CN107283826A - A kind of solid propellant 3D printing forming method solidified based on ultraviolet light - Google Patents
A kind of solid propellant 3D printing forming method solidified based on ultraviolet light Download PDFInfo
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- CN107283826A CN107283826A CN201710507202.9A CN201710507202A CN107283826A CN 107283826 A CN107283826 A CN 107283826A CN 201710507202 A CN201710507202 A CN 201710507202A CN 107283826 A CN107283826 A CN 107283826A
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- ultraviolet light
- shower nozzle
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y10/00—Processes of additive manufacturing
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y70/00—Materials specially adapted for additive manufacturing
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Abstract
The invention discloses a kind of solid propellant 3D printing preparation method based on UV-curing technology, the raw materials such as photosensitive resin, primary binder, curing agent, oxidant, solid fuel are well mixed, and transport material to extrusion shower nozzle at continuously extruded, and ultraviolet light is delivered at extrusion shower nozzle, by the continuous precuring of the material of extrusion.The motion path of extrusion shower nozzle and the extruded velocity of material are controlled using 3D printing software, layer upon layer solidifies layer by layer, finally by molded samples in insulating box further heat preservation solidification.This method can safely prepare the thermoset solid propellant of any shape under lower temperature and pressure condition, with process safety, do not need mould, it is applied widely the characteristics of.
Description
Technical field
The present invention relates to the method for processing forming of propellant, particularly a kind of solid propellant 3D solidified based on ultraviolet light
Printing shaping method.
Background technology
Conventional thermosetting composite solidpropellant shaping manufacture mainly uses casting method moulding process, is by liquid master
After the raw material such as adhesive, curing agent, solid oxidizer and metal fuel are well mixed directly in mould or engine shell body
Casting, then obtains solid propellant finished product by being incubated solidification for a long time.The solid propellant of the demoulding is needed, is had to shape
Certain limitation, especially complex irregular grain is extremely difficult using this technological forming.Therefore, casting process can not meet one
It is prepared by the solid propellant shaping of a little complicated shapes.
Ultraviolet light solidification 3D printing is a kind of on the basis of traditional prints, the raw material based on light-sensitive material, additional purple
Outer light irradiation come make liquid resin material occur polymerisation, the principle that molecular weight increases rapidly and solidified.Forming process can be with
Divide modeling, digitalized sliced sheet (format transformation and layer face treatment), 3D printing shaping etc..
At present, the raw material of the ultraviolet light solidification 3D printing technique of document report is all the photosensitive resin of liquid, in ultraviolet light
Irradiation under curing molding.Because a large amount of constituents are solid in solid propellant raw material, if directly that solid propellant is former
Material is mixed with photosensitive resin, and is molded using existing commercial ultraviolet light solidification 3D printer, then can be due to material system
Poor fluidity, translucency is poor, the scattered reason such as uneven causes shaping not carry out.There is presently no utilize ultraviolet light solidification
3D printing technique carries out the document report of highly filled composite shaping.Therefore, existing 3D printing technique can not expire
The forming requirements of the highly filled composite especially thermoset solid propellant of foot.
The content of the invention
It is an object of the invention to provide a kind of solid propellant molding method for preparing solidified based on ultraviolet light.
The technical solution for realizing the object of the invention is：It is prepared by a kind of be molded based on the solid propellant that ultraviolet light solidifies
Method, is to be well mixed the raw materials such as photosensitive resin, primary binder, curing agent, oxidant, solid fuel, and material is used
Transfer unit is sent at extrusion shower nozzle and continuously extruded, and ultraviolet light is sent at extrusion shower nozzle using optical fiber, will be extruded
The continuous precuring of material.The motion path of extrusion shower nozzle and the extruded velocity of material are controlled by 3D printing software systems, layer by layer
Photocuring layer by layer is accumulated, will finally obtain carrying out insulation solidify afterwards in sample feeding insulating box.Concretely comprise the following steps：
Step 1, material is well mixed, the material includes photosensitive resin, primary binder, oxidant, solid fuel, solid
Agent；
Described photosensitive resin is epoxy acrylate, unsaturated-resin polyester acrylate, urethane acrylate, had
Machine silicon oligoester, acrylic resin, one or more kinds of mixtures of polyether acrylate；
Described primary binder is polyurethane elastomer, glycidyl azide polymer, 3- azido-methyl -3- methyl epoxy fourths
Double (azido-methyl) the epoxy butane polymer of alkane polymer, 3,3-, end hydroxy butadiene, polyethers, 3,3- are double (azido-methyl)
Mixture more than one or both of epoxy butane-tetrahydrofuran copolymer；
Described oxidant is ammonium perchlorate, ammonium nitrate, RDX, HMX, FOX-7, CL-20, TKX-50, dinitro
Mixture more than one or both of acid amides ammonium salt, hydrazine nitroform；
Described solid fuel is mixture more than one or both of aluminium powder, magnesium powder, boron powder or magnesium aluminum-alloy powder；
Curing agent is mixture one or more kinds of in IPDI, TDI, MAPO.
The content of photosensitive resin accounts for the 2~20% of material gross mass, the content of primary binder account for material gross mass 8~
40%, the content of oxidant accounts for the 40~85% of material gross mass, the content of solid fuel account for material gross mass 0%~
30%, the content of curing agent accounts for the 0.5~5% of material gross mass.
Oxidant, the particle diameter of solid fuel are less than 0.5mm.
Step 2, material of the step 1 after well mixed is transported at extrusion shower nozzle and continuously extruded；After well mixed
Material conveyed using screw mode of movement or piston type mode of movement.
Step 3, by the propellant three-dimensional model being pre-designed input computer in, using Slice Software carry out section at
Reason, the path for controlling extrusion shower nozzle to be planned according to Slice Software by 3D printing software carries out three-dimensional motion, and the material of extrusion is continuous
Ground is spread on print platform, and the material of extrusion continuously carries out precuring using ultraviolet light；Often complete one layer of material
Pile up rear shower nozzle and improve a thickness, the propellant shape being pre-designed until material is piled into；The material of extrusion is used
During ultraviolet light, ultraviolet ray intensity is 0.2mW/cm2To 20mW/cm2.Shower nozzle often raise one layer of distance for 0.05~
1.0mm, the horizontal movement speed of extrusion shower nozzle is less than 200mm/s, and the nozzle diameter of extrusion shower nozzle is 0.3~3.0mm.Ultraviolet light
The surface of extruded material is sent to by optical fiber, the optical fiber of transmission ultraviolet light goes out the optical interface three-dimensional shifting of progress synchronous with extrusion shower nozzle
It is dynamic.
Step 4, the product for obtaining step 3 printing, insert in constant temperature oven and consolidated after the completion of solidify afterwards, solidification
Body propellant finished product.
Compared with prior art, remarkable advantage of the invention is：1) can realize arbitrary shape solid propellant into
Type；2) housing need not be used just to complete curing molding, breach conventional thermosetting solid propellant must in housing or
The limitation of curing molding is completed in mould；3) ultraviolet source relatively enrich, it is safe and reliable, can be avoided other curing modes because
The potential safety hazard that localized hyperthermia brings；4) present invention first solidifies ultraviolet light the material forming of 3D printing technique and high solids content
Technology is combined, and realizes the insurmountable composite solidpropellant 3D printing shaping of conventional method；5) it is of the invention by photosensitive resin
Merga pass piston or Screw Extrusion are mixed with the raw material of solid propellant, shower nozzle is extruded by material by certain road by computer
Footpath and thickness are filled and accumulated, and following material extruder head to be irradiated with ultraviolet light makes material solidify in time, can be fine
Solution material system poor fluidity, translucency it is poor, it is scattered uneven the problem of so that curing molding can be smoothly molded.
Brief description of the drawings
Fig. 1 is the process flow diagram that ultraviolet light of the present invention solidifies 3D printing solid propellant.
Specific implementation method
With reference to accompanying drawing, a kind of solid propellant 3D printing forming method solidified based on ultraviolet light of the invention, including with
Lower step；
Step 1, photosensitive resin, primary binder, oxidant, solid fuel, curing agent and other auxiliary agents are well mixed.Institute
The photosensitive resin stated is that epoxy acrylate, unsaturated-resin polyester acrylate, urethane acrylate, organosilicon are oligomeric
The one or more kinds of mixture of ester, acrylic resin, polyether acrylate；Described primary binder is elastic polyurethane
Double (azido-methyl) epoxy butanes of body, glycidyl azide polymer, 3- azido-methyl -3- methyl epoxy butanes polymer, 3,3-
One kind in double (azido-methyl) epoxy butane-tetrahydrofuran copolymers of polymer, end hydroxy butadiene, polyethers, 3,3- or
More than one mixture；Described oxidant be ammonium perchlorate, ammonium nitrate, RDX, HMX, FOX-7, CL-20,
One or more kinds of mixtures in TKX-50, Zoamix ammonium salt, hydrazine nitroform；Described solid fuel is aluminium powder, magnesium
One or more kinds of mixtures in powder, boron powder or magnesium aluminum-alloy powder；Described curing agent is one in IPDI, TDI, MAPO
Plant or two or more mixtures.
The particle diameter of the solid materials such as described oxidant is less than 0.5mm.
Described photosensitive resin consumption accounts for the 2~20% of propellant gross mass.
Described primary binder consumption accounts for the 8~40% of propellant gross mass.
Described oxidizer accounts for the 40~85% of propellant gross mass.
Described solid fuel consumption accounts for the 0%~30% of propellant gross mass.
Described hardener dose accounts for the 0.5%~5% of propellant gross mass.
Step 2, material of the step 1 after well mixed is transported at extrusion shower nozzle and continuously extruded.
It is described it is well mixed after material conveyed using screw mode of movement or piston type mode of movement.
Step 3, the propellant three-dimensional model being pre-designed are input in computer, are carried out using Slice Software at section
Reason, the path for controlling extrusion shower nozzle planned according to Slice Software by 3D printing software systems carries out three-dimensional motion, extrusion
Material is continuously spread on print platform, and the material of extrusion continuously carries out precuring using ultraviolet light.Using ultraviolet
During light irradiation, ultraviolet ray intensity is 0.2mW/cm2To 20mW/cm2.The rear shower nozzle of piling up for often completing one layer of material improves a layer
Thickness, the propellant shape being pre-designed until material is piled into.
Ultraviolet light is sent by ultraviolet light source, and the surface of print platform is sent to using optical fiber, transmits the light of ultraviolet light
Fibre goes out the optical interface three-dimensional movement of progress synchronous with extrusion shower nozzle, and synchronous precuring is realized while continuous extruded material.
The distance that shower nozzle often raises one layer is 0.05~1.0mm, and the horizontal movement speed of extrusion shower nozzle is less than 200mm/s,
The nozzle diameter for extruding shower nozzle is 0.3~3.0mm.
Step 4, the solid propellant for obtaining step 3 printing, insert and solidify afterwards are carried out in constant temperature oven, after the completion of solidification
Obtain solid propellant finished product.
The raw material of photosensitive resin and solid propellant is mixed merga pass piston or Screw Extrusion by the present invention, by computer
Material is filled and accumulated by certain path and thickness by extrusion shower nozzle, and follows material extruder head to be shone with ultraviolet light
Penetrating makes material solidify in time, the problem of solving that material system poor fluidity, translucency are poor well, disperse uneven so that
Curing molding can be smoothly molded.
In order to which the implementation of the present invention is better described, citing elaboration is carried out below.
Embodiment 1
It is compound with end hydroxy butadiene primary binder from epoxy acrylate type photosensitive resin as auxiliary binder
Use, oxidant uses ammonium perchlorate, metallic aluminium powder selects TDI as solid fuel, curing agent.The quality percentage of said components
Content is respectively：Photosensitive resin 5%, end hydroxy butadiene 12%, ammonium perchlorate 72%, aluminium powder 5%, TDI curing agent 3%,
Other components 3%.It is good by above-mentioned material weighing, it is well mixed using kneader, the material mixed is extruded using screw
Machine is sent at shaping shower nozzle and continuously extruded.The propellant three-dimensional model being pre-designed is input in computer, using section
Software carries out slicing treatment, and the path for controlling extrusion shower nozzle planned according to Slice Software by 3D printing software systems carries out three
Maintenance and operation is moved, and the material of extrusion is continuously spread on print platform, and the material of extrusion is continuously carried out pre- using ultraviolet light
Solidification.Ultraviolet light is sent by ultraviolet light source, and the surface of print platform is sent to using optical fiber, transmits the optical fiber light extraction of ultraviolet light
Interface is synchronous with extrusion shower nozzle to carry out three-dimensional mobile, the synchronous precuring of realization while continuous extruded material.It is from wavelength
245nm uviol lamps are as light source, and ultraviolet light intensity is 5mW/cm2.The rear shower nozzle of piling up for often completing one layer of material improves one
Individual thickness, the propellant shape being pre-designed until material is piled into.The sample of forming is inserted in constant temperature oven after progress
Solidification, obtains solid propellant finished product after the completion of solidification.Sample rate is the 96.5% of solid density.Sampling and testing propellant into
The tensile strength of product is 7.0MPa.Fig. 1 is present invention process schematic flow sheet.
In order to compare, using same material, the propellant sample actual density prepared with casting process is theoretical value
96.8%, tensile strength is 7.6MPa.As can be seen that the solid propellant prepared using traditional casting molding process, nothing
Should properties of sample of the mechanical strength without method preparation of the invention by density.
Embodiment 2
It is compound with end hydroxy butadiene primary binder from epoxy acrylate type photosensitive resin as auxiliary binder
Use, oxidant uses ammonium perchlorate, and metallic aluminium powder is as solid fuel, and curing agent is from the mixed of the mass ratioes such as TDI and MAPO
Compound.The weight/mass percentage composition of said components is respectively：Photosensitive resin 5%, end hydroxy butadiene 12%, ammonium perchlorate
72%, aluminium powder 5%, curing agent 3.0%, other components 3%.It is good by above-mentioned material weighing, it is well mixed using kneader, will be mixed
The material got togather is sent at shaping shower nozzle using screw-type extruder and continuously extruded.The propellant three-dimensional model being pre-designed
Be input in computer, using Slice Software carry out slicing treatment, by 3D printing software systems control extrusion shower nozzle carry out according to
The path of Slice Software planning carries out three-dimensional motion, and the material of extrusion is continuously spread on print platform, and the material of extrusion is adopted
Precuring is continuously carried out with ultraviolet light.Ultraviolet light is sent by ultraviolet light source, and print platform is sent to using optical fiber
Surface, the optical fiber of transmission ultraviolet light goes out the optical interface three-dimensional movement of progress synchronous with extrusion shower nozzle, while continuous extruded material
Realize synchronous precuring.From wavelength be 245nm uviol lamps as light source, ultraviolet light intensity is 0.2mW/cm2.Often complete
The rear shower nozzle of piling up of one layer of material improves a thickness, the propellant shape being pre-designed until material is piled into.Forming
Sample insert solidify afterwards carried out in constant temperature oven, solid propellant finished product is obtained after the completion of solidification.Sample rate is theoretical close
The 97.1% of degree.The tensile strength of sampling and testing propellant finished product is 7.6MPa.
Embodiment 3
From epoxy acrylate type photosensitive resin as auxiliary binder, with polyethers primary binder compound use, oxidation
Agent uses ammonium perchlorate, and metallic aluminium powder selects IPDI as solid fuel, curing agent.The weight/mass percentage composition difference of said components
For：Photosensitive resin 7%, polyethers 10%, ammonium perchlorate 72%, aluminium powder 5%, curing agent 2.0%, other components 4%.By above-mentioned thing
Material is weighed, well mixed using kneader, and the material mixed is sent at shaping shower nozzle using plunger type extruder and carried out
Continuous extrusion.The propellant three-dimensional model being pre-designed is input in computer, slicing treatment is carried out using Slice Software, by 3D
The path that print software system control extrusion shower nozzle planned according to Slice Software carries out three-dimensional motion, and the material of extrusion is continuous
Ground is spread on print platform, and the material of extrusion continuously carries out precuring using ultraviolet light.Ultraviolet light is by ultraviolet light
Source is sent, and the surface of print platform is sent to using optical fiber, and the optical fiber of transmission ultraviolet light goes out optical interface and the extrusion same stepping of shower nozzle
Row is three-dimensional mobile, and synchronous precuring is realized while continuous extruded material.From wavelength light is used as 365nm uviol lamp
Source, ultraviolet light intensity is 20mW/cm2.The rear shower nozzle of piling up for often completing one layer of material improves a thickness, until by material
It is piled into the propellant shape being pre-designed.The sample of forming, which is inserted in constant temperature oven, obtained after the completion of solidify afterwards, solidification
Obtain solid propellant finished product.Sample rate is the 97.4% of solid density.The tensile strength of sampling and testing propellant finished product is
6.4MPa。
Embodiment 4-12
Using process same as Example 1, change photosensitive resin species and consumption, the species of oxidant and consumption,
The species and consumption of solid fuel metal powder, the consumption of primary binder etc. carry out contrast test, and primary binder all selects 3,3-
Double (azido-methyl) epoxy butane-tetrahydrofuran copolymers, other specification is all same as Example 1, prepares the material of propellant
Proportioning, density and mechanical property are as shown in the table.
It is can be seen that from embodiment 4-12 result from different photosensitive resins, with traditional composite solidpropellant
Compound use is formulated, compact-type and the preferable propellant sample of mechanical property can be prepared.
Embodiment 13-18
Using molding process and technological parameter same as Example 1, only change the species of primary binder in formula,
The propellant density and mechanical property of preparation are as shown in the table.
Embodiment 19-24
Using molding process and technological parameter same as Example 1, technological parameter when being only molded, preparation is pushed away
Enter agent density and mechanical property is as shown in the table.
Can be seen that from embodiment 19-24 result can be made compact-type and mechanics using different technological parameters
The good solid propellant of the combination properties such as intensity.
By above example as can be seen that preparing solid propellant using the inventive method, technical process is simple to operate, no
Need to prepare mould, propellant shaping efficiency can be significantly improved, pushed away for preparing the special shape that common process is difficult to prepare
Enter the sample of agent.
Claims (8)
1. a kind of solid propellant 3D printing forming method solidified based on ultraviolet light, it is characterised in that comprise the following steps：
Step 1, material is well mixed, the material includes photosensitive resin, primary binder, oxidant, solid fuel, solidification
Agent；
Step 2, material of the step 1 after well mixed is transported at extrusion shower nozzle and continuously extruded；
Step 3, by the propellant three-dimensional model being pre-designed input computer in, using Slice Software carry out slicing treatment, by
The path that 3D printing software control extrusion shower nozzle is planned according to Slice Software carries out three-dimensional motion, and the material of extrusion is continuously sprawled
Onto print platform, the material of extrusion continuously carries out precuring using ultraviolet light；Often complete after the piling up of one layer of material
Shower nozzle improves a thickness, the propellant shape being pre-designed until material is piled into；
Step 4, the product for obtaining step 3 printing, are inserted and solidify afterwards are carried out in constant temperature oven, and solid is obtained after the completion of solidification and is pushed away
Enter agent finished product.
2. the solid propellant 3D printing forming method according to claim 1 solidified based on ultraviolet light, it is characterised in that
Photosensitive resin described in step 1 is epoxy acrylate, unsaturated-resin polyester acrylate, urethane acrylate, had
Machine silicon oligoester, acrylic resin, one or more kinds of mixtures of polyether acrylate；
Described primary binder is polyurethane elastomer, glycidyl azide polymer, 3- azido-methyl -3- methyl epoxy butane gather
Double (azido-methyl) the epoxy butane polymer of compound, 3,3-, end hydroxy butadiene, polyethers, double (azido-methyl) epoxies of 3,3-
Mixture more than one or both of butane-tetrahydrofuran copolymer；
Described oxidant is ammonium perchlorate, ammonium nitrate, RDX, HMX, FOX-7, CL-20, TKX-50, Zoamix
Mixture more than one or both of ammonium salt, hydrazine nitroform；
Described solid fuel is mixture more than one or both of aluminium powder, magnesium powder, boron powder or magnesium aluminum-alloy powder；
Curing agent is mixture one or more kinds of in IPDI, TDI, MAPO.
3. the solid propellant 3D printing forming method according to claim 2 solidified based on ultraviolet light, it is characterised in that
The content of photosensitive resin accounts for the 2~20% of material gross mass, and the content of primary binder accounts for the 8~40% of material gross mass, oxidation
The content of agent accounts for the 40~85% of material gross mass, and the content of solid fuel accounts for the 0%~30% of material gross mass, curing agent
Content accounts for the 0.5~5% of material gross mass.
4. the solid propellant 3D printing forming method according to claim 2 solidified based on ultraviolet light, it is characterised in that
Oxidant, the particle diameter of solid fuel are less than 0.5mm.
5. the solid propellant 3D printing forming method according to claim 2 solidified based on ultraviolet light, it is characterised in that
Material after being well mixed in step 2 is conveyed using screw mode of movement or piston type mode of movement.
6. the solid propellant 3D printing forming method according to claim 2 solidified based on ultraviolet light, it is characterised in that
When using ultraviolet light to the material of extrusion in step 3, ultraviolet ray intensity is 0.2mW/cm2To 20mW/cm2。
7. the solid propellant 3D printing forming method according to claim 2 solidified based on ultraviolet light, it is characterised in that
The distance that shower nozzle often raises one layer in step 3 is 0.05~1.0mm, and the horizontal movement speed of extrusion shower nozzle is less than 200mm/s, squeezed
The nozzle diameter for going out shower nozzle is 0.3~3.0mm.
8. the solid propellant 3D printing forming method according to claim 2 solidified based on ultraviolet light, it is characterised in that
Step 3 ultraviolet light is sent to the surface of extruded material by optical fiber, and it is synchronous with extruding shower nozzle that the optical fiber of transmission ultraviolet light goes out optical interface
Carry out three-dimensional mobile.
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