CN104496731A - Method for coating nitroamine explosives by adopting atomic layer deposition technique - Google Patents
Method for coating nitroamine explosives by adopting atomic layer deposition technique Download PDFInfo
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Abstract
The invention belongs to the field of energetic materials, and discloses a method for coating nitroamine explosives by adopting an atomic layer deposition technique. In the method, two reaction precursors alternatively pass through a reaction cavity, and chemical reaction occurs on the surfaces of nitroamine explosive particles to form coating films. The coating film completely and uniformly covers the whole outer surface of each nitroamine explosive particle, and the thickness of the coating film can be precisely adjusted within a nanoscale range. The method is suitable for coating nitroamine explosive particles in micron order, nanometer order or millimeter order. When the thickness of the coating film is controlled to be within the nanoscale range, the content of the coating films only accounts for 0.1 percent to 5 percent of the total mass of the system, and therefore, the coating films have little influence on the nitroamine explosives. The electrostatic spark sensitivity of the nitroamine explosives coated through the method disclosed in the invention is significantly reduced. The method has the advantages of high degree of automation and good safety performance. The coated nitroamine explosive particles can be directly used without postprocessing, so that the method is easy to realize and generalize in industry.
Description
Technical field
The present invention relates to the treatment process of nitro-amine compound explosive particle, belong to explosive field.
Background technology
Nitro-amine compound explosive is the simple substance military explosive that current performance is excellent, can be widely used in various modified solid propelling agent as high energy additive.But, nitro-amine compound explosive as octogen (HMX) self clash into external world, rub and electrostatic reaction more responsive, cause New Explosives and propelling agent to there is risk in development, storing and use procedure, thus limit its further application in the field such as solid propellant and high explosive to a certain extent.The method of current reduction sensitivity mainly adopts inert substance to carry out coated to blasting explosive granules, changes the surface properties of explosive.
According to the difference of physical environment residing for reactant in coated process, solid phase cladding process, liquid phase coating method and gas phase cladding specifically can be divided into.Solid phase and liquid phase coating method are cladding process the most conventional at present, and gas phase cladding report seldom.Solid phase method mainly refers to and adopts such as stearic acid, paraffin and graphite etc. to feel agent immediately to be undertaken coated by the method for carrying out mechanically mixing with explosive.Liquid phase method mainly covers the coated etc. of the coated and matrix material of polymer overmold, tensio-active agent, and coated process completes in the liquid phase, and product realizes separation by means such as filtrations, solvent evaporates.Although can explosive sensitivity be reduced to a certain extent by traditional solid phase and liquid phase coating method, but this type of method for coating lacks the accurate control to process, coating thickness is difficult to regulate, and its integrity, lack of homogeneity, be easy to the loss causing energetic material energy density; These class methods need to carry out a large amount of manual operation simultaneously, there is larger potential safety hazard.(the Li Maoguo such as Li Maoguo, Du Ziwei, the coated research of vapour deposition of Liao Hong .HMX particle, vacuum, 2013,50 (6): 23-26) adopted vacuum PVD method at HMX Surface coating paraffin and paralene film, the HMX mechanical sensitivity after paraffin is coated and electric spark sensitivity the liquid phase coating method that sense effect is better than equal paraffinicity is fallen.But what this vapor phase process realized on HMX surface is that physics is coated, and coating film and HMX surface reaction forces are weak, be easy to stripping and come off when being subject to External Force Acting.In addition, this gas phase cladding can not realize the accurate control to coating film thickness.
Summary of the invention
For the shortcomings and deficiencies that existing energetic material coating technology exists, the invention provides a kind of method adopting the coated nitro-amine compound explosive particle of technique for atomic layer deposition gas phase.The method can form even, fine and close nanoscale coating film at nitro-amine compound explosive particle surface, effectively reduces the electric spark sensitivity of nitro-amine compound explosive.
In order to realize above-mentioned technical assignment, the present invention adopts following technical scheme:
Adopt a method for the coated nitro-amine compound explosive particle of technique for atomic layer deposition, the method comprises the following steps:
Step one, nitro-amine compound explosive particle is placed in gas phase atomic layer deposition system reaction chamber, sealed reaction chamber, in gas phase atomic layer deposition system, passes into inert carrier gas and vacuumize, cavity pressure controls within the scope of 133Pa ~ 1000Pa, and temperature is within the scope of 35 DEG C ~ 150 DEG C;
Step 2, carries out ald to nitro-amine compound explosive particle and forms coating film, and the one-period of ald growth comprises following four processes:
(1) in reaction chamber, inject the first reaction precursor make it with HMX, saturated surface chemical reaction occur and replace surface functional group;
(2) inert carrier gas cleaning unreacted the first reaction precursor and by product is passed into;
(3) in reaction chamber, inject the second reaction precursor, with the first the precursors generation surface reaction being adsorbed on nitro-amine compound explosive surface, again replace surface functional group;
(4) pass into inert carrier gas and clean unreacted the second reaction precursor and by product;
The first described precursors is trimethyl aluminium, triethyl aluminum, zinc methide, zinc ethyl or silicon tetrachloride;
Described the second precursors is deionized water, hydrogen peroxide, ethylene glycol or glycerol;
Described inert carrier gas is nitrogen, helium or argon gas;
According to above-mentioned steps (1) to the order of step (4), precursors pulse sequence represents with t1-t2-t3-t4, wherein: t1 is the injection length of the first precursors, t3 is the injection length of the second precursors, t2 and t4 is the scavenging period of inert carrier gas;
Step 3, repeats the step 2 of respective cycle number, and nitro-amine compound explosive particle carries out ald, make coating film content be coated after nitro-amine compound explosive particle gross weight 0.1% ~ 5% scope in.
Advantage of the present invention, the present invention is adopted to carry out coated to nitro-amine compound explosive particle, coating film is complete, whole outside surfaces of uniform fold particle, thickness to be controlled within the scope of nanoscale and accurately adjustable, its content only accounts for 0.1% ~ 5% of system total mass, less to the energy affect of nitro-amine compound explosive.Because coated film is within the scope of nanoscale, can not there is essence change in the surface topography of the nitro-amine compound explosive after coated and physico-chemical property.The electric spark sensitivity of the nitro-amine compound explosive of coated aluminum oxide of the present invention or zinc-oxide film is adopted obviously to decline.Level of automation of the present invention is high, safety performance is good, directly can using without the need to aftertreatment after nitro-amine compound explosive particles coat completes, be easy to industrially realize and promote, for realizing the safety applications of nitro-amine compound explosive in high explosive or propellant formulation, there is realistic meaning.
Accompanying drawing explanation
Fig. 1 is unprocessed, coated through 150 cycle ALD aluminum oxide films and the XPS full scan collection of illustrative plates of HMX after 300 cycle ALD aluminum oxide films are coated.
Fig. 2 is unprocessed, coated through 150 cycle ALD aluminum oxide films and the XPS N element fine scanning collection of illustrative plates of HMX after 300 cycle ALD aluminum oxide films are coated.
Fig. 3 is the SEM photo that undressed HMX particle amplifies 10000 times.
Fig. 4 be through 300 cycle ALD aluminum oxide films coated after HMX particle amplify the SEM photo of 10000 times.
Embodiment
Below in conjunction with drawings and Examples, the present invention will be further described.
Ald (Atomic Layer Deposition is called for short ALD) technology is a kind of nanostructure manufacture and surface modification technology of forward position.This technical basis nanostructure assembling thought from bottom to top, realizes the controlled film growth of atom level precision by periodicity gaseous reactant presoma and the saturated chemical reaction of substrate material surface.The plastics thickness control mechanism of ALD technology uniqueness makes this technology can be used for the finishing of high specific surface area granular, dusty material.Another characteristic of ALD technology is lower film growth temperature.This advantage is particularly important to the energetic material of temperature extreme sensitivity for process.
ALD technology is adopted to carry out to HMX particle whole outside surfaces that Surface coating process can make coating film complete, uniform covering HMX particle.When coating film thickness is controlled within the scope of nanoscale, its content only accounts for 0.1% ~ 5% of system total mass, less to the energy affect of HMX.Adopt the coating film of present method synthesis to have coating layer densification, complete, even, thickness is adjustable (nano level tolerance range) accurately, and HMX granule-morphology remains intact, without the need to advantages such as aftertreatments, significant for the safety applications realizing HMX.
Through lot of experiment validation, the repeat cycle number that the coating film thickness on HMX particle and ald grow is linear.For coating material involved in the present invention, the coating film thickness that each atomic layer deposition cycle generates is between 0.05 ~ 0.2nm.By repeating the ald of some cycles number, the coating film of appointed thickness can be generated at HMX particle surface.
Agents useful for same and instrument:
HMX particle, median size 10 μm, median size 200 μm, Gansu Yinguang Chemical Industry Group Co., Ltd..
Trimethyl aluminium (TMA) (purity is 99%), zinc ethyl (DEZ) (purity is 99%), silicon tetrachloride (SiCl
4) (purity is 99%).
Deionized water (H
2o), hydrogen peroxide (H
2o
2), ethylene glycol (purity is 99%), glycerol (purity is 99%).
Gas phase atomic layer deposition system (ALD system), with reference to the document (J.W.Elam that Elam etc. delivers, M.D.Groner, andS.M.George.Viscous flow reactor with quartz crystal microbalance for thin film growth by atomiclayer deposition.Rev.Sci.Instrum, 2002,73 (8): 2981-2987.).
X-ray photoelectron power spectrum (Thermo Scientific K-Alpha XPS).
Scanning electronic microscope (FEI Quanta 600FEG SEM).
Electric spark sensitivity test method is carried out with reference to the space flight forth academy 42 company standard QJ-1469-88, the test condition of HT-201B type fixed interval (FI) used electric spark sensitivity instrument is: temperature is 25 DEG C, relative humidity is 50%, electrical condenser 0.01 ± 0.0005 μ F, output voltage range is 0 ~ ± 30KV, pulverized specimen electrode gap is 0.50 ± 0.01mm, dose 20mg, and the electric spark sensitivity firing energy E50 of 50% represents.By the requirement of GJB/Z377A-1997 sensitivity test mathematical statistics method, carry out lifting test with constant step size d, test effective degree is that 25-30 sends out, and last two test-results need contrary.
Below provide specific embodiments of the invention, it should be noted that the present invention is not limited to following specific embodiment.
Embodiment 1:
The present embodiment provides a kind of method adopting the coated Otto of technique for atomic layer deposition gram gold (HMX) particle, and the method specifically comprises the following steps:
Step one, HMX particulate samples (median size 10 μm) is placed in gas phase atomic layer deposition system reaction chamber, sealed reaction chamber, in gas phase atomic layer deposition system, pass into nitrogen and vacuumize, adjustment nitrogen flow is 80sccm, regulates reaction chamber outlet valve to make cavity pressure control at 133Pa; And make sample temperature be in 100 DEG C by heating;
Step 2, carries out ald to HMX particulate samples and forms coating film, and the one-period of ald growth comprises following four processes:
(1) in reaction chamber, inject the first reaction precursor trimethyl aluminium (TMA) make it with HMX, saturated surface chemical reaction occur and replace surface functional group, concrete chemical equation is as follows:
||-OH+Al(CH
3)
3→||-O-Al(CH
3)
2+CH
4
" ‖ " represents the surface of substrate material in the present invention, i.e. HMX;
(2) nitrogen purge unreacted the first reaction precursor and by product is passed into;
(3) in reaction chamber, inject the second reaction precursor deionized water, with the first the precursors generation surface reaction being adsorbed on HMX surface, again replace surface functional group, concrete chemical equation is as follows:
||-O-Al(CH
3)
2+2H
2O→||-O-Al(-OH)
2+2CH
4
(4) pass into nitrogen purge unreacted the second reaction precursor and by product, final coating film consist of Al
2o
3;
According to above-mentioned steps (1) to the order of step (4), precursors pulse sequence represents with t1-t2-t3-t4, wherein: t1 is the injection length of the first precursors, t3 is the injection length of the second precursors, t2 and t4 is the scavenging period of nitrogen.The pulse sequence adopted in the present embodiment is 8s-30s-8s-30s;
Find through research and experimental verification, for the HMX particle that the present embodiment adopts, the surface reaction of the first precursors and the second precursors all can complete in 8s, and the thickness increasing reaction times coating layer further also can not increase along with the increase in reaction times;
Step 3, repeats the step 2 of 150 cycle lifies, and HMX particle carries out ald, generates at HMX particle surface the alumina-coated film that thickness is about 18nm.Coating film content be coated after HMX particle gross weight 2.6%, coating film average growth rate is the 0.12nm/ cycle.
Electric spark sensitivity test result shows, compared to not coated HMX particle, HMX 50% firing energy through 150 cycle ALD alumina-coated process is increased to 69.0mJ by 29.9mJ, and electric spark sensitivity significantly reduces.
Embodiment 2:
The present embodiment provides a kind of method adopting the coated Otto of technique for atomic layer deposition gram gold (HMX) particle.The method is identical with embodiment 1, and difference is only in the step 3 of the present embodiment, needs the step 2 repeating 300 cycles.The mean sheet growth velocity of coating film is the 0.12nm/ cycle, and coating film thickness is 36nm, occupies 4.6% of HMX quality.HMX particle is achieved complete, coated uniformly by described coating film.Electric spark sensitivity test result shows, compared to not coated HMX particle, HMX 50% firing energy through 300 cycle ALD alumina-coated process is increased to 73.5mJ by 29.9mJ, and electric spark sensitivity significantly reduces.
The cycle life grown as can be seen from the coating film thickness on above-described embodiment 1 and embodiment 2, HMX particle and ald is linear.Under these experimental conditions, the mean sheet growth velocity of coating film is the 0.12nm/ cycle.By repeating the ald of respective cycle number, the coating film needing thickness can be generated.Therefore, the thickness of the coating film of HMX particle surface is accurately adjustable within the scope of nanoscale.
Fig. 1 is unprocessed, coated through 150 cycle ALD aluminum oxide films and the full scan collection of illustrative plates of the XPS of HMX particle after 300 cycle ALD aluminum oxide films are coated; Fig. 2 is corresponding XPS N element fine scanning collection of illustrative plates.Can draw from Fig. 1 and Fig. 2, HMX particulate samples upper layer element mainly consists of O, C, N and a small amount of Si.And after 150 cycle ALD alumina-coated process, HMX sample surfaces N element signal disappears substantially, Si elemental signals obviously weakens, and shows that the original components of sample surfaces is covered substantially.After 300 cycle ALD alumina-coated process, it is aluminum oxide that sample surfaces forms substantially.These results suggest that above-mentioned atomic layer deposition process at HMX Surface Creation fine and close aluminum oxide film, what achieve HMX is complete coated, and coating layer covers other impurity of all HMX molecules of sample surfaces and existence.
Fig. 3 is that undressed HMX particle amplifies 10000 times of photos obtained in the secure execution mode (sem; Fig. 4 be through 300 cycle ALD aluminum oxide films coated after HMX particle amplify 10000 times of photos obtained in the secure execution mode (sem.By comparison diagram 3, Fig. 4, can find out that the HMX granule-morphology after 300 cycle ALD aluminum oxide films are coated remains intact, basically identical with undressed HMX granule-morphology.This illustrates that alumina-coated film is in the growth of HMX surface uniform, thus can not change the primary morphology of HMX particle.
Above-mentioned XPS and SEM characterization result can prove after 300 cycle ALD alumina-coated, the aluminum oxide film of even compact at HMX Surface Creation, achieves complete coated of HMX, maintains the primary morphology of HMX particle simultaneously.
Embodiment 3:
The present embodiment provides a kind of method adopting the coated Otto of technique for atomic layer deposition gram gold (HMX) particle; the method is identical with embodiment 1; difference is only in the step one of the present embodiment, is that the HMX particle of 10 μm changes the HMX particle that median size is 200 μm into by median size.Through the ald in 150 cycles, generate at HMX particle surface the coating film (coating film average growth rate is the 0.12nm/ cycle) that thickness is about 18nm, coating film content is 0.11% of coated rear HMX particle gross weight.Electric spark sensitivity test result shows, compared to not coated HMX particle, HMX particle 50% firing energy through 150 cycle ALD alumina-coated process is increased to 60.7mJ by 29.9mJ, and electric spark sensitivity significantly reduces.Comparative example 1,2, and 3 find, when experiment condition is constant, along with the increase of HMX particle diameter, the growth velocity of coating film and thickness can not change substantially, and the ratio that coating film content accounts for coated rear HMX particle gross weight reduces.In embodiment 3, thickness is that 18nm coating film content only accounts for 0.11% of coated rear HMX particle gross weight, very little on the energy density impact of HMX.
Embodiment 4:
The present embodiment provides a kind of method adopting the coated Otto of technique for atomic layer deposition gram gold (HMX) particle, and the method specifically comprises the following steps:
Step one, HMX particulate samples (median size 10 μm) is placed in gas phase atomic layer deposition system reaction chamber, sealed reaction chamber, in gas phase atomic layer deposition system, pass into helium and vacuumize, adjustment helium gas flow is 80sccm, regulates reaction chamber outlet valve to make cavity pressure control at 250Pa; And make sample temperature be in 150 DEG C by heating;
Step 2, carries out ald to HMX particulate samples and forms coating film, and the one-period of ald growth comprises following four processes:
(1) in reaction chamber, inject the first reaction precursor zinc ethyl (DEZ) make it with HMX, saturated surface chemical reaction occur and replace surface functional group, concrete chemical equation is as follows:
||-OH+Zn(C
2H
5)
2→||-O-Zn-C
2H
5+C
2H
6
(2) helium cleaning unreacted the first reaction precursor and by product is passed into;
(3) in reaction chamber, inject the second reaction precursor deionized water, with the first the precursors generation surface reaction being adsorbed on HMX surface, again replace surface functional group, concrete chemical equation is as follows:
||-O-Zn-C
2H
5+H
2O→||-O-Zn-OH+C
2H
6
(4) pass into helium and clean unreacted the second reaction precursor and by product, final coating film consist of ZnO;
According to above-mentioned steps (1) to the order of step (4), precursors pulse sequence represents with t1-t2-t3-t4, wherein: t1 is the injection length of the first precursors, t3 is the injection length of the second precursors, t2 and t4 is the scavenging period of inert carrier gas helium; The pulse sequence adopted in the present embodiment is 8s-30s-8s-30s;
Step 3, repeats the step 2 of 300 cycle lifies, and HMX particle carries out ald.
Generate at HMX particle surface the coating film that thickness is about 24nm, coating film content be coated after HMX particle gross weight 4.4%, the average growth rate of coating film is the 0.08nm/ cycle.HMX particle is achieved complete, coated uniformly by this coating film.Electric spark sensitivity test result shows, compared to not coated HMX particle, HMX 50% firing energy through 300 cycle ALD oxide coated by zinc process is increased to 46.0mJ by 29.9mJ, and electric spark sensitivity significantly reduces.
Embodiment 5:
The present embodiment provides a kind of method adopting the coated Otto of technique for atomic layer deposition gram gold (HMX) particle, and the method specifically comprises the following steps:
Step one, HMX particulate samples (median size 10 μm) is placed in gas phase atomic layer deposition system reaction chamber, sealed reaction chamber, in gas phase atomic layer deposition system, pass into argon gas and vacuumize, adjustment argon flow amount is 80sccm, regulates reaction chamber outlet valve to make cavity pressure control at 350Pa; And make sample temperature be in 35 DEG C by heating;
Step 2, carries out ald to HMX particulate samples and forms coating film, and the one-period of ald growth comprises following four processes:
(1) in reaction chamber, inject the first reaction precursor silicon tetrachloride (SiCl
4) and catalyst pyridine make it with HMX, saturated surface chemical reaction occur and replace surface functional group, concrete chemical equation is as follows:
||-OH+SiCl
4→||-O-SiCl
3+HCl
(2) argon purge unreacted the first reaction precursor and by product is passed into;
(3) in reaction chamber, inject the second reaction precursor deionized water and catalyst pyridine, with the first the precursors generation surface reaction being adsorbed on HMX surface, again replace surface functional group, concrete chemical equation is as follows:
||-O-SiCl
3+3H
2O→||-O-Si(OH)
3+3HCl
(4) pass into argon purge unreacted the second reaction precursor and by product, final coating film consist of SiO
2;
According to above-mentioned steps (1) to the order of step (4), precursors pulse sequence represents with t1-t2-t3-t4, wherein: t1 is the injection length of the first precursors, t3 is the injection length of the second precursors, t2 and t4 is the scavenging period of inert carrier gas argon gas; The pulse sequence adopted in the present embodiment is 8s-30s-8s-30s;
Step 3, repeats the step 2 of 150 cycle lifies, and HMX particle carries out ald,
Generate at HMX particle surface the coating film that thickness is about 24nm, coating film content be coated after HMX particle gross weight 2.5%, the average growth rate of coating film is the 0.16nm/ cycle.This coating film achieves complete, coated uniformly to HMX particle.Electrostatic sensitivity test result shows, compared to not coated HMX particle, HMX 50% firing energy through the coated process of 150 cycle ALD silicon oxide is increased to 56.5mJ by 29.9mJ, and electric spark sensitivity significantly reduces.
Embodiment 6:
The present embodiment provides a kind of method adopting the coated Otto of technique for atomic layer deposition gram gold (HMX) particle, and the method specifically comprises the following steps:
Step one, repeats the ald in 50 cycles according to the method for embodiment 1 and condition coated, obtains the first layer Al
2o
3coating film.The average growth rate of coating film is the 0.12nm/ cycle, and thickness is about 6nm;
Step 2, repeats the ald in 150 cycles by the HMX particulate samples of coated 50 cyclic oxidation aluminium according to the method for embodiment 4 and condition coated, obtains second layer ZnO coating film.The average long speed of coating film is the 0.12nm/ cycle, and thickness is about 18nm.
Finally generate at HMX particle surface the two-layer compound coating film that total thickness is about 24nm.Coating film content be coated after HMX particle gross weight 3.8%, this two-layer compound coating film achieves complete, coated uniformly to HMX particle.Electric spark sensitivity test result shows, compared to not coated HMX particle, HMX 50% firing energy through 50 cycle ALD aluminum oxide and 150 cycle ALD oxide coated by zinc process is increased to 45.7mJ by 29.9mJ, and electric spark sensitivity significantly reduces.
Embodiment 7:
The present embodiment provides a kind of method adopting the coated Otto of gas phase deposition technology gram gold (HMX) particle, and the method specifically comprises the following steps:
Step one, repeats the ald in 50 cycles according to the method for embodiment 1 and condition coated, obtains the first layer Al
2o
3coating film.The average growth rate of coating film is the 0.12nm/ cycle, and thickness is about 6nm;
Step 2, the HMX particulate samples of coated 50 cyclic oxidation aluminium films is placed in gas phase atomic layer deposition system reaction chamber, sealed reaction chamber, in gas phase atomic layer deposition system, pass into argon gas and vacuumize, adjustment argon flow amount is 80sccm, regulates reaction chamber outlet valve to make cavity pressure control at 500Pa; And make sample temperature be in 80 DEG C by heating;
Step 3, carries out inorganic-organic hybrid atomic layer deposition thin film to the HMX particulate samples of coated 50 cyclic oxidation aluminium films coated.The one-period of second layer coating film ald growth comprises following four processes:
(1) in reaction chamber, inject the first reaction precursor zinc ethyl (DEZ) make it with HMX, saturated surface chemical reaction occur and replace surface functional group, concrete chemical equation is as follows:
||-OH+Zn(C
2H
5)
2→||-O-Zn-C
2H
5+C
2H
6
(2) argon purge unreacted the first reaction precursor and by product is passed into;
(3) in reaction chamber, inject the second reaction precursor ethylene glycol, with the first the precursors generation surface reaction being adsorbed on HMX surface, again replace surface functional group, concrete chemical equation is as follows:
||-O-Zn-C
2H
5+HOC
2H
4OH→||-O-Zn-O-C
2H
4OH+C
2H
6
(4) pass into argon purge unreacted the second reaction precursor and by product, final coating film consist of (-ZnOC
2h
4o)
x-;
According to above-mentioned steps (1) to the order of step (4), precursors pulse sequence represents with t1-t2-t3-t4, wherein: t1 is the injection length of the first precursors, t3 is the injection length of the second precursors, t2 and t4 is the scavenging period of inert carrier gas argon gas; The pulse sequence adopted in the present embodiment is 8s-60s-8s-60s;
Step 4, repeats the step 3 of 400 cycle lifies, and be about the coating film of 20nm at the HMX particle surface generation thickness of coated 50 cyclic oxidation aluminium, the average growth rate of coating film is the 0.05nm/ cycle.
Finally generate at HMX particle surface the two-layer compound coating film that total thickness is about 26nm, coating film content be coated after HMX particle gross weight 4.6%.This two-layer compound coating film achieves complete, coated uniformly to HMX particle.Electric spark sensitivity test result shows, compared to not coated HMX particle, through 50 cycle ALD aluminum oxide and 400 cycle ALD (-ZnOC
2h
4o)
xhMX particle 50% firing energy of-coated process is increased to 55.0mJ by 29.9mJ, and electric spark sensitivity significantly reduces.
In above-described embodiment, trimethyl aluminium can adopt triethyl aluminum to replace, and effect is identical; Zinc ethyl can adopt zinc methide to replace, and effect is identical; Deionized water can adopt hydrogen peroxide to replace, and effect is identical; Ethylene glycol can adopt glycerol to replace, and effect is identical.In addition, deionized water and ethylene glycol arbitrarily than mixture, deionized water and glycerol arbitrarily than mixture also can as the second precursors.In view of length, contriver only provides the chemical equation of relevant surfaces reaction.
The chemical equation of triethyl aluminum and deionized water is as follows:
||-OH+Al(C
2H
5)
3→||-O-Al(C
2H
5)
2+C
2H
6
||-O-Al(C
2H
5)
2+2H
2O→||-O-Al(-OH)
2+2C
2H
6
The chemical equation of zinc methide and deionized water is as follows:
||-OH+Zn(CH
3)
2→||-O-Zn-CH
3+CH
4
||-O-Zn-CH
3+H
2O→||-O-Zn-OH+CH
4
The chemical equation of trimethyl aluminium and hydrogen peroxide is as follows:
||-OH+Al(CH
3)
3→||-O-Al(CH
3)
2+CH
4
||-O-Al(CH
3)
2+2H
2O
2→||-O-Al(-OH)
2+2CH
4+O
2
The chemical equation of zinc ethyl and hydrogen peroxide is as follows:
||-OH+Zn(C
2H
5)
2→||-O-Zn-C
2H
5+C
2H
6
The chemical equation of zinc ethyl and glycerol is as follows:
||-OH+Zn(C
2H
5)
2→||-O-Zn-C
2H
5+C
2H
6
||-O-Zn-C
2h
54HOCH
2cHOHCH
2oH → ||-O-Zn-O-CH
2cHOHCH
2oH+C
2h
6except HMX, the present invention is also suitable for other to shock, friction and electrostatic reaction than more sensitive nanometer, micron or grade nitro-amine compound explosive (as RDX, CL-20 etc.).By formed on blasting explosive granules surface complete, uniformly inorganic or Coated with Organic Matter film reduce explosive sensitivity.The method of concrete enforcement and step and description of the invention basically identical.
Claims (8)
1. adopt a method for the coated nitro-amine compound explosive of technique for atomic layer deposition, it is characterized in that step is as follows:
Step one: nitro-amine compound explosive particle is placed in gas phase atomic layer deposition system reaction chamber, sealed reaction chamber, in gas phase atomic layer deposition system, pass into inert carrier gas and vacuumize, cavity pressure controls within the scope of 133Pa ~ 1000Pa, and temperature is within the scope of 35 DEG C ~ 150 DEG C;
Step 2: ald is carried out to nitro-amine compound explosive particle and forms coating film, the one-period of ald growth comprises following four processes: (1) injects the first reaction precursor in reaction chamber to be made it with nitro-amine compound explosive, saturated surface chemical reaction occur and replace surface functional group; (2) inert carrier gas cleaning unreacted the first reaction precursor and by product is passed into; (3) in reaction chamber, inject the second reaction precursor, with the first the precursors generation surface reaction being adsorbed on HMX surface, again replace surface functional group; (4) pass into inert carrier gas and clean unreacted the second reaction precursor and by product; According to above-mentioned steps (1) to the order of step (4), precursors pulse sequence represents with t1-t2-t3-t4, wherein: t1 is the injection length of the first precursors, t3 is the injection length of the second precursors, t2 and t4 is the scavenging period of inert carrier gas;
Step 3: the step 2 repeating respective cycle number, nitro-amine compound explosive particle carries out ald, make coating film content be coated after nitro-amine compound explosive particle gross weight 0.1% ~ 5% scope in.
2. the method adopting the coated nitro-amine compound explosive of technique for atomic layer deposition as claimed in claim 1, it is characterized in that, described nitro-amine compound explosive is HMX, RDX or CL-20.
3. the method adopting the coated nitro-amine compound explosive of technique for atomic layer deposition as claimed in claim 1, it is characterized in that, the particle diameter of described nitro-amine compound explosive is nano level, micron order or grade.
4. the method adopting the coated nitro-amine compound explosive of technique for atomic layer deposition as claimed in claim 1, it is characterized in that, the first described precursors is trimethyl aluminium, triethyl aluminum, zinc methide, zinc ethyl or silicon tetrachloride.
5. the method adopting the coated nitro-amine compound explosive of technique for atomic layer deposition as claimed in claim 1, it is characterized in that, described the second precursors is deionized water, hydrogen peroxide, ethylene glycol or glycerol.
6. the method adopting the coated nitro-amine compound explosive of technique for atomic layer deposition as claimed in claim 1, it is characterized in that, described inert carrier gas is nitrogen, helium or argon gas.
7. the method adopting the coated HMX of technique for atomic layer deposition as claimed in claim 1, it is characterized in that, each described ald growth cycle time is 1-10000s.
8. the method adopting the coated nitro-amine compound explosive of technique for atomic layer deposition as claimed in claim 1, it is characterized in that, described atomic layer deposition cycle number is 1-5000.
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|---|---|---|---|
| CN201410667087.8A CN104496731A (en) | 2014-11-20 | 2014-11-20 | Method for coating nitroamine explosives by adopting atomic layer deposition technique |
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| CN105624647A (en) * | 2016-03-22 | 2016-06-01 | 西安近代化学研究所 | Preparation method of nanoscale core-shell structure super thermite |
| CN105750541A (en) * | 2016-04-13 | 2016-07-13 | 西安近代化学研究所 | Method for reducing electrostatic spark sensitivity of zirconium powder by utilizing ALD (Atomic Layer Deposition) coating layer |
| CN105839078A (en) * | 2016-04-13 | 2016-08-10 | 西安近代化学研究所 | Method for preparing graphene nano-composite energetic material through atomic-layer deposition technology |
| CN106220458A (en) * | 2016-07-28 | 2016-12-14 | 中国工程物理研究院化工材料研究所 | A kind of high explosion velocity low sense binary explosive and preparation method thereof |
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103668113A (en) * | 2013-11-26 | 2014-03-26 | 西安近代化学研究所 | Method for maintaining morphology of ADN (ammonium dinitramide) spherical particle |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103668113A (en) * | 2013-11-26 | 2014-03-26 | 西安近代化学研究所 | Method for maintaining morphology of ADN (ammonium dinitramide) spherical particle |
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| CN105624647A (en) * | 2016-03-22 | 2016-06-01 | 西安近代化学研究所 | Preparation method of nanoscale core-shell structure super thermite |
| CN105750541A (en) * | 2016-04-13 | 2016-07-13 | 西安近代化学研究所 | Method for reducing electrostatic spark sensitivity of zirconium powder by utilizing ALD (Atomic Layer Deposition) coating layer |
| CN105839078A (en) * | 2016-04-13 | 2016-08-10 | 西安近代化学研究所 | Method for preparing graphene nano-composite energetic material through atomic-layer deposition technology |
| CN105839078B (en) * | 2016-04-13 | 2018-04-27 | 西安近代化学研究所 | A kind of method that graphene nano Composite Energetic Materials are prepared using technique for atomic layer deposition |
| CN106220458A (en) * | 2016-07-28 | 2016-12-14 | 中国工程物理研究院化工材料研究所 | A kind of high explosion velocity low sense binary explosive and preparation method thereof |
| CN109701513A (en) * | 2018-11-19 | 2019-05-03 | 西安近代化学研究所 | A kind of batch preparation of Piercing reaming degradation photochemical catalyst |
| CN109701513B (en) * | 2018-11-19 | 2022-11-15 | 西安近代化学研究所 | Batch preparation method of explosive wastewater degradation photocatalyst |
| CN114736086A (en) * | 2021-01-08 | 2022-07-12 | 西安近代化学研究所 | Boron powder compound with high combustion performance and preparation method thereof |
| CN114736086B (en) * | 2021-01-08 | 2023-03-17 | 西安近代化学研究所 | Boron powder compound with high combustion performance and preparation method thereof |
| CN114988972A (en) * | 2022-07-13 | 2022-09-02 | 西南科技大学 | Method for reducing mechanical and electrostatic sensitivity of explosive by coating with nano carbon material |
| CN114988972B (en) * | 2022-07-13 | 2023-09-29 | 西南科技大学 | Method for reducing mechanical and electrostatic sensitivity of explosive by coating nano carbon material |
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