CN107478674A - Stability in microcalorimetric method evaluation 10 year storage period of single-base gun propellant - Google Patents
Stability in microcalorimetric method evaluation 10 year storage period of single-base gun propellant Download PDFInfo
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- CN107478674A CN107478674A CN201710621449.3A CN201710621449A CN107478674A CN 107478674 A CN107478674 A CN 107478674A CN 201710621449 A CN201710621449 A CN 201710621449A CN 107478674 A CN107478674 A CN 107478674A
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Abstract
The present invention relates to the new method of the stability in a kind of microcalorimetric method evaluation 10 year storage period of single-base gun propellant, it is characterized in that, this method utilizes and tracks the small heat that single-base gun propellant discharged or absorbed in each moment, the stable kinetics of research, establish the time temperature equivalence relation of storage process, simultaneously according to the equation of heat balance being thermally generated and heat transfer is established, study heat accumulation effect and obtain thermal explosion critical pumping rate, form the microcalorimetric method interpretational criteria of the single-base gun propellant storing stability comprising dimensional effect, evaluate the thermal response signal exported during storing stability according to micro heat test, comparative evaluation's criterion, provide the stability evaluation result in 10 year storage period.Using the stability in microcalorimetric method evaluation single-base gun propellant storage period, it is possible to achieve the stability in 10 storage periods is provided in 10 days, measurement process is quick, safe, lossless, environmentally friendly, convenient.
Description
Technical field
The invention belongs to single-base gun propellant security evaluation field, is related in a kind of single-base gun propellant storage process
Stability appraisal procedure.It is particularly a kind of to utilize microcalorimetric method research single-base gun propellant storage stability, establish interpretational criteria
And test method, form the single-base gun propellant storage stability Slope map of pixels of support size effect and time scale.
Background technology
Single-base gun propellant keeps its physical and chemical properties not occur to be referred to as stabilizing more than the ability of allowed band change
Property.Single-base gun propellant (NC is main body) contains-C-ONO2Or-C-NO2Structure.Molecular structure shows, C-N fractures, on the one hand releases
Liberated heat is the energy source of expansion work, on the other hand, and slowly decomposes, causes heat accumulation to draw burn, quick-fried
Where fried root, the chemical safety of storage is influenceed.
In order to meet wartime to the wilderness demand of single-base gun propellant, it is necessary to which single-base gun propellant is largely stored for a long time.And
Large scale powder charge easily causes heat accumulation as the non-conductor of heat, influences the stability of storage.Other single-base gun propellant is in length
During phase storage, production and processing and onsite application, the test of environment can be withstood, physical property and chemically does not occur
The significant changes of energy, unexpected burning and explosion accident are occurred without, be highly important in single-base gun propellant research and application ask
Topic.
The principal element for influenceing chemical change has thermal decomposition, hydrolysis, oxidation, degraded, solidification and crosslinking etc..Single base is sent out
Penetrate medicine keeps its physical and chemical properties not occur to be referred to as hot stabilize more than the ability of allowed band change under the action of heat
Property.Thermally-induced chemical change is change most basic during single-base gun propellant is deposited, and influences the main of stability
Change.
Currently used stability evaluation method is investigated, and summarizes the principle, the scope of application and deficiency (being shown in Table 1) of method
The conventional stability evaluation method of table 1
First two method test paper method (dimension also in, Abel, crystal violet) and vacuum stability method be qualitatively method, only
Evaluation can be provided to the transient state stability of single-base gun propellant material, the clear and definite time limit can not be provided, do not had the faintest notion of time.And two
The defects of different degrees of and deficiency be present in kind method.1. test paper method subjective error is larger, 2. two methods sample pre-treatments need
Sample is crushed, it is dangerous high.
Bromination method and gas chromatography belong to quantitative evaluation method, can provide the specific time.But still be can only
Evaluation is provided to the stability of single-base gun propellant material, lacks dimensional effect.1. clearly disadvantageous show uses both sides
When method is evaluated stability, to carry out thermal acceleration degradation, thermal acceleration degradation need at least use 4 at 50 DEG C -95 DEG C
Temperature spot, each temperature spot need to weigh 50g-60g samples, and each temperature spot sampling number is at least 6 times, that is, carries out aging
Experiment at least needs 240g sample size.Sample requirements are big first, secondly sampled in ageing process, dangerous high.It is old in addition
Changing experiment needs the time of at least 2 years, extremely time-consuming.2. bromination method and gas chromatography need head when obtaining stable agent content
The stabilization agent in sample, first low boiling point solvent ether are first crushed using aether backflow even longer time extraction in 24 hours
It is inflammable and explosive, and air pollution be present.Secondly the sample itself sensitivity of aging raises significantly, is sent out by mechanical crushing list base
Security is poor when penetrating medicine aging sample.3. stabilization agent can gradually use up in ageing process, produce different types of stabilization agent and derive
Thing, during using gas chromatography to stabilization agent content quantitative, also exist and separate between different derivatives difficult and lack reference material
The problems such as matter, so gas chromatography is not used widely so far.
The thermostability for the single-base gun propellant part that above method can not shape to oneself is analyzed and researched；Nothing
Clear and definite evaluating, actual poor operability；With the fast development of high energy damaging techniques, dimensional effect and stability
Contradiction increasingly highlights, and turns into the premise technology of powder charge stability design.It is badly in need of establishing comprising temperature on the basis of thermal explosion theory
Du-when m- scale effect theoretical model.
Micro heat is exactly that the small thermal change of sample is determined under high-precision constant temperature, can be from the angle of heat
Subtly reflect the performance change of single-base gun propellant, be to further investigate single base hair from the theoretic of decomposition kinetics
Penetrate the hot property of medicine and stability provides good technology platform.Compared with conventional method, Microcalorimetric method have it is sensitive can
Lean on, the small heat that single-base gun propellant discharged or absorbed in each moment can be tracked, with reference to thermal explosion threshold limit value mould
Intend, establish the New Evaluation Method of the segmentation storage stability based on micro Thermal test result, quick, safe and environment-friendly can obtain
Obtain the stability of single-base gun propellant material and size powder charge.Establish the stability evaluation mould comprising Temperature-time-scale effect
Type.
The content of the invention
It is an object of the invention to solve existing qualitatively stability evaluation method not providing clear and definite setting time,
Sample pretreatment process is cumbersome, dangerous height, and the experiment of quantitative stability evaluation method is time-consuming, process is cumbersome, dangerous height；
A kind of and the deficiencies of thermostability of size powder charge can not being analyzed, there is provided single-base gun propellant for including dimensional effect
The microcalorimetric method Slope map of pixels of storage stability, this method, can be directly to single bases without complicated sample pretreatment process
Propellant material or size powder charge carry out shakedown analysis, safe and environment-friendly, cost is low.And analysis method convenient quickly, it is existing
Stability quantitative evaluation method needs more than 2 years, and the time of experiment is greatly reduced in micro- calorimetric method, can obtaining in 10 days
Obtain the single-base gun propellant material and powder charge stability assessment result in 10 years.Above all micro hot evaluation method can be direct
Stability evaluation is carried out to size powder charge, has filled up the blank of size powder charge stability evaluation method.
In order to realize above-mentioned task, the present invention takes following technical scheme：
Stability in microcalorimetric method evaluation 10 year storage period of single-base gun propellant, it is characterised in that this method utilizes tracking
The small heat that single-base gun propellant discharged or absorbed in each moment, stable kinetics is studied, establishes storage process
Time temperature equivalence relation, meanwhile, according to the equation of heat balance being thermally generated and heat transfer is established, research heat accumulation effect obtains heat
Explode critical pumping rate, forms the microcalorimetric method interpretational criteria of the single-base gun propellant storing stability comprising dimensional effect, evaluation storage
The thermal response signal exported during security according to micro heat test is deposited, comparative evaluation's criterion, provides the safety in 10 year storage period
Evaluation result is stored, this method need not be crushed and be extracted pretreatment in detection process, can be provided in 10 days 10 years
Stability in storage period, in order to realize above-mentioned task, the present invention takes following technical scheme：
Step 1, establish the time temperature equivalence relation of storage process；Isothermal reaction dynamics uses following equation：
In formula：α is reaction depth, and t is the reaction time, and f (α) is the mechanism function of reaction, and A is pre-exponential factor, and E is anti-
The activation energy answered, TmFor reaction temperature, tmReach α for reaction depth0Required time, QtTo react liberated heat, △ H0
The total amount of heat released for reaction, separating variables are carried out to above formula and are integrated, then in TmAt a temperature of reaction depth reach α0Required
Reaction time tmIt can be calculated by following formula：
Under the conditions of 25 DEG C of normal temperature, reaction depth reaches α0Required time t25Equally meet above formula：
Formula (2) and formula (3) are divided by, then carry out separating variables, then in experimental temperature TmBe issued to at 25 DEG C of normal temperature
Reaction time needed for same reaction depth：
Step 2, the acquisition of activation energy, about 1000mg single-base gun propellant is put into aluminium crucible, at 60 DEG C -90 DEG C
Carry out the micro heat experiment of isothermal, then experimental period is long less than 60 DEG C for temperature, and temperature higher than 90 DEG C then with actual store by experimental temperature
The situation of depositing has big difference, and prediction error is big.The isothermal calorimetric curve of sample is obtained by micro- calorimeter, determines performance change
Critical point.Liberated heat is converted into the corresponding extent of reaction, obtains the time of reaction depth and reaction under different temperatures
Relation.According to the Arrhenius Equation, equation representation is as follows
In formula：E is apparent activation energy；Z is pre-exponential factor, and T is absolute temperature, and R is gas constant, and τ is the time.Setting
Different experiments temperature repetition above step obtains a series of activation energy under gunpowder different temperatures, and a temperature spot is selected every 5 DEG C
Carry out experiment, the minimum value of segmentation selection activation energy.
Step 3, the criterion evaluated using single-base gun propellant sample heat flow rate as stability.Go out from thermal explosion theory
Hair, carries out mathematical analysis, with reference to micro- with the philosophy and principle of chemical kinetics and thermal conduction study to the criticality of thermal desorption system
Calorimetric experiment and thermal explosion simulation are calculated so as to conclude and propose thermal explosion criterion.Computation model uses the Thomas of extensive type
Thermal explosion model, calculating process are realized by NETZSCH Thermal Simulation (Version 2014.02) software.Meter
The diameter that parameter selection 230mm calculates as simulation is calculated, selectes heat transfer coefficient χ=0.001w/ (cm2K), Environment temperature
Spend for 71 DEG C.More than selection worst storage environment, it is to obtain one conservative and that applicability is wide result.Other ginsengs
Number uses average result, takes loading density ρ=1g/cm3, thermal conductivity λ=0.00122W/ (cmK), specific heat capacity CP=0.205
+0.00325T(J/g·K).Its formula is as follows：
ρ is sample loading density in formula；cvFor specific heat capacity；△H0For heat release enthalpy；TaFor environment temperature.For other environment
At a temperature of, corresponding critical rate of heat generation can be calculated by following formula：
E is activation energy in formula, TmFor test temperature, P71Critical rate of heat release when for environment temperature being 71 DEG C, PmTo face
Boundary's rate of heat release.
Step 4, the acquisition of maximum rate of heat flow：Take single-base gun propellant sample, sample size≤1g, experimental study is from sample
As a result amount show that laboratory sample amount spans an order of magnitude from 20mg to 1000mg, the reaction depth of sample initial reaction with
Obvious change does not occur for the reaction time.Because initial reaction is zero-order reaction, therefore initial reaction is not by sample size
Influence.It can be considered that laboratory sample amount is also not enough to produce heat accumulation, the selection of sample size mainly considers that sample takes
Sample representativeness and instrument test limit.In order to prevent the excessive infringement instrument of sample size, laboratory sample amount≤1g of final choice.Sample
Product state can be solid powder, particle or size powder column, and an integer temperature is selected between 60 DEG C -90 DEG C, carry out isothermal amount
Heat experiment, the confirmation of test period is according to time temperature equivalence relation.Rate of heat flow and the relation curve of time are drawn, calculates experimental period
It is interior to obtain maximum rate of heat flow.
Step 5, the judgement of single-base gun propellant stability：According to optional test temperature, calculate and obtain according to equation (9)
Critical heat flux at this temperature；Critical heat flux is compared with the maximum hot-fluid that experiment obtains, if maximum hot-fluid ＜ critical heats
Stream, then the single-base gun propellant is stable within 10 year storage period；If maximum hot-fluid >=critical heat flux, the single-base gun propellant is 10
Unstability in storage period in year.
Stability in microcalorimetric method evaluation 10 year storage period of single-base gun propellant of the present invention, the Advantageous effect brought
Fruit is embodied in the following aspects：
1. test paper method and vacuum stability method can only evaluate the transient state stability of single-base gun propellant, can not provide specific
Setting time.Microcalorimetric method obtains temperature etc. when in storage process from the decomposition kineticses of the angle research single-base gun propellant of heat
Effect relation.The stability of the single-base gun propellant of different time as defined in can providing.
2. bromination method and gas chromatography evaluation single-base gun propellant ultimate stage are prescribed a time limit, the heat that need to carry out at least four temperature adds
Fast aging, sample size at least need 240g, and sample size is big；Ageing time takes 2 years, and even longer time, experiment are time-consuming；It is and old
Sampled during change dangerous high.Microcalorimetric method only needs 1g sample sizes, can realize that single-base gun propellant is stored for 10 years in 10 days
Stability evaluation in time limit, the problems such as solving that time-consuming, efficiency is low and be dangerous high.
3. overcoming a variety of stabilization agent derivatives prepares asking for difficult shortage stabilization agent derivative standard substance (chromatography)
Topic.Method is practical.
4. the stability in microcalorimetric method evaluation single-base gun propellant storage period, without the sample pre-treatments of complexity, solid powder
End, particle and size powder charge can be tested directly, avoid the high sample comminution of complicated danger, extraction process, convenient, peace
Entirely, low cost, environmental protection.
5. studying the stability of single-base gun propellant using microcalorimetric method, decomposed without being heated to sample, test bar
Part is relatively mild, is more nearly the actual storage requirement of single-base gun propellant, and experimental result reliability is high.Solves traditional heat point
Analysis method evaluates stability and the problem of larger deviation be present with actual stability.
6. the thermostability for overcoming the existing single-base gun propellant part that can not be shaped to oneself is analyzed and researched；
The theoretical model for including Temperature-time-scale effect is established using Microcalorimetric method on the basis of thermal explosion theory.It is suitable
Stability evaluation for certain time limit of different size powder charges.
Brief description of the drawings
Fig. 1 experiment process figures
Calorimetric curve map at three temperature of Fig. 2 single-base gun propellants
The relation of conversion ratio and test period at three temperature of Fig. 3 single-base gun propellants
Fig. 4 230mm diameter single-base gun propellant powder-charge temperatures DYNAMIC DISTRIBUTION simulates (71 DEG C)
Fig. 5 10mm diameter single-base gun propellant powder-charge temperatures DYNAMIC DISTRIBUTION simulates (71 DEG C)
The micro heating curve figure of single-base gun propellant at 89 DEG C of Fig. 6
Embodiment
Embodiment 1
Stability in microcalorimetric method evaluation 10 year storage period of single-base gun propellant of the present invention, it is characterised in that this method
Without any complicated, dangerous sample pretreatment process, the hot-fluid in the Isothermal microcalorimetry tracking samples state time is utilized
Rate, the thermal explosion critical pumping rate comprising scale effect is calculated by simulation；Under development single-base gun propellant different temperatures etc.
The micro heat experiment of temperature, the decomposition reaction in different temperatures section is obtained with the changing rule of test temperature by decomposition peak's temperature and lived
Change energy, the minimum value of segmentation selection activation energy obtains time temperature equivalence relation in storage process；Then it is micro- to carry out single temperature isothermal
Calorimetric is tested, and is calculated in specimen the maximum rate of heat flow that obtains and compared with thermal explosion critical pumping rate, is obtained single-base gun propellant
Stability in 10 year storage period.Rough flow figure is shown in Fig. 1, specifically follows these steps to carry out：
Step 1, the time temperature equivalence relation of storage process
Isothermal reaction dynamics meets following equation：
In formula：α is reaction depth；T is the reaction time；F (α) is the mechanism function of reaction；A is pre-exponential factor；E is anti-
The activation energy answered；TmFor reaction temperature；tmReach α for reaction depth0The required time；QtTo react liberated heat；△H0
The total amount of heat released for reaction.Separating variables are carried out to above formula and are integrated, then in TmAt a temperature of reaction depth reach α0Required
Reaction time tmIt can be calculated by following formula：
Under the conditions of 25 DEG C of normal temperature, reaction depth reaches α0Required time t25Equally meet above formula：
Formula (2) and formula (3) are divided by, then carry out separating variables, then in experimental temperature TmBe issued to at 25 DEG C of normal temperature
Reaction time needed for same reaction depth：
Step 2, the acquisition of activation energy
About 1000mg certain single-base gun propellant is put into aluminium crucible, passes through the micro heat of C80 at 65 DEG C, 70 DEG C, 75 DEG C
Instrument obtains the isothermal calorimetric curve of sample, sees Fig. 1.Determine the critical point of performance change.
It is reaction depth by converting heat, obtains reaction depth and the time relationship of reaction at four temperature, see Fig. 2.Choosing
Reaction depth 30% is taken, according to the Arrhenius Equation, equation representation is as follows
In formula：E is apparent activation energy；Z is pre-exponential factor；T is absolute temperature；R is gas constant；τ is the time.
Make ln τ -1/T linear regressions, the kinetic parameter E=120.0kJ/mol, lnA=of single-base gun propellant is calculated
39.8(s-1).Set different storage temperatures and repeat above steps and obtain activation energy under different temperatures, the results are shown in Table 2
Calorimetric activation energy under the single-base gun propellant different temperatures of table 2
Select the minimum value 120kJ/mol of activation energy.
Step 3, thermal explosion theory is based on this, with the philosophy and principle of chemical kinetics and thermal conduction study to heat release
The criticality of system carries out mathematical analysis, so as to conclude and propose thermal explosion criterion.230mm is selected to be calculated as simulation straight
Footpath, select heat transfer coefficient χ=0.001w/ (cm2K), Environment temperature is 71 DEG C.More than selection worst storage ring
Border, it is to obtain one conservative and that applicability is wide result.Other parameters use average result, take loading density ρ=1g/
cm3, thermal conductivity λ=0.00122W/ (cmK), specific heat capacity CP=0.205+0.00325T (J/gK).Computation model is using wide
The Thomas thermal explosion models of general type, its formula are as follows：
In formula：ρ is sample loading density；cvFor specific heat capacity；△H0For heat release enthalpy；TaFor environment temperature.Pass through change zero
The pre-exponential factor of order reaction changes rate of heat release, so that it is determined that a suitable critical rate of heat release will not both cause powder column
Being risen so high in central temperature will not also make it that reaction rate is too fast.Calculating passes through NETZSCHThermal Simulation
(Version2014.02) software is realized.
Natural storage process is zero-order reaction, obtains the distribution of powder column temperature dynamic by changing kinetic parameter, just not
Rate of heat release corresponding to the critical-temperature exploded is critical pumping rate.
As shown in figure 3,230mm diameter single-base gun propellant powder charges, when rate of heat release is in 39uw/g, central interior is stored
Temperature rise in 808 days is about 0.9 DEG C, and general critical thermal explosion temperature rise is at 10 DEG C -20 DEG C；10mm diameter single-base gun propellant powder charges are put
Hot speed, which corresponds to samming aging in 39uw/g, needs 904 days (Fig. 4), and such result is acceptable.Therefore 71
Under conditions of DEG C, it is that can avoid enough during heat accumulation causes to select rate of heat release P=39uw/g as critical rate of heat generation
Heart temperature is crossed the too fast phenomenon of high reaction rate and occurred.Corresponding critical rate of heat generation can be calculated by following formula：
Wherein：E=120kJ/mol；TmFor test temperature；P71For 39uw/g.
Step 4, the acquisition of maximum rate of heat flow：Single-base gun propellant sample is taken, sample size 1000mg, is put into sample cell, is tried
To test temperature and select 89 DEG C, carry out isothermal calorimetric experiment, test period is 3.83 days, draws rate of heat flow and the relation curve of time,
It is interior during calculating experiment to obtain maximum rate of heat flow.Test data is shown in Table 3, and micro heating curve is shown in Fig. 5.
The micro heat test data of 3 89 DEG C of table
| Test period (d) | Maximum hot-fluid (μ W/g) |
| 3.83 | 141.3 |
Step 5, the judgement of single-base gun propellant stability：Calculating the critical heat flux at 89 DEG C of acquisition according to equation (18) is
313.6 μ W/g are shown in Table 4.Critical heat flux is compared with the maximum hot-fluid that experiment obtains, maximum hot-fluid ＜ critical heat fluxes, explanation
The single-base gun propellant was stabilized within 10 year storage period.
The different test temperature T of table 4iUnder critical heat flux
| Ti(℃) | Pi(μW/g) |
| 60 | 9.8 |
| 70 | 34.5 |
| 80 | 113.6 |
| 89 | 313.6 |
Claims (1)
1. the stability in microcalorimetric method evaluation 10 year storage period of single-base gun propellant, it is characterised in that comprise the following steps：
Step 1, establish the time temperature equivalence relation of storage process；Isothermal reaction dynamics uses following equation：
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In formula：α is reaction depth, and t is the reaction time, and f (α) is the mechanism function of reaction, and A is pre-exponential factor, and E is the work of reaction
Change energy, TmFor reaction temperature, tmReach α for reaction depth0Required time, QtTo react liberated heat, △ H0For reaction
The total amount of heat of releasing, separating variables are carried out to above formula and are integrated, then in TmAt a temperature of reaction depth reach α0During required reaction
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Under the conditions of 25 DEG C of normal temperature, reaction depth reaches α0Required time t25Equally meet above formula：
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Step 2, the acquisition of activation energy ,≤1000mg single-base gun propellant is put into aluminium crucible, carried out at 60 DEG C -90 DEG C
The micro heat experiment of isothermal, the isothermal calorimetric curve of sample is obtained by micro- calorimeter, determines the critical point of performance change.It will put
The converting heat gone out is the corresponding extent of reaction, reaction depth and the time relationship of reaction under different temperatures is obtained, according to Ah tiring out
Ni Wusi equations obtain the activation energy of decomposition reaction, and setting different experiments temperature repeats above step and obtains a series of gunpowder not equality of temperature
Activation energy under degree, carry out experiment every 5 DEG C of selections, one temperature spot, the minimum value of segmentation selection activation energy is as reliable activation
Energy.
Step 3, the criterion evaluated using single-base gun propellant sample heat flow rate as stability.From thermal explosion theory, with change
The philosophy and principle for learning dynamics and thermal conduction study carry out mathematical analysis to the criticality of thermal desorption system, with reference to micro heat experiment
And thermal explosion simulation is calculated so as to conclude and propose thermal explosion criterion.Computation model uses the Thomas thermal explosion moulds of extensive type
Type, calculating process are realized by NETZSCH Thermal Simulation (Version 2014.02) software.Calculating parameter is selected
The diameter that 230mm calculates as simulation is selected, selectes heat transfer coefficient χ=0.001w/ (cm2K), Environment temperature is 71 DEG C.
More than selection worst storage environment, it is to obtain one conservative and that applicability is wide result.Other parameters are using average
As a result, loading density ρ=1g/cm is taken3, thermal conductivity λ=0.00122W/ (cmK), specific heat capacity CP=0.205+0.00325T (J/
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</mrow>
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<msub>
<mi>c</mi>
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</msub>
<mfrac>
<mrow>
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</mrow>
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<mi>t</mi>
</mrow>
</mfrac>
<mo>=</mo>
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<mi>H</mi>
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<mi>f</mi>
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<mi>&alpha;</mi>
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ρ is sample loading density in formula；cvFor specific heat capacity；△H0For heat release enthalpy；TaFor environment temperature.For other environment temperatures
Under, corresponding critical rate of heat generation can be calculated by following formula：
<mrow>
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<mn>71</mn>
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E is activation energy in formula, TmFor test temperature, P71Critical rate of heat release when for environment temperature being 71 DEG C, PmFor critical heat release
Speed.
Step 4, the acquisition of maximum rate of heat flow：Single-base gun propellant sample, sample size≤1g are taken, sample state can be solid powder
End, particle or size powder column, an integer temperature is selected between 60 DEG C -90 DEG C, carry out isothermal calorimetric experiment, test period is really
Recognize according to time temperature equivalence relation.Rate of heat flow and the relation curve of time are drawn, it is interior during calculating experiment to obtain maximum rate of heat flow.
Step 5, the judgement of single-base gun propellant stability：According to optional test temperature, calculated according to equation (8) and obtain the temperature
Critical heat flux under degree；Critical heat flux is compared with the maximum hot-fluid that experiment obtains, should if maximum hot-fluid ＜ critical heat fluxes
Single-base gun propellant was stabilized within 10 year storage period；If maximum hot-fluid >=critical heat flux, the single-base gun propellant was in 10 year storage period
Interior unstability.
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