CN112033997A - Explosive thermal stability grading method based on differential scanning calorimetry - Google Patents

Explosive thermal stability grading method based on differential scanning calorimetry Download PDF

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CN112033997A
CN112033997A CN202010827599.1A CN202010827599A CN112033997A CN 112033997 A CN112033997 A CN 112033997A CN 202010827599 A CN202010827599 A CN 202010827599A CN 112033997 A CN112033997 A CN 112033997A
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丁黎
黄蒙
禄旭
周静
安静
华栋
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Xian Modern Chemistry Research Institute
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Abstract

The method obtains the thermal decomposition reaction kinetic parameters according to the thermal decomposition characteristic quantity of the materials in the explosive manufacturing process, and further obtains the maximum reaction rate reaching time TMR of different danger levels under the heat insulation conditionadRequired process temperature TpAnd process temperature T in different hazard classespThe specific operation time is taken as a scale, and the actual process temperature T of the materials in the process is compared and measuredpsAnd actual process operating time tsQuantitatively obtaining the temperature correction coefficient gamma of the thermal stability of the material1And correcting the coefficient gamma by the temperature1And performing quantitative grading evaluation as the thermal stability grade of the materials in the process.

Description

Explosive thermal stability grading method based on differential scanning calorimetry
Technical Field
The invention belongs to the technical field of explosives and powders, and mainly relates to a process temperature T with different danger gradespAnd a new method for testing and grading evaluation of thermal stability of materials in the process of manufacturing explosives and powders by using a specific operation time coefficient as a scale, in particular to a method for grading the thermal stability of explosives and powders based on differential scanning calorimetry.
Background
The explosives and powders as energetic materials have the characteristics of easy combustion and explosion under the stimulation action of heat, static electricity, machinery and the like, and the development of combustion and explosion risk evaluation in the explosive and powder manufacturing process is an important content for safety production design and management and control. Materials in the process of manufacturing the explosives and powders are poor thermal conductors and are extremely sensitive to thermal stimulation, autocatalytic decomposition exothermic reaction can occur when the materials are heated, thermal explosion caused by heat accumulation is extremely easy to generate, and the thermal explosion is an inducing factor of a large number of safety accidents, so that the evaluation of the risk of combustion and explosion in the process first needs quantitative grading evaluation on the thermal stability of the materials in the process. The invention carries out quantitative grading evaluation on the thermal stability of the materials in the process of the process aiming at the explosive materials.
In order to qualitatively know and quantitatively estimate the risk of combustion and explosion, a quantitative assessment method for major hazard sources of fire and explosive and product enterprises (BZA for short) is made in China according to the characteristics of weapon fire and explosive and ammunition enterprises and by referring to the assessment experience abroad-1Method). BZA-1The hazard source evaluation mathematical model and the physical significance proposed by the method are as follows:
H＝Hinner part+HOuter cover (1)
In the formula: h is the actual risk of the explosion hazard system, HInner partIs the real risk level in the system, HOuter coverThe risk degree is the real risk degree outside the system.
Wherein HInner partThe calculation method of (2) is as follows:
Hinner part＝V+KB (2)
In the formula: v is a material risk coefficient, namely the inherent static risk degree of the explosive, K is a controllable risk behavior controlled degree coefficient in the system, and B is the controllable risk degree in the system.
The controllable risk degree B in the system is calculated by the following formula:
B＝WB·D·P (3)
in the formula: wBThe calculation formula of the material energy danger coefficient of the explosive and the device thereof is shown in the specification.
WB＝V·γ (4)
Wherein gamma is a process risk coefficient, and the calculation formula is as follows:
γ＝γ1+γ2+γ3+γ4+γ5 (5)
in the formula: gamma ray1Is a temperature correction coefficient, which is positively correlated with the temperature rise, gamma2For correction of coefficients by chemical agents, gamma3As a coefficient of compression correction, gamma4Correction of the coefficient for other mechanical effects (e.g. cutting, drilling, sawing, abrading, etc.), gamma5Is the static electricity correction coefficient.
Temperature correction coefficient gamma related to thermal stability in the current technological process1The value conditions are as follows (see table 1) table 1 shows the value conditions of the risk coefficient gamma of the process
Figure BDA0002636774880000021
As can be seen from Table 1, the temperature correction coefficient γ1The determination method is a semi-quantitative method, although corresponding evaluation parameter values exist, the actual operability is poor, the values cannot be accurately quantized one by one, the concept of the value condition is ambiguous, the quantitative criterion is lacked, and the risk degree of the process material is difficult to evaluate by effectively combining with the actual process condition.
As the materials in the process of manufacturing the explosives and powders are energetic materials and can be decomposed and exothermally reacted under the action of heat to cause combustion and explosion accidents, whether the materials can keep stable after being stimulated by the process temperature in the process of the materials is one of important indexes of process dangerousness, therefore, accurate evaluation of the thermal stability is an important way for realizing the intrinsic process safety, and scientific basis is provided for quantitative evaluation of the dangerousness, formulation of early warning and prevention and control measures of the whole process production line, so that a quantitative grading method for the thermal stability of the materials in the process of manufacturing the explosives and powders is urgently needed.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a process temperature T with different danger levelspAnd a specific operating time coefficient ofThe scale is a method for testing and grading the thermal stability of materials in the explosive manufacturing process. According to the thermal decomposition characteristic quantity of the materials in the process of manufacturing the explosives and powders at different heating rates, the thermal decomposition reaction kinetic parameters are obtained, and further the maximum reaction rate reaching time TMR of different danger levels under the adiabatic conditions is obtainedadRequired process temperature TpAnd process temperature T in different hazard classespAnd the specific operation time coefficient is used as a scale for comparing and measuring the actual process temperature T of the materials in the processpsAnd actual process operating time tsQuantitatively obtaining the temperature correction coefficient gamma of the thermal stability of the material1And performing quantitative grading evaluation as the thermal stability grade of the materials in the process.
In order to realize the task, the invention adopts the following technical scheme:
a method for grading thermal stability of explosives and powders based on differential scanning calorimetry comprises the steps of testing thermal decomposition reaction of materials by adopting the differential scanning calorimetry or thermal weight loss test to obtain thermal decomposition characteristic quantities at different heating rates, and obtaining kinetic parameter apparent activation energy E of the thermal decomposition reaction of the materials according to Kissinger equation regressionaAnd a pre-exponential factor A, and further obtaining the maximum reaction rate reaching time TMR of adiabatic conditions with different danger levelsadRequired process temperature TpProcess temperature T at different hazard classespAnd the specific operation time coefficient is used as a scale for comparing and measuring the actual process temperature T of the materials in the processpsAnd actual process temperature time tsQuantitatively obtaining material temperature correction coefficient gamma1And performing quantitative grading evaluation as the thermal stability grade of the materials in the process. The flow chart of the classification scheme of the thermal stability of the explosive material is shown in figure 1 and is specifically carried out according to the following steps.
Further, the method for grading the thermal stability of the explosives and powders based on differential scanning calorimetry specifically comprises the following technical steps:
step one, obtaining apparent activation energy E of material thermal decomposition reaction kinetic parameters in the explosive manufacturing process through a differential scanning calorimetry testaAnd pre-finger factor a.
Utilizing a differential scanning calorimetry test to obtain the thermal decomposition reaction of the materials in the explosive manufacturing process, and obtaining the peak temperature of the exothermic reaction which causes the materials to be rapidly decomposed; obtaining the kinetic parameter apparent activation energy E of the material thermal decomposition reaction by using Kissinger equation formula (I) regressionaAnd pre-finger factor a.
Figure BDA0002636774880000041
In the formula: beta is aiThe heating rate is K/s; t isiTo decompose the peak temperature, K, A is a pre-exponential factor, s-1；EaIs the apparent activation energy of the reaction, J/mol; r is a gas constant, J/(mol. K); then is formed by
Figure BDA0002636774880000042
To pair
Figure BDA0002636774880000043
Drawing to obtain a straight line, and calculating E from the slope of the straight lineaA is determined from the intercept.
Obtaining TMR (maximum reaction rate arrival time) of materials under different danger grades of adiabatic conditionsadRequired process temperature Tp。
TMRadThe formula (c) is shown in formula (ii):
Figure BDA0002636774880000044
in the formula: eaIs apparent activation energy, J/mol; a is a pre-exponential factor, s-1；TpIs the process temperature, K; r is a gas constant, J/(mol. K); cpThe specific heat capacity of the materials, J/(g.K); qrThe specific heat release of the material thermal decomposition is J/g.
TMR adopts 6 grade criterion proposed by Zurich Hazard Analysis as judgment conditionadThe divided key nodes are respectively 100h, 50h, 24h, 12h, 8h and 1h, and are represented by a formula(7) Respectively obtain up to 6 TMRsadRequired process temperature TpSequentially comprises the following steps: t isD100、TD50、TD24、TD12、TD8、TD1。
Step three, reaching time TMR of maximum reaction rate under 6 adiabatic conditions with different danger levelsadTemperature T of the dividing processpAt a process temperature TpFor a scale, the actual process temperature T of the materials is compared and measuredpsQuantitatively obtaining the material temperature correction coefficient gamma1And determining a grading scheme of the thermal stability of the material.
Due to TMRadProcess temperature T required for 100hpIs TD100Thus, for TMRadNot less than 100h, when the actual process temperature T of the material isps≤TD100When, gamma 11, the thermal stability of the material is grade 1;
due to TMRad50h required process temperature TpIs TD50Thus, for a TMR of 50h ≦adLess than 100h, when the actual process temperature T of the materialD100＜Tps≤TD50When, gamma 12, the thermal stability of the material is grade 2;
due to TMR ad24h required process temperature TpIs TD24Thus, for a TMR of 24h ≦adLess than 50h, when the actual process temperature T of the materialD50＜Tps≤TD24When, gamma1The thermal stability of the material is grade 3;
due to TMRadProcess temperature T required for 12hpIs TD12Thus, for a TMR of 12h ≦adLess than 24h, when the actual process temperature T of the material isD24＜Tps≤TD12When, gamma 14, the thermal stability of the material is grade 4;
due to TMRadProcess temperature T required for 8hpIs TD8Thus, for 8h ≦ TMRadLess than 12h, when the actual process temperature T of the material isD12＜Tps≤TD8When, gamma1The thermal stability of the material is grade 5 ═ 5；
Due to TMR ad1h required process temperature TpIs TD1Thus, for 1h ≦ TMRadLess than 8h, when the actual process temperature T of the material isD8＜Tps≤TD1When, gamma16-9, wherein the thermal stability of the material is 6-9 grade;
due to TMR ad1h required process temperature TpIs TD1Thus, for TMRadLess than 1h, when the actual process temperature T of the materialps＞TD1When, gamma1The thermal stability of the material is 10 grades.
Correction coefficient gamma of material temperature1The values of (a) and the thermal stability classification scheme are shown in table 2.
TABLE 2 temperature correction coefficient gamma for explosives and powders1Grading scheme for value taking and thermal stability
TMRad Tps γ1 Thermal stability grade of material
TMRad≥100h Tps≤TD100 1 1
50h≤TMRad＜100h TD100＜Tps≤TD50 2 2
24h≤TMRad＜50h TD50＜Tps≤TD24 3 3
12h≤TMRad＜24h TD24＜Tps≤TD12 4 4
8h≤TMRad＜12h TD12＜Tps≤TD8 5 5
1h≤TMRad＜8h TD8＜Tps≤T D1 6～9 6～9
TMRad＜1h Tps＞TD1 10 10
Further, the material temperature is corrected by a coefficient gamma1When the value range is 6-9, namely the actual process temperature TD8＜Tps≤TD1At specific operating times of different hazard classesThe coefficient is a scale, and the material temperature correction coefficient gamma is further quantitatively obtained1。
γ1When the value range is 6-9, TMR is utilizedadAnd further determining the operation time in the actual process of the material, and calculating a specific operation time coefficient by a formula (III):
Figure BDA0002636774880000061
in the formula: TMRadThe time for the maximum reaction rate to reach adiabatic conditions at the process temperature, h; t is the operation time of the material in the process, h. The physical meaning of the specific operation time coefficient is the safety margin of the process operation time, the specific operation time coefficient is 1, 2.5 and 4 times of the safety margin, namely the specific operation time coefficient is 2.54 and 4 is used as a scale, the material danger grades are divided, and the material temperature correction coefficient gamma is1The values at 6-9 hours and the thermal stability ratings are shown in Table 3.
TABLE 3 temperature correction coefficient gamma for explosive materials1Value taking scheme at 6-9 hours
δ δ＜1 1≤δ＜2.5 2.5≤δ＜4 δ＞4
γ 1 6 7 8 9
Grade of thermal stability of material 6 7 8 9
Compared with the prior art, the method for grading the thermal stability of explosives and powders based on differential scanning calorimetry has the following beneficial technical effects:
1. temperature correction coefficient gamma of the invention1The process temperatures of different danger levels are used as a measuring scale for determining, the process temperatures are obtained from thermal decomposition kinetic parameters based on the intrinsic thermal decomposition characteristics of materials in the explosive manufacturing process, the material attributes of different process production lines are reflected by combining process conditions, and the method has universality and is suitable for evaluating the thermal stability of the materials in the different explosive manufacturing process.
2. Temperature correction coefficient gamma of the invention1The process and specific operation time coefficient required by the maximum reaction rate reaching time of the adiabatic conditions with different danger levels is determined within the range of 6-9, wherein the specific operation time coefficient scale is determined based on the safety margin of the process operation time, and the actual process temperature and the actual operation time are evaluated, so that the evaluation of the thermal stability of the material is comprehensive and reliable, and the operability is high.
3. Temperature correction coefficient gamma for quantitatively obtaining stability of material1And the thermal stability of the materials in the process is evaluated in a grading manner, so that a scientific basis is provided for quantitative risk assessment, early warning and prevention and control measures of the whole process production line.
4. The invention adopts TMR (maximum reaction rate arrival time) under adiabatic conditionadDetermining a temperature correction coefficient gamma according to the corresponding temperature1The value range of (A) is the most severe condition that the heat generated by the decomposition reaction of the materials under the adiabatic condition is not dissipatedThe temperature obtained under the adiabatic condition is the most conservative temperature, the grading result of evaluating the thermal stability of the material is conservative, and the reliability of safe use is high.
Drawings
FIG. 1 is a flow chart of a thermal stability classification scheme for explosives and powders of the present invention;
FIG. 2 is a DSC curve showing the temperature rise rate beta of the GX modified double-base propellant material of the embodiment of the present invention at 2.5, 5, 10 and 20 ℃/min;
FIG. 3 kinetic parameters of the thermal decomposition reaction of an example GX modified biradical propellant material of the present invention;
the invention is described in further detail below with reference to the accompanying drawings and specific embodiments.
Detailed Description
Example 1
The invention relates to a method for testing and grading the thermal stability of materials in the process of manufacturing explosives and powders, which comprises the following steps: the material in the GX modified double-base propellant manufacturing process is taken as a research object, the material thermal decomposition reaction is tested by adopting a differential scanning calorimetry method to obtain the thermal decomposition characteristic quantity at different heating rates, and the kinetic parameter apparent activation energy E of the material thermal decomposition reaction is obtained according to Kissinger equation regressionaAnd a pre-exponential factor A, thereby obtaining TMR between the arrival of maximum reaction rates of adiabatic conditions of different danger levelsadRequired process temperature TpAnd process temperature T in different hazard classespAnd the specific operation time coefficient is used as a scale for comparing and measuring the actual process temperature T of the materials in the processpsAnd actual process temperature time tsQuantitatively obtaining material temperature correction coefficient gamma1And correcting the coefficient gamma by the temperature1And performing quantitative grading evaluation as the thermal stability grade of the materials in the process. Temperature correction coefficient gamma1The determination flowchart is shown in fig. 1, and is specifically performed according to the following steps:
the method comprises the following steps: differential scanning calorimetry test for obtaining apparent activation energy E of material thermal decomposition reaction kinetic parameters in GX modified double-base propellant formula manufacturing processaAnd pre-finger factor a.
Performing Differential Scanning Calorimetry (DSC) tests by using a Differential Scanning Calorimeter (DSC), and performing temperature programmed test on the material thermal decomposition reaction at a temperature rise rate β of 2.5, 5, 10, 20 ℃/min, respectively, to obtain a thermal decomposition curve as shown in fig. 2, wherein the material has two exothermic peaks in the thermal decomposition process, the first exothermic heat of decomposition of the material causes the subsequent material to rapidly decompose and cause the subsequent material to rapidly release heat, so that kinetic parameters are calculated by using the peak temperature of the first exothermic peak, and the peak temperatures are shown in table 4:
TABLE 4 exothermic peak temperatures of the GX modified biradical propellant formulations at different ramp rates to cause rapid decomposition of the material
β[℃/min] T1[℃]
2.5 195.3
5 202.8
10 206.7
20 214.6
Obtaining the kinetic parameter apparent activation energy E of the material thermal decomposition reaction by adopting Kissinger equation formula (I) regressionaAnd pre-finger factor a:
Figure BDA0002636774880000081
in the formula: beta is aiThe heating rate is K/s; t isiDecomposition peak temperature, K; a is a pre-exponential factor, s-1；EaTo react
Apparent activation energy, J/mol; r is a gas constant, J/(mol. K); then is formed by
Figure BDA0002636774880000082
To pair
Figure BDA0002636774880000083
Plotting, a straight line can be obtained, and as shown in FIG. 3, the apparent activation energy E is obtained from the slope of the straight linea201.42kJ/mol, the pre-factor A is determined from the intercept46.32 s-1。
Step two: TMR for obtaining maximum reaction rate reaching time under adiabatic condition of different danger gradesadRequired process temperature Tp。
TMRadIs calculated as follows:
Figure BDA0002636774880000084
in the formula: eaIs apparent activation energy, J/mol; a is a pre-exponential factor, s-1；TpIs the process temperature, K; r is a gas constant, J/(mol. K); cpSpecific heat capacity of material, J/(g.K), QrThe specific heat release of the material thermal decomposition is J/g.
Will have apparent activation energy Ea201.42kJ/mol, meaning that the factor A is e46.32 s-1The gas constant R is 8.314J/(mol.K), and the specific heat capacity of the explosive material is CpCalculated as 2J/(kg. K), the heat release Q of the material pyrolysisrThe maximum reaction rate reaching time TMR of adiabatic conditions under 6 different danger grades is calculated and obtained by substituting the formula (7) into 1994.4J/gadThe required process temperature T is 100h, 50h, 24h, 12h, 8h and 1h respectivelyD100，TD50，TD24，TD12，TD8，TD1:
TMRadProcess temperature T required for 100hpIs TD100＝104.0℃，
TMRadThe required process temperature T is 50hpIs TD50＝108.3℃，
TMRadProcess temperature T required at 24hpIs TD24＝112.8℃，
TMRadProcess temperature T required for 12hpIs TD12＝117.3℃，
TMRadProcess temperature T required for 8hpIs TD8＝120.0℃，
TMRadProcess temperature T required for 1hpIs TD1＝134.2℃。
Step three: maximum reaction rate arrival time TMR at 6 adiabatic conditions of different hazard classesadTemperature T of the dividing processpAt a process temperature TpFor a scale, the actual process temperature T of the materials is compared and measuredpsQuantitatively obtaining the material temperature correction coefficient gamma1Determining a grading scheme of the thermal stability of the material:
due to TMRadProcess temperature T required for 100hpIs TD100104.0 ℃, hence, for TMRadNot less than 100h, when the actual process temperature T of the material isps≤TD100I.e. Tps≤104.0℃，γ1The thermal stability of the material is grade 1.
Due to TMRadThe required process temperature T is 50hpIs TD50108.3 ℃ and therefore TMR for 50h ≦ TMRadLess than 100h, when the actual process temperature T of the materialD100＜Tps≤TD50I.e. 104.0 ℃ Tps≤108.3℃，γ1The thermal stability of the material is grade 2.
Due to TMRadProcess temperature T required at 24hpIs TD24112.8 ℃ and therefore TMR for 24h ≦ TMRadLess than 50h, when the actual process temperature T of the materialD50＜Tps≤TD24I.e. 104.0 ℃ Tps≤112.8℃，γ1The material thermal stability rating is 3 ═ 3.
Due to TMRadProcess temperature T required for 12hpIs TD12117.3 ℃, therefore, TMR ≦ 12hadLess than 24h, when the actual process temperature T of the material isD24＜Tps≤TD12I.e. 112.8 ℃ Tps≤117.3℃，γ1The material thermal stability rating is 4 ═ 4.
Due to TMRadProcess temperature T required for 8hpIs TD8120.0 ℃ and therefore TMR for 8h ≦ TMRadLess than 12h, when the actual process temperature T of the material isD12＜Tps≤TD8I.e. 117.3 ℃ Tps≤120.0℃，γ1The material thermal stability rating is 5 ═ 5.
Due to TMRadProcess temperature T required for 1hpIs TD1134.2 ℃, therefore:
TMR for 1hadLess than 8h, when the actual process temperature T of the material isD8＜Tps≤TD1I.e. 120.0 ℃ Tps≤134.2℃，γ16-9, and the thermal stability grade of the material is 6-9.
TMRadLess than 1h, when the actual process temperature T of the materialps＞TD1I.e. Tps＞134.2℃，γ1The thermal stability of the material is grade 10.
Further, the GX modified double-base propellant material temperature correction coefficient gamma1When the value range is 6-9, namely the actual process temperature TD8＜Tps≤TD1In the time, the specific operation time coefficients of different danger grades are taken as a scale, and the material temperature correction coefficient gamma is further quantitatively obtained1。
γ1When the value range is 6-9, TMR is utilizedadAnd further determining the operation time t of the actual material process, and calculating a specific operation time coefficient by a formula (III):
Figure BDA0002636774880000101
in the formula: TMRadThe time for the maximum reaction rate to reach adiabatic conditions at the process temperature, h; t is the actual process operation time of the material, h. The physical meaning of the specific operation time coefficient is the safety margin of the process operation time, the specific operation time coefficient is 1, 2.5 and 4 times of the safety margin, namely the specific operation time coefficient is 2.5 and 4 is used as a scale for dividing the danger grades of the materials, and the material temperature correction coefficient gamma is1The grading schemes for values at 6-9 hours and thermal stability are shown in Table 5.
TABLE 5 temperature correction coefficient γ1Value taking scheme at 6-9 hours
δ δ＜1 1≤δ＜2.5 2.5≤δ＜4 δ＞4
γ 1 6 7 8 9
Grading of thermal stability of materials 6 7 8 9
According to the above results, the classification scheme of the thermal stability of the GX modified biradical propellant material is shown in Table 6.
TABLE 6 temperature correction coefficient of explosives and powders Process materials gamma1Value-taking scheme
Figure BDA0002636774880000111
When the actual process temperature of the materials in the process of the GX modified double-base propellant is 90 ℃, gamma is determined1The value is 1, and the thermal stability of the material is grade 1, which shows that the material has good thermal stability under the process condition and is almost impossible to generate thermal explosion accidents.

Claims (3)

1. A method for grading thermal stability of explosives and powders based on differential scanning calorimetry is characterized in that: the method adopts differential scanning calorimetry to test the material thermal decomposition reaction to obtain the apparent activation energy E of the thermodynamic parameter of the materialaAnd a pre-factor A is given, so that the process temperature T required by the maximum reaction rate reaching time of adiabatic conditions of different danger grades of the materials is obtainedpAnd process temperature T in different hazard classespAnd the specific operation time coefficient is used as a scale for comparing and measuring the actual process temperature T of the materials in the processpsAnd actual process temperature time tsThe material temperature correction coefficient gamma obtained quantitatively1And the thermal stability grade of the materials in the process is used for quantitative grading evaluation.
2. The differential scanning calorimetry based explosive thermal stability classification method according to claim 1, which comprises the following technical steps:
step one, adopting a differential scanning calorimetry to test the material thermal decomposition reaction to obtainMaterial(s)Apparent activation energy E of thermodynamic parametersaAnd pre-finger factor a;
using differential scanning quantitiesThe thermal test obtains the thermal decomposition reaction of the material in the explosive manufacturing process, obtains the peak temperature of the exothermic reaction causing the rapid decomposition of the material, and obtains the kinetic parameter apparent activation energy E of the material thermal decomposition reaction by utilizing the calculation method of thermal analysis kinetics, namely formula (I) regressionaAnd pre-finger factor a:
Figure FDA0002636774870000011
in the formula: beta is aiThe heating rate is K/s; t isiTo decompose the peak temperature, K, A is a pre-exponential factor, s-1；EaIs the apparent activation energy of the reaction, J/mol; r is a gas constant, J/(mol. K);
obtaining TMR (maximum reaction rate arrival time) of materials under different danger grades of adiabatic conditionsadRequired process temperature Tp；
TMRadIs calculated according to formula (ii):
Figure FDA0002636774870000012
in the formula: eaIs apparent activation energy, J/mol; a is a pre-exponential factor, s-1；TpIs the process temperature, K; r is a gas constant, J/(mol. K); cpThe specific heat capacity of the materials, J/(g.K); qrThe heat release of the material thermal decomposition is J/g;
TMR using Zurich Risk analysis method 6 grade criterion as determination conditionadRespectively 100h, 50h, 24h, 12h, 8h and 1h, and respectively obtaining up to 6 TMRs by formula (II)adRequired process temperature TpSequentially comprises the following steps: t isD100、TD50、TD24、TD12、TD8、TD1；
Step three, reaching time TMR of maximum reaction rate under 6 adiabatic conditions with different danger levelsadTemperature T of the dividing processpAt a process temperature TpFor a scale, the actual process temperature T of the materials is compared and measuredpsQuantitatively obtaining the material temperature correction coefficient gamma1Determining a grading scheme of the thermal stability of the material as follows:
TMRad Tps γ1 thermal stability grade of material TMRad≥100h Tps≤TD100 1 1 50h≤TMRad＜100h TD100＜Tps≤TD50 2 2 24h≤TMRad＜50h TD50＜Tps≤TD24 3 3 12h≤TMRad＜24h TD24＜Tps≤TD12 4 4 8h≤TMRad＜12h TD12＜Tps≤TD8 5 5 1h≤TMRad＜8h TD8＜Tps≤TD1 6～9 6～9 TMRad＜1h Tps＞TD1 10 10
3. The differential scanning calorimetry-based explosive thermal stability classification method according to claim 2, characterised in that step three is carried out if the material temperature correction coefficient γ1When the value range is 6-9, namely the actual process temperature TD8≤Tps＜TD1In the process, the specific operation time coefficients of different danger grades are taken as a scale, and a formula (III) is further adopted to quantitatively solve a material temperature correction coefficient gamma1：
Figure FDA0002636774870000021
In the formula: TMRadIs at the same timeThe time h for reaching the maximum reaction rate under adiabatic conditions at the process temperature; t is the operation time h of the material in the process; the safety margin of the specific operation time coefficient representing the process operation time is divided into material danger grades by using 1 time, 2.5 times and 4 times of safety margin, namely the specific operation time coefficient is 1, 2.5 and 4 as a scale, and the material temperature correction coefficient gamma1The value and the thermal stability of the product are classified as follows in 6-9 days:
δ δ＜1 1≤δ＜2.5 2.5≤δ＜4 δ＞4 γ1 6 7 8 9 grade of thermal stability of material 6 7 8 9
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