CN107119301A - Al/CuO nanotube thermites and preparation method thereof - Google Patents
Al/CuO nanotube thermites and preparation method thereof Download PDFInfo
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- CN107119301A CN107119301A CN201710290462.5A CN201710290462A CN107119301A CN 107119301 A CN107119301 A CN 107119301A CN 201710290462 A CN201710290462 A CN 201710290462A CN 107119301 A CN107119301 A CN 107119301A
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- cuo
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D9/00—Electrolytic coating other than with metals
- C25D9/04—Electrolytic coating other than with metals with inorganic materials
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- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B33/00—Compositions containing particulate metal, alloy, boron, silicon, selenium or tellurium with at least one oxygen supplying material which is either a metal oxide or a salt, organic or inorganic, capable of yielding a metal oxide
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D7/00—Electroplating characterised by the article coated
- C25D7/006—Nanoparticles
Abstract
Al/CuO nanotube thermites and preparation method thereof, this method includes：CuO nano-pipe array thin films are prepared using electrodeposition process, chemical etching and calcination method joint；The electrophoresis using CuO nano-pipe array thin films as negative electrode is used to prepare Al/CuO thermites.The present invention prepares new CuO nano-tube arrays using electrochemical deposition, chemical etching and calcining integrated processes first; then Al/CuO nanometers of thermites are assembled in conjunction with electrophoretic deposition technique; overcome magnetron sputtering method preparation process complexity, cost high; the process safety of electrostatic self-assembled law part harshness and other method is low; the deficiencies such as reaction time length, preparation time is short, the protection without inert gas; the film thickness of preparation is uniform, free from flaw, function admirable, and reappearance is good.
Description
Technical field
The present invention relates to Al/CuO thermites and preparation method thereof.
Background technology
The features such as nanometer thermite has that high combustion efficiency, energyreleaserate are fast, had a safety feature, in synthesizing new material
The fields such as material, welding, priming system, propellant have wide practical use.
Nanometer thermite is a kind of by nano-aluminium particle and the molecular mixture of nano-metal-oxide grain.Common aluminothermy
The type of agent has Al/Fe2O3,Al/CuO,Al/MoO3Deng.At present, the preparation method of nanometer thermite common are solid phase reaction
Method；Suppress reaction ball milling method；Magnetron sputtering method；Self-assembly method；Sol-gel process.(Zhang the K L, Rossi such as Zhang K L
C, Ardila Rodriguez G A, Physics Letters A, 2007,91,113117-1) using the method for magnetron sputtering
Nano-aluminium particle is sputtered in the silicon base that growth there are CuO nano wires, Al/CuO nano composite materials are formed.Research finds synthesis
Composite have begun to react before nanometer aluminium powder fusing point is reached, thermal discharge is up to 2950J/g.But, the preparation
The use that method manufacturing process wastes time and energy, cost of manufacture is high, only limit several metal oxides limits its application；Malchi J
Y etc. (Malchi J Y, Foley T J, Yetter R A, ACS Applied Materials and Interfaces,
2009,11,2420-2423) Al/CuO composites have been synthesized by the method for electrostatic self-assembled, and by itself and physical mixed
Nanometer Al/CuO contrasts, find after its igniting can self-sustaining burning, and the latter then can not, illustrate after self assembly Al and CuO it
Between contact even closer, so as to improve its reactivity.Self-assembling method, weak point is the mistake for preparing nano-oxide
Organic toxicant is used in journey and cost is higher, and polymer used can substantially reduce nanometer thermite in preparation process
Energy density.
Accordingly, it would be desirable to effectively increase the specific surface area of nanometer thermite, the reaction effect of nanometer thermite is further improved
Rate, strengthens thermal discharge.
The content of the invention
It is an object of the invention to provide the more excellent Al/CuO thermites of performance.
According to the first aspect of the invention there is provided a kind of preparation method of Al/CuO thermites, including：
Sheet metal is provided as the negative electrode of electrochemical deposition, while providing platinum plate electrode is used as anode；
Electrochemical deposition solution is prepared, wherein Cu in the electrochemical deposition solution2+Content be 0.6~0.8mol/L, K+Concentration is 0.4~0.5mol/L,
Using the electrochemical deposition solution, the negative electrode and the anode, using electrodeposition process on the sheet metal
Copper film is deposited, wherein current density is 0.003~0.005A/cm2, 10~30min of time, 30 ± 1 DEG C of constant temperature；
Chemical etching solution is prepared, wherein naoh concentration is 0.6-0.8mol/L, persulfuric acid in the etching solution
Ammonium concentration is 0.06-0.08mol/L, distilled water 10-20mL；
There is copper film one side level to immerse institute upward after the sheet metal that electro-deposition has copper film is dried up in atmosphere of inert gases
State in etching solution, 10~20min is etched at room temperature；
The sheet metal after etching copper film is cleaned with deionized water, then dried up in nitrogen atmosphere；Next using high
Warm tube furnace is calcined to the sheet metal after drying, 200~400 DEG C of temperature, 2~4h of soaking time；
Electrophoresis solution is configured, the wherein mass fraction of nanometer aluminium powder is 0.1~0.2%, and solvent is ethanol and acetylacetone,2,4-pentanedione
Volume ratio is 1:1 mixed liquor；
Using the sheet metal after the calcining as electrophoresis negative electrode, and the same metal sheet of blank is provided as electrophoresis anode；
Using the electrophoresis solution, the electrophoresis negative electrode and the electrophoresis anode, on the electrophoresis negative electrode prepared by electrophoresis
Al/CuO thermites, wherein extra electric field scope 20-40V/cm2, the electrophoretic deposition time is 10-15min, and constant temperature keeps 25 ± 1
℃。
In the preparation method of the present invention, CuO nanotubes battle array is obtained by designing electro-deposition, chemical etching and calcining first
Row, are evenly distributed, 5~7 μm of " pipe range ", 100~200nm of caliber；Make nano-aluminium particle equably followed by design electrophoresis
Its surface is interspersed between CuO nanotubes or be covered in, fine and close Al/CuO compounds are formed.Its performance characterization result is shown：
Al/CuO nanometers of thermite burnings are violent, and thermal discharge is high.
Preparation in accordance with the present invention, the material of the sheet metal is preferably titanium, nickel or iron, more preferably titanium.
In the case that titanium is as sheet metal, its purity can be 99.99%, specification 1cm × 5cm.In addition, the sheet metal is being used as electricity
Corresponding pre-treatment can be first passed through before pole, the pre-treatment is smooth including being polishing to the sand paper of 400~800 mesh, then
Sequentially pass through acetone (analysis is pure), ethanol (analysis is pure), deionized water to be cleaned by ultrasonic, last 25 ± 1 DEG C of supersound washings 10 of constant temperature
~20min.
Preparation in accordance with the present invention, does not take any stirring measure preferably in electro-deposition and electrophoresis process.Hair
A person of good sense has been surprisingly found that, stirring measure can influence the form of CuO array films and make the Al/CuO thermite performances that are finally formed
Deteriorate.
Preparation in accordance with the present invention, can use Cu (NO3)2·3H20、CuSO4·5H2O or CuCl2Electrification is provided
Learn the copper in deposition, it is preferred to use nitrate trihydrate copper (Cu (NO3)2·3H20)。
Preparation in accordance with the present invention, to improve electrophoretic property, it is preferred to use plastic packaging film seals the electrophoresis solution, and
25 ± 1 DEG C of constant temperature is to its ultrasonically treated 15-20min in Ultrasound Instrument.
Preparation in accordance with the present invention, to be further ensured that being uniformly distributed in CuO nano-pipe array thin films, nanometer
The diameter of aluminium powder is preferably 50~100nm.
Preparation in accordance with the present invention, to ensure that the heating rate in the form of CuO nano-tube arrays, calcination process is excellent
Elect 3-5min/ DEG C as.
According to the second aspect of the invention there is provided a kind of Al/CuO thermites, prepared by the above method.
The electricity of nanometer CuO pipe array film prepared by electro-deposition of the present invention, etching and calcining joint in conjunction with the present invention
The nanometer thermite finally prepared of swimming has advantages below：
Al/CuO nanometers of thermites are prepared using electrophoretic deposition, magnetron sputtering method preparation process complexity, cost is overcome
The process safety of height, electrostatic self-assembled law part harshness and other method is low, and the deficiency such as reaction time length, this method need not
Large-scale instrument, preparation time is short, and this method does not need the protection of inert gas, the film thickness of preparation is uniform, free from flaw,
Function admirable, reappearance is good.
Brief description of the drawings
Fig. 1 is the CuO nanotubes SEM figures according to prepared by the present invention；
Fig. 2 is that the Al/CuO nanometer thermites SEM being composited according to electrophoretic deposition method of the present invention schemes；
Fig. 3 is to be burnt to scheme according to the Al/CuO nanometers thermite of the present invention；
Fig. 4 is to be schemed according to the Al/CuO nanometer thermite thermal discharges DSC of the present invention.
Embodiment
The present invention is further illustrated below by embodiment.It should be appreciated by those skilled in the art that following examples are
In order to be better understood from and realize the present invention, it is not intended to limit the invention.
400#, 600# are used successively, and 800# sand paper is 1 × 5cm to size2Negative electrode titanium sheet polished after, spend from
Sub- water is clean by surface washing, and acetone, ethanol, deionized water supersound washing (25 ± 1 DEG C) 20min are then used respectively, is finally adopted
Dried up with protective gas nitrogen.Titanium sheet after above-mentioned processing and platinum electrode are placed in electroplate liquid, 1cm is spaced therebetween, is adopted
The smooth copper film of one layer of densification is deposited in negative electrode titanium sheet with electrochemical deposition method.Plating solution composition is Cu (NO3)2·3H20 content
For 0.8mol/L, KOH content is 0.5mol/L, respectively takes 50mL solution to be well mixed, constant current density is 0.005A/cm2, electricity
Sedimentation time 20min；
The copper film surface that electro-deposition is obtained in titanium substrate is smooth, and thickness is uniform, and section thickness is about 10 μm.
The copper film that electro-deposition is obtained is dried up in atmosphere of inert gases, is coated with the one side of copper film upward (to ensure etching
Effect), it is immersed in the etching liquid prepared and etches 20min, etching liquid includes sodium hydroxide solution (0.8mol/L) 8mL, mistake
Ammonium sulfate (0.08mol/L) 4mL, deionized water 18mL；Copper film deionized water rinsing after etching, blows in nitrogen stream
It is dry, calcined with tube furnace, condition setting：200 DEG C, 2h, 3min/ DEG C of heating rate.
Fig. 1 is for the CuO nanotubes SEM figures according to prepared by the present invention.The present invention is prepared using the method for chemical etching
Go out pattern uniform, open, the big CuO nanotubes of specific surface area, CuO nano-tube arrays are evenly distributed, 5~7 μm of pipe range, caliber
100~200nm.
0.1000g nanometer aluminium powders are weighed in beaker, ethanol and each 50mL of acetylacetone,2,4-pentanedione, ultrasonic mixing is separately added into
20min, with the titanium sheet without growth CuO nanotubes after pre-treatment as anode, growth has the titanium sheet of CuO nanotubes as the moon
Pole, electrophoretic voltage 200V, electrophoresis time 10min；The Al/CuO compounds that electrophoresis is synthesized are dried in vacuum drying chamber, condition
Set：Pressure 0.08MPa, dries 3h by 60 DEG C.
Nanometer Al is equably interspersed between CuO nanotubes or is covered in its surface, Al/CuO nano composite materials
Specific surface area is up to 43.5g/cm2, acutely, thermal discharge is up to 3264J/g for burning.Fig. 2 is according to electrophoretic deposition method of the present invention
The Al/CuO nanometer thermites SEM figures being composited；Fig. 3 is to be burnt to scheme according to the Al/CuO nanometers thermite of the present invention；Fig. 4 is
Schemed according to the Al/CuO nanometer thermite thermal discharges DSC of the present invention.
The present invention combines electrochemical deposition method, chemical etching method and electrophoretic deposition technique, there is provided it is a kind of it is simple,
The preparation method for the l/CuO nanometers of thermites of new A that even film layer, free from flaw, specific surface area are big, burning is violent, thermal discharge is high.
This method is safe and reliable, low to equipment, material requirements, and available for mass producing, the quality of production is significantly improved.
Claims (5)
1. a kind of preparation method of Al/CuO thermites, including：
Sheet metal is provided as the negative electrode of electrochemical deposition, while providing platinum plate electrode is used as anode；
Electrochemical deposition solution is prepared, wherein Cu in the electrochemical deposition solution2+Content be 0.6~0.8mol/L, K+It is dense
Spend for 0.4~0.5mol/L,
Using the electrochemical deposition solution, the negative electrode and the anode are deposited using electrodeposition process on the sheet metal
Copper film, wherein current density are 0.003~0.005A/cm2, 10~30min of time, 30 ± 1 DEG C of constant temperature；
Chemical etching solution is prepared, wherein naoh concentration is 0.6-0.8mol/L in the etching solution, ammonium persulfate is dense
Spend for 0.06-0.08mol/L, distilled water 10-20mL；
There is copper film one side level to immerse the quarter upward after the sheet metal that electro-deposition has copper film is dried up in atmosphere of inert gases
Lose in solution, 10~20min is etched at room temperature；
The sheet metal after etching copper film is cleaned with deionized water, then dried up in nitrogen atmosphere；Next high temperature pipe is used
Formula stove is calcined to the sheet metal after drying, 200~400 DEG C of temperature, 2~4h of soaking time；
Electrophoresis solution is configured, the wherein mass fraction of nanometer aluminium powder is 0.1~0.2%, and solvent is ethanol and acetylacetone,2,4-pentanedione volume
Than for 1:1 mixed liquor；
Using the sheet metal after the calcining as electrophoresis negative electrode, and the same metal sheet of blank is provided as electrophoresis anode；
Using the electrophoresis solution, the electrophoresis negative electrode and the electrophoresis anode, electrophoresis prepares Al/ on the electrophoresis negative electrode
CuO thermites, wherein extra electric field scope 20-40V/cm2, the electrophoretic deposition time is 10-15min, and constant temperature is kept for 25 ± 1 DEG C.
2. preparation method according to claim 1, wherein the material of the sheet metal is titanium, nickel or iron.
3. preparation method according to claim 1, wherein not taking any stirring to arrange in electro-deposition and electrophoresis process
Apply.
4. preparation method according to claim 1, wherein using using nitrate trihydrate copper (Cu (NO3)2·3H20) electricity is provided
Copper in chemical deposition.
5. it is prepared by a kind of Al/CuO thermites, the method according to one of claim 1-4.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201710290462.5A CN107119301A (en) | 2017-04-28 | 2017-04-28 | Al/CuO nanotube thermites and preparation method thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107583311A (en) * | 2017-09-19 | 2018-01-16 | 重庆大学 | A kind of preparation method of the oily-water seperating equipment of high-efficiency and continuous |
| 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 |
| CN109680309A (en) * | 2019-03-06 | 2019-04-26 | 重庆大学 | Super hydrophobic porous Al/CuO nanometers of aluminothermy composite material containing energy |
| CN111607815A (en) * | 2020-07-15 | 2020-09-01 | 南昌航空大学 | Method for preparing aluminide coating on surface of nickel-based metal through electrophoresis |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103928690A (en) * | 2014-04-10 | 2014-07-16 | 华中科技大学 | Visible light photocatalytic fuel cell and preparation method thereof |
| CN105390688A (en) * | 2015-03-23 | 2016-03-09 | 昆明理工大学 | Manufacturing method for copper oxide loaded titanium dioxide nano through tube array and application of copper oxide loaded titanium dioxide nano through tube array |
| CN105689724A (en) * | 2016-02-01 | 2016-06-22 | 南京师范大学 | Preparing method of nano Al/CuO-AP energy-contained composite particles |
-
2017
- 2017-04-28 CN CN201710290462.5A patent/CN107119301A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103928690A (en) * | 2014-04-10 | 2014-07-16 | 华中科技大学 | Visible light photocatalytic fuel cell and preparation method thereof |
| CN105390688A (en) * | 2015-03-23 | 2016-03-09 | 昆明理工大学 | Manufacturing method for copper oxide loaded titanium dioxide nano through tube array and application of copper oxide loaded titanium dioxide nano through tube array |
| CN105689724A (en) * | 2016-02-01 | 2016-06-22 | 南京师范大学 | Preparing method of nano Al/CuO-AP energy-contained composite particles |
Non-Patent Citations (4)
| Title |
|---|
| DAIXIONG ZHANG 等: ""Fabrication and kinetics study of nano-Al/NiO thermite film by electrophoretic deposition"", 《THE JOURNAL OF PHYSICAL CHEMISTRY》 * |
| JONATHAN Y.MALCHI 等: ""Electrostatically self-assembled nanocomposite reactive microspheres"", 《APPLIED MATERIALS & INTERFACES》 * |
| 张代雄: ""电泳沉积法制备新型纳米铝热剂膜的研究"", 《中国博士学位论文全文数据库 工程科技I辑》 * |
| 郭茜 等: ""水溶液中电泳沉积制备纳米铝热剂Al/Fe2O3"", 《化工新型材料》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107583311A (en) * | 2017-09-19 | 2018-01-16 | 重庆大学 | A kind of preparation method of the oily-water seperating equipment of high-efficiency and continuous |
| 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 |
| CN109295418B (en) * | 2018-10-10 | 2020-09-25 | 重庆大学 | High-heat-release Al/CuO 3D core-shell array structure thermite with extremely high load capacity |
| CN109680309A (en) * | 2019-03-06 | 2019-04-26 | 重庆大学 | Super hydrophobic porous Al/CuO nanometers of aluminothermy composite material containing energy |
| CN111607815A (en) * | 2020-07-15 | 2020-09-01 | 南昌航空大学 | Method for preparing aluminide coating on surface of nickel-based metal through electrophoresis |
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Application publication date: 20170901 |