CN106018333B - Accumulate double-base propellant ultimate stage rapid Estimation method - Google Patents
Accumulate double-base propellant ultimate stage rapid Estimation method Download PDFInfo
- Publication number
- CN106018333B CN106018333B CN201610614508.XA CN201610614508A CN106018333B CN 106018333 B CN106018333 B CN 106018333B CN 201610614508 A CN201610614508 A CN 201610614508A CN 106018333 B CN106018333 B CN 106018333B
- Authority
- CN
- China
- Prior art keywords
- double
- effective content
- sample
- base propellant
- infrared
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000003380 propellant Substances 0.000 title claims abstract description 93
- 238000000034 method Methods 0.000 title claims abstract description 62
- 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 claims abstract description 100
- 230000032683 aging Effects 0.000 claims abstract description 49
- 230000001133 acceleration Effects 0.000 claims abstract description 44
- 239000000126 substance Substances 0.000 claims abstract description 38
- 238000009825 accumulation Methods 0.000 claims abstract description 24
- 238000003860 storage Methods 0.000 claims abstract description 23
- 238000002329 infrared spectrum Methods 0.000 claims abstract description 19
- 238000005086 pumping Methods 0.000 claims abstract description 17
- 238000001514 detection method Methods 0.000 claims abstract description 9
- 238000003333 near-infrared imaging Methods 0.000 claims abstract description 9
- 238000005259 measurement Methods 0.000 claims abstract description 7
- 230000015556 catabolic process Effects 0.000 claims description 21
- 238000006731 degradation reaction Methods 0.000 claims description 21
- 238000004448 titration Methods 0.000 claims description 19
- 239000003795 chemical substances by application Substances 0.000 claims description 15
- 238000009795 derivation Methods 0.000 claims description 10
- 238000001228 spectrum Methods 0.000 claims description 10
- 238000012360 testing method Methods 0.000 claims description 9
- 238000012795 verification Methods 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 238000004128 high performance liquid chromatography Methods 0.000 claims description 7
- 230000006641 stabilisation Effects 0.000 claims description 7
- 238000011105 stabilization Methods 0.000 claims description 7
- 238000012937 correction Methods 0.000 claims description 6
- 238000010606 normalization Methods 0.000 claims description 6
- 230000003595 spectral effect Effects 0.000 claims description 6
- 238000013213 extrapolation Methods 0.000 claims description 4
- 238000007689 inspection Methods 0.000 claims description 4
- 238000005457 optimization Methods 0.000 claims description 4
- 238000010561 standard procedure Methods 0.000 claims description 4
- 238000007781 pre-processing Methods 0.000 claims description 3
- 238000012417 linear regression Methods 0.000 claims description 2
- 238000004587 chromatography analysis Methods 0.000 claims 1
- 239000007791 liquid phase Substances 0.000 claims 1
- 239000012071 phase Substances 0.000 claims 1
- 230000000087 stabilizing effect Effects 0.000 claims 1
- 238000006467 substitution reaction Methods 0.000 claims 1
- 239000000843 powder Substances 0.000 abstract description 3
- 238000003483 aging Methods 0.000 description 15
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 12
- 239000003814 drug Substances 0.000 description 8
- 238000005070 sampling Methods 0.000 description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 239000002360 explosive Substances 0.000 description 5
- 229940079593 drug Drugs 0.000 description 4
- 238000004880 explosion Methods 0.000 description 4
- 239000002351 wastewater Substances 0.000 description 4
- 238000002512 chemotherapy Methods 0.000 description 3
- 230000001066 destructive effect Effects 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 239000004615 ingredient Substances 0.000 description 3
- 238000004811 liquid chromatography Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 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
- 238000003556 assay Methods 0.000 description 2
- 238000005844 autocatalytic reaction Methods 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 229960003711 glyceryl trinitrate Drugs 0.000 description 2
- 229920001220 nitrocellulos Polymers 0.000 description 2
- 238000002203 pretreatment Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 229910004679 ONO2 Inorganic materials 0.000 description 1
- 230000031709 bromination Effects 0.000 description 1
- 238000005893 bromination reaction Methods 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000002790 cross-validation Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000010238 partial least squares regression Methods 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing 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
- 238000012827 research and development Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
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
- 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
- G01N21/3563—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light for analysing solids; Preparation of samples therefor
Landscapes
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Investigating Or Analysing Materials By Optical Means (AREA)
Abstract
A kind of accumulation double-base propellant ultimate stage rapid Estimation method, No. II centralite effective content near-infrared quantitative model modeling sample of double-base propellant is prepared using thermal acceleration aging process, near infrared spectrum is acquired, No. II centralite effective content near-infrared quantitative model is established by Chemical Measurement；With reliable temperature coefficient r0Establish ultimate stage predicting equation；Near-infrared method tracing detection accumulates No. II centralite effective content in double-base propellant thermal acceleration ageing process, the crash time that effective content reaches critical pumping rate consumption is obtained, the accumulation propellant powder ultimate stage at a temperature of the operating mode and storage environment of being extrapolated by ultimate stage predicting equation.This method only needs a sample difference ageing time effective content at near-infrared method one temperature of lossless tracking that can obtain ultimate stage, and sample size reduces 96%, safety, low cost.
Description
Technical field
The invention belongs to explosive wastewater security evaluation field, it is related to a kind of explosive wastewater operating mode, storage process ultimate stage
Rapid Estimation method.It is especially a kind of to be diffused spectrometry detection accumulation double-base propellant (SF) single temperature heat using near-infrared
No. II centralite effective content of accelerated ageing sample obtains the time that No. II centralite effective content reaches critical pumping rate consumption,
According to the method for accumulating double-base propellant ultimate stage at a temperature of ultimate stage predicting equation rapid Estimation operating mode and storage environment.
Background technology
Explosive wastewater chemical stability is that explosive wastewater keeps its chemical property to be no more than permission under operating mode, storage requirement
Range is so that cause the ability of safety accident.
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 heated or storage process, O-NO2Key fracture releases energy,
The nitrogen oxides with autocatalysis is generated simultaneously, and nitrogen oxides is further catalyzed energy ingredient decomposition, continues slow heat release
And heat accumulation is generated, chemical stability is reduced, leads to burning, explosion, influences production and storing stability.
It is No. II centralite conduct of addition in double-base propellant to improve the effective method of double-base propellant chemical stability
Stabilization agent, it can absorb the nitrogen oxides that double-base propellant decomposes to give off, to inhibit nitrogen oxides to decompose double-base propellant
Autocatalysis, while generating still there is stable No. II centralite derivative of effect, energy ingredient is delayed to decompose, improve pair
Base propellant powder chemical stability.No. II centralite and its derivative total content are known as No. II centralite effective content, operating mode and storage
The time undergone under the conditions of depositing when No. II centralite effective content drops to critical pumping rate is double-base propellant ultimate stage, is being pacified
Double-base propellant chemical stability is good in periodically.
Double-base propellant obtains ultimate stage using the method that hot thermal acceleration degradation tracks No. II centralite effective content,
In common chemical titration (bromine reacts the chemical method for generating bromide with stabilization agent) or high effective liquid chromatography for measuring II
Determine agent effective content, No. II centralite effective content of sample crushed using aether backflow even longer time extraction in 24 hours,
Low boiling point solvent ether is inflammable and explosive, and by pacifying when mechanical crushing double-base propellant aging sample preparation extracted by ether sample
Full property is poor, and the bromide that cumbersome, time-consuming and chemical titration generates brings pollution.It is obtained by hot thermal acceleration degradation
Different temperatures under No. II centralite effective content changing rule of aging sample, with the Arrhenius Equation obtain ultimate stage when,
Since thermal acceleration degradation at least uses 4 temperature spots (65 DEG C, 75 DEG C, 85 DEG C, 95 DEG C), each temperature spot sampling number is extremely
It it is less 6 times, the aged samples amount needed is big, and duration of test runs 6 months or more extremely takes, and long-time high temperature thermal acceleration
Aging is dangerous high, it is difficult to meet chemical stability design and evaluation demand in new formula research and development and technical process.
There is the double-base propellant of certain size for operating mode and storage process, it is old by thermal acceleration when ultimate stage is estimated
Change experiment thermal histories and will produce heat accumulation, on the one hand leads to thermal field uneven distribution, cause stabilization agent content distribution uneven,
Easily because of heat accumulation burning and explosion accident occur for another aspect double-base propellant multi-temperature point degradation, accordingly, it is difficult to logical
It crosses the multiple temperature spot thermal acceleration degradations of double-base propellant and is stabilized using chemical titration or high performance liquid chromatography
Agent content judges ultimate stage, it is difficult to meet the needs of chemical stability is evaluated in double-base propellant storage process.
Near-infrared spectrum technique is that the frequency multiplication, sum of fundamental frequencies information based on X-H (X-C, N, O) in organic molecule carry out substance
The spectral technique of qualitative and quantitative analysis has the advantages that convenient, lossless, green.The stable biradical transmitting of accumulation of No. II centralite
Medicine ultimate stage rapid Estimation method, can safely, time saving, inexpensive, the stable biradical hair of accumulation of environmentally friendly No. II centralite of acquisition
Penetrate medicine ultimate stage.
Invention content
Exist for defect or deficiency, the purpose of the present invention existing for above-mentioned existing accumulation double-base propellant ultimate stage technology
In, a kind of accumulation double-base propellant ultimate stage rapid Estimation method is provided, this method can safely, it is time saving, inexpensive, environmentally friendly obtains
Double-base propellant ultimate stage must be accumulated.
In order to realize that above-mentioned task, the present invention take the following technical solution：
A kind of accumulation double-base propellant ultimate stage rapid Estimation method, which is characterized in that this method utilizes thermal acceleration aging
Method prepares No. II centralite effective content near-infrared quantitative model modeling sample of double-base propellant, using chemical titration or efficiently
Liquid chromatography obtain No. II centralite effective content chemical score, using near-infrared diffuse spectrometer acquire spectrum, passing through
It learns meterological and establishes No. II centralite effective content near-infrared quantitative model；Double-base propellant thermal acceleration degradation is carried out, is led to
It crosses No. II centralite effective content changing rule and obtains reliable temperature coefficient r0, establish ultimate stage predicting equation；Then carry out single
One temperature accumulates double-base propellant thermal acceleration degradation, double-base propellant II in near-infrared method tracing detection ageing process
Centralite effective content obtains the time that No. II centralite effective content reaches critical pumping rate consumption, according to the ultimate stage side of estimating
Ultimate stage at a temperature of journey and reliable temperature coefficient extrapolation operating mode and storage environment.Specifically follow these steps to carry out：
(1) thermal acceleration aging process prepares No. II centralite effective content near-infrared modeling sample
Double-base propellant is fitted into capillary exhaust pipe ground decrement bottle the thermal acceleration degradation at single temperature, when interval
Between sample, prepare the double-base propellant sample of different No. II centralite effective contents.It is divided into calibration set sample and verification collection sample.
(2) No. II centralite effective content near-infrared quantitative models
1, No. II centralite effective content chemistry of double-base propellant is obtained according to chemical titration or high performance liquid chromatography
Value, determines content range；
2, using near infrared spectrometer, to calibration set sample and verification collection sample collection near infrared spectrum.Sample mode is
Diffusing reflection, sampling wave band are 700nm-2500nm, optimize spectral scan parameter, determine optimum resolution, scanning times and sample
Duplicate measurements number.Collected near infrared spectrum is transmitted to computer.
3, pretreatment and linear fit are carried out to the near infrared spectrum of calibration set sample using chemometrics method.Selection
Key band, in normalization, baseline is smooth, first derivation, second order derivation, selects in multiplicative scatter correction preprocessing procedures
Mode pre-processes acquisition spectrum alone or in combination, then Partial Least Squares, that is, PLS methods is used to carry out regression fit, built
Vertical calibration model carries out external certificate, the internal inspection according to model and external certificate phase with verification collection sample to institute's established model
In conjunction with appraisement system, successive optimization model.
According to foundation No. II centralite effective content near-infrared quantitative model, using near infrared spectrometer to selected sample
Product carry out the assay of effective stabilizer, obtain near-infrared predicted value.Chemical score and the worst error of near-infrared predicted value are answered
Less than standard method repeatability error.
(3) ultimate stage predicting equation
Nitrate esters energetic material decomposes the chemical reaction for causing No. II centralite effective content of double-base propellant to change, clothes
From the Arrhenius Equation, indicate that the accurate empirical formula of k-T relationships is：
The temperature coefficient r for defining reaction speed is the variation multiplying power that temperature often rises 10 DEG C of rate constants：
R=kT+10/kTFormula (2)
In formula：R indicates that the temperature difference is 10 DEG C of reaction rate temperature coefficient；
kTIndicate T DEG C when rate constant；
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/k2Formula (3)
If：Tn-Tn-1=10 DEG C
It can be obtained by formula (1) (2)：
In formula：R indicates that the temperature difference is 10 DEG C of reaction rate temperature coefficient；
t0Indicate storage environment temperature ultimate stage, d；
tnIndicate high temperature thermal acceleration ageing time, d；
TnIndicate high temperature thermal acceleration degradation temperature, DEG C；
T0Indicate operating mode or storage environment temperature, DEG C.
(4) reliable temperature coefficient r0
Logarithm is taken to formula (4) both sides, is obtained after arrangement：
Tn=A+BlgtnFormula (5)
Wherein, B=-10/lgr
Temperature coefficient r=10-10/B, using near-infrared method tracking and testing sample different temperatures TniLower thermal acceleration aging examination
No. II centralite effective content of different time is tested, No. II centralite effective content of different temperatures is obtained and changes over time relationship song
Line obtains different temperatures T using No. II centralite effective content consumption 50% as critical pumping rateniCorresponding time tni, through generation
Enter (5) formula and carry out one-variable linear regression, coefficient B is obtained using least square method, and then temperature coefficient r is calculated.
In double-base propellant ultimate stage predicting equation, reliable temperature coefficient ensure that chemical stability is good in ultimate stage.
Reliable temperature coefficient value is less than normal, and acquisition ultimate stage is short, and reliability is high, but value is too small, and ultimate stage is overly conservative, destroys in advance
It causes to waste；Conversely, the value of reliable temperature coefficient is excessive, acquisition ultimate stage is long, when being more than safe storage life, causes thermal explosion
It is fried.Therefore, using 0.9 times of the mean value of a variety of typical double-base propellant temperatures coefficient and standard deviation difference as reliable temperature system
Number r0。
(5) thermal acceleration degradation and ultimate stage
For accumulating double-base propellant, double-base propellant is positioned over and is reduced in case (attached drawing 2) with capillary exhaust pipe, system
Standby double-base propellant accumulates sample, in single temperature TnLower thermal acceleration degradation, Selection Center region carry out near infrared spectrum
Scanning, obtains No. II centralite effective content of different ageing times, using effective content consumption 50% as critical pumping rate, obtains
Temperature TniThe time t of lower stabilization agent consumptionn, according to accumulating biradical transmitting at a temperature of formula (4) rapid Estimation operating mode and storage environment
Medicine ultimate stage.
The accumulation double-base propellant ultimate stage rapid Estimation method of the present invention, the advantageous effects brought are embodied in following
Several aspects：
1, during No. II centralite of double-base propellant plays stable effect, not only No. II centralite itself has stable
Effect, No. II centralite derivative still have stable effect, are the important components of No. II centralite effective content, because
This, the stable agent content in double-base propellant ageing process is No. II centralite effective content.Due to No. II centralite derivative
Type is more, complicated, it is difficult to obtain, obtaining No. II centralite effective content of near-infrared by thermal acceleration degradation models sample
The method of product overcomes a variety of No. II centralite derivatives and prepares and match problem, avoided the high biradical hair of complicated danger
Penetrate medicine manufacturing process, convenient, safety, low cost, environmental protection.
2, No. II centralite effective content modeling sample of near-infrared prepared by thermal acceleration aging process is by controlling sample time
The sample for obtaining different No. II centralite effective contents, reaches and is evenly distributed in variation range, solves technique manufacture and brings
The non-uniform defect of low content sample distribution.
3, chemical titration and high performance liquid chromatography are that stable agent content damages detection method, are needed to biradical transmitting
Medicine sample detects No. II centralite effective content after carrying out mechanical crushing, and near infrared light has very strong penetration capacity, examining
When sample, any pre-treatment need not be carried out, the scanning of near infrared spectrum is directly done to sample, you can measure double-base propellant
On the one hand No. II centralite effective content of sample has been avoided in chemical titration and high performance liquid chromatography without extraction, titration
Sample needs the inflammable process of refluxing extraction for 24 hours in low boiling point ether solvent when the separation of No. II centralite, solve time-consuming,
The problems such as efficiency is low and pollutes, saves a large amount of reagent expense, while improving safety；On the other hand, near infrared spectrum
Minute is short, and the test job of a double-base propellant sample can be completed in 2-5min, is had the advantages that quick.
When 4, obtaining the temperature coefficient of double-base propellant in the past, destructive detection is carried out using chemical titration, tracking is not
Synthermal difference No. II centralite effective content of ageing time is determined with obtaining 6 ageing times at a temperature of at least four with No. II
The correspondence of agent effective content, and then be fitted and obtain temperature coefficient, it is seen then that temperature coefficient is obtained using chemical titration, until
25 or more samples are needed to measure No. II centralite effective content less.After the modeling of near-infrared effective stabilizer content, 4 temperature are tracked
When spending thermal acceleration aging sample stabilization agent changes of contents, only 4 samples is needed to carry out non-damaged data, avoided chemical titration
It needs repeatedly to take out aging sample and carries out destructive detection, sample size reduces 84%, while having avoided repeatedly that (each temperature spot is extremely
Few 6 times) sampling carries out the risky operation process of mechanical crushing, more quickly, convenient, it is greatly reduced while realizing essential safety
Cost.
5, the temperature coefficient that a variety of typical double-base propellants are obtained by thermal acceleration degradation, take temperature coefficient mean value with
The 0.9 of standard deviation difference is as reliable temperature coefficient r0.Using No. II centralite effective content consumption 50% as critical pumping rate,
Using predicting equationUltimate stage is obtained, the stable biradical hair of accumulation of No. II centralite is established
Penetrate medicine ultimate stage rapid Estimation method.This method is without carrying out multiple temperature thermal acceleration agings and repeatedly sampling progress II
The destructive detection of centralite effective content titration, it is only necessary to which it is different old that near-infrared method tracks a sample at a temperature
Ultimate stage can be obtained by changing No. II centralite effective content of time, and more quickly, convenient, sample size reduces 96%, realizes No. II
The stable accumulation double-base propellant ultimate stage rapid Estimation of centralite.
Description of the drawings
Fig. 1 capillary exhaust pipe grounds are reduced bottle .1- capillary exhaust pipes, and 2- grounds are reduced bottle cap, and 3- grounds are reduced bottle.
Fig. 2 capillary exhaust pipes are reduced case .4- capillary exhaust pipes, and 5- is reduced case lid, and 6- is reduced babinet.
Fig. 3 double-base propellant SF-1 calibration set sample spectrum diagrams.
No. II centralite effective content of Fig. 4 SF-1 different temperatures changes over time relation curve.
Specific implementation mode
The accumulation double-base propellant ultimate stage rapid Estimation method of the present invention, it is fixed in No. II to be prepared using thermal acceleration aging process
Agent effective content near-infrared quantitative model modeling sample obtains No. II centralite using chemical titration or high performance liquid chromatography
Effective content chemical score, using near-infrared diffuse spectrometer acquire spectrum, establishing No. II centralite by Chemical Measurement has
Imitate content near-infrared quantitative model；Using No. II centralite effective content consumption 50% as the critical pumping rate of ultimate stage, carry out heap
Product double-base propellant thermal acceleration degradation obtains temperature coefficient, with a variety of by No. II centralite effective content changing rule
Double-base propellant temperature coefficient mean value is used as reliable temperature coefficient r with the 0.9 of standard deviation difference0, obtain the ultimate stage side of estimating
Journey；Then carry out single temperature thermal acceleration degradation, No. II centralite of sample in near-infrared method tracing detection ageing process
Effective content obtains the crash time that No. II centralite effective content reaches critical pumping rate consumption, according to ultimate stage predicting equation
And the ultimate stage at a temperature of reliable temperature coefficient extrapolation operating mode and storage environment.Specifically follow these steps to carry out：
(1) thermal acceleration aging process prepares No. II centralite effective content near-infrared modeling sample
Double-base propellant is fitted into hot at single temperature in capillary exhaust pipe ground decrement bottle (semi-enclosed condition, attached drawing 1)
Accelerated aging test, interval time sampling prepare the double-base propellant sample of different No. II centralite effective contents, are divided into correction
Collect sample and verification collection sample.
(2) No. II centralite effective content near-infrared quantitative models
1, the device used includes near infrared spectrometer, computer, high performance liquid chromatography, chemical titration II
Device and chemo metric software of centralite effective content etc..
No. II centralite according to chemical titration or all double-base propellant samples of high effective liquid chromatography for measuring is effective
Content determines content range.
2, using near infrared spectrometer to calibration set sample and verification collection sample collection near infrared spectrum.Sample mode is unrestrained
Reflection, sampling wave band are 700nm-2500nm, optimize spectral scan parameter, determine optimum resolution, scanning times and sample weight
Multiple pendulous frequency.Collected near infrared spectrum is transmitted to computer.
3, pretreatment and linear fit are carried out to calibration set sample near infrared spectrum using chemometrics method.Selection is special
Levy bands of a spectrum, in normalization, baseline is smooth, first derivation, second order derivation, select in multiplicative scatter correction preprocessing procedures it is single
Solely or combination pre-processes acquisition spectrum, then Partial Least Squares, that is, PLS methods is used to carry out regression fit, established
Calibration model carries out external certificate with verification collection sample to institute's established model, and the internal inspection according to model is mutually tied with external certificate
The appraisement system of conjunction, successive optimization model.
According to foundation No. II centralite effective content near-infrared quantitative model, using hand near infrared spectrometer to selected
Sample carries out the assay of effective stabilizer, obtains near-infrared predicted value.The worst error of chemical score and near-infrared predicted value
Less than standard method repeatability error.
(3) ultimate stage predicting equation
Accumulate double-base propellant stability predicting equation
In formula：r0Indicate that the temperature difference is 10 DEG C of reaction rate reliable temperature coefficient；
t0Indicate storage environment temperature ultimate stage, d；
tnIndicate high temperature thermal acceleration ageing time, d；
TnIndicate high temperature thermal acceleration degradation temperature, DEG C；
T0Indicate operating mode or storage environment temperature, DEG C.
(4) reliable temperature coefficient r0
1, safety-type oil bath baking oven is debugged, keeps it constant in 4 different temperatures, temperature interval is 10 DEG C.
2, double-base propellant is placed on capillary exhaust pipe ground decrement bottle (semi-enclosed condition, Fig. 1), is respectively placed in 4 not
Thermal acceleration aging is carried out in synthermal safety-type constant temperature oil bath baking oven, it is fixed according to foundation No. II centralite effective content near-infrared
Model is measured, tracking and measuring is carried out using No. II centralite effective content of near infrared spectrometer pair, with No. II centralite effective content
Consumption 50% is used as ultimate stage critical pumping rate, 4 temperature and high temperature thermal acceleration aging crash time correspondence is obtained, using public affairs
Formula (5), fitting obtain temperature coefficient：
R=10-10/B
The temperature coefficient of a variety of typical double-base propellants is obtained using the above method.The value of reliable temperature coefficient is less than normal,
It is short to obtain ultimate stage, reliability is high, but value is too small, and ultimate stage is overly conservative, destroys cause to waste in advance；Reliable temperature coefficient
Value it is excessive, obtain ultimate stage it is long, be more than safe storage life when, cause thermal explosion.Therefore, with a variety of biradical transmittings of typical case
The mean value of medicine temperature coefficient is with 0.9 times of standard deviation difference as reliable temperature coefficient r0。
(5) thermal acceleration degradation and ultimate stage
Double-base propellant accumulation is positioned over and is reduced in case (attached drawing 2) with capillary exhaust pipe, double-base propellant heap is prepared
Product sample, the T at single temperaturenLower thermal acceleration degradation, Selection Center region carry out near infrared spectrum scanning, obtain different
No. II centralite effective content of ageing time obtains temperature T using effective content consumption 50% as critical pumping rateniIt is lower stable
The time t of agent consumptionn, according to accumulation double-base propellant ultimate stage at a temperature of formula (6) extrapolation operating mode or storage environment.
Embodiment 1
It is illustrated as representative using typical double-base propellant SF-1.
(1) thermal acceleration aging process prepares No. II centralite effective content near-infrared modeling sample
Typical double-base propellant SF-1 is packed into (semi-hermetic item in capillary exhaust pipe ground decrement bottle (Φ=4cm, H=8cm)
Part, attached drawing 1) the thermal acceleration aging at 95 DEG C, it samples within every 5 hours, prepares the biradical transmitting of different No. II centralite effective contents
Medicine sample collects 60 SF-1 samples, wherein 29 samples (number 1-29) are used as calibration set, carries out linear fit and inside
Cross validation, 31 samples integrate (number is 30-60) for external certificate as 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 of measurement, and using the silent winged generation that science and technology chemo metric software TQ Analyst of match
Deng.
2, according to National Military Standard (GJB770B-2005 methods 210.1)《Centralite bromination method》, measure all SF-1
No. II centralite effective content of sample, in the range of 2.53%~0.30%.
3, using near infrared spectrometer to above-mentioned selected double-base propellant calibration set sample collection near infrared spectrum.Sampling
Mode is diffusing reflection, and sampling wave band is 700nm-2500nm, resolution ratio 8cm-1, scan 64 times, each sample duplicate measurements 5
It is secondary.Collected near infrared spectrum is transmitted to computer (attached drawing 3) by USB data line.
Pretreatment and Linear Quasi are carried out to calibration set sample near infrared spectrum using chemo metric software TQ Analyst
It closes.Key band is selected, using normalization method, baseline is smooth and the derivation of first derivation second order, multiplicative scatter correction or combinations thereof
Form pre-processes calibration set sample spectra, then uses Partial Least Squares,
I.e. PLS methods carry out regression fit, establish No. II centralite effective content near-infrared quantitative model.Collect sample with verification
External certificate is carried out to institute's established model, the appraisement system that the internal inspection and external certificate according to model are combined, successive optimization
Model.Table 1 gives the parameter of preferable spectral model when several different pretreatments methods, different dimensions.
The parameter of 1 preferable spectral model of table
| Preprocess method | Dimension | R | RMSEP |
| Min-max normalizes | 5 | 0.9952 | 0.241 |
| Multiplicative scatter correction | 5 | 0.9993 | 0.089 |
| 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 using normalization, baseline within the scope of 1600nm-2400nm
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 recurrence has as No. II centralite of double-base propellant SF-1
Imitate content near-infrared quantitative model.
According to No. II centralite effective content near-infrared Quantitative Prediction Model of double-base propellant SF-1 of foundation, with close red
External spectrum instrument predicts 10 samples for accurately measuring No. II centralite effective content with chemical titration, detailed results
2 are shown in Table, chemical score and the worst error of near-infrared predicted value are not more than -0.04%.The maximum of chemical score and near-infrared predicted value
Error should be less than standard method repeatability error.
The table centralite effective content prediction results of sample to be tested II of 2 double-base propellant SF-1 10
(3) reliable temperature coefficient r0It obtains
1, safety-type oil bath baking oven is debugged, keeps its temperature constant at 95 ± 1 DEG C, 85 ± 1 DEG C, 75 ± 1 DEG C and 65 ± 1 DEG C
2, double-base propellant SF-1 is packed into (semi-hermetic item in capillary exhaust pipe ground decrement bottle (Φ=4cm, H=8cm)
Part, attached drawing 1), it is respectively placed in 95 ± 1 DEG C, 85 ± 1 DEG C, 75 ± 1 DEG C and 65 ± 1 DEG C safety-type oil bath baking ovens and carries out thermal acceleration
Aging effectively contains the sample of different ageing times using No. II centralite of near infrared spectrometer and double-base propellant SF-1
Measure near-infrared quantitative model, No. II centralite effective content variation (being shown in Table 3) of tracking and measuring.Obtain ageing time at 4 temperature
With the correspondence of No. II centralite content.
Ageing time and No. II centralite effective content at table 3 double-base propellant SF-1,4 temperature
Fig. 4 gives using No. II centralite effective content consumption 50% as the critical pumping rate of ultimate stage, obtains 4 groups of temperature
With thermal acceleration aging crash time correspondence.
4 different temperatures of table and thermal acceleration aging crash time correspondence
| Temperature/DEG C | 95 | 85 | 75 | 65 |
| Ultimate stage/d | 4.5454 | 18.3386 | 78.2132 | 337.2148 |
Using Bei Seluote equation models, obtain：
T=105.4025-16.0214lgt (R=0.9980)
Temperature coefficient：
r10=4.21
The temperature coefficient of 13 kinds of typical double-base propellants is obtained according to the method described above, as shown in table 5 below.13 kinds of typical cases are biradical
The mean value of the temperature coefficient of propellant powder is 4.07, standard deviation 0.38, and mean value is taken to be used as reliable temperature with the 0.9 of standard deviation difference
Spend coefficient, r0=3.32.
The temperature coefficient of more than 5 kinds of double-base propellant of table
(4) thermal acceleration degradation and ultimate stage
Accumulate double-base propellant ultimate stage predicting equation
Double-base propellant accumulation is positioned over (attached drawing in capillary exhaust pipe decrement case (25cm × 25cm × 25cm)
2) double-base propellant accumulation sample, the thermal acceleration aging at 71 DEG C, near-infrared method inspection center region II centralite, are prepared
Effective content is consumed to critical pumping rate 50% and obtains high temperature thermal acceleration ageing time tn=131d, using accumulation double-base propellant peace
Regular predicting equation (6), it is 49.2a to estimate the accumulation double-base propellant ultimate stage at 30 DEG C of storage environment temperature.
Claims (1)
1. a kind of accumulation double-base propellant ultimate stage rapid Estimation method, which is characterized in that this method utilizes accelerated ageing legal system
No. II centralite effective content near-infrared quantitative model modeling sample of standby double-base propellant, according to chemical titration or efficient liquid phase
Chromatography obtain No. II centralite effective content chemical score, using near-infrared diffuse spectrometer acquire spectrum, pass through chemistry meter
Amount is learned and establishes No. II centralite effective content near-infrared quantitative model；Using No. II centralite effective content consumption 50% as stabilizing
The critical pumping rate of phase monitors a variety of typical double-base propellant thermal acceleration ageing process stabilization agent changes of contents and obtains temperature coefficient,
Using a variety of double-base propellant temperature coefficient mean values and the 0.9 as reliable temperature coefficient r of standard deviation difference0, establish ultimate stage
Predicting equation；Carry out single temperature accelerated aging test, double-base propellant sample in near-infrared method tracing detection ageing process
No. II centralite effective content obtains the time that No. II centralite effective content reaches critical pumping rate consumption, pre- according to ultimate stage
Estimate equation and reliable temperature coefficient estimates the ultimate stage of accumulation double-base propellant at a temperature of operating mode and storage environment, specifically presses following
Step carries out：
(1) accelerated ageing method prepares No. II centralite effective content near-infrared modeling sample
Double-base propellant be fitted into capillary exhaust pipe ground decrement bottle at single temperature thermal acceleration degradation, interval time take
Sample prepares the double-base propellant sample of different No. II centralite effective contents, is divided into calibration set sample and verification collection sample；
(2) No. II centralite effective content near-infrared quantitative models
1, No. II centralite effective content chemistry of double-base propellant sample is obtained according to chemical titration or high performance liquid chromatography
Value, determines content range；
2, using near infrared spectrometer, to above-mentioned selected sample collection near infrared spectrum, sample mode is diffusing reflection, characteristic wave
Section is 1600nm-2400nm, optimizes spectral scan parameter, determines optimum resolution, scanning times and sample duplicate measurements number,
Collected near infrared spectrum is transmitted to computer；
3, pretreatment and linear fit are carried out to above-mentioned near infrared spectrum using chemometrics method, it is flat in normalization, baseline
Selected in cunning, first derivation, second order derivation, multiplicative scatter correction preprocessing procedures alone or in combination mode to acquire spectrum
It is pre-processed, then Partial Least Squares, that is, PLS methods is used to carry out regression fit, establish calibration model, collect sample with verification
External certificate is carried out to institute's established model, the appraisement system that the internal inspection and external certificate according to model are combined, successive optimization
Model；
According to foundation No. II centralite effective content near-infrared quantitative model, using near infrared spectrometer to selected sample into
The worst error of No. II centralite effective content measurement of row, acquisition near-infrared predicted value, chemical score and near-infrared predicted value is answered small
In standard method repeatability error；
(3) ultimate stage predicting equation
Accumulate double-base propellant ultimate stage predicting equation
In formula：r0Indicate that the temperature difference is 10 DEG C of reaction rate reliable temperature coefficient；
t0Indicate storage environment temperature ultimate stage, d；
tnIndicate high temperature accelerated ageing time, d；
TnIndicate high temperature accelerated aging test temperature, DEG C；
T0Indicate operating mode or storage environment temperature, DEG C；
(4) reliable temperature coefficient r0
Logarithm is taken to formula (1) both sides, is obtained after arrangement：
Tn=A+BlgtnFormula (2)
A, B are coefficient, wherein B=-10/lgr in formula
Temperature coefficient r=10-10/B, using near-infrared method tracking and testing double-base propellant different temperatures TniLower accelerated aging test
No. II centralite effective content of different ageing times obtains No. II centralite effective content of different temperatures and changes over time relationship
Curve obtains different temperatures T using No. II centralite effective content consumption 50% as critical pumping rateniCorresponding time tni, warp
(2) formula of substitution carries out one-variable linear regression, obtains coefficient B using least square method, and then temperature coefficient r is calculated；
The temperature coefficient that a variety of typical double-base propellants are obtained using the above method, with its mean value and the 0.9 of standard deviation difference
It is used as reliable temperature coefficient r again0；
(5) thermal acceleration degradation and ultimate stage
Double-base propellant is positioned over and is reduced in case with capillary exhaust pipe, double-base propellant accumulation sample is prepared, in single temperature
Spend TnLower accelerated aging test, Selection Center region carry out near infrared spectrum scanning, and it is fixed in No. II of different ageing times to obtain
Agent effective content obtains temperature T using effective content consumption 50% as critical pumping ratenThe time t of lower stabilization agent consumptionn, according to public affairs
The ultimate stage of double-base propellant is accumulated at a temperature of formula (1) extrapolation storage environment.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610614508.XA CN106018333B (en) | 2016-07-29 | 2016-07-29 | Accumulate double-base propellant ultimate stage rapid Estimation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610614508.XA CN106018333B (en) | 2016-07-29 | 2016-07-29 | Accumulate double-base propellant ultimate stage rapid Estimation method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106018333A CN106018333A (en) | 2016-10-12 |
| CN106018333B true CN106018333B (en) | 2018-10-12 |
Family
ID=57115068
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610614508.XA Active CN106018333B (en) | 2016-07-29 | 2016-07-29 | Accumulate double-base propellant ultimate stage rapid Estimation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106018333B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107478674B (en) * | 2017-07-27 | 2019-12-10 | 西安近代化学研究所 | Microcalorimetry for evaluation of stability of single-base propellant during 10-year storage |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1904584A (en) * | 2006-07-26 | 2007-01-31 | 哈尔滨工业大学 | Fast analysis method of ammonium perchlorate particle size in solid propellant |
| CN102608160A (en) * | 2012-03-01 | 2012-07-25 | 西安近代化学研究所 | Testing system for critical pressure during thermal explosion of explosives |
| CN103499551A (en) * | 2013-09-25 | 2014-01-08 | 武汉大学 | Method for identifying aging degree of bonding interface of binders |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002077608A2 (en) * | 2001-03-22 | 2002-10-03 | University Of Utah | Optical method and apparatus for determining status of agricultural products |
-
2016
- 2016-07-29 CN CN201610614508.XA patent/CN106018333B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1904584A (en) * | 2006-07-26 | 2007-01-31 | 哈尔滨工业大学 | Fast analysis method of ammonium perchlorate particle size in solid propellant |
| CN102608160A (en) * | 2012-03-01 | 2012-07-25 | 西安近代化学研究所 | Testing system for critical pressure during thermal explosion of explosives |
| CN103499551A (en) * | 2013-09-25 | 2014-01-08 | 武汉大学 | Method for identifying aging degree of bonding interface of binders |
Non-Patent Citations (7)
| Title |
|---|
| ASE-HPLC 检测某型号球形发射药中的叠氮硝胺、硝化甘油、Ⅱ号中定剂含量的研究;贾林等;《分析测试技术与仪器》;20081231;第14卷(第4期);全文 * |
| 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》;20111231;第20卷;全文 * |
| 丁羟推进剂的热加速老化力学性能及寿命预估;王国强等;《火炸药学报》;20150228;第38卷(第1期);全文 * |
| 含AP的浇铸PBX 炸药的热安全性;王琼等;《含能材料》;20150725;第23卷(第7期);全文 * |
| 国外固体推进剂及其粘结界面贮存老化研究进展;赵永俊等;《火箭推进》;20080630;第34卷(第3期);全文 * |
| 湿热环境对RDX/AP-NEPE推进剂热安全性及力学性能的影响;朱一举等;《火炸药学报》;20141231;第37卷(第6期);全文 * |
| 高温加速老化对DNTF性能的影响;祝艳龙等;《2014年含能材料与钝感弹药技术学术研讨会论文集》;20141231;全文 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106018333A (en) | 2016-10-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106290236B (en) | Nitrate esters explosive wastewater powder charge ultimate stage rapid Estimation method | |
| CN103018195B (en) | Method for determination of PCTFE content in PBX explosive by near infrared spectrum | |
| Baptista et al. | Multivariate near infrared spectroscopy models for predicting the iodine value, CFPP, kinematic viscosity at 40 C and density at 15 C of biodiesel | |
| CN106290231B (en) | Nitrate esters explosive wastewater powder charge safe storage life predictor method | |
| CN101413885A (en) | Near-infrared spectrum method for rapidly quantifying honey quality | |
| CN106290232B (en) | Accumulation storage single-base gun propellant safe storage life predictor method | |
| CN106525761A (en) | Nitrite detection method based on terahertz spectroscopy scanning | |
| CN106018333B (en) | Accumulate double-base propellant ultimate stage rapid Estimation method | |
| CN103063599B (en) | The method of prediction oil density is composed by transmitted infrared light | |
| CN106290237B (en) | Composite modified double-base propellant powder charge ultimate stage rapid Estimation method | |
| CN106645020A (en) | Method for quickly determining oxidation stability of gasoline | |
| CN204255854U (en) | A kind of system simultaneously detecting 7 indexs in coal sample | |
| CN103592256A (en) | Mid-infrared spectroscopic method for distinguishing normal edible vegetable oil from refined hogwash oil based on Fourier transform | |
| CN106290172B (en) | Accumulate triple-base propellant ultimate stage rapid Estimation method | |
| CN106290222B (en) | Composite modified double-base propellant powder charge safe storage life predictor method | |
| CA2635930C (en) | Fourier transform infrared (ftir) chemometric method to determine cetane number of diesel fuels containing fatty acid alkyl ester additives | |
| CN103134764B (en) | The method of prediction true boiling point curve of crude oil is composed by transmitted infrared light | |
| CN106290235B (en) | Accumulate single-base gun propellant ultimate stage rapid Estimation method | |
| CN106290223B (en) | Accumulation storage triple-base propellant safe storage life predictor method | |
| CN106290233B (en) | Double base propellant powder charge ultimate stage rapid Estimation method | |
| CN106093292B (en) | A kind of NEPE propellant loadings safe storage life predictor method | |
| CN106290234B (en) | Accumulate double-base propellant safe storage life predictor method | |
| CN102954945B (en) | A kind of method by infrared spectrum measurement acid value for crude oil | |
| CN104568811A (en) | Novel rapid detection method of calorific values in coal samples | |
| CN106226266B (en) | A kind of double base propellant powder charge safe storage life predictor method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |