CN110530817A - A kind of β-HMX crystal form purity detection method of the spectral technology that diffuses infrared based in - Google Patents
A kind of β-HMX crystal form purity detection method of the spectral technology that diffuses infrared based in Download PDFInfo
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- 239000013078 crystal Substances 0.000 title claims abstract description 113
- UZGLIIJVICEWHF-UHFFFAOYSA-N octogen Chemical compound [O-][N+](=O)N1CN([N+]([O-])=O)CN([N+]([O-])=O)CN([N+]([O-])=O)C1 UZGLIIJVICEWHF-UHFFFAOYSA-N 0.000 title claims abstract description 90
- 238000001514 detection method Methods 0.000 title claims abstract description 36
- 230000003595 spectral effect Effects 0.000 title claims abstract description 18
- 238000005516 engineering process Methods 0.000 title claims abstract description 15
- 238000001228 spectrum Methods 0.000 claims abstract description 55
- 238000000034 method Methods 0.000 claims abstract description 22
- 238000013094 purity test Methods 0.000 claims abstract description 8
- 239000000126 substance Substances 0.000 claims abstract description 8
- 238000005259 measurement Methods 0.000 claims abstract description 7
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 claims description 20
- 238000002156 mixing Methods 0.000 claims description 13
- 238000002360 preparation method Methods 0.000 claims description 10
- 238000012937 correction Methods 0.000 claims description 7
- 239000003153 chemical reaction reagent Substances 0.000 claims description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 5
- 238000010606 normalization Methods 0.000 claims description 5
- 239000003085 diluting agent Substances 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- 238000003113 dilution method Methods 0.000 claims description 2
- 238000001238 wet grinding Methods 0.000 claims description 2
- 239000012535 impurity Substances 0.000 abstract description 5
- 239000000028 HMX Substances 0.000 description 26
- 238000000227 grinding Methods 0.000 description 14
- 239000002360 explosive Substances 0.000 description 8
- 239000000843 powder Substances 0.000 description 6
- 238000004611 spectroscopical analysis Methods 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 4
- 239000002351 wastewater Substances 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- 238000012935 Averaging Methods 0.000 description 3
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 238000002790 cross-validation Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000012895 dilution Substances 0.000 description 3
- 238000010790 dilution Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- UOYIYWCAYFTQLH-UHFFFAOYSA-N 3,7-dinitro-1,3,5,7-tetrazabicyclo[3.3.1]nonane Chemical class C1N2CN([N+](=O)[O-])CN1CN([N+]([O-])=O)C2 UOYIYWCAYFTQLH-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000012417 linear regression Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000007781 pre-processing Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 238000009827 uniform distribution Methods 0.000 description 2
- 241000208340 Araliaceae Species 0.000 description 1
- 238000004497 NIR spectroscopy Methods 0.000 description 1
- 235000005035 Panax pseudoginseng ssp. pseudoginseng Nutrition 0.000 description 1
- 235000003140 Panax quinquefolius Nutrition 0.000 description 1
- 238000001069 Raman spectroscopy Methods 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000002512 chemotherapy Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 235000008434 ginseng Nutrition 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 238000000491 multivariate analysis Methods 0.000 description 1
- 238000001225 nuclear magnetic resonance method Methods 0.000 description 1
- 238000010238 partial least squares regression Methods 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000003380 propellant Substances 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 239000012898 sample dilution Substances 0.000 description 1
- 238000005464 sample preparation method Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000004449 solid propellant Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
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- 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
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Abstract
The invention belongs to technical fields, and in particular to a kind of β-HMX crystal form purity detection method of the spectral technology combination Chemical Measurement Partial Least Squares that diffuses infrared based in.The infrared spectral technology combination Chemical Measurement Partial Least Squares that diffuses establishes β-HMX crystal form purity quantitative calibration models and corresponding crystal form purity test method in detection method use.Built multivariate calibration model can analyze overlapped spectra and broad band, and the crystal form purity suitable for the β-HMX product containing α-HMX impurity crystal form is analyzed.
Description
Technical field
The invention belongs to explosive wastewater technical fields, and in particular to one kind be based in it is infrared diffuse spectral technology combine chemistry
β-HMX crystal form purity the detection method of meterological Partial Least Squares.
Background technique
Octogen (HMX) is that density is big, energy is high, sensitivity is low in current single chmical compound explosive, the explosive of high comprehensive performance,
It is widely used to the model powder charge in the fields such as high energy composite explosives, solid propellant and propellant powder.HMX has tetra- kinds of α, β, γ, δ
Crystal form, with 3,7- dinitro -1,3,5,7- tetra- azabicyclo [3,3,1] nonanes (DPT) are the HMX terminal that intermediate is synthetically prepared
Product is there are two kinds of crystal forms of α-HMX and β-HMX, and wherein β-HMX sensitivity is low, energy is high, is the practical crystal form haveing excellent performance, α-
HMX is impurity crystal form.In order to control HMX product quality, need to establish the test method of β-HMX crystal form purity；In addition, β-HMX
Crystal form purity detection for the stable crystal form Journal of Sex Research and its corresponding weapons and ammunitions during explosive wastewater technical process, long storage
Safety, reliability consideration have great significance and are worth.
The crystal form quantitative approach of allomorphism have x-ray powder diffraction, Raman spectroscopy, in infrared/near infrared light
Spectrometry, terahertz light spectrometry, solid-state nuclear magnetic resonance method and differential scanning calorimetry etc., above-mentioned each method is quantitatively divided in drug crystal forms
It is not yet universal in explosive wastewater field using more in analysis.There is scholar to establish β-HMX crystal form using near infrared spectroscopy in recent years
Method for detecting purity, this method is only applicable to the sample detection that sample size is greater than 5g, for synthetic sample lab scale stage, product thing
Therefore study carefully because the detection of micro-example crystal form purity has certain limitation in the links such as analysis；Further, since explosive wastewater material on friction,
The sensibility of the environmental stimulis such as shock, heat should be selected in the selection of test method as far as possible for the technical security for guaranteeing detection process
Select the detection method that sample dosage is few, safety coefficient is high.Mid-infrared light spectrometry is since amount of samples is few, the safety of photoinduction etc.
Feature has significant advantage in single chmical compound explosive crystal form quantitative detection.
It is retrieved through domestic and foreign literature, has no the phase for carrying out the measurement of β-HMX crystal form purity using Diffuse Reflectance FTIR
Close document report.
Summary of the invention
(1) technical problems to be solved
The present invention proposes a kind of β-HMX crystal form purity detection method of spectral technology that diffuses infrared based in, to solve
The technical issues of how β-HMX to sample size less than 10mg, containing α-HMX impurity crystal form carries out crystal form purity detection.
(2) technical solution
In order to solve the above-mentioned technical problem, the present invention proposes that one kind infrared spectral technology that diffuses in combines based on chemistry
Amount learns the detection method of the β-HMX crystal form purity of Partial Least Squares, and detection method includes the following steps for this:
The preparation of S1, calibration set sample: β-HMX, α-HMX the mixing crystal form samples for preparing a series of different component contents are made
For calibration set sample, β-HMX crystal form purity is calculated as follows:
In formula: ωβFor β-HMX crystal form purity in sample, it is expressed as a percentage；mβFor the title sample matter of β-HMX crystal form in sample
Amount；mαFor the title sample quality of α-HMX crystal form in sample；
Infrared diffusing reflection spectrum acquisition in S2, calibration set sample: attached using mid-infrared light spectrometer combination diffusing reflection spectrum
Part carries out spectra collection to calibration set sample；
The foundation of S3, β-HMX crystal form purity quantitative calibration models: it is pre- that spectrum is carried out to diffusing reflection spectrum infrared in acquisition
Processing, using Partial Least Squares establish in correlation between infrared diffusing reflection spectrum and β-HMX crystal form purity, obtain β-
HMX crystal form purity quantitative calibration models；
The crystal form purity detection of S4, sample to be tested: the β-HMX crystal form purity quantitative calibration models based on foundation treat test sample
Product are detected, and each sample is measured in parallel twice, take its average value as β-HMX crystal form purity testing result.
Further, in step sl, the preparation of calibration set sample is carried out using wet grinding, vacuum drying mode
The mixing of different crystal forms component.
Further, in step sl, chromatographically pure normal hexane is selected to grind reagent as wet-mixing.
Further, in step s 2, collection sample is corrected using mid-infrared light spectrometer combination diffusing reflection spectrum attachment
Spectra collection, and carry out Kubelka-Munk correction；Spectral scanning range 4000cm-1~400cm-1, resolution ratio 2cm-1, sweep
It retouches number 128 times.
Further, in step s 2, sample preparation methods are dilution method, the mixed proportion of sample and diluent potassium bromide
For 1:100.
Further, in step s3, β-HMX crystal form purity quantitative calibration models are established using chemometrics method,
And the detection of β-HMX crystal form purity is carried out to sample to be tested based on this model.
Further, in step s3, preprocessing procedures include that vector normalizes, min-max normalizes, is polynary
Scatter correction.
(3) beneficial effect
β-HMX crystal form purity the detection method of the spectral technology that diffuses infrared based in proposed by the present invention, it is red in
Outside diffuse spectral technology combination Chemical Measurement Partial Least Squares establish β-HMX crystal form purity quantitative calibration models and accordingly
Crystal form purity test method.Built multivariate calibration model can analyze overlapped spectra and broad band, be suitable for containing α-HMX
The crystal form purity of the β-HMX product of impurity crystal form is analyzed.
The invention has the following advantages that
(1) the present invention is based on multivariate data analysis methods, can intersect, extract effectively letter in the spectra bands characteristic of overlapping
Breath, the crystal form quantitative analysis suitable for no independent characteristic bands of a spectrum.
(2) present invention can within 10min~15min time Accurate Determining β-HMX crystal form purity, and amount of samples is less than
10mg solves the synthetic sample lab scale stage, product accident is studied carefully because micro-example crystal form purity is difficult to detect in the links such as analysis
The problem of, the stable crystal form Journal of Sex Research for β-HMX control of product quality, production technology and long storage process provides detection foundation.
Detailed description of the invention
Fig. 1 is the spectrum and standard spectrum comparison diagram after different crystal forms HMX sample pretreatment:
Fig. 1 a is spectrum after β-HMX sample pretreatment and standard spectrum comparison diagram, after Fig. 1 b is α-HMX sample pretreatment
Spectrum and standard spectrum comparison diagram；
Fig. 2 is sample and the infrared spectrogram that diffuses in the β-HMX of potassium bromide different mixing proportion in the content of present invention；
Fig. 3 is the infrared spectrogram that diffuses in the β-HMX of different resolution in the content of present invention；
Fig. 4 is infrared diffusing reflection spectrum in calibration set sample in embodiment: Fig. 4 a is infrared unrestrained in calibration set sample
Reflection absorption spectrum, Fig. 4 b are the Kubelka-Munk spectrum of calibration set sample.
Specific embodiment
To keep the purpose of the present invention, content and advantage clearer, with reference to the accompanying drawings and examples, to tool of the invention
Body embodiment is described in further detail.
The present embodiment proposes a kind of spectral technology combination Chemical Measurement Partial Least Squares that diffuses infrared based in
β-HMX crystal form purity detection method, this method use in infrared dioffuse spectrum instrument, diffusing reflection spectrum attachment combination Chemical Measurement it is soft
Part detects β-HMX crystal form purity.
Specifically sequentially include the following steps:
The preparation of S1, calibration set sample: β-HMX, the α-HMX for preparing a series of (no less than 36) different component contents are mixed
Crystal form samples are closed as calibration set sample, the quality of single calibration set sample is about 200mg, content >=80% of β-HMX, and
It is in more uniform distribution in 80%~100% range.According to single sample quality and crystal form constituent content in the design of above-mentioned calibration set
Requirement, weigh two kinds of β-HMX, α-HMX crystal form standard specimens, be accurate to 0.01mg.Two kinds of crystal form standard specimens are placed in same agate to grind
In alms bowl, 5ml~8ml chromatographically pure normal hexane is moved into, the weighing bottle of Ф 25mm × 25mm is transferred to after mixed grinding 3min, is placed in 40
Dry 2h, spare in DEG C vacuum oven.
β-HMX crystal form purity is calculated as follows:
In formula: ωβFor β-HMX crystal form purity in sample, it is expressed as a percentage；mβFor the title sample matter of β-HMX crystal form in sample
Amount；mαFor the title sample quality of α-HMX crystal form in sample.
Preparation for calibration set sample:
(1) selection about calibration set sample number: having used mean value centralization in modeling, needs a sample ginseng of 6 (k+1)
With modeling, wherein k is number of main factor.The main gene numerical digit of model built of the present invention is 5, therefore calibration set sample should be no less than 36
It is a.
(2) selection about wet-mixing grinding reagent: selected reagent should be the non-solvent of HMX, and secondly the reagent should expire
Sufficient impurity content is low, boiling range is short, is easy to volatilize, and in crystal the features such as noresidue, therefore selects chromatographically pure normal hexane as wet
Method mixed grinding reagent.
(3) about the selection of mixed grinding: selection of the present invention for milling time is by black, white two kinds different face
The solid powder of color observes its mixing uniformity under same sample size and experimental condition after mixed grinding 1min, 2min, 3min
Determining experimental condition.By the naked eye, two kinds of powder elementary mixings of black and white are uniform after mixed grinding 3min, therefore in calibration set
3min mixed grinding experimental condition is selected during sample preparation.
(4) selection about mixed grinding post processing mode: the drying for low boiling point residual solvent is general to use 40 DEG C
Vacuum oven dries 2h.The present invention uses for reference conventional method, and infrared diffusing reflection spectrum follow-up observation β-HMX, α-HMX warp in use
The variation of chemical structure, crystalline structure after wet-mixing grinding, drying.As shown in Figure 1, β-HMX, α-HMX sample are located in advance
The spectrogram acquired after reason is consistent with standard spectrogram, and there is no the drifts of the generation of bands of a spectrum, disappearance and bands of a spectrum, shows three kinds of crystalline substances
There is no crystal transfer and thermal decompositions in the process for pattern product, and wet-mixing grinding, vacuum drying are as mixing crystal form
The preparation method of sample is feasible.
Infrared diffusing reflection spectrum acquisition in S2, calibration set sample.The single calibration set sample of 10mg is weighed, with 1g potassium bromide
Powder mixed grinding 3min such as is divided at three parts of quality, be respectively adopted in infrared diffusing reflection technology carry out the spectra collection of sample,
It is averaging spectrum and carries out Kubelka-Munk correction；Spectral scanning range 4000cm-1~400cm-1, resolution ratio 2cm-1, scanning
Number 128 times.
Diffusing reflection spectrum infrared in calibration set sample is acquired:
(1) instrument is Fourier Transform Infrared Spectrometer, scanning range 4000cm-1~400cm-1In it is infrared
Wave band, and it is equipped with diffusing reflection spectrum attachment.
(2) selection of sample dilution ratio: in diffusing reflection spectrum experiment, need to select potassium bromide diluent to sample into
Row dilution, to obtain preferable spectrum effects.To select suitable dilution ratio, by β-HMX sample and different amounts of potassium bromide
Mixed grinding uniformly carry out afterwards in infrared diffusing reflection spectrum detection, the mass ratio of sample and potassium bromide is respectively 1:25,1:50,
1:100,1:200 (as shown in Figure 2), when sample and potassium bromide mixed proportion are 1:100 in figure, key band related with crystal form
Absorbance meet the requirement of quantitative spectrometric between 0.2~0.7, therefore the present invention selects sample and potassium bromide mass ratio 1:100
Dilution ratio as sample.
(3) selection of sample number is acquired: due to the sample size only 3mg of single spectra collection, to make modeling sample spectrogram
It is more representative, the inhomogeneities bring deviation of sample is avoided, 10mg sample is divided into etc. three parts of quality, is respectively adopted
In infrared diffusing reflection technology carry out the spectra collection of sample, be averaging spectrum.
(4) selection of spectral resolution: the selection of spectral resolution will meet identification fingerprint region key band and finely tie
The demand of structure, meets the needs of signal-to-noise ratio again.Fig. 3 is the infrared spectrogram that diffuses in the β-HMX of different resolution.It can by figure
Know, resolution ratio is higher, and the data point of acquisition is more, and the fine structure of key band is more obvious, it is deeper to split point depth.With 4,8,
16、32cm-1It compares, 2cm-1And 1cm-1Spectrogram can differentiate the fine structure of key band well, showed in figure
For 1567cm-1、1395cm-1、760cm-1Place's key band is split point；But 1cm-1Spectrogram poor signal to noise, especially 1700~
1500cm-1There is serious steam noise, is easier to introduce noise error in modeling, unnecessary shadow is caused to testing result
It rings.Meanwhile high resolution ratio leads to the extension of Spectral acquisition times, influences detection cycle, therefore the present invention selects 2cm-1As
The spectra collection parameter of sample.
The foundation of S3, β-HMX crystal form purity quantitative calibration models: to infrared diffusing reflection in being corrected through Kubelka-Munk
Spectrum carries out Pretreated spectra, using Partial Least Squares by pretreated spectroscopic data and β-HMX crystal form purity data into
Row multiple linear regression, excluding outlier Optimized model establish a series of quantitative calibration models, and determine system by evaluation parameter
Number (R2) and cross validation standard deviation (RMSECV) superiority and inferiority of model built is ranked up, select optimal models as β-
HMX crystal form purity quantitative calibration models.
Foundation for β-HMX crystal form purity quantitative calibration models:
(1) this step need to use chemo metric software.
(2) preprocessing procedures include the methods of vector normalization, min-max normalization, multiplicative scatter correction.
(3) for model evaluation parameter R2 closer to 1, models fitting effect is better；RMSECV is smaller, shows the prediction of model
Precision and accuracy are higher, and prediction effect is better.
(4) the built β-HMX crystal form purity quantitative calibration models of the present invention are using the normalized preprocess method of vector, master
The Partial Least-Squares Regression Model established when because of subnumber being 5.
The crystal form purity detection of S4, sample to be tested: the β-HMX crystal form purity quantitative calibration models based on foundation treat test sample
Product are detected, and each sample is measured in parallel twice, take its average value as β-HMX crystal form purity testing result.
Embodiment
The preparation of S1, calibration set sample: β-HMX, the α-HMX for preparing 51 different component contents mix crystal form samples conduct
Calibration set sample, the quality of single calibration set sample are about 200mg, content >=80% of β-HMX, and in 80%~100% model
In more uniform distribution in enclosing.According to the requirement of single sample quality and crystal form constituent content in the design of above-mentioned calibration set, β-is weighed
Two kinds of crystal form standard specimens of HMX, α-HMX, are accurate to 0.01mg.Two kinds of crystal form standard specimens are placed in same agate mortar, immigration 5ml~
8ml chromatographically pure normal hexane is transferred to the weighing bottle of Ф 25mm × 25mm after mixed grinding 3min, is placed in 40 DEG C of vacuum ovens
Dry 2h, it is spare.
β-HMX crystal form purity is calculated as follows:
In formula: ωβFor β-HMX crystal form purity in sample, it is expressed as a percentage；mβFor the title sample matter of β-HMX crystal form in sample
Amount；mαFor the title sample quality of α-HMX crystal form in sample.
The weighing value of calibration set sample and the calculated value of β-HMX crystal form purity are shown in Table 1.
The weighing value of 1 calibration set sample of table and the calculated value of β-HMX crystal form purity
Infrared diffusing reflection spectrum acquisition in S2, calibration set sample.Using 870 type Fourier transform infrared of U.S. Nexus
Spectrometer is corrected infrared diffusing reflection spectrum acquisition in collection sample.The single calibration set sample of 10mg is weighed, with 1g potassium bromide
Powder mixed grinding 3min such as is divided at three parts of quality, be respectively adopted in infrared diffusing reflection technology carry out the spectra collection of sample,
It is averaging spectrum and carries out Kubelka-Munk correction (as shown in Figure 4)；Spectral scanning range 4000cm-1~400cm-1, differentiate
Rate 2cm-1, scanning times 128 times.
The foundation of S3, β-HMX crystal form purity quantitative calibration models: using Germany's Bruker company OPUS meterological software,
Pretreated spectra is carried out to diffusing reflection spectrum infrared in correcting through Kubelka-Munk, will be pre-processed using Partial Least Squares
Spectroscopic data and β-HMX crystal form purity data afterwards carries out multiple linear regression, rejects 2 exceptional value Optimized models, establishes one
Serial quantitative calibration models, and pass through the evaluation parameter coefficient of determination (R2) and cross validation standard deviation (RMSECV) to being modeled
The superiority and inferiority of type is ranked up, and selects optimal models as β-HMX crystal form purity quantitative calibration models.
Table 2 is the major parameter of the 6 β-HMX crystal form purity quantitative calibration models preferably gone out, is determined by evaluation parameter
Coefficient (R2) and cross validation standard deviation (RMSECV) sequence, obtain optimal β-HMX crystal form purity quantitative calibration models
Parameter: vector normalization, number of main factor 5, modeling spectral region 4000cm-1~1840cm-1、1480cm-1~1120cm-1。
The crystal form purity detection of S4, sample to be tested: 17 β-HMX, α-HMX are prepared according to the method for step S1 and mix crystal form
Sample calculates the β-HMX crystal form purity of sample as true value as sample to be tested.β-HMX crystal form purity based on foundation is fixed
Amount calibration model detects sample to be tested, and each sample is measured in parallel twice, takes its average value as β-HMX crystal form purity
Testing result the results are shown in Table 3.As shown in Table 3, β-HMX crystal form purity testing result is compared with true value, and accidentally absolute value of the difference is small
In 1.5%, show that the model can meet crystal form purity detection demand.
The major parameter of the preferred β-HMX quantitative calibration models of table 2
3 β-HMX crystal form purity testing result list of table
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, without departing from the technical principles of the invention, several improvement and deformations can also be made, these improvement and deformations
Also it should be regarded as protection scope of the present invention.
Claims (7)
1. a kind of β-HMX crystal form purity of the spectral technology combination Chemical Measurement Partial Least Squares that diffuses infrared based in
Detection method, which is characterized in that described detection method includes the following steps:
The preparation of S1, calibration set sample: β-HMX, α-HMX the mixing crystal form samples of a series of different component contents are prepared as school
Positive collection sample, β-HMX crystal form purity are calculated as follows:
In formula: ωβFor β-HMX crystal form purity in sample, it is expressed as a percentage；mβFor the title sample quality of β-HMX crystal form in sample；
mαFor the title sample quality of α-HMX crystal form in sample；
Infrared diffusing reflection spectrum acquisition in S2, calibration set sample: mid-infrared light spectrometer combination diffusing reflection spectrum attachment pair is used
Calibration set sample carries out spectra collection；
The foundation of S3, β-HMX crystal form purity quantitative calibration models: spectrum is carried out to diffusing reflection spectrum infrared in acquisition and is located in advance
Reason, using Partial Least Squares establish in correlation between infrared diffusing reflection spectrum and β-HMX crystal form purity, obtain β-HMX
Crystal form purity quantitative calibration models；
S4, sample to be tested crystal form purity detection: the β-HMX crystal form purity quantitative calibration models based on foundation to sample to be tested into
Row detection, each sample are measured in parallel twice, take its average value as β-HMX crystal form purity testing result.
2. crystal form purity detection method as described in claim 1, which is characterized in that in the step S1, calibration set sample
Preparation be that the mixing of different crystal forms component is carried out using wet grinding, vacuum drying mode.
3. crystal form purity detection method as claimed in claim 2, which is characterized in that in the step S1, select chromatographically pure
Normal hexane grinds reagent as wet-mixing.
4. crystal form purity detection method as described in claim 1, which is characterized in that infrared in the step S2
Spectrometer combination diffusing reflection spectrum attachment is corrected the spectra collection of collection sample, and carries out Kubelka-Munk correction；Spectrum
Scanning range 4000cm-1~400cm-1, resolution ratio 2cm-1, scanning times 128 times.
5. crystal form purity detection method as claimed in claim 3, which is characterized in that in the step S2, sample preparation side
Method is dilution method, and the mixed proportion of sample and diluent potassium bromide is 1:100.
6. crystal form purity detection method as described in claim 1, which is characterized in that in the step S3, counted using chemistry
Amount method establishes β-HMX crystal form purity quantitative calibration models, and carries out β-HMX crystal form purity to sample to be tested based on this model
Detection.
7. crystal form purity detection method as described in claim 1, which is characterized in that in the step S3, Pretreated spectra
Method includes vector normalization, min-max normalization, multiplicative scatter correction.
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| CN112067641A (en) * | 2020-08-24 | 2020-12-11 | 西安近代化学研究所 | Method for determining crystal form purity of alpha-HMX crystal form standard substance |
| CN112067642A (en) * | 2020-08-24 | 2020-12-11 | 西安近代化学研究所 | Method for determining crystal form purity of beta-HMX crystal form standard substance |
| CN112098623A (en) * | 2020-08-24 | 2020-12-18 | 西安近代化学研究所 | Method for determining crystal form purity value of alpha-HNIW crystal form standard substance |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112067640A (en) * | 2020-08-24 | 2020-12-11 | 西安近代化学研究所 | Method for determining crystal form purity value of HNIW crystal form standard substance |
| CN112067641A (en) * | 2020-08-24 | 2020-12-11 | 西安近代化学研究所 | Method for determining crystal form purity of alpha-HMX crystal form standard substance |
| CN112067642A (en) * | 2020-08-24 | 2020-12-11 | 西安近代化学研究所 | Method for determining crystal form purity of beta-HMX crystal form standard substance |
| CN112098623A (en) * | 2020-08-24 | 2020-12-18 | 西安近代化学研究所 | Method for determining crystal form purity value of alpha-HNIW crystal form standard substance |
| CN112098444A (en) * | 2020-08-24 | 2020-12-18 | 西安近代化学研究所 | Gamma-HNIW crystal form standard substance crystal form purity value determination method |
| CN112067641B (en) * | 2020-08-24 | 2022-10-25 | 西安近代化学研究所 | Method for determining crystal form purity of alpha-HMX crystal form standard substance |
| CN112067640B (en) * | 2020-08-24 | 2022-10-25 | 西安近代化学研究所 | Crystal form purity value-defining method for epsilon-HNIW crystal form standard substance |
| CN112067642B (en) * | 2020-08-24 | 2022-10-25 | 西安近代化学研究所 | Method for determining crystal form purity of beta-HMX crystal form standard substance |
| CN112098623B (en) * | 2020-08-24 | 2022-10-25 | 西安近代化学研究所 | Method for determining crystal form purity value of alpha-HNIW crystal form standard substance |
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