CN103554524A - Ultrafine dispersion method for single-compound explosive in energetic composite material - Google Patents
Ultrafine dispersion method for single-compound explosive in energetic composite material Download PDFInfo
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Abstract
The invention discloses an ultrafine dispersion method for a single-compound explosive in an energetic composite material. The ultrafine dispersion method comprises the following steps: dissolving the single-compound explosive in a solvent to obtain a single-compound explosive solution; dissolving a macromolecular composite material in a solvent to obtain a macromolecular sol; uniformly mixing the single-compound explosive solution with the macromolecular sol in a stirring state to obtain a single-compound explosive-containing macromolecular sol; dispersing the single-compound explosive-containing macromolecular sol into an aqueous solution containing a dispersing agent in a stirring state to form spherical droplets; distilling the solvent in the system step by step to obtain single-compound explosive-containing energetic composite particles. The method has the advantages that the single-compound explosive is not required to be subjected to ultrafine crushing treatment, the technological process is safe, the dispersion particle diameter of the explosive is small, the materials are uniformly mixed and the like, and is suitable for ultrafine dispersion of the energetic composite material of various single-compound explosives.
Description
Technical field
The present invention relates to polymer composite working method, particularly the super-refinement dispersing method of a kind of single chmical compound explosive in composite material containing energy.
Background technology
Single chmical compound explosive is the important component part of solid energetic material, and the solid energetic material that contains single chmical compound explosive is widely applied to the fields such as propelling agent, propelling charge, explosive and priming system.The particle diameter of single chmical compound explosive and the dispersion effect of such material in energetic material directly have influence on its effect.Conventionally the dispersion of single chmical compound explosive in polymer or adhesive composition adopts physical dispersion method more, but along with the reducing of single chmical compound explosive granularity, the mixing of material becomes more and more difficult.The ultra-fine Cyclotrimethylene trinitramine of for example using in typical high energy composite modified double-base propellant, first to adopt the means of superfine grinding to be ground into micron-sized particle the larger technical grade Cyclotrimethylene trinitramine of particle diameter, then by solvent, in kneading process, be distributed in double-base powder matrix, jitter time is long, and dispersion effect and product stability should not be controlled.For solid propellant, the particle diameter of single chmical compound explosive is less conventionally, and pressure index is lower, and while being applied to rocket engine, stability or reliability are just better.Therefore, traditional super-refinement explosive is in the dispersion of composite material containing energy, and not only operation is more, and jitter time is longer, and dispersing uniformity and stability are difficult to guarantee.
Summary of the invention
The object of the present invention is to provide the dispersing method of a kind of single chmical compound explosive in polymer composite, the particularly a kind of single chmical compound explosive super-refinement dispersing method in composite material containing energy.
The technical solution that realizes the object of the invention is: the super-refinement dispersing method of a kind of single chmical compound explosive in composite material containing energy, comprises the following steps:
Step 1, single chmical compound explosive is dissolved into and in solvent, obtains single chmical compound explosive solution, polymer composite is dissolved into and in solvent, obtains polymeric sol;
Described single chmical compound explosive is the hereby mixture of one or more in alkane, hexanitro-stilbene, trinitro-isophthalic triamine, TNAZ, diamino-dinitroethylene, tritonal of Cyclotrimethylene trinitramine, octogen, hexanitro-six azepine isoamyls;
Described polymer composite contains nitro-cotton, polyvinyl butyral acetal, cellulose acetate butyrate, cellulose acetate, polyurethane-type thermoplastic elastomer, glycidyl azide polymer, 3-azido-methyl-3-methyl butylene oxide ring polymkeric substance, 3, a kind of and more than one mixture in two (azido-methyl) butylene oxide ring polymkeric substance of 3-;
The solvent of described dissolving single chmical compound explosive is one or more mixture of ethyl acetate, butylacetate, butanols, butanone, pimelinketone, and the mass ratio of this solvent and single chmical compound explosive is 10-50;
The solvent that dissolves polymer composite is one or more mixture of ethyl acetate, butylacetate, butanols, butanone, pimelinketone, and the mass ratio of this solvent and polymer composite is 2-20.
Step 2, the single chmical compound explosive solution that step 1 is obtained mix under whipped state with polymeric sol, obtain the polymeric sol containing single chmical compound explosive; The volume ratio of single chmical compound explosive solution and polymeric sol is: (1:10)～and (5:1).
Step 3, the polymeric sol containing single chmical compound explosive that step 2 is obtained are distributed in the aqueous solution containing dispersion agent and disperse under whipped state, and the polymeric sol that contains single chmical compound explosive is dispersed into spherical droplets;
Described dispersion agent is: gelatin, gelatine, gum arabic, polyoxyethylene glycol, polyacrylamide, polyvinyl alcohol or methylcellulose gum; The concentration of aqueous dispersant is: 0.05%-1%; Aqueous dispersant with the volume ratio that contains the polymeric sol of single chmical compound explosive is: 1.0-3.0; Temperature of charge during dispersion is: 20 ℃-65 ℃.
Solvent in step 4, material that step 3 is obtained distills away, is dispersed in spherical droplets in the aqueous solution and progressively hardens and be transformed into containing can solid particulate;
Compared with prior art, its remarkable advantage is in the present invention: 1) method of the present invention does not need through superfine grinding, directly oarse-grained single chmical compound explosive is distributed in macromolecular material, and the particle diameter of single chmical compound explosive is dropped to micron order or nano level.2) dispersing and mixing process is to carry out under the condition existing at large water gaging, and technological process is safer.3) single chmical compound explosive disperses more evenly in polymer, can significantly improve the stability of composite material containing energy.
Embodiment
Be described in detail below, the super-refinement dispersing method of single chmical compound explosive of the present invention in composite material containing energy, step is:
(1) material dissolution: step 1, single chmical compound explosive is dissolved into and in solvent, obtains single chmical compound explosive solution, solvent load be polymer composite quality 10-50 doubly, solvent ratio is 10-50.Polymer composite is dissolved in solvent and obtains polymeric sol, and solvent ratios is polymer composite quality 2-20 times.Described single chmical compound explosive is the hereby mixture of one or more in alkane, hexanitro-stilbene, trinitro-isophthalic triamine, TNAZ, diamino-dinitroethylene of Cyclotrimethylene trinitramine, octogen, hexanitro-six azepine isoamyls.Described polymer composite at least contains nitro-cotton, polyvinyl butyral acetal, cellulose acetate butyrate, cellulose acetate, polyurethane-type thermoplastic elastomer, glycidyl azide polymer, 3-azido-methyl-3-methyl butylene oxide ring polymkeric substance, 3, a kind of in two (azido-methyl) butylene oxide ring polymkeric substance of 3-.Described solvent is one or more mixture of ethyl acetate, butylacetate, butanols, butanone, pimelinketone, preferably selects solvent single chmical compound explosive and polymer composite all to excellent dissolution performance.Solvent temperature determines according to solvent species used, should be not higher than the azeotropic point of boiling point or the mixed solvent of solvent.The material dissolution time determines according to material category and granular size, and under room temperature or heating condition, dissolution time is 10-120min.Can also adopt independent dissolver batch process or prepare continuously polymeric sol.
(2) mixing of materials: single chmical compound explosive solution mixes under whipped state with polymeric sol, obtains the polymeric sol containing single chmical compound explosive; Single chmical compound explosive solution is 1:10-5:1 with the relative volume ratio of polymeric sol.In mixing of materials process, in solution or colloidal sol, can add the nonionic surface active agent of the series such as OP or TX, more even to guarantee material dispersion and mixing of materials state; The add-on of tensio-active agent determines according to its kind, and add-on is the 0.002%-0.05% of solvent total mass used conventionally.Under room temperature or heating condition, carry out mixing of materials, the temperature of heating is not higher than the azeotropic point of boiling point or the mixed solvent of solvent, and the mixing of materials time is preferably 10min-240min; The temperature of mixing of materials process system is consistent with material dissolution process substantially.
(3) disperse balling-up: the polymeric sol containing single chmical compound explosive obtaining after mixing of materials is distributed in the aqueous solution containing dispersion agent and is disperseed under whipped state, and the polymeric sol that contains single chmical compound explosive under the acting in conjunction of stirring shearing force and interfacial tension is dispersed into spherical droplets; The kind of dispersion agent can be selected the water-soluble natural polymers such as gelatin, gelatine, gum arabic, also can select the water-soluble synthetic polymers such as polyoxyethylene glycol, polyacrylamide, polyvinyl alcohol, methylcellulose gum.In aqueous dispersant, the mass concentration of dispersion agent is 0.05%-1%.The described aqueous solution containing dispersion agent can be the mother liquor that last time, single chmical compound explosive dispersion process reclaimed.The effect that adds dispersion agent in the aqueous solution is that spherical droplets protection is prevented to the spherical droplets that contains single chmical compound explosive and macromolecular material assembles mutually.As disperseing balling-up by volume to measure containing the aqueous solution of dispersion agent or the add-on of mother liquor, for material dissolution stage gained containing the 1.0-3.0 of the polymeric sol volume of single chmical compound explosive doubly.Single chmical compound explosive dispersion process time used is preferably at 10min-90min; System temperature is basic to be consistent with mixing of materials process, when employing ethyl acetate solvent, keeps 20 ℃-65 ℃, and single chmical compound explosive dispersion process temperature can slowly promote, but should not surpass the boiling point of solvent for use or the azeotropic point of mixed solvent.
(4) solvent distillation: at normal pressure Elevated Temperature Conditions or vacuumize under state, or heating up and vacuumizing under condition simultaneously, solvent in the material that disperses balling-up process to obtain distill away, be dispersed in spherical droplets in the aqueous solution and progressively harden and be transformed into containing energy solid particulate; The main operating parameters of described solvent still-process is: the time is at 20min-240min, and temperature is along with the recovery of solvent progressively improves, and when temperature surpasses the boiling point of solvent or mixed solvent azeotropic point when more than 10 ℃, keeps 10min can stop above solvent and distills.When adopting ethyl acetate to make solvent, as molten in adopted normal pressure to steam, temperature reaches 87 ℃ and keeps 10min can stop above solvent distillation.
(5) feed separation: after solvent distillation finishes, adopt the general type of cooling that the temperature of material is dropped to and approaches room temperature, or directly by the mode of centrifugation or filtration, the solid particulate containing single chmical compound explosive is separated with the aqueous solution, the filtrate of separating is called mother liquor, in mother liquor, contain tensio-active agent, dispersion agent and solvent, can be as dispersion medium recycle when next single chmical compound explosive disperses.Adopt hot water to wash solid particles surface, drive away the dispersion agent that particle surface adheres to, then solid particulate is dried.
(6) dry: adopt conventional method to carry out drying and processing solid particulate, obtain the composite material containing energy containing ultra-fine single chmical compound explosive.The solid particulate that solid-liquid separation obtains can adopt conventional mode to carry out drying and processing, and the best warm air of drying plant used, hot water etc. are as heat source, and top temperature is preferably lower than 100 ℃, to guarantee safety.About drying and dehydration equipment should have good anti-static precautions to guarantee safety.
For implementation condition of the present invention is described better, the elaboration of giving an example below, these processes and processing condition do not represent the whole of invention, as long as can be used without prejudice to the measure of innovative idea of the present invention.
Embodiment 1:
Selecting median size is that the Cyclotrimethylene trinitramine of 150 microns is single chmical compound explosive raw material, select that nitro-cotton 68%, nitroglycerine are 30%, the double-base powder of tranquilizer 1.5% is as polymer composite, adopts the inventive method that Cyclotrimethylene trinitramine is distributed to and in double-base powder matrix, prepares the composite modified double-base powder particle of high energy.First, at 60-65 ℃ of temperature, Cyclotrimethylene trinitramine is dissolved in 10 times of ethyl acetate solvents with respect to its quality, obtains the ethyl acetate solution containing hexogen.Double-base powder is dissolved in the ethyl acetate with respect to 9 times of its quality at same temperature, dissolution time is 30min-60min again, obtains the polymeric sol containing nitro-cotton.Then, the ethyl acetate solution of Cyclotrimethylene trinitramine is mixed with the polymeric sol containing nitro-cotton, the mass ratio of two kinds of liquid materials is 1:3, obtains the polymeric sol containing Cyclotrimethylene trinitramine.Under 50 ℃ of-65 ℃ of temperature condition, the polymeric sol containing Cyclotrimethylene trinitramine is distributed to 2 times and containing in the aqueous solution of dispersion agent of its volume, disperses, adopt gelatin as dispersion agent, the mass concentration of aqueous dispersant is 0.5%.Under the mixing speed of 300-350rpm, disperse 30min, the polymeric sol that contains Cyclotrimethylene trinitramine is progressively dispersed into more uniform spherical drop.Then, slowly heat up solvent is progressively distilled, spherical droplets is hardened gradually, and molecularity Cyclotrimethylene trinitramine crystallizes out from colloidal sol simultaneously, and is distributed in spheroidal particle equably.After temperature is raised to 85 ℃, continue to keep 10min, cooling down material, carries out solid particulate and the aqueous solution separated, and the mother liquor of separating saves in upper once dispersion process and is used as dispersion medium.The solid particulate of separating, is placed in safe baking oven and is dried 24 hours at 50 ℃ of temperature.To the Cyclotrimethylene trinitramine content measuring result in sample, be 24.6%, the median size measuring containing the Cyclotrimethylene trinitramine in energy solid particulate by Electronic Speculum is 3.4 μ m.Fig. 1 is the shape appearance figure by observation by light microscope containing the modification double-base powder particle of ultra-fine Cyclotrimethylene trinitramine that the present embodiment obtains.
Embodiment 2
Selecting median size is that the Cyclotrimethylene trinitramine of 150 microns is single chmical compound explosive raw material, select nitro-cotton and polyvinyl butyral acetal respectively to account for 50% mixing material as polymer composite, adopt the inventive method that Cyclotrimethylene trinitramine is distributed in polymer composite to preparation containing can composite particles.First, at 40-50 ℃ of temperature, Cyclotrimethylene trinitramine is dissolved in 19 times of ethyl acetate solvents with respect to its quality, obtains the ethyl acetate solution containing hexogen.Nitro-cotton and polyvinyl butyral acetal are dissolved in the ethyl acetate with respect to 15 times of its quality at same temperature, dissolution time is 30min-60min, obtains the polymeric sol containing nitro-cotton and polyvinyl butyral acetal again.Then, the ethyl acetate solution of Cyclotrimethylene trinitramine is mixed with polymeric sol, the ethyl acetate solution of Cyclotrimethylene trinitramine and the mass ratio of polymeric sol are 1:2, obtain the polymeric sol containing Cyclotrimethylene trinitramine after mixing.Under 40 ℃ of-50 ℃ of temperature condition, the polymeric sol containing Cyclotrimethylene trinitramine is distributed to 1 times and containing in the aqueous solution of dispersion agent of its volume, disperses, adopt gelatine as dispersion agent, the mass concentration of aqueous dispersant is 0.5%.Under the mixing speed of 300-350rpm, disperse 30min, the polymeric sol that contains Cyclotrimethylene trinitramine is progressively dispersed into more uniform spherical drop.Then, slowly heat up solvent is progressively distilled, spherical droplets is hardened gradually, and molecularity Cyclotrimethylene trinitramine crystallizes out from colloidal sol simultaneously, and is distributed in spheroidal particle equably.After temperature is raised to 85 ℃, continue to keep 10min, cooling down material, carries out solid particulate and the aqueous solution separated, and the mother liquor of separating saves in upper once dispersion process and is used as dispersion medium.The solid particulate of separating, is placed in safe baking oven and is dried 24 hours at 50 ℃ of temperature.To the Cyclotrimethylene trinitramine content measuring result in sample, be 35.6%, the median size measuring containing the Cyclotrimethylene trinitramine in energy solid particulate by Electronic Speculum is 7.9 μ m.Fig. 2 is the shape appearance figure by observation by light microscope containing the composite particles of ultra-fine Cyclotrimethylene trinitramine that the present embodiment obtains.
Embodiment 3
Select median size be the octogen of 180 microns and median size be 150 microns of Cyclotrimethylene trinitramine etc. the mixture of mass ratio as single chmical compound explosive raw material, select single-base powder containing nitro-cotton 97% as polymer composite, adopt the inventive method that octogen and Cyclotrimethylene trinitramine are distributed in polymer composite to preparation containing can composite particles.First, at 30-40 ℃ of temperature, the mixture of Cyclotrimethylene trinitramine and octogen is dissolved in the ethyl acetate solvent of 29 times with respect to its quality, obtains the ethyl acetate solution containing single chmical compound explosive.Single-base powder is dissolved in the ethyl acetate with respect to 14 times of its quality at same temperature, dissolution time is 30min-60min again, obtains the polymeric sol containing nitro-cotton.Then, the ethyl acetate solution of single chmical compound explosive is mixed with polymeric sol, the ethyl acetate solution of single chmical compound explosive and the mass ratio of polymeric sol are 2:1, obtain the polymeric sol containing single chmical compound explosive after mixing.Under 20 ℃ of-40 ℃ of temperature condition, the polymeric sol containing single chmical compound explosive is distributed to 3 times and containing in the aqueous solution of dispersion agent of its volume, disperses, adopt gum arabic as dispersion agent, the mass concentration of aqueous dispersant is 0.5%.Under the mixing speed of 300-350rpm, disperse 30min, the polymeric sol that contains single chmical compound explosive is progressively dispersed into more uniform spherical drop.Then, slowly heat up solvent is progressively distilled, spherical droplets is hardened gradually, and molecularity single chmical compound explosive crystallizes out from colloidal sol simultaneously, and is distributed in spheroidal particle equably.After temperature is raised to 85 ℃, continue to keep 10min, cooling down material, carries out solid particulate and the aqueous solution separated, and the mother liquor of separating saves in upper once dispersion process and is used as dispersion medium.The solid particulate of separating, is placed in safe baking oven and is dried 24 hours at 50 ℃ of temperature.Content measuring result to Cyclotrimethylene trinitramine in sample and octogen adds up to 48.6%, and the median size measuring containing the single chmical compound explosive particle in energy solid particulate by Electronic Speculum is 6.5 μ m.Fig. 3 is the figure of the SEM containing the composite particles of ultra-fine single chmical compound explosive that the present embodiment obtains.
Embodiment 4-11
Adopt the technological process identical with embodiment 1, select different types of single chmical compound explosive, the double-base powder that employing nitroglycerine content is 30% is as polymer composite, select ethyl acetate as the solvent that dissolves explosive raw material and polymer composite, dispersion balling-up aqueous dispersant consumption used is 2 times containing the polymeric sol volume of single chmical compound explosive, the kind of single chmical compound explosive, the solvent ratio that single chmical compound explosive solution is used, the solvent ratio that double-base powder colloidal sol is used, the relative volume ratio of single chmical compound explosive solution and polymeric sol, the median size containing single chmical compound explosive in energy composite particles obtaining sees the following form.
Embodiment 12-18
Adopt the technological process identical with embodiment 1, selecting median size is that the octogen of 180 microns is single chmical compound explosive raw material, select the polymer composite containing different sorts tackiness agent, adopt acetic acid ethyl dissolution explosive raw material and polymer composite, dispersion balling-up aqueous dispersant consumption used is 2 times containing the polymeric sol volume of single chmical compound explosive, solvent species, preparation single chmical compound explosive solution and double-base powder colloidal sol solvent ratio used, the relative volume ratio of single chmical compound explosive solution and polymeric sol, the median size containing single chmical compound explosive in energy composite particles obtaining sees the following form.
Embodiment 19-23
Adopt the technological process identical with embodiment 1, selecting median size is that the Cyclotrimethylene trinitramine of 150 microns is single chmical compound explosive raw material, the double-base powder that employing nitroglycerine content is 30% is as polymer composite, select different dissolution with solvents explosive raw material and polymer composite, dispersion balling-up aqueous dispersant consumption used is 2 times containing the polymeric sol volume of single chmical compound explosive, solvent species, preparation single chmical compound explosive solution solvent ratio used, preparation double-base powder colloidal sol solvent ratio used, the relative volume ratio of single chmical compound explosive solution and polymeric sol, the median size containing single chmical compound explosive in energy composite particles obtaining sees the following form.
Embodiment 24-29
Adopt the technological process identical with embodiment 1, selecting median size is that the Cyclotrimethylene trinitramine of 150 microns is single chmical compound explosive raw material, the double-base powder that employing nitroglycerine content is 40% is as polymer composite, adopt ethyl acetate as the solvent that dissolves Cyclotrimethylene trinitramine and double-base powder, solvent load is respectively Cyclotrimethylene trinitramine and double-base powder quality 20 times, single chmical compound explosive solution is 1:2 with the relative volume ratio of polymeric sol, dispersion balling-up aqueous dispersant consumption used is 2 times containing the polymeric sol volume of single chmical compound explosive, only change dispersant used in material dispersion process and concentration, other conditions are identical with embodiment 1.The median size containing single chmical compound explosive in energy composite particles obtaining sees the following form.
By above embodiment, can be illustrated, adopt the inventive method can safely and efficiently single chmical compound explosive be distributed to polymer composite, and single chmical compound explosive is distributed to micron order, do not need through superfine grinding, just can directly oarse-grained single chmical compound explosive be distributed in macromolecular material equably.Dispersing and mixing process is to carry out under the condition existing at large water gaging, process safety.
Claims (4)
1. the super-refinement dispersing method of single chmical compound explosive in composite material containing energy, is characterized in that, comprises the following steps:
Step 1, single chmical compound explosive is dissolved into and in solvent, obtains single chmical compound explosive solution, polymer composite is dissolved into and in solvent, obtains polymeric sol;
Step 2, the single chmical compound explosive solution that step 1 is obtained mix under whipped state with polymeric sol, obtain the polymeric sol containing single chmical compound explosive;
Step 3, the polymeric sol containing single chmical compound explosive that step 2 is obtained are distributed in the aqueous solution containing dispersion agent and disperse under whipped state, and the polymeric sol that contains single chmical compound explosive is dispersed into spherical droplets;
Solvent in step 4, material that step 3 is obtained distills away, is dispersed in spherical droplets in the aqueous solution and progressively hardens and be transformed into containing can solid particulate;
Step 5, process solid-liquid separation, solid particles surface washing and oven dry, obtaining including containing of ultra-fine single chmical compound explosive can composite particles.
2. the super-refinement dispersing method of single chmical compound explosive according to claim 1 in composite material containing energy, it is characterized in that, the single chmical compound explosive described in step 1 is the hereby mixture of one or more in alkane, hexanitro-stilbene, trinitro-isophthalic triamine, TNAZ, diamino-dinitroethylene, tritonal of Cyclotrimethylene trinitramine, octogen, hexanitro-six azepine isoamyls;
Described polymer composite contains nitro-cotton, polyvinyl butyral acetal, cellulose acetate butyrate, cellulose acetate, polyurethane-type thermoplastic elastomer, glycidyl azide polymer, 3-azido-methyl-3-methyl butylene oxide ring polymkeric substance, 3, a kind of and more than one mixture in two (azido-methyl) butylene oxide ring polymkeric substance of 3-;
The solvent of described dissolving single chmical compound explosive is one or more mixture of ethyl acetate, butylacetate, butanols, butanone, pimelinketone, and the mass ratio of this solvent and single chmical compound explosive is 10-50;
The solvent that dissolves polymer composite is one or more mixture of ethyl acetate, butylacetate, butanols, butanone, pimelinketone, and the mass ratio of this solvent and polymer composite is 2-20.
3. the super-refinement dispersing method of single chmical compound explosive according to claim 1 in composite material containing energy, is characterized in that, in step 2, the volume ratio of single chmical compound explosive solution and polymeric sol is: (1:10)～and (5:1).
4. the super-refinement dispersing method of single chmical compound explosive according to claim 1 in composite material containing energy, is characterized in that, in step 3, dispersion agent is: gelatin, gelatine, gum arabic, polyoxyethylene glycol, polyacrylamide, polyvinyl alcohol or methylcellulose gum;
The concentration of aqueous dispersant is: 0.05%-1%; Aqueous dispersant with the volume ratio that contains the polymeric sol of single chmical compound explosive is: 1.0-3.0; Temperature of charge during dispersion is: 20 ℃-65 ℃.
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| CN108456334A (en) * | 2018-02-28 | 2018-08-28 | 中国人民解放军国防科技大学 | Granular nano-porous thermosetting nitrocellulose and preparation method thereof |
| CN108774328A (en) * | 2018-06-19 | 2018-11-09 | 武汉工程大学 | A kind of preparation method of Azide graft modification nitrocellulose microballoon |
| CN110357753A (en) * | 2019-08-20 | 2019-10-22 | 西安近代化学研究所 | A kind of octogen dispersion cladding process |
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| CN104193564A (en) * | 2014-09-09 | 2014-12-10 | 中国工程物理研究院化工材料研究所 | Fine-particle high-energy low-sensitivity explosive compound and preparation method thereof |
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| CN110357753A (en) * | 2019-08-20 | 2019-10-22 | 西安近代化学研究所 | A kind of octogen dispersion cladding process |
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