CN112067612B - In-situ analysis method for crystal transformation rate of HNIW crystal form in propellant material - Google Patents
In-situ analysis method for crystal transformation rate of HNIW crystal form in propellant material Download PDFInfo
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- 239000013078 crystal Substances 0.000 title claims abstract description 280
- 238000000034 method Methods 0.000 title claims abstract description 81
- NDYLCHGXSQOGMS-UHFFFAOYSA-N CL-20 Chemical compound [O-][N+](=O)N1C2N([N+]([O-])=O)C3N([N+](=O)[O-])C2N([N+]([O-])=O)C2N([N+]([O-])=O)C3N([N+]([O-])=O)C21 NDYLCHGXSQOGMS-UHFFFAOYSA-N 0.000 title claims abstract description 80
- 230000009466 transformation Effects 0.000 title claims abstract description 46
- 239000000463 material Substances 0.000 title claims abstract description 33
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- 238000010249 in-situ analysis Methods 0.000 title claims abstract description 20
- 238000012360 testing method Methods 0.000 claims abstract description 87
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- 238000003490 calendering Methods 0.000 claims description 18
- 238000007789 sealing Methods 0.000 claims description 18
- 238000002360 preparation method Methods 0.000 claims description 16
- 239000003054 catalyst Substances 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000000706 filtrate Substances 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 7
- 238000003825 pressing Methods 0.000 claims description 7
- 238000001228 spectrum Methods 0.000 claims description 7
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- 239000002808 molecular sieve Substances 0.000 claims description 6
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 5
- 239000002360 explosive Substances 0.000 claims description 5
- GDDNTTHUKVNJRA-UHFFFAOYSA-N 3-bromo-3,3-difluoroprop-1-ene Chemical compound FC(F)(Br)C=C GDDNTTHUKVNJRA-UHFFFAOYSA-N 0.000 claims description 4
- 238000010521 absorption reaction Methods 0.000 claims description 4
- 239000000853 adhesive Substances 0.000 claims description 4
- 230000001070 adhesive effect Effects 0.000 claims description 4
- 239000007800 oxidant agent Substances 0.000 claims description 4
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- SNIOPGDIGTZGOP-UHFFFAOYSA-N Nitroglycerin Chemical compound [O-][N+](=O)OCC(O[N+]([O-])=O)CO[N+]([O-])=O SNIOPGDIGTZGOP-UHFFFAOYSA-N 0.000 description 5
- 239000000006 Nitroglycerin Substances 0.000 description 5
- 239000003575 carbonaceous material Substances 0.000 description 5
- 239000003814 drug Substances 0.000 description 5
- 229960003711 glyceryl trinitrate Drugs 0.000 description 5
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- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 2
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- 239000002994 raw material Substances 0.000 description 2
- XTFIVUDBNACUBN-UHFFFAOYSA-N 1,3,5-trinitro-1,3,5-triazinane Chemical compound [O-][N+](=O)N1CN([N+]([O-])=O)CN([N+]([O-])=O)C1 XTFIVUDBNACUBN-UHFFFAOYSA-N 0.000 description 1
- 239000000028 HMX Substances 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
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- 125000000852 azido group Chemical group *N=[N+]=[N-] 0.000 description 1
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- 239000003610 charcoal Substances 0.000 description 1
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- 239000003795 chemical substances by application Substances 0.000 description 1
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- 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 description 1
- 238000013021 overheating Methods 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
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- 229920000570 polyether Polymers 0.000 description 1
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- 238000012216 screening 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
- G01N21/84—Systems specially adapted for particular applications
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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
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/65—Raman scattering
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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
- G01N21/84—Systems specially adapted for particular applications
- G01N2021/8477—Investigating crystals, e.g. liquid crystals
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Abstract
The invention provides an in-situ analysis method for the crystal transformation rate of HNIW crystal forms in propellant materials, which comprises the following steps: step one, compactly and flatly placing a sample on a glass slide: step two, determining a crystal area under an optical microscope: step three, carrying out microscopic Raman on the crystal in-situ test to obtain an HNIW Raman spectrum: step four, acquiring single crystal Raman data, identifying a crystal form, counting a crystal transformation rate, and analyzing the crystal transformation rate of the HNIW crystal form in the propellant material according to the crystal transformation rate; step 401, standard raman spectrum acquisition of single crystals: preparing epsilon-HNIW single crystals, alpha-HNIW single crystals and gamma-HNIW single crystals, wherein after the epsilon-HNIW single crystals, the alpha-HNIW single crystals and the gamma-HNIW single crystals are subjected to crystal structure confirmation by an X-ray single crystal diffractometer, placing the single crystals under a microscope, and testing a Raman spectrum to obtain a crystal form standard Raman spectrum; step 402, crystal form identification; step 403, counting the crystal transformation rate. The method has the advantages of high efficiency, low detection limit, accuracy, reliability and feasibility.
Description
Technical Field
The invention belongs to the field of explosives, relates to hexanitrohexaazaisowurtzitane, and in particular relates to an in-situ analysis method for the crystal transformation rate of HNIW crystal forms in propellant materials.
Background
The high energy density material hexanitrohexaazaisowurtzitane (HNIW, CL-20) is applied to the propellant to greatly improve the energy, but as HNIW is a polycrystalline compound, the HNIW is loaded by solvents, components and temperature contacted in the process, and epsilon crystal form is taken as a raw material to be input into a formula and the process, and epsilon-gamma, epsilon-alpha crystal transformation problem can exist. Because of the differences of the properties of different crystal forms of explosives, including density, sensitivity, stability, combustion performance and the like, maintaining the crystal form stability of epsilon-HNIW in the propellant formulation process is a key quality index of the propellant formulation process design.
The components of the formula containing HNIW propellant relate to oxidants such as ammonium perchlorate, hexogen, octogen and the like; the plasticizer is Jina, nitroglycerin and the like; a catalyst; adhesive polybutadiene, azido polyether, nitrocotton, etc.; curing agent isocyanates; aluminum powder; carbon black. The technical process of the HNIW-containing propellant is contacted with water, solvent and the like; the curing temperature is 70-80 ℃; the drying temperature is 100-105 ℃.
Under the contact and temperature loading of HNIW and other components in the formula process, whether the HNIW crystal form is influenced or not is judged, and epsilon-HNIW of the optimal crystal form is used as the raw material input of the propellant, and the mechanism for generating crystal transformation is as follows: (1) epsilon-HNIW is transformed into gamma crystal form at high temperature, such as: the epsilon-HNIW undergoes crystal transformation at 157 ℃ at the temperature rising rate of 10 ℃/min of DSC; (2) epsilon-HNIW is transformed into alpha crystal form in a polar solvent or an aqueous system, epsilon-HNIW is in melted Gerner, and then is cooled to generate transformed gamma crystal form. (3) Aluminum powder and carbon powder in the formula are heat absorption components, heat is absorbed more easily in heating, and local overheating is caused to convert epsilon crystal form into gamma crystal form.
Microscopes are widely used for microscopic morphological observation of crystals, but generally only obtain images of the surface morphology of a substance, but cannot identify the chemical nature of the crystal. The analysis of the crystal structure is usually realized by adopting a Fourier transform infrared spectrum and an X-ray diffraction technology, different crystal forms correspond to different spectrograms, the crystal forms are judged by comparing with a standard sample spectrogram, but the detection area of conventional infrared and diffraction is larger (3 mm-5 mm), and the multi-component superposition spectrum is obtained by the general test of a composite system sample. Compared with the conventional infrared spectrum and X-ray diffraction, the laser confocal Raman spectrum can test smaller areas, the minimum detection particle size of the laser confocal Raman spectrum can reach 0.8 mu m, in-situ analysis of complex system crystals can be realized, and interference of other chemical components is eliminated. The propellant material of the composite system is analyzed in diffraction and infrared crystal forms, HNIW crystal form characteristics are distinguished from a multi-component addition spectrum of the composite system, and other component interference exists, so that the defect of lower accuracy is caused.
At present, no effective method exists for in-situ testing of HNIW crystal forms in materials of various working procedures of propellants, the existing paper is realized by adopting a Fourier transform infrared spectrum and X-ray diffraction technology, but the detection area of conventional infrared and diffraction is large (3 mm-5 mm), the general test of a composite system sample is a multi-component superposition spectrum, the accuracy of identifying the crystal forms is low, and in-situ identification of the micron-scale crystal forms cannot be realized, and the main reasons are that: (1) The applied HNIW has micron granularity, so that the accurate positioning is difficult; (2) Even if accurate positioning is realized, in-situ analysis of micron order cannot be realized at the same time. Compared with the conventional infrared spectrum and X-ray diffraction, the laser confocal Raman spectrum can test smaller areas, the minimum detection particle size of the laser confocal Raman spectrum can reach 0.8 mu m, in-situ analysis of complex system crystals can be realized, and interference of other chemical components is eliminated.
The application publication number is CN111122633A, the patent name is Chinese patent of 'method for in-situ identification of solid surface nano plastic particles based on scanning electron microscope-Raman technology', which can in-situ identify nano-grade plastics, but can not identify chemical characteristics of crystals because plastics are different from HNIW crystals in chemical characteristics.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide an in-situ analysis method for the crystal transformation rate of HNIW crystal forms in propellant materials, which aims to solve the technical problem that in-situ analysis cannot be carried out on HNIW crystal forms with micrometer dimensions in the prior art.
In order to solve the technical problems, the invention adopts the following technical scheme:
an in-situ analysis method for the crystal transformation rate of HNIW crystal forms in propellant materials, which comprises the following steps:
Step one, compactly and flatly placing a sample on a glass slide:
step two, determining a crystal area under an optical microscope:
Step three, carrying out microscopic Raman on the crystal in-situ test to obtain an HNIW Raman spectrum:
Step four, acquiring single crystal Raman data, identifying a crystal form, and counting a crystal transformation rate;
step 401, standard raman spectrum acquisition of single crystals:
Preparing epsilon-HNIW single crystals, alpha-HNIW single crystals and gamma-HNIW single crystals, wherein after the epsilon-HNIW single crystals, the alpha-HNIW single crystals and the gamma-HNIW single crystals are subjected to crystal structure confirmation by an X-ray single crystal diffractometer, placing the single crystals under a microscope, and testing a Raman spectrum to obtain a crystal form standard Raman spectrum;
Step 402, crystal form identification;
Step 403, counting the crystal transformation rate.
The invention also has the following technical characteristics:
The specific process of the first step is as follows:
the material samples of different working procedures of the propellant are divided into light-color samples and dark-color samples, white filter paper is adhered to a glass slide by using a double-sided adhesive tape and used for placing the dark-color samples, and the light-color samples are directly placed on the glass slide;
the sample is weighed to 0.5g, accurate to 0.2g, the dark sample is flatly laid on the glass slide with filter paper stuck, the light sample is directly flatly laid on the glass slide, and then the flat pressing is carried out by a blade until the density is reached. Dividing four areas by blade tips, and collecting 4-5 HNIW crystal test points in each area; placing the slide with the sample on an optical platform;
Wherein, the propellant has different material adding components in different working procedures, the color of the material is light color and dark color, the compound of main explosive, oxidant and adhesive is light color, when the compound is added with endothermic aluminum powder, carbon powder or lead catalyst, the compound is dark color;
the specific process of the second step is as follows:
Under an optical microscope, focusing is firstly performed under a 10-time magnifying glass, the positions of crystals are determined by using a knob on an optical platform, and the crystals are gradually focused at 10 times, 20 times and 50 times of magnification, and the magnification is small to large until clear target crystals are obtained.
The specific process of the third step is as follows:
setting Raman test parameters to be 785nm,1200 grating, exposure time of 10s, scanning range of 1700cm -1～150cm-1, scanning times of 1-2 times, and in order to inhibit data distortion caused by crystal transformation in the test process due to heat absorption of dark color components, the maximum laser power of a light-color sample is 25mW, and the laser power of a dark-color sample is 1.5-15 mW;
And (3) testing under a 50-time microscope, wherein each sample is tested in 4 areas of up, down, left and right, each area is tested in 4-5 HNIW crystal test points, and if the crystal Raman spectrogram found under the optical microscope is Jina, ammonium perchlorate and black-wire, the crystal points need to be found again, and 16-20 HNIW crystal test points are tested in total.
The specific procedure of step 401 is as follows:
Step 40101, epsilon-HNIW single crystal preparation: dissolving 5gHNIW ml of ethyl acetate dehydrated by a molecular sieve into concentrated HNIW solution, filtering, taking 10ml of filtrate, placing into a test tube, sealing by a sealing film, pricking 10-15 holes by a needle, and standing at room temperature until single crystals grow;
Step 40102, γ -HNIW single crystal preparation: dissolving 5gHNIW in 20ml of ethyl acetate dehydrated by molecular sieve to prepare HNIW concentrated solution, filtering, taking 10ml of filtrate, placing into a test tube, sealing with a sealing film, pricking 10-15 holes with a needle, and standing in 75 ℃ oil bath until single crystal grows;
Step 40103, α -HNIW single crystal preparation: dissolving 3gHNIW in 20ml of mixed solvent of acetone and water in the volume ratio of 4:1, preparing into concentrated solution of HNIW, filtering, taking 10ml of filtrate, placing into a test tube, sealing with a sealing film, pricking 10-15 holes with a needle, standing at room temperature until single crystal grows;
step 40104, after the crystal structures of epsilon-HNIW single crystal, alpha-HNIW single crystal and gamma-HNIW single crystal are confirmed by an X-ray single crystal diffractometer, placing the single crystal under a microscope, testing a Raman spectrum to obtain a crystal form standard Raman spectrum, setting Raman test parameters under a 50-time long-focus microscope, wherein the laser wavelength is 785nm, the wavelength of 1200 gratings is split, the exposure time is 10s, the scanning range is 1700cm -1～150cm-1, the scanning times are 2 times, and the laser power is 100 mW-200 mW.
The specific procedure of step 402 is as follows:
And (3) comparing the Raman spectrograms of the test points with the epsilon-HNIW crystal form, the alpha-HNIW crystal form and the gamma-HNIW crystal form standard Raman spectrograms obtained in the step (401), and judging the crystal form of the test points when the Raman intensity distribution and the characteristic wave number of each region of ：450cm-1～200cm-1、900cm-1～850cm-1、1400cm-1～1200cm-1、1700cm-1～1500cm-1, are the same as the standard Raman spectrograms from strong to weak in sequence in the spectrum regions with the obvious difference of the Raman spectrograms of the three crystal forms.
The specific procedure of step 403 is as follows:
the experimental points of the alpha-HNIW crystal form and the gamma-HNIW crystal form are expressed as the percentage of the total experimental points. The calculation formula is as follows:
Wherein:
c-crystal transformation rate expressed as percentage;
n α -judging the number of the experimental points of the alpha-HNIW crystal form, and if the number of the experimental points is 0.5, counting the number of alpha and epsilon mixed crystals;
n γ -judging the number of experimental points of the gamma-HNIW crystal form, and if the number of experimental points is 0.5, counting the number of gamma-HNIW crystal forms;
N-total number of test samples.
Compared with the prior art, the invention has the following technical effects:
And (I) the method finds HNIW crystal particles from materials in different working procedures on a microscopic platform through an optical lens, then ensures that the light source does not influence the stability of HNIW crystals under specific laser wavelength or laser power, and tests microscopic Raman spectra of crystal areas in situ. According to the crystal transformation types possibly caused by the process environment, three crystal preparation methods of epsilon-, gamma-, alpha-HNIW are established to obtain standard Raman crystal data, the Raman spectrogram of a test crystal micro-area is compared with a monocrystal spectrogram, crystal form analysis is performed for counting the number of the test crystals, and the HNIW crystal form crystal transformation rate of the propellant process formula material is calculated to evaluate the HNIW crystal form stability. The method has the advantages of high efficiency, low detection limit, accuracy, reliability and feasibility.
Aiming at the defects of in-situ identification and the blank of crystal transformation rate test in the prior art, the microscopic laser confocal Raman technology is introduced into in-situ identification of the crystal form of the propellant composite system, the crystal structure of the HNIW is ensured not to be influenced by laser to transform or decompose through dividing a sample area and setting test parameters, the crystal form identification and in-situ identification are realized, and Raman HNIW crystal form standard data is established for judging the HNIW crystal form in real time.
Drawings
Fig. 1 is an image of the HNIW crystalline form in the propellant material under an optical microscope, 10, 20 and 50 times in order from top to bottom.
FIG. 2 is a standard Raman spectrum of an epsilon-HNIW single crystal.
FIG. 3 is a standard Raman spectrum of an alpha-HNIW single crystal.
FIG. 4 is a standard Raman spectrum of a gamma-HNIW single crystal.
FIG. 5 is a comparison of standard Raman spectra of epsilon-HNIW, alpha-HNIW, gamma-HNIW single crystals.
FIG. 6 shows the epsilon identification of test points of HNIW in the rolling and stretching process of nitrocotton nitroglycerin.
Fig. 7 is a diagram showing the crystal transformation gamma recognition of the test point of the HNIW in the ginna nitrocotton calendaring stretching process.
Fig. 8 is a graph of HNIW recognition of the epsilon mixed crystal form at catalyst system test point gamma.
Fig. 9 is a diagram showing the crystal form identification of HNIW at the catalyst system test point α.
The following examples illustrate the invention in further detail.
Detailed Description
In the invention, the screw extrusion process refers to a process of manufacturing a molded grain by a screw extrusion process. The method comprises the following steps:
(1) And (3) an absorbent preparation process: the components are uniformly mixed and firmly combined with each other.
(2) The medicine material water-driving procedure: the absorbed medicine pulp contains 90% of water, and is completed by a water-driving machine in three times.
(3) And (3) calendaring: the absorbent medicine particles after water driving still contain 5 to 10 percent of water and are extruded by larger pressure.
(4) And (3) a drying procedure: the hot air and the medicine materials move reversely to take away the water.
(5) And (3) a spiral extrusion and stretching process: and extruding and forming the dried calendaring drug granules by a screw extrusion machine (screw press for short).
According to the granularity range (100-10 mu m) of HNIW in the propellant and the characteristics of other components, the invention designs a method for in-situ testing HNIW crystal form based on micro-laser confocal Raman spectrum, and a method for evaluating crystal form stability by calculating crystal transformation rate statistically.
Environmental analysis of epsilon-HNIW in materials: in the initial ingredients, epsilon-HNIW is fully contacted with all solid components, liquid components or low-melting point components, the encountered liquid components are nitroglycerin, the encountered low-melting point components are Jina, water and a small amount of diluting solvents of ethyl acetate and ethanol, and the encountered temperature load is generally 60-100 ℃ in the processes of drying and screw pressing.
The following examples provide an in situ analysis method for the rate of conversion of HNIW crystal forms in propellant materials, which comprises the following steps:
Step one, compactly and flatly placing a sample on a glass slide:
the material samples of different working procedures of the propellant are divided into light-color samples and dark-color samples, white filter paper is adhered to a glass slide by using a double-sided adhesive tape and used for placing the dark-color samples, and the light-color samples are directly placed on the glass slide;
the sample is weighed to 0.5g, accurate to 0.2g, the dark sample is flatly laid on the glass slide with filter paper stuck, the light sample is directly flatly laid on the glass slide, and then the flat pressing is carried out by a blade until the density is reached. Dividing four areas by blade tips, and collecting 4-5 HNIW crystal test points in each area; placing the slide with the sample on an optical platform;
The propellant has different additive components, and has light color and dark color, and the composite of main explosive, oxidant and adhesive has light color and dark color when heat absorbing aluminum powder, carbon powder or lead catalyst is added.
Step two, determining a crystal area under an optical microscope:
Under an optical microscope, focusing is firstly performed under a 10-time magnifying glass, the positions of crystals are determined by using a knob on an optical platform, and the crystals are gradually focused at 10 times, 20 times and 50 times of magnification, and the magnification is small to large until clear target crystals are obtained.
Step three, carrying out microscopic Raman on the crystal in-situ test to obtain an HNIW Raman spectrum:
setting Raman test parameters to be 785nm,1200 grating, exposure time of 10s, scanning range of 1700cm -1～150cm-1, scanning times of 1-2 times, and in order to inhibit data distortion caused by crystal transformation in the test process due to heat absorption of dark color components, the maximum laser power of a light-color sample is 25mW, and the laser power of a dark-color sample is 1.5-15 mW;
And (3) testing under a 50-time microscope, wherein each sample is tested in 4 areas of up, down, left and right, each area is tested in 4-5 HNIW crystal test points, and if the crystal Raman spectrogram found under the optical microscope is Jina, ammonium perchlorate and black-wire, the crystal points need to be found again, and 16-20 HNIW crystal test points are tested in total.
Step four, acquiring single crystal Raman data, identifying a crystal form, counting a crystal transformation rate, and analyzing the stability of the HNIW crystal form in the propellant material according to the crystal transformation rate;
step 401, standard raman spectrum acquisition of single crystals:
Preparing epsilon-HNIW single crystals, alpha-HNIW single crystals and gamma-HNIW single crystals, wherein after the epsilon-HNIW single crystals, the alpha-HNIW single crystals and the gamma-HNIW single crystals are subjected to crystal structure confirmation by an X-ray single crystal diffractometer, placing the single crystals under a microscope, and testing a Raman spectrum to obtain a crystal form standard Raman spectrum;
Step 40101, epsilon-HNIW single crystal preparation: dissolving 5gHNIW ml of ethyl acetate dehydrated by a molecular sieve into concentrated HNIW solution, filtering, taking 10ml of filtrate, placing into a test tube, sealing by a sealing film, pricking 10-15 holes by a needle, and standing at room temperature until single crystals grow;
Step 40102, γ -HNIW single crystal preparation: dissolving 5gHNIW in 20ml of ethyl acetate dehydrated by molecular sieve to prepare HNIW concentrated solution, filtering, taking 10ml of filtrate, placing into a test tube, sealing with a sealing film, pricking 10-15 holes with a needle, and standing in 75 ℃ oil bath until single crystal grows;
Step 40103, α -HNIW single crystal preparation: dissolving 3gHNIW in 20ml of mixed solvent of acetone and water in the volume ratio of 4:1, preparing into concentrated solution of HNIW, filtering, taking 10ml of filtrate, placing into a test tube, sealing with a sealing film, pricking 10-15 holes with a needle, standing at room temperature until single crystal grows;
step 40104, after the crystal structures of epsilon-HNIW single crystal, alpha-HNIW single crystal and gamma-HNIW single crystal are confirmed by an X-ray single crystal diffractometer, placing the single crystal under a microscope, testing a Raman spectrum to obtain a crystal form standard Raman spectrum, setting Raman test parameters under a 50-time long-focus microscope, wherein the laser wavelength is 785nm, the wavelength of 1200 gratings is split, the exposure time is 10s, the scanning range is 1700cm -1～150cm-1, the scanning times are 2 times, and the laser power is 100 mW-200 mW.
Step 402, crystal form identification:
And (3) comparing the Raman spectrograms of the test points with the epsilon-HNIW crystal form, the alpha-HNIW crystal form and the gamma-HNIW crystal form standard Raman spectrograms obtained in the step (401), and judging the crystal form of the test points when the Raman intensity distribution and the characteristic wave number of each region of ：450cm-1～200cm-1、900cm-1～850cm-1、1400cm-1～1200cm-1、1700cm-1～1500cm-1, are the same as the standard Raman spectrograms from strong to weak in sequence in the spectrum regions with the obvious difference of the Raman spectrograms of the three crystal forms.
Step 403, counting the crystal transformation rate:
the experimental points of the alpha-HNIW crystal form and the gamma-HNIW crystal form are expressed as the percentage of the total experimental points. The calculation formula is as follows:
Wherein:
c-crystal transformation rate expressed as percentage;
n α -judging the number of the experimental points of the alpha-HNIW crystal form, and if the number of the experimental points is 0.5, counting the number of alpha and epsilon mixed crystals;
n γ -judging the number of experimental points of the gamma-HNIW crystal form, and if the number of experimental points is 0.5, counting the number of gamma-HNIW crystal forms;
N-total number of test samples.
The following specific embodiments of the present application are given according to the above technical solutions, and it should be noted that the present application is not limited to the following specific embodiments, and all equivalent changes made on the basis of the technical solutions of the present application fall within the protection scope of the present application.
Example 1: in-situ analysis of HNIW crystal forms in nitrocotton and other composite materials
According to the technical scheme, the embodiment provides an in-situ analysis method for the crystal transformation rate of the HNIW crystal form in the propellant material, wherein:
Sample preparation: the composition of the sample formula is shown in Table 1, and the rolling process conditions are that the temperature is 90 ℃ and the pressure is about 10 MPa; the pressure and stretching process conditions are about 70 ℃ and 40 MPa. The sample was a light solid, and after the water was removed by blotting the sample with filter paper, 0.5g of the sample was spread on a glass slide, flattened, and partitioned according to step one.
Table 1 and nitrocotton (calendering at 90 ℃ C., stretching at 70 ℃ C.)
The sample was placed on an optical stage according to step two, and the test area was adjusted with a coarse tuning knob, focused and found at 10-fold, 20-fold, 50-fold, respectively (fig. 1).
And (3) setting Raman test parameters according to the light-colored sample in the step (III) to obtain Raman spectrograms of HNIW crystals of four different test points.
In this embodiment, raman test is performed to obtain standard spectrograms as shown in fig. 2 to 5.
And (4) identifying the Raman spectrogram and the standard spectrogram (figure 6) of each test point according to the step (402).
The seeding rate was counted as 403 in step four (table 2). According to the formula, epsilon-HNIW is mixed with absorbent (nitrocotton and nitroglycerin) at a ratio of 10% -50%, and the crystal transformation rate in the calendaring and deep pressing processes is 0.
Table 2 HNIW Table of test results of deep calendering process in nitrocotton nitroglycerin system
Example 2: in-situ analysis of HNIW crystal forms in nitrocotton Jina and other composite materials
According to the technical scheme, the embodiment provides an in-situ analysis method for the crystal transformation rate of the HNIW crystal form in the propellant material, wherein:
sample preparation: the composition of the sample formula is shown in Table 3, and the rolling process conditions are that the temperature is 80 ℃ and the pressure is about 10 MPa; the pressure and stretching process conditions are about 80 ℃ and 40 MPa. The sample was a light solid, and 0.5g of the sample was tiled on a glass slide, flattened, and partitioned as per step one.
Table 3 and nitrocotton (calendaring at 80 ℃ C., stretching at 80 ℃ C.)
The sample was placed on an optical stage according to step two, and the test area was adjusted with a coarse tuning knob, focused and found at 10-fold, 20-fold, 50-fold, respectively (fig. 1).
And (3) setting Raman test parameters according to the light-colored sample in the step (III) to obtain Raman spectrograms of HNIW crystals of four different test points.
In this embodiment, raman test is performed to obtain standard spectrograms as shown in fig. 2 to 5.
And (4) identifying the Raman spectrogram and the standard spectrogram of each test point according to the step (402).
The seeding rate was counted as 403 in step four (table 4). According to the formula, the epsilon-HNIW is mixed with nitrocotton and Jina at 10 percent, the crystal transformation rate in the calendaring process is 25 percent, and the crystal transformation rate in the deep pressing process is 30 percent; epsilon-HNIW is mixed with nitrocotton at 50%, the crystal transformation rate in calendaring is 35%, the crystal transformation rate in deep pressing process is 50%, and the typical spectrum of gamma-HNIW is shown in figure 7.
Table 4 HNIW Table of test results of deep calendering process in Gna system of nitrocotton
Example 3: in-situ analysis of HNIW crystal forms added to catalyst materials in calendering process
According to the technical scheme, the embodiment provides an in-situ analysis method for the crystal transformation rate of the HNIW crystal form in the propellant material, wherein:
Sample preparation: the composition of the sample formulation is shown in Table 5, and the sample is prepared by calendaring at 90℃and 10MPa. The sample is dark solid, 0.5g of the sample is flatly paved on a glass slide of white test paper according to the first step, flattened and partitioned.
TABLE 5 calendering procedure catalyst sample formulation
The sample was placed on an optical stage according to step two, and the test area was adjusted with a coarse tuning knob, focused and found at 10-fold, 20-fold, 50-fold, respectively (fig. 1).
And (3) setting Raman test parameters according to the dark color sample in the step (III) to obtain Raman spectrograms of HNIW crystals of four different test points.
In this embodiment, raman test is performed to obtain standard spectrograms as shown in fig. 2 to 5.
And (4) identifying the Raman spectrogram and the standard spectrogram of each test point according to the step (402).
And (3) counting the crystal transformation rate according to 403 in the fourth step. Table 6 shows the results of the crystal form recognition in the catalyst addition step. In the catalyst adding process, the influence of four catalysts on the HNIW crystal form is examined, the crystal transformation rate is 32.5% when the CB addition amount is 0.5%, and the crystal transformation rates of the other three catalysts added in the process are all 0, and the crystal transformation patterns are typical (figures 8 and 9).
Table 6 HNIW table of results of in situ testing of crystalline forms during the catalyst addition procedure
Example 4: in-situ analysis of HNIW crystal form added into carbon material in calendaring process
According to the technical scheme, the embodiment provides an in-situ analysis method for the crystal transformation rate of the HNIW crystal form in the propellant material, wherein:
Sample preparation: the composition of the sample formulation is shown in Table 7, and the sample is prepared by calendaring at a temperature of 90℃and a pressure of about 10 MPa. The sample is dark solid, 0.5g of the sample is flatly paved on a glass slide of white test paper according to the first step, flattened and partitioned.
TABLE 7 calendaring process adding charcoal Material formulation
The sample was placed on an optical stage according to step two, and the test area was adjusted with a coarse tuning knob, focused and found at 10-fold, 20-fold, 50-fold, respectively (fig. 1).
And (3) setting Raman test parameters according to the dark color sample in the step (III) to obtain Raman spectrograms of HNIW crystals of four different test points.
In this embodiment, raman test is performed to obtain standard spectrograms as shown in fig. 2 to 5.
And (4) identifying the Raman spectrogram and the standard spectrogram of each test point according to the step (402).
And (3) counting the crystal transformation rate according to 403 in the fourth step. Table 8 shows the results of the crystal form recognition of various carbon materials in the carbon material addition process. In the procedure of adding the catalyst, the influence of 4 carbon materials on the HNIW crystal form is examined, and the addition of acetylene black, extra black, graphene and carbon nano tubes does not influence the HNIW crystal form.
Table 8 HNIW in situ test results table of screening crystalline forms in the procedure of adding 4 carbon materials
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Claims (1)
1. An in-situ analysis method for the crystal transformation rate of HNIW crystal forms in propellant materials is characterized in that; the preparation method of the sample of the propellant material comprises the following steps:
the conditions of the calendaring process are that the temperature is 90 ℃ and the pressure is 10MPa; the pressure and stretching process conditions are that the temperature is 70 ℃ and the pressure is 40Mpa;
Or the condition of the calendaring process is that the temperature is 80 ℃ and the pressure is 10MPa; the pressure and stretching process conditions are that the temperature is 80 ℃ and the pressure is 40Mpa;
the method comprises the following steps:
Step one, compactly and flatly placing a sample on a glass slide:
The specific process of the first step is as follows:
the material samples of different working procedures of the propellant are divided into light-color samples and dark-color samples, white filter paper is adhered to a glass slide by using a double-sided adhesive tape and used for placing the dark-color samples, and the light-color samples are directly placed on the glass slide;
Weighing 0.5g of sample to 0.2g accurately, spreading dark color sample on a glass slide adhered with filter paper, directly spreading light color sample on the glass slide, and flatly pressing with a blade until the sample is compact; dividing four areas by blade tips, and collecting 4-5 HNIW crystal test points in each area; placing the slide with the sample on an optical platform;
Wherein, the propellant has different material adding components in different working procedures, the color of the material is light color and dark color, the compound of main explosive, oxidant and adhesive is light color, when the compound is added with endothermic aluminum powder, carbon powder or lead catalyst, the compound is dark color;
step two, determining a crystal area under an optical microscope:
the specific process of the second step is as follows:
Under an optical microscope, focusing under a 10-time magnifying glass, determining the position of a crystal by using a knob on an optical platform, and gradually focusing at 10 times, 20 times and 50 times of magnification respectively until a clear target crystal is obtained;
Step three, carrying out microscopic Raman on the crystal in-situ test to obtain an HNIW Raman spectrum:
The specific process of the third step is as follows:
setting Raman test parameters to be 785nm,1200 grating, exposure time of 10s, scanning range of 1700cm -1～150cm-1, scanning times of 1-2 times, and in order to inhibit data distortion caused by crystal transformation in the test process due to heat absorption of dark color components, the maximum laser power of a light-color sample is 25mW, and the laser power of a dark-color sample is 1.5-15 mW;
Testing under a 50-time microscope, wherein each sample is tested in 4 areas of up, down, left and right, each area is tested in 4-5 HNIW crystal test points, and if the crystal Raman spectrogram found under the optical microscope is Jina, ammonium perchlorate and Heijin, the crystal points need to be found again, and 16-20 HNIW crystal test points are tested in total;
Step four, acquiring single crystal Raman data, identifying a crystal form, and counting a crystal transformation rate;
step 401, standard raman spectrum acquisition of single crystals:
Preparing epsilon-HNIW single crystals, alpha-HNIW single crystals and gamma-HNIW single crystals, wherein after the epsilon-HNIW single crystals, the alpha-HNIW single crystals and the gamma-HNIW single crystals are subjected to crystal structure confirmation by an X-ray single crystal diffractometer, placing the single crystals under a microscope, and testing a Raman spectrum to obtain a crystal form standard Raman spectrum;
the specific procedure of step 401 is as follows:
Step 40101, epsilon-HNIW single crystal preparation: dissolving 5gHNIW in ethyl acetate dehydrated by a 20ml molecular sieve to prepare HNIW concentrated solution, filtering, taking 10ml of filtrate, placing into a test tube, sealing by a sealing film, pricking 10-15 holes by a needle, and standing at room temperature until single crystals grow;
step 40102, γ -HNIW single crystal preparation: dissolving 5gHNIW in ethyl acetate dehydrated by a20 ml molecular sieve to prepare HNIW concentrated solution, filtering, taking 10ml of filtrate, placing into a test tube, sealing by a sealing film, pricking 10-15 holes by a needle, and standing in an oil bath at 75 ℃ until single crystals grow;
Step 40103, α -HNIW single crystal preparation: dissolving 3gHNIW in 20ml of mixed solvent of acetone and water in the volume ratio of 4:1, preparing into concentrated solution of HNIW, filtering, taking 10ml of filtrate, placing into a test tube, sealing with a sealing film, pricking 10-15 holes with a needle, standing at room temperature until single crystal grows;
Step 40104, after the epsilon-HNIW single crystal, the alpha-HNIW single crystal and the gamma-HNIW single crystal are subjected to crystal structure confirmation by an X-ray single crystal diffractometer, placing the single crystal under a microscope, testing a Raman spectrum to obtain a crystal form standard Raman spectrum, setting Raman test parameters under a 50-time long-focus microscope to be 785nm, 1200 grating light splitting, exposure time of 10s, scanning range of 1700cm -1～150 cm-1, scanning times of 2 times and laser power of 100 mW-200 mW;
step 402, crystal form identification:
The specific procedure of step 402 is as follows:
comparing the Raman spectrogram of the test point with the ɛ -HNIW crystal form, the alpha-HNIW crystal form and the gamma-HNIW crystal form standard Raman spectrogram obtained in the step 401, and judging the crystal form of the test point when the Raman intensity distribution and the characteristic wave number of each region of ：450cm-1～200cm-1、900cm-1～850cm-1、1400cm-1～1200cm-1、1700cm-1～1500cm-1, are the same from strong to weak in sequence in the spectrum regions with the obvious difference of the Raman spectrograms of the three crystal forms;
step 403, counting the crystal transformation rate:
the specific procedure of step 403 is as follows:
the experimental points of the alpha-HNIW crystal form and the gamma-HNIW crystal form are represented by the percentage of the total experimental points; the calculation formula is as follows:
Wherein:
c-crystal transformation rate expressed as percentage;
n α -judging the number of the experimental points of the alpha-HNIW crystal form, and if the number of the experimental points is 0.5, counting the number of alpha and ɛ mixed crystals;
n γ -judging the number of experimental points of the gamma-HNIW crystal form, and if the number of experimental points is 0.5 for gamma and ɛ mixed crystals;
N-total number of test samples.
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