CN105172142B - A kind of 3D printing prepares carbon/carbon compound material method - Google Patents
A kind of 3D printing prepares carbon/carbon compound material method Download PDFInfo
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- CN105172142B CN105172142B CN201510593651.0A CN201510593651A CN105172142B CN 105172142 B CN105172142 B CN 105172142B CN 201510593651 A CN201510593651 A CN 201510593651A CN 105172142 B CN105172142 B CN 105172142B
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Abstract
The carbon/carbon compound material preparation method of a kind of 3D printing, after the etched solution etches processing of carbon fiber, with being mixed to get solidliquid mixture for dissolving the solvent of thermosetting resin；The thermosetting resin and curing agent are sufficiently mixed to obtain solid mixture；The solidliquid mixture, solid mixture are separately added into reaction vessel, after stirring and dissolving solid mixture, the mixture in reaction vessel is then dried to obtain mixture block and is crushed；The raw material prepared is poured into progress carbon/carbon compound material green compact 3D printing in 3D printer powder feeding cylinder；Gained carbon/carbon compound material green compact are placed in heat-treatment furnace and is cured, is carbonized and density handles to obtain carbon/carbon compound material.Carbon/carbon compound material prepared by this method has good mechanical performance and technological forming performance, makes the application extension of carbon/carbon compound material to the construction applications of more accurate complexity.
Description
Technical field
The present invention relates to a kind of carbon/carbon compound material preparation methods based on 3D printing technique.
Background technology
Carbon/carbon compound material is carbon fiber and its carbon-based composite material, have low-density (<2.0g/cm3), high intensity,
It is excellent that high ratio modulus, high-termal conductivity, low-expansion coefficient, frictional behaviour are good and thermal shock resistance is good, dimensional stability is high etc.
Point is nowadays in a small number of candidate materials of 1650 DEG C of use above, and highest theoretical temperatures are more up to 3000 DEG C, therefore are considered as
One of most promising high-temperature material.The existing more mature preparation method of the material mainly has 1. long fibre precast bodies
Braiding, and such method is more mature in production application, but there is preparation processes to answer for this method
It is miscellaneous and the shortcomings that be difficult to prepare Complex Parts.2. die forming, such method is only suitable for producing part in batches and there is grinding tool systems
The shortcomings that standby complex process.
3D printing technique is a kind of widely applied rapid shaping technique, and production technology principle is：Pass through calculating first
Machine establishes the three-dimensional data model of target manufactured parts, and then threedimensional model is sliced by corresponding three-dimensional demixing technology
Processing combines so as to obtain a data information using section as unit, under control of the computer, passes through pair of unit section
Data are answered, it is successively laser sintered to the progress of fusible powder material, it is finally completed the processing and manufacturing of corresponding complex parts.At present,
3D printing has been applied to the preparation of the materials complex parts such as metal, resin, ceramics.
But the combination in currently available technology between carbon fiber and pyrolytic carbon belongs to mechanical bond and is not suitable for 3D printing, and
All there is mechanical properties the problem of to be hoisted for 3D printing composite materials property.Therefore, a kind of preparation method letter is found
Folk prescription can prepare just and effective for 3D printing the preparation method of carbon/carbon compound material, and can promote the carbon/carbon printed
The mechanical property of composite material is a problem of solution required for those skilled in the art.
Invention content
The purpose of the present invention is intended to provide a kind of carbon/carbon compound material preparation method of 3D printing technique, and this method is made
Standby carbon/carbon compound material has good mechanical performance and technological forming performance, makes the application extension of carbon/carbon compound material to more
For accurate, complicated construction applications.
A kind of carbon/carbon compound material preparation method of 3D printing, this method include the following steps：
(1) prepared by raw material：Take thermosetting resin, carbon fiber, curing agent and flow promortor spare；When carbon/carbon compound material is given birth to
When the mass fraction of base is 100 parts, carbon fiber mass fraction is 30-70 parts, a diameter of 3 μm~15 μm of the carbon fiber, long
Spend is 200 μm~600 μm；After the etched solution etches processing of described carbon fiber, and for dissolving the molten of thermosetting resin
Agent is mixed to get solidliquid mixture；The thermosetting resin and curing agent are sufficiently mixed to obtain solid mixture；By described in
Solidliquid mixture, solid mixture be separately added into reaction vessel, after stirring and dissolving solid mixture, then by reaction vessel
In mixture be dried to obtain mixture block and be broken for grain size as 10 μm~600 μm raw materials；
(2) green compact print：By step (1) in the printing raw material for preparing pour into 3D printer powder feeding cylinder, import parts
Then threedimensional model is carried out slicing treatment by three-dimensional graph with delamination software, obtain parts each processing levels
Data information regulates the corresponding print procedure control parameter of computer, is finally completed the preparation of carbon/carbon compound material green compact；
(3) curing, carbonization and and density：By step, (2) gained carbon/carbon compound material green compact are placed in heat-treatment furnace and are consolidated
Change, carbonization and density handle to obtain carbon/carbon compound material.
The present invention by performing etching processing to the carbon fiber in 3D printing carbon/carbon compound material raw material after, by thermosetting
Property resin dissolving after the carbon fiber after cladding etching is precipitated again, so as to realize the stronger combination of carbon fiber and interlaminar resin, improve
The mechanical property of 3D printing carbon/carbon compound material.Meanwhile with the present invention the powder material for 3D printing carbon/carbon compound material
The prepared carbon/carbon compound material of material has procedure of processing simply and can prepare the advantage of structure Complex Parts, makes carbon/carbon compound material
Applications expanding to more accurate, complicated construction applications.
Inventor has found the raising with carbon fiber content during research and development 3D printing prepares carbon/carbon compound material,
Ascendant trend is presented in carbon/carbon compound material bending strength substantially, but when carbon fiber content is excessively high, carbon in carbon/carbon compound material
Contact surface between fiber and carbon fiber will increase, though this contact is a kind of weak contact, the meeting when reaching certain amount
The intensity of carbon/carbon compound material is reduced, when the mass content of carbon fiber in the feed is more than 60%, carbon/carbon compound material
Intensity will will appear the phenomenon that not increasing anti-drop, when the mass content of carbon fiber in the feed is more than 70%, then the carbon prepared/
The mechanical property of carbon composite can be relatively low, is not suitable for application request instead.
In addition, inventor also found that although carbon fiber is longer under study for action, enhancing effect is better, if carbon fiber length
It is too long more than 600 μm, can prepare 3D printing carbon/carbon compound material dusty material in can but carbon fiber be caused to be reunited
Phenomenon (referring to Fig. 2) so as to form floccule, causes during 3D printing powdering difficult, and computer powdering normally also can be
The phenomenon that being pushed during laser printing.Based on above research, inventor proposes to control in the preparation process of the present invention
Carbon fiber mass fraction is 30-70 parts, and a diameter of 3 μm~15 μm of the carbon fiber, length is 200 μm~600 μm.
Inventor further study show that, a diameter of 5 μm -11 μm of particularly preferred carbon fiber in the method for the present invention are long
Spend is 150 μm -400 μm.
Present invention further optimization also resides in, when the mass fraction of carbon/carbon compound material green compact is 100 in step (1)
During part, thermosetting resin mass fraction is 20-60 parts, and carbon fiber mass fraction is 30-70 parts, and flow promortor mass fraction is
0.1-0.8 parts, curing agent mass fraction is 2-10 parts.
The present invention's still more preferably also resides in, when the mass fraction of carbon/carbon compound material green compact is in step (1)
At 100 parts, thermosetting resin mass fraction is 35-60 parts, and carbon fiber mass fraction is 35-60 parts, flow promortor mass fraction
It it is 0.1-0.8 parts, curing agent mass fraction is 2-8 parts.
The present invention step (1) described in thermosetting resin toner be phenolic resin, furane resins, pitch, polyphenyl
And imidazoles, epoxy novolac one of which or several compositions.Its particle size distribution range is 50 μm
~300 μm.
In step, (2) middle filling power is the present invention：10W~80W, sweep span are 20 μm~500 μm, and sweep speed is
20inch/s~500inch/s.Power specifically preferred according to the invention of filling is 20~70w, 50-350 μm of sweep span, sweep speed
For 150inch/s-450inch/s.
In step, (3) middle heating makes resin cure temperature be 100 DEG C~300 DEG C to the present invention.Wherein heating rate is 0.1~5
DEG C/min, hardening time is 1h~10h.
In step, (4) middle carbonization temperature is 250 DEG C~1300 DEG C to the present invention.Wherein heat-treatment furnace heating rate for 0.1 DEG C/
Min~10 DEG C/min.
Carbon/carbon compound material parts of the present invention after density, whole apparent density are 0.5g/cm3~2.2g/
cm3。
Present invention further optimization also resides in, and the flow promortor is aerosil, gaseous oxidation aluminium, nano-sized carbon
One or more of SiClx.
Present invention further optimization also resides in, and the curing agent is hexamethylenetetramine.
Present invention further optimization also resides in, and etching solution can be a kind of or several in nitric acid, sulfuric acid, phosphoric acid solution
One kind in kind or hydrogen peroxide and ammonia spirit.
Present invention further optimization also resides in, for dissolving the solvent of thermosetting resin for ethyl alcohol, acetone, chloroform, four
One or more of chlorination carbon, benzene,toluene,xylene.
The present invention's preferably also resides in, and the carbon fiber with that can be for dissolving the solvent quality ratio of thermosetting resin
0.1~10:1.
The present invention's preferably also resides in, and drying temperature is no more than 100 DEG C and is advisable.
The present invention using increases material manufacturing technology, so as to avoid at this stage traditional carbon/carbon compound material prepare the later stage because
Machining and caused by clout waste.The present invention can realize the production of no mold, eliminate conventional powder metallurgy prepare carbon/
Die fabrication step early period of carbon composite, so as to simplify production stage.
This preparation method realizes material disposal molding, and the carbon/carbon compound material of required shape can be prepared in early period
Then green body disposably realizes curing, carbonization and density process, so as to can ensure that the one of final products and 3-D graphic in stove
Cause property, realizes the preparation of Complex Parts.Generated in preparation process without clout, leftover pieces, utilization rate of raw materials up to 100%, so as to
Clout caused by preparing the later stage when the machining to avoid traditional carbon/carbon compound material at this stage wastes.The material of the present invention is former
Material can be production waste, as used in production process carbon fiber can be conventional method in machining caused by leftover pieces and
Clout can save manufacturing cost and and can reduce environmental pollution and waste of raw materials.
At present, the application of carbon/carbon compound material can only be confined to Aeronautics and Astronautics and large scale industry production equipment etc.
Application, the application in terms of miniature precision instrument also quite limits to.The it is proposed of the present invention can overcome the disadvantages that carbon/carbon compound material application
The vacancy in field, this preparation method can realize that carbon/carbon compound material is produced without mold, eliminate conventional powder metallurgy system
Die fabrication step early period of standby carbon/carbon compound material, so as to simplify production stage, shortens the material shape design cycle,
Accelerate speed of the carbon/carbon compound material in complicated precision equipment field application.
Carbon/carbon compound material bending strength prepared by this preparation method can reach more than 80MPa, fully ensure that its power
Performance is learned, general industry parts needs can be met substantially.
Description of the drawings
Fig. 1 is the corresponding threedimensional model of final part figure of the embodiment of the present invention 7,8.
Fig. 2 is 700 μm -800 μm of carbon fiber length, so as to which agglomeration occur.
Specific embodiment
The present invention is further described below in conjunction with the accompanying drawings.
Embodiment 1
(1) go out each component according to data below precise：Carbon fiber, 2kg, average diameter are 7 μm, length range
201μm-300μm；Phenolic resin powder, 3kg, 50 μm -150 μm of particle size range；Aerosil, 10g；Hexa-methylene four
Amine, 300g；
(2) carbon fiber is dispersed in 50 DEG C of salpeter solutions (67%) 3 hours with ultrasonic stirrer, in this process,
Carbon fiber surface is by Nitric acid etching；In 140 DEG C of vacuum filter driers by sample drying for 24 hours, after finally obtaining Nitric acid etching
Carbon fiber, the carbon fiber after etching is with acetone with 1:1 mass ratio mixes 1h in ultrasonic stirrer；
(3) Phenolic resin powder is with 10:It is small that 1 mass ratio with hexa in V-arrangement blender is sufficiently mixed 2
When；
(4) liquid mixture and mixture of powders that are obtained in (2) and (3) are added in simultaneously in the reaction vessel of 10L, so
Container is sealed afterwards, by powder being made to be completely dissolved in acetone soln the stirring of mixed solution, agitator speed 100r/
After min, 3h, the liquid in reaction vessel is imported into evaporating dish.Evaporating dish is put into 60 DEG C of baking ovens and obtains mixing block for 24 hours；
(5) mixing block is put into omnipotent crusher and carries out broken 2h, obtained grain size and be broken for 100-200 μm of powder；
(6) it is target that broken powder, which adds in aerosil and 1-3h is stirred in V-arrangement blender, in step (5)
Powder.
Embodiment 2
(1) go out each component according to data below precise：Carbon fiber 2Kg, average diameter are 7 μm, length range 201
μm-300μm；Phenolic resin powder, 2Kg, 50 μm -150 μm of particle size range；Aerosil, 10g；Hexa,
200g；
(2) carbon fiber is dispersed in 50 DEG C of salpeter solutions (67%) 3 hours with ultrasonic stirrer, in this process,
Carbon fiber surface is by Nitric acid etching；In 140 DEG C of vacuum filter driers by sample drying for 24 hours, after finally obtaining Nitric acid etching
Carbon fiber, the carbon fiber after etching is with acetone with 1:1 mass ratio mixes 1h in ultrasonic stirrer；
(3) Phenolic resin powder is with 10:It is small that 1 mass ratio with hexa in V-arrangement blender is sufficiently mixed 2
When；
(4) liquid mixture and mixture of powders that are obtained in (2) and (3) are added in simultaneously in the reaction vessel of 10L, so
Container is sealed afterwards, by powder being made to be completely dissolved in acetone soln the stirring of mixed solution, agitator speed 100r/
After min, 3h, the liquid in reaction vessel is imported into evaporating dish.Evaporating dish is put into 60 DEG C of baking ovens and obtains mixing block for 24 hours；
(5) mixing block is put into omnipotent crusher and carries out broken 2h, obtained grain size and be broken for 100-200 μm of powder；
(6) it is target that broken powder, which adds in aerosil and 1-3h is stirred in V-arrangement blender, in step (5)
Powder.
Embodiment 3
(1) go out each component according to data below precise：Carbon fiber 3Kg, average diameter are 7 μm, length range 201
μm-300μm；Phenolic resin powder, 2Kg, 50 μm -150 μm of particle size range；Gas-phase silica, 10g；Hexa,
200g；
(2) carbon fiber is dispersed in 50 DEG C of salpeter solutions (67%) 3 hours with ultrasonic stirrer, in this process,
Carbon fiber surface is by Nitric acid etching；In 140 DEG C of vacuum filter driers by sample drying for 24 hours, after finally obtaining Nitric acid etching
Carbon fiber, the carbon fiber after etching is with acetone with 1:1 mass ratio mixes 1h in ultrasonic stirrer；
(3) Phenolic resin powder is with 10:It is small that 1 mass ratio with hexa in V-arrangement blender is sufficiently mixed 2
When；
(4) liquid mixture and mixture of powders that are obtained in (2) and (3) are added in simultaneously in the reaction vessel of 10L, so
Container is sealed afterwards, by powder being made to be completely dissolved in alcoholic solution the stirring of mixed solution, agitator speed 100r/
After min, 3h, the liquid in reaction vessel is imported into evaporating dish.Evaporating dish is put into 60 DEG C of baking ovens and obtains mixing block for 24 hours；
(5) mixing block is put into omnipotent crusher and carries out broken 2h, obtained grain size and be broken for 100 μm of -200 μm of powder
End；
(6) it is target powder that broken powder, which adds in gas-phase silica and 1-3h is stirred in V-arrangement blender, in step (5)
End.
Embodiment 4
(1) go out each component according to data below precise：Carbon fiber 2Kg, average diameter are 7 μm, length range 201
μm-300μm；Phenolic resin powder, 3Kg, 50 μm -150 μm of particle size range；Gas-phase silica, 10g；Hexa,
300g；
(2) carbon fiber is dispersed in 50 DEG C of salpeter solutions (67%) 3 hours with ultrasonic stirrer, in this process,
Carbon fiber surface is by Nitric acid etching；In 140 DEG C of vacuum filter driers by sample drying for 24 hours, after finally obtaining Nitric acid etching
Carbon fiber, the carbon fiber after etching is with acetone with 1:1 mass ratio mixes 1h in ultrasonic stirrer；
(3) Phenolic resin powder is with 10:It is small that 1 mass ratio with hexa in V-arrangement blender is sufficiently mixed 2
When；
(4) liquid mixture and mixture of powders that are obtained in (2) and (3) are added in simultaneously in the reaction vessel of 10L, so
Container is sealed afterwards, by powder being made to be completely dissolved in alcoholic solution the stirring of mixed solution, agitator speed 100r/
After min, 3h, the liquid in reaction vessel is imported into evaporating dish.Evaporating dish is put into 60 DEG C of baking ovens and obtains mixing block for 24 hours；
(5) mixing block is put into omnipotent crusher and carries out broken 2h, obtained grain size and be broken for 100-200 μm of powder；
(6) it is target powder that broken powder, which adds in gas-phase silica and 1-3h is stirred in V-arrangement blender, in step (5)
End.
Embodiment 5
(1) go out each component according to data below precise：Carbon fiber 2Kg, average diameter are 7 μm, length range 250
μm-350μm；Phenolic resin powder, 2Kg, 50 μm -150 μm of particle size range；Gas-phase silica, 10g；Hexa,
200g；
(2) carbon fiber is dispersed in 50 DEG C of salpeter solutions (67%) 3 hours with ultrasonic stirrer, in this process,
Carbon fiber surface is by Nitric acid etching；In 140 DEG C of vacuum filter driers by sample drying for 24 hours, after finally obtaining Nitric acid etching
Carbon fiber, the carbon fiber after etching is with alcohol with 1:1 mass ratio mixes 1h in ultrasonic stirrer；
(3) Phenolic resin powder is with 10:It is small that 1 mass ratio with hexa in V-arrangement blender is sufficiently mixed 2
When；
(4) liquid mixture and mixture of powders that are obtained in (2) and (3) are added in simultaneously in the reaction vessel of 10L, so
Container is sealed afterwards, by powder being made to be completely dissolved in acetone soln the stirring of mixed solution, agitator speed 100r/
After min, 3h, the liquid in reaction vessel is imported into evaporating dish.Evaporating dish is put into 60 DEG C of baking ovens and obtains mixing block for 24 hours；
(5) mixing block is put into omnipotent crusher and carries out broken 2h, obtained grain size and be broken for 100-200 μm of powder；
It is target powder that broken powder, which adds in gas-phase silica and 1-3h is stirred in V-arrangement blender, in step (5).
Embodiment 6
(1) go out each component according to data below precise：Carbon fiber 3Kg, average diameter are 7 μm, length range 250
μm-350μm；Phenolic resin powder, 2Kg, 50 μm -150 μm of particle size range；Aerosil, 10g；Hexa,
200g；
(2) carbon fiber is dispersed in 50 DEG C of salpeter solutions (67%) 3 hours with ultrasonic stirrer, in this process,
Carbon fiber surface is by Nitric acid etching；In 140 DEG C of vacuum filter driers by sample drying for 24 hours, after finally obtaining Nitric acid etching
Carbon fiber, the carbon fiber after etching is with alcohol with 1:1 mass ratio mixes 1h in ultrasonic stirrer；
(3) Phenolic resin powder is with 10:It is small that 1 mass ratio with hexa in V-arrangement blender is sufficiently mixed 2
When；
(4) liquid mixture and mixture of powders that are obtained in (2) and (3) are added in simultaneously in the reaction vessel of 10L, so
Container is sealed afterwards, by powder being made to be completely dissolved in acetone soln the stirring of mixed solution, agitator speed 100r/
After min, 3h, the liquid in reaction vessel is imported into evaporating dish.Evaporating dish is put into 60 DEG C of baking ovens and obtains mixing block for 24 hours；
(5) mixing block is put into omnipotent crusher and carries out broken 2h, obtained grain size and be broken for 100-200 μm of powder；
(6) it is target that broken powder, which adds in aerosil and 1-3h is stirred in V-arrangement blender, in step (5)
Powder.
Comparative example 1
(1) go out each component according to data below precise：Carbon fiber 3Kg, average diameter are 7 μm, 50 μ of length range
m-150μm；Phenolic resin powder, 2Kg, 50 μm -150 μm of particle size range；Aerosil, 10g；Hexa,
200g；
(2) carbon fiber is dispersed in 50 DEG C of salpeter solutions (67%) 3 hours with ultrasonic stirrer, in this process,
Carbon fiber surface is by Nitric acid etching；In 140 DEG C of vacuum filter driers by sample drying for 24 hours, after finally obtaining Nitric acid etching
Carbon fiber, the carbon fiber after etching is with alcohol with 1:1 mass ratio mixes 1h in ultrasonic stirrer；
(3) Phenolic resin powder is with 10:It is small that 1 mass ratio with hexa in V-arrangement blender is sufficiently mixed 2
When；
(4) liquid mixture and mixture of powders that are obtained in (2) and (3) are added in simultaneously in the reaction vessel of 10L, so
Container is sealed afterwards, by powder being made to be completely dissolved in acetone soln the stirring of mixed solution, agitator speed 100r/
After min, 3h, the liquid in reaction vessel is imported into evaporating dish.Evaporating dish is put into 60 DEG C of baking ovens and obtains mixing block for 24 hours；
(5) mixing block is put into omnipotent crusher and carries out broken 2h, obtained grain size and be broken for 100-200 μm of powder；
(6) it is target that broken powder, which adds in aerosil and 1-3h is stirred in V-arrangement blender, in step (5)
Powder.
Comparative example 2
(1) go out each component according to data below precise：Carbon fiber 3Kg, average diameter are 7 μm, length range 700
μm-800μm；Phenolic resin powder, 2Kg, 50 μm -150 μm of particle size range；Aerosil, 10g；Hexa,
200g；
(2) carbon fiber is dispersed in 50 DEG C of salpeter solutions (67%) 3 hours with ultrasonic stirrer, in this process,
Carbon fiber surface is by Nitric acid etching；In 140 DEG C of vacuum filter driers by sample drying for 24 hours, after finally obtaining Nitric acid etching
Carbon fiber, the carbon fiber after etching is with alcohol with 1:1 mass ratio mixes 1h in ultrasonic stirrer；
(3) Phenolic resin powder is with 10:It is small that 1 mass ratio with hexa in V-arrangement blender is sufficiently mixed 2
When；
(4) liquid mixture and mixture of powders that are obtained in (2) and (3) are added in simultaneously in the reaction vessel of 10L, so
Container is sealed afterwards, by powder being made to be completely dissolved in acetone soln the stirring of mixed solution, agitator speed 100r/
After min, 3h, the liquid in reaction vessel is imported into evaporating dish.Evaporating dish is put into 60 DEG C of baking ovens and obtains mixing block for 24 hours；
(5) mixing block is put into omnipotent crusher and carries out broken 2h, obtained grain size and be broken for 100-200 μm of powder；
(6) it is target that broken powder, which adds in aerosil and 1-3h is stirred in V-arrangement blender, in step (5)
Powder.
Since carbon fiber length is excessively high in this comparative example, powdering effect is poor, so as to the phenomenon that sample formation is poor occur, so as to
Lead to poor-performing.
Comparative example 3
(1) go out each component according to data below precise：Carbon fiber 2Kg, average diameter are 7 μm, length range 201
μm-300μm；Phenolic resin powder, 2Kg, 50 μm -150 μm of particle size range；Aerosil, 10g；Hexa,
200g；
(2) it is carbon fiber, phenolic resin, hexa and aerosil in (1) is abundant in V-arrangement blender
Mix 2h；
(3) carbon fiber of all drying with 80 mesh is sieved and sieved, the part reunited in carbon fiber and impurity are screened out；
Broken powder is target powder in step (3).
Comparative example 4
(1) go out each component according to data below precise：Carbon fiber 2Kg, average diameter are 7 μm, length range 250
μm-350μm；Phenolic resin powder, 2Kg, 50 μm -150 μm of particle size range；Aerosil, 10g；Hexa,
200g；
(2) it is carbon fiber, phenolic resin, hexa and aerosil in (1) is abundant in V-arrangement blender
Mix 2h；
(3) carbon fiber of all drying with 80 mesh is sieved and sieved, the part reunited in carbon fiber and impurity are screened out；
Broken powder is target powder in step (3).
Following table is phenolic resin molded part, the dusty material of the present invention is prepared the intensity of carbon/carbon compound material and
Modulus versus：
Embodiment 7：
Fig. 1 a and c illustrate an internal diameter and outer diameter is respectively the three-dimensional digital model and present invention process system of 20mm and 30mm
The corresponding 3D printing carbon/carbon compound material gear obtained.
(1) prepared by raw material：With (1) step in embodiment 2.
(2) green compact print：By step (1) in the printing raw material for preparing pour into 3D printer powder feeding cylinder, import parts
Three-dimensional graph (the present embodiment is gear as shown in Figure 1), then carries out slicing treatment by threedimensional model with delamination software, obtains
To the data information of each processing level of parts, the corresponding print procedure control parameter of computer is regulated, wherein filling work(
Rate is：30W, sweep span are 100 μm, and sweep speed is 280inch/s, is finally completed carbon/carbon compound material green compact system
It is standby.
(3) cure：(2) middle gained heat-preservation cylinder precast body is put into chemical vapor deposition stove step, is vacuumized, is passed through argon gas,
It heats up under protection of argon gas, curing solidification temperature is 180 DEG C, and heating rate cures soaking time for 0.5 DEG C/min and is
1h。
Carbonization：Carbon/carbon compound material green body obtained by curing process is continued to be placed in CVI stoves, CVI stoves continue heating so as to
Carbonization treatment is carried out to green body, carbonization temperature is 1100 DEG C.
Density：By the carbon/carbon compound material green body obtained by carbonization treatment through chemical vapor deposition density be required density, sink
Accumulated temperature degree is 950 DEG C~1250 DEG C, and 10min~120min is kept the temperature after reaching depositing temperature, then passes to natural gas and carries out chemistry
Vapor deposition, gas discharge are 2L/min~50L/min, and sedimentation time is 80h；Carbon/carbon compound material after density,
Apparent density is 1.5g/cm3。
Embodiment 8：
It is corresponding by present invention process system that Fig. 1 b and d illustrate a complex-shaped complex parts three-dimensional digital model
The corresponding 3D printing carbon/carbon compound material parts obtained, wherein contain cylinder, the structures such as level and cambered surface, wherein parts
There was only 0.5mm in most thin position.
The present invention step (2) in, import complex parts three-dimensional data figure as shown in Figure 1 b in a computer.
Remaining is the same as embodiment 1.
In this way, the present invention has the ability for having and preparing minimum thickness 0.5mm carbon/carbon compound material parts, and parts
Complex-shaped, including cylinder, curved surface, lamellar structure etc., parts bending strength is more than 60MPa, can substantially meet
Various industrial parts need.
Claims (6)
1. the carbon/carbon compound material preparation method of a kind of 3D printing, which is characterized in that including following preparation process：
(1) prepared by raw material：Take thermosetting resin, carbon fiber, curing agent and flow promortor spare；When carbon/carbon compound material green compact
When mass fraction is 100 parts, a diameter of 3 μm~15 μm of the carbon fiber, length is 200 μm~600 μm；The carbon is fine
After tieing up etched solution etches processing, with being mixed to get solidliquid mixture for dissolving the solvent of thermosetting resin；It will be described
Thermosetting resin is sufficiently mixed to obtain solid mixture with curing agent；The thermosetting resin particle size distribution range for 50 μm-
300μm；The solidliquid mixture, solid mixture are separately added into reaction vessel, after stirring and dissolving solid mixture, so
The mixture in reaction vessel is dried afterwards, obtained mixture block is broken for grain size after 10 μm~600 μm, to add in flowing
Auxiliary agent stirs into raw material powder；
(2) green compact print：(1) the raw material prepared in is poured into 3D printer powder feeding cylinder, zero is imported in control computer
Then threedimensional model is carried out slicing treatment by part three-dimensional graph with delamination software, obtain parts each processing levels
Data information, 3D printer is vacuumized, then passes to protective gas, regulates the control of control computer corresponding print procedure
Parameter is finally completed the preparation of carbon/carbon compound material green compact；
(3) curing, carbonization and density:By step (2) gained carbon/carbon compound material green compact be placed in heat-treatment furnace cured, carbon
Change and density handles to obtain carbon/carbon compound material；
In step (1) when the mass fraction of carbon/carbon compound material green compact is 100 parts, thermosetting resin mass fraction is 35-60
Part, carbon fiber mass fraction is 35-60 parts, and flow promortor mass fraction is 0.1-0.8 parts, and curing agent mass fraction is 2-8 parts；
Step (1) in required thermosetting resin resin be phenolic resin, furane resins, pitch, polybenzimidazoles, epoxy novolac its
Middle one or more；
Flow promortor described in step (1) is one or more of aerosil, gaseous oxidation aluminium, nanometer silicon carbide；
The curing agent used in step (1) is hexa.
2. preparation method according to claim 1, it is characterized in that step (2) in, the control parameter is to fill work(
Rate is：10W~80W, sweep span are 20 μm~500 μm, and sweep speed is 20inch/s~500inch/s.
3. preparation method according to claim 2, it is characterized in that, step (2) in, filling power is 20~70w, scanning
50-350 μm of spacing, sweep speed 150inch/s-450inch/s.
4. preparation method according to claim 3, which is characterized in that step (3) in need to carry out heating and make resin solidification,
Solidification temperature is 100 DEG C~250 DEG C；Heating rate is 0.1~5 DEG C/min in solidification process, and hardening time is 1h~10h.
5. preparation method according to claim 1, it is characterized in that, in step, (3) middle carburizing temperature is 250 DEG C~1300 DEG C,
Heat-treatment furnace heating rate is 0.1 DEG C/min~10 DEG C/min.
6. preparation method according to claim 1, it is characterized in that, the carbon/carbon compound material zero after step (3) middle density
Component, whole apparent density are 0.5g/cm3~2.2g/cm3。
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| DE102016100103A1 (en) * | 2016-01-04 | 2017-07-06 | Gianfranco Di Natale | Launching lever and method for its production |
| CN105693194B (en) * | 2016-01-08 | 2017-11-24 | 石棉县亿欣钙业有限责任公司 | The compound 3D printing material of high strength carbon carbon |
| CN106927846B (en) * | 2017-04-13 | 2018-05-04 | 华中科技大学 | A kind of preparation method of C/C-SiC composite material parts and products thereof |
| CN108929113B (en) * | 2017-05-24 | 2021-11-12 | 赵晴堂 | Manufacturing method of three-dimensional additive forming material |
| CN108947533B (en) * | 2018-08-31 | 2022-02-15 | 万华化学集团股份有限公司 | Preparation method of porous carbon material and application of obtained porous carbon material |
| CN112979334B (en) * | 2021-02-25 | 2022-12-02 | 攀枝花容则钒钛有限公司 | Preparation method of carbon fiber reinforced pantograph carbon slide plate based on 3D printing |
| CN113386349B (en) * | 2021-06-16 | 2022-07-12 | 西南交通大学 | 3D printing method of carbon fiber reinforced resin-based plate |
| CN115256927B (en) * | 2022-09-30 | 2023-01-31 | 北京壹碳氢源科技有限公司 | Carbon/carbon composite thermal insulation material prepared by 3D printing and preparation method thereof |
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