CN106290234B - Accumulate double-base propellant safe storage life predictor method - Google Patents
Accumulate double-base propellant safe storage life predictor method Download PDFInfo
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- CN106290234B CN106290234B CN201610615160.6A CN201610615160A CN106290234B CN 106290234 B CN106290234 B CN 106290234B CN 201610615160 A CN201610615160 A CN 201610615160A CN 106290234 B CN106290234 B CN 106290234B
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- 239000003380 propellant Substances 0.000 title claims abstract description 85
- 238000003860 storage Methods 0.000 title claims abstract description 78
- 238000000034 method Methods 0.000 title claims abstract description 70
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 93
- 230000006641 stabilisation Effects 0.000 claims abstract description 85
- 238000011105 stabilization Methods 0.000 claims abstract description 85
- 230000032683 aging Effects 0.000 claims abstract description 49
- 230000001133 acceleration Effects 0.000 claims abstract description 39
- 239000000126 substance Substances 0.000 claims abstract description 31
- 238000009825 accumulation Methods 0.000 claims abstract description 23
- 238000004448 titration Methods 0.000 claims abstract description 19
- 230000015556 catabolic process Effects 0.000 claims abstract description 18
- 238000006731 degradation reaction Methods 0.000 claims abstract description 18
- 238000005086 pumping Methods 0.000 claims abstract description 18
- 238000001514 detection method Methods 0.000 claims abstract description 11
- 238000001228 spectrum Methods 0.000 claims abstract description 11
- 238000005259 measurement Methods 0.000 claims abstract description 10
- 238000003333 near-infrared imaging Methods 0.000 claims abstract description 8
- 238000004128 high performance liquid chromatography Methods 0.000 claims abstract description 6
- 239000000843 powder Substances 0.000 claims description 17
- 238000002329 infrared spectrum Methods 0.000 claims description 16
- 238000005070 sampling Methods 0.000 claims description 11
- 239000003381 stabilizer Substances 0.000 claims description 9
- 238000009795 derivation Methods 0.000 claims description 8
- 238000010606 normalization Methods 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 238000007689 inspection Methods 0.000 claims description 5
- 238000013213 extrapolation Methods 0.000 claims description 4
- 238000005457 optimization Methods 0.000 claims description 4
- 238000010521 absorption reaction Methods 0.000 claims description 3
- 238000012417 linear regression Methods 0.000 claims description 2
- 230000035508 accumulation Effects 0.000 abstract description 19
- 239000000523 sample Substances 0.000 description 65
- PZIMIYVOZBTARW-UHFFFAOYSA-N centralite Chemical compound C=1C=CC=CC=1N(CC)C(=O)N(CC)C1=CC=CC=C1 PZIMIYVOZBTARW-UHFFFAOYSA-N 0.000 description 25
- 238000003483 aging Methods 0.000 description 15
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 7
- 239000002360 explosive Substances 0.000 description 6
- 230000003595 spectral effect Effects 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 239000002351 wastewater Substances 0.000 description 5
- 238000012937 correction Methods 0.000 description 4
- 239000003814 drug Substances 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 230000031709 bromination Effects 0.000 description 3
- 238000005893 bromination reaction Methods 0.000 description 3
- 230000001066 destructive effect Effects 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 239000004615 ingredient Substances 0.000 description 3
- 150000002823 nitrates Chemical class 0.000 description 3
- 238000007781 pre-processing Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- SNIOPGDIGTZGOP-UHFFFAOYSA-N Nitroglycerin Chemical compound [O-][N+](=O)OCC(O[N+]([O-])=O)CO[N+]([O-])=O SNIOPGDIGTZGOP-UHFFFAOYSA-N 0.000 description 2
- 238000005844 autocatalytic reaction Methods 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000002512 chemotherapy Methods 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 235000013399 edible fruits Nutrition 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000004880 explosion Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 229960003711 glyceryl trinitrate Drugs 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229920001220 nitrocellulos Polymers 0.000 description 2
- 238000004611 spectroscopical analysis Methods 0.000 description 2
- 229910004679 ONO2 Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000013068 control sample Substances 0.000 description 1
- 238000002790 cross-validation Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000009659 non-destructive testing Methods 0.000 description 1
- 238000010238 partial least squares regression Methods 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000004451 qualitative analysis Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
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- 238000000926 separation method Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
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Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
- G01N21/35—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light
- G01N21/359—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light using near infrared light
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N31/00—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods
- G01N31/16—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods using titration
Abstract
The present invention relates to a kind of accumulations to store double-base propellant safe storage life predictor method, this method prepares stabilization agent effective content near-infrared quantitative model modeling sample using thermal acceleration aging process, double-base propellant sample stabilization agent effective content is obtained using chemical titration or high performance liquid chromatography, using near-infrared diffuse spectrometer acquisition spectrum, stabilization agent effective content near-infrared quantitative model is established by Chemical Measurement；Critical quantity is consumed as critical pumping rate using stabilization agent effective content, carries out thermal acceleration degradation, temperature coefficient is obtained by stabilization agent effective content changing rule, establishes safe storage life predicting equation；Critical quantity is consumed as critical pumping rate using stabilization agent effective content, sample stabilization agent effective content in the single temperature thermal acceleration ageing process of near-infrared method tracing detection, the crash time that stabilization agent effective content reaches critical pumping rate consumption is obtained, the safe storage life of double-base propellant at a temperature of storage environment is obtained by safe life predicting equation.
Description
Technical field
The invention belongs to explosive wastewater security evaluation fields, are related to a kind of explosive wastewater storage process safe storage life
Predictor method.Especially it is a kind of using near-infrared diffuse spectrometry detection accumulation the single temperature thermal acceleration aging of double-base propellant
Sample stabilization agent effective content obtains the crash time that stabilization agent effective content reaches critical pumping rate consumption, is store according to propellant powder
Life prediction equation is deposited, the method for accumulating double-base propellant safe storage life under storage environment is estimated.
Background technique
Explosive wastewater safe storage life is under storage requirement, and explosive wastewater does not occur to accelerate the catalysis pervious storage of accelerated decomposition
Deposit the time.
Nitrocotton, nitroglycerine are the energy ingredients in double-base propellant, in nitrocotton and nitroglycerine molecular structure all
Contain-C-ONO2Structure, double-base propellant occurs slowly to decompose in storage process, O-NO2Key fracture releases energy, and generates simultaneously
Nitrogen oxides with autocatalysis, nitrogen oxides are further catalyzed energy ingredient decomposition, continue slow heat release and generate heat
Accumulation leads to burning, explosion, influences storing stability.Therefore, need to be added No. II centralite in double-base propellant as stable
Agent, for absorbing the nitrogen oxide that double-base propellant decomposes to give off, so that nitrogen oxides be inhibited to decompose double-base propellant
Autocatalysis, while No. II centralite derivative still with stable effect is generated, delay energy ingredient to decompose, improves double
Base propellant powder safe storage life.No. II centralite and its derivative total content are known as stabilization agent effective content, under storage requirement
The time undergone when stabilization agent effective content drops to critical pumping rate is double-base propellant safe storage life, in safe storage
Double-base propellant chemical safety is good in service life.
Using thermal acceleration aging process tracking stabilization agent effective content, (GJB770B-2005 method 506.1 estimated storage in the past
Service life thermal acceleration aging process) accumulation double-base propellant safe storage life is estimated, commonly using chemical titration, (bromine is reacted with stabilization agent
Generate the chemical method of bromide) or chromatography determination stabilization agent effective content, it is even longer using aether backflow 24 hours
Time, which extracts, crushes sample stabilization agent effective content, and low boiling point solvent ether is inflammable and explosive, accumulates biradical hair by being mechanically pulverized
Safety is poor when penetrating medicine aging sample preparation extracted by ether sample, the bromination that cumbersome, time-consuming and chemical titration generates
Object brings pollution.
By double-base propellant aging sample stabilization agent effective content changing rule under the different temperatures of acquisition, with Bei Seluo
When special (Berthelot) equation estimates safe storage life, due to thermal acceleration degradation at least use 4 temperature spots (65 DEG C,
75 DEG C, 85 DEG C, 95 DEG C), each temperature spot sampling number is at least 6 times, and the aged samples amount needed is big, duration of test runs 6
It is a month or more, extremely time-consuming, and long-time high temperature thermal acceleration aging and pass through mechanical cutting composite modified double-base propellant aging
Risk is high when sample prepares extraction sample.
Heat accumulation can be generated for the accumulation double-base propellant thermal acceleration degradation thermal histories with certain size, one
Aspect leads to thermal field uneven distribution, causes stabilization agent content distribution uneven, on the other hand accumulates double-base propellant multi-temperature
Point degradation is easily because burning and explosion accident occur for heat accumulation, accordingly, it is difficult to pass through the multiple temperature spot degradations of powder charge
And stable agent content is obtained using chemical titration or chromatography, filled in newly formula long-life powder charge design and storage process
Medicine safe storage life is estimated, it is therefore desirable to use new method.
Near-infrared spectrum technique be frequency multiplication, sum of fundamental frequencies information based on X-H (X-C, N, O) in organic molecule to substance into
The spectral technique of row qualitative and quantitative analysis has the advantages that convenient, lossless, green.The stable biradical hair of accumulation of No. II centralite
Penetrate medicine safe storage life rapid Estimation method, can safely, time saving, inexpensive, environmentally friendly acquisition accumulation double-base propellant safety
Storage life.
Summary of the invention
For defect or deficiency existing for above-mentioned existing double-base propellant safe storage life technology, the purpose of the present invention exists
In, a kind of accumulation double-base propellant safe storage life predictor method based near infrared detection stabilization agent effective content is provided,
This method can safe, time saving, inexpensive, environmentally friendly accumulation double-base propellant safe storage life.
In order to realize above-mentioned task, the invention adopts the following technical scheme:
A kind of accumulation double-base propellant safe storage life predictor method, which is characterized in that this method is old using thermal acceleration
Change method prepares double-base propellant and stabilizes agent content near-infrared quantitative model modeling sample, using chemical titration or high-efficient liquid phase color
Spectrometry obtain double-base propellant sample stabilization agent effective content chemical score, using near-infrared diffuse spectrometer acquisition spectrum, lead to
Over-stoichiometric establishes stabilization agent effective content near-infrared quantitative model；Critical quantity is consumed as facing using stabilization agent effective content
Boundary's criterion carries out double-base propellant powder charge thermal acceleration degradation, obtains temperature system by stabilization agent effective content changing rule
Number establishes accumulation double-base propellant safe storage life predicting equation；Critical quantity is consumed as critical using stabilization agent effective content
Criterion, the single temperature thermal acceleration ageing process of Near-Infrared Absorption Method tracing detection are accumulated double-base propellant stabilization agent effective content, are obtained
Stabilization agent effective content reaches the crash time of critical pumping rate consumption, and it is biradical to obtain accumulation by safe storage life predicting equation
Safe storage life at a temperature of propellant powder storage environment.
Specifically follow these steps to carry out:
(1) thermal acceleration aging process prepares near-infrared method detection stabilization agent effective content modeling sample
Double-base propellant sample is fitted into the accelerated ageing under certain temperature in capillary exhaust pipe ground decrement bottle, interval time
Sampling, prepares the double-base propellant sample of different stabilization agent effective contents.It is divided into internal calibrations collection sample and external certificate collection sample
Product.
(2) stabilization agent effective content near-infrared quantitative model
1. obtaining double-base propellant sample stabilization agent effective content chemistry using chemical titration or high performance liquid chromatography
Value, determines content range.
2. acquiring near infrared spectrum to internal calibration set sample and external certificate collection sample using near infrared spectrometer.Sampling
Mode is diffusing reflection, and sampling wave band is 700nm~2500nm, optimizes spectral scan parameter, determines optimum resolution, scanning times
And sample duplicate measurements number.Collected near infrared spectrum is transmitted to computer by USB data line.
3. carrying out pretreatment and linear fit to internal calibration set sample near infrared spectrum using chemometrics method.Choosing
Key band is selected, in normalization, baseline is smooth, first derivation, second order derivation, selects in multiplicative scatter correction preprocessing procedures
It selects mode alone or in combination to pre-process acquisition spectrum, regression fit is then carried out using Partial Least Squares, that is, PLS method,
Calibration model is established, external certificate is carried out to model built with external certificate collection sample, internal inspection and outside according to model
Verify the appraisement system combined, successive optimization model.
According to the effective stabilizer content near-infrared quantitative model of foundation, using near infrared spectrometer to selected sample into
The worst error of the measurement of row stabilization agent effective content, acquisition near-infrared predicted value, chemical score and near-infrared predicted value should be less than marking
Quasi- method repeatability error.
(3) safe storage life predicting equation
Nitrate esters energetic material, which decomposes, causes the chemical reaction of No. II centralite changes of contents of double-base propellant, obey Ah
Tired Ni Wusi equation, indicates the accurate empirical formula of k-T relationship are as follows:
The temperature coefficient r for defining reaction speed is the every variation multiplying power for rising 10 DEG C of rate constants of temperature:
R=kT+10/kT (1)
In formula: r- indicates that the temperature difference is 10 DEG C of reaction rate temperature coefficient
kTRate constant at T DEG C of expression
kT+10Indicate rate constant when (T+10) DEG C
Due in T1And T2At two temperature, same reaction, aA+bB+ ... → lL+ ..., all from same initial dense are carried out respectively
Degree proceeds to identical conversion ratio, and required time is respectively t1And t2, k1With k2Respectively T1And T2When rate constant, then have
t2/t1=k1/k2 (2)
If: Tn-Tn-1=10 DEG C
It can be obtained by formula (1) (2):
(4) temperature coefficient r
Logarithm is taken to formula (3) both sides, is obtained after arrangement:
Tn=A+Blgtn (4)
Wherein, A, B are coefficient, B=-10/lgr
Temperature coefficient r=10-10/B, sample different temperatures T is tracked using near-infrared methodniLower accelerated aging test is different
The stabilization agent effective content of ageing time obtains stabilization agent effective content-time changing curve, with the consumption of stabilization agent effective content
50% is used as critical pumping rate, obtains different temperatures TniCorresponding crash time tni, through substituting into
(4) formula carries out one-variable linear regression, obtains coefficient B using least square method, and then temperature coefficient r is calculated.
(5) thermal acceleration degradation and life prediction
By double-base propellant, T at Yu Danyi temperaturenLower thermal acceleration degradation carries out near-infrared to charge center region
Spectral scan obtains the stabilization agent effective content of different ageing times, using effective content consumption 50% as critical pumping rate, obtains
Temperature TnThe crash time t of lower stabilization agent consumptionn, according to the powder charge safe storage life at a temperature of formula (3) extrapolation storage environment.
Accumulation double-base propellant safe storage life near-infrared rapid Estimation method of the invention, bring Advantageous effect
Fruit is embodied in the following aspects:
1. during stabilization agent plays stable effect in double-base propellant, not only No. II centralite itself has stable effect
Fruit, No. II centralite derivative still have stable effect, are the important components of stabilization agent effective content, therefore, biradical
No. II centralite content in propellant powder ageing process is stabilization agent effective content.Since the derivative species of No. II centralite are more,
Structure is complicated, it is difficult to obtain, the method for obtaining near-infrared stabilization agent effective content modeling sample by degradation overcomes more
The preparation of kind stabilization agent derivative and proportion problem, have avoided the high double-base propellant manufacturing process of complicated risk, and quickly, just
Prompt, low cost, environmental protection.
2. the near-infrared stabilization agent effective content modeling sample of accelerated ageing method preparation is obtained not by control sample time
With stabilization agent effective content, reach and be evenly distributed in variation range, solves technique manufacture bring low content sample distribution
Non-uniform defect.
3. near-infrared method measurement stabilization agent effective content process is quick, safe, lossless, easy to operate, reduce bromination
Sample needs the inflammable process of refluxing extraction for 24 hours in low boiling point ether solvent when No. II centralite separation in analysis by titration,
Solve common bromine reacted with No. II centralite generate bromide chemical titration detection time-consuming, low efficiency bring pollution
The problems such as.There is near infrared light very strong penetration capacity not need to carry out any pre-treatment, can wear in test sample
Saturating glass and plastics package are directly detected, and any chemical reagents, near infrared ray double-base propellant sample are not needed yet
The method of product chemical stability, sample only do the scanning of near infrared spectrum, and it is effective can to measure double-base propellant sample stabilization agent
Content is compared without extracting, titrating with titration assay method, and this method has avoided 24 hours or more aether backflows and extracted peace
The inflammable process for determining agent, neither can cause environmental pollution, and save a large amount of reagent expense, while improving safety.It is close red
The minute of external spectrum is short, and the test job of a double-base propellant sample can be completed in 2-5min, has quick
Advantage.
4. when the previous temperature coefficient for obtaining typical double-base propellant, destructive detection is carried out using chemical titration, with
Track different temperatures difference ageing time typical case's double-base propellant stabilization agent effective content, to obtain 6 agings at a temperature of at least four
The corresponding relationship of time and stabilization agent effective content, and then be fitted and obtain temperature coefficient, it is seen then that temperature is obtained using chemical titration
Coefficient is spent, 25 or more sample measurement stabilization agent effective contents are at least needed.After the modeling of near-infrared stabilization agent effective content, tracking
When 4 temperature thermal acceleration aging sample stabilization agent changes of contents, only 4 samples is needed to carry out non-damaged data, avoided chemistry
Titration needs repeatedly to take out aging sample and carries out destructive detection, and sample size reduces 84%, while having avoided multiple (each temperature
Degree point at least 6 times) the risky operation process that is mechanically pulverized of sampling more quickly, convenient realizes big while essential safety
Width reduces costs.
5. using the consumption 50% of stabilization agent effective content as critical pumping rate, using predicting equationPowder charge safe storage life is obtained, it is pre- to establish accumulation double-base propellant safe storage life
Estimate method.It is this to carry out the near-infrared non-destructive testing of stabilization agent effective content using single temperature thermal acceleration aging and to simple sample
Method add compared with GJB770B-2005 method 506.1 estimates storage life thermal acceleration aging process without carrying out multiple temperature
Fast aging and repeatedly sampling carry out the destructive detection of stabilization agent effective content titration, it is only necessary to which near-infrared method tracks one
At a temperature of a powder charge sample difference ageing time stabilization agent effective content can obtain safe storage life, more quickly,
Convenient, sample size reduces 96%, realizes double-base propellant safe storage life rapid Estimation.
Detailed description of the invention
Fig. 1 capillary exhaust pipe ground is reduced bottle, 1- capillary exhaust pipe, and 2- ground is reduced bottle cap, and 3- ground is reduced bottle body
Fig. 2 capillary exhaust pipe is reduced case, 1- capillary exhaust pipe, and 2- is reduced case lid, and 3- is reduced cabinet
Fig. 3 double-base propellant SF-1 internal calibrations collection sample atlas of near infrared spectra
Fig. 4 double-base propellant SF-1 different temperatures effective stabilizer content changes over time relation curve
Below in conjunction with drawings and examples, the present invention is described in further detail.
Specific embodiment
Accumulation double-base propellant safe storage life predictor method of the invention, which is characterized in that this method is added using heat
Fast aging process prepares stabilization agent effective content near-infrared modeling sample, is obtained using chemical titration or high performance liquid chromatography double
Base propellant powder sample stabilization agent effective content chemical score, using near-infrared diffuse spectrometer acquisition spectrum, pass through stoichiometry
Establish stabilization agent effective content near-infrared quantitative model；Using effective stabilizer content consumption 50% as safe storage life
Critical pumping rate carries out double-base propellant thermal acceleration degradation, obtains temperature coefficient by effective stabilizer changes of contents rule,
Establish safe storage life predicting equation；Using effective stabilizer content consumption 50% as critical pumping rate, Near-Infrared Absorption Method tracking inspection
Single temperature thermal acceleration ageing process accumulation double-base propellant stabilization agent effective content is surveyed, the arrival of stabilization agent effective content is obtained and faces
The crash time of boundary's criterion consumption is obtained by safe storage life predicting equation at a temperature of accumulating double-base propellant storage environment
Safe storage life.
(1) thermal acceleration aging process prepares stabilization agent effective content near-infrared modeling sample
Double-base propellant is fitted into capillary gas vent ground decrement bottle accelerated aging test, interval time at single temperature
Sampling, prepares the propellant powder sample of different stabilization agent effective contents, is divided into internal calibrations collection sample and external certificate collection sample.
(2) stabilization agent effective content near-infrared quantitative model
1. obtaining nitrate esters explosive wastewater sample stabilization agent effective content using chemical titration or high performance liquid chromatography
Chemical score determines content range.
2. acquiring near infrared spectrum to internal calibration set sample and verifying collection sample using near infrared spectrometer.Sample mode
For diffusing reflection, sampling wave band is 1600nm~2400nm, optimizes spectral scan parameter, determine optimum resolution, scanning times and
Sample duplicate measurements number.Collected near infrared spectrum is transmitted to computer.
3. carrying out pretreatment and linear fit to internal calibration set sample near infrared spectrum using chemometrics method.Choosing
Key band is selected, in normalization, baseline is smooth, first derivation, second order derivation, selects in multiplicative scatter correction preprocessing procedures
It selects mode alone or in combination to pre-process acquisition spectrum, regression fit is then carried out using Partial Least Squares, that is, PLS method,
Calibration model is established, external certificate is carried out to model built with external certificate collection sample, internal inspection and outside according to model
Verify the appraisement system combined, successive optimization model.
According to the stabilization agent effective content near-infrared quantitative model of foundation, using near infrared spectrometer to selected sample into
The worst error of the measurement of row stabilization agent effective content, acquisition near-infrared predicted value, chemical score and near-infrared predicted value should be less than marking
The repeatability error of quasi- method.
(3) safe storage life
Double-base propellant chemical stability predicting equation
In formula: t0- indicate storage environment temperature safety storage life, d；
tn- indicate high temperature accelerated ageing time, d；
The reaction rate temperature coefficient that r-expression temperature difference is 10 DEG C；
Tn- indicate high temperature accelerated aging test temperature, DEG C；
T0- indicate storage environment temperature, DEG C.
(4) temperature coefficient r
1. debugging safety-type constant temperature oil bath baking oven, keep it constant in 4 different temperatures, temperature interval is 10 DEG C.
2. double-base propellant is placed on capillary gas vent ground decrement bottle, it is respectively placed in 4 safety-type constant temperature of different temperatures
Thermal acceleration aging is carried out in oil bath baking oven, according to the stabilization agent effective content near-infrared quantitative model of foundation, using near infrared light
Spectrometer carries out tracking and measuring to stabilization agent effective content, critical as safe storage life using the consumption 50% of stabilization agent effective content
Criterion obtains 4 groups of temperature and high temperature thermal acceleration aging crash time corresponding relationship, and using formula (4), fitting obtains temperature system
Number:
R=10-10/B
(5) thermal acceleration degradation and life prediction
Double-base propellant is stacked in capillary exhaust pipe decrement bottle, gun propellant charge sample, Yu Dan are prepared
T at a temperature of onenLower thermal acceleration degradation, Selection Center region carry out near infrared spectrum scanning, obtain different ageing times
Stabilization agent effective content obtains temperature T using effective content consumption 50% as critical pumping ratenThe time t of lower stabilization agent consumptionn,
According to the safe storage life t at a temperature of formula (4) extrapolation double-base propellant powder charge storage environment0。
Embodiment 1: nitrate esters gun propellant charge safe storage life
(1) thermal acceleration aging process prepares No. II centralite effective content near-infrared modeling sample
Typical double-base propellant SF-1 is fitted into the thermal acceleration aging at 95 DEG C in capillary gas vent ground decrement bottle, and every 4 is small
When sample, prepare the double-base propellant samples of different stable agent contents, 60 SF-1 aged samples collected, wherein 29 samples
(number 1-29) is used as internal calibrations collection, carries out linear fit and cross-validation, 31 samples are as external certificate collection
(number 30-60) is used for external certificate.
(2) No. II centralite effective content near-infrared quantitative models
1. the device used, which includes that match is silent, flies the scientific and technological near infrared spectrometer Antaris II of generation that, computer, chemical titration
The device of No. II centralite effective content is measured, and using silent winged scientific and technological chemo metric software TQAnalyst of generation that of match etc..
2. No. II centralite effective content chemical score is obtained according to National Military Standard (GJB770B-2005 method in SF-1
210.1) " centralite bromination method " measures No. II centralite effective content of all samples, in the range of for 2.53%~
0.37%.
3. close red to double-base propellant internal calibrations collection sample and the acquisition of external certificate collection sample using near infrared spectrometer
External spectrum.Sample mode is diffusing reflection, and sampling wave band is 700nm~2500nm, resolution ratio 8cm-1, scan 64 times, each sample
Product duplicate measurements 5 times.Collected internal calibrations collection near infrared spectrum (attached drawing 3) is transmitted to computer by USB data line.
Using your science and technology chemo metric software TQAnalyst of the silent winged generation of match to internal calibration set sample near infrared spectrum into
Row pretreatment and linear fit.Key band is selected, using normalization method, baseline is smooth, first derivation and multiplicative scatter correction
The methods of carry out preprocessing procedures, establish calibration model, external certificate carried out to model built with external certificate collection sample,
The appraisement system that internal inspection and external certificate according to model combine, successive optimization model.Table 1 gives several different pre-
The parameter of processing method, the preferable spectral model of different dimensions.
The parameter of the preferable spectral model of table 1
| Preprocess method | Dimension | R | RMSEP |
| Min-max normalization | 5 | 0.9952 | 0.241 |
| Multiplicative scatter correction | 5 | 0.9993 | 0.089 |
| Full spectrum normalization+baseline is smooth+first derivation | 5 | 0.9999 | 0.088 |
| First derivative+MSC | 6 | 0.9997 | 0.154 |
| First derivative+SNC | 6 | 0.9994 | 0.214 |
As can be seen from Table 1, it is smoothly combined in advance with first derivation within the scope of 1600nm~2400nm using normalization, baseline
The model of processing is optimal.The preprocess method is finally used, it is most that dimension, which selects the Partial Least-Squares Regression Model established when 5,
It is good, the evaluation index R=0.9999, RMSEP=0.088 of model.The regression model is as fixed in double-base propellant SF-1 II
Agent effective content near-infrared quantitative model.
It is right near infrared spectrometer Antaris II according to the double-base propellant SF-1 near-infrared Quantitative Prediction Model of foundation
10 samples for accurately measuring No. II centralite effective content with chemical titration are predicted that detailed results are shown in Table 2, chemistry
The worst error of value and near-infrared predicted value should be less than the repeatability error of standard method.
No. II centralite effective content prediction result of 2 10 samples to be tested of table
| Sample number into spectrum | Chemical score/% | Near-infrared predicted value/% | Error/% |
| 1 | 2.53 | 2.52 | -0.01 |
| 2 | 2.22 | 2.25 | 0.03 |
| 3 | 1.96 | 1.97 | 0.01 |
| 4 | 1.75 | 1.74 | -0.01 |
| 5 | 1.33 | 1.29 | -0.04 |
| 6 | 1.15 | 1.12 | -0.03 |
| 7 | 1.03 | 1.05 | 0.02 |
| 8 | 0.74 | 0.74 | 0.00 |
| 9 | 0.59 | 0.61 | 0.02 |
| 10 | 0.37 | 0.36 | -0.01 |
(3) reliable temperature coefficient r
1. debugging safety-type oil bath baking oven, keep its temperature constant at 95 ± 1 DEG C, 85 ± 1 DEG C, 75 ± 1 DEG C and 65 ± 1 DEG C；
2. by double-base propellant SF-1 be fitted into capillary gas vent ground decrement bottle in (attached drawing 1), be respectively placed in 95 ± 1 DEG C,
Thermal acceleration aging is carried out in 85 ± 1 DEG C, 75 ± 1 DEG C and 65 ± 1 DEG C safety-type oil bath baking ovens, for the sample of different ageing times
Product, using No. II centralite effective content near-infrared quantitative model of near infrared spectrometer and double-base propellant SF-1, tracking and measuring
No. II centralite effective content changes (being shown in Table 3).Obtain the corresponding pass of ageing time and No. II centralite content at 4 temperature
System.
No. II centralite effective content of 3 SF-1 of table
Fig. 4 gives the critical pumping rate using No. II centralite consumption 50% as safe storage life, obtain 4 groups of temperature and
Accelerated ageing corresponding time relationship.
4 different temperatures of table and setting time corresponding relationship
| Temperature/DEG C | 95 | 85 | 75 | 65 |
| Safe storage life/d | 4.5454 | 18.3386 | 78.2132 | 337.2148 |
Using Bei Seluote equation model, obtain:
T=105.4025-16.0214lgt (R2=0.9998)
Temperature coefficient:
R=4.21
(4) thermal acceleration degradation and life prediction
Double-base propellant powder charge safe storage life predicting equation
Double-base propellant SF-1 is stacked in being reduced case with capillary exhaust pipe, double-base propellant accumulation examination is prepared
Sample, the thermal acceleration aging at 71 DEG C, near-infrared method inspection center region II centralite effective content are consumed to critical pumping rate
50% obtains high temperature thermal acceleration aging crash time tn=131d, according to biradical hair at 30 DEG C of storage environment temperature of formula (5) extrapolation
Penetrate the safe storage life 130.2a of medicine SF-1 powder charge.
Claims (1)
1. double-base propellant safe storage life predictor method is stored in a kind of accumulation, which is characterized in that this method utilizes thermal acceleration
Aging process prepares stabilization agent effective content near-infrared quantitative model modeling sample, using chemical titration or high performance liquid chromatography
Obtain double-base propellant sample stabilization agent effective content chemical score, using near-infrared diffuse spectrometer acquisition spectrum, passing through
It learns meterological and establishes stabilization agent effective content near-infrared quantitative model；Using stabilization agent effective content consumption 50% as safe storage
The critical pumping rate in service life carries out accumulation storage double-base propellant thermal acceleration degradation, is changed by stabilization agent effective content and advised
Rule obtains temperature coefficient, establishes powder charge safe storage life predicting equation；Using the consumption 50% of stabilization agent effective content as critical
Criterion, the single temperature thermal acceleration ageing process accumulation storage double-base propellant stabilization agent effective content of Near-Infrared Absorption Method tracing detection,
The crash time that stabilization agent effective content reaches critical pumping rate consumption is obtained, is accumulated by safe storage life predicting equation
Safe storage life at a temperature of storage double-base propellant storage environment, specifically follows these steps to carry out:
(1) accelerated ageing method prepares near-infrared method detection effective stabilizer content modeling sample
Double-base propellant is fitted into the accelerated ageing under certain temperature in capillary exhaust pipe ground decrement bottle, interval time sampling, system
The double-base propellant sample of standby different stabilization agent effective contents, is divided into internal calibrations collection sample and external certificate collection sample；
(2) effective stabilizer content near-infrared quantitative model
1. obtaining double-base propellant sample stabilization agent effective content chemical score using chemical titration or high performance liquid chromatography, really
Determine content range；
2. acquiring near infrared spectrum, sample mode to internal calibration set sample and external certificate collection sample using near infrared spectrometer
For diffusing reflection, sampling wave band is 700nm~2500nm, resolution ratio 8cm-1, scan 64 times, each sample duplicate measurements 5 times is adopted
The near infrared spectrum collected is transmitted to computer；
3. carrying out pretreatment and linear fit, 1600nm to internal calibration set sample near infrared spectrum using chemometrics method
Use normalization, baseline smooth within the scope of~2400nm and first derivation combined method progress Pretreated spectra, then using partially
Least square method, that is, PLS method carries out regression fit, establishes calibration model, is carried out with external certificate collection sample to model built external
It is effectively stable to obtain it for verifying, the appraisement system that internal inspection and external certificate according to model combine, successive optimization model
Agent content near-infrared quantitative model；
According to the effective stabilizer content near-infrared quantitative model of foundation, selected sample is pacified using near infrared spectrometer
Determine the measurement of agent effective content, obtain near-infrared predicted value, chemical score and the worst error of near-infrared predicted value should be less than standard side
The repeatability error of method；
(3) safe storage life predicting equation
Accumulation storage double-base propellant safe storage life predicting equation
In formula: r- indicates that the temperature difference is 10 DEG C of reaction rate temperature coefficient；
t0Indicate storage environment temperature safety storage life, d；
tnIndicate high temperature thermal acceleration ageing time, d；
TnIndicate high temperature thermal acceleration degradation temperature, DEG C；
T0Indicate storage environment temperature, DEG C；
(4) temperature coefficient r
Logarithm is taken to formula (1) both sides, is obtained after arrangement:
Tn=A+Blgtn (2)
Wherein, A, B indicate coefficient, A=T0+10×lgt0/ lgr, B=-10/lgr, temperature coefficient r=10-10/B, using near-infrared
Method tracks sample different temperatures TniThe stabilization agent effective content of lower thermal acceleration degradation difference ageing time obtains stabilization agent
Effective content-time changing curve obtains different temperatures T using effective stabilizer content consumption 50% as critical pumping rateniIt is corresponding
Crash time tni, substituted into (2) formula and carry out one-variable linear regression, coefficient B is obtained using least square method, and then be calculated
Temperature coefficient r；
(5) thermal acceleration degradation and life prediction
Double-base propellant is stacked in capillary exhaust pipe decrement case, double-base propellant sample is prepared, in single temperature
Spend lower TnLower thermal acceleration degradation, Selection Center region carries out near infrared spectrum scanning, close according to its stabilization agent effective content
Infrared quantitative model obtains the stabilization agent effective content of different ageing times, using effective content consumption 50% as critical pumping rate,
Obtain temperature TniThe time t of lower stabilization agent consumptionn, according to the peace at a temperature of formula (1) extrapolation double-base propellant powder charge storage environment
Full storage life t0。
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103543248A (en) * | 2013-10-17 | 2014-01-29 | 西安近代化学研究所 | Method for evaluating pouring PBX (polymer bonded explosive) storage life based on compressibility |
| CN104792964A (en) * | 2015-05-04 | 2015-07-22 | 西安近代化学研究所 | Method for predicting storage life of NEPE (nitrate ester plasticized polyether) propellant based on deadweight induced pressure condition |
| CN104820083A (en) * | 2015-05-04 | 2015-08-05 | 西安近代化学研究所 | Predicting method of large-size NEPE propellant loading storage life |
-
2016
- 2016-07-29 CN CN201610615160.6A patent/CN106290234B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103543248A (en) * | 2013-10-17 | 2014-01-29 | 西安近代化学研究所 | Method for evaluating pouring PBX (polymer bonded explosive) storage life based on compressibility |
| CN104792964A (en) * | 2015-05-04 | 2015-07-22 | 西安近代化学研究所 | Method for predicting storage life of NEPE (nitrate ester plasticized polyether) propellant based on deadweight induced pressure condition |
| CN104820083A (en) * | 2015-05-04 | 2015-08-05 | 西安近代化学研究所 | Predicting method of large-size NEPE propellant loading storage life |
Non-Patent Citations (5)
| Title |
|---|
| "NEPE推进剂贮存寿命预估方法的比较";刘文亮 等;《化学分析计量》;20111205;第20卷(第S1期);第77-80页 |
| "NEPE推进剂贮存老化性能研究";赵永俊 等;《含能材料》;20070831;第15卷(第4期);第332-335页 |
| "基于湿热老化试验的NEPE推进剂贮存寿命预估";常新龙 等;《上海航天》;20101225;第27卷(第6期);第57-60页 |
| "硝酸酯液体推进剂长时储存性能";贾林 等;《含能材料》;20140425;第22卷(第2期);第165-169页 |
| "硝酸酯火药安全贮存寿命的预估方法和结果";衡淑云 等;《火炸药学报》;20060831;第29卷(第4期);第71-76页 |
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