CN110395986A - A kind of method of long wavelength laser printed material - Google Patents
A kind of method of long wavelength laser printed material Download PDFInfo
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- CN110395986A CN110395986A CN201910717058.0A CN201910717058A CN110395986A CN 110395986 A CN110395986 A CN 110395986A CN 201910717058 A CN201910717058 A CN 201910717058A CN 110395986 A CN110395986 A CN 110395986A
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- B22F12/00—Apparatus or devices specially adapted for additive manufacturing; Auxiliary means for additive manufacturing; Combinations of additive manufacturing apparatus or devices with other processing apparatus or devices
- B22F12/40—Radiation means
- B22F12/41—Radiation means characterised by the type, e.g. laser or electron beam
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- 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
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Abstract
The present invention provides a kind of methods of long wavelength laser printed material characterized by comprising step S1: weighing resin and silicon carbide or metal-powder；Composite dispersing agent and initiator are added in resin, and mixed solution is made；Silicon carbide or metal-powder and boron carbide powder are added in the mixed solution, silicon carbide or metal paste is prepared；The silicon carbide or metal paste SZQ type four sides wet film maker are taken, it is equably coated on plate；It is scanned heating using the laser that wavelength is 600nm~11 μm, makes the silicon carbide or metal paste solidification；To after solidification silicon carbide or metal green compact be sintered, silicon carbide or metal device is made.The present invention solves the problems, such as the accurate control " shape " of the structure in carbofrax material.
Description
Technical field
The present invention relates to a kind of methods of long wavelength laser printed material.
Background technique
Silicon carbide ceramics has preferable mechanical strength, excellent corrosion resistance and antioxygenic property, and heating conduction
Height, thermal expansion coefficient are small, are best one of the materials of ceramic material high temperature mechanical property, are widely used in national defence, machine
The fields such as tool, chemical industry, metallurgy and electronics.Since silicon carbide ceramics has the characteristics that hardness is high, brittleness is big, its machine-shaping band is given
Very big difficulty is carried out.The device of simple structure can be prepared with conventional method, not need 3D printing.High-densit irregular shape
The manufacture of the silicon carbide components of shape is a difficult point.
The method of the silicon carbide components of research preparation at present, uses prefabricated presoma, injection forming and the side of extrusion molding more
Method.But the method and process of prefabricated presoma is more complex, higher cost, and the silicon carbide ceramics intensity prepared is not high.And slip casting at
Type yield rate is lower, and the period is longer, is unfavorable for mechanization and automates and be difficult to ensure product quality.Using extrusion molding system
The method of standby silicon carbide, it is lower to squeeze out precision.
Summary of the invention
It is an object of the present invention to provide a kind of methods of long wavelength laser printed material, are able to solve and are preparing hard material
Accurate control " shape " problem of structure in production process.
In order to achieve the above object, the present invention provides a kind of methods of long wavelength laser printed material, which is characterized in that
Include:
Step S1: the resin and silicon carbide or metal-powder that volume ratio is 1:1~1:2 are weighed；Carbon is added in resin
The composite dispersing agent of 2~10wt% of SiClx or metal-powder total amount is mixed 5-10 minutes, continues to add resin total amount
The initiator of 0.5wt%~2wt% is mixed 5-10 minutes, and mixed solution is made；
Step S2, boron carbide powder is weighed according to the 1.4-1.6wt% of silicon carbide or metal-powder total amount, by weighed carbon
SiClx or metal-powder and boron carbide powder are added in the mixed solution, continues to mix stirring until powder divides completely
It dissipates, the silicon carbide or metal paste that solid concentration is 35vol%~55vol% is prepared；
Step S3, the silicon carbide or metal paste SZQ type four sides wet film maker are taken, it is equably coated in flat
On plate, with a thickness of 45-55 μm；
Step S4, it is scanned heating using the laser that wavelength is 600nm~11 μm, makes the silicon carbide or metal
Slurry curing；
Step S5, SZQ type four sides wet film maker is reused, silicon carbide or metal paste are equably coated in cured
Silicon carbide or metal surface, with a thickness of 45-55 μm；
Step S6, it is repeated in step S4 and S5, silicon carbide or metal green compact after being solidified；
Step S7, to after solidification silicon carbide or metal green compact be sintered, silicon carbide or metal device is made.
Preferably, the metal is the metal of molding and sintering of being heating and curing suitable for laser, as stainless steel, mould steel,
Copper alloy, aluminium alloy etc..
Preferably, the resin of the step S1 is hydroxyethyl methacrylate (HEMA), 2- phenoxyethyl acrylate
(PHEA), 1,6 hexanediol diacrylate (HDDA), polyethylene glycol dimethacrylate (PEGDMA), trimethylolpropane
Triacrylate (TMPTA), pentaerythritol triacrylate (PET3A), ethoxylated bisphenol A dimethylacrylate
(BPA4DMA) any one in or two or more combinations.
It is highly preferred that the resin of the step S1 by volume ratio be the hydroxyethyl methacrylate of 3:4:3,1,6- oneself two
Alcohol diacrylate and trimethylolpropane trimethacrylate mix.
Simple function group resin monomer can reduce the viscosity and reactivity of silicon carbide slurry, increase solid concentration, green compact
Brittleness is lower, unsticking more rapidly.Multi-functional resin monomer increases resin reaction, green body brittleness is higher, unsticking more
Slowly.The suitable reactivity of resin needs of the invention and unsticking, sample that is too fast and being all unfavorable for acquisition even tissue slowly excessively,
Lead to its mechanical heterogeneity, simple function group resin and polyfunctional group resin are matched according to a certain percentage and obtain power by the present invention
Learn the uniform sample of performance.
Preferably, the composite dispersing agent of the step S1 is BYK-2012, BYK-110, BYK-180, BYK-106, oil
Two or more in acid, stearic acid and polyacrylic acid are composed.
Preferably, the composite dispersing agent is made of the BYK-2012 and BYK-106 that mass ratio is 1:1~3:2.Dispersion
Agent effectively prevent ceramic powder to settle, and reunites, realizes the high stability of slurry.The silicon carbide slurry of good dispersion, when 3D printing
Slurry is easier to form.The lower slurry of the available preferable viscosity of dispersibility of composite dispersing agent, can further be promoted solid
Phase content, and can be good at weakening shear thickening phenomenon existing for silicon carbide slurry, silicon carbide powder can be improved in resin
In dispersing uniformity, be conducive to sintering density and performance uniformity.
Preferably, dibenzoyl peroxide and N that the initiator of the step S1 is 1:1 by mass ratio, N- dimethyl
Acetamide composition.Composite initiator is photo-thermal curing, can reduce solidification temperature and curing time.
Preferably, laser selected in the step S4 is the laser of low-power long wavelength, optical maser wavelength model
It is trapped among 600~11 μm.Low-power long wavelength advantageously reduces the impact of laser particle, and highlights its heating properties, favorably
In raising solidification effect.
Preferably, sintering is silicon carbide green body after printing under the conditions of 2100 DEG C of argon atmospheres in the step S7
30~60min of sintered heat insulating.
Compared with prior art, the beneficial effects of the present invention are:
The present invention is based on the technical principles of 3D printing, by the type for selecting suitable resin, dispersing agent and initiator
The silicon carbide slurry that dispersing agent is preferable, viscosity is lower and is suitable for 3D printing is prepared with adding proportion.And it prepares
Silicon carbide device precision with higher and compactness efficiently solve and prepare carbonization silicon complex currently with other moulding process
The low problem of device yield, precision overcomes material structure and orthofunction design, control " property " and complicated shape increasing material manufacturing
Control the technical problem of " shape " perfect combination.
The present invention adds thermal property using long wavelength laser, so that passing through 3D printing technique preparation high-precision, high strength carbon
SiClx ceramics become with more feasibility.The method of long wavelength laser printing simultaneously can also be used for metallic print, has opened up 3D and has beaten
The application prospect of print in a metal.
Specific embodiment
Present invention will be further explained below with reference to specific examples.It should be understood that these embodiments are merely to illustrate the present invention
Rather than it limits the scope of the invention.In addition, it should also be understood that, after reading the content taught by the present invention, those skilled in the art
Member can make various changes or modifications the present invention, and such equivalent forms equally fall within the application the appended claims and limited
Range.
Embodiment 1
A kind of method of long wavelength laser printed material, specific steps are as follows:
Step S1, weigh volume ratio be 1:1 resin and silicon carbide powder, resin be volume ratio be 2:1:4:3 HEMA,
The mixed uniformly hybrid resin of PHEA, HDDA and TMPTA；
Step S2, the composite dispersing agent of silicon carbide powder total amount 2wt% is added in resin, composite dispersing agent is mass ratio
For the BYK-110 and BYK-106 of 1:1, it is mixed 5 minutes；
Step S3, the composite initiator of resin total amount 1.5wt% is added, composite initiator is the peroxide that mass ratio is 1:1
Change dibenzoyl and n,N-dimethylacetamide, be mixed 5 minutes, mixed solution is made；
Step S4, weigh boron carbide powder according to the 1.5wt% of silicon carbide powder total amount, by weighed silicon carbide powder and
Boron carbide powder is added in the mixed solution, continuess to mix stirring 60 minutes until powder is completely dispersed, is prepared into solid phase
Content is the silicon carbide slurry of 50vol%；
Step S5, silicon carbide slurry SZQ type four sides wet film maker is taken, it is uniformly coated on plate,
With a thickness of 50 μm；
Step S6, the laser for the use of wavelength being 684nm selects 800mw) power and 1.5m/s scanning speed be to choosing
Region is scanned heating, solidifies the silicon carbide slurry；
Step S7, SZQ type four sides wet film maker is reused, silicon carbide slurry is evenly coated in cured silicon carbide
Surface layer, with a thickness of 50 μm；
Step S8, step S6 and S7, the silicon carbide ceramics green compact after being solidified are repeated in.
Step S9, to the silicon carbide ceramic body after solidification under the conditions of argon atmosphere and 2100 DEG C of temperature sintered heat insulating
Silicon carbide ceramics is made in 30min, and the strength of materials is high, and precision is high, and precision can achieve positive and negative 0.05mm.
Embodiment 2
A kind of method of long wavelength laser printed material, specific steps are as follows:
Step S1, weigh volume ratio be 2:3 resin and silicon carbide powder, resin be volume ratio be 3:4:3 HEMA,
The mixed uniformly hybrid resin of HDDA and TMPTA；
Step S2, the composite dispersing agent of silicon carbide powder total amount 4wt% is added in resin, composite dispersing agent is mass ratio
For the BYK-2012 and BYK-106 of 1:2, it is mixed 8 minutes；
Step S3, continue the composite initiator of addition resin total amount 2wt%, composite initiator is the mistake that mass ratio is 1:1
Dibenzoyl and n,N-dimethylacetamide are aoxidized, is mixed 7 minutes, mixed solution is made；
Described step S4, by the addition of the boron carbide powder of weighed carborundum powder and silicon carbide powder total amount 1.5wt%
In mixed solution, continuess to mix stirring and be completely dispersed to powder for 60 minutes, the solid concentration that suitable extrusion molding is prepared is
The paste slurry of 50vol%, in order to better extrusion molding and preparation high density finished product；
Step S5, silicon carbide slurry SZQ type four sides wet film maker is taken, it is uniformly coated on plate, with a thickness of
50μm；
Step S6, the laser for the use of wavelength being 1064nm selects 3w power and 1.5m/s scanning speed to the area chosen
Domain is scanned heating, solidifies the silicon carbide slurry；
Step S7, SZQ type four sides wet film maker is reused, silicon carbide slurry is evenly coated in cured silicon carbide
Surface layer, with a thickness of 50 μm；
Step S8, step S6 and S7, the silicon carbide ceramics green compact after being solidified are repeated in.
Step S9, to the silicon carbide green body after solidification under the conditions of argon atmosphere and 2100 DEG C of temperature sintered heat insulating 45min,
Silicon carbide ceramics is made, the strength of materials is high, and precision is high, and precision can achieve positive and negative 0.05mm.
Embodiment 3
A kind of method of long wavelength laser printed material, specific steps are as follows:
Step S1, weigh volume ratio be 2:3 resin and silicon carbide powder, resin be volume ratio be 3:2:3:2 HEMA,
The mixed uniformly hybrid resin of HDDA, PHEA and TMPTA；
Step S2, the composite dispersing agent of silicon carbide powder total amount 5wt% is added in resin, composite dispersing agent is mass ratio
For the BYK-2012 and BYK-106 of 1:3, it is mixed 8 minutes；
Step S3, continue the composite initiator of addition resin total amount 2wt%, composite initiator is the mistake that mass ratio is 1:1
Dibenzoyl and n,N-dimethylacetamide are aoxidized, is mixed 7 minutes, mixed solution is made；
Described step S4, by the addition of the boron carbide powder of weighed carborundum powder and silicon carbide powder total amount 1.5wt%
In mixed solution, continuess to mix stirring and be completely dispersed to powder for 60 minutes, the solid concentration that suitable extrusion molding is prepared is
The paste slurry of 50vol%, in order to better extrusion molding and preparation high density finished product；
Step S5, silicon carbide slurry SZQ type four sides wet film maker is taken, it is uniformly coated on plate, with a thickness of
50μm；
Step S6, the laser for the use of wavelength being 831nm selects 2w) power and 1.5m/s scanning speed be to the area chosen
Domain is scanned heating, solidifies the silicon carbide slurry；
Step S7, SZQ type four sides wet film maker is reused, silicon carbide slurry is evenly coated in cured silicon carbide
Surface layer, with a thickness of 50 μm；
Step S8, step S6 and S7, the silicon carbide ceramics green compact after being solidified are repeated in.
Step S9, to the silicon carbide green body after solidification under the conditions of argon atmosphere and 2100 DEG C of temperature sintered heat insulating 60min,
Silicon carbide ceramics is made, the strength of materials is high, and precision is high, and precision can achieve positive and negative 0.05mm.
Embodiment 4
A kind of method of long wavelength laser printed material, specific steps are as follows:
Step S1, the resin and silicon carbide powder that volume ratio is 3:4 are weighed, resin is that volume ratio is 1:2:3:2:2
The mixed uniformly hybrid resin of HEMA, HDDA, PHEA, TMPTA and BPA4DMA；
Step S2, the composite dispersing agent of silicon carbide powder total amount 6wt% is added in resin, composite dispersing agent is mass ratio
For BYK-2012, BYK-180 and oleic acid of 1:1:1, it is mixed 8 minutes；
Step S3, continue the composite initiator of addition resin total amount 1.5wt%, composite initiator is that mass ratio is 1:1's
Dibenzoyl peroxide and n,N-dimethylacetamide are mixed 5 minutes, and mixed solution is made；
Described step S4, by the addition of the boron carbide powder of weighed carborundum powder and silicon carbide powder total amount 1.5wt%
In mixed solution, continuess to mix stirring and be completely dispersed to powder for 60 minutes, the solid concentration that suitable extrusion molding is prepared is
The paste slurry of 50vol%, in order to better extrusion molding and preparation high density finished product；
Step S5, silicon carbide slurry SZQ type four sides wet film maker is taken, it is uniformly coated on plate, with a thickness of
50μm；
Step S6, the laser for the use of wavelength being 1064nm selects 3w power and 1.5m/s scanning speed to the area chosen
Domain is scanned heating, solidifies the silicon carbide slurry；
Step S7, SZQ type four sides wet film maker is reused, silicon carbide slurry is evenly coated in cured silicon carbide
Surface layer, with a thickness of 50 μm；
Step S8, step S6 and S7, the silicon carbide ceramics green compact after being solidified are repeated in.
Step S9, to the silicon carbide green body after solidification under the conditions of argon atmosphere and 2100 DEG C of temperature sintered heat insulating 60min,
Silicon carbide ceramics is made, the strength of materials is high, and precision is high, and precision can achieve positive and negative 0.05mm.
Embodiment 5
A kind of method of long wavelength laser printed material, specific steps are as follows:
Step S1, the resin and silicon carbide powder that volume ratio is 2:3 are weighed, resin is that volume ratio is 1:2:2:2:2:1
The mixed uniformly hybrid resin of HEMA, PHEA, PEGDMA, HDDA, PET3A and BPA4DMA；
Step S2, the composite dispersing agent of silicon carbide powder total amount 5wt% is added in resin, composite dispersing agent is mass ratio
For BYK-106, SA and PAA-NH of 1:1:13, it is mixed 8 minutes；
Step S3, continue the composite initiator of addition resin total amount 2wt%, composite initiator is the mistake that mass ratio is 1:1
Dibenzoyl and n,N-dimethylacetamide are aoxidized, is mixed 7 minutes, mixed solution is made；
Described step S4, by the addition of the boron carbide powder of weighed carborundum powder and silicon carbide powder total amount 1.5wt%
In mixed solution, continuess to mix stirring and be completely dispersed to powder for 60 minutes, the solid concentration that suitable extrusion molding is prepared is
The paste slurry of 50vol%, in order to better extrusion molding and preparation high density finished product；
Step S5, silicon carbide slurry SZQ type four sides wet film maker is taken, it is uniformly coated on plate, with a thickness of
50μm；
Step S6, the laser for the use of wavelength being 10.64 μm selects 5w power and 1.5m/s scanning speed to the area chosen
Domain is scanned heating, solidifies the silicon carbide slurry；
Step S7, SZQ type four sides wet film maker is reused, silicon carbide slurry is evenly coated in cured silicon carbide
Surface layer, with a thickness of 50 μm；
Step S8, step S6 and S7, the silicon carbide ceramics green compact after being solidified are repeated in.
Step S9, to the silicon carbide green body after solidification under the conditions of argon atmosphere and 2100 DEG C of temperature sintered heat insulating 60min,
Silicon carbide ceramics is made, the strength of materials is high, and precision is high, and precision can achieve positive and negative 0.05mm.
Embodiment 6
A kind of method of long wavelength laser printed material, specific steps are as follows:
Step S1, weigh volume ratio be 1:3 resin and 343L stainless steel powder, resin be volume ratio be 3:4:3 HEMA,
The mixed uniformly hybrid resin of HDDA and TMPTA；
Step S2, the composite dispersing agent of stainless steel powder powder total amount 4wt% is added in resin, composite dispersing agent is quality
Than the BYK-180 and BYK-106 for 2:1, it is mixed 8 minutes；
Step S3, continue the initiator dibenzoyl peroxide of addition resin total amount 2wt%, be mixed 7 minutes, be made
Mixed solution；
Described step S4, by the addition of the boron carbide powder of weighed stainless steel powder and stainless steel powder total amount 1.5wt%
In mixed solution, continuess to mix stirring and be completely dispersed to powder for 60 minutes, the solid concentration that suitable extrusion molding is prepared is
The paste slurry of 50vol%, in order to better extrusion molding and preparation high density finished product；
Step S5, stainless steel slurry SZQ type four sides wet film maker is taken, it is uniformly coated on plate, with a thickness of
50μm；
Step S6, the laser for the use of wavelength being 1064nm selects 3w power and 1.5m/s scanning speed to the area chosen
Domain is scanned heating, makes the slurry curing；
Step S7, SZQ type four sides wet film maker is reused, slurry is evenly coated in cured stainless steel slurry table
Layer, with a thickness of 50 μm；
Step S8, step S6 and S7, the stainless steel green compact after being solidified are repeated in.
Step S9, to the stainless steel blank after solidification hydrogen and nitrogen mixed atmosphere, under in 1250 DEG C of temperature conditions
Lower sintered heat insulating 60min, is made stainless steel device, and the strength of materials is high, and precision is high, and precision can achieve positive and negative 0.05mm.
Claims (9)
1. a kind of method of long wavelength laser printed material characterized by comprising
Step S1: the resin and silicon carbide or metal-powder that volume ratio is 1:1~1:2 are weighed；Silicon carbide is added in resin
Or the composite dispersing agent of 2~10wt% of metal-powder total amount, it is mixed 5-10 minutes, continues to add resin total amount 0.5wt%
The initiator of~2wt% is mixed 5-10 minutes, and mixed solution is made；
Step S2, boron carbide powder is weighed according to the 1.4-1.6wt% of silicon carbide or metal-powder total amount, by weighed silicon carbide
Or metal-powder and boron carbide powder are added in the mixed solution, continues to mix stirring until powder is completely dispersed, make
It is standby to obtain the silicon carbide or metal paste that solid concentration is 35vol%~55vol%；
Step S3, the silicon carbide or metal paste SZQ type four sides wet film maker are taken, it is equably coated in plate
On, with a thickness of 45-55 μm；
Step S4, it is scanned heating using the laser that wavelength is 600nm~11 μm, makes the silicon carbide or metal paste
Solidification；
Step S5, SZQ type four sides wet film maker is reused, silicon carbide or metal paste are equably coated in cured carbon
SiClx or metal surface, with a thickness of 45-55 μm；
Step S6, it is repeated in step S4 and S5, silicon carbide or metal green compact after being solidified；
Step S7, to after solidification silicon carbide or metal green compact be sintered, silicon carbide or metal device is made.
2. the method for long wavelength laser printed material as described in claim 1, which is characterized in that the resin of the step S1 is
Hydroxyethyl methacrylate, 2- phenoxyethyl acrylate, 1,6 hexanediyl esters, polyethylene glycol dimethyl allene
Acid esters, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, in ethoxylated bisphenol A dimethylacrylate
Any one or two or more combinations.
3. the method for long wavelength laser printed material as claimed in claim 2, which is characterized in that the resin of the step S1
Hydroxyethyl methacrylate, 1,6 hexanediol diacrylate and the trimethylolpropane tris acrylic acid for being 3:4:3 by volume ratio
Ester mixes.
4. the method for long wavelength laser printed material as described in claim 1, which is characterized in that the step S1's is compound
Dispersing agent is two or more groups in BYK-2012, BYK-110, BYK-180, BYK-106, oleic acid, stearic acid and polyacrylic acid
It closes.
5. the method for long wavelength laser printed material as described in claim 1, which is characterized in that the composite dispersing agent by
The BYK-2012 and BYK-106 that mass ratio is 1:1~3:2 are formed.
6. the method for long wavelength laser printed material as described in claim 1, which is characterized in that the initiation of the step S1
Agent is made of the dibenzoyl peroxide that mass ratio is 1:1 and DMAC N,N' dimethyl acetamide.
7. the method for long wavelength laser printed material as described in claim 1, which is characterized in that selected in the step S4
The laser selected is the laser of low-power long wavelength.
8. the method for long wavelength laser printed material as described in claim 1, which is characterized in that be sintered in the step S7
It is the 30~60min of sintered heat insulating under the conditions of 2100 DEG C of argon atmospheres of the silicon carbide green body after printing.
9. the method for long wavelength laser printed material as described in claim 1, which is characterized in that the metal is stainless
Steel, mould steel, copper alloy or aluminium alloy.
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