CN109837515A - Nano combined film containing energy and preparation method thereof - Google Patents
Nano combined film containing energy and preparation method thereof Download PDFInfo
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- CN109837515A CN109837515A CN201711223368.4A CN201711223368A CN109837515A CN 109837515 A CN109837515 A CN 109837515A CN 201711223368 A CN201711223368 A CN 201711223368A CN 109837515 A CN109837515 A CN 109837515A
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- film
- azide
- metal
- containing energy
- magnetron sputtering
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Abstract
The invention discloses it is a kind of it is nano combined containing can film and preparation method thereof using porous nano aluminium oxide as backing material the carbon nanotube of embedded azide is set in the backing material duct up to described containing can film.Azide is embedded in the aligned carbon nanotube hollow lumen in aluminium oxide duct by the present invention, form the composite energy-containing thin-film material of a kind of novel nano structure, the material can not only solve the safety issue that azide uses, and it can be improved the explosion property of azide to a certain extent, while meeting the stability requirement of energetic material engineering application.
Description
Technical field
The present invention relates to a kind of nanostructure composite energy-containing films and preparation method thereof, more specifically a kind of embedded folded
Carbon nanotube/alumina composite of nitride film containing energy and preparation method thereof.
Background technique
With the development of weapon technologies, volume, cost and the reliability of traditional priming system have been difficult to meet demand, fire
Work product technology just develops towards the direction of miniaturization, intelligence, low cost and high reliability.Wherein MEMS (Micro-
Electro-Mechanical System, MEMS) technology be priming system miniaturization Main way.MEMS technology goes out
Now make it possible that initiation system realizes low cost, small size, high reliability, while it is more to accommodate to reserve more spaces
Sensor and main charge so that the accuracy and lethality of ammunition greatly improve.
So far, mainly there are lead azide and lead styphnate as the solid energetic material of priming, both medicines
Agent has toxicity because of leaded, larger to the harm of environment.Copper azide has good explosion property, simultaneously as being free of
There is lead and more environmental-friendly, so it promises to be the substitute for commonly using toxic priming at present.But copper azide is higher
Sensitivity limit its practical application.
Copper azide is a kind of to make it in reality friction, shock and the extremely sensitive priming of electrostatic, its safety
It is difficult to be applied in the engineering of border.Gerald in 2008 proposes a kind of patent that apparatus to cause bursting is prepared in situ in substrate, technology
Including depositing one layer of metal layer, the reacted formation priming layer of metal layer in substrate.Later numerous researchers are prepared for more
The copper azide in hole and its carbon composite, but they do not solve the problems, such as integrated and safety, later
Powder charge and sensibility do not obtain actual solution.
Summary of the invention
The purpose of the invention is to provide it is a kind of it is more safe and environment-friendly, can be used for MEMS priming system containing can powder charge it is thin
Membrane material and preparation method thereof.
In order to achieve the above object, the invention provides the following technical scheme:
The nano combined film containing energy of one kind is arranged in the backing material duct using porous nano aluminium oxide as backing material
The carbon nanotube of embedded azide is up to the film containing energy.
Further, azide is copper azide or Azide nickel.
Further, the backing material is arranged in substrate by a transition zone, wherein the transition zone uses
V, any one in Cr, Zr and Ti metal layer, with a thickness of 10-200nm；The substrate uses with a thickness of 200 ~ 1000 μm of lists
Crystal silicon chip, sheet metal or sheet glass.
Further, containing can film with a thickness of 500 ~ 800 nanometers.
Further, the aperture of porous nano aluminium oxide is 20-300nm.
Further, the carbon nanotube of azide is embedded by the deposited metal nanoparticle into carbon nanotube duct,
It carries out Azide processing to the metal nanoparticle again to be made, wherein metal nanoparticle is copper or nickel.
The preparation method of the above-mentioned nano combined film containing energy, includes the following steps:
(1) use magnetron sputtering deposited metal layer as transition zone first in substrate；
(2) magnetron sputtering deposited metal aluminium is used on transition zone, then is carried out anodized and obtained porous nano aluminium oxide
As backing material；
(3) with chemical vapor carbon deposition nanotube；
(4) use electrochemical deposition deposited metal nanoparticle into carbon nanotube duct, then to the metal nanoparticle into
The processing of row Azide, obtains the film.
Further, in step (1), magnetron sputtering deposition process parameters are as follows: the purity of transition metal target is
99.99%, operating air pressure is 0.2-0.8Pa when magnetron sputtering, and Ar throughput is 20-40Sccm, and sputtering power is controlled in 150-
300W, deposition of metal rate are 10-20nm/min.
Further, in step (2), magnetron sputtering deposition process parameters are as follows: the purity degree 99.999% of aluminium target, magnetic control
Operating air pressure is 0.2-0.5Pa when sputtering, and Ar throughput is 20-40Sccm, and in 150-300W, metal layer is heavy for sputtering power control
Product rate is 10-20nm/min；Anodized technological parameter are as follows: aluminium layer is made as anode using sulfuric acid, oxalic acid or phosphoric acid
Anodic oxidation, electrolyte concentrations 0.1-0.5M, oxidation voltage 20-120V are carried out for electrolyte.
Further, in step (3), chemical vapor deposition process parameter are as follows: using iron, cobalt or nickel as catalyst, with second
The unsaturated olefins such as alkynes, ethylene are controlled as carbon source, gas flow in 100-130Sccm；Using argon gas as carrier gas, gas flow
Control is in 300-400Sccm；Using hydrogen as reducing gas, throughput control is controlled in 50-70Sccm, reaction temperature in 600-
800 DEG C, reaction time 60-120min.
Further, in step (4), electrochemical deposition process parameter are as follows: the current density of deposition is controlled in 0.05-0.6
MA, electrodeposition time 1-3h；Azide treatment process parameter are as follows: using nitrine acid gas as gas phase, wherein nitrine acid gas
It is generated by stearic acid and sodium azide or nitric acid and reaction of sodium azide, gas concentration is 7.7-30.8 mM, and the reaction time is
48-120h。
Compared with prior art, the invention has the advantages that
Azide is embedded in the aligned carbon nanotube hollow lumen in aluminium oxide duct by the present invention, is formd a kind of novel
The composite energy-containing thin-film material of nanostructure, the material can not only solve the safety issue that azide uses, Er Qieyi
Determine the explosion property that can be improved azide in degree, while meeting the stability requirement of energetic material engineering application.
Detailed description of the invention
Fig. 1 is the nano combined membrane structure schematic diagram containing energy.
Fig. 2 is Scanning Electron microscope (SEM) picture of the nano-porous alumina surface texture after anodized.
Fig. 3 is to use porous aluminas as support, is aoxidized by nanoporous prepared by the method for chemical vapor deposition
Aluminium supports the section SEM figure of carbon nano tube structure.
Fig. 4 deposited metal in the carbon nanotube duct that nano-porous alumina supports for the method by electrochemical deposition
Section SEM figure after nanoparticle.
Specific embodiment
Such as Fig. 1, it is of the present invention it is nano combined containing can film, it is described using porous nano aluminium oxide as backing material
Backing material is arranged in substrate by a transition zone, carbon nanotube is arranged in the backing material duct, and in carbon nanometer
Pipe deposited metal nanoparticle, then Azide is carried out to the metal nanoparticle and is handled up to the film containing energy.
Embodiment
The organic impurities and metal impurities for being removed silicon chip surface using mixed acid solution first, are then distinguished substrate silicon wafer
It is successively immersed in acetone, alcohol and ultrapure water and carries out ultrasonic cleaning 20min, blow away silicon chip surface with ear washing bulb after cleaning
Water droplet dries spare.
By the silicon wafer sticking double faced adhesive tape cleaned up on circular sample platform, guarantee the attachment between silicon wafer and substrate
Power is good, and then titanium target and aluminium target are fixed on target, closes vacuum chamber hatch door.Circulating condensing water is opened, is successively opened total
Power supply, mechanical pump, other pumping valve, compound vacuum gauge, flowmeter, radio frequency source power switch, molecular pump general supply.It is read to vacuum meter
When being shown as 8Pa, switch other pumping valve, opens molecular pump, subsequent standard-sized sheet slide valve, up to chamber vacuum degree to 5 × 10-3Pa.It is logical
Enter 99.99% argon gas, and adjust flowmeter and flow is adjusted to 32 Sccm, slide valve, which is turned down waiting vacuum meter reading, is
Starter when 8Pa, adjusting sputtering power are 200W, then make vacuum degree 0.4Pa by adjusting slide valve, and adjusting radio frequency adaptation makes
It is minimum to obtain reflection power.The ti interlayer that thickness is about 100nm or so is obtained after titanium target sputters 10min, then with identical item
The aluminum metal layer that thickness is about 1 μm or so is obtained after sputtering 60min by aluminium target under part.Each open successively is closed after the completion of plated film
It closes, after cooling a period of time, opens vacuum chamber and take out sample, it is spare.
Weigh 18.9g oxalic acid, be dissolved in ultrapure water, prepare obtain concentration be 0.3M oxalic acid solution it is spare, then point
1.8g chromium trioxide and the phosphoric acid of 6g also known as are taken, is dissolved in ultrapure water, the acid solution that configuration obtains 100g is spare, finally again
5g phosphoric acid is weighed, it is spare that preparation obtains the phosphoric acid solution that mass fraction is 5wt %.The sample that magnetron sputtering is obtained is placed on electricity
Trench bottom is solved, is sealed by polytetrafluoroethylene gasket, prevents electrolyte from revealing, the anode of constant-current supply is connected by conducting wire, is made
With stainless steel substrates cathode the most, face sample connects the cathode of power supply, is poured slowly into electrolytic cell into electrolytic cell until will not
Rust steel disc floods, and opens constant-current supply, and setting voltage is 45V, carries out anodic oxidation, oxidization time 15min takes after the completion
Sample out is dried with pure water rinsing.Then, the sample after oxidation is immersed in 70 DEG C of 1.8wt % chromium trioxide and 6wt %
30min in phosphoric acid solution removes the obtained alumina layer of anodic oxidation, takes out and uses ultrapure water, dries.According to for the first time
The condition of anodic oxidation carries out second of anodic oxidation, obtains alumina layer, obtained sample is then immersed in 30 DEG C
In the phosphoric acid solution of 5wt %, the channel diameter of porous aluminas is expanded to 100nm or so, sample is taken out, uses ultrapure water
Afterwards, it dries.
Sample obtained above is placed in porcelain boat, is put into vacuum tube furnace, is vacuumized, temperature programming is to 750 DEG C
Afterwards, the hydrogen of the argon gas of 350Sccm, the ethylene of 110Sccm and 50Sccm is each led into, after reacting 70min, is reduced the temperature to often
Temperature is taken out, obtains the carbon nano-tube coextruded film of alumina-supported.
Finally, weighing 2.5g copper sulphate and 2.5 boric acid respectively, and the additive of 1mg being added, preparation obtains 100mL solution,
The sample obtained before is placed on electrolytic cell bottom end, as cathode, using platinum electrode as anode, control current density exists
0.1mA carries out depositing nano metal particle 1h, after deposition, takes out sample and is dried with ultrapure water, finally by sample
It is put into homemade azido reaction device, carries out Azide 72h, the last carbon nanotube to embedded copper azide/porous
The laminated film of nano aluminium oxide.
Fig. 2 is Scanning Electron microscope (SEM) picture of the nano-porous alumina surface texture after anodized,
As can be seen from Figure 2, nano aluminium oxide aperture is about 100 nm, and pore size is relatively uniform, the less surfacing of defect.
Fig. 3 is to use porous aluminas as support, is aoxidized by nanoporous prepared by the method for chemical vapor deposition
Aluminium supports the section SEM figure of carbon nano tube structure.As can be seen from Figure 3, after having deposited carbon nanotube, carbon pipe is close to nanoporous
Aluminium oxide duct inner wall, bottom end are connected to Ti layer surface, replicate the pattern in original duct, upper end opening, bottom end closure completely
In test tube shape.
Fig. 4 deposited metal in the carbon nanotube duct that nano-porous alumina supports for the method by electrochemical deposition
Section SEM figure after nanoparticle.As can be seen from Figure 4, it is shown in figure after completing electro-deposition, carbon nanotube duct is by metal nano
Particle fills up, and filling rate is higher.
Claims (10)
1. the nano combined film containing energy, using porous nano aluminium oxide as backing material, which is characterized in that in the backing material hole
The carbon nanotube of embedded azide is set in road up to the film containing energy.
2. the film as described in claim 1 containing energy, which is characterized in that azide is copper azide or Azide nickel.
3. the film as described in claim 1 containing energy, which is characterized in that the backing material is arranged by a transition zone in base
On bottom, wherein the transition zone is using any one in V, Cr, Zr and Ti metal layer, with a thickness of 10-200nm.
4. the film as claimed in claim 3 containing energy, which is characterized in that the substrate uses with a thickness of 200 ~ 1000 μm of monocrystalline
Silicon wafer, sheet metal or sheet glass.
5. as described in claim 1 containing can film, which is characterized in that containing can film with a thickness of 500 ~ 800 nanometers.
6. the film as described in claim 1 containing energy, which is characterized in that the aperture of porous nano aluminium oxide is 20-300nm.
7. as described in claim 1 containing can film, which is characterized in that the carbon nanotube of embedded azide is by carbon nanometer
Deposited metal nanoparticle in pore road, then Azide processing is carried out to the metal nanoparticle and is made, wherein metal nano
Particle is copper or nickel.
8. the preparation method of the film as claimed in claim 1 containing energy, which comprises the steps of:
(1) use magnetron sputtering deposited metal layer as transition zone first in substrate；
(2) magnetron sputtering deposited metal aluminium is used on transition zone, then is carried out anodized and obtained porous nano aluminium oxide
As backing material；
(3) with chemical vapor carbon deposition nanotube；
(4) use electrochemical deposition deposited metal nanoparticle into carbon nanotube duct, then to the metal nanoparticle into
The processing of row Azide, obtains the film.
9. preparation method as claimed in claim 8, which is characterized in that in step (1), magnetron sputtering deposition process parameters are as follows:
The purity of transition metal target is 99.99%, and operating air pressure is 0.2-0.8Pa when magnetron sputtering, and Ar throughput is 20-
40Sccm, in 150-300W, deposition of metal rate is 10-20nm/min for sputtering power control.
10. preparation method as claimed in claim 8, which is characterized in that in step (2), magnetron sputtering deposition process parameters are as follows:
The purity degree 99.999% of aluminium target, operating air pressure is 0.2-0.5Pa when magnetron sputtering, and Ar throughput is 20-40Sccm, sputtering
For power control in 150-300W, deposition of metal rate is 10-20nm/min.
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Cited By (4)
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| CN110373646A (en) * | 2019-08-07 | 2019-10-25 | 南京理工大学 | A kind of micro-thruster loading method based on magnetron sputtering powder charge |
| WO2021042921A1 (en) * | 2019-09-06 | 2021-03-11 | 南京理工大学 | Method for preparing copper azide and cuprous azide for conductive metal organic frame packaging |
| CN112899746A (en) * | 2021-02-05 | 2021-06-04 | 南京理工大学 | Method for reducing electrostatic sensitivity of cuprous azide film |
| CN113307710A (en) * | 2021-06-02 | 2021-08-27 | 南京理工大学 | Porous azide/high-energy explosive micro-explosion sequence film and preparation method thereof |
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| US20120060984A1 (en) * | 2010-07-16 | 2012-03-15 | Drexel University | Carbon Nanotubes Containing Confined Copper Azide |
| CN103382567A (en) * | 2013-06-24 | 2013-11-06 | 西安近代化学研究所 | Carbon nanotube with surface modified with azido groups and preparation method thereof |
| CN103864034A (en) * | 2014-03-17 | 2014-06-18 | 南京理工大学 | Method and device for synthesizing copper azide |
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| CN103382567A (en) * | 2013-06-24 | 2013-11-06 | 西安近代化学研究所 | Carbon nanotube with surface modified with azido groups and preparation method thereof |
| CN103864034A (en) * | 2014-03-17 | 2014-06-18 | 南京理工大学 | Method and device for synthesizing copper azide |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110373646A (en) * | 2019-08-07 | 2019-10-25 | 南京理工大学 | A kind of micro-thruster loading method based on magnetron sputtering powder charge |
| CN110373646B (en) * | 2019-08-07 | 2021-05-04 | 南京理工大学 | Micro-thruster charging method based on magnetron sputtering charging |
| WO2021042921A1 (en) * | 2019-09-06 | 2021-03-11 | 南京理工大学 | Method for preparing copper azide and cuprous azide for conductive metal organic frame packaging |
| CN112899746A (en) * | 2021-02-05 | 2021-06-04 | 南京理工大学 | Method for reducing electrostatic sensitivity of cuprous azide film |
| CN113307710A (en) * | 2021-06-02 | 2021-08-27 | 南京理工大学 | Porous azide/high-energy explosive micro-explosion sequence film and preparation method thereof |
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| CN109837515B (en) | 2021-05-04 |
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