CN110078033A - A kind of preparation method of the high-density copper azide with constraint shell - Google Patents
A kind of preparation method of the high-density copper azide with constraint shell Download PDFInfo
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- CN110078033A CN110078033A CN201910430800.XA CN201910430800A CN110078033A CN 110078033 A CN110078033 A CN 110078033A CN 201910430800 A CN201910430800 A CN 201910430800A CN 110078033 A CN110078033 A CN 110078033A
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- copper
- density
- azide
- shell
- constraint
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/08—Hydrazoic acid; Azides; Halogen azides
-
- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B35/00—Compositions containing a metal azide
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F42—AMMUNITION; BLASTING
- F42B—EXPLOSIVE CHARGES, e.g. FOR BLASTING, FIREWORKS, AMMUNITION
- F42B3/00—Blasting cartridges, i.e. case and explosive
- F42B3/10—Initiators therefor
- F42B3/12—Bridge initiators
- F42B3/128—Bridge initiators characterised by the composition of the pyrotechnic material
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- Engineering & Computer Science (AREA)
- General Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Powder Metallurgy (AREA)
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Abstract
The present invention relates to a kind of preparation methods of high-density copper azide with constraint shell, belong to priming system field.Using storage after nano porous copper or nanoporous copper oxide are loaded in constraint shell, prepared again through gas-solid in-situ chemical reaction with highdensity copper azide with nitrine acid gas using preceding；The risk of traditional priming production, transport and later period pressing is avoided in operating process, prepared has the intracorporal copper azide loading density of constraint shell high, filling process is without danger, transport and storage safety, power of detonating is big, the single-shot constraint intracorporal copper azide dose of shell belongs to sub- milligram grade, preparation process green non-pollution.1.4~3.2g/cm of loading density can be made using the method for the present invention3High-density copper azide, the prepared loading density that can detonate when constraining the intracorporal high-density copper azide dose of shell in >=0.4mg is theoretical density 75%-92%, the explosives such as diameter >=0.5mm HNS-IV, CL-20, PETN and RDX and lights B/KNO3Equal ignition charges.
Description
Technical field
The present invention relates to a kind of preparation methods of high-density copper azide with constraint shell, belong to priming system neck
Domain.
Background technique
Current copper azide priming reported in the literature mainly uses liquid phase method to synthesize, obtained copper azide detonation
The loading density of medicine is lower, use that cannot be safe in MEME fuse and civilian detonator.
The method for preparing the micro- powder charge of metal azide in use gas solid chemical reaction in situ of lot of documents report at present
In, presoma nano porous metal is mainly prepared using bubble hydrogen template and metal salt high-temperature decomposition.Open the equal (Zhang in side
Fang,Wang Yanlan,Bai Yingwei,et al.Preparation and characterization of copper
Azide nanowire array [J] .Materials Letters, 2012,89:176-179) it is heavy by electricity using AAO template
Product is prepared for Cu nano wire, then by Cu nano wire and HN3Gas reaction is prepared for copper azide nano wire.(the Xie Rui such as Xie Ruizhen
Treasure, Liu Lan, the powder charge in situ of the micro- detonator of silicon substrate such as Xiao Ming and performance study [J] war industry's journal, 2014, (12): 1972-
1977) nano porous copper is prepared by bubble hydrogen template, and passes through itself and HN3Gas reaction in-situ is prepared for Porous Cu nitrine
Compound energetic material.The size of powder charge of the cavity is 1.0 × 1.0mm of Φ, explosive payload 0.47mg, degree of packing 0.60g/
cm3.(fabricated in situ of the Porous Cu azide such as Zhang Zhidong, Zhang Fang, Wang Yanlan and performance characterization [J] the firer such as Zhang Zhidong
Product, 2015, (02): 26-28.) by bubble hydrogen template electro-deposition nano porous copper, and reaction in-situ prepares copper azide.
(carbon nano pipe array [J] of Wang Yanlan, Zhang Fang, the in-situ reaction preparation filling copper azide such as flower bud contain energy to Wang Yanlan etc.
Material, 2016, (04): 386-392.).The filling of corresponding prepared copper azide reported in the literature few in number
Density is not higher than 1.0g/cm3。
Therefore using the nano porous metal of bubble hydrogen template preparation, for hole at tens microns, microstructure is loose, leads
The product density for causing azido reaction to generate is too low, reduces initiating ability significantly, is unable to reach required highly dense in MEMS fuse
Spend the requirement of priming.And the nano porous metal of higher density can be prepared using organic metal salt pyrolytic, and receive
Rice porous metals have macropore penetrating enough, so as to realize that nitrine acid gas and nano metal/metal oxide carry out
Gas-solid in-situ chemical reaction prepares high desnity metal azide.High-density copper azide may be implemented in the method for the present invention
It prepares to solve the preparation problem of high loading density priming urgently needed for current MEMS fuse.
Summary of the invention
The object of the present invention is to provide a kind of preparation methods with the constraint intracorporal high-density copper azide of shell, about
The loading density of copper azide is up to 1.4~3.0g/cm in beam shell3.The powder charge of copper azide in single constraint shell
Amount >=0.4mg avoids copper azide in the danger of use, transport, filling and pressing.
The purpose of the present invention is what is be achieved through the following technical solutions.
A kind of preparation method of the high-density copper azide with constraint shell, the specific steps are as follows:
Step 1: preparing organic copper salt nano microcrystalline presoma；
Step 2: using organic copper salt nano microcrystalline precursor preparation nano porous copper made from step 1；
Step 3: having the high-density copper azide of constraint shell using the preparation of nano porous copper made from step 2；
Nano porous copper made from step 2 is loaded in constraint shell, is then integrally placed in reactor and hydrazoic acid
Gas carries out gas-solid in-situ chemical reaction, takes out after fully reacting, obtains the high-density copper azide with constraint shell；
Type of feed described in step 3 is to be loaded using external pressure mode；
A kind of preparation method of the high-density copper azide with constraint shell, the specific steps are as follows:
Step 1: preparing organic copper salt nano microcrystalline presoma；
Step 2: using organic copper salt nano microcrystalline precursor preparation nanoporous copper oxide made from step 1；
Step 3: having the high-density copper Azide of constraint shell using the preparation of nanoporous copper oxide made from step 2
Object；
Nanoporous copper oxide made from step 2 is loaded in constraint shell, is then integrally placed in reactor and folds
Nitronic acid gas carries out gas-solid in-situ chemical reaction, takes out after fully reacting, obtains the high-density copper Azide with constraint shell
Object；
Type of feed described in step 3 is to be loaded using external pressure mode；
Nano porous copper/copper oxide is the preparation method comprises the following steps: using organic copper salt, soluble copper salt and organic acid or organic salt
Reaction prepares organic copper salt nano microcrystalline, obtains nano porous copper/copper oxide through high-temperature calcination.
Constraint shell described in step 3 is the slab construction with through-hole；
Pressure >=0.01MPa of the external pressure, the nano porous copper/copper oxide are in the constraint intracorporal loading density of shell
≥0.60g/cm3。
A kind of application of the high-density copper azide with constraint shell,
Using one
Prepare miniature initiator
The miniature initiator is made of the copper azide of substrate, belt restraining shell with initiating bridge；
The miniature initiator is by the copper azide of substrate, belt restraining shell with initiating bridge, film flying and accelerates thorax
Composition.
Using two
Prepare miniature Explosive sequence or miniature biography fire sequence
The miniature Explosive sequence is by the high-density copper azide of substrate, belt restraining shell with initiating bridge and fried
Medicine composition；
The miniature Explosive sequence by the high-density copper azide of substrate, belt restraining shell with initiating bridge, film flying,
Accelerate thorax and explosive composition；
The miniature biography fire sequence by substrate, belt restraining shell with initiating bridge high-density copper azide and point
Gunpowder composition；
The miniature Explosive sequence by the high-density copper azide of substrate, belt restraining shell with initiating bridge, film flying,
Accelerate thorax and ignition charge composition.
Organic copper salt nano microcrystalline presoma the preparation method comprises the following steps: 1) with solid organic acid and solid copper described in step 1
The molar ratio of obtained nanometer organic copper salt microcrystalline solids powder after salt mixed grinding, the solid organic acid and solid mantoquita is 1
~6:1；2) precipitation reaction is occurred in a solvent with organic acid or soluble organic acid salt and mantoquita, collects precipitating and drying and crushing
Organic copper salt nanocrystalline solid powder can be made, the molar ratio of the organic acid/acylate and mantoquita is 1~6:1；Institute
The molar ratio for stating organic acid/acylate and mantoquita is 1~6:1；
Nano porous copper described in step 2 the preparation method comprises the following steps: organic copper salt nano microcrystalline obtained by step 1 is existed
Nano porous copper can be made through high-temperature calcination and held for some time under inert gas shielding or vacuum condition；
Nanoporous copper oxide described in step 2 the preparation method comprises the following steps: organic copper salt nanometer obtained by step 1 is micro-
Nanoporous copper oxide can be made in air or under conditions of have oxygen through high-temperature calcination and held for some time in crystalline substance；
Type of feed described in step 3 is that nano porous copper/copper oxide is transferred to constraint shell by the way of external pressure
In through-hole.
Azido reaction time described in step 3 is 3min~72 hour, and the temperature of azido reaction is 20~150 DEG C.
Thickness >=0.1mm of constraint shell plate described in step 3 with through-hole, through-hole diameter >=0.3mm.
High-temperature calcination temperature described in step 3 is 280~700 DEG C, and soaking time is 10~180min.
The constraint case material with through-hole of the preparatory pore-forming is stainless steel, titanium, ceramics, silicon, epoxy resin, polyamides
Imines plate or glass fiber material plate.It is described constraint the intracorporal nano porous copper/copper oxide of shell loading density be >=
0.60g/cm3。
The generation of the nitrine acid gas by sodium azide solid and higher boiling acid (such as stearic acid, the concentrated sulfuric acid, concentrated phosphoric acid and
The concentrated sulfuric acid+concentrated phosphoric acid mixed acid etc.) heating reaction generation.
(such as stearic acid, the concentrated sulfuric acid, concentrated phosphoric acid and the concentrated sulfuric acid+concentrated phosphoric acid mix the sodium azide solid with higher boiling acid
Acid etc.) molar ratio be 1:3~20.The loading density of the obtained copper azide in constraint shell can achieve 1.4
~3.0g/cm3。
Initiation process makes the detonation of high-density copper azide simultaneously to initiating bridge electric discharge by DC power supply (or battery) or capacitor
By explosive initiation or light B/KNO3Simultaneously the accelerated thorax of driven flyer plates impacts for equal ignition charges or the detonation of high-density copper azide
Bursting charge lights B/KNO3Equal ignition charges.
The explosive is HNS-IV, CL-20, PETN and RDX etc..
The ignition charge is B/KNO3Equal ignition charges.
The size of the explosive is diameter >=0.5mm.
The loading density of the explosive is theoretical density 75%-92%.
It can successfully detonate when dose >=0.4mg of the single intracorporal high-density copper azide of the constraint shell
The explosives such as HNS-IV, CL-20, PETN and RDX light B/KNO3Equal ignition charges
The miniature initiator structural schematic diagram is as shown in attached drawing 9 and attached drawing 10.
The miniature propagation of explosion passes fiery sequential structure schematic diagram as shown in attached drawing 11 and attached drawing 12.
The Azide gas-solid in-situ chemical reaction process schematic is as shown in Fig. 13.
The detonation mode of the miniature Explosive sequence is high-density copper azide direct initiation or high-density copper nitrine
Compound detonation drives 5~50 μm of thickness of the accelerated thorax percussion powder of titanium film flying.
The miniature biography fire sequence sparking mode is the direct-fire of high-density copper azide or high-density copper Azide
Object detonation drives 5~50 μm of thickness of the accelerated thorax impact of titanium film flying to light B/KNO3Equal ignition charges.
The acceleration thorax length >=0.3mm.Acceleration thorax material is glass mat, ceramics, metal, glass, epoxy resin
And hard plastic board etc..
The baseplate material with initiating bridge is to be welded with nickel-chrome igniter wire or sputtering containing metal bridges films such as nickel-chrome, nickel-aluminums
The hard plates material such as glass mat, ceramics, epoxy resin, glass and the metal that has insulating layer.
The present invention is using solid organic acid mantoquita, solid organic acid or SOLID ORGANIC hydrochlorate and solid mantoquita in solid phase or molten
Organic acid mantoquita nano microcrystalline powder is prepared in agent, it is more that after dinectly bruning nanometer can be made in organic acid mantoquita nano microcrystalline
Nano porous copper or nanoporous copper oxide are loaded in constraint shell, by the constraint shell by hole copper or nanoporous copper oxide
Body is placed in reactor to be taken out after a certain period of time with nitrine acid gas progress gas-solid in-situ chemical reaction, is obtained with constraint shell
And it is 1.4~3.0g/cm that density is filled in shell3High-density copper azide, the single intracorporal high density of constraint shell
It can successfully detonate when dose >=0.4mg of copper azide and the explosives such as HNS-IV, CL-20, PETN and RDX or light B/KNO3
Equal ignition charges.
Beneficial effect
1. copper azide prepared by the present invention is synthesized using gas-solid in-situ chemical reaction, prepared in constraint shell
Copper azide has loading density high, and detonation power is big, belongs to sub- milligram grade.
2. presoma nano porous copper/copper oxide of safety is loaded on constraint shell in advance in preparation process of the present invention
In, so as to avoid the risk of the filling of priming traditional after preparation, transport and pressing, it is raw to greatly improve priming
The safety for producing, transporting and storing.
3. preparation condition of the present invention is simply mild, the reaction time is short；
4. preparation facilities of the present invention is simple, low for equipment requirements, technological operation is easy；
5. preparation process of the present invention is low in cost, process operation expense is few；
6. being discharged in preparation process of the present invention without waste liquid exhaust gas, safe preparation process green non-pollution.Use the method can be with
It is 1.4~3.0g/cm that loading density, which is made,3High-density copper azide, copper Azide in prepared single constraint shell
Object explosive payload can successfully detonate the explosives such as HNS-IV, CL-20, PETN and RDX and successful ignition B/KNO in >=0.4mg3Equal points
Gunpowder.Be widely used prospect in MEMS fuse and civilian detonator.
Detailed description of the invention
The SEM phenogram of nano porous metal copper prepared by Fig. 1 embodiment of the present invention 1；
The XRD characterization figure of nano porous metal copper prepared by Fig. 2 embodiment of the present invention 1；
The SEM phenogram of high-density copper azide prepared by Fig. 3 embodiment of the present invention 1；
The XRD characterization figure of high-density copper azide prepared by Fig. 4 embodiment of the present invention 1；
There is the high-density copper azide schematic diagram of constraint shell prepared by Fig. 5 embodiment of the present invention 1；
The SEM phenogram of high-density copper azide prepared by Fig. 6 embodiment of the present invention 2；
The XRD characterization figure of nanoporous copper oxide prepared by Fig. 7 embodiment of the present invention 3；
The SEM phenogram of high-density copper azide prepared by Fig. 8 embodiment of the present invention 3；
The structural schematic diagram of miniature initiator prepared by Fig. 9 embodiment of the present invention 4；
The structural schematic diagram of miniature initiator prepared by Figure 10 embodiment of the present invention 6；
Miniature propagation of explosion prepared by Figure 11 embodiment of the present invention 7 passes fiery sequential structure schematic diagram；
Miniature propagation of explosion prepared by Figure 12 embodiment of the present invention 11 passes fiery sequential structure schematic diagram；
Figure 13 present invention is used for the fabricated in situ chemical reaction process of the azide containing high-density copper with constraint shell
Schematic diagram；
Specific embodiment
The invention will be further described with embodiment with reference to the accompanying drawing.
Embodiment 1: there is the preparation of the azide containing high-density copper of constraint shell
It takes oxalic acid 2g and copper nitrate 1g grinding 60min to be placed in tube furnace to be warming up to 550 DEG C under nitrogen protection and protect
Warm 150min obtains nano porous copper after cooling.Fig. 1 is the SEM phenogram of nano porous copper prepared by the present embodiment, by Fig. 1
It can be seen that nano porous copper particle is uniform, partial size has a large amount of holes in 100nm or so, and Fig. 2 is nanometer prepared by the present embodiment
The standard spectrogram (JCPDS No.04-0836) of the XRD characterization figure of Porous Cu, XRD spectra and copper exactly matches, no any impurity
Peak shows that end product is fine copper.
Nano porous copper is transferred to a thickness of 0.4mm, through-hole diameter is to constrain and receive in shell in the constraint shell of 0.8mm
The density of rice Porous Cu is about 1.2g/cm3.This constraint shell is integrally placed in reactor and carries out gas-solid original with nitrine acid gas
Position chemical reaction 12h, the density for constraining the copper azide in shell after reaction is about 2.2g/cm3, this single constraint shell
The explosive payload of internal copper azide is about 0.44mg.Fig. 3 is the high-density copper prepared by the present embodiment in constraint shell
The SEM phenogram of azide, copper azide particle close-packed arrays, hole are small as shown in Figure 4；Fig. 4 is that the present embodiment is made
Copper azide XRD diffracting spectrum, the peak in spectrogram positioned at 11.76 °, 27.95 ° and 31.94 ° respectively corresponds Cu (N3)2
(110), (230) and (021) crystal face three strongest peak, show main component of the nano porous copper after azido reaction 12 hours
For Cu (N3)2.Fig. 5 is the structural schematic diagram prepared by the present embodiment with the high-density copper azide of constraint shell.
Embodiment 2: there is the preparation of the azide containing high-density copper of constraint shell
Take oxalic acid 1g and copper nitrate 0.5g to be dissolved in 10mL dehydrated alcohol respectively, by after two kinds of solution mixing 30min with from
The heart is filtered to remove solvent, is directly warming up to after solid is dried or under nitrogen protection 450 DEG C and keeps the temperature 120min, after cooling
Obtain nano porous copper；
Nano porous copper is transferred to a thickness of 0.4mm, through-hole diameter is to constrain and receive in shell in the constraint shell of 0.8mm
The density of rice Porous Cu is about 1.5g/cm3。
Nano porous copper with constraint shell is integrally placed in reactor and carries out gas-solid original positionization with nitrine acid gas
Learn reaction for 24 hours.The loading density with constraint shell that obtains after reaction is about 2.3g/cm3High-density copper azide, this
The quality of copper azide in single constraint shell is about 0.46mg.
Fig. 6 is the SEM phenogram of high-density copper azide prepared by the present embodiment, as shown in Figure 6 copper azide
Close-packed arrays, hole obviously become smaller.
Embodiment 3: there is the preparation of the azide containing high-density copper of constraint shell
Oxalic acid 2g and copper nitrate 1g is taken to be dissolved in 10mL anhydrous methanol respectively, slow solvent evaporated after two kinds of solution mixing,
Collection solids, which is placed in tube furnace, to be warming up to 350 DEG C in air conditions and keeps the temperature 100min, obtains nanoporous oxygen after cooling
Change copper, Fig. 7 is the XRD spectrum phenogram of nanoporous copper oxide prepared by the present embodiment, be located in spectrogram 35.46 °,
38.64 ° and 48.70 ° of peak corresponds respectively to (11-1), (111) and (20-2) crystal face of CuO, the peak in all spectrograms with
Peak position exact matching in CuO standard card (JCPDS No.48-1548), the not appearance of impurity peaks show cupric oxalate solid-state
Powder is sintered available pure CuO in air.Nanoporous copper oxide is transferred to a thickness of 0.4mm, diameter is
In the constraint shell of 0.8mm, the density for constraining nano porous copper in shell is about 1.6g/cm3.It is placed in reactor and nitrine
Acid gas carries out gas-solid in-situ chemical reaction 48h.Obtaining after reaction is 2.1g/cm with the loading density of constraint shell3's
High-density copper azide, the quality for constraining copper azide in shell is about 0.42mg.Fig. 8 is height prepared by the present embodiment
The SEM phenogram of density copper azide, copper azide crystal grain close-packed arrays, porosity are low as shown in Figure 8.
Figure 13 be constrain shell in nano porous copper/nanoporous copper oxide and nitrine acid gas generation in-situ chemical it is anti-
The reaction process schematic diagram of the high-density copper azide with constraint shell should be generated.
Embodiment 4: the preparation of miniature initiator
By the substrate for having Ni-Cr bridge, the high-density copper azide with constraint shell prepared by embodiment 1,25 μ
The miniature initiator of copper azide is made with a thickness of 660 μm of acceleration thorax laminated structure in m titanium film flying, fiberglass sheet material.
Fig. 9 is miniature initiator structural schematic diagram prepared by the present embodiment.The miniature initiator is in the base with initiating bridge
Successively close superposition has the copper azide of constraint shell, film flying, accelerates thorax composition on plate.
Embodiment 5: the preparation of miniature initiator
There is the azide containing high-density copper for constraining shell by the substrate for having Ni-Cr bridge, by prepared by embodiment 3,
Micro- powder charge initiator is made by 660 μm of acceleration thorax laminated structure prepared by fiberglass sheet material in 10 μm of titanium film flyings.
Embodiment 6: the preparation of miniature initiator
By the substrate with Ni-Cr bridge and the azide containing high-density copper with constraint shell prepared by embodiment 2
Miniature initiator is made in superposition.
Figure 10 is miniature initiator structural schematic diagram prepared by the present embodiment.The miniature initiator is in the base with initiating bridge
Successively close superposition has the high-density copper azide composition of constraint shell on plate.
Embodiment 7: the application (miniature Explosive sequence) of high-density copper azide
Add HNS-IV transmitting powder charge that can form miniature Explosive sequence by miniature initiator prepared by the present embodiment 4, uses
3V battery is powered to the initiating bridge of the miniature initiator, which successfully detonates HNS-IV explosive.
Figure 11 is miniature Explosive sequence structural schematic diagram prepared by the present embodiment.The miniature Explosive sequence is in band initiating bridge
Substrate on successively close superposition there is azide containing high-density copper, film flying, acceleration thorax and explosive or the igniting of constraint shell
Medicine composition.
Embodiment 8:
The application (miniature Explosive sequence) of high-density copper azide
Preparing miniature initiator by the present embodiment 5 adds PETN transmitting powder charge that can form miniature Explosive sequence, straight using 1A
Galvanic electricity source is powered to the initiating bridge of the miniature initiator, which successfully detonates PETN explosive.
Embodiment 9:
The application (miniature biography fire sequence) of high-density copper azide
B/KNO is added by miniature initiator prepared by the present embodiment 43Transmitting ignition charge can form miniature biography fire sequence, adopt
It is powered with initiating bridge of the 3V battery to the miniature initiator, the miniature biography fire sequence successful ignition B/KNO3。
Embodiment 10:
The application (miniature Explosive sequence) of high-density copper azide
Add CL-20 transmitting powder charge that can form miniature Explosive sequence by miniature initiator prepared by the present embodiment 5, uses
15V voltage, the capacitor of 1mF are powered to the initiating bridge of the miniature initiator, which successfully detonates CL-20 explosive.
Embodiment 11:
The application (miniature Explosive sequence) of high-density copper azide
Preparing miniature initiator by the present embodiment 6 adds HNS-IV transmitting powder charge that can form miniature Explosive sequence, using 3V
Battery is powered to the initiating bridge of the miniature initiator, which successfully detonates HNS-IV explosive.
Figure 12 is micro- powder charge Explosive sequence structural schematic diagram prepared by the present embodiment.Micro- powder charge Explosive sequence is in band
Successively close superposition has the high-density copper azide for constraining shell and explosive or ignition charge composition on the substrate of initiating bridge.
Embodiment 12:
The application (miniature biography fire sequence) of high-density copper azide
B/KNO is added by miniature initiator prepared by the present embodiment 63Transmitting powder charge can form miniature biography fire sequence, use
3V battery is powered to the initiating bridge of the miniature initiator, the miniature biography fire sequence successful ignition B/KNO3。
Above-described specific descriptions have carried out further specifically the purpose of invention, technical scheme and beneficial effects
It is bright, it should be understood that the above is only a specific embodiment of the present invention, the protection model being not intended to limit the present invention
It encloses, all within the spirits and principles of the present invention, any modification, equivalent substitution, improvement and etc. done should be included in the present invention
Protection scope within.
Claims (14)
1. a kind of preparation method of the high-density copper azide with constraint shell, it is characterised in that: specific step is as follows:
Step 1: preparing organic copper salt nano microcrystalline presoma；
Step 2: using organic copper salt nano microcrystalline precursor preparation nano porous copper made from step 1；
Step 3: having the high-density copper azide of constraint shell using the preparation of nano porous copper made from step 2；
Nano porous copper made from step 2 is loaded in constraint shell, is then integrally placed in reactor and nitrine acid gas
Gas-solid in-situ chemical reaction is carried out, is taken out after fully reacting, the high-density copper azide with constraint shell is obtained.
2. a kind of preparation method of the high-density copper azide with constraint shell, it is characterised in that: specific step is as follows:
Step 1: preparing organic copper salt nano microcrystalline presoma；
Step 2: using organic copper salt nano microcrystalline precursor preparation nanoporous copper oxide made from step 1；
Step 3: having the high-density copper azide of constraint shell using the preparation of nanoporous copper oxide made from step 2；
Nanoporous copper oxide made from step 2 is loaded in constraint shell, is then integrally placed in reactor and hydrazoic acid
Gas carries out gas-solid in-situ chemical reaction, takes out after fully reacting, obtains the high-density copper azide with constraint shell.
3. nano porous copper/copper oxide as claimed in claim 1 or 2 the preparation method comprises the following steps: using organic copper salt, soluble copper
Salt and organic acid or organic reactant salt are prepared with machine mantoquita nano microcrystalline, obtain nano porous copper/copper oxide through high-temperature calcination.
4. a kind of preparation method of high-density copper azide with constraint shell as claimed in claim 1 or 2, feature
Be: type of feed described in step 3 is to be loaded using external pressure mode；Constraint shell described in step 3 is with through-hole
Plate (sheet) structure.
5. the application for the high-density copper azide that method as claimed in claim 1 or 2 is prepared, it is characterised in that: for making
Standby miniature initiator；
The miniature initiator is made of the copper azide of substrate, belt restraining shell with initiating bridge；
The miniature initiator is by the copper azide of substrate, belt restraining shell with initiating bridge, film flying and thorax is accelerated to form.
6. the application for the high-density copper azide that method as claimed in claim 1 or 2 is prepared, it is characterised in that: for making
Standby miniature Explosive sequence or miniature biography fire sequence；
The miniature Explosive sequence by substrate, belt restraining shell with initiating bridge high-density copper azide and explosive group
At；
The miniature Explosive sequence is by substrate, the high-density copper azide of belt restraining shell, film flying, acceleration with initiating bridge
Thorax and explosive composition；
The miniature biography fire sequence by substrate, belt restraining shell with initiating bridge high-density copper azide and ignition charge
Composition；
The miniature Explosive sequence is by substrate, the high-density copper azide of belt restraining shell, film flying, acceleration with initiating bridge
Thorax and ignition charge composition.
7. a kind of preparation method of high-density copper azide with constraint shell as claimed in claim 1 or 2, feature
Be: organic copper salt nano microcrystalline presoma described in step 1 the preparation method comprises the following steps: 1) with solid organic acid and solid mantoquita
It is made nanometer organic copper salt microcrystalline solids powder after mixed grinding, the molar ratio of the solid organic acid and solid mantoquita is 1~
6:1；2) precipitation reaction is occurred in a solvent with organic acid or soluble organic acid salt and mantoquita, collects precipitating and drying and crushing can
With obtained organic copper salt nanocrystalline solid powder, the molar ratio of the organic acid/acylate and mantoquita is 1~6:1；It is described
The molar ratio of organic acid/acylate and mantoquita is 1~6:1.
8. a kind of preparation method of high-density copper azide with constraint shell as described in claim 1, feature exist
In: nano porous copper described in step 2 the preparation method comprises the following steps: by organic copper salt nano microcrystalline obtained by step 1 in inertia
Nano porous copper can be made through high-temperature calcination and held for some time under gas shield or vacuum condition.
9. a kind of preparation method of high-density copper azide with constraint shell as claimed in claim 2, feature exist
In: nanoporous copper oxide described in step 2 the preparation method comprises the following steps: organic copper salt nano microcrystalline obtained by step 1 is existed
Air has nanoporous copper oxide can be made through high-temperature calcination and held for some time under conditions of oxygen.
10. a kind of preparation method of high-density copper azide with constraint shell as claimed in claim 1 or 2, special
Sign is: type of feed described in step 3 is that nano porous copper/copper oxide is transferred to the through-hole of constraint shell by the mode of external pressure
It is interior；
Constraint shell described in step 3 is the slab construction with through-hole；
Pressure >=0.01MPa of the external pressure, the nano porous copper/copper oxide constraint the intracorporal loading density of shell be >=
0.60g/cm3；
Azido reaction time described in step 3 is 3min~72 hour, and the temperature of azido reaction is 20~150 DEG C；
Thickness >=0.1mm of constraint shell plate described in step 3 with through-hole, through-hole diameter >=0.3mm；
High-temperature calcination temperature described in step 3 is 280~700 DEG C, and soaking time is 10~180min；
The constraint case material with through-hole of preparatory pore-forming described in step 3 is stainless steel, titanium, ceramics, silicon, epoxy resin, gathers
Acid imide plate or glass fiber material plate；
The generation of nitrine acid gas described in step 3 reacts generation with the heating of higher boiling acid by sodium azide solid；
The inert gas that azido reaction process is passed through described in step 3 is nitrogen or argon gas；The volume ratio of oxygen and inert gas
For 1~10:100；
The molar ratio of sodium azide solid described in step 3 and higher boiling acid is 1:3~20；It is obtained in constraint shell
The loading density of copper azide can be up to 1.4~3.0g/cm3；
11. application as claimed in claim 5, it is characterised in that: the baseplate material with initiating bridge is to be welded with nickel-chrome bridge
Silk or sputtering are containing nickel-chrome, the glass mat of nickel-aluminum metal bridge film, ceramics, epoxy resin, glass and the metal for having insulating layer
Hard plate material.
12. application as claimed in claim 6, it is characterised in that: the size of the explosive is diameter >=0.5mm；The explosive
For HNS-IV, CL-20, PETN and RDX, the loading density of explosive is the 75%-92% of theoretical density；The ignition charge is B/
KNO3Ignition charge；The acceleration thorax length >=0.3mm；Acceleration thorax material is glass mat, ceramics, metal, glass, asphalt mixtures modified by epoxy resin
Rouge and hard plastic board.
13. method as claimed in claim 10, it is characterised in that: the titanium film flying is with a thickness of 5~50 μm；The higher boiling acid
It include: stearic acid, the concentrated sulfuric acid, concentrated phosphoric acid or the concentrated sulfuric acid and concentrated phosphoric acid mixed acid.
14. a kind of preparation method of high-density copper azide with constraint shell as claimed in claim 1 or 2, special
Sign is: the HNS-IV that can successfully detonate when dose >=0.4mg of the single constraint intracorporal high-density copper azide of shell,
The explosives such as CL-20, PETN and RDX light B/KNO3Equal ignition charges.
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| 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 |
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