CN115286473A - Multi-scale energetic microsphere continuous preparation device and method - Google Patents
Multi-scale energetic microsphere continuous preparation device and method Download PDFInfo
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- CN115286473A CN115286473A CN202211147910.3A CN202211147910A CN115286473A CN 115286473 A CN115286473 A CN 115286473A CN 202211147910 A CN202211147910 A CN 202211147910A CN 115286473 A CN115286473 A CN 115286473A
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- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
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- 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
- C06B21/0066—Shaping the mixture by granulation, e.g. flaking
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Manufacturing Of Micro-Capsules (AREA)
Abstract
The invention belongs to the field of energetic materials, and particularly relates to a device and a method for preparing multi-scale energetic microspheres in a pipeline continuous flow control auxiliary manner. The device for preparing the multi-scale energetic microspheres by pipeline continuous flow control assistance comprises a continuous phase fluid control unit, a circulating pipeline and an explosive slurry injection unit; a heating system; the device comprises a shell, a temperature control device, a finished product collecting container and a three-way joint. The preparation process of the energy-containing microspheres comprises five steps of preparation and pre-circulation of continuous phase fluid, preparation of explosive suspension slurry, injection of the explosive suspension slurry, solidification and molding of the energy-containing microspheres in a pipeline, collection of finished products and post-treatment. The invention combines the pipeline reaction principle and the water suspension granulation process, solves the defect that the traditional kettle type process can not be continuous, can realize the continuous preparation of multi-scale molding powder microsphere particles with the magnitude of micron to millimeter, and has the advantages of high sphericity, good free-running property, narrow particle size distribution and the like.
Description
Technical Field
The invention belongs to the field of energetic materials, and particularly relates to a continuous preparation device and method for multi-scale energetic microspheres.
Background
A high polymer bonded explosive (PBX) is one of mixed explosives, and is an explosive compound prepared by taking one or more high-energy explosives as a main body, adding a high polymer bonding agent and possibly containing functional additives such as a plasticizer, an insensitive agent and the like. The high polymer bonded explosive has the characteristics of high forming density, high detonation energy, good stability and mechanical property, uniform explosive column, less internal pores, excellent safety performance and the like, and is widely applied to weapon charging. The press-fitting PBX explosive is a typical variety of high polymer bonded explosive, the bonding agent of the press-fitting PBX explosive is generally selected from solid high polymers, mainly comprising rubber, cellulose and resin polymers, and the insensitive agent is mainly selected from paraffin, stearic acid, graphite and the like. According to the physical and chemical properties of the explosive and the binding agent, the main explosive and other components can be compounded by methods such as water suspension granulation, solution suspension granulation, paste extrusion granulation and the like to prepare solid granular molding powder. The water suspension granulation method has become the most common method for preparing molding powder by virtue of the advantages of high safety of the process, simple operation and the like. The granulation technology needs to be carried out in a closed reaction kettle, and the particle size and the morphology of the molding powder are mainly regulated and controlled by controlling the stirring speed, the temperature and the solvent volatilization speed. Although various molding powder particles have been prepared by the aqueous suspension granulation process, there are significant limitations in the following areas: (1) the process cannot be continuous; (2) The particle size distribution of the molding is wide, the consistency is poor, and the particle size is difficult to regulate and control; (3) The sphericity of the molding powder is not high, and the free-running property has a space for further improving.
Disclosure of Invention
The invention overcomes the defects of the prior art, combines the pipeline reaction and the water suspension granulation process, and provides a continuous preparation device and a continuous preparation method of multi-scale energetic microspheres.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows: a multi-scale energetic microsphere continuous preparation device comprises a continuous phase fluid control unit, a circulating pipeline, an explosive slurry injection unit, a heating system, a shell, a temperature control device, a finished product collecting container and a three-way joint; the continuous phase fluid control unit is connected with the circulating pipeline through a pipeline joint, continuous phase fluid is sucked from the finished product collecting container and pumped into the finished product collecting container after circulation so as to complete circulation; part of the circulating pipeline is in a continuously bent shape, the shell is sleeved outside the continuously bent circulating pipeline, a heating system is attached to one side of the inner wall of the shell, and a temperature control device is arranged on the shell and used for controlling the temperature of the heating system; the explosive slurry injection unit is communicated with the circulating pipeline of the continuous bending part through a three-way joint, and the three-way joint is positioned at the liquid inlet end inside the shell.
Further, the explosive slurry injection unit is any one of a pressure-driven flow controller, an injection pump and a micro peristaltic pump.
Furthermore, the continuous phase fluid control unit mainly comprises a pump and a joint, wherein the pump is a peristaltic pump, a centrifugal pump, a gear pump or a diaphragm pump; the circulating pipeline is a silicone tube, a polytetrafluoroethylene tube, a stainless steel tube or a glass tube, the inner diameter of the pipeline is 2mm-10mm, the length of the pipeline ensures that the surface of the microsphere is primarily hardened and formed, the distance between two adjacent parallel pipelines of the part of the circulating pipeline which is located in the shell and is in a continuous bending shape is 4-10cm, and the pipeline is connected at the bending part through a U-shaped bent pipe.
A multi-scale energetic microsphere continuous preparation method is carried out by adopting the multi-scale energetic microsphere continuous preparation device, and comprises the following steps:
s1 continuous phase fluid preparation and pre-circulation
Dissolving the metered surfactant and the metered water-soluble polymer in deionized water to prepare a continuous phase solution, starting a heating system to raise the temperature of a pipeline to a certain temperature, and starting a continuous phase fluid control unit to pre-circulate fluid in the pipeline at a certain speed;
preparation of S2 explosive suspension slurry
Dissolving a required binder in an oil phase solvent, preparing a binder solution with a certain concentration, dispersing explosive particles in the binder solution to prepare explosive suspension slurry, and adding the explosive suspension slurry into a liquid storage tank or a charging barrel for later use;
s3 injection of explosive suspension slurry
Starting a magnetic stirring or ultrasonic device to uniformly disperse the explosive suspension slurry in the liquid storage tank or the charging barrel, and uniformly mixing all the components; starting an explosive slurry injection unit, setting parameters such as pressure, flow and the like, and injecting the explosive suspension slurry into the continuous phase circulation pipeline at a certain speed;
s4 curing and forming of energetic microspheres in pipeline
Adjusting the flow rate of the continuous phase to the required flow rate, enabling the explosive suspension slurry liquid drops to move in the pipeline along with the flow of the continuous phase fluid, gradually separating out the solvent from the liquid drops in the moving process, and completing liquid-solid phase conversion of the binding agent and the explosive in a suspension state under the action of the continuous phase fluid of the pipeline to form energetic microspheres;
s5, collecting and post-processing finished products
And (5) filtering and washing the finished product obtained in the step (S4), and putting the product into an oven for drying to obtain the energy-containing microsphere finished product.
Further, the HLB value of the surfactant is 8 to 18, and the surfactant is at least one of Tween series and alkyl glycoside compounds of polyoxyethylene fatty alcohol ether surfactant; the continuous phase solution is a high polymer material aqueous solution, the concentration is 2% -5%, the high polymer material is required to be capable of being dissolved or swelled in water, and the content of the surfactant is 1% -10% of that of the continuous phase liquid, preferably 2% -5%.
Further, the heating temperature of the continuous phase fluid is 0-70 ℃, and preferably 15-50 ℃.
Preferably, the polymer material includes, but is not limited to, polyvinyl alcohol or chitosan.
Furthermore, the oil phase solvent is required to be insoluble in water, the boiling point is lower than 100 ℃, the binder is one or more thermoplastic binders soluble in the oil phase solvent, and the concentration of the binder solution is 1-20%, preferably 3-10%; the mass ratio of the explosive to the binder solution is 1/50 to 3/20, preferably 1/20.
Preferably, the oil phase solvent includes, but is not limited to, ethyl acetate or methylene chloride, and the binder includes, but is not limited to, at least one of acrylic resin, polyurethane, phenolic resin, styrene-butadiene rubber, polysulfide rubber, fluororubber, and Nitrocellulose (NC).
Further, the flowing speed of the continuous phase fluid in the pipe is 60-200 ml/min, the injection speed of the explosive suspension slurry is 0.01-0.5 ml/min, the temperature of the pipeline is 20-90 ℃, and preferably 30-50 ℃; the oven drying temperature is 40-90 ℃, preferably 50-70 ℃.
Preferably, the flowing speed of the continuous phase fluid in the tube is 90 to 120 ml/min; the injection speed of the explosive suspension slurry is 0.05 to 0.2 ml/min.
Compared with the prior art, the invention has the following beneficial effects:
(1) The invention combines the pipeline principle and the water suspension granulation process, and overcomes the defect that the traditional kettle type process cannot be continuous. In addition, the inner diameter of the pipeline used by the invention is millimeter magnitude, the problem of pipeline blockage of a micro-reaction system can be effectively solved, and the preparation of multi-scale molding powder microsphere particles from micron magnitude to millimeter magnitude can be realized through the regulation and control of process parameters.
(2) The pipeline continuous flow control device designed by the invention can accurately control the process conditions such as the volume of dispersed phase liquid drops, the flow rate of continuous phase fluid, the temperature and the like, ensures the monodispersity of the liquid drops and the consistency of an assembly forming environment, and has the advantages of good sphericity, narrow particle size distribution, good uniformity and the like.
Drawings
FIG. 1 is a schematic structural diagram of a multi-scale energetic microsphere continuous preparation device of the present invention.
FIG. 2 is RDX @ F prepared in example 1 2602 SEM image of @ NC energetic composite microsphere.
FIG. 3 is RDX @ F prepared in example 1 2602 The distribution diagram of the particle size of the @ NC energetic composite microsphere.
FIG. 4 is an SEM image of an HMX @ B-GAP @ NC energetic composite microsphere prepared in example 2.
FIG. 5 is a distribution diagram of the particle size of the HMX @ B-GAP @ NC energetic composite microsphere prepared in example 2.
FIG. 6 is HNS @ F prepared in example 3 2311 SEM image of @ NC energetic composite microsphere.
FIG. 7 is HNS @ F prepared in example 3 2311 The distribution diagram of the particle size of the energy-containing composite microsphere is @ NC.
The figures are labeled as follows:
1-continuous phase fluid control unit, 2-circulation pipeline, 3-pressure driving flow controller, 4-injection pump, 5-micro peristaltic pump, 6-heating system, 7-shell, 8-temperature control device, 9-finished product collection container and 10-three-way joint.
Detailed Description
The present invention is further illustrated by the following examples.
As shown in fig. 1, a multi-scale energetic microsphere continuous preparation device comprises a continuous phase fluid control unit 1, a circulating pipeline 2, an explosive slurry injection unit, a heating system 6, a shell 7, a temperature control device 8, a finished product collection container 9 and a tee joint 10; the continuous phase fluid control unit 1 is connected with the circulating pipeline 2 through a pipeline joint, continuous phase fluid is sucked from the finished product collecting container 9, and is pumped into the finished product collecting container 9 after circulation to complete circulation, and the continuous phase fluid control unit mainly has the function of controlling the flow speed and flow of the fluid in the pipeline; part of the circulating pipeline 2 is in a continuously bent shape (similar to a snake shape), a shell 7 is sleeved on the outer side of the continuously bent part of the circulating pipeline 2, a heating system 6 is attached to one side of the inner wall of the shell 7, a temperature control device 8 is arranged on the shell 7, and the temperature control device 8 is used for controlling the temperature of the heating system; the explosive slurry injection unit is communicated with the circulating pipeline 2 of the continuous bending part through a three-way joint 10, and the three-way joint 10 is positioned at the liquid inlet end inside the shell 7.
The continuous phase fluid control unit 1 is mainly composed of a pump and a joint, and the pump is of a type including but not limited to a peristaltic pump, a centrifugal pump, a gear pump or a diaphragm pump;
the circulation pipeline 2 comprises but is not limited to a silicone tube, a polytetrafluoroethylene tube, a stainless steel tube or a glass tube, the inner diameter of the pipeline is 2mm-10mm, the length of the pipeline ensures that the surface of the microsphere is initially hardened and formed, the distance between two adjacent parallel pipelines of the part of the circulation pipeline 2 which is located in the shell 7 and is in a continuous bending shape is 4-10cm, and the pipelines are connected at the bending position through n-shaped bent pipes with a U-shaped radian.
The explosive slurry injection unit is any one of a pressure-driven flow controller 3, an injection pump 4 and a micro peristaltic pump 5.
The pressure driving flow controller 3 comprises a liquid storage tank, a pressure driving controller, a flow sensor and a PTFE (polytetrafluoroethylene) pipe, wherein the pressure driving controller pumps air into the liquid storage tank to increase the internal air pressure of the pressure driving controller, so that a dispersed phase in the liquid storage tank is pressed into the PTFE pipe (the inner diameter of a thin pipe is 0.2 to 1.5 mm), the dispersed phase flows through the flow sensor and then is injected into a continuous phase, and the flow sensor feeds flow data back to the pressure driving controller to achieve the purpose of adjusting the flow.
The syringe pump 4 is equipped with an ultrasonic device outside the cylinder to prevent the particles in the dispersed phase from settling.
The micro peristaltic pump 5 is connected with a liquid storage tank through a pipeline, and a stirring device is arranged in the liquid storage tank to prevent particles in a disperse phase from settling.
The connection mode of the three-way joint 10 and the disperse phase output part is shown in fig. 1, and different droplet generation modes (T-shaped modes or coaxial modes) can be realized through different connection modes.
The caliber of the dispersed phase (namely, explosive slurry) injection pipe is adjustable within 0.2-2mm.
The above apparatus was used to prepare the energetic microspheres of examples 1-3 below.
Example 1
A device and a method for preparing multi-scale energetic microspheres by pipeline continuous flow control assistance are used for preparing hexogen (RDX) base molding powder microspheres, and the device comprises the following components: fluororubber (F) 2602 ) 2.5wt.%, nitrocotton (NC) 2.5wt.%, RDX 95wt.% (class 5).
(1) Continuous phase fluid preparation and pre-circulation
25ml of Tween-80 and 10g of PVA (1788) were dissolved in 475ml of deionized water, and the continuous phase was pre-circulated in the tube by starting the peristaltic pump.
(2) Preparation of explosive suspension slurry
0.075g of F 2602 type And 0.075g of NC is dissolved in 9g of ethyl acetate, 2.85g of class 5 RDX is added after complete dissolution, explosive particles are uniformly dispersed under the ultrasonic condition, and the explosive slurry is placed into a explosive storage tank for later use under the stirring condition.
(3) Injection of explosive suspension slurries
Setting the injection speed of the dispersed phase to be 0.2ml/min and the inner diameter of the needle to be 0.84mm, starting magnetic stirring to enable a rotor in the dispersed phase liquid storage tank to rotate at a certain speed, and starting a pressure and flow driving controller to inject the precursor liquid (dispersed phase) prepared in the step (2) into the pre-circulated continuous phase.
(4) Assembling, solidifying and forming of binder/explosive particles
And (4) adjusting the flow of the continuous phase to be 112ml/min, forming monodisperse uniform liquid drops in the tube by the dispersed phase injected in the step (3), and gradually solidifying into balls in the moving process of the tube.
(5) Finished product collection and post-treatment
And (4) sieving the sample obtained in the step (3), washing until no foam is generated, and drying in an oven to obtain the composite energetic microsphere.
RDX @ F prepared as shown in attached figures 2 and 3 2602 The @ NC energetic composite microsphere is a compact particle formed by bonding explosive particles through an adhesive, the sphericity can reach 0.92, the particle size is distributed between 850-985 mu m, the composite microsphere is in unimodal distribution, and the fluidity is good.
Example 2
A device and a method for preparing multi-scale energetic microspheres in an auxiliary manner by virtue of continuous flow control of a pipeline are used for preparing octogen (HMX) based energetic composite microspheres, and the device comprises the following components in percentage by mass: 2.5% of branched polyaziridine glycidyl ether (B-GAP), 2.5% of Nitrocotton (NC) and 95% of main explosive HMX powder (median particle size 200 nm).
(1) Preparation and pre-circulation of continuous phase solution
25ml of Tween-80 and 10g of polyvinyl alcohol (PVA) 1788 ) Dissolved in 475ml of deionized water and the continuous phase is pre-cycled by starting the peristaltic pump.
(2) Preparation of nano explosive particles
Mixing 10g of raw materials HMX,200g of zirconium beads, deionized water and 50ml of alcohol in a ball milling tank, putting the mixture into a planetary ball mill, carrying out ball milling for 4 hours at the rotating speed of 360rpm, separating explosive suspension and the zirconium beads after the ball milling is finished, carrying out suction filtration on the explosive suspension, and carrying out freeze drying to obtain explosive particles with the median particle size of 200 nm.
(3) Preparation of precursor liquid (dispersed phase)
Dissolving 0.075g of B-GAP and 0.075g of NC in 9g of ethyl acetate, adding 2.85g of nano HMX after complete dissolution, uniformly dispersing explosive particles under an ultrasonic condition, and sucking explosive slurry into a needle tube for later use under a stirring condition.
(4) Injection of explosive suspension slurries
Setting the injection speed of the dispersed phase to be 0.1ml/min and the inner diameter of the needle to be 0.84mm, and starting a charging barrel ultrasonic device and an injection pump to inject the precursor liquid (the dispersed phase) prepared in the step (3) into the pre-circulated continuous phase.
(5) Assembling, solidifying and forming of binder/nano explosive particles
And (4) adjusting the flow rate of the continuous phase to 112ml/min, forming monodisperse uniform liquid drops in the tube by the dispersed phase injected in the step (4), and gradually solidifying into balls in the moving process of the tube.
(6) Finished product collection and post-treatment
And (4) sieving the finished product obtained in the step (4), washing until no foam is generated, and drying in an oven to obtain the composite energetic microspheres.
As can be seen from FIGS. 4 and 5, the prepared HMX @ B-GAP @ NC energetic composite microsphere is a compact particle consisting of a binder and ultrafine HMX particles, the sphericity can reach 0.91, the particle size distribution is 575 to 655 μm, the particle size distribution is unimodal, and the free-running property is good.
Example 3
A device and a method for preparing multi-scale energetic microspheres by pipeline continuous flow control assistance are used for preparing Hexanitrostilbene (HNS) based energetic composite microspheres, and the mass percentages of the components are as follows: fluororubber (F) 2311 ) 2.5 percent of Nitrocotton (NC) and 95 percent of main explosive HNS (median particle size of 80 nm).
(1) Preparation and pre-circulation of continuous phase solution
25ml of Tween-80 and 10g of polyvinyl alcohol (PVA) 1788 ) Dissolved in 475ml of deionized water and the continuous phase is pre-circulated by starting the peristaltic pump.
(2) Preparation of nano explosive particles
Mixing 10g of II-type HNS,200g of zirconium beads, deionized water and 50ml of alcohol in a ball milling tank, putting the mixture into a planetary ball mill, ball milling for 3 hours at the rotating speed of 360rpm, separating explosive suspension and the zirconium beads after the ball milling is finished, carrying out suction filtration on the explosive suspension, and carrying out freeze drying to obtain the nano-scale explosive particles.
(3) Preparation of precursor liquid (dispersed phase)
0.075g of F 2311 And 0.075g of NC is dissolved in 9g of ethyl acetate, 2.85g of nano HNS is added after complete dissolution, explosive particles are uniformly dispersed under the ultrasonic condition, and the explosive slurry is placed into a explosive storage tank for later use under the stirring condition.
(4) Injection of explosive suspension slurries
Setting the injection speed of the disperse phase to be 0.02ml/min, setting the inner diameter of the needle to be 0.84mm, starting magnetic stirring to enable a rotor in a disperse phase liquid storage tank to rotate at a certain speed, and starting a pressure and flow driving controller to inject the precursor liquid (disperse phase) prepared in the step (3) into the pre-circulated continuous phase.
(5) Assembling, solidifying and forming of binder/nano explosive particles
And (5) regulating the flow rate of the continuous phase to 96ml/min, forming monodisperse uniform liquid drops in the tube by the dispersed phase injected in the step (4), and gradually solidifying into balls in the moving process in the tube.
(6) Finished product collection and post-treatment
Sieving the finished product obtained in the step (4), washing until no foam is generated, and drying in an oven to obtain HNS @ F 2311 @ NC composite energetic microsphere.
As can be seen from FIGS. 6 and 7, the HNS-based energetic microspheres prepared are a compound consisting of a binder and HNS explosive particles, the sphericity is 0.90, the particle size distribution is 850-975 μm, the particle size distribution is unimodal, and the HNS-based energetic microspheres have good free-running property.
Claims (10)
1. A multi-scale energetic microsphere continuous preparation device is characterized by comprising a continuous phase fluid control unit (1), a circulating pipeline (2), an explosive slurry injection unit, a heating system (6), a shell (7), a temperature control device (8), a finished product collecting container (9) and a three-way joint (10); the continuous phase fluid control unit (1) is connected with the circulating pipeline (2) through a pipeline joint, continuous phase fluid is sucked from the finished product collecting container (9), and the continuous phase fluid is pumped into the finished product collecting container (9) after circulation so as to complete circulation; part of the circulating pipeline (2) is in a continuously bent shape, a shell (7) is sleeved outside the continuously bent part of the circulating pipeline (2), a heating system (6) is attached to one side of the inner wall of the shell (7), a temperature control device (8) is arranged on the shell (7), and the temperature control device (8) is used for controlling the temperature of the heating system; the explosive slurry injection unit is communicated with the circulating pipeline (2) of the continuous bending part through a three-way joint (10), and the three-way joint (10) is located at the liquid inlet end inside the shell (7).
2. The continuous preparation device of multi-scale energetic microspheres according to claim 1, wherein the explosive slurry injection unit is any one of a pressure-driven flow controller (3), an injection pump (4) and a micro peristaltic pump (5).
3. The continuous preparation device of multi-scale energetic microspheres according to claim 1, wherein the continuous phase fluid control unit (1) mainly comprises a pump and a joint, wherein the pump is a peristaltic pump, a centrifugal pump, a gear pump or a diaphragm pump; the circulating pipeline (2) is a silicone tube, a polytetrafluoroethylene tube, a stainless steel tube or a glass tube, the inner diameter of the pipeline is 2mm-10mm, the length of the pipeline ensures that the surface of the microsphere is initially hardened and formed, the distance between two adjacent parallel pipelines of the part of the circulating pipeline (2) which is positioned in the shell (7) and is in a continuous bending shape is 4-10cm, and the pipelines are connected at the bending position through a U-shaped bent pipe.
4. A continuous preparation method of multi-scale energetic microspheres, which is carried out by adopting the continuous preparation device of multi-scale energetic microspheres as claimed in any one of claims 1 to 3, and is characterized by comprising the following steps:
preparation and pre-circulation of S1 continuous phase fluid
Dissolving the metered surfactant and the metered water-soluble polymer in deionized water to prepare a continuous phase solution, starting a heating system (6) to raise the temperature of a pipeline to a certain temperature, and starting a continuous phase fluid control unit (1) to pre-circulate fluid in the pipeline at a certain speed;
preparation of S2 explosive suspension slurry
Dissolving a required binder in an oil phase solvent, preparing a binder solution with a certain concentration, dispersing explosive particles in the binder solution to prepare explosive suspension slurry, and adding the explosive suspension slurry into a liquid storage tank or a charging barrel for later use;
s3 injection of explosive suspension slurry
Starting a magnetic stirring or ultrasonic device to uniformly disperse the explosive suspension slurry in the liquid storage tank or the charging barrel, and uniformly mixing all the components; starting an explosive slurry injection unit, setting parameters such as pressure and flow rate, and injecting the explosive suspension slurry into the continuous phase circulation pipeline (2) at a certain speed;
s4 curing and forming energetic microspheres in pipeline
Adjusting the flow rate of the continuous phase to a required flow rate, enabling the explosive suspension slurry droplets to move in the pipeline along with the flow of the continuous phase fluid, gradually separating out the solvent from the droplets in the moving process, and completing liquid-solid phase conversion of the binding agent and the explosive in a suspension state under the action of the continuous phase fluid of the pipeline to form energetic microspheres;
s5, collecting and post-processing finished products
And (5) filtering and washing the finished product obtained in the step (S4), and putting the product into an oven for drying to obtain the energy-containing microsphere finished product.
5. The continuous preparation method of the multi-scale energetic microspheres according to claim 4, wherein the HLB value of the surfactant is 8 to 18, and the surfactant is at least one of a Tween series of polyoxyethylene fatty alcohol ether surfactants and alkyl glycoside compounds; the continuous phase solution is an aqueous solution of a high polymer material, the concentration of the aqueous solution is 2-5%, the high polymer material is required to be dissolved or swelled in water, and the content of the surfactant is 1-10% of that of the continuous phase solution; the heating temperature of the continuous phase fluid is 0 to 70 ℃.
6. The continuous preparation method of the multi-scale energetic microspheres according to claim 5, wherein the polymer material is polyvinyl alcohol or chitosan.
7. The continuous preparation method of the multi-scale energetic microspheres according to claim 4, wherein the oil phase solvent is required to be insoluble in water, the boiling point is lower than 100 ℃, the binder is one or more thermoplastic binders soluble in the oil phase solvent, and the concentration of the binder solution is 1-20%; the mass ratio of the explosive to the binder solution is 1/50 to 3/20.
8. The continuous preparation method of the multi-scale energetic microspheres according to claim 7, wherein the oil phase solvent is ethyl acetate or dichloromethane, and the binder is at least one of acrylic resin, polyurethane, phenolic resin, styrene butadiene rubber, polysulfide rubber, fluororubber and nitrocellulose.
9. The continuous preparation method of the multi-scale energetic microspheres according to claim 4, wherein the flow speed of the continuous phase fluid in the tube is 60-200 ml/min, the injection speed of the explosive suspension slurry is 0.01-0.5 ml/min, the temperature of the pipeline is 20-90 ℃, and the drying temperature of the oven is 40-90 ℃.
10. The continuous preparation method of the multi-scale energetic microspheres according to claim 9, wherein the flow speed of the continuous phase fluid in the tube is 90-120 ml/min; the injection speed of the explosive suspension slurry is 0.05 to 0.2 ml/min.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB201103365D0 (en) * | 2010-03-16 | 2011-04-13 | Qinetiq Ltd | MEMS detonator |
| AU2012356500A1 (en) * | 2011-12-22 | 2014-07-17 | Roxel (Uk Rocket Motors) Limited | Processing explosives |
| CN110357757A (en) * | 2019-07-23 | 2019-10-22 | 南京理工大学 | A kind of nanometer thermite preparation method based on block stream |
| CN113248338A (en) * | 2021-05-12 | 2021-08-13 | 中北大学 | Preparation system and method of HMX-based energetic microspheres based on droplet microfluidic technology |
| CN114100461A (en) * | 2020-08-28 | 2022-03-01 | 南京理工大学 | Preparation system and method of high polymer bonded explosive based on microfluidics |
-
2022
- 2022-09-21 CN CN202211147910.3A patent/CN115286473B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB201103365D0 (en) * | 2010-03-16 | 2011-04-13 | Qinetiq Ltd | MEMS detonator |
| AU2012356500A1 (en) * | 2011-12-22 | 2014-07-17 | Roxel (Uk Rocket Motors) Limited | Processing explosives |
| US20140367003A1 (en) * | 2011-12-22 | 2014-12-18 | Roxel (Uk Rocket Motors)Limited | Processing explosives |
| CN110357757A (en) * | 2019-07-23 | 2019-10-22 | 南京理工大学 | A kind of nanometer thermite preparation method based on block stream |
| CN114100461A (en) * | 2020-08-28 | 2022-03-01 | 南京理工大学 | Preparation system and method of high polymer bonded explosive based on microfluidics |
| CN113248338A (en) * | 2021-05-12 | 2021-08-13 | 中北大学 | Preparation system and method of HMX-based energetic microspheres based on droplet microfluidic technology |
Non-Patent Citations (3)
| Title |
|---|
| 刘换敏等: "微流控技术制备球形发射药及其表征", 含能材料, vol. 25, no. 9, pages 717 - 721 * |
| 周近强等: "液滴微流控技术制备TATB 基PBX 复合微球", 含能材料, vol. 30, no. 5, pages 439 - 445 * |
| 骆广生;兰文杰;李少伟;徐建鸿;吕阳成;: "微流控技术制备功能材料的研究进展", 石油化工, no. 01 * |
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