CN110686567A - Method for preparing bridgeless electric initiating explosive device by utilizing functionalized carbon fibers - Google Patents
Method for preparing bridgeless electric initiating explosive device by utilizing functionalized carbon fibers Download PDFInfo
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- CN110686567A CN110686567A CN201810725894.9A CN201810725894A CN110686567A CN 110686567 A CN110686567 A CN 110686567A CN 201810725894 A CN201810725894 A CN 201810725894A CN 110686567 A CN110686567 A CN 110686567A
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F42—AMMUNITION; BLASTING
- F42B—EXPLOSIVE CHARGES, e.g. FOR BLASTING, FIREWORKS, AMMUNITION
- F42B3/00—Blasting cartridges, i.e. case and explosive
- F42B3/10—Initiators therefor
- F42B3/195—Manufacture
Abstract
The invention discloses a method for preparing a bridgeless electric initiating explosive device by utilizing functionalized carbon fibers. The invention utilizes the functionalized carbon fiber as a conductive and heat-conducting medium, forms partial discharge and heat accumulation in the nano energetic material, and then realizes the ignition or detonation function; the orderliness of each component in the nano thermite is improved to a great extent, the agglomeration among particles is reduced, and the reaction rate and the energy of the nano thermite are improved; meanwhile, the functionalized carbon fibers reduce the electrostatic sensitivity of the nano thermite, so that the nano thermite can be effectively applied to the application of the bridgeless electric initiating explosive device to form the bridgeless electric initiating explosive device.
Description
Technical Field
The invention relates to an electric initiating explosive device, in particular to a method for preparing a bridgeless electric initiating explosive device by assembling a nano energetic material by utilizing functionalized carbon fibers, belonging to the electric initiating explosive device technology.
Background
The traditional transducer of electric initiating explosive device is generally in bridge wire or bridge belt type structure, which is to generate joule heat after being electrified by means of fine resistance wire (or resistance film) to initiate chemical reaction of energetic medicament attached around the bridge wire (bridge belt). Taking a bridge wire product as an example, from the view of the manufacturing process, the biggest process difficulty is that the bridge wire is welded on a leg line, and the bridge wire must be welded firmly and cannot cause adverse harm to the quality of subsequent products. The adopted welding method is free of non-conventional soldering and more advanced energy storage welding, ultrasonic welding or laser welding. The problems that exist are mainly: the solder joints may have cold solder joints, the bridge wire has a large resistance value and is damaged by inconspicuous force, and so on, thereby requiring a technical enhancement to detect the quality level of the solder bridge process. If soldering is adopted, the procedures of cleaning, dehydration, drying and the like are required to be added, once the soldering is not cleaned, the corrosion phenomenon of welding points can occur, the product quality is reduced rapidly, and the defects of long storage and instability and incapability of ensuring the service life of the product are overcome. The bridge belt is complex to manufacture, and comprises a series of procedures such as target processing, sputtering, deposition, masking, etching, wire bonding, post-processing and the like, which directly results in low yield and high cost.
The newly developed semiconductor bridge energy transducer technology adopts the processing and manufacturing method of electronic devices, namely monocrystalline silicon is doped to obtain a microscale film with controllable electron density, when external input electric energy is input, the microscale film undergoes the processes of temperature rise, melting and gasification to form electric explosion plasma, and the electric explosion plasma acts on the contacted energetic medicament to initiate the combustion or explosion of the medicament to complete the initial excitation function. The whole manufacturing process of the semiconductor bridge comprises the following steps: the processes of drawing monocrystalline silicon, compounding insulating layers, growing polycrystalline silicon, doping, (multi) etching, bonding, coating silver paste and the like are very complicated and complicated, the manufacturing cost is inevitably increased, and the general use is difficult to achieve. On the basis of semiconductor bridge film, the energetic bridge film containing zirconium active bridge and composite thermite is obtained by physical method, and is still in the technical development stage, and has a certain distance from engineering application.
The electric spark product with conductive agent is formed by coating graphite with energetic agent, and the former conductive component is limited to graphite powder, so that the problem is that the resistance of the formed agent is very large, the sensitivity to electric energy is high, and the formed agent is unsafe in daily production, storage and use and is eliminated. The document (Jucisiant, Zhanglin, Liyan, and the like, a carbon crystal film electric ignition bridge characteristic research [ J ] an initiating explosive device, 2015(2015 03):1-4.) reports that the initiating voltage of the initiating explosive device taking carbon crystal as a transducer element can reach 17.3V at the lowest, the initiating explosive device is reliable in ignition at 70 ℃ and 50 ℃ below zero, and the initiating explosive device has better antistatic capability.
Disclosure of Invention
The invention aims to provide a method for simply and effectively preparing a bridgeless electric initiating explosive device by assembling functionalized carbon fibers and nano energetic materials.
The technical solution for realizing the purpose of the invention is as follows: a method for preparing a bridgeless electric initiating explosive device by utilizing functionalized carbon fibers comprises the steps of assembling a nano thermite on the surface of oxidized carbon fibers through self-assembly to obtain a ternary nano composite energetic material, and pressing the energetic material into a bridgeless electrode plug to prepare the bridgeless electric initiating explosive device.
In a preferred embodiment of the invention, the oxidized carbon fiber is prepared by oxidizing clean Carbon Fiber (CF) with an oxidizing agent, wherein the oxidizing agent is preferably mixed nitric-sulfuric acid with a volume ratio of 2:1, the oxidizing time is preferably 120-480 min, and the oxidizing temperature is preferably 50-150 ℃.
In a preferred embodiment of the invention, the nano thermite is composed of nano aluminum and nano metal oxide, wherein the nano metal oxide is one or more of copper oxide, bismuth oxide, ferric oxide, tungsten oxide, zinc oxide, cobalt oxide and molybdenum oxide.
In a preferred embodiment of the invention, the mass content of the oxidized carbon fibers in the obtained ternary nano composite energetic material is 5-30%.
Compared with the prior art, the invention has the advantages that:
(1) the addition of the oxidized carbon fiber (functionalized carbon fiber) enhances the conductivity of the nano thermite, reduces the static sensitivity of the nano thermite, realizes the energy storage pulse ignition of the bridgeless belt nano thermite, has low required energy, and can apply the ternary nano composite energetic material to bridgeless electric initiating explosive devices.
(2) The prepared nano composite energetic material has good assembly effect, and improves the orderliness and the reaction activity of the nano thermite.
(3) The prepared oxidized carbon fiber contains more oxygen-containing groups on the surface, the dispersion of the oxidized carbon fiber in a medium is facilitated, a self-assembly process can be initiated through long-range electrostatic force, so that the nano aluminum is assembled on the oxidized carbon fiber through a short-range covalent bond, and then the ternary nano composite energetic material is obtained through the action of a non-covalent bond and a nano metal oxide.
Drawings
FIG. 1 is a functionalized CF/Al/Bi2O prepared in example 13Scanning electron microscope images of the nanocomposite energetic material.
FIG. 2 is the functionalized CF/Al/Bi obtained in example 12O3Scanning electron microscope images of the nanocomposite energetic material.
FIG. 3 is the functionalized CF/Al/Bi obtained in example 22O3Scanning electron microscope images of the nanocomposite energetic material.
FIG. 4 is the functionalized CF/Al/MoO prepared in example 33Scanning electron microscope images of the nanocomposite energetic material.
FIG. 5 is the functionalized CF/Al/MoO prepared in example 43Scanning electron microscope images of the nanocomposite energetic material.
Detailed Description
The invention adopts carbon fiber powder as a self-assembly carrier and a conductive heating substance, can adopt common carbon fibers on the market, such as T300, T300B and T400HB under Toray, HTA40 and HTS45 under TEIJIN, and the like, and the carbon fibers are ground into fiber powder with a certain length and oxidized by an oxidizing agent to form the functionalized oxidized carbon fibers. The energy-containing ternary nano material is prepared by ultrasonic dispersion and self-assembly with different nano thermites, the energy-containing ternary nano material is prepared by regulating and controlling the content of oxidized carbon fibers, and the energy-containing ternary nano material is pressed into a bridgeless electrode plug and ignited by energy storage pulse.
The oxidized carbon fiber adopted in the following implementation is prepared by firstly cleaning the carbon fiber with alkali liquor, then further cleaning the carbon fiber with acetone and then oxidizing the carbon fiber with an oxidant, wherein the oxidant is preferably mixed nitric-sulfuric acid with the volume ratio of 2:1, the oxidation time is preferably 120-480 min, and the oxidation temperature is preferably 50-150 ℃.
Example 1
Weighing 500mg of carbon fiber powder of 50 meshes, dispersing the carbon fiber powder in a NaOH solution with the concentration of 20 percent, carrying out ultrasonic treatment for 8 hours, washing and drying; dispersing the obtained carbon fiber powder in an acetone solution, performing ultrasonic treatment for 10 hours, washing and drying; weighing 300mg of treated carbon fiber, oxidizing with 60ml of 65% nitric acid for 6h at 100 ℃, washing a product to be neutral, and drying in vacuum for 12 h; respectively dispersing 10.6mg of functionalized carbon fiber, 17.9mg of nano Al powder and 77.4mg of nano bismuth oxide in isopropanol uniformly, wherein the dosage of the isopropanol is respectively 4ml, 3ml and 3 m; performing ultrasonic treatment for 8h, 4h and 4h at 100kHz respectively; dispersing nano Al powder into the functional CF, performing ultrasonic treatment for 1h, finally performing ultrasonic treatment on the mixture of the nano Al powder and the functional CF for 1h, performing centrifugal separation at 5000r/min, removing clear liquid, performing vacuum drying, and drying at 55 ℃ for 12h to obtain a product; weighing 10mg of the medicament, pressing the medicament into a PCB sleeve with a polar distance of 0.28mm and a medicament pressing pressure of 100 MPa. By using pulse energy storage discharge, the minimum ignition voltage is 25V when the capacitance is 47 muF. As can be seen from fig. 1, at a magnification of 10000 times, it can be clearly seen that the oxidized carbon fiber shows that the AI and Bi2O3 nanoparticles are uniformly loaded and the two particles are in contact with each other. As can be seen from fig. 2, when the magnification is 100000 times, the contact between the nano aluminum particles and the nano Bi2O3 is good, and the spherical particles are nano aluminum particles, and the cubic particles are nano Bi2O3, which is favorable for the reaction.
Example 2
Weighing 500mg of carbon fiber powder of 50 meshes, dispersing the carbon fiber powder in a NaOH solution with the concentration of 20 percent, carrying out ultrasonic treatment for 8 hours, washing and drying; dispersing the obtained carbon fiber powder in an acetone solution, performing ultrasonic treatment for 10 hours, washing and drying; 300mg of treated carbon fiber was weighed out and mixed with 60ml of a 1: 2, oxidizing the sulfuric acid and the nitric acid mixed acid for 2 hours at the temperature of 100 ℃, washing the product to be neutral, and drying the product in vacuum for 10 hours; respectively adding functional CF10.6mg, nano Al powder 17.9mg and nano bismuth oxide 77.4mg in the weight ratio of isopropanol and petroleum ether 1: 1, dispersing the dispersing agent uniformly, wherein the using amount of the dispersing agent is respectively 4ml, 3ml and 3 m; performing ultrasonic treatment for 6 hours, 4 hours and 4 hours at 100kHz respectively; dispersing nano Al powder into the functional CF, performing ultrasonic treatment for 1h, finally performing ultrasonic treatment on the mixture of the nano Al powder and the functional CF for 1h, performing centrifugal separation at 4000r/min, removing clear liquid, performing vacuum drying, and drying at 60 ℃ for 8h to obtain a product; weighing 15mg of the medicament, pressing the medicament into a PCB sleeve with a polar distance of 0.28mm and a medicament pressing pressure of 100 MPa. By using pulse energy storage discharge, the minimum ignition voltage is 60V when the capacitance is 47 muF. As can be seen from fig. 3, under a magnification of 3000 times, it can be clearly seen that the oxidized carbon fiber shows that the AI and Bi2O3 nanoparticles are uniformly loaded and the two particles are in contact with each other.
Example 3
Weighing 500mg of carbon fiber powder of 50 meshes, dispersing the carbon fiber powder in a NaOH solution with the concentration of 20 percent, carrying out ultrasonic treatment for 8 hours, washing and drying; dispersing the obtained carbon fiber powder in an acetone solution, performing ultrasonic treatment for 10 hours, washing and drying; 300mg of treated carbon fiber was weighed out and mixed with 60ml of a 1: 2, oxidizing the sulfuric acid and the nitric acid mixed acid for 4 hours at the temperature of 100 ℃, washing the product to be neutral, and drying the product in vacuum for 10 hours; respectively and uniformly dispersing functional CF25mg, nano Al powder 30mg and nano molybdenum oxide 70mg in isopropanol, wherein the dosage of the dispersing agent is respectively 4ml, 3ml and 3 m; performing ultrasonic treatment for 6 hours, 4 hours and 4 hours at 100kHz respectively; dispersing nano Al powder into the functional CF, performing ultrasonic treatment for 1h, finally performing ultrasonic treatment on the mixture of the nano Al powder and the functional CF for 1h, performing centrifugal separation at 5000r/min, removing clear liquid, performing vacuum drying, and drying at 55 ℃ for 10h to obtain a product; weighing 15mg of the medicament, pressing the medicament into a PCB sleeve with a polar distance of 0.28mm and a medicament pressing pressure of 100 MPa. By using pulse energy storage discharge, the minimum ignition voltage is 80V when the capacitance is 47 muF. As can be seen from fig. 4, at 2500 x magnification, it can be clearly seen that the oxidized carbon fibers show a uniform loading of AI and MoO3 nanoparticles, and that the two particles are in contact with each other.
Example 4
Weighing 500mg of carbon fiber powder of 50 meshes, dispersing the carbon fiber powder in a NaOH solution with the concentration of 20 percent, carrying out ultrasonic treatment for 8 hours, washing and drying; dispersing the obtained carbon fiber powder in an acetone solution, performing ultrasonic treatment for 10 hours, washing and drying; 300mg of treated carbon fiber was weighed out and mixed with 60ml of a 1: 2, oxidizing the sulfuric acid and the nitric acid mixed acid for 4 hours at the temperature of 100 ℃, washing the product to be neutral, and drying the product in vacuum for 10 hours; respectively and uniformly dispersing functional CF25mg, 18.4mg of nano Al powder and 81.6mg of nano copper oxide in isopropanol, wherein the dosage of the dispersing agent is respectively 4ml, 3ml and 3 m; performing ultrasonic treatment for 6 hours, 4 hours and 4 hours at 100kHz respectively; dispersing nano Al powder into the functional CF, performing ultrasonic treatment for 1h, finally performing ultrasonic treatment on the mixture of the nano Al powder and the functional CF for 1h, performing centrifugal separation at 5000r/min, removing clear liquid, performing vacuum drying, and drying at 60 ℃ for 10h to obtain a product; weighing 15mg of the medicament, pressing the medicament into a PCB sleeve, wherein the polar distance is 0.28mm, and the medicament pressing pressure is 100 MPa. By using the pulse energy storage discharge, the minimum ignition voltage is 100V when the capacitance is 47 muF. As can be seen from fig. 5, at a magnification of 2500 times, it can be clearly seen that the oxidized carbon fibers indicate that AI and CuO nanoparticles are uniformly supported and the two particles are in contact with each other.
Table 1 shows CF/Al/Bi for different oxidized carbon fiber contents2O3The measurement of electrostatic sensitivity, the addition of the oxidized carbon fiber, reduces and improves the electrostatic sensitivity of the material.
TABLE 1 CFO/Al/Bi2O3 Electrostatic sensitivity Change Table for different CFO contents
Claims (10)
1. The method for preparing the bridgeless electric initiating explosive device by utilizing the functionalized carbon fibers is characterized in that a nano thermite is assembled on the surface of oxidized carbon fibers through self-assembly to obtain a ternary nano composite energetic material, and then the energetic material is pressed into a bridgeless electrode plug to prepare the bridgeless electric initiating explosive device.
2. The method of claim 1, wherein the mass content of the oxidized carbon fibers in the obtained ternary nanocomposite energetic material is 5% -30%.
3. The method of claim 1, wherein the oxidized carbon fibers are produced by oxidizing clean carbon fibers with an oxidizing agent.
4. The method as claimed in claim 2, wherein the oxidant is mixed nitric-sulfuric acid with a volume ratio of 2:1, the oxidation time is 120-480 min, and the oxidation temperature is 50-150 ℃.
5. The method of claim 1, wherein the nano thermite is composed of nano aluminum and nano metal oxide, wherein the nano metal oxide is selected from one or more of copper oxide, bismuth oxide, ferric oxide, tungsten oxide, zinc oxide, cobalt oxide and molybdenum oxide.
6. The method of claim 5, wherein the nano-aluminum has a particle size of 50 to 110 nm.
7. The method according to claim 1, characterized in that it comprises in particular the steps of:
step 1, dispersing carbon fibers in alkali liquor for ultrasonic treatment, washing and drying under a vacuum condition;
step 2, dispersing the carbon fiber obtained in the step 1 in an acetone solution, performing ultrasonic treatment, performing suction filtration washing, and drying under a vacuum condition;
step 3, placing the carbon fiber obtained in the step 2 in an oxidant for oxidation, diluting, neutralizing, filtering, washing and drying the reaction solution under a vacuum condition to obtain oxidized carbon fiber;
step 4, adding the dispersion liquid of the nano aluminum powder into the dispersion liquid of the oxidized carbon fibers and continuing ultrasonic treatment;
step 5, adding the dispersion liquid of the nano metal oxide into the mixed dispersion liquid of the nano aluminum and the oxidized carbon fiber in the step 4 to continue ultrasonic treatment to obtain a suspension liquid;
step 6, centrifugally separating the suspension, removing supernatant, and drying the precipitate in vacuum to obtain the nano composite energetic material;
and 7, pressing the obtained nano composite energetic material into a bridgeless electrode plug to finally obtain the bridgeless electric initiating explosive device.
8. The method as claimed in claim 7, wherein the oxidant is mixed nitric-sulfuric acid with a volume ratio of 2:1, the oxidation time is 120-480 min, and the oxidation temperature is 50-150 ℃.
9. The method of claim 7, wherein the nano-metal oxide is selected from one or more of copper oxide, bismuth oxide, ferric oxide, tungsten oxide, zinc oxide, cobalt oxide and molybdenum oxide.
10. The method according to claim 7, wherein the dispersing agent in the dispersion of nano aluminum powder, the dispersion of oxidized carbon fibers and the dispersion of nano metal oxide is selected from one or more solvents selected from the group consisting of isopropanol, N-dimethylformamide, N-pentane and petroleum ether.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111521070A (en) * | 2020-04-29 | 2020-08-11 | 西安工业大学 | Preparation method of carbon-based low-voltage ignition switch |
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