CN109576765A - Nanometer Mg/Fe2O3The low pressure preparation method of the film containing energy - Google Patents
Nanometer Mg/Fe2O3The low pressure preparation method of the film containing energy Download PDFInfo
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- CN109576765A CN109576765A CN201910029971.1A CN201910029971A CN109576765A CN 109576765 A CN109576765 A CN 109576765A CN 201910029971 A CN201910029971 A CN 201910029971A CN 109576765 A CN109576765 A CN 109576765A
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D15/00—Electrolytic or electrophoretic production of coatings containing embedded materials, e.g. particles, whiskers, wires
Abstract
Nanometer Mg/Fe2O3The low pressure preparation method of the film containing energy, comprising: prepare nanometer Fe using iron chloride, hydrochloric acid, polyethylene glycol (PEG), water and ethyl alcohol and sodium hydroxide2O3；By gained nanometer Fe2O3Powder and Mg powder are added to the water to form dispersion liquid；Recycle (beta-methoxy ethyoxyl) silane of vinyl three and cetyl trimethyl quaternary ammonium ammonium bromide that above-mentioned dispersion liquid is formed stable suspension；Nanometer Mg/Fe is finally formed on cathode sheet substrate using low-voltage electrophoresis2O3The film containing energy.Preparation cost of the present invention is cheap, efficient, not only breaches nanometer Mg powder and a Fe2O3The predicament of high effective deposition in the same direction, while voltage is greatly reduced, therefore prepare safety and greatly improve.Also, the super energetic material adhesive force that the present invention is prepared is strong, and good stability, in defence and military, MEMS, the fields such as explosion are with a wide range of applications.
Description
Technical field
The present invention relates to a kind of preparation methods for preparing Energetic Nanomaterials, specifically, being related to a kind of novel Mg/Fe2O3
It is prepared by the low pressure of Energetic Nanomaterials laminated film.
Background technique
Energetic material (Energetic Materials) is used as a kind of reactive explosive, broadly refers to certain external
Under trigger condition, fast chemical reaction can be independently carried out, and discharges a substance of big energy.The material containing energy studied at present
Material includes mainly propellant powder, propellant, explosive and pyrotechnic compound, and is had broad application prospects.Nanometer thermite etc. contains
Energy material is gradually aroused people's interest because of its high reaction activity and high-energy density.
Currently, the method for preparing Energetic Nanomaterials mainly has magnetron sputtering method, physical mixed, semar technique, high-energy ball milling
Method, vapour deposition method, electrodeposition process etc..Wherein electrochemical-assembly method rather draws because of its convenient and fast preparation process and quick film forming efficiency
People gazes at, but there are operational risks and security risk caused by overtension (being greater than 100V)；In addition, gained film containing energy
Adhesive force is insufficient.
Summary of the invention
The object of the present invention is to provide a kind of methods that low-pressure process electrophoresis prepares super energetic material, can effectively overcome
Above-mentioned certain or certain disadvantages.
Nanometer Mg/Fe according to the present invention2O3The preparation method of the film containing energy, comprising:
Iron chloride, hydrochloric acid and polyethylene glycol (PEG) are added in the water and ethyl alcohol of isometric ratio and form mixed liquor, wherein
The concentration of iron chloride be 0.02~0.1mol/L, concentration of hydrochloric acid be 0.1~0.6mol/L, PEG concentration be 0.0001~
0.001mol/L,
Mixed liquor is heated in water bath with thermostatic control under the conditions of 55 DEG C~75 DEG C, and instills sodium hydroxide into mixed liquor and generated with reacting
Fe2O3, wherein the molar ratio of the sodium hydroxide and the iron chloride is about 20:1；
Mixed liquor is centrifugated to obtain Fe2O3Powder, and be dried in vacuo；
By gained Fe2O3Powder and Mg powder are added in (dispersing agent) water, under confined conditions (isolation air) ultrasonic disperse 10~
30min is to form dispersion liquid, wherein Fe2O3Molar ratio with Mg is 1:1.5~1:2.5, and the total concentration of the two is 1.0g/L
~4.0g/L；
(beta-methoxy ethyoxyl) silane of vinyl three and cetyl trimethyl quaternary ammonium ammonium bromide of isometric ratio are added again
Continue ultrasonic disperse 20min or so after entering above-mentioned dispersion liquid with acquisition (stable state) suspension, the addition total volume of the two and dispersion
The volume ratio of liquid is 2:100~10:100；
By the sheet electrode comprising cathode and anode to electrophoresis is executed in the above-mentioned suspension of insertion, to be formed on cathode
Nanometer Mg/Fe2O3The film containing energy, wherein electrode spacing is 0.6~1.4cm, and electrophoretic voltage is 1~5V, and temperature is 298 ± 2K.
In alternative embodiments of the present invention, octadecyl dimethyl benzyl quaternary ammonium ammonium chloride and 3- methyl also can be used
Acryloyloxypropyltrimethoxysilane substitutes three (beta-methoxy of cetyl trimethyl quaternary ammonium ammonium bromide and vinyl respectively
Ethyoxyl) silane.
It according to the method for the present invention, can also include: that vacuum drying cooling is carried out to gained film containing energy；It is preferable over vacuum
Temperature fall after dry 1h under the conditions of 80 DEG C in drying box.Later, can also by as the cathodic disbonding of substrate or removal in institute
Must contain can film.
According to the present invention, cathode can be formed by titanium sheet, copper sheet or nickel sheet, preferably titanium sheet；Anode can also be similarly formed.
According to the present invention, sheet electrode is to simultaneously constant spacing is 1cm in preferred vertical insertion suspension.
In the present invention, it is preferred to use PEG4000.
According to the second aspect of the invention, a kind of film containing energy is provided, is prepared by the above method.
Preparation cost of the present invention is cheap, efficient, not only breaches nanometer Mg powder and a Fe2O3The predicament of high effective deposition in the same direction, together
When greatly reduce voltage, therefore prepare safety and greatly improve.Also, the super energetic material that the present invention is prepared is attached
Put forth effort by force, good stability, in defence and military, MEMS, the fields such as explosion are with a wide range of applications.
Plate-like cathode substrate of the invention is further preferably further provided with geosutures, to form the suitable piece of required size
Area, consequently facilitating subsequent removing.In addition, as needed, can only remove (such as it is disconnected by simply being broken along geosutures execution
Movement) required amount of section, to facilitate the storage and carrying of remaining energetic material.
In short, the present invention has at least the following advantages:
1. the technological operation that the present invention uses is simple, high-efficient, pressure can greatly improve operation down to 1V or so
Safety, and a large amount of preparation cost is saved, it is suitble to industrialized production；
2. novel Mg/Fe prepared by the present invention2O3Super nanometer membrane structure containing energy is novel, exothermicity and combustibility
Well；
3. novel Mg/Fe prepared by the present invention2O3Super Energetic Nanomaterials are evenly distributed, and there's almost no agglomeration；
4. the stability of suspension in the present invention is good；
5. novel Mg/Fe of the invention2O3The adhesive force of super Energetic Nanomaterials is substantially improved, and can satisfy military project etc.
The more harsh requirement of extreme environment.
Detailed description of the invention
Fig. 1 (a) and Fig. 1 (b) are novel nano Mg/Fe obtained according to the present invention respectively2O3Containing can film low range and
High magnification field emission scanning electron microscope figure；
Fig. 2 is novel nano Mg/Fe obtained according to the present invention2O3The DSC exotherm of the film containing energy；
Fig. 3 is novel nano Mg/Fe obtained according to the present invention2O3The combustion flame figure of the film containing energy；
Fig. 4 be according to the present invention provided by cathode substrate schematic diagram.
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.
As shown in figure 4, present invention firstly provides the cathode sheet substrate 10 of suitable size, such as titanium sheet.It is set in substrate 10
Geosutures 11 and 12 are set or are formed with, in order to subsequent strip operation: for example, following be made after the thin-film material containing energy, it can
To get rid of upper right a quarter shown in Fig. 4 along geosutures 11 and 12, and the substrate 10 adhered to thereon is removed.Anode sheet material is big
Small and material can be the same as cathode sheet material.
The present invention uses field emission scanning electron microscope (FESEM), differential scanning calorimeter (DSC), and high-speed camera etc. is to multiple
It closes film product and carries out surface topography and performance study analysis and characterization.
Embodiment 1
0.02mol/L iron chloride is accurately weighed, 2 drop concentrated hydrochloric acids and 0.0005mol/L polyethylene glycol-4000 are dissolved in 200mL
Water and alcohol mixeding liquid in, wherein the volume ratio of water and ethyl alcohol is 1:1, then ultrasonic mixing 2h, power 200W；Then it sets
In heating water bath 0.5h, temperature control is 70 DEG C, has reflux unit.Then by a certain concentration 0.4mol/L sodium hydroxide
200mL solution is dropwisely added above-mentioned cooling solution, is then thoroughly mixed, time 0.5h.Then by above-mentioned mixed solution
Fe is repeatedly centrifugally separating to obtain after constant temperature water bath heating 0.5h2O3Powder, sufficiently processing is stand-by in a vacuum drying oven for juxtaposition.It will
Above-mentioned Mg and Fe2O3Powder is to sequentially add in 100mL water after 1:2 is weighed in molar ratio, lower ultrasonic at room temperature after plastic packaging film sealing
20min.(beta-methoxy ethyoxyl) silane of vinyl three and cetyl trimethyl quaternary ammonium ammonium bromide for then weighing 2mL respectively add
Enter after upper suspension ultrasound 20min under equality of temperature, wherein both volume equivalent.With anodic-cathodic piece is inserted perpendicularly into stable suspersion
In liquid, voltage 2V, electrophoresis built-up time is 15min, and depositing temperature is 298 ± 2K.Then the novel super deposited contains
Can material be transferred in vacuum oven at 80 DEG C dry 1h, after be cooled to room temperature.Obtain novel nano Mg/Fe2O3Containing energy
Film.
As seen in figure la and lb, the super film containing energy for using the method for the present invention to prepare is nanoscale and is evenly distributed.Such as
Novel nano Mg/Fe shown in Fig. 22O3The exotherm of the film containing energy, thermal discharge are up to 4.5MJ Kg-1.As shown in figure 3,
To it is super containing can film have good burning performance.The assembling voltage of the super film containing energy is still efficient when being 5V, and uses glue
The standard testing standard class for carrying out adhesive force with method is 4B.
Comparative example 2
The other the same as in Example 1, assembling voltage are reduced to 1V, and packaging efficiency has a certain upgrade, by sediment quality rate
It is calculated and halves, energy fan-out capability is basically unchanged, and corresponding DSC exotherm fits thermal discharge under this condition and is about
4.4MJ Kg-1.It remains unchanged still in addition, measuring adhesive force grade as 4B.
Comparative example 3
The other the same as in Example 1, bath temperature control is at 80 DEG C, gained Fe2O3Powder particle mainly based on micron grain size,
Greatly reduce Fe2O3With the contact area of Al powder so that the novel nano Mg/Fe that final electrophoresis assembles2O3It is thin containing energy
The thermal discharge of film is about 65% in example 1.
Comparative example 4
The other the same as in Example 1, the difference is that cetyl trimethyl quaternary ammonium ammonium bromide is not added, packaging efficiency is almost
Zero, i.e., super energetic material film assembling cannot achieve.
Comparative example 5
The other the same as in Example 1, the difference is that vinyl three (beta-methoxy ethyoxyl) silicon, super energetic material film are not added
It assembles and successfully realizes, however measure adhesive force grade down to 2B.
Comparative example 6
The other the same as in Example 1, the difference is that changing cetyl trimethyl quaternary ammonium ammonium bromide into octadecyldimethyl benzyl
Base quaternary ammonium ammonium chloride changes vinyl three (beta-methoxy ethyoxyl) silane into 3- methacryloxypropyl trimethoxy silicon
Alkane, the super film containing energy successfully prepare, measure adhesive force grade and be slightly above 4B, thermal discharge is almost unchanged.
Comparative example 7
The other the same as in Example 1, the difference is that changing cetyl trimethyl quaternary ammonium ammonium bromide into octadecyldimethyl benzyl
Base quaternary ammonium ammonium chloride, the super film containing energy is successfully prepared, however is measured adhesive force and be greatly reduced, and is unfavorable for practical application.
As described above, the present invention obtains exothermicity by means such as the suspension compositions of design stability using low-pressure process
The practical Mg/Fe of excellent and strong adhesive force Novel portable2O3Energetic material film.
Claims (4)
1. a kind of nanometer of Mg/Fe2O3The preparation method of the film containing energy, comprising:
Iron chloride, hydrochloric acid and polyethylene glycol (PEG) are added in the water and ethyl alcohol of isometric ratio and form mixed liquor, wherein chlorination
The concentration of iron is 0.02~0.1mol/L, and concentration of hydrochloric acid is 0.1~0.6mol/L, and PEG concentration is 0.0001~0.001mol/L,
Mixed liquor is heated in water bath with thermostatic control under the conditions of 55 DEG C~75 DEG C, and instills sodium hydroxide into mixed liquor and generated with reacting
Fe2O3, wherein the molar ratio of the sodium hydroxide and the iron chloride is about 20:1；
Mixed liquor is centrifugated to obtain Fe2O3Powder, and be dried in vacuo；
By gained Fe2O3Powder and Mg powder are added to the water, and 10~30min of ultrasonic disperse to be under confined conditions to form dispersion liquid, wherein
Fe2O3Molar ratio with Mg is 1:1.5~1:2.5, and the total concentration of the two is 1.0g/L~4.0g/L；
(beta-methoxy ethyoxyl) silane of vinyl three and cetyl trimethyl quaternary ammonium ammonium bromide of isometric ratio are added again
Continue ultrasonic disperse 20min or so after stating dispersion liquid to obtain suspension, the volume ratio of the addition total volume and dispersion liquid of the two
For 2:100~10:100；
By the sheet electrode comprising cathode and anode to electrophoresis is executed in the above-mentioned suspension of insertion, to form nanometer on cathode
Mg/Fe2O3The film containing energy, wherein electrode spacing is 0.6~1.4cm, and electrophoretic voltage is 1~5V, and temperature is 298 ± 2K.
2. the method according to claim 1, further includes: carry out vacuum drying cooling to gained film containing energy.
3. method according to claim 2, further includes: can film by containing as the cathodic disbonding of substrate or removal in gained.
4. according to the method in claim 3, wherein cathode is formed by titanium sheet, copper sheet or nickel sheet.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1557998A (en) * | 2004-01-14 | 2004-12-29 | 重庆大学 | Method for preparing thin film by electric field deposition |
| CN101985770A (en) * | 2010-11-11 | 2011-03-16 | 北京科技大学 | Method for improving wear resistance of magnesium alloy cathodic electrophoretic coating |
| US20140102605A1 (en) * | 2008-10-23 | 2014-04-17 | The Johns Hopkins University | Layered reactive particles with controlled geometries, energies, and reactivities, and methods for making the same |
| 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 |
| CN107245746A (en) * | 2017-04-28 | 2017-10-13 | 重庆大学 | Al/CuO thermites and preparation method thereof |
-
2019
- 2019-01-10 CN CN201910029971.1A patent/CN109576765B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1557998A (en) * | 2004-01-14 | 2004-12-29 | 重庆大学 | Method for preparing thin film by electric field deposition |
| US20140102605A1 (en) * | 2008-10-23 | 2014-04-17 | The Johns Hopkins University | Layered reactive particles with controlled geometries, energies, and reactivities, and methods for making the same |
| CN101985770A (en) * | 2010-11-11 | 2011-03-16 | 北京科技大学 | Method for improving wear resistance of magnesium alloy cathodic electrophoretic coating |
| 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 |
| CN107245746A (en) * | 2017-04-28 | 2017-10-13 | 重庆大学 | Al/CuO thermites and preparation method thereof |
Non-Patent Citations (4)
| Title |
|---|
| SHERIF ELBASUNEY等: ""Infrared Signature of Novel Super-Thermite (Fe2O3/Mg) Fluorocarbon Nanocomposite for Effective Countermeasures of Infrared Seekers"", 《JOURNAL OF INORGANIC AND ORGANOMETALLIC POLYMERS AND MATERIALS》 * |
| 任慧等: "《微纳米含能材料》", 30 April 2015, 北京理工大学出版社 * |
| 姜国华等: ""棒状γ-Fe2O3纳米粒子的制备及表征"", 《无机材料学报》 * |
| 郭茜等: ""水溶液中电泳沉积制备纳米铝热剂AlFe2O3"", 《化工新型材料》 * |
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