CN106547039B - A kind of preparation method of SiC photonic crystal - Google Patents
A kind of preparation method of SiC photonic crystal Download PDFInfo
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- CN106547039B CN106547039B CN201610979345.5A CN201610979345A CN106547039B CN 106547039 B CN106547039 B CN 106547039B CN 201610979345 A CN201610979345 A CN 201610979345A CN 106547039 B CN106547039 B CN 106547039B
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Abstract
The invention discloses a kind of preparation methods of SiC photonic crystal, and SiC powder, boron powder, carbon dust, ethyl alcohol and dispersing agent are added in ball mill and carry out ball milling, dissociation；Above-mentioned solid powder is added in photo-curing monomer, dispersing agent is added, and free radical photo-initiation is added under the conditions of being protected from light, stirs evenly, obtain suspension；Defoaming agent is finally added in suspension, obtains uniform, bubble-free suspension；Suspension is added in optical soliton interaction equipment, according to the three-dimensional modeling data of photon crystal structure, multi-shell curing is carried out to suspension using ultraviolet light, prepares green structure；Green compact are finally subjected to degreasing and sintering processes, obtain the SiC photonic crystal of compact structure.Preparation method of the invention gets rid of the limitation of structure, can be designed on demand to crystal structure, and largely reduction processing duration and manufacturing cost.
Description
Technical field
The invention belongs to optical soliton interaction technical fields, and in particular to a kind of preparation method of SiC photonic crystal.
Background technique
Photonic crystal refers to that cardinal principle is exactly to forbid falling with photon band gap, with the artificial material of periodic structure
The propagation of wave in photon band gap, the advantage of this material be exactly can manual change's crystal periodic structure according to demand, formed
Different band gap, to limit the propagation of different waves.Since photonic crystal has this specific function, make it in optical fiber, laser
The numerous areas such as device, waveguide, reflecting mirror and filter have a wide range of applications.Silicon carbide (SiC) material has high forbidden band wide
Degree, low dielectric constant, in recent years material preparation, in terms of make a breakthrough so that SiC become third
For one of material most popular in semiconductor material, thus SiC material is currently to prepare in photon crystal material most to dive
The material of power.The connectivity of photon crystal structure, dielectric constant and dielectric all plays a decisive role to the performance of photonic crystal.
But it since photonic crystal has miniature periodical labyrinth, lattice scale and the wavelength order of magnitude having the same, manufactures
Whole, complicated, symmetrical photonic crystal technology becomes current huge challenge.
The processing method of conventional photonic crystals mainly has tradition machinery processing method, colloid self-organizing method, bis- (more) photons poly-
Conjunction method, multiple-beam interference method etc., these methods mainly have the disadvantages that
1) manufacturing process is complicated, and labyrinth is difficult to realize；
2) preparation cost is high, and activity time is too long；
3) structural controllability is poor, and the introducing of defect is more difficult；
4) be not suitable for the batch production with customization.
Summary of the invention
The object of the present invention is to provide a kind of preparation methods of SiC photonic crystal, solve existing preparation method and are difficult to make
The problem of standby labyrinth photonic crystal.
The technical scheme adopted by the invention is that a kind of preparation method of SiC photonic crystal, comprising the following steps:
Step 1, prepared by SiC suspension
Step 1-1, solid powder preparation
SiC powder, boron powder, carbon dust, ethyl alcohol and dispersing agent are added in ball mill and carry out ball milling, dissociation, then by ball
Mixture after mill carries out low-temperature evaporation, obtains the solid powder that surface has organic matter；
Step 1-2, suspension mixing
Photocuring is added in above-mentioned solid powder by the ratio for being 1-9:1 according to solid powder and photo-curing monomer mass ratio
In monomer, dispersing agent is added, and free radical photo-initiation is added under the conditions of being protected from light, stirred evenly, obtain suspension；
Step 1-3, suspension processing
Defoaming agent is added in suspension, obtains uniform, bubble-free suspension；
Step 2, the manufacture of part green compact
SiC suspension is added in optical soliton interaction equipment, according to the three-dimensional modeling data of photon crystal structure, utilizes purple
Outer light carries out multi-shell curing to suspension, prepares SiC photonic crystal green structure；
Step 3, aftertreatment technology
Progress degreasing, sintering processes in high temperature sintering furnace is put the green body into, the SiC photonic crystal of compact structure is obtained.It should
The characteristics of method, also resides in:
Wherein, photo-curing monomer is urethane acrylate, 1,6- hexanediyl ester monomer, epoxy resin, third
Olefin(e) acid ester or one of acrylic acid and organic silicon acrylic ester are a variety of；Free radical photo-initiation is benzophenone, double benzene first
Aminosulfonylphenyl phosphorous oxide, azodiisobutyronitrile, 2,4,6- trimethylbenzoyl phosphinic acid ethyl esters or benzoin dimethylether, freely
The quality of base photoinitiator is the 0.2%~3% of photo-curing monomer.
Preferably, the quality sum of boron powder and carbon dust is the 0.02%~2% of SiC powder quality；Ethyl alcohol accounts for SiC powder matter
The 20%~60% of amount；Dispersing agent is one of poly- sodium propionate, quaternary ammonium acetate or phosphate, and quality is SiC powder quality
0.5%~5%；Wherein, the dispersing agent quality being added when prepared by solid powder is the 0.05%~1.5% of SiC powder quality, is hanged
The dispersing agent quality that supernatant liquid is added when mixing is the 0.45%~3.5% of SiC powder quality.Defoaming agent is lower alcohol, You Jigai
Property compound, mineral oil, organic polymer or organic siliconresin, quality be suspension quality 0.03%~0.1%.
Step 1-1 ball milling controls powder size between 0.1 μm~5 μm.
Further, in suspension mixed process, suspension is preheated, the control of suspension final viscosity is made to exist
Between 1500mPas~2000mPas.Preheating temperature is preferably shorter than 75 DEG C
Further, be additionally added diluent in step 1-2, diluent be cyclohexanone, n-butanol, styrene or methyl ethyl ketone it
One, quality is the 0.03%~3% of suspension quality；It is additionally added sagging inhibitor in step 1-3, prevents suspension from placing
It is layered in journey, sagging inhibitor is one of polyoxyethylene fatty amine, ethylene oxide aliphatic alcohol sulfate, and quality is suspension matter
The 0.02%~0.1% of amount.
The optical wavelength range of photocuring is 240-400nm in step 2, and layer thickness control is between 20-40 μm.
The ungrease treatment technique of step 3 are as follows: photonic crystal green compact room temperature is entered into furnace, with 10 DEG C/min~15 DEG C/min speed
Degree is warming up to 100 DEG C~200 DEG C, is warming up to 300 DEG C~400 DEG C with 4 DEG C/min~6 DEG C/min, 1h~1.5h is kept the temperature, with 2.5
DEG C/min~3.0 DEG C/min is warming up to 450-500 DEG C, 0.5h~1h is kept the temperature, is warming up to 600 with 0.5 DEG C/min~1.5 DEG C/min
DEG C~700 DEG C, keep the temperature 2h~4h.
The sintering processes technique of step 3 are as follows: 1500 DEG C~1600 DEG C are warming up to 15 DEG C/min~20 DEG C/min speed, with
2.5 DEG C/min~5 DEG C/min is warming up to 1700 DEG C~1800 DEG C, keeps the temperature 1h~1.5h, with 0.5 DEG C/min~1 DEG C/min heating
It to 1900 DEG C~2300 DEG C, is sintered, keeps the temperature 2h~4h.
The invention has the advantages that the preparation method of SiC photonic crystal of the invention breaches traditional handicraft, use
SiC material realizes the photocuring technology of fine and close part.This method can prepare the photonic crystal of any labyrinth, as crystal lacks
The design etc. of sunken introducing, periodic structure.Meanwhile this method can be shortened processing duration, reduce production cost.
Specific embodiment
The present invention is described in further detail With reference to embodiment, but the present invention is not limited to these realities
Apply mode.
SiC photonic crystal of the invention the preparation method is as follows:
Step 1, prepared by SiC suspension
The property of suspension drastically influences the performance of part, thus prepares fine and close, part with high accuracy, and suspension is solid
The control of the properties such as body content of powder and viscosity is particularly important.Suspension is drawn by SiC solid powder, boron powder, carbon dust, light
The materials such as hair agent, monomer, dispersing agent, defoaming agent, auxiliary agent are mixed.Specific suspension preparation process is broadly divided into following mistake
Journey:
Step 1-1, solid powder preparation
SiC powder, boron powder and carbon dust are added in ball mill and carry out ball milling, dissociation, controls the powder of final solid powder
Last granularity is maintained between 0.1 μm~5 μm, and powder sphericity is high.The quality sum of boron powder and carbon dust is SiC powder quality
0.02%~2%, function as later period sintering aid.
In order to sufficiently dissociate solid powder, ethyl alcohol is added simultaneously in the ball mill and dispersing agent carries out ball milling, so as to more
Adequately dissociation.Ethyl alcohol quality accounts for the 20%~60% of SiC powder quality；Dispersing agent is poly- sodium propionate, quaternary ammonium acetate or phosphorus
One of acid esters, quality are the 0.05%~1.5% of SiC powder quality.
Then, the material after ball milling is carried out to solvent evaporation under 30-50 DEG C of low temperature, obtains solid powder, guarantees powder
Particle surface adheres to organic matter, increases the subsequent dissolubility in photo-curing monomer of solid powder, convenient for solid powder in monomer
High solid phase, low viscosity, uniform suspension are capable of forming in solution.
Step 1-2, suspension mixing
Photocuring is added in above-mentioned solid powder by the ratio for being 1-9:1 according to solid powder and photo-curing monomer mass ratio
It in monomer, stirs evenly, and free radical photo-initiation is added under the conditions of being protected from light.Photo-curing monomer be urethane acrylate,
1,6 hexanediol diacrylate monomer, epoxy resin, acrylate or one of acrylic acid and organic silicon acrylic ester or
A variety of mixtures, preferably 1,6- hexanediyl ester monomer.The quality of free radical photo-initiation is photo-curing monomer
0.2%~3%, it is excellent for benzophenone, double benzoylphenyl phosphorous oxides, azodiisobutyronitrile or benzoin dimethylether etc.
Select benzoin dimethylether.
In order to dissolve in solid powder more fully in photo-curing monomer, while dispersion identical with step 1-1 is added
Agent, dispersing agent quality are the 0.45%~3.5% of SiC powder.If suspension viscosity is excessively high to be reduced by the way that diluent is added
The viscosity of suspension, diluent are one of cyclohexanone, n-butanol, styrene, methyl ethyl ketone, and additional amount is suspension quality
0.03%~3%.Simultaneously also suspension can be stirred without interruption, preheated in entire suspension mixed process, and is pre-
Hot temperature is lower than 75 DEG C.The reason of preheating is that the viscosity of suspension reduces as the temperature rises.
Step 1-3, suspension processing
To prevent suspension to be layered in placement process, sagging inhibitor is added in suspension, sagging inhibitor is poly-
One of ethylene oxide fatty amine, polyoxyethylene fatty alcohol sulfate, the quality of sagging inhibitor be suspension quality 0.02%~
0.1%.In suspension whipping process, there can be a large amount of bubble, thus also need that defoaming agent is added.Common defoaming agent has
Lower alcohol, organically-modified compound, mineral oil, organic polymer, organic siliconresin etc..The introducing of defoaming agent can eliminate suspension
Influence of the middle bubble to part quality.The dosage of defoaming agent is controlled the 0.03%~0.1% of suspension quality.
It after defoaming agent is added, is slowly stirred, after bubble recession, obtains uniform, bubble-free suspension, final obtained hangs
Supernatant liquid should be high solid phase, viscosity in 1500mPas~2000mPas.
Step 2, the manufacture of part green compact
Processing is designed to photon crystal structure using three-dimensional graphics software, and model is imported into data processing software
In, carry out layered shaping.SiC suspension is added in optical soliton interaction equipment, according to three-dimensional modeling data, utilizes ultraviolet light pair
Suspension is solidified, and optical wavelength range is 240-400nm, and layer thickness control finally prepares SiC photon between 20-40 μm
Crystal green structure.
Step 3, aftertreatment technology
The resulting green compact of photocuring are the mixtures of part and binder, need to put the green body into high temperature sintering furnace and be taken off
Rouge and sintering post-processing.
Skimming temp is determined according to thermogravimetry (TG), chooses the apparent temperature range of mass change as skimming temp, originally
The skimming temp of invention is 600 DEG C~700 DEG C, and sintering temperature is generally 0.7~0.9 times of material melting point, i.e., 1900 DEG C~
2300℃.Degreasing and sintering all should slowly be warming up to corresponding temperature, rationally control heating rate, it is ensured that binder can be steady
Fixed, uniform, thorough removal, while guaranteeing to form high-precision SiC photonic crystal.Preferred process technique is as follows:
Step 3-1, degreasing
Photonic crystal green compact are put into high temperature sintering furnace.Room temperature enters furnace, with 10 DEG C/min~15 DEG C/min speed liter
Temperature is warming up to 300 DEG C~400 DEG C to 100 DEG C~200 DEG C, with 4 DEG C/min~6 DEG C/min, keeps the temperature 1h~1.5h, with 2.5 DEG C/
Min~3.0 DEG C/min is warming up to 450-500 DEG C, keeps the temperature 0.5h~1h, is warming up to 600 DEG C with 0.5 DEG C/min~1.5 DEG C/min
~700 DEG C, keep the temperature 2h~4h.
Step 3-2, sintering
After skimming processes are completed, it is sintered.1500 DEG C are warming up to 15 DEG C/min~20 DEG C/min speed
~1600 DEG C, 1700 DEG C~1800 DEG C are warming up to 2.5 DEG C/min~5 DEG C/min, 1h~1.5h is kept the temperature, with 0.5 DEG C/min~1
DEG C/min is warming up to 1900 DEG C~2300 DEG C, is sintered, keep the temperature 2h~4h.
Note: in entire part forming process, it should be noted that the control of oxygen content is no more than 100ppm, is because the present invention makes
It is free radical photo-initiation, oxygen can react with free radical, to reduce solidification rate, inhibit curing reaction.
The present invention uses the technology of optical soliton interaction, the limitation of conventional machining structure is got rid of, according to demand to photonic crystal
Modelling is carried out, realizes the structural periodicity and complexity of photonic crystal.Meanwhile using the slurry with above-mentioned formulation ratio
Material improves the uniformity of slurry mixing, in combination with specific degreasing, agglomerant while guarantee slurry solid phase high accounting
Skill step, it is ensured that the high-precision of photonic crystal, high-performance.
Embodiment 1
1. preparing suspension
Firstly, choosing the SiC powder of 800g specification I, powder size is 0.4 μm~0.8 μm, chooses 800g specification II
SiC powder, powder size are 0.8 μm~2.0 μm.The B powder and C powder of 5g are chosen respectively, and powder size is 0.5 μm~1.0 μm.
The SiC powder of two kinds of specifications is uniformly mixed with B powder, C powder, is divided into five parts.3g quaternary ammonium acetate is chosen, dispersing agent is divided into
Five parts.First part of SiC mixed-powder and corresponding dispersing agent are added in ball mill, ball milling is carried out, dissociates, after 30min,
Second part of solid powder and dispersing agent is added, successively carries out, until solid powder be uniformly mixed, nodularization.After the completion of ball milling, add
Enter the ethanol solution of 600g, stirs, low-temperature evaporation.
Secondly, taking 1, the 6- hexanediyl ester monomer solution of 1250g, by the SiC solid powder after ball milling and divide
Powder is gradually added in monomer solution, and the quality of dispersing agent is 10g, and the benzoin dimethylether of 4g is added in darkroom.It is entire outstanding
For the mixed process of supernatant liquid all in heated condition, temperature is maintained at 50 DEG C or so, and is constantly stirred.The different of 1.8g is added
The polyoxyethylene fatty amine of propyl alcohol and 1.2g eliminates the bubble in suspension, guarantees the stability of suspension storage, prevents point
Layer.
2. optical soliton interaction
The photonic crystal threedimensional model of design is imported in data processing software, layered shaping is carried out.SiC suspension is added
Enter in the feed bin of uv equipment, setting machined parameters as optical wavelength range is 253nm, and thickness is 20 μm, is successively formed by curing
Green compact.
3. degreasing and sintering
Photonic crystal green compact room temperature is put into sintering furnace, carries out the removing of binder first.With the speed liter of 10 DEG C/min
Temperature is warming up to 300 DEG C to 100 DEG C, with 5 DEG C/min, keeps the temperature 1h, is warming up to 450 DEG C with 2.5 DEG C/min, 1h is kept the temperature, with 1 DEG C/min
700 DEG C are warming up to, 2h is kept the temperature.After the completion of skimming processes, part sintering is carried out.1500 DEG C are warming up to 20 DEG C/min speed,
1800 DEG C are warming up to 2.5 DEG C/min, 1h is kept the temperature, is warming up to 2100 DEG C with 1 DEG C/min, is sintered, keeps the temperature 2.5h.It has been sintered
It at later, is cooled to room temperature, takes out part.
Embodiment 2
1. preparing suspension
Firstly, choosing the SiC powder of 800g specification I, powder size is 0.6 μm~1.0 μm, chooses 800g specification II
SiC powder, powder size are 1.1 μm~2.0 μm.The B powder and C powder of 8g are chosen respectively, and powder size is 1 μm~2 μm.By two
The SiC powder of kind specification is uniformly mixed with B powder, C powder, is divided into five parts.8g quaternary ammonium acetate is chosen, dispersing agent is divided into five
Part.First part of SiC mixed-powder and corresponding dispersing agent are added in ball mill, ball milling is carried out, dissociates, after 30min, add
Enter second part of solid powder and dispersing agent, successively carry out, until solid powder be uniformly mixed, nodularization.After the completion of ball milling, it is added
The ethanol solution of 630g, stirring, low-temperature evaporation.
Secondly, taking 1, the 6- hexanediyl ester monomer solution of 1200g, by the SiC solid powder after ball milling and divide
Powder is gradually added in monomer solution, and the quality of dispersing agent is 15g, and the benzoin dimethylether of 9g is added in darkroom.It is entire outstanding
For the mixed process of supernatant liquid all in heated condition, temperature is maintained at 55 DEG C or so, and is constantly stirred.The different of 2.5g is added
The polyoxyethylene fatty amine of propyl alcohol and 2.5g eliminates the bubble in suspension, guarantees the stability of suspension storage, prevents point
Layer.
2. optical soliton interaction
The photonic crystal threedimensional model of design is imported in data processing software, layered shaping is carried out.SiC suspension is added
Enter in the feed bin of uv equipment, setting machined parameters as optical wavelength range is 253nm, and thickness is 30 μm, is successively formed by curing
Green compact.
3. degreasing and sintering
Photonic crystal green compact room temperature is put into sintering furnace, carries out the removing of binder first.With the speed liter of 15 DEG C/min
Temperature is warming up to 300 DEG C to 100 DEG C, with 5 DEG C/min, keeps the temperature 1h, is warming up to 450 DEG C with 2.5 DEG C/min, 1h is kept the temperature, with 1 DEG C/min
600 DEG C are warming up to, 3h is kept the temperature.After the completion of skimming processes, part sintering is carried out.1500 DEG C are warming up to 15 DEG C/min speed,
1800 DEG C are warming up to 2.5 DEG C/min, 1h is kept the temperature, is warming up to 2090 DEG C with 1 DEG C/min, is sintered, keeps the temperature 2.5h.It has been sintered
It at later, is cooled to room temperature, takes out part.
Embodiment 3
1. preparing suspension
Firstly, choosing the SiC powder of 650g specification I, powder size is 0.5 μm~1.0 μm, chooses 650g specification II
SiC powder, powder size are 1.0 μm~2.0 μm.B the and C powder of 4g is chosen respectively, and powder size is 0.6 μm~1.2 μm.It will
The powder of two kinds of specifications is uniformly mixed with B and C powder, is divided into five parts.The poly- sodium propionate dispersing agent of 3g is chosen, dispersing agent is divided equally
It is five parts.First part of SiC mixed-powder and corresponding dispersing agent are added in ball mill, carry out ball milling, dissociation, 40min it
Afterwards, second part of solid powder and dispersing agent is added, successively carries out, until solid powder be uniformly mixed, nodularization.Ball milling is completed
Afterwards, the ethanol solution of 500g is added, stirs, low-temperature evaporation.
Secondly, take the epoxy resin of 500g with organic silicon acrylic ester mixed solution as monomer (mixed proportion 1:2), it will
SiC solid powder and dispersing agent after ball milling, are gradually added in monomer solution, and the quality of dispersing agent is 6g, are added in darkroom
The n-butanol diluent of 6g is added in the azodiisobutyronitrile of 2.0g.The mixed process of entire suspension is all in heated condition, temperature
Degree is maintained at 55 DEG C or so, and is constantly stirred.The dimethyl silicone polymer of 1.7g and the polyoxyethylene of 1.8g is added
Fatty amine eliminates the bubble in suspension, guarantees the stability of suspension storage, prevents from being layered.
2. optical soliton interaction
Defect is introduced during model, destroys original periodic structure characteristic, forms defect level, it is ensured that specific
The light wave of frequency can pass through.The photonic crystal threedimensional model of design is imported in data processing software, layered shaping is carried out.It will
SiC suspension is added in the feed bin of uv equipment, and setting machined parameters as optical wavelength range is 345nm, and thickness is 30 μm, by
Layer is formed by curing green compact.
3. degreasing and sintering
Photonic crystal green compact room temperature is put into sintering furnace, is roasted.The removing of binder is carried out first.With 10 DEG C/min
Speed be warming up to 200 DEG C, be warming up to 300 DEG C with 6 DEG C/min, keep the temperature 1h, be warming up to 450 DEG C with 2.5 DEG C/min, keep the temperature 1h,
650 DEG C are warming up to 1 DEG C/min, keeps the temperature 2h.After the completion of skimming processes, part sintering is carried out.With the heating of 15 DEG C/min speed
To 1500 DEG C, 1800 DEG C are warming up to 3.0 DEG C/min, 1h is kept the temperature, is warming up to 1900 DEG C with 0.5 DEG C/min, is sintered, is kept the temperature
2h.It after sintering is completed, is cooled to room temperature, takes out part.
Embodiment 4
1. preparing suspension
Firstly, choosing the SiC powder of 650g specification I, powder size is 0.5 μm~1.0 μm, chooses 650g specification II
SiC powder, powder size are 1.0 μm~2.0 μm.B the and C powder of 7g is chosen respectively, and powder size is 0.6 μm~1.2 μm.It will
The powder of two kinds of specifications is uniformly mixed with B and C powder, is divided into five parts.The poly- sodium propionate dispersing agent of 9g is chosen, dispersing agent is divided equally
It is five parts.First part of SiC mixed-powder and corresponding dispersing agent are added in ball mill, carry out ball milling, dissociation, 40min it
Afterwards, second part of solid powder and dispersing agent is added, successively carries out, until solid powder be uniformly mixed, nodularization.Ball milling is completed
Afterwards, the ethanol solution of 500g is added, stirs, low-temperature evaporation.
Secondly, take the epoxy resin of 450g with organic silicon acrylic ester mixed solution as monomer (mixed proportion 1:1), it will
SiC solid powder and dispersing agent after ball milling, are gradually added in monomer solution, and the quality of dispersing agent is 12g, are added in darkroom
The n-butanol diluent of 10g is added in the azodiisobutyronitrile of 4.0g.The mixed process of entire suspension all in heated condition,
Temperature is maintained at 55 DEG C or so, and is constantly stirred.The dimethyl silicone polymer of 1.6g and the polyoxy second of 1.5g is added
Alkene fatty amine eliminates the bubble in suspension, guarantees the stability of suspension storage, prevents from being layered.
2. optical soliton interaction
Defect is introduced during model, destroys original periodic structure characteristic, forms defect level, it is ensured that specific
The light wave of frequency can pass through.The photonic crystal threedimensional model of design is imported in data processing software, layered shaping is carried out.It will
SiC suspension is added in the feed bin of uv equipment, and setting machined parameters as optical wavelength range is 345nm, and thickness is 20 μm, by
Layer is formed by curing green compact.
3. degreasing and sintering
Photonic crystal green compact room temperature is put into sintering furnace, is roasted.The removing of binder is carried out first.With 15 DEG C/min
Speed be warming up to 100 DEG C, be warming up to 400 DEG C with 4 DEG C/min, keep the temperature 1h, be warming up to 450 DEG C with 2.5 DEG C/min, keep the temperature 1h,
600 DEG C are warming up to 1 DEG C/min, keeps the temperature 2h.After the completion of skimming processes, part sintering is carried out.With the heating of 18 DEG C/min speed
To 1500 DEG C, 1800 DEG C are warming up to 2.5 DEG C/min, 1h is kept the temperature, is warming up to 1950 DEG C with 0.5 DEG C/min, is sintered, is kept the temperature
2h.It after sintering is completed, is cooled to room temperature, takes out part.
Embodiment 5
1. preparing suspension
Firstly, choosing the SiC powder of 800g specification I, powder size is 0.7 μm~1.5 μm, chooses 800g specification II
SiC powder, powder size are 1.5m~3.0 μm.B the and C powder of 3.5g is chosen respectively, and powder size is 0.7 μm~1.0 μm.
The powder of two kinds of specifications is uniformly mixed with B and C powder, is divided into five parts.4g quaternary ammonium acetate is chosen, dispersing agent is divided into five
Part.First part of SiC mixed-powder and corresponding dispersing agent are added in ball mill, ball milling is carried out, dissociates, after 30min, add
Enter second part of solid powder and dispersing agent, successively carry out, until solid powder be uniformly mixed, nodularization.After the completion of ball milling, it is added
The ethanol solution of 400g, stirring, low-temperature evaporation.
Secondly, (the two mass ratio is as monomer for the epoxy resin and the mixed solution of urethane acrylate that take 255g
1:2), it by the SiC solid powder and dispersing agent after ball milling, is gradually added in monomer solution, the quality of dispersing agent is 11g, dark
The benzophenone of 2.5g is added in room, the styrene of 8g is added.The mixed process of entire suspension is all in heated condition, temperature
50 DEG C or so are maintained at, and is constantly stirred.The mineral oil of 1.7g is added, eliminates the bubble in suspension, guarantees to suspend
The stability of liquid storage, prevents from being layered.
2. optical soliton interaction
Defect striped is introduced in a model, forms one " light-path ", destroys original structure, is reached only along " light is logical
The photon that road " passes through is able to the effect propagated.The photonic crystal threedimensional model of design is imported in data processing software, is divided
Layer processing.Will SiC suspension be added uv equipment feed bin in, set machined parameters as optical wavelength range be 255nm, thickness
It is 40 μm, is successively formed by curing green compact.
3. degreasing and sintering
Photonic crystal green compact room temperature is put into sintering furnace, is roasted.The removing of binder is carried out first.With 10 DEG C/min
Speed be warming up to 100 DEG C, be warming up to 300 DEG C with 5 DEG C/min, keep the temperature 1h, be warming up to 500 DEG C with 2.5 DEG C/min, keep the temperature 1h,
700 DEG C are warming up to 0.8 DEG C/min, keeps the temperature 2h.After the completion of skimming processes, part sintering is carried out.With 20 DEG C/min speed liter
Temperature is warming up to 1800 DEG C to 1500 DEG C, with 2.5 DEG C/min, keeps the temperature 1h, is warming up to 1950 DEG C with 1 DEG C/min, is sintered, and keeps the temperature
2.5h.It after sintering is completed, is cooled to room temperature, takes out part.
Embodiment 6
1. preparing suspension
Firstly, choosing the SiC powder of 700g specification I, powder size is 0.5 μm~1.0 μm, chooses 700g specification II
SiC powder, powder size are 1.0m~2.5 μm.B the and C powder of 6g is chosen respectively, and powder size is 0.5 μm~1.0 μm.It will
The powder of two kinds of specifications is uniformly mixed with B and C powder, is divided into five parts.8g quaternary ammonium acetate is chosen, dispersing agent is divided into five
Part.First part of SiC mixed-powder and corresponding dispersing agent are added in ball mill, ball milling is carried out, dissociates, after 40min, add
Enter second part of solid powder and dispersing agent, successively carry out, until solid powder be uniformly mixed, nodularization.After the completion of ball milling, it is added
The ethanol solution of 500g, stirring, low-temperature evaporation.
Secondly, take 250g epoxy resin and acrylate mixed solution as monomer (the two mass ratio be 1:1), will
SiC solid powder and dispersing agent after ball milling, are gradually added in monomer solution, and the quality of dispersing agent is 16g, are added in darkroom
The 2,4,6- trimethylbenzoyl phosphinic acid ethyl ester of 3g.The mixed process of entire suspension is kept all in heated condition, temperature
It is stirred at 50 DEG C or so, and constantly.The mineral oil of 1.6g and the polyoxyethylene fatty amine of 1.6g is added, eliminates and suspends
Bubble in liquid guarantees the stability of suspension storage, prevents from being layered.
2. optical soliton interaction
Defect striped is introduced in a model, forms one " light-path ", destroys original structure, is reached only along " light is logical
The photon that road " passes through is able to the effect propagated.The photonic crystal threedimensional model of design is imported in data processing software, is divided
Layer processing.Will SiC suspension be added uv equipment feed bin in, set machined parameters as optical wavelength range be 370nm, thickness
It is 30 μm, is successively formed by curing green compact.
3. degreasing and sintering
Photonic crystal green compact room temperature is put into sintering furnace, is roasted.The removing of binder is carried out first.With 10 DEG C/min
Speed be warming up to 100 DEG C, be warming up to 300 DEG C with 5 DEG C/min, keep the temperature 1h, be warming up to 500 DEG C with 2.5 DEG C/min, keep the temperature 1h,
630 DEG C are warming up to 0.8 DEG C/min, keeps the temperature 2h.After the completion of skimming processes, part sintering is carried out.With 15 DEG C/min speed liter
Temperature is warming up to 1800 DEG C to 1500 DEG C, with 4 DEG C/min, keeps the temperature 1h, is warming up to 2000 DEG C with 1 DEG C/min, is sintered, and keeps the temperature
2.5h.It after sintering is completed, is cooled to room temperature, takes out part.
Claims (4)
1. a kind of preparation method of SiC photonic crystal, which comprises the following steps:
Step 1, prepared by SiC suspension
Step 1-1, solid powder preparation
SiC powder, boron powder, carbon dust, ethyl alcohol and dispersing agent are added in ball mill and carry out ball milling, dissociation, it then will be after ball milling
Mixture carry out low-temperature evaporation, obtain surface have organic matter solid powder；
Step 1-2, suspension mixing
Photo-curing monomer is added in above-mentioned solid powder by the ratio for being 1-9:1 according to solid powder and photo-curing monomer mass ratio
In, dispersing agent is added, and free radical photo-initiation is added under the conditions of being protected from light, stirred evenly, obtains suspension；
Diluent is additionally added in the step 1-2, diluent is one of cyclohexanone, n-butanol, styrene or methyl ethyl ketone, quality
It is the 0.03%~3% of suspension quality；
Step 1-3, suspension processing
Defoaming agent is added in suspension, obtains uniform, bubble-free suspension；
And/or sagging inhibitor is additionally added in the step 1-3, sagging inhibitor is polyoxyethylene fatty amine, polyoxyethylene fatty alcohol
One of sulfate, quality are the 0.02%~0.1% of suspension quality；
In suspension mixed process, suspension is preheated, make suspension final viscosity control 1500mPas~
Between 2000mPas；
Step 2, the manufacture of part green compact
SiC suspension is added in optical soliton interaction equipment, according to the three-dimensional modeling data of photon crystal structure, utilizes ultraviolet light
Multi-shell curing, optical wavelength range 240-400nm are carried out to suspension, layer thickness control prepares SiC light between 20-40 μm
Sub- crystal green structure；
Step 3, aftertreatment technology
Progress degreasing, sintering processes in high temperature sintering furnace is put the green body into, the SiC photonic crystal of compact structure is obtained；
The ungrease treatment technique are as follows: photonic crystal green compact room temperature is entered into furnace, with the heating of 10 DEG C/min~15 DEG C/min speed
To 100 DEG C~200 DEG C, 300 DEG C~400 DEG C are warming up to 4 DEG C/min~6 DEG C/min, 1h~1.5h is kept the temperature, with 2.5 DEG C/min
~3.0 DEG C/min is warming up to 450-500 DEG C, keeps the temperature 0.5h~1h, with 0.5 DEG C/min~1.5 DEG C/min be warming up to 600 DEG C~
700 DEG C, keep the temperature 2h~4h；
The sintering processes technique are as follows: be warming up to 1500 DEG C~1600 DEG C with 15 DEG C/min~20 DEG C/min speed, with 2.5 DEG C/
Min~5 DEG C/min is warming up to 1700 DEG C~1800 DEG C, keeps the temperature 1h~1.5h, is warming up to 1900 with 0.5 DEG C/min~1 DEG C/min
DEG C~2300 DEG C, it is sintered, keeps the temperature 2h~4h.
2. the preparation method of SiC photonic crystal according to claim 1, which is characterized in that the photo-curing monomer is poly-
In urethane acrylate, 1,6 hexanediol diacrylate, epoxy resin, acrylate or acrylic acid and organic silicon acrylic ester
It is one or more；The free radical photo-initiation be benzophenone, double benzoylphenyl phosphorous oxides, azodiisobutyronitrile,
2,4,6- trimethylbenzoyl phosphinic acid ethyl esters or benzoin dimethylether, quality are the 0.2%~3% of photo-curing monomer.
3. the preparation method of SiC photonic crystal according to claim 1, which is characterized in that the matter of the boron powder and carbon dust
The sum of amount is the 0.02%~2% of SiC powder quality；The ethyl alcohol accounts for the 20%~60% of SiC powder quality；The dispersing agent
For one of poly- sodium propionate, quaternary ammonium acetate or phosphate；The dispersing agent quality that solid powder is added when preparing is SiC powder quality
0.05%~1.5%, the dispersing agent quality that is added is the 0.45%~3.5% of SiC powder quality when suspension mixes；It is described
Defoaming agent is lower alcohol, organically-modified compound, mineral oil, organic polymer or organic siliconresin, and quality is suspension matter
The 0.03%~0.1% of amount.
4. the preparation method of SiC photonic crystal according to claim 1, which is characterized in that solid powder described in step 1-1
Granularity be 0.1 μm~5 μm.
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| CN103802315A (en) * | 2013-12-31 | 2014-05-21 | 中国科学院深圳先进技术研究院 | Method for preparing photonic crystals through 3D (Three-Dimensional) printing |
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| JP2006213534A (en) * | 2005-02-01 | 2006-08-17 | Kawamura Inst Of Chem Res | Inorganic oxide periodic structure |
| CN102520480B (en) * | 2011-12-08 | 2014-09-03 | 西安交通大学 | Multi-medium-coupling three-dimensional photonic crystal and method for designing and manufacturing multi-medium-coupling three-dimensional photonic crystal |
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| CN103802315A (en) * | 2013-12-31 | 2014-05-21 | 中国科学院深圳先进技术研究院 | Method for preparing photonic crystals through 3D (Three-Dimensional) printing |
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