CN110231363B - Method for researching reaction mechanism of energetic material and evaluating safety - Google Patents

Method for researching reaction mechanism of energetic material and evaluating safety Download PDF

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CN110231363B
CN110231363B CN201910433410.8A CN201910433410A CN110231363B CN 110231363 B CN110231363 B CN 110231363B CN 201910433410 A CN201910433410 A CN 201910433410A CN 110231363 B CN110231363 B CN 110231363B
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energetic material
combustion chamber
pressure
visual
energetic
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CN110231363A (en
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汤成龙
杨猛
丁晓倩
杨锐
黄佐华
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Xian Jiaotong University
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    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N25/00Investigating or analyzing materials by the use of thermal means
    • G01N25/02Investigating or analyzing materials by the use of thermal means by investigating changes of state or changes of phase; by investigating sintering
    • G01N25/12Investigating or analyzing materials by the use of thermal means by investigating changes of state or changes of phase; by investigating sintering of critical point; of other phase change
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N25/00Investigating or analyzing materials by the use of thermal means
    • G01N25/18Investigating or analyzing materials by the use of thermal means by investigating thermal conductivity
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N25/00Investigating or analyzing materials by the use of thermal means
    • G01N25/20Investigating or analyzing materials by the use of thermal means by investigating the development of heat, i.e. calorimetry, e.g. by measuring specific heat, by measuring thermal conductivity
    • G01N25/22Investigating or analyzing materials by the use of thermal means by investigating the development of heat, i.e. calorimetry, e.g. by measuring specific heat, by measuring thermal conductivity on combustion or catalytic oxidation, e.g. of components of gas mixtures
    • G01N25/26Investigating or analyzing materials by the use of thermal means by investigating the development of heat, i.e. calorimetry, e.g. by measuring specific heat, by measuring thermal conductivity on combustion or catalytic oxidation, e.g. of components of gas mixtures using combustion with oxygen under pressure, e.g. in bomb calorimeter
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N33/00Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
    • G01N33/22Fuels; Explosives
    • G01N33/227Explosives, e.g. combustive properties thereof

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Abstract

The invention discloses a method for researching energetic material reaction mechanism and evaluating safety, which utilizes a fast compressor and a visual combustion chamber to realize the rapid and uniform thermal stimulation loading of energetic materials and the recording of the visual process of the reaction process, wherein the heating rate of thermal stimulation can reach 2 × 104K/s, thermodynamic parameters are easy to determine and control. The method is suitable for different types of energetic materials, and the shapes of the energetic materials are block-shaped, flocculent and powder. The dosage of the energetic material is 1-100mg, the cost is low, and the experimental safety coefficient is high. By using the method, the ignition boundary conditions and the reaction mechanism of the energetic material sample can be obtained by comparing different experimental results.

Description

Method for researching reaction mechanism of energetic material and evaluating safety
Technical Field
The invention belongs to the field of energetic material reaction mechanism and safety evaluation, and particularly relates to a method for researching energetic material reaction mechanism and safety evaluation, which is used for researching boundary conditions of ignition and non-ignition of energetic materials, chemical activity evaluation of energetic materials, guidance on safe use of energetic materials and the like.
Background
The energetic material is a compound or a mixture which contains explosive groups or oxidant and combustible substances, can independently carry out chemical reaction and output energy, and is an important component of military explosives, propellant powder and rocket propellant formulas. In the military field, energetic materials are a necessary trend. However, with the high energy of energetic materials, the safety of bombs, missiles and propellants is reduced, and the practicability of energetic materials is affected. The risk of the NEPE which is a high-energy propellant with the specific impulse of 255s is measured to be gradually increased (being a dangerous article of grade 1.1); the loading of the remote rocket and the medium-remote missile is increased from hundreds of kilograms to dozens of tons; furthermore, the burning rate of the propellant increases from 2mm/s to 100 mm/s. Such energetic materials can be very serious when subjected to thermal or shock stimuli. Therefore, it is necessary to research the reaction mechanism and safety evaluation of energetic materials stimulated by external conditions according to the development trend of energetic materials.
At present, the response mechanism of external stimulation of energetic materials and a safety evaluation method are mainly baking and burning. The fire-baking test is designed for the possibility that energetic materials are subjected to unexpected thermal stimulation in manufacturing, storage, transportation and actual combat environments, and is used for testing the sensitivity of ammunition to the unexpected thermal stimulation and the severity of the reaction. Generally, the baking test is divided into slow baking and fast baking. The slow-burning test is mainly used for researching the reaction type of the energetic material when the energetic material is subjected to external slow heating. The burning time is usually several hours or even tens of hours. The kinetic parameters related to the energetic material, such as activation energy, pre-exponential factors, heat of formation and the like, can be obtained at the same time through slow baking. Because the slow baking time is long, the environmental variables in the experimental process are not easy to control; unlike the slow fire experiments, the fast fire experiments primarily evaluated the extent of reaction of energetic materials when subjected to an external fire. And the energetic material has a temperature gradient under the condition of quick roasting combustion. When the safety test of the energetic material is carried out by using the roasting and burning method, the sample demand is large, the safety of the experiment is poor, and the cost is high. At the same time, the response of energetic materials to rapid thermal and force stimuli in manufacturing, storage, transportation, and practical environments has yet to be studied. The research on the reaction process, rule and mechanism of the energetic material under the external stimulation is lacked. At present, only by means of macroscopic experience, measures can be taken to prevent accidents, the critical threshold value of energetic material reaction cannot be effectively quantized, the occurrence of combustion or detonation cannot be fundamentally controlled, and the development progress of high-performance weapons is restricted.
In conclusion, a new rapid and uniform thermal stimulation mode is developed, so that the sample amount of the energetic material for the test is small, the thermodynamic state is clear, and the research on the reaction mechanism and the safety performance of the energetic material to the thermal stimulation has important practical significance.
Disclosure of Invention
The invention aims to provide a method for researching a reaction mechanism of an energetic material and evaluating safety. The method utilizes the characteristics of a quick compressor device to realize the purposes of high test safety, small sample amount of energetic materials, quick and uniform thermal stimulation and the like.
The invention is realized by adopting the following technical scheme:
a method for researching a reaction mechanism of an energetic material and evaluating safety comprises the following steps:
1) in order to research the reaction mechanism and safety of the energetic material, firstly, determining the type, shape and weight of an energetic material sample;
2) determining the components of mixed gas in the visual combustion chamber of the rapid compressor, namely determining the volume fractions X1 and X2 of oxygen and diluent gas;
3) determining total pressure P of the mixture in the visual combustion chamber of the rapid compressor, and calculating respective partial pressure according to the volume fraction of each gas in the step 2) by using a partial pressure formula Pi-P × Xi, i-1, 2;
4) placing the energetic material sample into a visual combustion chamber of a rapid compressor device, and sealing the visual combustion chamber through an end cover;
5) after the sealed visual combustion chamber is vacuumized by a vacuum pump, a pressure value a0 in the combustion chamber is recorded by a pressure sensor;
6) filling oxygen into the visual combustion chamber until the reading of a pressure gauge is a1, so that a1-a0 is P1;
7) filling a diluent gas into the visual combustion chamber until the reading of a pressure gauge is a2, so that a 2-a 1 is P2;
8) compressing the energetic material sample and the mixed gas in the visual combustion chamber by using a rapid compressor, recording the change of the pressure in the visual combustion chamber by using a pressure sensor in the compression process, and synchronously shooting and recording the reaction process of the energetic material sample in the thermal loading process by using a high-speed camera;
9) determining thermodynamic parameters of the experimental compression end point, namely compression end point pressure, wherein the pressure curve recorded by the pressure sensor is obtained, and the compression end point temperature is obtained by calculation through an ideal gas adiabatic equation;
10) and judging whether the energetic material sample catches fire under the thermodynamic condition of the experiment or not through a pressure curve recorded by the pressure sensor and a reaction process recorded by the high-speed camera.
The invention has the further improvement that the reaction mechanism of the energetic material is the corresponding law of energetic materials with different types, shapes and weights on thermal stimulation and the effects of heat transfer, phase change and interface reaction in the combustion process.
The invention further improves the safety evaluation of the energetic material, namely obtaining the critical thermodynamic threshold value of the ignition result and failure of the energetic material and establishing an empirical model of the critical threshold value.
The invention further improves that the energetic material samples are explosives, propellant powder and rocket propellant.
The invention further improves that the energetic material is in the shapes of block, floccule and powder.
The invention is further improved in that the weight of the energetic material is 1-100 mg.
In a further development of the invention, the visual combustion chamber is a cylindrical combustion chamber with a quartz glass window.
In a further improvement of the invention, the diluent gas is nitrogen, argon or carbon dioxide.
The invention has the following beneficial technical effects:
1) according to the invention, the boundary condition of the energetic material sample on fire can be accurately found, and important contribution is made to safety performance evaluation. Meanwhile, the reaction mechanism of the energetic material can be more clearly and visually explained according to the pictures shot by the high-speed camera.
2) The invention provides a rapid and uniform thermal stimulation environment by using the rapid compression device, and the heating rate can reach 2 × 104K/s, simple operation and easy control of thermodynamic parameters.
3) The energy-containing sample for the experiment is only 1-100mg, the experiment is safe and reliable, and the cost is low.
4) By adjusting different proportions of diluent gases such as argon, nitrogen, carbon dioxide and the like, the response condition of the energetic material sample in different thermodynamic states is realized.
Drawings
Fig. 1 is a schematic view of a configuration of a rapid compressor used in the present invention.
Fig. 2 is a schematic view of a visual combustion chamber used in the present invention.
FIG. 3 shows NC/NG samples of different shapes used in example 1 of the present invention, in which FIG. 3(a) shows a block shape, FIG. 3(b) shows a floc shape, and FIG. 3(c) shows a powder shape.
Fig. 4 is a pressure curve of NC/NG samples of different shapes obtained by a pressure sensor in embodiment 1 of the present invention.
Fig. 5 is a pressure curve of different samples obtained by using a pressure sensor in embodiment 2 of the present invention.
Fig. 6 is a pressure curve of different thermodynamic parameters obtained by using a pressure sensor in embodiment 3 of the present invention.
Detailed Description
The present invention will be described in further detail with reference to the following drawings and examples.
As shown in fig. 1-2, the structural schematic diagram of the rapid compressor and the visual combustion chamber used in the present invention includes an oil tank 1, a compression cylinder 2, a visual combustion chamber system 3, a light source 4, a high-speed camera 5, a first lens 6, a control and acquisition system 7, an oil cylinder 8, a connecting rod 9, a driving cylinder 10, a metal hose 11, a high-pressure air storage tank 12, an air compressor 13, a manual butterfly valve 14, an electric butterfly valve 15, a visual combustion chamber 16, a bolt hole 17, an object stage 18, a fixing bolt 19, an energetic material sample 20, a quartz glass 21, a sealing ring 22, a window end cover 23, a first reflector 24, a second reflector 25, and a second lens 26.
A certain amount of gas is filled into the high-pressure gas storage tank 12 through the air compressor 13 to serve as a driving source, the pressure is kept basically constant in the process of driving the piston, the high-pressure gas storage tank 12 is directly connected with the driving cylinder 10, and the middle of the high-pressure gas storage tank is provided with an electric butterfly valve 15 for blocking the high-pressure gas. Then, the oil cylinder 8 is supplied with a sufficient oil pressure by the oil supply system to withstand the driving pressure of the right high pressure air tank 12, and the electric butterfly valve 15 between the high pressure air tank 12 and the driving cylinder 10 is in an open state. Therefore, the high-pressure gas in the high-pressure gas storage tank 12 is directly contacted with the driving piston in the driving cylinder 10, and the driving piston can be smoothly pushed forward under the driving of the high-pressure gas after the compression starts. The gas-driven process is substantially complete at this point. Next, in fig. 2, an energetic material sample 20 is placed in the center of a quartz glass 21 by means of a stage 18. The quartz glass 21 and the visual combustion chamber 16 are fixed by fixing bolts 19. The light source 4 is turned on, light generated by the light source 4 is emitted into the visual combustion chamber 16 through one quartz glass 21 by the first lens 6 and the first reflector 24 to illuminate the energetic material sample 20, and the light is emitted from the other quartz glass 21 and absorbed by the high-speed camera 5 through the second reflector 25 and the second lens 26 to form an image. And finally, the control and acquisition system 7 simultaneously controls an oil drainage solenoid valve, a pressure sensor and the high-speed camera 5 in the hydraulic system. The electromagnetic valve is controlled to be opened through a computer, high-pressure oil built in the oil cylinder 8 flows back to the oil tank 1 through the oil return pipe, the oil pressure in the oil cylinder 8 is rapidly reduced, and the driving force generated by high-pressure gas in the driving cylinder 10 is higher than the force generated by hydraulic oil in the oil cylinder 8 for stopping the movement of the piston. Therefore, the driving piston can rapidly advance under the driving of the high-pressure gas, so that instant pressure impact on the energetic material sample 20 in the visual combustion chamber 16 is realized, and meanwhile, the pressure sensor arranged on the visual combustion chamber 16 and the high-speed camera 5 synchronously acquire pressure data and image information.
Example 1:
as shown in FIG. 3, block, flocculent, and powder samples of energetic material NC/NG were prepared at 30mg each. The composition of the mixed gas in the visual combustion chamber of the rapid compressor is determined to be 0.21bar of oxygen, and 0.78bar of nitrogen and 0.5bar of argon are used as diluent gas. Placing a block energetic material sample NC/NG 30mg on a visual combustion chamber objective table, and sealing the visual combustion chamber by using an end cover.
The visual combustion chamber is evacuated by a vacuum pump, and the pressure value in the combustion chamber is recorded by a pressure sensor to be 0.006 bar. The combustion chamber was charged with oxygen until the pressure gauge reading was 0.216bar, with nitrogen continuing until the pressure gauge reading was 0.996bar, and finally with argon until the pressure gauge reading was 1.496 bar.
And compressing the block NC/NG sample and the mixed gas in the visual combustion chamber by using a rapid compressor. The pressure profile of the compression process was recorded by means of a pressure sensor, as shown by the black curve in fig. 4. The compression end pressure was found to be 27.3bar by the pressure curve and the compression end temperature was found to be 720K calculated from the ideal gas adiabatic equation. If the pressure after the end of compression recorded by the rapid compressor tends to rise, it indicates that the energetic material is on fire. The absence of a pressure rise indicates that the energetic material is safe and no fire occurs. The pressure curve can judge that the 30mg block energetic material sample NC/NG does not catch fire under the thermodynamic condition, and belongs to a safe sample.
The above steps are repeated to sequentially carry out reaction mechanism and safety evaluation experiments of the NC/NG sample under the same mass of 30mg under the shapes of flocculent and powder. The resulting pressure curves are shown in red and blue in figure 4. By comparing the pressure curves of the NC/NG energetic material samples in three different shapes, the NC/NG samples in different shapes have different reaction mechanisms and different safety performances. The block NC/NG is most stable, and the safety factor is high. And the flocculent NC/NG has the highest reaction activity, is most easy to burn and has poor safety.
Example 2:
powdery energetic material samples RDX and NC/NG were prepared at 20mg each. The composition of the mixed gas in the visual combustion chamber of the rapid compressor is determined to be 0.21bar of oxygen, and 0.78bar of nitrogen and 0.5bar of argon are used as diluent gas. And putting the powdery energetic material sample RDX 20mg on a visual combustion chamber objective table, and sealing the visual combustion chamber by using an end cover.
The visual combustion chamber is vacuumized by a vacuum pump, and the pressure value in the combustion chamber is recorded by a pressure sensor to be 0.0058 bar. The combustion chamber was charged with oxygen until the pressure gauge read 0.2158bar, with continued charging of nitrogen until the pressure gauge read 0.9958bar, and finally with argon until the pressure gauge read 1.4958 bar.
And compressing the powdery RDX sample and the mixed gas in the visual combustion chamber by using a rapid compressor. The course of the compression process pressure is recorded by means of a pressure sensor, as shown by the blue curve in fig. 5. The compression end pressure was found to be 27.0bar by the pressure curve and the compression end temperature was found to be 718K by calculation according to the ideal gas adiabatic equation. The pressure curve can judge that the 20mg powdery energetic material sample RDX does not catch fire under the thermodynamic condition, and belongs to a safe sample.
The above steps were repeated to conduct the reaction mechanism and safety evaluation experiments of NC/NG samples in the form of powder at the same mass of 20 mg. The resulting pressure curve is shown in red in fig. 5. By comparing the pressure curves of two different energetic material samples, the NC/NG sample in the same shape is spontaneously combusted, and the pressure curve after the compression end point has a rising trend and is low in safety. For the RDX sample, the pressure curve after compression does not rise, which indicates that no combustion occurs and the safety is high. The RDX sample under the same experimental conditions is more stable and safer than the NC/NG sample.
Example 3:
powdery energetic material samples NC/NG were prepared at 20 mg. The composition of the mixed gas in the visual combustion chamber of the rapid compressor is determined to be 0.21bar of oxygen, and 0.78bar of nitrogen is used as the diluent gas. Placing a powdery energetic material sample NC/NG (20 mg) on a visual combustion chamber objective table, and sealing the visual combustion chamber by using an end cover.
And (3) vacuumizing the visual combustion chamber by using a vacuum pump, and recording a pressure value of 0.0061bar in the combustion chamber through a pressure sensor. The combustion chamber was charged with oxygen until the pressure gauge read 0.2161bar and continued to be charged with nitrogen until the pressure gauge read 0.9961 bar.
And compressing the powdery NC/NG sample and the mixed gas in the visual combustion chamber by using a rapid compressor. The course of the compression process pressure is recorded by means of a pressure sensor, as shown by the blue curve in fig. 6. The compression end pressure was found to be 16.0bar by the pressure curve and the compression end temperature was found to be 638K by calculation according to the ideal gas adiabatic equation. The 20mg powdery energetic material sample NC/NG can be judged to be safe because no fire occurs under the thermodynamic condition through the pressure curve.
The above steps were repeated to perform the reaction mechanism and safety evaluation test of the NC/NG sample in the form of powder of the same mass of 20mg, at which the composition of the mixed gas was 0.21bar of oxygen, 0.78bar of nitrogen and 0.5bar of argon. The resulting pressure curve is shown in red in fig. 5. By comparing the pressure curves of energetic material samples under two different gas mixture ratios, the NC/NG sample under the thermodynamic condition of 27bar and 718K is found to be spontaneously combusted, and the pressure curve after the compression end point has rising tendency and low safety. And for the NC/NG sample under the thermodynamic condition of 16bar and 638K, the pressure curve after compression does not rise, which indicates that no combustion occurs and the safety is high.

Claims (8)

1. A method for researching a reaction mechanism of an energetic material and evaluating safety is characterized by comprising the following steps:
1) in order to research the reaction mechanism and safety of the energetic material, firstly, determining the type, shape and weight of an energetic material sample;
2) determining the components of mixed gas in the visual combustion chamber of the rapid compressor, namely determining the volume fractions X1 and X2 of oxygen and diluent gas;
3) determining total pressure P of the mixture in the visual combustion chamber of the rapid compressor, and calculating respective partial pressure according to the volume fraction of each gas in the step 2) by using a partial pressure formula Pi-P × Xi, i-1 and 2;
4) placing the energetic material sample into a visual combustion chamber of a rapid compressor device, and sealing the visual combustion chamber through an end cover;
5) after the sealed visual combustion chamber is vacuumized by a vacuum pump, a pressure value a0 in the combustion chamber is recorded by a pressure sensor;
6) filling oxygen into the visual combustion chamber until the reading of a pressure gauge is a1, so that a1-a0 is P1;
7) filling a diluent gas into the visual combustion chamber until the reading of a pressure gauge is a2, so that a 2-a 1 is P2;
8) compressing the energetic material sample and the mixed gas in the visual combustion chamber by using a rapid compressor, recording the change of the pressure in the visual combustion chamber by using a pressure sensor in the compression process, and synchronously shooting and recording the reaction process of the energetic material sample in the thermal loading process by using a high-speed camera;
9) determining thermodynamic parameters of the experimental compression end point, namely compression end point pressure and compression end point temperature, wherein the compression end point pressure is obtained through a pressure curve recorded by a pressure sensor, and the compression end point temperature is obtained through calculation of an ideal gas adiabatic equation;
10) and judging whether the energetic material sample catches fire under the thermodynamic condition of the experiment or not through a pressure curve recorded by the pressure sensor and a reaction process recorded by the high-speed camera.
2. The method for researching the reaction mechanism and safety evaluation of the energetic material according to claim 1, wherein the reaction mechanism of the energetic material is the corresponding law of energetic materials with different types, shapes and weights on thermal stimulation and the effects of heat transfer, phase change and interface reaction in a combustion process.
3. The method of claim 1, wherein the energetic material safety assessment is an empirical model for obtaining a critical thermodynamic threshold for success and failure of ignition of the energetic material and establishing a critical threshold.
4. The method of claim 1, wherein the energetic material sample is selected from the group consisting of explosives, propellants and rocket propellants.
5. The method of claim 1, wherein the energetic material is in the form of block, flake or powder.
6. The method for studying the reaction mechanism and safety evaluation of the energetic material according to claim 1, wherein the weight of the energetic material is 1-100 mg.
7. The method of claim 1, wherein the visual combustion chamber is a cylindrical combustion chamber with a quartz glass window.
8. The method of claim 1, wherein the diluent gas is nitrogen, argon or carbon dioxide.
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CN112611782A (en) * 2020-11-30 2021-04-06 北京理工大学 Dynamic manometric thermal analysis method for low-melting-point and volatile energetic material
CN116696609B (en) * 2023-06-02 2024-04-09 西安交通大学 Method for simulating and analyzing ignition process of propellant in solid rocket engine

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