CN109706508A - Hollow Mg/MnO2The preparation of super energetic material - Google Patents
Hollow Mg/MnO2The preparation of super energetic material Download PDFInfo
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- CN109706508A CN109706508A CN201910186770.2A CN201910186770A CN109706508A CN 109706508 A CN109706508 A CN 109706508A CN 201910186770 A CN201910186770 A CN 201910186770A CN 109706508 A CN109706508 A CN 109706508A
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Abstract
Hollow Mg/MnO2Novel MnO is prepared in the preparation of super energetic material, including hydrothermal synthesis method2Porous hollow microballoon, then obtains MnO by electrophoretic deposition2Film, and by the composite deposition of vacuum vapour deposition progress magnesium film, finally realize hollow Mg/MnO2The preparation and design of super energetic material.Ingehious design of the present invention goes out the film containing energy of structure novel, in addition, finding that its thermal discharge is up to 5.2MJ/Kg by heat analysis, detonation test etc., burning degree is violent, with the obvious advantage.In addition, the technique is not limited by metallic substrates, be suitable for labyrinth, can with MEMS device is good combines, be conducive to exploitation a new generation containing can device.
Description
Technical field
The present invention relates to a kind of preparations for preparing micro-nano energetic material, specifically, being related to a kind of porous hollow Mg/
MnO2The preparation process of super energetic material.
Background technique
Micro-nano energetic material (EMs) be a kind of emerging and performance compared with traditional material have significant increase comprising a kind of or
The mixture of more than one micro-nano rank components.The study found that the component of such Composite Energetic Materials is because its size is small, it is active
The features such as height, contact area is big, therefore surface has certain skin effect, bulk effect and quantum size effect etc., thus one
When the outside energy stimulation that denier is subject to is more than energy release threshold value, vigorous reaction will occur immediately between component, some are with quick-fried
At the top of one's voice, bright flame, white smoke etc..Since the classification of component is different, the mode to release energy is different, but induces component
Between chemically react needed for outside energy to be offered to be significantly smaller than the demand of conventional composite energetic material.Such material is due to it
Special composition and performance is widely used in propellant, gunpowder and initiating bridge containing energy etc..
Metastable state energetic material (MICs) is used as a kind of novel branch, mainly by nano-metal-oxide (such as CuO, Fe2O3、
NiO etc.) and nano metal particles fuel (such as Al, Mg) composition, there is high-energy density, high oxygen carrying content, high mass density, component
The advantages that range of choice is wide, formula is flexible, easily molded.It is simultaneously also that can solve the most promising of green priming problem at present
One of method, therefore, MICs causes the extensive concern of researcher in recent years.Wherein, Mg/MnO2Energetic material always with
Being all the representative outstanding as highly exothermic amount (theoretical thermal discharge is up to 5539J/g) and burning velocity, there is far-reaching research
Meaning and value.
Although the micro-nano Mg/MnO reported at present2The synthetic method of energetic material has semar technique, template, high-energy ball milling
Method, vapour deposition method etc..But the contact between metal and oxidant is still more insufficient.For thermit reaction, thermal discharge
Significantly depend on the component mass transfer distance of MICs material internal.In addition, the preparation method reported at present has technique multiple
Miscellaneous, operation difficulty is big, and industrial application is relatively difficult to achieve.
Summary of the invention
The object of the present invention is to provide a kind of hollow Mg/MnO2The preparation process of super energetic material, can be effective gram
Take above-mentioned certain or certain disadvantages.
According to the first aspect of the invention, a kind of hollow Mg/MnO is provided2The preparation method of energetic material, comprising:
Manganese sulfate and maltose are formed by mixed liquor to be placed in reaction kettle, wherein the concentration of manganese nitrate be 0.05~
The molar ratio of 0.2mol/L and manganese nitrate and maltose is 1:10-2Left and right；Reaction is improved with the heating rate of 20 DEG C/min or so
Kettle temperature degree is to 4~12h is reacted after 100~240 DEG C, then cooled to room temperature；
Porous hollow MnO is obtained after centrifugation, washing and drying2Powder；
By gained porous hollow MnO2Powder is scattered in the mixed dispersant of glycerine, acetylacetone,2,4-pentanedione and chlorosulfonated polyethylene
In obtain stable suspension, wherein the porous hollow MnO of 2mg or so is added in every 100mL mixed dispersant2Powder, mixing point
The volume ratio of glycerine, acetylacetone,2,4-pentanedione and chlorosulfonated polyethylene is 1:1:10 in powder-2To 1:4:10-2；
Pellet electrode is inserted perpendicularly into suspension and executes electrophoresis, to deposit MnO on the electrode2Film, wherein between electrode
Away from for 0.8~1.2cm, extra electric field is 5~20V mm-1, sedimentation time is 6~20min, and room temperature carries out；And
The MnO that will be deposited in pellet electrode (substrate)2Film vacuum drying process is moved back into vacuum evaporation room, with Mg
Band carries out vapor deposition treatment as evaporation source to which hollow Mg/MnO be made2Energetic material, wherein vacuum degree control 3~3.5 ×
10-3Pa, Mg band purity are not less than 99.5%, and evaporation time control is controlled in 5~20min, discharge current in 60~120mA.
According to the present invention, pellet electrode material can be selected from titanium sheet, stainless steel substrates, nickel sheet and electro-conductive glass ITO.
Preparation method according to the present invention can also include: to remove the pellet electrode as substrate or remove in gained
Energetic material.
The ingenious combination hydrothermal synthesis method of the present invention, electrophoretic deposition and vacuum vapour deposition etc., to be made novel more
The hollow Mg/MnO in hole2Super energetic material.
According to another aspect of the present invention, a kind of hollow Mg/MnO is additionally provided2Energetic material, it is made by the above method
It is standby.
Electrode basement of the invention is further preferably further provided with geosutures, to form the suitable section of required size, from
And it is convenient for subsequent removing.In addition, as needed, can only remove (such as by simply breaking disconnected movement along geosutures execution)
Required amount of section, to facilitate the storage and carrying of remaining energetic material.
Compared with existing preparation method, hollow Mg/MnO according to the present invention2The preparation process's of super energetic material
Advantage includes at least:
Present invention process preparation is easy, low in cost；
Synthesize obtained hollow Al/MnO2Super energetic material realizes coming into full contact between metal Mg and oxidant,
It overcomes conventional method and the problems such as MICs mass transfer distance has been prepared, and then greatly enhance heat fan-out capability；
Stability of suspension used in the present invention is good, can be realized the controllable self assembly of nanoparticle；
In addition, the present invention is not limited by metallic substrates, it is suitable for labyrinth, can be risen with the good combination of MEMS device
Come, is conducive to the device containing energy of exploitation a new generation.
Detailed description of the invention
Fig. 1 is porous hollow Mg/MnO2The SEM photograph of super thermite；
Fig. 2 is porous hollow Mg/MnO2The BET curve graph of super thermite；
Fig. 3 is porous hollow Mg/MnO2The DSC curve of super thermite；
Fig. 4 is evaporation time to porous hollow Mg/MnO2The affecting laws figure of super thermite exothermicity.
Specific embodiment
The present invention is further illustrated below by embodiment.It should be appreciated by those skilled in the art that following embodiment is
In order to better understand and realize the present invention, it is not intended to restrict the invention.
The offer of electrode material
Electrode material used in the present invention provides by the following method: nickel sheet is cut into 2 × 8cm2Afterwards by difference
The SiC sand paper of mesh number is polished；Glycerine rinses；Distilled water flushing and etc. etc. a series of processing, then dislocation is in vacuum drying
Case saves.
Embodiment 1
In 100mL conical flask a small amount of maltose is added, wherein manganese nitrate in accurate configuration 0.1mol/L manganese nitrate solution
With the molar ratio 1:10 of maltose-2, then continuously stir, until maltose is fully dissolved in conical flask, then by mixed liquor
It moves in the reaction kettle of 100mL.Heating rate is 20 DEG C/min, and reaction temperature and reaction time are controlled as 200 DEG C and 8h.
After completion of the reaction, cooled to room temperature.Then it carries out being centrifuged repeatedly drying, revolving speed is controlled in 1000r/min, is placed on vacuum
8h is dried at 25 DEG C in drying box.The powder precise 2mg that will be obtained, being scattered in volume ratio is 1:2:10-2The third three
In the dispersion liquid 100mL of alcohol, acetylacetone,2,4-pentanedione and chlorosulfonated polyethylene, it is placed in ultrasonic disperse in Ultrasound Instrument and handles 30min.It will be negative
Positive electrode is respectively perpendicular in the above-mentioned dispersion liquid of insertion, and extra electric field is selected as 10Vmm-1, low voltage electrophoresis assembling is carried out, time control exists
10min obtains MnO2Film.It after the film vacuum is dried, moves in electron beam coater, vacuum degree is arranged 3.0
×10-3Pa is vapor deposition raw material, discharge current 100mA, evaporation time selection with the magnesium ribbon of a height of 2 × 2 × 2mm of length and width
10min then takes out sample vacuum and saves for use.
Using field emission scanning electron microscope (FESEM), the instruments such as differential scanning calorimeter (DSC) carry out the film product containing energy
Surface topography and performance study are analyzed and characterized.As shown in Figure 1, the hollow Mg/MnO prepared using the method for the present invention2It is super to contain energy
Film has apparent hollow structure.Fig. 2 indicates that the novel super thermite of preparation has good porosity, corresponding to compare table
Area is 9.2m2/ g can provide the useful space for the heat release of product.As shown in figure 3, obtained novel hollow Mg/MnO2It is super
The exotherm of the film containing energy, thermal discharge (Q) can arrive~5.2MJ Kg through DSC-software calculating-1.As shown in figure 4, Mg
Evaporation process can be controlled by the adjusting of technological parameter such as time, and then realize novel hollow Mg/MnO2It is super thin containing energy
The heat of film optimizes output, in addition, using the standard testing standard class of tape method for 4B.
Embodiment 2
The other the same as in Example 1, electrophoresis assembling voltage are reduced to the half of example 1, the deposition in packaging efficiency, that is, unit time
Quality approximation halves, but energy fan-out capability falls sharply nearly 40%.Corresponding DSC exotherm fits heat release under this condition
Amount is about 3.2MJ Kg-1.It is held essentially constant in addition, measuring adhesive force grade.
Embodiment 3
The other the same as in Example 1, the difference is that the concentration of manganese nitrate is 0.05mol/L, other conditions are constant, MnO2Microballoon
Hole disappears totally, is about 0.9m by the specific surface area that specific surface instrument measures resulting print under this condition2/ g, about example
10%.Porous hollow Mg/MnO2The preparation of super thermite cannot achieve.It is right at this time although remaining to that exothermic reaction occurs
The thermal discharge answered is about the 30% of example, directly affects its combined coefficient and the preparation efficiency of performance output and performance output.
Embodiment 4
The other the same as in Example 1, the difference is that being not added with maltose, experiment discovery can not effectively obtain porous MnO2It is micro-
Ball.
Embodiment 5
The other the same as in Example 1, unlike be not added chlorosulfonated polyethylene, super porous aluminothermy agent film assembling still at
Function is realized, however measures adhesive force grade down to 2B.
Embodiment 6
The other the same as in Example 1, evaporation time are reduced to 5min, although adhesive force grade still remains unchanged, heat output
Ability declines to a great extent, about 2.5MJ Kg-1。
To sum up comparison discovery, manganese nitrate and maltose can be just prepared suitable porous with suitable concentration and ratio
MnO2Microballoon.In addition, chlorosulfonated polyethylene can be conducive to promote porous hollow Mg/MnO2The adhesive force of super thermite and substrate,
Its adhesive force grade reaches 4B.
The present invention pass through in fact hydrothermal synthesis method, electrophoresis construction from part, vapor coating method inventive combination, efficiently easily make
Standby structure novel out and the excellent porous hollow Mg/MnO of exothermicity2Super thermite, corresponding thermal discharge are theoretical value
94%, up to 5.2MJ Kg-1。
Claims (4)
1. a kind of hollow Mg/MnO2The preparation method of energetic material, comprising:
Manganese sulfate and maltose are formed by mixed liquor to be placed in reaction kettle, wherein the concentration of manganese nitrate be 0.05~
The molar ratio of 0.2mol/L and manganese nitrate and maltose is 1:10-2Left and right；Reaction is improved with the heating rate of 20 DEG C/min or so
Kettle temperature degree is to 4~12h is reacted after 100~240 DEG C, then cooled to room temperature；
Porous hollow MnO is obtained after centrifugation, washing and drying2Powder；
By gained porous hollow MnO2Powder, which is scattered in the mixed dispersant of glycerine, acetylacetone,2,4-pentanedione and chlorosulfonated polyethylene, to be obtained
To stable suspension, wherein the porous hollow MnO of 2mg or so is added in every 100mL mixed dispersant2Powder, mixed dispersant
The volume ratio of middle glycerine, acetylacetone,2,4-pentanedione and chlorosulfonated polyethylene is 1:1:10-2To 1:4:10-2；
Pellet electrode is inserted perpendicularly into suspension and executes electrophoresis, to deposit MnO on the electrode2Film, wherein electrode spacing be
0.8~1.2cm, extra electric field are 5~20V mm-1, sedimentation time is 6~20min, and room temperature carries out；And
The MnO that will be deposited on pellet electrode2Film vacuum drying process is moved back into vacuum evaporation room, using Mg band as vapor deposition
Source carries out vapor deposition treatment to which hollow Mg/MnO be made2Energetic material, wherein vacuum degree control is 3~3.5 × 10-3Pa, Mg band
Purity is not less than 99.5%, and evaporation time control is controlled in 5~20min, discharge current in 60~120mA.
2. preparation method according to claim 1, wherein the pellet electrode material is selected from titanium sheet, stainless steel substrates, nickel
Piece and electro-conductive glass ITO.
3. preparation method according to claim 2, further includes: remove the pellet electrode as substrate or remove in gained containing energy
Material.
4. a kind of hollow Mg/MnO2Energetic material, as prepared by the method for one of claim 1-3.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111850655A (en) * | 2020-07-27 | 2020-10-30 | 重庆工商大学 | Method for preparing high-adhesion nano thermite coating by electrophoretic deposition and coating prepared by method |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101327959A (en) * | 2008-08-01 | 2008-12-24 | 中国科学院电工研究所 | Preparation of epsilon-MnO2 laminate structure nanosphere |
| CN101372363A (en) * | 2008-09-26 | 2009-02-25 | 中国科学院电工研究所 | Synthetic alpha-MnO 2 Method for micron hollow sphere and nanocluster |
| CN101624213A (en) * | 2009-08-13 | 2010-01-13 | 陕西师范大学 | Preparation method for manganese dioxide hollow sphere |
| CN102259929A (en) * | 2011-06-27 | 2011-11-30 | 北京工业大学 | Method for preparing porous nano or submicron rod-like manganese oxide |
| CN102925120A (en) * | 2012-11-08 | 2013-02-13 | 中国人民解放军理工大学 | Thermit and preparation method thereof |
| CN103936078A (en) * | 2014-04-28 | 2014-07-23 | 福州大学 | Preparation method of hollow nano-manganese dioxide |
| CN104988560A (en) * | 2015-07-29 | 2015-10-21 | 重庆大学 | Production method of Al/MoO3 nano-thermite energetic film |
| CN105016935A (en) * | 2014-01-29 | 2015-11-04 | 香港城市大学 | Structure of energetic materials and the method for preparing thereof |
| CN106467977A (en) * | 2016-10-13 | 2017-03-01 | 重庆大学 | One kind prepares Al/Bi2O3The method of Energetic Nanomaterials laminated film |
| CN108557892A (en) * | 2018-06-07 | 2018-09-21 | 江苏大学 | A kind of oxide preparation method and application for the manganese that object is mutually controllable |
| CN109295418A (en) * | 2018-10-10 | 2019-02-01 | 重庆大学 | Highly exothermic amount Al/CuO 3D nucleocapsid array structure thermite with high load capacity |
-
2019
- 2019-03-13 CN CN201910186770.2A patent/CN109706508A/en active Pending
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101327959A (en) * | 2008-08-01 | 2008-12-24 | 中国科学院电工研究所 | Preparation of epsilon-MnO2 laminate structure nanosphere |
| CN101372363A (en) * | 2008-09-26 | 2009-02-25 | 中国科学院电工研究所 | Synthetic alpha-MnO 2 Method for micron hollow sphere and nanocluster |
| CN101624213A (en) * | 2009-08-13 | 2010-01-13 | 陕西师范大学 | Preparation method for manganese dioxide hollow sphere |
| CN102259929A (en) * | 2011-06-27 | 2011-11-30 | 北京工业大学 | Method for preparing porous nano or submicron rod-like manganese oxide |
| CN102925120A (en) * | 2012-11-08 | 2013-02-13 | 中国人民解放军理工大学 | Thermit and preparation method thereof |
| CN105016935A (en) * | 2014-01-29 | 2015-11-04 | 香港城市大学 | Structure of energetic materials and the method for preparing thereof |
| CN103936078A (en) * | 2014-04-28 | 2014-07-23 | 福州大学 | Preparation method of hollow nano-manganese dioxide |
| CN104988560A (en) * | 2015-07-29 | 2015-10-21 | 重庆大学 | Production method of Al/MoO3 nano-thermite energetic film |
| CN106467977A (en) * | 2016-10-13 | 2017-03-01 | 重庆大学 | One kind prepares Al/Bi2O3The method of Energetic Nanomaterials laminated film |
| CN108557892A (en) * | 2018-06-07 | 2018-09-21 | 江苏大学 | A kind of oxide preparation method and application for the manganese that object is mutually controllable |
| CN109295418A (en) * | 2018-10-10 | 2019-02-01 | 重庆大学 | Highly exothermic amount Al/CuO 3D nucleocapsid array structure thermite with high load capacity |
Non-Patent Citations (3)
| Title |
|---|
| MAO-WEN XU等: "An architectural development for energy conversion materials: morphology-conserved transformation synthesis of manganese oxides and their application in lithium ion batteries", 《JOURNAL OF MATERIALS CHEMISTRY A》 * |
| 橡胶工业原材料与装备简明手册编审委员会编著: "《橡胶工业原材料与装备简明手册》", 30 November 2016, 北京：北京理工大学出版社 * |
| 王宁 等主编: "《有机化学》", 31 January 2018, 南京：江苏凤凰及科学技术出版社 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111850655A (en) * | 2020-07-27 | 2020-10-30 | 重庆工商大学 | Method for preparing high-adhesion nano thermite coating by electrophoretic deposition and coating prepared by method |
| CN111850655B (en) * | 2020-07-27 | 2023-02-28 | 重庆工商大学 | Method for preparing high-adhesion nano thermite coating by electrophoretic deposition and coating thereof |
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Application publication date: 20190503 |