CN108381908A - A kind of continuous lod thermosetting resin based composites 3D printing technique - Google Patents
A kind of continuous lod thermosetting resin based composites 3D printing technique Download PDFInfo
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- CN108381908A CN108381908A CN201810130086.8A CN201810130086A CN108381908A CN 108381908 A CN108381908 A CN 108381908A CN 201810130086 A CN201810130086 A CN 201810130086A CN 108381908 A CN108381908 A CN 108381908A
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- 229920001187 thermosetting polymer Polymers 0.000 title claims abstract description 54
- 238000010146 3D printing Methods 0.000 title claims abstract description 47
- 238000000034 method Methods 0.000 title claims abstract description 25
- 239000000805 composite resin Substances 0.000 title claims abstract description 20
- 239000011347 resin Substances 0.000 claims abstract description 56
- 229920005989 resin Polymers 0.000 claims abstract description 56
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 30
- 238000001723 curing Methods 0.000 claims abstract description 30
- 239000000463 material Substances 0.000 claims abstract description 29
- 239000000835 fiber Substances 0.000 claims abstract description 28
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- 238000013007 heat curing Methods 0.000 claims abstract description 21
- 239000002131 composite material Substances 0.000 claims abstract description 17
- 238000000465 moulding Methods 0.000 claims abstract description 10
- 238000001816 cooling Methods 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 238000007598 dipping method Methods 0.000 claims abstract description 5
- 238000007639 printing Methods 0.000 claims abstract description 5
- 239000002994 raw material Substances 0.000 claims abstract description 5
- 238000002844 melting Methods 0.000 claims abstract description 4
- 230000008018 melting Effects 0.000 claims abstract description 4
- 238000006116 polymerization reaction Methods 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 8
- 238000004132 cross linking Methods 0.000 claims description 7
- 230000009477 glass transition Effects 0.000 claims description 7
- 230000002787 reinforcement Effects 0.000 claims description 4
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 3
- 239000004917 carbon fiber Substances 0.000 claims description 3
- 239000003365 glass fiber Substances 0.000 claims description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 3
- 229920013657 polymer matrix composite Polymers 0.000 claims description 3
- 239000011160 polymer matrix composite Substances 0.000 claims description 3
- 230000005855 radiation Effects 0.000 claims description 3
- 238000004513 sizing Methods 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 2
- 239000003999 initiator Substances 0.000 claims 1
- 238000007493 shaping process Methods 0.000 abstract description 2
- 238000007711 solidification Methods 0.000 description 5
- 230000008023 solidification Effects 0.000 description 5
- 229920005992 thermoplastic resin Polymers 0.000 description 4
- 230000007547 defect Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000002708 enhancing effect Effects 0.000 description 3
- 230000005284 excitation Effects 0.000 description 3
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 2
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 2
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000011199 continuous fiber reinforced thermoplastic Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 238000013178 mathematical model Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000000016 photochemical curing Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004626 polylactic acid Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000004781 supercooling Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
- B29C64/10—Processes of additive manufacturing
- B29C64/106—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material
- B29C64/118—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material using filamentary material being melted, e.g. fused deposition modelling [FDM]
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
- B29C64/30—Auxiliary operations or equipment
- B29C64/307—Handling of material to be used in additive manufacturing
- B29C64/314—Preparation
-
- 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
- B33Y40/00—Auxiliary operations or equipment, e.g. for material handling
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Mechanical Engineering (AREA)
- Optics & Photonics (AREA)
Abstract
A kind of continuous lod thermosetting resin based composites 3D printing technique, thermosetting resin prepolymer, high-temperature curing agent, light-cured resin prepolymer and photoinitiator are first chosen as preimpregnation raw material, it is heated after mixing, this resin prepolymer objects system is presoaked using continuous dry fibers tow, continuous lod thermosetting resin base composite material silk material is made in the postcooling of dipping；Composite material silk material is transported in 3D printing head, is heated again, the silk material of melting is pulled out from printing nozzle, tow ventilating and cooling immediately after pulling out, when irradiated by servo-actuated ultraviolet source, complete precuring；Cycle successively prints, to which preformed member be made；Preformed member is finally placed in curing molding under the temperature environment that can cause heat cure reaction, finally obtained 3D printing shaped component, the present invention realize the 3D printing rapid shaping of continuous lod thermosetting resin based composite material component.
Description
Technical field
The present invention relates to composite material 3D printing technique fields, and in particular to a kind of continuous lod thermosetting resin base
Composite material 3D printing technique.
Background technology
3D printing technique is one kind based on mathematical model, by can with the linear silk material etc. of metal powder or plastics
The material of bonding, in a manner of successively printing or successively selectively bond, to construct the quick increases material manufacturing technology of entity.3D is beaten
Print consumptive material is the material base of 3D printing, and the bottleneck of the limitation further development and application of 3D printing.Currently, 3D printing consumptive material master
It is divided into ceramic-like, metal class, composite material class and four kinds of species of polymerization, common 3D printing consumptive material is mainly pure thermoplastic filaments
Material, including acrylonitrile-butadiene-styrene copolymer (ABS), polylactic acid (PLA) etc..Its defect is apparent：Bearing capacity
Weak, interlayer performance is very poor, tensile strength deficiency etc., these defects seriously limit its further application and development.
It is shown according to newest document, domestic and international colleges and universities and esbablished corporation R＆D team begin attempt to using fiber as increasing
The strong common 3D printing consumptive material of bluk recombination carries out 3D printing experiment.Currently, chopped strand enhancing thermoplastic resin based composite material 3D
Printing technique has been carried out, but due to the additive amount of chopped strand, draw ratio etc. has the limit, and thermoplastic resin always
Itself existing shrinkage cracking, buckling deformation, heat resistance poor corrosion resistance, intensity hardness is low to wait shortcomings, for final
The enhancing of composite molding element mechanics performance is limited.In order to thoroughly solve the above problems, fiber-reinforced resin is greatly improved
The mechanical property of based composites 3D printing shaped component, can meet engineering field requirement, and existing mechanism starts from heat
Thermosetting resin matrix and continuous fiber reinforcement are started with, develop chopped strand enhancing the 3D printing of thermosetting resin based composites and
Continuous fiber reinforced thermoplastic resin based composites 3D printing.
In conclusion there is no the 3D of realization continuous lod thermosetting resin based composites to beat for currently available technology
Print.
Invention content
In order to overcome the disadvantages of the above prior art, the purpose of the present invention is to provide a kind of continuous lod thermosetting properties
Polymer matrix composites 3D printing technique realizes that the 3D printing of continuous lod thermosetting resin based composite material component is quick
Molding.
To achieve the above object, the present invention adopts the following technical scheme that：
A kind of continuous lod thermosetting resin based composites 3D printing technique, includes the following steps：
Step 1 is chosen under room temperature as the thermosetting resin prepolymer of glassy state, high-temperature curing agent, light-cured resin pre-polymerization
Object and photoinitiator are heated to the viscous stream temperature of thermosetting resin prepolymer or more, hot setting as preimpregnation raw material
Agent starts to cause the critical-temperature of heat cure reaction hereinafter, after mixing, directly using continuous dry fibers tow, presoaking this tree
Fat prepolymer system has been added by cooling temperature to the glass transition temperature of thermosetting resin prepolymer hereinafter, being made after dipping
Add the curing agent uncured continuous lod thermosetting resin base composite material silk material suitable for 3D printing；
Step 2, using continuous lod thermosetting resin base composite material silk material made from step 1, convey its into
Enter into 3D printing head, again more than the viscous stream temperature of heating temperature to thermosetting resin prepolymer, high-temperature curing agent starts
Cause the critical-temperature of heat cure reaction hereinafter, the silk material of melting passes through print head and is attached to the filament on print platform
Beam, tow ventilating and cooling immediately after pulling out solidify sizing to be attached to rapidly on print platform, at the same by with
Dynamic ultraviolet source irradiation, completes precuring；The cycle above process successively prints, multiple to which fiber reinforced thermosetting resin base be made
Condensation material 3D printing preformed member；
Preformed member prepared by step 2 is placed under the temperature environment that can cause heat cure reaction by step 3, excitation
High-temperature curing agent causes heat cure polymerization crosslinking and reacts thorough curing molding, the fiber reinforcement heat of final obtained excellent combination property
Thermosetting resin based composites 3D printing shaped component.
In the step one, the glass transition temperature of the thermosetting resin prepolymer of selection is higher than 30 DEG C, solid less than high temperature
Agent starts to cause the critical-temperature of heat cure reaction, is in glassy state under room temperature, in strong viscous of viscosity lazy flow after heating
Fluidised form；The light-cured resin prepolymer mass fraction of selection between 0%-50%, two kinds of resin prepolymers and high-temperature curing agent,
The mixing temperature of photoinitiator and the preimpregnation temperature of dry fibers tow are in the temperature range.
The dry fibers tow chosen in the step one be one kind in carbon fiber, glass fibre, Kafra fiber or
It is a variety of, one or more.
The temperature of temperature environment causes the critical-temperature of heat cure reaction, root higher than high-temperature curing agent in the step three
Environment attribute is added according to setting high pressure, inert gas atmosphere, infrared radiation or microwave irradiation is needed.
Compared with prior art, the device have the advantages that：
1) present invention can meet a variety of plurality of fibers tow preimpregnation throwing simultaneously, be suitable for a variety of high-performance thermosetting resins
And its mixture, preparing 3D printing silk material in advance by the method for fractional steps, the resin content of tow is made in throwing link independent control,
Resin distribution is controllable.
2) raw material of the present invention directly uses continuous dry fibers tow, is fitted by presoaking thermosetting resin prepolymer system
For the continuous lod thermosetting resin base composite material silk material of 3D printing, thermosetting resin and continuous fiber are combined
The advantages of beam, compensates for the deficiency of chopped strand and thermoplastic resin, and the properties of shaped component are substantially improved；It is prior
It is that the silk material is suitable for the 3D printing molding based on Layered manufacturing principle, is different from the molding mode of conventional composite materials, passes through
The extensive utilization of 3D printing technique at present greatly can popularize and expand the application field of composite element.
3) continuous lod thermosetting resin based composites are effectively applied to 3D printing technique field by the present invention,
Common 3D printing thermoplasticity silk material is replaced using the continuous fiber tow of high intensity and the thermosetting resin of superior performance,
Complicated composite material process planning has directly been simplified to the short-cut method that everybody can use by 3D printing technique, and
And solve the defects of common 3D printing formed parts intensity is low, and deformation is big, and size is unstable, thermo-labile, not corrosion-resistant, make it
It disclosure satisfy that engineering field requirement, there is great economic value and development potentiality.
Specific implementation mode
The present invention is described further with reference to embodiments.
A kind of continuous lod thermosetting resin based composites 3D printing technique, includes the following steps：
Step 1 is chosen under room temperature as the thermosetting resin prepolymer of glassy state, high-temperature curing agent, light-cured resin pre-polymerization
Object and photoinitiator are heated to the viscous stream temperature of thermosetting resin prepolymer or more, hot setting as preimpregnation raw material
Agent starts to cause the critical-temperature of heat cure reaction hereinafter, two kinds of resin prepolymers are in strong viscous of viscosity lazy flow at this time
Fluidised form waits for high-temperature curing agent, photoinitiator after mixing, directly using continuous dry fibers tow, presoaking this resin prepolymer
Objects system, by cooling temperature to the glass transition temperature of thermosetting resin prepolymer hereinafter, the resin prepolymer object after dipping
Glassy state restores again in system, and the curing agent uncured continuous lod thermosetting property suitable for 3D printing has been added to be made
Polymer matrix composites silk material；
Step 2, using continuous lod thermosetting resin base composite material silk material made from step 1, convey its into
Enter into 3D printing head, again more than the viscous stream temperature of heating temperature to thermosetting resin prepolymer, high-temperature curing agent starts
Cause the critical-temperature of heat cure reaction hereinafter, the silk material of melting passes through print head and is attached to the filament on print platform
Beam is pulled out from printing nozzle, tow ventilating and cooling immediately after pulling out, to be attached on print platform rapidly
Solidification sizing, while being irradiated again by being servo-actuated ultraviolet source, excitation photoinitiator causes photocuring and polymerize cross-linking reaction, completes pre-
Solidification；The cycle above process is successively printed according to model needs, to which fiber reinforced thermosetting resin based composites 3D be made
Print preformed member；
Preformed member prepared by step 2 is placed under the temperature environment that can cause heat cure reaction by step 3, excitation
High-temperature curing agent causes heat cure polymerization crosslinking and reacts thorough curing molding, the fiber reinforcement heat of final obtained excellent combination property
Thermosetting resin based composites 3D printing shaped component.
In the step one, the glass transition temperature of the thermosetting resin prepolymer of selection is higher than 30 DEG C, solid less than high temperature
Agent starts to cause the critical-temperature of heat cure reaction, is in glassy state under room temperature, in strong viscous of viscosity lazy flow after heating
Fluidised form；Attachment type approval requirements of the light-cured resin prepolymer of selection according to step 3, precuring require and final
Performance requirement after solidification adds, and between 0%-50%, two kinds of resin prepolymers draw mass fraction with high-temperature curing agent, light
The preimpregnation temperature of the mixing temperature and dry fibers tow of sending out agent is in the temperature range, it is ensured that in viscosity lazy flow
Under strong heating condition, resin prepolymer is uniformly mixed with curing agent, and the preimpregnation of dry fibers tow is uniform, is passed through after tow dipping is complete
Supercooling, temperature drops to the glass transition temperature of thermosetting resin prepolymer hereinafter, resin prepolymer objects system restores glassy state again, protects
It is not sticky each other between tow after card gets up the tow winding after preimpregnation, there is some strength, hardness, toughness, and this mistake
Any curing reaction does not occur for journey.
The dry fibers tow chosen in the step one be one kind in carbon fiber, glass fibre, Kafra fiber or
It is a variety of, one or more.
Tow need to be previously threaded through print head in the step two, then heat printhead temperature to thermosetting resin pre-polymerization
More than the viscous stream temperature of object, high-temperature curing agent starts to cause the critical-temperature of heat cure reaction hereinafter, the tree impregnated in tow
Fat prepolymer system becomes viscous state again, after being drawn through nozzle, touches printing plane, using cooled and solidified and
Ultraviolet lighting precuring provides tractive force, adhesive force needed for print procedure and maintains the shaping force of component form.
The temperature of temperature environment causes the critical-temperature of heat cure reaction higher than high-temperature curing agent in the step three, high
Warm curing agent causes the reaction of heat cure polymerization crosslinking by the thorough curing molding of preformed member, uncured in preformed member at this time
Resin while carrying out polymerization crosslinking reaction also because becoming the strong viscous state of viscosity lazy flow in hot environment, but
After the ultraviolet light irradiation precuring described in step 2, its mobility has been fettered, it is ensured that preforming in this solidification process
It is not in that deformation or resin are lost in that component, which remains form completely, in addition to heating, can be arranged as required to high pressure, inertia
The additional environment attribute such as gas atmosphere, infrared radiation or microwave irradiation, reinforced resin flowing, filling pore improve solidification effect,
To after depth polymerization crosslinking reacts curing molding, finally obtain the fiber reinforced thermosetting resin base of excellent combination property
Composite material 3D printing shaped component.
Claims (4)
1. a kind of continuous lod thermosetting resin based composites 3D printing technique, which is characterized in that include the following steps：
Step 1, choose under room temperature for the thermosetting resin prepolymer of glassy state, high-temperature curing agent, light-cured resin prepolymer and
Photoinitiator is heated to the viscous stream temperature of thermosetting resin prepolymer or more, high-temperature curing agent is opened as preimpregnation raw material
Begin to cause the critical-temperature of heat cure reaction hereinafter, after mixing, directly use continuous dry fibers tow, it is pre- to presoak this resin
Polymeric systems, after dipping by cooling temperature to the glass transition temperature of thermosetting resin prepolymer hereinafter, be made added it is solid
The agent uncured continuous lod thermosetting resin base composite material silk material suitable for 3D printing；
Step 2 conveys it and enters using continuous lod thermosetting resin base composite material silk material made from step 1
In 3D printing head, again more than the viscous stream temperature of heating temperature to thermosetting resin prepolymer, high-temperature curing agent starts to cause
The critical-temperature of heat cure reaction hereinafter, the silk material of melting passes through and print head and is attached to the fibre bundle on print platform, from
Printing nozzle pulls out, and tow ventilating and cooling immediately after pulling out solidifies to be attached to rapidly on print platform
Sizing, while being irradiated by being servo-actuated ultraviolet source, complete precuring；The cycle above process successively prints, and increases to which fiber be made
Heat-flash thermosetting resin based composites 3D printing preformed member；
Preformed member prepared by step 2 is placed under the temperature environment that can cause heat cure reaction by step 3, excites high temperature
Curing agent causes heat cure polymerization crosslinking and reacts thorough curing molding, the fiber reinforcement thermosetting of final obtained excellent combination property
Polymer matrix composites 3D printing shaped component.
2. a kind of continuous lod thermosetting resin based composites 3D printing technique according to claim 1, special
Sign is：In the step one, the glass transition temperature of the thermosetting resin prepolymer of selection is higher than 30 DEG C, is less than hot setting
Agent starts to cause the critical-temperature of heat cure reaction, is in glassy state under room temperature, in the viscosity flow that viscosity lazy flow is strong after heating
State；The light-cured resin prepolymer mass fraction of selection is between 0%-50%, two kinds of resin prepolymers and high-temperature curing agent, light
The mixing temperature of initiator and the preimpregnation temperature of dry fibers tow are in the temperature range.
3. a kind of continuous lod thermosetting resin based composites 3D printing technique according to claim 1, special
Sign is：The dry fibers tow chosen in the step one is one kind or more in carbon fiber, glass fibre, Kafra fiber
Kind, one or more.
4. a kind of continuous lod thermosetting resin based composites 3D printing technique according to claim 1, special
Sign is：The temperature of temperature environment causes the critical-temperature of heat cure reaction, root higher than high-temperature curing agent in the step three
Environment attribute is added according to setting high pressure, inert gas atmosphere, infrared radiation or microwave irradiation is needed.
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| CN201810130086.8A CN108381908B (en) | 2018-02-08 | 2018-02-08 | 3D printing process for continuous fiber reinforced thermosetting resin matrix composite material |
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| CN201810130086.8A CN108381908B (en) | 2018-02-08 | 2018-02-08 | 3D printing process for continuous fiber reinforced thermosetting resin matrix composite material |
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| CN108381908B CN108381908B (en) | 2020-04-10 |
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| CN110355995A (en) * | 2019-08-19 | 2019-10-22 | 航天特种材料及工艺技术研究所 | It is a kind of that 3D printing forming method and the thus object construction that forms and application are carried out using continuous fiber |
| CN110667114A (en) * | 2019-10-17 | 2020-01-10 | 吉林大学 | Integrated printing device and printing method for continuous fiber embedded material |
| CN111117103A (en) * | 2019-12-22 | 2020-05-08 | 同济大学 | Reinforced wire rod for fused deposition molding and preparation method thereof |
| CN111607217A (en) * | 2020-07-07 | 2020-09-01 | 四川大学 | 3D printing continuous fiber amidourea polymer composite material and preparation method thereof |
| WO2020211656A1 (en) * | 2019-04-12 | 2020-10-22 | 珠海赛纳三维科技有限公司 | Three-dimensional object molding method and molding device |
| CN112341297A (en) * | 2020-11-09 | 2021-02-09 | 北京航空航天大学 | Safe and efficient forming method of energetic explosive column |
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