CN109824462A - A kind of nanometer of high activity reaction material and its low temperature preparation method - Google Patents
A kind of nanometer of high activity reaction material and its low temperature preparation method Download PDFInfo
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- CN109824462A CN109824462A CN201910046119.5A CN201910046119A CN109824462A CN 109824462 A CN109824462 A CN 109824462A CN 201910046119 A CN201910046119 A CN 201910046119A CN 109824462 A CN109824462 A CN 109824462A
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Abstract
The present invention relates to a kind of nanometer of high activity reaction material and its low temperature preparation method, the high reaction material living of this nanometer is suitable as the active fragmentation of weapon warhead, belongs to a nanometer high activity reaction material preparation technical field.It is mixed by nano metal filler, nano-oxide and high fluoropolymer, compared with the reaction material of micro-sized metal filler, the threshold of reaction of nanoscale reaction material substantially reduces, reactivity greatly enhances, and dispersion is more uniform, low temperature processing techniques make processing temperature be substantially less than its hot self-ignition point, solve the problems, such as the process safety of conventional sintering method.
Description
Technical field
The present invention relates to a kind of nanometer of high activity reaction material and its low temperature preparation method, this nanometer of high activity reaction materials
Suitable for the active fragmentation of weapon warhead, belong to a nanometer high activity reaction material preparation technical field.
Background technique
Member killing target is injured using metal, is the basic fundamental theory that ammunition warhead design is routinely injured in active service.By
Member is injured in metal to injure target implementation with kinetic energy penetration mechanism and the mechanical mode that runs through, and largely constrains warhead
The performance and raising of power.To improve warhead power efficiency, reaction material injures member in recent years and its warhead technology obtains
Development.Reaction material injure member distinguishing feature and it is a technical advantage that: firstly, it be one kind by being filled in high polymer
The powder containing energy such as metal, alloy and intermetallic compound, then be prepared through special process, it is compound with good mechanical strength
Formula solid energetic material injures member；Secondly, when this activity is containing that can injure member with certain speed impacts target, due to by strong
The effect of shock loading can concurrently give birth to detonation reaction from line activating, release a large amount of chemical energy, thus in kinetic energy penetration and interior
Under the synergy of two kinds of destruction mechanisms of quick-fried effect, realizes to the Structure Damage of target efficient, obtain the damage effects of warhead
It must increase substantially.Since high activity reaction material has good mechanical property and formability, controlled fragment can be made into,
Under conditions of explosive driving, the active fragmentation of large area distribution is formed, and then causes kinetic energy penetration and detonation dual target
It injures.
Known reaction material includes aluminium and polytetrafluoroethylene (PTFE) (" PTFE "), i.e. " Al/PTFE " reaction material.PTFE due to
With high fluorine content, so acting also as strong oxidizer.The melting temperature of PTFE is 342 DEG C, so preparation PTFE base reaction material
Required temperature is higher than 350 DEG C, therefore the sintering temperature of Al/PTFE reaction material is usually 350-390 DEG C.It is currently by PTFE
It mixes with aluminium, and dries in an oven in a solvent, then suppress dry composition in 185 DEG C of mold, finally will
The prefabricated rods of compacting are heated to 350-390 DEG C and are sintered, then with the prefabricated component of the cooling sintering of the rate of setting, so that crack
It minimizes and maximizes mechanical performance.
Take condition processing Ta/PTFE and W/PTFE reaction material identical with Al/PTFE.Ta/PTFE reaction material is burnt
Junction temperature is only second to 375 DEG C of exothermic temperature, and violent exothermic reaction makes Ta/PTFE reaction material in 307 DEG C of sintering
Hypergolic reaction occurs.Ta/PTFE and W/PTFE reaction material produces high volatile reaction product during the sintering process --- trace
It measures hydrofluoric acid (" HF ")；W/PTFE reaction material forms high volatile fluorination tungsten compound (such as WF in process6With
WOF4), Ta/PTFE produces the tantalum fluoride with high volatile.This method not only makes compacting prefabricated component seriously crack, but also acute
Strong exothermic reaction has seriously threatened the safety that Ta/PTFE reaction material is processed under high temperature.
Summary of the invention
The purpose of the invention is to overcome the deficiencies in the prior art, a kind of nanometer of high activity reaction material and its low is proposed
Warm preparation method.
The technical solution of the present invention is as follows:
A kind of nanometer of high activity reaction material, this nanometer of high activity reaction material include nano metal filler and the polymerization of high fluorine
Object is 100 parts of calculating with the gross mass of this nanometer of high activity reaction material, and the mass content of nano metal filler is 50-70 parts,
The mass content of high fluoropolymer is 30-50 parts；
This nanometer of high activity reaction material can also include nano-oxide, with total matter of this nanometer of high activity reaction material
Amount is 100 parts of calculating, and the mass content of nano metal filler is 45-51 parts, and the mass content of high fluoropolymer is 20-27 parts,
The mass content of nano-oxide is 23-34 parts；
The nano metal filler is one of Mg, Al, Fe, Cu, Zn, Ta, Ti, Zr or Mo；Nano metal filler
To be powdered, particle size range 10-100nm；
The high fluoropolymer is one or more of THV 220, THV X 310, THV 415, THV 500
Mixture；High fluoropolymer is powdered；
The nano-oxide is one of bismuth oxide, silica or titanium oxide, and nano-oxide is powdered, grain
Diameter range is 10-100nm.
The step of preparation method of a kind of nanometer of high activity reaction material, this method includes:
(1) nano metal filler is prepared；
(2) in vacuum glove box, the nano metal filler that step (1) is prepared is dispersed in the anhydrous second of organic carrier liquid
In alcohol, in-stiu coating is then carried out to nano metal filler using organic surface modification agent, and stood, had during standing
Airborne liquid volatilization obtains mixture A after organic carrier liquid volatilization；
(3) high fluoropolymer is dispersed in acetone, obtains mixture B；
(4) the mixture A that step (2) obtains and the mixture B that step (3) obtains are mixed, stands curing molding
Obtain precast body；
(5) precast body for obtaining step (4) carries out low temperature injection molding, obtains a nanometer high activity reaction material.
In the step (1), the method for preparing nano metal filler are as follows: use aumospheric pressure cvd method or vacuum
Arc melting method prepares nano metal filler；
When wherein, using aumospheric pressure cvd method, H2Concentration is at 10 times of required stoichiometric ratio or more, depositing temperature
1000 DEG C or more, carrier gas flux H22-5 times of flow obtains the particle of 10-100nm；
When using vacuum arc melting method, discharge under conditions of electrical current 100-120A, voltage 15-30V, discharge process
Continue 15-40min, is passed through inert gas and the pressure of reaction chamber is made to reach 30-45MPa, obtain the particle of 10-100nm scale；
In the step (2), organic surface modification agent is high molecular type surfactant, including but not limited to polyethylene
One of pyrrolidones or Sodium Polyacrylate；
In the step (5), in low temperature injection moulding process, precast body is placed into die head, heats die head to precast body
It heating up, die head temperature is 180-200 DEG C, it then pressurizes to precast body, precast body is molded into mold, mold temperature
Degree is 80-160 DEG C；
When the mass content of high fluoropolymer is 30 parts, die head temperature preferably 200, works as height by preferably 160 DEG C of mold temperature
When the mass content of fluoropolymer is 40 parts, preferably 190 DEG C of die head temperature, preferably 120 DEG C of mold temperature, when high fluoropolymer
When mass content is 50 parts, preferably 180 DEG C of die head temperature, preferably 80 DEG C of mold temperature.
The step of preparation method of a kind of nanometer of high activity reaction material, this method includes:
(1) nano metal filler is prepared；
(2) in vacuum glove box, nano metal filler and nano-oxide that step (1) is prepared have been dispersed in
In airborne liquid dehydrated alcohol, packet in situ is then carried out to nano metal filler and nano-oxide using organic surface modification agent
It covers, obtains mixture C；
(3) high fluoropolymer is mixed with the mixture C that step (2) obtains, and is carried out using double screw extruder
Extrusion molding obtains precast body；
(4) precast body for obtaining step (3) carries out low temperature injection molding, obtains a nanometer high activity reaction material.
In the step (1), the method for preparing nano metal filler are as follows: use aumospheric pressure cvd method or vacuum
Arc melting method prepares nano metal filler；
When wherein, using aumospheric pressure cvd method, H2Concentration is at 10 times of required stoichiometric ratio or more, depositing temperature
1000 DEG C or more, carrier gas flux H22-5 times of flow obtains the particle of 10-100nm；
When using vacuum arc melting method, discharge under conditions of electrical current 100-120A, voltage 15-30V, discharge process
Continue 15-40min, is passed through inert gas and the pressure of reaction chamber is made to reach 30-45MPa, obtain the particle of 10-100nm scale；
In the step (2), organic surface modification agent is high molecular type surfactant, including but not limited to polyethylene
One of pyrrolidones or Sodium Polyacrylate；
In the step (4), in low temperature injection moulding process, precast body is placed into die head, heats die head to precast body
It heating up, die head temperature is 200-230 DEG C, it then pressurizes to precast body, precast body is molded into mold, mold temperature
Degree is 160-220 DEG C；
When the mass content of high fluoropolymer is 20 parts, preferably 230 DEG C of die head temperature, preferably 220 DEG C of mold temperature, when
When the mass content of high fluoropolymer is 24 parts, preferably 215 DEG C of die head temperature, preferably 190 DEG C of mold temperature, when high fluoropolymer
Mass content be 27 parts when, preferably 160 DEG C of die head temperature, preferably 160 DEG C of mold temperature.
Beneficial effect
It is mixed by nano metal filler, nano-oxide and high fluoropolymer, it is anti-with micro-sized metal filler
Material is answered to compare, the threshold of reaction of nanoscale reaction material substantially reduces, and reactivity greatly enhances, and dispersion is more uniform,
Low temperature processing techniques make processing temperature be substantially less than its hot self-ignition point, solve the problems, such as the process safety of conventional sintering method.
Specific embodiment
The present invention prepares nano metal particles using vacuum arc melting method and aumospheric pressure cvd method, then true
In empty-handed casing, in-stiu coating is carried out to it using organic surface modification agent in anhydrous conditions, and its is evenly dispersed to having
It in airborne liquid, is uniformly mixed with the diluted high fluoropolymer of organic solution, using twin-screw extrusion technology by nano active metal
Particle, high fluoropolymer and nano-metal-oxide are uniformly mixed and pre-formed, and a nanometer high activity reaction wood is obtained
Expect precast body, a nanometer high activity reaction material is finally obtained by low temperature injection molding technology in injection molding machine.Below with reference to specific
The present invention is described in detail for embodiment.Following embodiment will be helpful to those skilled in the art and further understand this hair
It is bright, but the invention is not limited in any way.
Embodiment 1
A kind of nanometer of high activity reaction material, this nanometer of high activity reaction material include nano metal filler and the polymerization of high fluorine
Object is 100 parts of calculating with the gross mass of this nanometer of high activity reaction material, and the mass content of nano metal filler is 70 parts, high
The mass content of fluoropolymer is 30 parts；
The nano metal filler is Ta, and nano metal filler is powdered, average particle size range 100nm；
The high fluoropolymer is THV 220, and high fluoropolymer is powdered.
The step of preparation method of a kind of nanometer of high activity reaction material, this method includes:
(1) nano metal filler Ta is prepared；
(2) in vacuum glove box, the nano-tantalum filler that step (1) is prepared is dispersed in the anhydrous second of organic carrier liquid
In alcohol, in-stiu coating is then carried out to nano-tantalum filler using organic surface modification agent, obtains mixture D；
(3) THV 220 is dispersed in dispersing agent, dispersing agent is acetone, obtains mixture E；
(4) mixture D that step (2) obtains and the mixture E that step (3) obtains are mixed, stand curing molding,
Dehydrated alcohol and acetone volatilization obtain precast body after dehydrated alcohol and acetone volatilize during standing；Dwell temperature is
40 DEG C, at this temperature, carrier fluid loss rate is low, and precast body will not crack；
(5) precast body for obtaining step (4) carries out low temperature injection molding, obtains a nanometer high activity reaction material.
In the step (1), the method for preparing nano-tantalum filler are as follows: use aumospheric pressure cvd method or vacuum
Arc melting method；
When wherein, using aumospheric pressure cvd method, H2Concentration is in 10 times of required stoichiometric ratio, depositing temperature 1100
DEG C or more, carrier gas flux H22 times of flow, obtain the particle of 100nm；
In the step (2), organic surface modification agent is polyvinylpyrrolidone, dosage 0.35g；
In the step (5), in low temperature injection moulding process, precast body is placed into die head, heats die head to precast body
It heats up, die head temperature is 200 DEG C, then pressurizes to precast body, precast body is molded into mold, mold temperature is
160℃。
Embodiment 2
A kind of nanometer of high activity reaction material, this nanometer of high activity reaction material includes nano metal filler, nano oxidized
Object and high fluoropolymer, are 100 parts of calculating with the gross mass of this nanometer of high activity reaction material, and the quality of nano metal filler contains
Amount is 44 parts, and the mass content of nano-oxide is 36 parts, and the mass content of high fluoropolymer is 20 parts；
The nano metal filler is Ta, and nano metal filler is powdered, average particle size range 100nm；
The nano-oxide is bismuth oxide, and nano-oxide is powdered, average particle size range 100nm；
The high fluoropolymer is THV 220, and high fluoropolymer is powdered.
(1) nano metal filler is prepared；
(2) in vacuum glove box, nano metal filler and nano-oxide that step (1) is prepared have been dispersed in
In airborne liquid dehydrated alcohol, packet in situ is then carried out to nano metal filler and nano-oxide using organic surface modification agent
It covers, obtains mixture F；
(3) high fluoropolymer is mixed with the mixture F that step (2) obtains, and is carried out using double screw extruder
Extrusion molding obtains precast body；
(4) precast body for obtaining step (3) carries out low temperature injection molding, obtains a nanometer high activity reaction material.
In the step (1), the method for preparing nano metal filler are as follows: use aumospheric pressure cvd method or vacuum
Arc melting method prepares nano-tantalum filler；
When wherein, using vacuum arc melting method, discharges, put under conditions of electrical current 100-120A, voltage 15-30V
Electric process continues 15-40min, is passed through inert gas and the pressure of reaction chamber is made to reach 30-45MPa, obtain the tantalum of 100nm scale
Powder；
In the step (2), organic surface modification agent is polyvinylpyrrolidone, quality 4g；
In the step (4), in low temperature injection moulding process, precast body is placed into die head, heats die head to precast body
It heats up, die head temperature is 230 DEG C, then pressurizes to precast body, precast body is molded into mold, mold temperature is
220℃；
In conclusion the present invention greatly reduces processing peace relevant to high activity reacting metal and fluoropolymer reaction material
Full problem.Compared with processing temperature needed for PTFE reaction material and pressure, processing temperature needed for the reaction material in the present invention
Degree and pressure have apparent reduction；Sintering step needed for eliminating processing PTFE, improves the efficiency of processing, when having saved
Between；In addition, using the reactivity of nanometer reaction material made from arc melting method and aumospheric pressure cvd method have compared with
It is big to improve, and increase contact area and the degree that is uniformly dispersed, improve mechanical property；Reaction material can be reused and be followed again
Ring is into New Parent, to reduce waste.
Claims (6)
1. a kind of nanometer of high activity reaction material, it is characterised in that: this nanometer of high activity reaction material includes nano metal filler
It is 100 parts of calculating, the mass content of nano metal filler with the gross mass of this nanometer of high activity reaction material with high fluoropolymer
It is 50-70 parts, the mass content of high fluoropolymer is 30-50 parts；
The nano metal filler is one of Mg, Al, Fe, Cu, Zn, Ta, Ti, Zr or Mo；
The high fluoropolymer is the mixed of one or more of THV 220, THV X 310, THV 415, THV 500
Close object.
2. a kind of nanometer of high activity reaction material according to claim 1, it is characterised in that: the nanometer high activity is anti-
Answering material further includes nano-oxide, is 100 parts of calculating, nano metal filler with the gross mass of this nanometer of high activity reaction material
Mass content be 45-51 part, the mass content of high fluoropolymer is 20-27 parts, and the mass content of nano-oxide is 23-34
Part；
The nano-oxide is one of bismuth oxide, silica or titanium oxide.
3. a kind of preparation method of nanometer high activity reaction material described in claim 1, it is characterised in that the step of this method
Include:
(1) nano metal filler is prepared；
(2) in vacuum glove box, the nano metal filler that step (1) is prepared is dispersed in organic carrier liquid dehydrated alcohol
In, in-stiu coating is then carried out to nano metal filler using organic surface modification agent, obtains mixture A；
(3) high fluoropolymer is dispersed in dispersing agent, dispersing agent is acetone, obtains mixture B；
(4) the mixture A that step (2) obtains and the mixture B that step (3) obtains are mixed, stands curing molding, stood
Organic carrier liquid and dispersing agent volatilization obtain precast body after organic carrier liquid and dispersing agent volatilize in the process；Dwell temperature is
40-50℃；
(5) precast body for obtaining step (4) carries out low temperature injection molding, obtains a nanometer high activity reaction material.
4. the preparation method of a kind of nanometer of high activity reaction material according to claim 3, it is characterised in that: the step
Suddenly in (1), the method for preparing nano metal filler are as follows: received using aumospheric pressure cvd method or vacuum arc melting method preparation
Rice metal packing；
When wherein, using aumospheric pressure cvd method, H2Concentration is at 10 times of required stoichiometric ratio or more, depositing temperature 1000
DEG C or more, carrier gas flux H22-5 times of flow obtains the particle of 10-100nm；
When using vacuum arc melting method, discharge under conditions of electrical current 100-120A, voltage 15-30V, discharge process is lasting
15-40min is passed through inert gas and the pressure of reaction chamber is made to reach 30-45MPa, obtains the particle of 10-100nm scale；
In the step (2), organic surface modification agent is high molecular type surfactant, including but not limited to polyvinyl pyrrole
One of alkanone or Sodium Polyacrylate；
In the step (5), in low temperature injection moulding process, precast body is placed into die head, heating die head carries out precast body
Heating, die head temperature are 180-200 DEG C, then pressurize to precast body, precast body is molded into mold, mold temperature is
80-160℃；
When the mass content of high fluoropolymer is 30 parts, die head temperature 200, mold temperature is 160 DEG C, when high fluoropolymer
Mass content be 40 parts when, die head temperature be 190 DEG C, mold temperature be 120 DEG C, when high fluoropolymer mass content be 50
When part, die head temperature is 180 DEG C, and mold temperature is 80 DEG C.
5. a kind of preparation method of nanometer high activity reaction material as claimed in claim 2, it is characterised in that the step of this method
Include:
(1) nano metal filler is prepared；
(2) in vacuum glove box, nano metal filler and nano-oxide that step (1) is prepared have been dispersed in airborne
In liquid dehydrated alcohol, in-stiu coating is then carried out to nano metal filler and nano-oxide using organic surface modification agent, is obtained
To mixture C；
(3) high fluoropolymer is mixed with the mixture C that step (2) obtains, and is squeezed out using double screw extruder
Molding obtains precast body；
(4) precast body for obtaining step (3) carries out low temperature injection molding, obtains a nanometer high activity reaction material.
6. the preparation method of a kind of nanometer of high activity reaction material according to claim 5, it is characterised in that: the step
Suddenly in (1), the method for preparing nano metal filler are as follows: received using aumospheric pressure cvd method or vacuum arc melting method preparation
Rice metal packing；
When wherein, using aumospheric pressure cvd method, H2Concentration is at 10 times of required stoichiometric ratio or more, depositing temperature 1000
DEG C or more, carrier gas flux H22-5 times of flow obtains the particle of 10-100nm；
When using vacuum arc melting method, discharge under conditions of electrical current 100-120A, voltage 15-30V, discharge process is lasting
15-40min is passed through inert gas and the pressure of reaction chamber is made to reach 30-45MPa, obtains the particle of 10-100nm scale；
In the step (2), organic surface modification agent is high molecular type surfactant, including but not limited to polyvinyl pyrrole
One of alkanone or Sodium Polyacrylate；
In the step (4), in low temperature injection moulding process, precast body is placed into die head, heating die head carries out precast body
Heating, die head temperature are 200-230 DEG C, then pressurize to precast body, precast body is molded into mold, mold temperature is
160-220℃；
When the mass content of high fluoropolymer is 20 parts, 230 DEG C of die head temperature, 220 DEG C of mold temperature, when high fluoropolymer
When mass content is 24 parts, 215 DEG C of die head temperature, preferably 190 DEG C of mold temperature, when the mass content of high fluoropolymer is 27 parts
When, 160 DEG C of die head temperature, 160 DEG C of mold temperature.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110903153A (en) * | 2019-12-17 | 2020-03-24 | 宜昌市恒益亚盛科技有限责任公司 | High plasticity energetic structure |
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2019
- 2019-01-18 CN CN201910046119.5A patent/CN109824462A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110903153A (en) * | 2019-12-17 | 2020-03-24 | 宜昌市恒益亚盛科技有限责任公司 | High plasticity energetic structure |
| CN110903153B (en) * | 2019-12-17 | 2024-02-06 | 胡滨 | High-plasticity energy-containing structure |
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Application publication date: 20190531 |