CN106116995B - A kind of method that aqueous suspension prepares press fitting aluminum composition modeling powder - Google Patents
A kind of method that aqueous suspension prepares press fitting aluminum composition modeling powder Download PDFInfo
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- CN106116995B CN106116995B CN201610478426.7A CN201610478426A CN106116995B CN 106116995 B CN106116995 B CN 106116995B CN 201610478426 A CN201610478426 A CN 201610478426A CN 106116995 B CN106116995 B CN 106116995B
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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
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B23/00—Compositions characterised by non-explosive or non-thermic constituents
- C06B23/009—Wetting agents, hydrophobing agents, dehydrating agents, antistatic additives, viscosity improvers, antiagglomerating agents, grinding agents and other additives for working up
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- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B45/00—Compositions or products which are defined by structure or arrangement of component of product
- C06B45/18—Compositions or products which are defined by structure or arrangement of component of product comprising a coated component
- C06B45/30—Compositions or products which are defined by structure or arrangement of component of product comprising a coated component the component base containing an inorganic explosive or an inorganic thermic component
- C06B45/32—Compositions or products which are defined by structure or arrangement of component of product comprising a coated component the component base containing an inorganic explosive or an inorganic thermic component the coating containing an organic compound
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Abstract
The invention discloses a kind of method that aqueous suspension prepares press fitting aluminum composition modeling powder.This method under the conditions of 60~70 DEG C using aqueous suspension comminution granulation by preparing press fitting aluminum composition modeling powder again after being anticipated to superfine aluminium power and explosive surface.Present invention is especially suited for prepare containing the press fitting aluminum composition modeling powder that the sensitive explosive such as CL 20 and HMX and particle diameter are 50nm~5um aluminium powders.The present invention provides the method that aqueous suspension prepares press fitting aluminum composition modeling powder, and necessary material guarantee and technical support are provided for the research and application of high energy aluminum composition.
Description
Technical field
The present invention relates to energetic material field, and in particular to a kind of preparation method for being pressed aluminum composition modeling powder.
Background technology
Press fitting aluminum composition is one kind of press fitting type polymer bonding explosive.It by high explosive, aluminium powder and other add
Add agent to be prepared into moulding powder particles with binding agent, then be process by compressing.Since press fitting aluminum composition density is high, energy
The more other type charges of amount are high, it greatly improves the acting ability of ammunition and damage effect, has in many warhead charges
Important application prospect, therefore paid high attention in recent years be subject to association area researcher.
However, the preparation of press fitting aluminum composition modeling powder is to restrict a major issue of press fitting aluminum composition development.It is logical
The modeling powder of the press fitting type polymer bonding explosive without aluminium can be granulated by water suspension method and be prepared in the case of often.But this method
It is not suitable for preparing press fitting aluminum composition modeling powder.Because aluminium powder (especially superfine aluminium power) is very easy to release hydrogen by water oxygenization
Gas and substantial amounts of heat, considerably increase the danger of operation.The aluminium powder generation aluminium hydroxide of reaction, aluminium hydroxide is not only to containing aluminium
Explosive energy output is not contributed, and can be reduced aluminium powder and be released energy efficiency in detonation reaction.For this problem, using pinching
It is a technological approaches to close extrusion molding and prepare press fitting aluminum composition modeling powder.It is i.e. that the compositions such as explosive, aluminium powder, binding agent is direct
The batch mixing in kneader, pasty mass is kneaded into again by banded extruder extrusion granulating after adding solvent.Avoided in whole process
Aluminium powder touches water.Picatinny factories of the U.S. are prepared for HMX base aluminum compositions using kneading extrusion molding, effectively solve
The problem of aluminium powder is reacted with water in prepared by press fitting aluminum composition modeling powder of having determined (Paul Anderson, et
al.Development,optimization,and application of combined effects explosives,
NDIA Insensitive Munitions&Energetic Materials Technology Symposium,2009).But
It is that it is big to mediate extrusion molding limitation itself.Many high explosive sensitivity are high, to rubbing, hitting, electrostatic etc. stimulate sensitive, mediate
Friction, shock are likely to result in explosive charge in extrusion molding operation, contain so being not suitable for press fitting of the preparation containing sensitive explosive
Al explosive modeling powder.
Another solution route for preparing the press fitting aluminum composition modeling powder containing sensitive explosive is granulated using aqueous suspension
The technological process of method.Aqueous medium is replaced using other solvents, is known as non-aqueous media suspension comminution granulation.For example, U.S. Pi Ke spits of fland
Buddhist nun factory substitutes water using a kind of medium, which does not react with aluminium powder.Ke Tingni factories are prepared for using this method
PAX-3 (HMX/CAB/plasticizer/Al), PAX-28 (RDX/DNAN/AP/Al) and PAX-30 (HMX/CAB/
) etc. plasticizer/Al press fitting aluminum composition modeling powder (Paul Anderson, et al.Development,
optimization,and application of combined effects explosives,NDIA Insensitive
Munitions&Energetic Materials Technology Symposium,2009).But this non-aqueous media is prepared and made
The problem of type powder, is of high cost, non-aqueous media recycling difficulty etc..The Liu Yong of China Engineering Physics Research Institute just waited using ethanol as
The medium of Dai Shui, is prepared for a series of press fitting aluminum composition modeling powder (Chinese invention patents using RDX, HMX as base
ZL201310181105.7).However, the method still has, deficiency includes high cost and granulation process control is difficult.
Researcher is all promoted further to develop in water the method for preparing press fitting aluminum composition modeling powder based on problem above.
US Army maneuver of tanks vehicle-weapon Research Development Engineering Center promotes researcher's cooperation research and development of company with polysulfide rubber
Novel C L-20 bases aluminum composition such as PAX-29 (15%Al, 77%CL-20,3.2%CAB, 4.8%BDNPA/F) and PAX-11
(15%Al, 79%CL-20,2.4%CAB, 3.6%BDNPA/F) modeling powder is prepared using aqueous suspension.It was granulated in order to prevent
Aluminium powder is reacted with water in journey, selects the larger aluminium powder of particle diameter, and modeling powder preparation is carried out under the conditions of 30 DEG C.Existing for this method
Problem is that temperature is too low, and the solvent in granulation process in binder solution is not volatile, causes the composition pole of explosive and aluminium powder
Difficulty is agglomerated into grain, disperses and forms moulding powder particles.
In conclusion the serious application for restricting high energy aluminum composition of the deficiency of press fitting aluminum composition moulding powder, preparation method thereof.
Therefore there is an urgent need for develop the preparation method of new press fitting aluminum composition modeling powder.
The content of the invention
[technical problems to be solved]
Present invention aim to address above-mentioned prior art problem, there is provided a kind of aqueous suspension prepares press fitting aluminum composition moulding
The method of powder.This method is adapted to the preparation for the high energy aluminum composition modeling powder that explosive sensitivity is high, is unsuitable for kneading method prepares, and is
The research and application of high energy aluminum composition provide necessary material guarantee and technical support.
[technical solution]
In order to reach above-mentioned technique effect, the present invention takes following technical scheme：
A kind of method that aqueous suspension prepares press fitting aluminum composition modeling powder, it comprises the following steps：
A, the surface preparation of aluminium powder
First, it is 1g by aluminium powder and solvent quality volume ratio：The ratio of 5mL adds solvent into the aluminium powder of vacuum drying,
Stirred 30 minutes under ultrasound condition after being then heated to 80 DEG C；Then dibutyl tin laurate and first are added into mixture
Phenylene diisocyanate, the addition of the dibutyl tin laurate and toluene di-isocyanate(TDI) and the mass ratio of aluminium powder are respectively
0.5：50 and 2：50, it is heated to reflux 2h after mixing；Continuously add glycidyl azide polymer and be heated to reflux 2h, the poly- nitrine
Glycidol ether addition is 1/5th of aluminium powder quality；After being finally cooled to room temperature, filter and rinsed filter with solvent
Cake 3~5 times, up to the aluminium powder of surface preparation after vacuum drying；
The solvent can be anhydrous acetonitrile, ethyl acetate or butyl acetate.
B, the surface preparation of explosive
Explosive is added in the solvent containing coating material, ultrasound simultaneously disperse after five minutes, explosive is taken out by mechanical agitation
Filter, drying.
C, aqueous suspension comminution granulation
What the coating material that the aluminium powder of the surface preparation obtained through processing of step A and step B processing are obtained coated
Explosive is added to the water, and heating stirring is uniform；Then prepared binder solution is added dropwise, when binder solution is added drop-wise to three/
When two, after being uniformly dispersed to the suitable water of mixed solution penetrating, continue that remaining binder solution is added dropwise, be added dropwise
Suitable moisture is sprayed into after 10min to dissipate, rinse；Then filter, vacuum drying, obtain the aqueous suspension preparation press fitting and fried containing aluminium
Medicine modeling powder.
The further technical solution of the present invention, in step, the solvent is butyl acetate.
The further technical solution of the present invention, in step, the aluminium powder is ball aluminum powder, its particle size range is
0.05~50 μm.The aluminium powder of the present invention is superfine aluminium power.
The further technical solution of the present invention, preferably 0.05~5 μm of the aluminium powder particle size range.
The further technical solution of the present invention, in stepb, explosive be high sensitivity explosive, its be CL-20, HMX,
One or more compositions in RDX, LLM-105, TATB, the particle diameter of the explosive is 1~120 μm.
The further technical solution of the present invention, in stepb, the solvent containing coating material refers to polyurethane
It is dissolved in dichloroethanes and forms the solvent that concentration is 0.25~1.0wt%.
The further technical solution of the present invention, the high polymer binder are total to for vinylidene and chlorotrifluoroethylene
Polymers or polyurethane polymer binding agent.
The further technical solution of the present invention, in step C, the aluminium for the surface preparation that the step A is obtained
The explosive of coating material cladding and the mass ratio of binding agent that powder, step B are obtained are 10~30：55~90：5~10.
The further technical solution of the present invention, in step C, described being heated to be is heated to temperature as 60~70 DEG C.
The further technical solution of the present invention, in step C, the drop rate of the binder solution is 3mL/min.
It will be described in detail the present invention below.
The present invention is first surface-treated aluminium powder, and oxidation reaction, and the present invention occurs after placing aluminium powder contact water
By using not having influential solvent to be surface-treated aluminium powder to explosive property, anhydrous acetonitrile or ethyl acetate, acetic acid fourth are utilized
Ester disperses aluminium powder, considers protection and reaction effect to environment and personnel, and the present invention preferably butyl acetate disperses aluminium
Powder；Then on the isocyanate groups and aluminium powder of catalysis Toluene diisocyanate one end of dibutyl tin laurate
Hydroxyl reaction, the isocyanate groups of the toluene di-isocyanate(TDI) other end are reacted with glycidyl azide polymer again.Due to poly- folded
The hydrophobicity of nitrogen glycidol ether changes the hydrophobicity on aluminium powder surface and the mechanical property of aluminum composition.Due to the mesh of the aluminium powder
Be to prepare aluminum composition modeling powder, excessive glycidyl azide polymer can make aluminium powder conglomeration be not easy to disperse, therefore, aluminium
The content of the glycidyl azide polymer on powder surface needs appropriate control.And the present invention is in the step that aluminium powder surface is modified
The usage amount of control solvent is needed, its principle is to reduce the use of organic solvent to the greatest extent in the case where ensuring that aluminium powder effectively disperses
Amount, can not only reduce cost, also beneficial to further mass production.The present invention changes due to having carried out surface to aluminium powder first
Property, therefore carry out to select to be heated to 60~70 DEG C in the step of aqueous suspension comminution granulation prepares modeling powder, which is high energy
It is pressed an important control parameter prepared by aluminum composition modeling powder, the temperature first does not influence the same of high energy hypersensitivity explosive
When also help aqueous suspension be granulated when binder solution in solvent volatilization, so as to be conducive to the formation of explosive molding powder.
Another key technology of the present invention is the pretreatment to explosive surface.Not surface treated explosive is fried containing aluminium
Cannot effectively it be coated by binding agent in medicine modeling powder, poor mechanical property.Explosive and binding agent can be improved to explosive surface preparation
Interaction, so as to improve the mechanical property of aluminum composition.During the surface preparation of explosive, blasting explosive granules surface quilt
Minimal amount of coating material cladding (<0.05%).The coating material is polyurethane, because polyurethane has explosive surface
Stronger bonding cladding, and the sensitivity of explosive can be reduced, it is also favourable to improving security；Dissolve the solution of coating material
It is required that insoluble explosive crystal, optimal with dichloroethanes.
Ultrasound described in step A and step B of the present invention refer to power be 400~500W, vibration frequency be 15~
20kHz, the ultrasound that ultrasonic time carries out under conditions of being 10~25min.The ultrasound condition should alternative condition it is comparatively warm
With and the quick condition of mixing, preparation process is pacified while to ensure that raw material can be sufficiently mixed uniform in modeling powder preparation process
Entirely.Drying in the present invention described in step B and step C is dried at being 50~60 DEG C in temperature.
[beneficial effect]
Compared with prior art, the present invention with following beneficial effect：
The preparation method of the present invention is especially suitable for preparing containing the explosive sensitivities such as CL-20, HMX height, is unsuitable for the preparation of kneading method
High energy aluminum composition modeling powder.High energy aluminum composition modeling powder is prepared using water suspension method, prilling temperature is set in 60~
The temperature that solvent volatilizees in 70 DEG C of suitable binder solutions so that explosive and aluminium powder ensure aluminium by well-bonded cladding granulating
Powder will not aoxidize in water.The press fitting aluminum composition moulding powder particles being prepared of the present invention are uniform, and bulk density is high, powder column
Mechanical property is good, and the content of activated aluminum is high in component, and explosive energy is high
Brief description of the drawings
Fig. 1 is the photo in kind for obtaining being pressed aluminum composition modeling powder prepared by the present invention.
Embodiment
With reference to the embodiment of the present invention, the invention will be further elaborated.
Embodiment 1：
A, the surface preparation of aluminium powder
First, 250mL butyl acetates are added in 500mL three-neck flasks, add the ultra-fine aluminium of 50g vacuum dryings thereto
Powder (average grain diameter 50nm).It is heated to after 80 DEG C stirring 30 minutes under conditions of ultrasound, 0.5g February is added to three-neck flask
Dilaurylate, then adds 2.0g toluene di-isocyanate(TDI)s (TDI), flows back under the conditions of 80 DEG C.2 it is small when after add
10.0g glycidyl azide polymers, and when reflux 2 is small under the conditions of 80 DEG C after stop heating, temperature is reduced to after room temperature will production
Thing filters, and collects filter cake after rinsing filter cake 3~5 times with butyl acetate, is put into vacuum drying oven and dries.Obtain pre-treating aluminium
The glycidyl azide polymer content of powder, wherein aluminium powder surface is 2.0%.
The critical process that water suspension method prepares press fitting aluminum composition modeling powder is that explosive and aluminium powder are pre-added to water
In, binder solution is then added dropwise, the temperature of water will be set to 60~70 DEG C, and the solvent in binder solution could volatilize, from
And binding agent is coated on explosive and aluminium powder.Therefore the pretreated aluminium powder of the present embodiment is tested in the water-bath first at 70 DEG C
Stability in water, the results showed that, 60 minutes whens, only have the aluminium powder of 1.5wt.% by water oxygen.
B, the surface preparation of explosive
Explosive CL-20 is added to concentration as in dichloroethanes of the 0.5wt% containing polyurethane, ultrasound simultaneously disperse by mechanical agitation
After five minutes, filter, dry, obtain blasting explosive granules surface by very small amount (<0.05%) coating material cladding.
C, aqueous suspension comminution granulation
The aluminium powder of the surface preparation obtained through processing of step A is coated with the coating material obtained through step B processing
Explosive CL-20 be added to the water, and be heated to 60 DEG C and stir evenly；Polymeric binder (Estane) is dissolved into dichloroethanes
The solution for later use that concentration is 5.0wt% is formed in solvent；Then prepared binder solution, rate of addition 3mL/ is added dropwise
Min, in the process, when binder solution is added dropwise 2/3, explosive crystal grain and modified aluminium powder are coated by binding agent and start to reunite
Granulating, slowly sprays into distilled water so that the material dispersion of reunion, stops after being dispersed into uniform little particle with wash bottle to kettle wall is granulated
Distilled water is only added, after stirring a period of time starts that remaining binder solution is added dropwise, binder solution is added dropwise 10 minutes
Afterwards, spray into suitable distilled water flushing and be granulated kettle inner wall；Then poured into after material is filtered in pallet, and 60 in vacuum drying oven
DEG C dry 6h after i.e. obtain drying press fitting aluminum composition modeling powder product.The performance of its modeling powder is as shown in table 1.Wherein, it is described
The explosive of coating material that aluminium powder, the step B for the surface preparation that step A is obtained are obtained cladding and the mass ratio of binding agent are
10：80：10.
Embodiment 2
A, the surface preparation of aluminium powder
First, 250mL anhydrous acetonitriles are added in 500mL three-neck flasks, add the ultra-fine aluminium of 50g vacuum dryings thereto
Powder (1 μm of average grain diameter).It is heated to after 80 DEG C stirring 30 minutes under conditions of ultrasound, bis- bays of 0.5g is added to three-neck flask
Sour dibutyl tin, then adds 2.0g toluene di-isocyanate(TDI)s (TDI), flows back under the conditions of 80 DEG C.2 it is small when after add 10.0g
Glycidyl azide polymer, and when reflux 2 is small under the conditions of 80 DEG C after stop heating, temperature takes out product after being reduced to room temperature
Filter, collects filter cake after rinsing filter cake 3~5 times with anhydrous acetonitrile, is put into vacuum drying oven and dries.Pre-treating aluminium powder is obtained, its
The glycidyl azide polymer content on middle aluminium powder surface is 0.8%.
The critical process that water suspension method prepares press fitting aluminum composition modeling powder is that explosive and aluminium powder are pre-added to water
In, binder solution is then added dropwise, the temperature of water will be set to 60~70 DEG C, and the solvent in binder solution could volatilize, from
And binding agent is coated on explosive and aluminium powder.Therefore the water-bath at 70 DEG C tests the pretreated aluminium powder of the present embodiment in water
In stability, the results showed that, there is the aluminium powder of 1.5wt.% in 60 minutes whens by water oxygen.
B, the surface preparation of explosive
Explosive HMX is added to concentration as in 0.5% dichloroethanes containing polyurethane, simultaneously mechanical agitation disperses 5 points to ultrasound
Zhong Hou, filters, drying；Obtained blasting explosive granules surface by very small amount (<0.05%) coating material cladding.
C, aqueous suspension comminution granulation
The explosive HMX that the coating material that the aluminium powder of the obtained surface preparations of step A and step B are obtained coats is added
In water, and it is heated to 70 DEG C and stirs evenly；By polymeric binder (vinylidene and chlorotrifluoroethylene 1：1 copolymer) it is dissolved into
The solution for later use that concentration is 5.0wt% is formed in ethyl acetate solvent；Then prepared binder solution, rate of addition is added dropwise
For 3mL/min, in the process, when binder solution is added dropwise 2/3, explosive crystal grain and modified aluminium powder are coated and opened by binding agent
Beginning reunion granulating, slowly sprays into distilled water so that the material dispersion of reunion, is dispersed into small uniform with wash bottle to kettle wall is granulated
Stop adding distilled water after grain, after stirring a period of time start that remaining binder solution is added dropwise, binder solution is added dropwise
After ten minutes, spray into suitable distilled water flushing and be granulated kettle inner wall.Then pour into pallet after material is filtered, and dried in vacuum
The press fitting aluminum composition modeling powder product of drying is obtained in case after 60 DEG C of baking 6h, product is as shown in Figure 1, the performance of its modeling powder
As shown in table 1.The explosive and glue that the coating material that aluminium powder, the step B for the surface preparation that the step A is obtained are obtained coats
The mass ratio for tying agent is 25：70：5.
Moulding powder particles manufactured in the present embodiment are uniform, spherical in shape, bulk density 0.80g/cm3；In the modeling powder of preparation
The proportion that activated aluminum accounts for aluminium powder is 98.2%.The grain density suppressed using prepared modeling powder is 1.980g/cm3, quality
Quick-fried heat reaches 7907J/g (1.94 times of TNT equivalents).The Compressive Mechanical intensity of powder column is 16.0MPa, and compression failure strain is up to
3.3%.
Embodiment 3
A, the surface preparation of aluminium powder
First, 250mL butyl acetates are added in 500mL three-neck flasks, add the ultra-fine aluminium of 50g vacuum dryings thereto
Powder (5 μm of average grain diameter), is heated to after 80 DEG C stirring 30 minutes under conditions of ultrasound, and bis- bays of 0.5g are added to three-neck flask
Sour dibutyl tin, then adds 2.0g toluene di-isocyanate(TDI)s (TDI), flows back under the conditions of 80 DEG C.2 it is small when after add 10.0g
Glycidyl azide polymer, and when reflux 2 is small under the conditions of 80 DEG C after stop heating, temperature takes out product after being reduced to room temperature
Filter, collects filter cake after rinsing filter cake 3~5 times with butyl acetate, is put into vacuum drying oven and dries, that is, obtain pre-treating aluminium powder, its
The glycidyl azide polymer content on middle aluminium powder surface is 0.5%.
The critical process that water suspension method prepares press fitting aluminum composition modeling powder is that explosive and aluminium powder are pre-added to water
In, binder solution is then added dropwise, the temperature of water will be set to 60~70 DEG C, and the solvent in binder solution could volatilize, from
And binding agent is coated on explosive and aluminium powder.Therefore the pretreated aluminium powder of the present embodiment is tested in the water-bath first at 70 DEG C
Stability in water, the results showed that, there is the aluminium powder of 0.5wt.% in 60 minutes whens by water oxygen.
B, the surface preparation of explosive
By explosive HMX and LLM-105 (mass ratio 50：20) it is 0.25% dichloroethanes containing polyurethane to be added to concentration
In, ultrasound and mechanical agitation disperse after five minutes, explosive to be filtered, is dried, obtained blasting explosive granules surface by very small amount (<
0.05%) coating material cladding.
C, aqueous suspension comminution granulation
The coating material cladding that the aluminium powder for the surface preparation that processing of step A is obtained is obtained with step B processing is fried
Medicine is added to the water, and is heated to 70 DEG C and stirs evenly；By polymeric binder (vinylidene and chlorotrifluoroethylene 1：3 copolymers)
It is dissolved into the solution for later use for forming that concentration is 5.0wt% in ethyl acetate solvent；Then prepared binder solution is added dropwise, drips
Acceleration is 3mL/min, and in the process, when binder solution is added dropwise 2/3, explosive crystal grain and modified aluminium powder are by binding agent bag
Cover and start reunion granulating, slowly spray into distilled water to kettle wall is granulated with wash bottle so that the material dispersion of reunion, is dispersed into uniformly
Little particle after stop adding distilled water, start to be added dropwise remaining binder solution, binder solution drop after stirring a period of time
Add and finish after ten minutes, spray into suitable distilled water flushing and be granulated kettle inner wall.Then poured into after material is filtered in pallet, and
The press fitting aluminum composition modeling powder product of drying, the performance such as institute of table 1 of its modeling powder are obtained in vacuum drying oven after 60 DEG C of baking 6h
Show.
The moulding powder particles of the present embodiment are uniform, spherical in shape；The proportion that activated aluminum accounts for aluminium powder in the modeling powder of preparation is
98.5%.The explosive and bonding for the coating material cladding that aluminium powder, the step B for the surface preparation that the step A is obtained are obtained
The mass ratio of agent is 13：80：7.
Embodiment 4
A, the surface preparation of aluminium powder
First, 250mL ethyl acetate is added in 500mL three-neck flasks, adds the ultra-fine aluminium of 50g vacuum dryings thereto
Powder (5 μm of average grain diameter), is heated to after 80 DEG C stirring 30 minutes under conditions of ultrasound, and bis- bays of 0.5g are added to three-neck flask
Sour dibutyl tin, then adds 2.0g toluene di-isocyanate(TDI)s (TDI), flows back under the conditions of 80 DEG C.2 it is small when after add 10.0g
Glycidyl azide polymer, and when reflux 2 is small under the conditions of 80 DEG C after stop heating, temperature takes out product after being reduced to room temperature
Filter, with filter cake is collected after ethyl acetate rinse filter cake 3~5 times, is put into vacuum drying oven and dries, that is, obtain pre-treating aluminium powder, its
The glycidyl azide polymer content on middle aluminium powder surface is 0.5%.
The critical process that water suspension method prepares press fitting aluminum composition modeling powder is that explosive and aluminium powder are pre-added to water
In, binder solution is then added dropwise, the temperature of water will be set to 60~70 DEG C, and the solvent in binder solution could volatilize, from
And binding agent is coated on explosive and aluminium powder.Therefore the pretreated aluminium powder of the present embodiment is tested in the water-bath first at 70 DEG C
Stability in water, the results showed that, there is the aluminium powder of 0.2wt.% in 60 minutes whens by water oxygen.
B, the surface preparation of explosive
Explosive RDX and TATB are added to concentration as in 1.0% dichloroethanes containing polyurethane, ultrasound simultaneously divide by mechanical agitation
Dissipate after five minutes, filter, drying；Obtained blasting explosive granules surface by very small amount (<0.05%) coating material cladding.
C, aqueous suspension comminution granulation
The explosive that the coating material that the aluminium powder of the obtained surface preparations of step A and step B are obtained coats adds water
In, and be heated to 70 DEG C and stir evenly；By polymeric binder (vinylidene and chlorotrifluoroethylene 1：4 copolymers) it is dissolved into second
The solution for later use that concentration is 5.0wt% is formed in acetoacetic ester solvent；Then prepared binder solution is added dropwise, rate of addition is
3mL/min, in the process, when binder solution is added dropwise 2/3, explosive crystal grain and modified aluminium powder are coated and started by binding agent
Reunion granulating, slowly sprays into distilled water so that the material dispersion of reunion, is dispersed into uniform little particle with wash bottle to kettle wall is granulated
Stop adding distilled water afterwards, after stirring a period of time start that remaining binder solution is added dropwise, binder solution is added dropwise 10
After minute, spray into suitable distilled water flushing and be granulated kettle inner wall.Then poured into after material is filtered in pallet, and in vacuum drying oven
In 60 DEG C dry the press fitting aluminum composition modeling powder product that drying is obtained after 6h, the performance of its modeling powder is as shown in table 1.
The moulding powder particles of the present embodiment are uniform, spherical in shape；The proportion that activated aluminum accounts for aluminium powder in the modeling powder of preparation is
99.5%.The explosive and bonding for the coating material cladding that aluminium powder, the step B for the surface preparation that the step A is obtained are obtained
The mass ratio of agent is 12：80：8.
Comparative example 1
The present embodiment is the comparative example as embodiment 2, to illustrate that explosive is directly used in aqueous suspension without surface preparation
Method prepares the mechanical property of modeling powder.
A, aluminium powder surface preparation
First, 250mL anhydrous acetonitriles are added in 500mL three-neck flasks, add the ultra-fine aluminium of 50g vacuum dryings thereto
Powder (1 μm of average grain diameter), is heated to after 80 DEG C stirring 30 minutes under conditions of ultrasound, and bis- bays of 0.5g are added to three-neck flask
Sour dibutyl tin, then adds 2.0g toluene di-isocyanate(TDI)s (TDI), flows back under the conditions of 80 DEG C.2 it is small when after add 10.0g
Glycidyl azide polymer, and when reflux 2 is small under the conditions of 80 DEG C after stop heating, temperature takes out product after being reduced to room temperature
Filter, collects filter cake after rinsing filter cake 3~5 times with anhydrous acetonitrile, is put into vacuum drying oven and dries.Pre-treating aluminium powder is obtained, its
The glycidyl azide polymer content on middle aluminium powder surface is 0.8%.
The critical process that water suspension method prepares press fitting aluminum composition modeling powder is that explosive and aluminium powder are pre-added to water
In, binder solution is then added dropwise, the temperature of water will be set to 60~70 DEG C, and the solvent in binder solution could volatilize, from
And binding agent is coated on explosive and aluminium powder.Therefore this comparative example to be tested in 70 DEG C of water-bath pretreated first
The stability of aluminium powder in water, the results showed that, there is the aluminium powder of 1.5wt.% in 60 minutes whens by water oxygen.
B, explosive surface preparation
Explosive HMX surfaces do not pre-process in the present embodiment.
C, aqueous suspension comminution granulation
The aluminium powder of the obtained surface preparations of step A is added to the water with explosive HMX, and is heated to 70 DEG C and stirs evenly；
By polymeric binder (vinylidene and chlorotrifluoroethylene 1：1 copolymer) be dissolved into ethyl acetate solvent formed concentration be
The solution for later use of 5.0wt%；Then it is added dropwise prepared binding agent solvent, rate of addition 3mL/min, in the process, when
When binder solution is added dropwise 2/3, explosive crystal grain and modified aluminium powder are coated by binding agent and start reunion granulating, with wash bottle to granulation
Kettle wall slowly sprays into distilled water so that the material dispersion of reunion, stops adding distilled water, stirring after being dispersed into uniform little particle
Start that remaining binder solution is added dropwise after a period of time, binder solution is added dropwise after ten minutes, sprays into suitable distillation
Water, which rinses, is granulated kettle inner wall.Then pour into pallet after material is filtered, and done after 60 DEG C of baking 6h in vacuum drying oven
Dry press fitting aluminum composition modeling powder product, the aluminium powder of the surface preparation that the explosive, processing of step A obtain and binding agent
Mass ratio is 70：25：5.The performance of its modeling powder is as shown in table 1.
Moulding powder particles prepared by this comparative example are uniform, spherical in shape, bulk density 0.72g/cm3；The moulding of preparation
The proportion that activated aluminum accounts for aluminium powder in powder is 98.0%.The grain density suppressed using prepared modeling powder is 1.975g/cm3,
The Compressive Mechanical intensity of powder column is 11.0MPa, and compression failure strain is 1.8%.
As it can be seen that compared with embodiment 2, if HMX surface frees pre-process, the aluminum composition modeling powder bulk density of preparation and
The grain density of compacting is all relatively low, and the mechanical property of powder column is also greatly reduced.To explosive and aluminium powder in this explanation the method for the present invention
Surface, which all carries out pretreatment, can effectively improve the mechanical property of powder column after the bulk density for preparing modeling powder and shaping.
Comparative example 2
The present embodiment is the comparative example as embodiment 2, to illustrate that aluminium powder cannot be used directly for water without surface preparation
Suspension method prepares modeling powder.
Aluminium powder average grain diameter is 1 μm in the present embodiment.The processing of surface free glycidyl azide polymer.
The critical process that water suspension method prepares press fitting aluminum composition modeling powder is that explosive and aluminium powder are pre-added to water
In, binder solution is then added dropwise, the temperature of water will be set to 60~70 DEG C, and the solvent in binder solution could volatilize, from
And binding agent is coated on explosive and aluminium powder.Therefore the water-bath test first at 70 DEG C pre-processes the stabilization of aluminium powder in water
Property, the results showed that, there is the aluminium powder of 46.6wt.% in 60 minutes whens by water oxygen.In the process, substantial amounts of hydrogen releases.Cause
This, it is contemplated that the low-activity of security and untreated aluminium powder, the aluminium powder cannot be used directly for water suspension method and prepare explosive molding powder.
The performance of press fitting aluminum composition modeling powder prepared by above-described embodiment 1~4 and comparative example 1 is as shown in table 1：
The performance of press fitting aluminum composition modeling powder prepared by 1 embodiment 1~4 of table and comparative example 1
It can be seen from the above that it is uniform-spherical using press fitting aluminum composition modeling powder its particle that the present invention is prepared.Utilize
Effective activity of aluminium powder is more than 98% in the modeling powder that the preparation method of the present invention is prepared, the energy of explosive detonation generation
It is high.And aluminum composition modeling powder bulk density height is prepared by the method for the present invention, compacting powder column mechanical property is excellent.The present invention
Necessary material guarantee and technical support are provided for the research and application of high energy aluminum composition.
Although reference be made herein to invention has been described for explanatory embodiment of the invention, and above-described embodiment is only this hair
Bright preferable embodiment, embodiments of the present invention are simultaneously not restricted to the described embodiments, it should be appreciated that people in the art
Member can be designed that a lot of other modifications and embodiment, these modifications and embodiment will fall in principle disclosed by the invention
Within scope and spirit.
Claims (6)
1. a kind of method that aqueous suspension prepares press fitting aluminum composition modeling powder, it is characterised in that it comprises the following steps：
A, the surface preparation of aluminium powder
First, it is 1g by the mass volume ratio of aluminium powder and solvent：The ratio of 5mL adds solvent into the aluminium powder of vacuum drying, so
After be heated to 80 DEG C after stirred 30 minutes under ultrasound condition；Then dibutyl tin laurate and toluene are added into mixture
Diisocyanate, the addition of the dibutyl tin laurate and toluene di-isocyanate(TDI) and the mass ratio of aluminium powder are respectively
0.5：50 and 2：50, it is heated to reflux 2h after mixing；Continuously add glycidyl azide polymer and be heated to reflux 2h, the poly- nitrine
The addition of glycidol ether is 1/5th of aluminium powder quality；After being finally cooled to room temperature, filter and with solvent washing filter cake 3
~5 times, up to the aluminium powder of surface preparation after vacuum drying；
The solvent is butyl acetate；
B, the surface preparation of explosive
Explosive is added to concentration as in dichloroethanes of the 0.25wt%~1.0wt% containing polyurethane, ultrasound simultaneously divide by mechanical agitation
Dissipate after five minutes, filter, drying, obtain the explosive of coating material cladding, polyurethane content on explosive<0.05%；
C, aqueous suspension comminution granulation
The explosive that the aluminium powder of the obtained surface preparations of step A is coated with the obtained coating materials of step B is added to the water, is added
Hot to 60~70 DEG C stir evenly；Then prepared binder solution is added dropwise, when binder solution is added drop-wise to 2/3rds,
After being uniformly dispersed to the suitable water of mixed solution penetrating, continue that remaining binder solution is added dropwise, sprayed after 10min is added dropwise
Enter suitable moisture to dissipate, rinse；Then filter, vacuum drying, obtain the aqueous suspension and prepare press fitting aluminum composition modeling powder；
The aluminium powder particle size range is 0.05~5 μm；
Ultrasonic power in step A and step B is 400~500W, vibration frequency is 15~20kHz.
2. the method that aqueous suspension according to claim 1 prepares press fitting aluminum composition modeling powder, it is characterised in that in step B
In, the explosive is high sensitivity explosive, its be CL-20, HMX, RDX, LLM-105, TATB in one or more compositions, institute
The particle diameter for stating explosive is 1~120 μm.
3. the method that aqueous suspension according to claim 1 prepares press fitting aluminum composition modeling powder, it is characterised in that in step C
In, the binder solution, which refers to high polymer binder being dissolved in ethyl acetate, butyl acetate or dichloroethanes, to be formed
Solution, its concentration is 4.0~8.0wt%.
4. the method that aqueous suspension according to claim 3 prepares press fitting aluminum composition modeling powder, it is characterised in that described
High polymer binder is vinylidene and the copolymer or polyurethane polymer binding agent of chlorotrifluoroethylene.
5. the method that aqueous suspension according to claim 1 prepares press fitting aluminum composition modeling powder, it is characterised in that in step C
In, the explosive of the coating material cladding that aluminium powder, the step B of the surface preparation that the step A is obtained are obtained and binding agent
Mass ratio is 10~30：55~90：5~10.
6. the method that aqueous suspension according to claim 1 prepares press fitting aluminum composition modeling powder, it is characterised in that in step C
In, the drop rate of the binder solution is 3mL/min.
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| CN107721778A (en) * | 2017-09-26 | 2018-02-23 | 中国工程物理研究院化工材料研究所 | A kind of method that blasting explosive granules bonding is carried out using high density suspensions |
| CN107473914A (en) * | 2017-10-09 | 2017-12-15 | 西安近代化学研究所 | A kind of high energy is pressed insensitive booster explosive and preparation method |
| CN108687340B (en) * | 2018-05-24 | 2020-03-20 | 淮阴师范学院 | Method for improving high-temperature heat reaction performance of aluminum powder through surface modification |
| CN109096020B (en) * | 2018-10-31 | 2020-08-14 | 中国工程物理研究院化工材料研究所 | Core-shell type aluminum-containing compound and preparation method thereof |
| CN109482860A (en) * | 2018-12-13 | 2019-03-19 | 中国工程物理研究院化工材料研究所 | A kind of micronized method of spherical shape of nanometer aluminium powder |
| CN113603987B (en) * | 2021-07-28 | 2022-07-26 | 中国工程物理研究院化工材料研究所 | Modified aluminum/fluorine-containing polymer compound and preparation method thereof |
| CN116143572A (en) * | 2023-03-06 | 2023-05-23 | 南京理工大学 | Boron-aluminum high-energy mixed explosive and preparation method thereof |
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