CN103980075A - Preparation method for explosive having micro-nano multistage structure - Google Patents
Preparation method for explosive having micro-nano multistage structure Download PDFInfo
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Abstract
The invention discloses a preparation method for an explosive having a micro-nano multistage structure. The preparation method includes following steps: step one: preparing an explosive having a micro-nano first stage structure by preparing a solvent adduct of an explosive and a solvent in a manner of solvation and removing the solvent from the solvent adduct by means of decomposing the solvent adduct through external active force; step two: carrying out a secondary solvation process to the explosive having the micro-nano first stage structure to obtain a solvent adduct having a micro-nano structure by means of forming a solvent vapor in a manner of heating the solvent, and then carrying out a secondary desolvation process through the external active force to the solvent adduct having a micro-nano structure to obtain an explosive having a micro-nano second-stage structure through the external active force; and step three: repeatedly carrying out the operation in the step two to obtain the explosive having the micro-nano multistage structure. With a multiple solvation-desolvation process, structure of explosive molecules is subjected to recombination, and explosive crystals with the micro-nano multistage structure are obtained further. The explosive is obviously improved in detonation performance and explosion propagation performance.
Description
Technical field
The invention belongs to design and the regulate and control method of explosive material microstructure, be specifically related to a kind of preparation method with micro-nano multilevel hierarchy explosive, the method adopts repeatedly solvation-desolvated method acquisition to have micro-nano multilevel hierarchy explosive.
Background technology
Material microstructure and its macro property are closely related.As special energetic material, the microstructure of explosive is also to determine the most important factor of its physics-chem characteristic.Research shows, the microstructure features such as blasting explosive granules size and distribution, specific surface area, exterior appearance, pore dimension, reunion state and crystalline structure, not only affect its macro-mechanical property, also affect its response sensitivity to particular stimulation.As the variation of pore dimension and distribution may make explosive initiation sensitivity, change, and granularity variation can cause that the performances such as shock sensitivity, mechanical sensitivity, energy output, detonation energy and heat-resistant quality produce change.Therefore,, by changing explosive microtexture, realize the focus that the improvement of some specified property or the lifting of over-all properties become current explosive area research.
In the means of existing explosive regulating microstructure, mainly contain two kinds of modes, the one, reduce crystal microdefect, obtain high-quality explosive crystal, as what Kr ǒ ber etc. utilized that recrystallization method obtained different microstructures, fall sense octogen (HMX), and confirm that its shock sensitivity and detonation energy tool improve significantly.Yet though high-qualityization explosive has reduced shock sensitivity to a certain extent, mechanical sensitivity is not well improved, and aspect the explosion transfer performance that detonates, there iing not larger lifting yet.Another kind is by reducing grain graininess, increase explosive specific surface area, making its structure micro-nano.Research shows to have the explosive crystal of micro-nano structure, and the difference of its microstructure stimulates the response of (as the mechanical stimulus under thermal stimulus, low pressure long pulse, the shockwave stimulation under high pressure short pulse etc.) obviously different to external world.Schoenitz etc. confirm explosive structure micro-nanos such as HMX, and its total specific surface area enlarges markedly, surfactivity atom and group increase, and is more conducive to the propagation of explosion that detonates.The explosive crystal that visible acquisition has micro-nano structure is to improve the important channel of explosive to particular stimulation response sensitivity.And micro-nano multilevel hierarchy is that a kind of to take low dimension nano particle be construction unit, the three-dimensional composite micro-nano structure of the multi-layer with special appearance and structure that self-assembly or artificial assembling obtain.Because the energetic material of this structure has the hole of wider distribution, the particle of different scale, specific surface area is larger, for explosive detonate and propagation of explosion stability has a very important role.Therefore, for realizing reliable initiation and the stable propagation of explosion of explosive, realize the regulation and control of explosive microtexture by diverse ways, it is crucial obtaining micro-nano multilevel hierarchy.
The present invention aims at just to the design of explosive microstructure and regulation and control, utilizes the solvation effect of explosive and solvent, utilizes repeatedly solvation-desolvation method, obtains the explosive crystal material with micro-nano multilevel hierarchy.Present method can design the multilevel hierarchy of different dimensions according to actual needs, and by relevant desolvation processing mode, obtains the multilevel hierarchy explosive of variable grain yardstick, and this micro-nano multilevel hierarchy can be realized the improvement of explosive property.
Summary of the invention
The object of this invention is to provide a kind of preparation method with micro-nano multilevel hierarchy explosive, this preparation method adopts repeatedly the microstructure of solvation-desolvated method regulation and control explosive, has obviously improved the microstructure of explosive.
In order to reach above-mentioned technique effect, the present invention takes following technical scheme:
A preparation method with micro-nano multilevel hierarchy explosive, comprises the following steps:
Step 1: the preparation of the explosive of micro-nano primary structure, by the mode of solvation, prepare the solvent adduct of explosive and solvent, then make solvent adduct decompose the explosive that removal solvent obtains having micro-nano primary structure by external influence power; In this step by the solvent adduct crystal obtaining, take the modes such as heat, chemical force separately or acting in conjunction it is decomposed, remove part or all of solvent molecule, impel the explosive molecules generation crystalline structure in solvent adduct to reset, under solid-phase crystallization condition, the limited growth of crystal obtains having the explosive micro-nano primary structure of certain mode of appearance.
Step 2: utilize heated solvent mode to form solvent vapo(u)r the explosive of micro-nano primary structure is carried out to the solvent adduct that secondary solvent obtains having micro-nano primary structure, then obtain having the explosive of micro-nano secondary structure by the solvent adduct secondary desolvation that external influence power makes to have micro-nano structure; Under the solvation of solvent vapo(u)r, assembling forms the solvent adduct with micro-nano primary structure again, again under the action conditions such as heat, chemical force, there is desolvation and decompose in the solvent adduct with micro-nano primary structure, remove solvent molecule wherein, limited by growing environment, explosive molecules in micro-nano primary structure again recurring structure is reset, and forms the micro-nano secondary structure of explosive.
Step 3: the operation of repeating step two obtains having the explosive of micro-nano multilevel hierarchy.
In above-mentioned preparation method, described solvent adduct is the co-crystallization compound that explosive molecules and solvent molecule form under weak interaction force condition.
In above-mentioned preparation method, described weak interaction force is one or more in hydrogen bond, electrostatic force, Van der Waals force.
In above-mentioned preparation method, described external influence power is a kind of in heat, pressure and chemical force.
In above-mentioned preparation method, described solvent vapo(u)r is the solvent molecule of gaseous form.
In above-mentioned preparation method, described heated solvent mode is a kind of in water-bath, oil bath and electrically heated.
The present invention compared with prior art, has following beneficial effect:
Present method adopts repeatedly solvation-desolvation method to the restructuring of explosive molecules recurring structure, and then obtains the explosive crystal structure with multi-layer micro-nano structure, has obviously improved the explosion transfer performance that detonates of explosive.
Accompanying drawing explanation
Fig. 1 is the shape appearance figure of HNS explosive in embodiment 1, and wherein a represents HNS explosive crystal; B represents the solvent adduct crystal of HNS and dioxane (Dioxane); C is HNS micro-nano primary structure; D represents to have HNS and the Dioxane solvent adduct of micro-nano primary structure; E is HNS micro-nano secondary structure; F is HNS and the Dioxane solvent adduct with micro-nano secondary structure; G is HNS micro-nano tertiary structure.
Fig. 2 is the XRD figure of HNS explosive in embodiment 1, and a represents HNS former state XRD figure; B represents the XRD figure of HNS and Dioxane solvent adduct; C represents to have the XRD figure of micro-nano primary structure HNS; D represents to have the XRD figure of HNS and the Dioxane solvent adduct of micro-nano primary structure; E represents to have the XRD figure of micro-nano secondary structure HNS; F represents to have the XRD figure of HNS and the Dioxane solvent adduct of micro-nano secondary structure; G represents to have the XRD figure of the HNS of micro-nano multilevel hierarchy.
Fig. 3 is the shape appearance figure of HMX explosive in embodiment 2, and wherein a represents the solvent adduct crystal of HMX and DMF (DMF); B is HMX micro-nano primary structure; C is HMX and the DMF solvent adduct with one-level micro-nano structure; D is HMX micro-nano secondary structure; E is HMX and the DMF solvent adduct with micro-nano secondary structure; F is HMX micro-nano tertiary structure.
Fig. 4 is the XRD figure of HMX explosive in embodiment 2, and a represents HMX former state XRD figure; B represents the XRD figure of HMX and DMF solvent adduct; C represents to have the XRD figure of micro-nano primary structure HMX; D represents to have the XRD figure of HMX and the DMF solvent adduct of micro-nano primary structure; E represents to have the XRD figure of micro-nano secondary structure HMX; F represents to have the XRD figure of HMX and the DMF solvent adduct of micro-nano secondary structure; G represents to have the XRD figure of the HMX of micro-nano multilevel hierarchy.
Embodiment
Below in conjunction with embodiments of the invention, the invention will be further elaborated.
Embodiment 1:
(1) take the HNS of 1.25g, be dissolved in the there-necked flask of dioxane (Dioxane) of 250mL, under 70 ℃～85 ℃ stirred in water bath states, dissolve completely, stablize after 1h opening program temperature control to the water-bath recrystallization of lowering the temperature, separate out gradually solvent adduct crystal, after near 15 ℃～20 ℃ of temperature, continue to stir 2h, until crystal is separated out completely; Then through vacuum filtration, obtain solvent adduct crystal.
(2) solvent adduct crystal step (1) being obtained is placed in the vacuum drying oven of 75 ℃～100 ℃, thermal degradation is removed the solvent molecule in solvent adduct, unlatching vacuum pump is bled, and can obtain having the HNS explosive of micro-nano primary structure after thermal treatment 2h.
(3) the HNS explosive with micro-nano primary structure step (2) being obtained is evenly laid in the nylon wire that size of mesh opening is 200 μ m (60 order～80 order) left and right, and be just placed on the Dioxane solution of 80 ℃～95 ℃ of heating, utilize Dioxane solvent vapo(u)r to carry out again the HNS solvent adduct that solvation obtains having micro-nano primary structure.
(4) the HNS solvent adduct with micro-nano primary structure step (3) being obtained is placed in the vacuum drying oven of 75 ℃～100 ℃ again, opens vacuum suction and heats desolvation, obtains having the HNS explosive of micro-nano secondary structure after 2h.
(5) according to step (3), step (4), carry out the micro-nano multilevel hierarchy that repeatedly solvation-desolventizing can obtain HNS.
(6) sample step (2), step (3), step (4), step (5) being obtained carries out structure and exterior appearance analysis, and HNS shape appearance figure and XRD figure refer to Fig. 1 and Fig. 2.
Embodiment 2:
(1) take the HMX of 5g, be dissolved in the there-necked flask of DMF of 45ml, in 65 ℃～85 ℃ water-baths, under whipped state, dissolve completely, after dissolving completely, stablize opening program temperature control after 1h, to the water-bath recrystallization of lowering the temperature, progressively separate out the solvent adduct crystal of HMX and DMF, after homo(io)thermism 2h, utilize vacuum cycle pump suction filtration to obtain solvent adduct crystal.
(2) solvent adduct crystal step (1) being obtained is placed in the vacuum drying oven of 80 ℃～120 ℃ and opens vacuum suction, and solvent adduct is carried out to pyrolysis desolvation, obtains having the HMX explosive of micro-nano primary structure after thermal treatment 2h～4h.
(3) the HMX explosive with micro-nano primary structure step (2) being obtained is evenly laid in the nylon wire that size of mesh opening is 200 μ m (60 order～80 order) left and right, and be placed in and just utilize water-bath on the DMF solution of 110 ℃～140 ℃ of heating, utilize DMF solvent vapo(u)r to carry out again the HMX solvent adduct that solvation assembling obtains having micro-nano primary structure.
(4) the HMX solvent adduct with micro-nano primary structure step (3) being obtained is again placed in the vacuum drying oven of 80 ℃～120 ℃ and opens vacuum suction, solvent adduct is carried out to pyrolysis desolvation, through Overheating Treatment 2h～3h, obtain having the HMX explosive of micro-nano secondary structure.
(5) according to step (3), step (4), HMX explosive is carried out repeatedly to the micro-nano multilevel hierarchy that solvation-desolvation can obtain HMX.
(6) sample step (2), step (3), step (4), step (5) being obtained carries out structure and exterior appearance analysis, and HMX shape appearance figure (SEM) and XRD figure refer to Fig. 3 and Fig. 4.
Although with reference to explanatory embodiment of the present invention, invention has been described here, above-described embodiment is only preferably embodiment of the present invention, embodiments of the present invention are not restricted to the described embodiments, should be appreciated that, those skilled in the art can design a lot of other modification and embodiments, and these are revised and within embodiment will drop on the disclosed principle scope and spirit of the application.
Claims (6)
1. a preparation method with micro-nano multilevel hierarchy explosive, is characterized in that comprising the following steps:
Step 1: the preparation of the explosive of micro-nano primary structure, by the mode of solvation, prepare the solvent adduct of explosive and solvent, then make solvent adduct decompose the explosive that removal solvent obtains having micro-nano primary structure by external influence power;
Step 2: utilize heated solvent mode to form solvent vapo(u)r the explosive of micro-nano primary structure is carried out to the solvent adduct that secondary solvent obtains having micro-nano structure, then obtain having the explosive of micro-nano secondary structure by the solvent adduct secondary desolvation that external influence power makes to have micro-nano structure;
Step 3: the operation of repeating step two obtains having the explosive of micro-nano multilevel hierarchy.
2. the preparation method with micro-nano multilevel hierarchy explosive according to claim 1, is characterized in that described solvent adduct is the co-crystallization compound that explosive molecules and solvent molecule form under weak interaction force condition.
3. the preparation method with micro-nano multilevel hierarchy explosive according to claim 2, is characterized in that described weak interaction force is one or more in hydrogen bond, electrostatic force, Van der Waals force.
4. the preparation method with micro-nano multilevel hierarchy explosive according to claim 1, is characterized in that described external influence power is a kind of in heat, pressure and chemical force.
5. the preparation method with micro-nano multilevel hierarchy explosive according to claim 1, is characterized in that described solvent vapo(u)r is the solvent molecule of gaseous form.
6. the preparation method with micro-nano multilevel hierarchy explosive according to claim 1, is characterized in that described heated solvent mode is a kind of in water-bath, oil bath and electrically heated.
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Cited By (3)
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| CN106966841A (en) * | 2017-03-29 | 2017-07-21 | 西安近代化学研究所 | One kind press-fits powder column circumferential crack method for prefabricating |
| CN107827835A (en) * | 2017-11-22 | 2018-03-23 | 中国工程物理研究院化工材料研究所 | A kind of simple method for preparing of explosive solvate |
| CN111908990A (en) * | 2020-07-17 | 2020-11-10 | 中北大学 | Energetic material filled layered framework composite structure and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106966841A (en) * | 2017-03-29 | 2017-07-21 | 西安近代化学研究所 | One kind press-fits powder column circumferential crack method for prefabricating |
| CN106966841B (en) * | 2017-03-29 | 2018-07-31 | 西安近代化学研究所 | A kind of press fitting powder column circumferential crack method for prefabricating |
| CN107827835A (en) * | 2017-11-22 | 2018-03-23 | 中国工程物理研究院化工材料研究所 | A kind of simple method for preparing of explosive solvate |
| CN107827835B (en) * | 2017-11-22 | 2021-09-28 | 中国工程物理研究院化工材料研究所 | Simple preparation method of explosive solvate |
| CN111908990A (en) * | 2020-07-17 | 2020-11-10 | 中北大学 | Energetic material filled layered framework composite structure and preparation method thereof |
| CN111908990B (en) * | 2020-07-17 | 2021-07-09 | 中北大学 | Energetic material filled layered framework composite structure and preparation method thereof |
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