balls is 1:11:25:50:100, the mass ratio of the grinding balls to raw materials consisting of Al, ti and CuO is (10-30): 1, filling protective gas into the grinding tank, sealing, and putting into a planetary ball mill;
the protective gas is inert gas or nitrogen, and the purity is more than 99.999%;
(3) Setting parameters of a planetary ball mill, wherein the rotating speed is 150-500 r/min, and the ball milling time is 1-4 h; suspending for 10min after ball milling for 30min, and exchanging the ball milling rotation direction when the ball mill is started automatically next time; the rotation direction is clockwise or anticlockwise;
(4) And after ball milling is finished, cooling for 10min, taking out a ball milling tank, vacuum drying the obtained composite metal powder until the solvent A is completely volatilized, and picking out grinding balls to obtain the Al/Ti/CuO micro-nano composite energetic material with the waxberry-shaped core-shell structure.
4. The preparation method of the waxberry-shaped core-shell structure Al/Ti/CuO micro-nano composite energetic material according to claim 3, which is characterized by comprising the following steps: the rotating speed is 180-300 r/min, and the ball milling time is 1-3 h.
5. The preparation method of the waxberry-shaped core-shell structure Al/Ti/CuO micro-nano composite energetic material according to claim 3 or 4, which is characterized by comprising the following steps: the mechanical dispersion is carried out by stirring for 10min by magnetic force and then ultrasonic dispersion for 5min; the temperature of the vacuum drying is 50-70 ℃, and the time of the vacuum drying is 3-6 hours.
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