CN105839078B - A kind of method that graphene nano Composite Energetic Materials are prepared using technique for atomic layer deposition - Google Patents

A kind of method that graphene nano Composite Energetic Materials are prepared using technique for atomic layer deposition Download PDF

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CN105839078B
CN105839078B CN201610228290.4A CN201610228290A CN105839078B CN 105839078 B CN105839078 B CN 105839078B CN 201610228290 A CN201610228290 A CN 201610228290A CN 105839078 B CN105839078 B CN 105839078B
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graphene
atomic layer
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CN105839078A (en
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闫宁
冯昊
秦利军
龚婷
惠龙飞
李建国
黄钰
张王乐
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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]
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    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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    • 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
    • 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
    • C23C16/4417—Methods specially adapted for coating powder

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Abstract

The invention discloses a kind of method that graphene nano Composite Energetic Materials are prepared using technique for atomic layer deposition.This method using the mixing of ultrasonic wave assisted solution and in-situ reducing method, prepares graphene-supported nano metal composite granule, realizes nano metal in the dispersed of graphene surface first.Then, using gas phase technique for atomic layer deposition, two kinds of different presomas are made to come into full contact with concurrent biochemical reaction generation oxide with graphene/nanometer metal composite powder surface alternately through reaction chamber.This method realizes oxide respectively in the uniform cladding on graphene surface and nano metal surface.The Composite Energetic Materials prepared by the present invention, oxide and the affinity increase on nano metal surface, spatial arrangement improve.The addition of graphene improves the scattered of nano metal, improves the energy release rate of energetic material.This method the degree of automation is high, has a safety feature, and product can be used directly without post processing, it is easy to accomplish the mass production of graphene nano Composite Energetic Materials.

Description

It is a kind of that graphene nano Composite Energetic Materials are prepared using technique for atomic layer deposition Method
Technical field
The present invention relates to a kind of preparation method of graphene nano Composite Energetic Materials, belongs to nano material preparation technology neck Domain.
Background technology
Nano metal powder is added in propellant, propellant burning property can be improved, and significantly improves its energy level.Receive Rice metal and oxidant, catalyst and propellant respectively containing can be between component the burning to propellant of affinity and spatial arrangement Performance and kinetics of combustion have significant impact.The contact area of the components such as nano-metal particle and oxidant is bigger, and burning is anti- Should be more abundant, propellant energy level is higher.But the specific surface area that Nano metal powder is high, typically resulting in powder reuniting makes Reactivity reduces, and constrains its further applying in propellant field to a certain extent.Nano metal powder is solved to disperse Conventional method be by the parcel of Nano metal powder using surfactant, polymer or end-capping reagent, hinder nano-particle group It is poly-.But the addition of auxiliary agent may cause nano-particle chemistry activity reduction, the practical application of nano-particle is influenced.
Graphene is the carbonaceous material with bi-dimensional cellular shape lattice structure that single layer of carbon atom is piled into, it has many Excellent performance：Great specific surface area (2630m2/ g), combustion reaction enthalpy (carbon-oxygen 32.8kJ/g, the carbon-aluminium of superelevation 1.6KJ/g) and high heat conduction, electric conductivity.At present, there are research team (Li, N.；Gong,Z.F.；Cao,M.H.；Ren, L.；Zhao,X.Y.；Liu,B.；Tian,Y.；Hu,C.W.,Well-dispersed ultrafine Mn3O4nanoparticles on graphene as a promising catalyst for the thermal decomposition of ammonium perchlorate.Carbon2013,54,124–132.)(Dey,A.；Athar, J.；Varma,P.；Prasant,H.；Sikder A.K.；Chattopadhyay,S.,Graphene-iron oxide nanocomposite(GINC):an efficient catalyst for ammonium perchlorate(AP) decomposition and burn rate enhancer for AP based composite propellant.RSC Advance.2015,5,1950-1960.) by the way that nano metal or oxide either physically or chemically are fixed on graphene table Face, can effectively prevent nano-particle reunion, keep the high-specific surface area and reactivity of particle.But above method is equal Lack effective control of the nano metal or oxide particle size, distribution and load density to being supported on graphene surface.Together When, above method can not regulate and control the affinity and spatial arrangement of metal fuel and oxidant.
The content of the invention
In view of the defects existing in the prior art with deficiency, the present invention provides one kind to use atomic layer deposition (Atomic Layer Deposition, abbreviation ALD) the technology method for preparing graphene nano Composite Energetic Materials.It is molten using ultrasonic wave added Liquid mixing method prepares graphene-supported nano metal composite granule, then by gas phase technique for atomic layer deposition above-mentioned compound Powder surface synthesis oxide.The Composite Energetic Materials prepared by the present invention, compared with traditional energetic material preparation method, Effective scattered and its surface affinity with oxide, the energetic material of preparation for improving Nano metal powder is released with energy Put the performance characteristics such as rate is high, the reaction was complete.
In order to realize above-mentioned technical assignment, the present invention adopts the following technical scheme that：
A kind of method that graphene nano Composite Energetic Materials are prepared using technique for atomic layer deposition, is comprised the following steps：
Step 1, the preparation of graphene-supported nano metal composite granule
(1) graphene oxide 0.01-100 mass parts and solvent 100-10000 mass parts are added in ultrasonic reactor, surpassed Acoustical power is 10-5000W, frequency 10-10000Hz, 20-100 DEG C of temperature, when ultrasonic disperse 5 minutes -10 is small, is aoxidized Graphene suspension；
(2) 100-10000 mass parts solvent orange 2 A, 100-10000 mass parts solvents B are mixedly configured into cosolvent, by nanometer Metal powder 1-100 mass parts add cosolvent, and when ultrasonic disperse 5 minutes -10 is small, the nano metal for obtaining stable dispersion suspends Liquid；Ultrasonic power 10-5000W, frequency 10-10000Hz, 20-100 DEG C of temperature；1-100 mass parts graphene oxide is suspended Liquid is added in 10-1000 mass parts nano metal suspension, when ultrasonic disperse 5 minutes -5 is small, adds reducing agent 1-5000 mass Part, continue ultrasonic disperse 5 minutes -10 it is small when, obtain stable graphene/nanometer metal material composite suspension liquid；
(3) it is above-mentioned graphene/nanometer metal material composite suspension liquid is small with high speed rotor centrifuge 10 minutes -2 When, 0-100 DEG C of temperature, rotating speed 3000-20000rpm, drying to constant weight in vacuum 0.01kPa-0.1MPa for product, obtains stone Black alkene nano metal composite granule；
The solvent of the graphene oxide suspension for water, ethanol, isopropanol, methyl acetate, toluene, tetrahydrofuran, At least one of acetone, hexane, hexamethylene and N, dinethylformamide；
The solvent orange 2 A of the Nano metal powder suspension is N, dinethylformamide, dimethyl sulfoxide (DMSO), N- methylpyrroles At least one of alkanone；Solvent B is at least one of ethylene glycol, isopropanol, glycerine；
The nano metal is at least one of nanometer aluminium powder, nanometer Mg powder, nano boron powder, nanometer zirconium powder；
The graphene is single or multiple lift, and monolithic graphite alkene size is micron order and submicron order；
The reducing agent of the graphene oxide is in hydrazine hydrate, ascorbic acid, sodium borohydride, hydroiodic acid and sodium citrate At least one.
Step 2：Atomic layer deposition prepares graphene nano Composite Energetic Materials
(1) graphene nano metal composite powder is placed in gas phase atomic layer deposition system reaction chamber, seals reaction chamber, Inert carrier gas is passed through into gas-phase deposition system and is vacuumized, cavity pressure is controlled in 133Pa-1000Pa, and temperature control is in 25- 400℃；
(2) atomic layer deposition is carried out to graphene nano metal composite powder and forms coating film, atomic layer deposition growth A cycle includes following four link：The first excessive precursors are injected into reaction chamber；It is passed through inert carrier gas；To Second excessive of precursors of injection in reaction chamber；Inert carrier gas is passed through again；Repeat the atom of respective cycle number Layer deposition so that the molar ratio of the oxide coating film of deposition and nano metal content in composite granule passes through institute in 0.1-1.0 The process of stating obtains graphene nano Composite Energetic Materials.
The first described precursors are ferrocene, nickel acetylacetonate, tetraphernl-lead, double (hexafluoroacetylacetone conjunctions Copper) close copper (II) hydrate, double (DPM dpm,dipivalomethane acid) cobalts, double (2,2,6,6- tetramethyls -3,5- heptan Two ketone acids) lead, three (2,2,6,6- tetramethyl -3,5- heptadione acid) bismuths, double (2,2,6,6- tetramethyl hept- 3, bis- ketone acids of 5-) copper At least one of；
Second of precursors are at least one of deionized water, hydrogen peroxide, oxygen, ozone；
The inert carrier gas is at least one of nitrogen, argon gas, helium；
Each described atomic layer deposition growth cycle time is 1-10000s；
The atomic layer deposition cycle number is 1-5000；
The advantageous effects of the present invention compared with prior art：
1. the ultrasonic wave added solution process for dispersing that the present invention uses makes Nano metal powder be dispersed in high-ratio surface Long-pending two-dimensional graphene surface, compared with traditional process for dispersing, the effective scattering problem for solving Nano metal powder of the present invention.
2. the present invention synthesizes oxygen using gas phase technique for atomic layer deposition on graphene-supported nano metal composite granule surface Compound.Sull is uniformly covered on nano metal surface and is closely connected by chemical bond.Compared with conventional art, oxygen The spatial arrangement and affinity of agent and Nano metal powder improve, and energetic material combustion reaction is more complete, and energy release rate is notable Improve.
3. the present invention is easy to operate, safe, the product of preparation has the controllability and reappearance of height.In addition the party Method the degree of automation is high, has a safety feature, synthesis step is simple, is easy to industrially realize and promote.The energetic material for Improve propellant burning property and improve energy level and have important practical significance.
Brief description of the drawings
Fig. 1 is the saturating of the graphene-supported nanometer aluminium powder GO/Al using the preparation of ultrasonic wave added solution blended process in embodiment 1 Penetrate electron microscope (TEM) figure.
Fig. 2 is the Al@Fe of stoichiometric ratio Φ=1.0 prepared in embodiment 1 using technique for atomic layer deposition2O3And GO/ Al@Fe2O3Composite Energetic Materials, and x-ray photoelectron spectroscopy (XPS) figure of GO/Al composite granules.
Fig. 3 is the GO/Al@Fe of stoichiometric ratio Φ=1.0 prepared in embodiment 1 using technique for atomic layer deposition2O3It is multiple Close scanning electron microscope (SEM) photo of energetic material.
Fig. 4 is the GO/Al@Fe of stoichiometric ratio Φ=1.0 prepared in embodiment 1 using technique for atomic layer deposition2O3It is multiple Close transmission electron microscope (TEM) photo of energetic material.
Fig. 5 is the GO/Al@Fe of stoichiometric ratio Φ=1.0 prepared in embodiment 1 using technique for atomic layer deposition2O3It is multiple Close Raman spectrum (Raman) figure of energetic material and GO/Al composite granules.
Fig. 6 is the GO/Al@Fe of stoichiometric ratio Φ=1.0 prepared in embodiment 1 using technique for atomic layer deposition2O3It is multiple Close FTIR spectrum (FTIR) figure of energetic material and GO/Al composite granules.
Fig. 7 is the Al@Fe of stoichiometric ratio Φ=1.0 prepared in comparative example 1 using technique for atomic layer deposition2O3 Scanning electron microscope (SEM) photo of thermite energetic material.
Fig. 8 is the GO/Al@Fe of stoichiometric ratio Φ=1.0 prepared in embodiment 1 using technique for atomic layer deposition2O3It is multiple Close the Al@Fe of stoichiometric ratio Φ=1.0 prepared in energetic material and comparative example 1 using technique for atomic layer deposition2O3Aluminium Means of differential scanning calorimetry (DSC) curve of thermit powder energetic material.
Fig. 9 is the GO/Al@Fe of stoichiometric ratio Φ=1.0 prepared in embodiment 1 using technique for atomic layer deposition2O3It is multiple Close the GO/Al-Fe prepared in energetic material and comparative example 2 using physical blending process2O3The differential scanning of Composite Energetic Materials Calorimetric (DSC) curve.
Embodiment
The present invention is specifically described below by embodiment and attached drawing.It is important to point out that following embodiments are only used It is further described in the present invention, it is impossible to be interpreted as limiting the scope of the invention, the researcher in the field can Some nonessential modifications and adaptations are made to the present invention according to the invention described above content.
Embodiment 1
Graphene-supported nanometer aluminium powder composite energy-containing material is prepared using technique for atomic layer deposition this gives one kind The method of material, this method specifically include following steps：
Step 1：The preparation of graphene-supported nanometer aluminium powder
(1) by graphene oxide 0.1g and n,N-Dimethylformamide 100g, add in ultrasonic reactor, in ultrasonic power For 1000W, frequency 200Hz, temperature 60 C, ultrasonic disperse time 2 h, obtains graphene oxide suspension.
(2) n,N-Dimethylformamide (100g) is configured, isopropanol (100g) cosolvent, nanometer aluminium powder 2g is added altogether In solvent, disperseed by ultrasonic wave added, ultrasonic power 1000W, frequency 200Hz, temperature 60 C, ultrasonic disperse time 2 h, Obtain the nanometer aluminium powder suspension of stable dispersion.Graphene oxide suspension 100g is added into nanometer aluminium powder cosolvent suspension In 200g, when ultrasonic disperse 5 is small, add hydrazine hydrate 0.5g, continue ultrasonic disperse 1 it is small when, obtain stable graphene-supported receive Rice aluminium powder composite suspension liquid.
(3) above-mentioned graphene-supported nanometer aluminium powder composite suspension liquid is placed in high speed rotor centrifuge, in 25 DEG C of temperature, turned Fast 12000rpm, centrifuges 20 minutes, drying to constant weight in vacuum 0.1kPa for product, obtains graphene-supported nanometer aluminium powder and answers Close powder.Product morphology is characterized using transmission electron microscope (TEM), the results are shown in Figure 1, and nanometer aluminium powder uniformly divides It is dispersed on graphene.
Step 2：Atomic layer deposition prepares graphene nano Composite Energetic Materials
Graphene-supported nanometer aluminium powder is placed in gas phase atomic layer deposition system reaction chamber, seals reaction chamber.To gas Nitrogen is passed through in phase depositing system and is vacuumized, control pressure is in 133Pa, and temperature control is at 350 DEG C.
Atomic layer deposition is carried out to graphene-supported nanometer aluminium powder and forms coating film, a week of atomic layer deposition growth Phase includes following four link：
(1) the first presoma ferrocene (FeCp is injected into reaction chamber2), it is allowed to and graphene-supported nanometer aluminium powder Composite granule surface occurs the chemical reaction of saturation and replaces surface functional group, and specific chemical equation is as follows：
||-O*+FeCp2→||-OFeCp+Cp
In the present invention " | | " represent substrate material surface, i.e., graphene-supported nanometer aluminium powder composite granule；
(2) it is passed through nitrogen and cleans unreacted ferrocene and accessory substance；
(3) oxygen is injected into reaction chamber, table occurs for the ferrocene presoma with adsorbing on graphene composite powder surface Face is reacted, and replaces surface functional group again, specific chemical equation is as follows：
(4) it is passed through nitrogen and cleans unreacted oxygen precursor and accessory substance.
(1) arrives (4) as procedure described above, and reaction precursor pulse sequence is represented with t1-t2-t3-t4, wherein：T1 is A kind of injection length of precursors, t3 are the injection lengths of second of precursors, and t2 and t4 are the cleaning of nitrogen Time.The pulse sequence used in this experimental example is 90s-60s-90s-60s.Repeat the atomic layer deposition of respective cycle number Product, the oxide coating film and the molar ratio of nanometer aluminium powder in composite granule for making deposition are respectively 1:2,1:2.2,1:2.4,1: 2.6,1:2.8,1:3.0,1:3.2.It is respectively Φ=1.0 to obtain stoichiometric ratio, 1.1,1.2,1.3,1.4,1.5 and 1.6 GO/Al@Fe2O3Composite Energetic Materials.
GO/Al@Fe using XPS, SEM, TEM, Raman, FTIR to stoichiometric ratio Φ=1.02O3Surface composition, shape Looks and structure are characterized, and the result is shown in Fig. 2, Fig. 3, Fig. 4, Fig. 5 and Fig. 6.As shown in Fig. 2, disappearing from XPS spectrum figure Al elemental signals Lose, the appearance of Fe elemental signals can illustrate nanometer Fe2O3Uniformly completely it is coated on a nanometer GO/Al surfaces.Such as Fig. 3 and Fig. 4 institutes Show, Fe2O3It is uniformly coated on graphene-supported nanometer aluminium powder surface, GO/Al@Fe2O3Surface topography is coarse, nanometer aluminium powder Size increase.As shown in figure 5, by Fe2O3The GO/Al composite granules uniformly coated, the D peaks (1341cm of graphene-1) and G peaks (1575cm-1) etc. Raman characteristic signals peak disappear, illustrate Fe2O3Completely, GO/Al surfaces are uniformly coated on.As shown in fig. 6, By Fe2O3The GO/Al composite granules uniformly coated, the infrared signature absorption peak C-O/C-OH (1100cm of graphene-1) and C= O(1595cm-1) disappear, illustrate Fe2O3Completely, GO/Al surfaces are uniformly coated on.
Embodiment 2
Graphene-supported nanometer aluminium powder composite energy-containing material is prepared using technique for atomic layer deposition this gives one kind The step of method of material, this method one, is identical with the step of embodiment 1 one, and difference lies in step 2.
Step 2：Atomic layer deposition prepares graphene nano Composite Energetic Materials
Graphene-supported nanometer aluminium powder is placed in gas phase atomic layer deposition system reaction chamber, seals reaction chamber.To gas Nitrogen is passed through in phase depositing system and is vacuumized, control pressure is in 133Pa, and temperature control is at 200 DEG C.
Atomic layer deposition is carried out to graphene-supported nanometer aluminium powder and forms coating film, a week of atomic layer deposition growth Phase includes following four link：
(1) three (DPM dpm,dipivalomethane acid bismuth) Bi (thd) are injected into reaction chamber3, it is allowed to and graphite Alkene composite granule surface occurs the surface chemical reaction of saturation and replaces surface functional group, and specific chemical equation is as follows：
||-O*+Bi(thd)3→||-OBi(thd)x+thd
(2) it is passed through nitrogen and cleans unreacted the first presoma and accessory substance；
(3) deionized water is injected into reaction chamber, the first presoma with adsorbing on graphene composite powder surface is sent out Raw surface reaction, replaces surface functional group again；Specific chemical equation is as follows：
(4) it is passed through nitrogen and cleans unreacted oxygen precursor and accessory substance.
(1) arrives (4) as procedure described above, and reaction precursor pulse sequence is represented with t1-t2-t3-t4, wherein：T1 is A kind of injection length of precursors, t3 are the injection lengths of second of precursors, and t2 and t4 are the cleaning of nitrogen Time.Presoma pulse sequence is 60s-30s-60s-30s in this experimental example.Repeat the atomic layer deposition of respective cycle number Product, the bismuth oxide coating film and the molar ratio of nanometer aluminium powder in composite granule for making deposition are respectively 1:2, i.e. stoichiometric ratio Φ= 1.0。
Embodiment 3
Graphene-supported nanometer aluminium powder composite energy-containing material is prepared using technique for atomic layer deposition this gives one kind The step of method of material, this method one, is identical with the step of embodiment 1 one, and difference lies in step 2.
Step 2：Atomic layer deposition prepares graphene nano Composite Energetic Materials
Graphene-supported nanometer aluminium powder is placed in gas phase atomic layer deposition system reaction chamber, seals reaction chamber.To gas Nitrogen is passed through in phase depositing system and is vacuumized, control pressure is in 133Pa, and temperature control is in room temperature.
The a cycle of atomic layer deposition is carried out to graphene-supported nanometer aluminium powder includes following four link：
(1) the first presoma butter of tin (SnCl is injected into reaction chamber4) be allowed to and graphene-supported nano aluminum Powder composite granule surface occurs the surface chemical reaction of saturation and replaces surface functional group, and specific chemical equation is as follows：
||-OH+SnCl4→||-OSnCl3+HCl
(2) it is passed through nitrogen and cleans unreacted the first presoma and accessory substance；
(3) second of presoma hydrogen peroxide (H is injected into reaction chamber2O2), with adsorbing on graphene composite powder surface Surface reaction occurs for the first presoma, replaces surface functional group again, specific chemical equation is as follows：
||-OSnCl3+3H2O→||-OSn(OH)3+3HCl+3/2O2
(4) it is passed through nitrogen and cleans unreacted oxygen precursor and accessory substance.
(1) arrives (4) as procedure described above, and reaction precursor pulse sequence is represented with t1-t2-t3-t4, wherein：T1 is A kind of injection length of precursors, t3 are the injection lengths of second of precursors, and t2 and t4 are the cleaning of nitrogen Time.Presoma pulse sequence is 30s-10s-30s-10s in this experimental example.Repeat the atomic layer deposition of respective cycle number Product, the tin oxide coating film and the molar ratio of nanometer aluminium powder in composite granule for making deposition are respectively 1:2, i.e. stoichiometric ratio Φ= 1。
Embodiment 4
Graphene-supported nanometer aluminium powder composite energy-containing material is prepared using technique for atomic layer deposition this gives one kind The step of method of material, this method one, is identical with the step of embodiment 1 one, and difference lies in step 2.
Step 2：Atomic layer deposition prepares graphene nano Composite Energetic Materials
Graphene-supported nanometer aluminium powder is placed in gas phase atomic layer deposition system reaction chamber, seals reaction chamber.To gas Nitrogen is passed through in phase depositing system and is vacuumized, control pressure is in 133Pa, and temperature control is at 190 DEG C.
The a cycle of atomic layer deposition is carried out to graphene-supported nanometer aluminium powder includes following four link：
(1) acetylacetone,2,4-pentanedione nickel (acac) is injected into reaction chamber2, it is allowed to and graphene-supported nanometer aluminium powder composite powder Body surface face occurs the surface chemical reaction of saturation and replaces surface functional group, and specific chemical equation is as follows：
||-OH+Ni(acac)2→||-ONi(acac)*+H(acac)
(2) it is passed through nitrogen and cleans unreacted the first presoma and accessory substance；
(3) deionized water is injected into reaction chamber, with adsorbing the first presoma second on graphene composite powder surface Surface reaction occurs for acyl acetone nickel, replaces surface functional group again, specific chemical equation is as follows：
||-ONi(acac)*+H2O→||-ONiOX+H2O+CO2
(4) it is passed through nitrogen and cleans unreacted oxygen precursor and accessory substance.
Presoma pulse sequence is 30s-10s-30s-10s in this experimental example.Repeat the atomic layer of respective cycle number Deposition, the nickel oxide coating film and the molar ratio of nanometer aluminium powder in composite granule for making deposition are respectively 1:2, i.e. stoichiometric ratio Φ =1.
Embodiment 5
Graphene-supported nanometer aluminium powder composite energy-containing material is prepared using technique for atomic layer deposition this gives one kind The step of method of material, this method one, is identical with the step of embodiment 1 one, and difference lies in step 2.
Step 2：Atomic layer deposition prepares graphene nano Composite Energetic Materials
Graphene-supported nanometer aluminium powder is placed in gas phase atomic layer deposition system reaction chamber, seals reaction chamber.To gas Nitrogen is passed through in phase depositing system and is vacuumized, control pressure is in 133Pa, and temperature control is at 200 DEG C.
The a cycle of atomic layer deposition is carried out to graphene-supported nanometer aluminium powder includes following four link：
(1) the first presoma tetraphernl-lead (PbPh is injected into reaction chamber4), it is allowed to and graphene-supported nano aluminum Powder composite granule surface occurs the surface chemical reaction of saturation and replaces surface functional group, and specific chemical equation is as follows：
||-O*+PbPh4→||-OPbPh*+H(Ph)X
(2) it is passed through nitrogen and cleans unreacted the first presoma and accessory substance；
(3) table occurs for the injection of ozone into reaction chamber, the first presoma with adsorbing on graphene composite powder surface Face is reacted, and replaces surface functional group again, specific chemical equation is as follows：
||-OPbPh*+O3→||-OPbOX+Ph4
(4) it is passed through nitrogen and cleans unreacted oxygen precursor and accessory substance.Presoma pulse sequence is in this experimental example 30s-10s-30s-10s.The atomic layer deposition of respective cycle number is repeated, makes the lead oxide coating film and composite granule of deposition The molar ratio of middle nanometer aluminium powder is respectively 1:2, i.e. stoichiometric ratio Φ=1.
Embodiment 6
Graphene-supported nanometer aluminium powder composite energy-containing material is prepared using technique for atomic layer deposition this gives one kind The step of method of material, this method one, is identical with the step of embodiment 1 one, and difference lies in step 2.
Step 2：Atomic layer deposition prepares graphene nano Composite Energetic Materials
Graphene-supported nanometer aluminium powder is placed in gas phase atomic layer deposition system reaction chamber, seals reaction chamber.To gas Nitrogen is passed through in phase depositing system and is vacuumized, control pressure is in 133Pa, and temperature control is at 250 DEG C.
The a cycle of atomic layer deposition is carried out to graphene-supported nanometer aluminium powder includes following four link：(1) to The first presoma acetyl acetone copper (Cu (acac) is injected in reaction chamber2), it is allowed to answer with graphene-supported nanometer aluminium powder Close powder surface the surface chemical reaction of saturation occurs and replaces surface functional group, specific chemical equation is as follows：
||-OH+Cu(acac)2→||-OCu(acac)*+H(acac)
(2) it is passed through nitrogen and cleans unreacted the first presoma and accessory substance；
(3) second of precursors ozone (O is injected into reaction chamber3), with adsorbing on graphene composite powder surface The first presoma occur surface reaction, replace surface functional group again, specific chemical equation is as follows：
||-OCu(acac)*+O3→||-OCuOX+H2O+CO2
(4) it is passed through nitrogen and cleans unreacted oxygen precursor and accessory substance.Presoma pulse sequence is in this experimental example 30s-10s-30s-10s.The atomic layer deposition of respective cycle number is repeated, makes the cupric oxide coating film and composite granule of deposition The molar ratio of middle nanometer aluminium powder is respectively 1:2, i.e. stoichiometric ratio Φ=1.
Embodiment 7
Graphene-supported nanometer Mg powder energetic material is prepared using technique for atomic layer deposition this gives a kind of Method, this method specifically include following steps：
Step 1：The preparation of graphene-supported nanometer Mg powder
(1) by graphene oxide 0.1g and methyl acetate 100g, add in ultrasonic reactor, be 500w in ultrasonic power, Frequency is 100Hz, and temperature 50 C, when the ultrasonic disperse time 5 is small, obtains graphene oxide suspension.
(2) methyl acetate quality (100g) is configured, glycerine (100g) cosolvent, cosolvent is added by nanometer Mg powder 2g In, disperseed by ultrasonic wave added, ultrasonic power 500W, frequency 200Hz, temperature 50 C, ultrasonic disperse time 2 h, obtains The nanometer Mg powder suspension of stable dispersion.Graphene oxide suspension 100g is added into 200g nanometer Mg powder cosolvent suspension In, when ultrasonic disperse 5 is small, ascorbic acid 1g is added, when continuation ultrasonic disperse 2 is small, stable graphene/nanometer magnesium powder is obtained and answers Close suspension.
(3) above-mentioned graphene/nanometer magnesium powder composite suspension liquid is placed in high speed rotor centrifuge, in 25 DEG C of temperature, rotating speed 12000rpm, centrifuges 20 minutes, drying to constant weight in vacuum 0.1kPa for product, obtains graphene-supported nanometer Mg powder composite wood Material.
Step 2：Atomic layer deposition prepares graphene nano Composite Energetic Materials
Graphene-supported nanometer Mg powder is placed in gas phase atomic layer deposition system reaction chamber, seals reaction chamber.To gas Nitrogen is passed through in phase depositing system and is vacuumized, control pressure is in 133Pa, and temperature control is at 350 DEG C.
Atomic layer deposition is carried out to graphene-supported nanometer Mg powder and forms coating film, a week of atomic layer deposition growth Phase includes following four link：
(1) ferrocene (FeCp is injected into reaction chamber2) it is allowed to anti-with the surface chemistry of composite granule surface generation saturation Surface functional group and should be replaced, specific chemical equation is as follows：
||-O*+FeCp2→||-OFeCp+Cp
In the present invention " | | " represent substrate material surface, i.e., graphene-supported nanometer Mg powder composite granule；
(2) it is passed through nitrogen and cleans unreacted ferrocene and accessory substance；
(3) oxygen is injected into reaction chamber, table occurs for the ferrocene presoma with adsorbing on graphene composite powder surface Face is reacted, and replaces surface functional group again, specific chemical equation is as follows：
(4) it is passed through nitrogen and cleans unreacted oxygen precursor and accessory substance.
(1) arrives (4) as procedure described above, and reaction precursor pulse sequence is represented with t1-t2-t3-t4, wherein：T1 is A kind of injection length of precursors, t3 are the injection lengths of second of precursors, the cleaning of t2 and the uniform nitrogen of t4 Time.The pulse sequence used in this experimental example is 90s-60s-90s-60s.Repeat the atomic layer deposition of respective cycle number Product, the iron oxide coating film and the molar ratio of nanometer Mg powder in composite granule for making deposition are respectively 1:2,1:2.2,1:2.4,1: 2.6,1:2.8,1:3.0,1:3.2.That is stoichiometric ratio Φ=1,1.1,1.2,1.3,1.4,1.5,1.6.
Comparative example 1
Comparative example gives a kind of method that nanometer thermite energetic material is prepared using technique for atomic layer deposition.
Nanometer aluminium powder is placed in gas phase atomic layer deposition system reaction chamber, seals reaction chamber.Into gas-phase deposition system It is passed through nitrogen and vacuumizes, control pressure is in 133Pa, and temperature control is at 350 DEG C.
Atomic layer deposition is carried out to aluminium powder and forms coating film, a cycle of atomic layer deposition growth includes following four ring Section：
(1) ferrocene (FeCp is injected into reaction chamber2) it is allowed to anti-with the surface chemistry of nanometer aluminium powder surface generation saturation Surface functional group and should be replaced, specific chemical equation is as follows：
||-O*+FeCp2→||-OFeCp+Cp；
(2) it is passed through nitrogen and cleans unreacted ferrocene and accessory substance；
(3) oxygen is injected into reaction chamber, surface reaction occurs for the ferrocene presoma with adsorbing on nanometer aluminium powder surface, Surface functional group is replaced again, and specific chemical equation is as follows：
(4) it is passed through nitrogen and cleans unreacted oxygen precursor and accessory substance.
(1) arrives (4) as procedure described above, and reaction precursor pulse sequence is represented with t1-t2-t3-t4, wherein：T1 is A kind of injection length of precursors, t3 are the injection lengths of second of precursors, and t2 and t4 are the cleaning of nitrogen Time.The pulse sequence used in this experimental example is 90s-60s-90s-60s.Repeat the atomic layer deposition of respective cycle number Product, it is 1 to make the iron oxide coating film of deposition and the molar ratio of nanometer aluminium powder:2, i.e. stoichiometric ratio Φ=1, obtain a nanometer aluminothermy Agent energetic material Al@Fe2O3。
Al@Fe using XPS and SEM to stoichiometric ratio Φ=1.02O3Surface composition, pattern and structure are characterized, The result is shown in Fig. 2 and Fig. 7.As shown in Fig. 2, from the disappearance of XPS spectrum figure Al elemental signals, the appearance of Fe elemental signals can illustrate to receive Rice Fe2O3Uniformly completely it is coated on a nanometer Al surfaces.As shown in fig. 7, Fe2O3It is uniformly coated on nanometer aluminium powder surface, Al@ Fe2O3Surface topography is coarse, the increase of nanometer aluminium powder size.As shown in figure 8, DSC test results show, counted in thermit reaction chemistry Under the conditions of amount ratio, the Al Fe with not graphene-containing2O3Sample is compared, the GO/Al@Fe prepared using technique for atomic layer deposition2O3 Composite Energetic Materials energy release rate improves 60%.
Comparative example 2
The step of this comparative example one, is identical with the step of embodiment 1 one, and difference lies in step 2.
Step 2, by graphene-supported nanometer aluminium powder 2g, with Fe2O3Powder 5.9g is mixed by slow mechanical agitation 1h, obtains the thermite of physical blending, nanometer aluminium powder and Fe2O3Molar ratio be 2:1, i.e. stoichiometric ratio Φ=1.
As shown in figure 9, DSC test results show, under thermit reaction stoichiometric conditions, compared to physical blending Method, the graphene nano Composite Energetic Materials GO/Al@Fe prepared by technique for atomic layer deposition2O3, thermit reaction initial action Temperature drops to 465 DEG C by 502 DEG C；The graphene nano Composite Energetic Materials GO/Al@Fe prepared by technique for atomic layer deposition2O3 556 DEG C and 720 DEG C occur two exothermic peaks, and physical blending process prepare graphene Composite Energetic Materials (GO/Al-Fe2O3) An only exothermic peak；Compared to physical mixed method, the graphene nano composite energy-containing material prepared by technique for atomic layer deposition Material energy release rate improves 130%.

Claims (6)

  1. A kind of 1. method that graphene nano Composite Energetic Materials are prepared using technique for atomic layer deposition, it is characterised in that step is such as Under：
    Step 1：The preparation of graphene-supported nano metal compound
    (1) graphene oxide 0.01-100 mass parts and solvent 100-10000 mass parts are added in ultrasonic reactor, ultrasonic work( Rate is 10-5000W, frequency 10-10000Hz, 20-100 DEG C of temperature, when ultrasonic disperse 5 minutes -10 is small, obtains graphite oxide Alkene suspension；
    (2) 100-10000 mass parts solvent orange 2 A, 100-10000 mass parts solvents B are mixedly configured into cosolvent, by nano metal Powder 1-100 mass parts add cosolvent, when ultrasonic disperse 5 minutes -10 is small, obtain the nano metal suspension of stable dispersion；It is super Acoustical power 10-5000W, frequency 10-10000Hz, 20-100 DEG C of temperature；The solvent orange 2 A is methyl acetate, N, N- dimethyl methyl At least one of acid amides, dimethyl sulfoxide (DMSO), 1-methyl-2-pyrrolidinone, solvent B is ethylene glycol, isopropanol, in glycerine extremely Few one kind；The Nano metal powder is at least one of nanometer aluminium powder, nanometer Mg powder, nanometer zirconium powder, nanometer beryllium powder；
    (3) 1-100 mass parts graphene oxide suspension is added in 10-1000 mass parts nano metal suspension, ultrasound point Dissipate 5 minutes -5 it is small when, add reducing agent 1-5000 mass parts, continue ultrasonic disperse 5 minutes -10 it is small when, obtain stable graphite Alkene/nano metal material composite suspension liquid；
    (4) by above-mentioned graphene/nanometer metal material composite suspension liquid with high speed rotor centrifuge 10 minutes -2 it is small when, temperature 0-100 DEG C, rotating speed 3000-20000rpm of degree, drying to constant weight in vacuum 0.01kPa-0.1MPa for product, obtains graphene and receives Rice metal composite powder；
    Step 2：Atomic layer deposition prepares graphene nano Composite Energetic Materials
    (1) graphene nano metal composite powder is placed in gas phase atomic layer deposition system reaction chamber, reaction chamber is sealed, to gas Inert carrier gas is passed through in phase depositing system and is vacuumized, cavity pressure is controlled in 133Pa-1000Pa, and temperature control is in 25-400 ℃；
    (2) to graphene nano metal composite powder carry out atomic layer deposition formed coating film, atomic layer deposition growth one Cycle includes following four link：The first excessive precursors are injected into reaction chamber；It is passed through inert carrier gas；To reaction Second excessive of precursors of intracavitary injection；Inert carrier gas is passed through again；Repeat the atomic layer deposition of respective cycle number Product so that the molar ratio of the oxide coating film of deposition and nano metal content in composite granule passes through the mistake in 0.1-1.0 Journey obtains graphene nano Composite Energetic Materials；The first described precursors are ferrocene, nickel acetylacetonate, tetraphenyl Lead, double (hexafluoroacetylacetone conjunction copper) close copper (II) hydrate, double (DPM dpm,dipivalomethane acid) cobalts, it is double (2, 2,6,6- tetramethyl -3,5- heptadione acid) lead, at least one of three (DPM dpm,dipivalomethane acid) bismuths；Institute Second of the precursors stated are at least one of deionized water, hydrogen peroxide, oxygen, ozone.
  2. 2. the method that graphene nano Composite Energetic Materials are prepared using technique for atomic layer deposition as claimed in claim 1, its Be characterized in that, the solvent of the graphene oxide suspension is water, ethanol, isopropanol, methyl acetate, toluene, tetrahydrofuran, At least one of acetone, hexane, hexamethylene and N, dinethylformamide.
  3. 3. the method that graphene nano Composite Energetic Materials are prepared using technique for atomic layer deposition as claimed in claim 1, its It is characterized in that, the reducing agent of the graphene oxide is hydrazine hydrate, ascorbic acid, sodium borohydride, hydroiodic acid and sodium citrate At least one of.
  4. 4. the method that graphene nano Composite Energetic Materials are prepared using technique for atomic layer deposition as claimed in claim 1, its It is characterized in that, the inert carrier gas is at least one of nitrogen, argon gas, helium.
  5. 5. the method that graphene nano Composite Energetic Materials are prepared using technique for atomic layer deposition as claimed in claim 1, its It is characterized in that, each atomic layer deposition growth cycle time is 1-10000s.
  6. 6. the method that graphene nano Composite Energetic Materials are prepared using technique for atomic layer deposition as claimed in claim 1, its It is characterized in that, the atomic layer deposition cycle number is 1-5000.
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Publication number Priority date Publication date Assignee Title
CN107297512B (en) * 2017-06-29 2019-04-09 南陵县生产力促进中心 A kind of graphene/Mg nano particle composite material and preparation method thereof
CN108940254B (en) * 2018-06-27 2021-02-02 天津大学 Preparation method of catalyst for synthesizing methanol by carbon dioxide hydrogenation
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CN110935444B (en) * 2019-12-14 2021-04-02 中国科学院大连化学物理研究所 Method for preparing precious metal alloy/reduced graphene oxide composite material
CN111892467B (en) * 2020-08-20 2021-07-09 西南科技大学 Al/Fe2O3Preparation method of nano energetic material
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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CN117720099B (en) * 2023-04-27 2024-08-06 哈尔滨工业大学 Stealth pigment, preparation method thereof and application thereof in flexible multispectral compatible optical stealth coating

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103035916A (en) * 2012-11-28 2013-04-10 华中科技大学 Preparation method of nano tin dioxide-graphene composite material and product thereof
CN103207222A (en) * 2013-04-12 2013-07-17 中国科学院山西煤炭化学研究所 Method for preparing graphene nano-material electrochemical sensor by atomic layer deposition process
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
CN104227014A (en) * 2014-09-18 2014-12-24 东南大学 Method for preparing gold nano particle and graphene composite material through fast reduction
CN104496731A (en) * 2014-11-20 2015-04-08 西安近代化学研究所 Method for coating nitroamine explosives by adopting atomic layer deposition technique
KR20150099091A (en) * 2014-02-21 2015-08-31 한국교통대학교산학협력단 Method of Manufacturing Nano Material from Graphite-Metal Composite by Mechanical Alloying and Collected Nano Material Using the Same

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103035916A (en) * 2012-11-28 2013-04-10 华中科技大学 Preparation method of nano tin dioxide-graphene composite material and product thereof
CN103207222A (en) * 2013-04-12 2013-07-17 中国科学院山西煤炭化学研究所 Method for preparing graphene nano-material electrochemical sensor by atomic layer deposition process
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
KR20150099091A (en) * 2014-02-21 2015-08-31 한국교통대학교산학협력단 Method of Manufacturing Nano Material from Graphite-Metal Composite by Mechanical Alloying and Collected Nano Material Using the Same
CN104227014A (en) * 2014-09-18 2014-12-24 东南大学 Method for preparing gold nano particle and graphene composite material through fast reduction
CN104496731A (en) * 2014-11-20 2015-04-08 西安近代化学研究所 Method for coating nitroamine explosives by adopting atomic layer deposition technique

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Hydrothermal preparation of Fe2O3/graphene nanocomposite and its enhanced catalytic activity on the thermal decomposition of ammonium perchlorate;Yuan Yuan et al.;《Applied Surface Science》;20140311;第303卷;第354-359页 *

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