CN105624647A - Preparation method of nanoscale core-shell structure super thermite - Google Patents

Preparation method of nanoscale core-shell structure super thermite Download PDF

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CN105624647A
CN105624647A CN201610164360.4A CN201610164360A CN105624647A CN 105624647 A CN105624647 A CN 105624647A CN 201610164360 A CN201610164360 A CN 201610164360A CN 105624647 A CN105624647 A CN 105624647A
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reaction
thermite
aluminium powder
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冯昊
秦利军
闫宁
龚婷
惠龙飞
李建国
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Xian Modern Chemistry Research Institute
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
    • C23C16/45523—Pulsed gas flow or change of composition over time
    • C23C16/45525—Atomic layer deposition [ALD]
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/40—Oxides

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Abstract

The invention discloses a preparation method of a nanoscale core-shell structure super thermite and belongs to the technical field of nano material preparation. According to the method, two reaction former bodies alternatively pass through a reaction chamber, and chemical reaction is generated on the surfaces of nano aluminum powder particles to produce a metal oxide cladding shell. The cladding shell completely and uniformly covers on the overall outer surface of nano aluminum powder, and the thickness of the cladding shell can be accurately adjusted in a nanoscale scope according to the stoichiometric ratio of thermite reaction. The super thermite prepared by adopting the method disclosed by the invention has the characteristics of being accurate and adjustable in shell thickness in nanoscale, perfect in shell structure, high in ignition speed, high in energy release efficiency and complete in reaction. The method is high in automation degree and good in safety performance, and the nano aluminum powder particles can be directly used without aftertreatment after cladding is completed and are easy to realize and popularize in industry.

Description

The preparation method of a kind of super thermite of nano level nucleocapsid structure
Technical field
The present invention relates to the preparation method of a kind of super thermite of nano level nucleocapsid structure, belong to technical field of nanometer material preparation.
Background technology
Super thermite (SuperThermites), it is commonly referred to as the mixture that a class is mixed to get on nanoscale by the metal oxide that nanometre metal powder (such as nanometer aluminium powder) and oxidisability are stronger also known as metastable state intermolecular complex (Metastableintermolecularcomposite, MIC). This type of material can cause violent solid oxide-reduction chemical reaction (thermitereaction thermite reaction) under strong heat or mechanical shock effect, discharges the huge energy based on heat energy. According to Theoretical Calculation result, MIC has extremely high unit volume energy density, has the TNT equivalent of more than three times. Super thermite have because of it excellent igniting and reactivity worth, raising energy release rate and the advantage such as efficiency of combustion, reduction material sensitivity can be provided and the class that becomes very potential be applied to the fields such as military project, smelting, pyrotechnics containing can inorganic materials. The method of the super thermite of preparation mainly contains mechanical-physical hybrid system, ball milled, spray heating decomposition, self-assembly method, sol-gel method, ultrasonic disperse compound etc. at present. Although above-mentioned traditional preparation method respectively has advantage when preparing super thermite, but these preparation methods generally also exist compound lack of homogeneity, bad dispersibility, shortage to accurate control, aftertreatment trouble, the poor stability of recombination process, be unfavorable for large-scale commercial production and the shortcoming such as cost is higher.
CN104551005A discloses a kind of method adopting liquid phase reduction-oxidation method to prepare the super thermite of nano level nucleocapsid structure. The method first by nanometer aluminium powder ultrasonic disperse in the reductibility solvent (highdensity unit alcohol or polyvalent alcohol) being dissolved with metal-salt, then add reagent (hydrazine hydrate or the NaBH of reductibility4) reduce, the atoms metal that reduction obtains or cluster adsorb and are deposited on aluminium core surface, form M0The intermediate of Al, M0The O being dissolved in reaction system2Oxidation, forms M (OH) on nanometer aluminium powder surfaceXCoating layer, realizes outer M (OH) by crystallization afterwardsXTo corresponding metal oxide MOx/2The transformation of phase, the final thermite MO forming nano level nucleocapsid structurex/2Al. Although MO prepared by the methodx/2The super thermite of Al has the features such as unit mass calorific value is higher, ignition temperature is low, but the method completes in the liquid phase, complex process, aftertreatment bothers, lack the accurate control to experimentation, the fine adjustment being difficult to realize metal oxide coating thickness, and the integrity of coating layer, homogeneity and compactness are poor, and also there is certain defect in nucleocapsid structure. The speed of reaction of super thermite and every thermal characteristics can be produced directly impact by the integrity of nucleocapsid structure and the quality of metal oxide coating layer.
Summary of the invention
For the shortcomings and deficiencies that prior art exists, the present invention provides a kind of and adopts ald (AtomicLayerDeposition is called for short ALD) technology gas phase to prepare the method for the super thermite of nano level nucleocapsid structure. The method can form even, the fine and close coated shell of Nanoscale metal oxide according to thermite reaction stoichiometric ratio on nanometer aluminium powder surface. The method provided has the advantages such as level of automation height, safety performance are good, economic environmental protection, the super thermite of nano level nucleocapsid structure of preparation have speed of ignition fast, release energy efficiency height, the performance characteristics such as react completely.
The super thermite of nano level nucleocapsid structure provided by the present invention, chemical general formula is AlMOx/2, wherein M is the one in Fe, Co, Ni, Sn, Ti, Cu, Zn, V, Mn, Zr, Bi, and X is the valency state of M, and the particle diameter of X=2-5, Al core is 10-500nm. Compared to super thermite prepared by physical mixed method, when best thermite reaction stoichiometric ratio, the super thermit reaction speed of nucleocapsid structure prepared by employing technique for atomic layer deposition improves 1��8 times, and reacting completely property reaches 90% and more than 95%.
A preparation method for the super thermite of nano level nucleocapsid structure, the method comprises the following steps:
Step one, is placed in nanometer aluminium powder particle in gas phase atomic layer deposition system reaction chamber, sealed reaction chamber, leads to into inert carrier gas and vacuumize, cavity pressure 133Pa��1000Pa in gas phase atomic layer deposition system, temperature 80 DEG C��400 DEG C;
Step 2, carries out ald and forms coating film nanometer aluminium powder particle, and the one-period of ald growth comprises following four processes: (1) injects the first reaction precursor in reaction chamber, makes it and aluminium powder generation saturated reaction; (2) lead to into inert carrier gas cleaning unreacted the first reaction precursor and by product; (3) in reaction chamber, inject the 2nd kind of reaction precursor, react with the first precursors being adsorbed on aluminium powder surface; (4) lead to into the unreacted 2nd kind of reaction precursor of inert carrier gas cleaning and by product; According to above-mentioned steps order, precursors pulse sequence represents with t1-t2-t3-t4, wherein: t1, t3 be respectively the first, injection time of the 2nd kind of precursors, t2 and t4 is the scavenging period of inert carrier gas;
Step 3, repeats the step 2 of respective cycle number, carries out ald on aluminum particle so that the mass ratio of the quality of coated shell and aluminium core meets the optimum chemical metering ratio of this thermite reaction.
The first precursors of the present invention is ferrocene (FeCp2), three (DPM dpm,dipivalomethane acid) iron (Fe (TMHD)3), acetylacetone cobalt (Co (acac)3), three (DPM dpm,dipivalomethane acid) cobalt (Co (TMHD)3), acetylacetonate nickel (Ni (acac)2), three (DPM dpm,dipivalomethane acid) nickel (Ni (TMHD)3), tin tetrachloride (SnCl4), titanium tetrachloride (TiCl4), titanium tetraisopropylate (Ti (OPr)4), two (hexafluoroacetylacetone) close copper (II) hydrate (Cu (hfac)2), zinc ethyl (DEZ), zinc methide (DMZ), three isopropoxy vanadium oxides (VOTP), two luxuriant manganese (MnCp2), three (DPM dpm,dipivalomethane acid) manganese (Mn (TMHD)3), four (dimethylin) zirconium (TDMAZr), four (the first and second amidos) zirconium (TEMAZr) or three (DPM dpm,dipivalomethane acid) bismuth (Bi (TMHD)3);
The 2nd kind of described precursors is deionized water (H2O), hydrogen peroxide (H2O2), oxygen (O2) or ozone (O3);
Described inert carrier gas is nitrogen, helium or argon gas;
The advantage of the present invention: adopt technique for atomic layer deposition to have the super thermite of nucleocapsid structure at nanometer aluminium powder surface deposition Preparation according to thermite reaction stoichiometric ratio. Compared to the super thermite of tradition preparation method's synthesis, the nanometer nuclear shell nano-structure that the present invention this kind is unique greatly facilitates fully contacting of oxygenant and nanometer aluminium powder in thermite mixture, making speed of response in combustion improve several times, the reacting completely property of nanometer aluminium powder is close to 100%. Super thermite based on this structure is expected to be applied to explosive and propellant formulation, for improving the energy density of mixture or regulate its structure of energy output. Safe, reliable, energy saving, environmental protection of the present invention, the super thermite of preparation has controllability and the circulation ratio of height. In addition, the method level of automation height, safety performance is good, synthesis step simple (nanometer aluminium powder particle can directly use without the need to extra aftertreatment after being covered to complete), it is easy to industrially realize and promote, has important practical significance as the application of novel energetic combustion catalyst in solid propellant propulsion agent prescription for realizing the super thermite of this nucleocapsid structure.
Accompanying drawing explanation
Fig. 1 is the AlSnO adopting ALD technique to prepare according to thermite reaction stoichiometric ratio in embodiment 12The SEM photograph of the super thermite of nano level nucleocapsid structure.
Fig. 2 is the AlSnO adopting ALD technique to prepare according to thermite reaction stoichiometric ratio in embodiment 12The TEM photo of the super thermite of nano level nucleocapsid structure.
Fig. 3 is the AlSnO adopting ALD technique and physical blending process to prepare respectively according to thermite reaction stoichiometric ratio in embodiment 12And Al-SnO2The DSC spectrogram of super thermite and nanometer aluminium powder.
Fig. 4 is the AlSnO adopting ALD technique and physical blending process to prepare respectively according to thermite reaction stoichiometric ratio in embodiment 12And Al-SnO2The laser ignition figure of super thermite.
Fig. 5 is the AlFe adopting ALD technique to prepare according to thermite reaction stoichiometric ratio in embodiment 22O3The XPS spectrum figure of the super thermite of nano level nucleocapsid structure and nanometer aluminium powder.
Fig. 6 is the AlFe adopting ALD technique to prepare according to thermite reaction stoichiometric ratio in embodiment 22O3The SEM photograph of the super thermite of nano level nucleocapsid structure.
Fig. 7 is the AlFe adopting ALD technique to prepare according to thermite reaction stoichiometric ratio in embodiment 22O3The TEM photo of the super thermite of nano level nucleocapsid structure.
Fig. 8 is the AlFe adopting ALD technique to prepare according to thermite reaction stoichiometric ratio in embodiment 22O3The EDAXTEM photo of the super thermite of nano level nucleocapsid structure.
Fig. 9 is the AlFe adopting ALD technique and physical blending process to prepare respectively according to thermite reaction stoichiometric ratio in embodiment 22O3And Al-Fe2O3The DSC spectrogram of super thermite and nanometer aluminium powder.
Figure 10 is the AlFe adopting ALD technique and physical blending process to prepare respectively according to thermite reaction stoichiometric ratio in embodiment 22O3And Al-Fe2O3The laser ignition figure of super thermite.
Embodiment
Below in conjunction with drawings and Examples, the present invention will be further described.
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.Viscousflowreactorwithquartzcrystalmicroba lanceforthinfilmgrowthbyatomiclayerdeposition.Rev.Sci.In strum, 2002,73 (8): 2981-2987.).
X-ray photoelectron power spectrum (ThermoScientificK-AlphaXPS).
Differential scanning calorimeter (NETZSCH204DSC).
Scanning electronic microscope (FEIQuanta600FEGSEM).
Flied emission transmission electron microscope (FEITecnaiG2F20S-TWIN)��
Laser ignition test set is used for super thermite is carried out laser ignition test. This testing apparatus the four parts compositions such as shoots with video-corder primarily of Laser Power Supply system, experiment container, test record system, ignition process. Wherein Laser Power Supply adopts peak power to be 120W, output wavelength to be the CO of 10.6 ��m2Continuous wave laser (model SLC110), the spot diameter of laser beam is 5.0mm. The LASER HEAT flow density scope adopted in experiment is 83.0W cm-2��340.4W cm-2, after in ignition process, laser lasts till that igniting reaction occurs; Experiment container specification is �� 300mm �� 400mm, there is form and can observe ignition process in container, built-in laboratory sample placement platform, test on the platform that fixed combustion device bottom the test specimen of sample is housed, will make laser beam can vertically act on and sample center surface before starting; Test record system by TEKDPO4034 high-performance digital oscilloscope, desk-top computer and photoelectricity test circuit, for the test of process of the test parameter, record and data processing.
Hereinafter providing specific embodiments of the invention, in embodiment, the median size of nanometer aluminium powder used is 130nm, and active aluminium content is 70%. It should be noted that the present invention is not limited to following specific embodiment, all equivalents done on technical scheme basis all fall into protection scope of the present invention.
Embodiment 1:
The present embodiment provides the preparation method of a kind of super thermite of nano level nucleocapsid structure, and the method specifically comprises the following steps:
Step one, nanometer aluminium powder particle is placed in gas phase atomic layer deposition system reaction chamber, sealed reaction chamber, leads to into nitrogen in gas phase atomic layer deposition system and vacuumize, adjustment nitrogen flow is 100sccm, regulates reaction chamber outlet valve to make cavity pressure control at 250Pa; And make sample temperature be in 300 DEG C by heating;
Step 2, carries out ald and forms coating film nanometer aluminium powder particle, and the one-period of ald growth comprises following four processes:
(1) in reaction chamber, inject the first reaction precursor tin tetrachloride (SnCl4) make it with aluminium powder, saturated surface chemical reaction to occur and replace surface functional group, concrete chemical equation is as follows:
||-OH*+SnCl4��||-OSnCl3 *+HCl
" �� " represents the surface of substrate material in the present invention, i.e. nanometer aluminium powder;
(2) lead to into nitrogen purge unreacted the first reaction precursor and by product;
(3) in reaction chamber, inject the 2nd kind of reaction precursor hydrogen peroxide (H2O2), with the first the precursors generation surface reaction being adsorbed on aluminium powder surface, again replace surface functional group, concrete chemical equation is as follows:
||-OSnCl3 *+3H2O2��||-OSn(OH)3 *+3HCl+3/2O2
(4) leading to into the unreacted 2nd kind of reaction precursor of nitrogen purge and by product, the coated shell on final aluminium powder surface is SnO2;
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 time of the first precursors, and t3 is the injection time of the 2nd kind of precursors, t2 and t4 is the scavenging period of nitrogen. The pulse sequence adopted in the present embodiment is 60s-60s-60s-60s;
Step 3, repeats the step 2 of 550 cycle lifies, carries out ald on nanometer aluminium powder particle so that the quality of coated shell and the mass ratio (2.4:1) of aluminium core meet the optimum chemical metering ratio of this thermite reaction. At the SnO of nanometer aluminium powder surface deposition2The thickness of shell is about 17nm, and the average production speed of this coating film is about the 0.03nm/ cycle.
Laser ignition experiment (as shown in table 1 and Fig. 4) and DSC test (as shown in Figure 3) result and show, compared to super thermite prepared by physical mixed method, when thermite reaction stoichiometric ratio, adopt AlSnO prepared by technique for atomic layer deposition2The super thermit reaction of nucleocapsid structure is more violent, and speed of response about improves 8 times, and reacting completely property is greater than 95%. Utilize scanning electronic microscope (SEM), Flied emission transmission electron microscope (TEM) product shape looks and structure to be characterized, the results are shown in Figure of description 1 and accompanying drawing 2. As shown in Figure 1, through 550 cycles SnO2Coated after, all nanometer aluminium powder particle surfaces are all evenly coated smooth SnO2Film, and the size of nanometer aluminium powder particle all becomes big. As shown in Figure 2, it is possible to obviously see taking nanometer aluminium powder as core and with SnO2For the appearance structure of the super thermite of shell, and the SnO of nanometer aluminium powder surface deposition2Shell is smooth, even, fine and close, complete. The nanometer nuclear shell nano-structure of the uniqueness that this kind is prepared according to thermite reaction stoichiometric ratio, facilitate fully contacting of oxygenant and nanometer aluminium powder in thermite mixture greatly, nanometer aluminium powder in combustion is fully burned, and speed of response obtains and obviously promotes.
Table 1AlSnO2The laser ignition result of the super thermite of nucleocapsid structure
Sample (Al/SnO2=1:2.4) Laser ignition time of lag (ms) Reaction times (ms)
AlSnO2(ALD) 38 17
Al-SnO2(physical mixed) 36 140
Embodiment 2:
The present embodiment provides the preparation method of a kind of super thermite of nano level nucleocapsid structure, and the method specifically comprises the following steps:
Step one, nanometer aluminium powder particle is placed in gas phase atomic layer deposition system reaction chamber, sealed reaction chamber, leads to into nitrogen in gas phase atomic layer deposition system and vacuumize, adjustment nitrogen flow is 120sccm, regulates reaction chamber outlet valve to make cavity pressure control at 133Pa; And make sample temperature be in 350 DEG C by heating;
Step 2, carries out ald and forms coating film nanometer aluminium powder particle, and the one-period of ald growth comprises following four processes:
(1) in reaction chamber, inject the first reaction precursor ferrocene (FeCp2) make it with aluminium powder, saturated surface chemical reaction to occur and replace surface functional group, concrete chemical equation is as follows:
||-O*+FeCp2��||-OFeCp*+Cp
" �� " represents the surface of substrate material in the present invention, i.e. nanometer aluminium powder;
(2) lead to into nitrogen purge unreacted the first reaction precursor and by product;
(3) in reaction chamber, inject the 2nd kind of reaction precursor oxygen (O2), with the first the precursors generation surface reaction being adsorbed on aluminium powder surface, again replace surface functional group, concrete chemical equation is as follows:
||-OFeCp*+O2��||-OFeOx *+Cp
(4) leading to into the unreacted 2nd kind of reaction precursor of nitrogen purge and by product, the coated shell on final aluminium powder surface is Fe2O3;
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 time of the first precursors, and t3 is the injection time of the 2nd kind of precursors, t2 and t4 is the scavenging period of nitrogen. The pulse sequence adopted in the present embodiment is 90s-60s-90s-60s;
Step 3, repeats the step 2 of 200 cycle lifies, carries out ald on nanometer aluminium powder particle so that the quality of coated shell and the mass ratio (2.1:1) of aluminium core meet the optimum chemical metering ratio of this thermite reaction. At the Fe of nanometer aluminium powder surface deposition2O3The thickness of shell is about 20nm, and the average production speed of this coating film is about the 0.1nm/ cycle.
Laser ignition experiment (as shown in table 2 and Figure 10) and DSC test (as shown in Figure 9) result and show, compared to super thermite prepared by physical mixed method, when thermite reaction stoichiometric ratio, adopt AlFe prepared by technique for atomic layer deposition2O3The super thermit reaction of nucleocapsid structure is more violent, and speed of response about improves 4 times, and reacting completely property is greater than 95%. Utilize x-ray photoelectron power spectrum (XPS), scanning electronic microscope (SEM) and Flied emission transmission electron microscope (TEM) product surface composition, shape looks and structure to be characterized, the results are shown in Figure 5, Fig. 6, Fig. 7 and Fig. 8. As shown in Figure 5, the disappearance of Al elemental signals from spectrogram, the appearance at the strong peak of Fe element is it can be shown that nanometer Fe2O3Film is evenly complete has been coated on nanometer aluminium powder surface. As shown in Figure 6, through 200 cycles Fe2O3Coated after, the surface topography of nanometer aluminium powder from smooth turn into coarse, and all evenly coated Fe of all nanometer aluminium powder particle surfaces2O3Film, the size of nanometer aluminium powder particle all becomes big. As shown in Figure 7, it is possible to obviously see taking nanometer aluminium powder as core and with Fe2O3For the appearance structure of the super thermite of shell, and the Fe of nanometer aluminium powder surface deposition2O3Shell is even, fine and close, complete. The EDAXTEAM spectrogram of Fig. 8 demonstrates AlFe further2O3The homogeneity of super thermite nucleocapsid structure, compactness and integrity. The nanometer nuclear shell nano-structure of the uniqueness that this kind is prepared according to thermite reaction stoichiometric ratio, facilitate fully contacting of oxygenant and nanometer aluminium powder in thermite mixture greatly, nanometer aluminium powder in combustion is fully burned, and speed of response obtains and obviously promotes.
Table 2AlFe2O3The laser ignition result of the super thermite of nucleocapsid structure
Sample (Al/Fe2O3=1:2.1) Laser ignition time of lag (ms) Reaction times (ms)
AlFe2O3(ALD) 34 68
Al-Fe2O3(physical mixed) 33 222
Embodiment 3:
The present embodiment provides the preparation method of a kind of super thermite of nano level nucleocapsid structure, and the method specifically comprises the following steps:
Step one, nanometer aluminium powder particle is placed in gas phase atomic layer deposition system reaction chamber, sealed reaction chamber, leads to into helium in gas phase atomic layer deposition system and vacuumize, adjustment helium gas flow is 120sccm, regulates reaction chamber outlet valve to make cavity pressure control at 133Pa; And make sample temperature be in 150 DEG C by heating;
Step 2, carries out ald and forms coating film nanometer aluminium powder particle, and the one-period of ald growth comprises following four processes:
(1) in reaction chamber, inject the first reaction precursor titanium tetraisopropylate (Ti (OPr)4) make it with aluminium powder, saturated surface chemical reaction to occur and replace surface functional group, concrete chemical equation is as follows:
||-OH*+Ti(OCH(CH3)2)4��||-OTi(OCH(CH3)2)3 *+HOCH(CH3)2
" �� " represents the surface of substrate material in the present invention, i.e. nanometer aluminium powder;
(2) lead to into helium cleaning unreacted the first reaction precursor and by product;
(3) in reaction chamber, inject the 2nd kind of reaction precursor water (H2O), with the first the precursors generation surface reaction being adsorbed on aluminium powder surface, again replacing surface functional group, concrete chemical equation is as follows:
||-OTi(OCH(CH3)2)3 *+3H2O��||-OTi(OH)3 *+3HOCH(CH3)2
(4) leading to into the unreacted 2nd kind of reaction precursor of helium cleaning and by product, the coated shell on final aluminium powder surface is TiO2;
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 time of the first precursors, and t3 is the injection time of the 2nd kind of precursors, t2 and t4 is the scavenging period of helium. The pulse sequence adopted in the present embodiment is 40s-60s-40s-60s;
Step 3, repeats the step 2 of 160 cycle lifies, carries out ald on nanometer aluminium powder particle so that the quality of coated shell and the mass ratio (1.55:1) of aluminium core meet the optimum chemical metering ratio of this thermite reaction. At the TiO of nanometer aluminium powder surface deposition2The thickness of shell is about 19nm, and the average production speed of this coating film is about the 0.12nm/ cycle.
Experimental result shows, compared to super thermite prepared by physical mixed method, when thermite reaction stoichiometric ratio, adopts AlTiO prepared by technique for atomic layer deposition2The super thermit reaction of nucleocapsid structure is more violent, and speed of response about improves 3 times, and reacting completely property is greater than 90%.
Embodiment 4:
The present embodiment provides the preparation method of a kind of super thermite of nano level nucleocapsid structure, and the method specifically comprises the following steps:
Step one, nanometer aluminium powder particle is placed in gas phase atomic layer deposition system reaction chamber, sealed reaction chamber, leads to into argon gas in gas phase atomic layer deposition system 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 2, carries out ald and forms coating film nanometer aluminium powder particle, and the one-period of ald growth comprises following four processes:
(1) injecting the first reaction precursor zinc ethyl (DEZ) in reaction chamber to make it with aluminium powder, saturated surface chemical reaction to occur and replace surface functional group, concrete chemical equation is as follows:
||-OH*+Zn(C2H5)2��||-OZnC2H5 *+C2H6
" �� " represents the surface of substrate material in the present invention, i.e. nanometer aluminium powder;
(2) lead to into argon purge unreacted the first reaction precursor and by product;
(3) in reaction chamber, inject the 2nd kind of reaction precursor water (H2O), with the first the precursors generation surface reaction being adsorbed on aluminium powder surface, again replacing surface functional group, concrete chemical equation is as follows:
||-OZnC2H5 *+H2O��||-OZnOH*+C2H6
(4) leading to into the unreacted 2nd kind of reaction precursor of argon purge and by product, the coated shell on final aluminium powder surface is 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 time of the first precursors, and t3 is the injection time of the 2nd kind of precursors, t2 and t4 is the scavenging period of argon gas. The pulse sequence adopted in the present embodiment is 20s-40s-20s-40s;
Step 3, repeats the step 2 of 225 cycle lifies, carries out ald on nanometer aluminium powder particle so that the quality of coated shell and the mass ratio (3.2:1) of aluminium core meet the optimum chemical metering ratio of this thermite reaction. Thickness at the ZnO shell of nanometer aluminium powder surface deposition is about 38nm, and the average production speed of this coating film is about the 0.17nm/ cycle.
Experimental result shows, compared to super thermite prepared by physical mixed method, when thermite reaction stoichiometric ratio, the super thermit reaction of AlZnO nucleocapsid structure prepared by employing technique for atomic layer deposition is more violent, speed of response about improves 2 times, and reacting completely property is greater than 90%.
Embodiment 5:
The present embodiment provides the preparation method of a kind of super thermite of nano level nucleocapsid structure, and the method specifically comprises the following steps:
Step one, nanometer aluminium powder particle is placed in gas phase atomic layer deposition system reaction chamber, sealed reaction chamber, leads to into nitrogen in gas phase atomic layer deposition system and vacuumize, adjustment nitrogen flow is 120sccm, regulates reaction chamber outlet valve to make cavity pressure control at 200Pa; And make sample temperature be in 110 DEG C by heating;
Step 2, carries out ald and forms coating film nanometer aluminium powder particle, and the one-period of ald growth comprises following four processes:
(1) injecting the first reaction precursor three isopropoxy vanadium oxide (VOTP) in reaction chamber to make it with aluminium powder, saturated surface chemical reaction to occur and replace surface functional group, concrete chemical equation is as follows:
||-OH*+VO(C3H7O)3��||-OV(C3H7O)2 *+C3H7OH
" �� " represents the surface of substrate material in the present invention, i.e. nanometer aluminium powder;
(2) lead to into nitrogen purge unreacted the first reaction precursor and by product;
(3) in reaction chamber, inject the 2nd kind of reaction precursor hydrogen peroxide (H2O2), with the first the precursors generation surface reaction being adsorbed on aluminium powder surface, again replace surface functional group, concrete chemical equation is as follows:
||-OV(C3H7O)2 *+H2O2��||-OV(OH)2 *+2C3H7OH+O2
(4) leading to into the unreacted 2nd kind of reaction precursor of nitrogen purge and by product, the coated shell on final aluminium powder surface is V2O5;
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 time of the first precursors, and t3 is the injection time of the 2nd kind of precursors, t2 and t4 is the scavenging period of nitrogen. The pulse sequence adopted in the present embodiment is 30s-60s-30s-60s;
Step 3, repeats the step 2 of 680 cycle lifies, carries out ald on nanometer aluminium powder particle so that the quality of coated shell and the mass ratio (1.4:1) of aluminium core meet the optimum chemical metering ratio of this thermite reaction. At the V of nanometer aluminium powder surface deposition2O5The thickness of shell is about 20nm, and the average production speed of this coating film is about the 0.03nm/ cycle.
Experimental result shows, compared to super thermite prepared by physical mixed method, when thermite reaction stoichiometric ratio, adopts AlV prepared by technique for atomic layer deposition2O5The super thermit reaction of nucleocapsid structure is more violent, and speed of response about improves 3 times, and reacting completely property is greater than 90%.
Embodiment 6:
The present embodiment provides the preparation method of a kind of super thermite of nano level nucleocapsid structure, and the method specifically comprises the following steps:
Step one, nanometer aluminium powder particle is placed in gas phase atomic layer deposition system reaction chamber, sealed reaction chamber, leads to into nitrogen in gas phase atomic layer deposition system and vacuumize, adjustment nitrogen flow is 200sccm, regulates reaction chamber outlet valve to make cavity pressure control at 1000Pa; And make sample temperature be in 300 DEG C by heating;
Step 2, carries out ald and forms coating film nanometer aluminium powder particle, and the one-period of ald growth comprises following four processes:
(1) in reaction chamber, inject the first reaction precursor acetylacetone cobalt (Co (acac)3) make it with aluminium powder, saturated surface chemical reaction to occur and replace surface functional group, concrete chemical equation is as follows:
||-OH*+Co(acac)3��||-OCo(acac)2 *+H(acac)
" �� " represents the surface of substrate material in the present invention, i.e. nanometer aluminium powder;
(2) lead to into nitrogen purge unreacted the first reaction precursor and by product;
(3) in reaction chamber, inject the 2nd kind of reaction precursor ozone (O3), with the first the precursors generation surface reaction being adsorbed on aluminium powder surface, again replace surface functional group, concrete chemical equation is as follows:
||-OCo(acac)2 *+O3��||-OCoOx *+H2O+CO2
(4) leading to into the unreacted 2nd kind of reaction precursor of nitrogen purge and by product, the coated shell on final aluminium powder surface is Co3O4;
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 time of the first precursors, and t3 is the injection time of the 2nd kind of precursors, t2 and t4 is the scavenging period of nitrogen. The pulse sequence adopted in the present embodiment is 120s-90s-120s-90s;
Step 3, repeats the step 2 of 460 cycle lifies, carries out ald on nanometer aluminium powder particle so that the quality of coated shell and the mass ratio (2.3:1) of aluminium core meet the optimum chemical metering ratio of this thermite reaction. At the Co of nanometer aluminium powder surface deposition3O4The thickness of shell is about 19nm, and the average production speed of this coating film is about the 0.04nm/ cycle.
Experimental result shows, compared to super thermite prepared by physical mixed method, when thermite reaction stoichiometric ratio, adopts AlCo prepared by technique for atomic layer deposition3O4The super thermit reaction of nucleocapsid structure is more violent, and speed of response about improves 5 times, and reacting completely property is greater than 95%.
Embodiment 7:
The present embodiment provides the preparation method of a kind of super thermite of nano level nucleocapsid structure, and the method specifically comprises the following steps:
Step one, nanometer aluminium powder particle is placed in gas phase atomic layer deposition system reaction chamber, sealed reaction chamber, leads to into nitrogen in gas phase atomic layer deposition system and vacuumize, adjustment nitrogen flow is 100sccm, regulates reaction chamber outlet valve to make cavity pressure control at 133Pa; And make sample temperature be in 250 DEG C by heating;
Step 2, carries out ald and forms coating film nanometer aluminium powder particle, and the one-period of ald growth comprises following four processes:
(1) in reaction chamber, inject the first reaction precursor acetylacetone copper (Cu (acac)2) make it with aluminium powder, saturated surface chemical reaction to occur and replace surface functional group, concrete chemical equation is as follows:
||-OH*+Cu(acac)2��||-OCu(acac)*+H(acac)
" �� " represents the surface of substrate material in the present invention, i.e. nanometer aluminium powder;
(2) lead to into nitrogen purge unreacted the first reaction precursor and by product;
(3) in reaction chamber, inject the 2nd kind of reaction precursor ozone (O3), with the first the precursors generation surface reaction being adsorbed on aluminium powder surface, again replace surface functional group, concrete chemical equation is as follows:
||-OCu(acac)*+O3��||-OCuOx *+H2O+CO2
(4) leading to into the unreacted 2nd kind of reaction precursor of nitrogen purge and by product, the coated shell on final aluminium powder surface is CuO;
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 time of the first precursors, and t3 is the injection time of the 2nd kind of precursors, t2 and t4 is the scavenging period of nitrogen. The pulse sequence adopted in the present embodiment is 90s-90s-90s-90s;
Step 3, repeats the step 2 of 380 cycle lifies, carries out ald on nanometer aluminium powder particle so that the quality of coated shell and the mass ratio (3.1:1) of aluminium core meet the optimum chemical metering ratio of this thermite reaction. Thickness at the CuO shell of nanometer aluminium powder surface deposition is about 23nm, and the average production speed of this coating film is about the 0.06nm/ cycle.
Experimental result shows, compared to super thermite prepared by physical mixed method, when thermite reaction stoichiometric ratio, the super thermit reaction of AlCuO nucleocapsid structure prepared by employing technique for atomic layer deposition is more violent, speed of response about improves 6 times, and reacting completely property about reaches 95%.

Claims (7)

1. the preparation method of the super thermite of nano level nucleocapsid structure, it is characterised in that step is as follows:
Step one, is placed in nanometer aluminium powder particle in gas phase atomic layer deposition system reaction chamber, sealed reaction chamber, leads to into inert carrier gas and vacuumize, cavity pressure 133Pa��1000Pa in gas phase atomic layer deposition system, temperature 80 DEG C��400 DEG C;
Step 2, carries out ald and forms coating film nanometer aluminium powder particle, and the one-period of ald growth comprises following four processes: (1) injects the first reaction precursor in reaction chamber, makes it and aluminium powder generation saturated reaction; (2) lead to into inert carrier gas cleaning unreacted the first reaction precursor and by product; (3) in reaction chamber, inject the 2nd kind of reaction precursor, react with the first precursors being adsorbed on aluminium powder surface; (4) lead to into the unreacted 2nd kind of reaction precursor of inert carrier gas cleaning and by product; According to above-mentioned steps order, precursors pulse sequence represents with t1-t2-t3-t4, wherein: t1, t3 be respectively the first, injection time of the 2nd kind of precursors, t2 and t4 is the scavenging period of inert carrier gas;
Step 3, repeats the step 2 of respective cycle number, carries out ald on aluminum particle so that the mass ratio of the quality of coated shell and aluminium core meets the optimum chemical metering ratio of this thermite reaction.
2. the preparation method of the super thermite of nano level nucleocapsid structure as claimed in claim 1, it is characterized in that, the first precursors described is ferrocene, three (2, 2, 6, 6-tetramethyl--3, the acid of 5-heptadione) iron, acetylacetone cobalt, three (2, 2, 6, 6-tetramethyl--3, the acid of 5-heptadione) cobalt, acetylacetonate nickel, three (2, 2, 6, 6-tetramethyl--3, the acid of 5-heptadione) nickel, tin tetrachloride, titanium tetrachloride, titanium tetraisopropylate, two (hexafluoroacetylacetone) closes copper (II) hydrate, zinc ethyl, zinc methide, three isopropoxy vanadium oxides, two luxuriant manganese, three (2, 2, 6, 6-tetramethyl--3, the acid of 5-heptadione) manganese, four (dimethylin) zirconium, four (the first and second amidos) zirconiums or three (2, 2, 6, 6-tetramethyl--3, the acid of 5-heptadione) bismuth.
3. the preparation method of the super thermite of nano level nucleocapsid structure as claimed in claim 1, it is characterised in that, described 2nd kind of precursors is deionized water, hydrogen peroxide, oxygen or ozone.
4. the preparation method of the super thermite of nano level nucleocapsid structure as claimed in claim 1, it is characterised in that, described inert carrier gas is nitrogen, helium or argon gas.
5. the preparation method of the super thermite of nano level nucleocapsid structure as claimed in claim 1, it is characterised in that, each ald growth cycle time described is 1-10000s.
6. the preparation method of the super thermite of nano level nucleocapsid structure as claimed in claim 1, it is characterised in that, described atomic layer deposition cycle number is 1-5000.
7. the super thermite of nano level nucleocapsid structure that according to claim 1 prepared by method, chemical general formula is AlMOx/2, wherein M is the one in Fe, Co, Ni, Sn, Ti, Cu, Zn, V, Mn, Zr, Bi, and X is the valency state of M, and the particle diameter of X=2-5, Al core is 10-500nm.
CN201610164360.4A 2016-03-22 2016-03-22 Preparation method of nanoscale core-shell structure super thermite Pending CN105624647A (en)

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CN114835540A (en) * 2022-04-28 2022-08-02 西安近代化学研究所 High-energy-density vanadium oxide-loaded boron fuel and impregnation preparation method
CN115440409A (en) * 2022-09-05 2022-12-06 宁夏大学 Silver-aluminum paste for N-TOPCon solar cell and preparation method and application thereof
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CN110694673A (en) * 2019-10-22 2020-01-17 淮阴师范学院 Aromatization catalyst of waste edible oil and preparation method and application thereof
CN111170816A (en) * 2020-01-19 2020-05-19 湖北航天化学技术研究所 Boron-containing fuel-rich propellant
CN115884956A (en) * 2020-07-07 2023-03-31 因特威尔P&A公司 Thermite reaction charge, method of forming triphasic rock-well barrier and well barrier formed therewith
US12203337B2 (en) 2020-07-07 2025-01-21 Interwell P&A As Thermite reaction charge, method for forming a threephased rock-to-rock well barrier, and a well barrier formed thereof
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CN112457597B (en) * 2020-12-04 2021-12-14 中国矿业大学 Perovskite metal nonmetal compound core-shell quantum dot polymer film and preparation method and application thereof
CN112708870A (en) * 2020-12-21 2021-04-27 西安近代化学研究所 Atomic layer deposition CuO on aluminum powder surfacexPreparation method and application of modification layer
CN112708870B (en) * 2020-12-21 2023-03-17 西安近代化学研究所 Atomic layer deposition CuO on surface of aluminum powder x Preparation method and application of modification layer
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