CN110451986A - Photocuring 3D printing SiCN ceramic precursor material and application thereof - Google Patents
Photocuring 3D printing SiCN ceramic precursor material and application thereof Download PDFInfo
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- CN110451986A CN110451986A CN201910847867.3A CN201910847867A CN110451986A CN 110451986 A CN110451986 A CN 110451986A CN 201910847867 A CN201910847867 A CN 201910847867A CN 110451986 A CN110451986 A CN 110451986A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B28—WORKING CEMENT, CLAY, OR STONE
- B28B—SHAPING CLAY OR OTHER CERAMIC COMPOSITIONS; SHAPING SLAG; SHAPING MIXTURES CONTAINING CEMENTITIOUS MATERIAL, e.g. PLASTER
- B28B1/00—Producing shaped prefabricated articles from the material
- B28B1/001—Rapid manufacturing of 3D objects by additive depositing, agglomerating or laminating of material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y10/00—Processes of additive manufacturing
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y70/00—Materials specially adapted for additive manufacturing
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
- C04B35/58—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
- C04B35/632—Organic additives
- C04B35/634—Polymers
- C04B35/63404—Polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/48—Organic compounds becoming part of a ceramic after heat treatment, e.g. carbonising phenol resins
- C04B2235/483—Si-containing organic compounds, e.g. silicone resins, (poly)silanes, (poly)siloxanes or (poly)silazanes
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/60—Aspects relating to the preparation, properties or mechanical treatment of green bodies or pre-forms
- C04B2235/602—Making the green bodies or pre-forms by moulding
- C04B2235/6026—Computer aided shaping, e.g. rapid prototyping
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Abstract
The invention provides a photocuring 3D printing SiCN ceramic precursor material which comprises the following components in percentage by weight: 40-75% of prepared liquid precursor, 20-65% of acrylic acid active monomer, 0.1-5% of photoinitiator, 0.1-1% of light absorber, 0.1-2% of flatting agent and 0.1-2% of defoaming agent, wherein the light absorber is a carbon nano tube. Also provided is a method for obtaining the SiCN ceramic material by using the composite material in photocuring 3D printing. The formula of the invention does not need to add solid components such as ceramic powder, clay and the like. The product has no impurity elements, the ceramic yield is high, and the method is suitable for rapidly preparing SiCN ceramic products with high-precision special-shaped structures and periodic complex structures.
Description
Technical field
The present invention relates generally to 3D printing ceramic precursor technical field more particularly to a kind of photocuring 3D printing SiCN
Pre-ceramic materials and its application.
Background technique
Now, ceramic material has high mechanical strength and hardness, good thermal stability, corrosion resistance and electromagnetically
Can, it has a wide range of applications in fields such as aerospace, new energy, high temperature simulation and stealthy and biologic medicals.Traditional ceramic material
Expect processing technology predominantly injection moulding, molding etc., these moulding process are at high cost, and the period is long, limit us using ceramics
The excellent performance of material.Compared with other materials, since ceramic material has high hardness and brittleness, processing is extremely difficult,
Especially high-accuracy shaped structure, periodical labyrinth, needless to say to reach good surface quality and dimensional accuracy
Difficulty.
There are many researchs to be dedicated to the preparation process of highly complex and accurate ceramic structure part and relevant
New material system, because they have great importance in different application fields.Up to the present, a variety of 3D printing technique fortune
For the preparation of ceramic material, wherein photocuring 3D printing technique (digital light processing (DLP) or stereolithography (SLA)) is most closed
Many researchs have been carried out in note, the photocuring 3D printing technique based on ceramic powder paste.Ceramic powder paste is usually will
Ceramic powders are dispersed in photo curable resin, and the filling rate of powder can be up to 60vol%, obtain ceramic green through photocuring
Base, then be sintered except glue.In order to obtain fine and close ceramic part, ceramic powder paste needs to increase powder to the greatest extent
Load capacity, while needing to keep suitable viscosity and optical characteristics, but not can avoid the remnants of crackle and hole still, cause to make pottery
The intensity and reliability of porcelain part are poor.
Polymer-derived-ceramics (PDCs) cause mainly for the preparation of ceramic fibre and the preparation of polymer impregnated pyrolysis (PIP) method
Close composite material, compared with conventional powder sintering process, PDCs can be pyrolyzed (1000~1300 DEG C) in relatively low temperature, this
It outside, can mechanical property, electromagnetic performance and life to PDCs by adjusting the chemical composition of preceramic polymer and molecular structure
Object compatibility etc. is regulated and controled, and is conducive to further apply.In recent years, PDCs is increasingly used in 3D printing.
SiCN ceramics are a kind of multifunctional materials, not only have excellent thermodynamic property and stable physical chemistry
Can, also there are unique dielectric properties, by adjusting parameters such as the precursor chemical composition of PDCs, cracking temperatures, may be implemented
Regulation of the SiCN ceramics from insulator to conductor.In conjunction with the production method of photocuring 3D printing, can obtain by periodically micro- knot
The mechanics part and high temperature of the low-density and high-strength of structure composition inhale wave part.
Photocurable precursor system activity is high, photosensitive sensitive, during 3D printing, sufficiently exposes to liquid precursor
Crosslinking is difficult to control cured thickness, and the dim light of exposed edge may also lead to photosensitive resin and crosslinking to a certain degree occurs admittedly
Change, printing precision is caused to reduce.Photocuring 3D printing improves printing precision usually using addition pigment, but the introducing of pigment makes
Occur impurity element in ceramics, the various aspects of performance of ceramics is impacted.Carbon nanotube has the outer absorption characteristic of light, uses carbon
Nanotube can effectively control cured thickness as light absorber, reduce edge exposure intensity, improve printing precision.Meanwhile carbon
Nanotube can improve ceramic green toughness, to improve printing success rate, and will not be introduced into impurity element in ceramics.
Photocuring 3D printing based on PDCs shows huge application prospect in field of ceramic processing.Suitable post-processing
Technique (such as hot isostatic pressing and chemical vapor infiltration) provides a possibility that improving performance in all respects.Utilize 3D printing skill
Art preparation has the ceramic of compact of specific function periodic three-dimensional structure, in conjunction with the unique dielectric properties of SiCN ceramics, can obtain
Obtain ultralight, the high-intensitive suction wave part suitable for aerospace.
Summary of the invention
The purpose of the present invention is overcoming the shortcomings of to mention in background above technology and defect, a kind of photocuring 3D printing is provided
SiCN pre-ceramic materials and the SiCN that high-accuracy shaped structure, periodical labyrinth are prepared using its photocuring 3D printing
The method of ceramic product.
The technical scheme is that a kind of photocuring 3D printing SiCN pre-ceramic materials, it includes following weight
The component of percentage: modulation liquid precursor 40-75%, acrylic acid activated monomer 20-65%, photoinitiator 0.1-5%, light are inhaled
Agent 0.1-1%, levelling agent 0.1-2%, defoaming agent 0.1-2% are received, wherein the light absorber is carbon nanotube.
Photocuring 3D printing SiCN pre-ceramic materials viscosity of the invention is low, because being free of solid component, no
The SiCN ceramic dense of sedimentation, printing can occur, there is good mechanical property and reliability.The present invention is made using carbon nanotube
π → π * that the absorption of ultraviolet light is occurred from surface π free electron resonance absorption energy for light absorber, carbon nanotube
Transition can effectively adjust the absorbance of material system, thus when controlling fixed exposure by regulating and controlling the additive amount of carbon nanotube
Interior cured thickness improves printing precision.Meanwhile carbon nanotube can also improve ceramic green toughness, be printed as to improve
Power, and element free from foreign meter.
Further, above-mentioned modulation liquid precursor includes the component of following weight ratio: solid-state polysilazane ceramic setter
Body: liquid polycarbosilane precusor: n-hexane is (30-50): (5-20): (20-40)；The preparation of the modulation liquid precursor
Method are as follows: take solid-state polysilazane ceramic precursor, liquid polycarbosilane precusor and the n-hexane of above-mentioned weight ratio, at room temperature
Mixing, stirring 4h to solid-state polysilazane ceramic precursor sufficiently dissolve.
Solid-state polysilazane ceramic precursor molecular weight is high, can effectively form cross-linked network, and n-hexane is solid for dissolving
State precursor, liquid polycarbosilane precusor molecular weight is low, and reactivity is high, good fluidity, for adjusting viscosity, improves reaction
Rate.The total content of precursor is higher, and sintered ceramic yield is higher.
Further, above-mentioned acrylic acid activated monomer includes hexanediyl and pentaerythritol triacrylate, and two
The weight ratio hexanediyl of person: pentaerythritol triacrylate is (5-15): (5-15).
Glycol diacrylate viscosity is low, and reactivity is high.There are three reactive groups for pentaerythritol triacrylate, can be effective
The raising degree of cross linking.According to the ratio of precursor, suitable ratio is added, improves reactivity and friendship to lower system viscosity
Connection degree.
Further, above-mentioned photoinitiator is selected from least one of TPO, ITX, 819,184, BDK.
It is anti-to cause free radical polymerization under exposure according to the suitable photoinitiator of light source waveband selection of printer
It answers.
Invention also provides the preparation methods of photocuring 3D printing SiCN pre-ceramic materials, it includes following step
It is rapid:
Acrylic acid activated monomer, photoinitiator, light absorber, stream are sequentially added in the modulation liquid precursor prepared
Flat agent and defoaming agent, be stirred overnight at room temperature to get.
The present invention also provides above-mentioned photocuring 3D printing SiCN pre-ceramic materials answering in photocuring 3D printing
With method, i.e., the method for preparing SiCN ceramics by photocuring 3D printing, it includes using photocurable ceramic precursor as consumption
Material carries out photocuring 3D printing and then post-exposure processes, is finally sintered.
Further, the above method specifically includes the following steps:
1) photocuring 3D printing SiCN pre-ceramic materials are transferred in the resin storage tank of photocuring 3D printer；
2) it under the control for the print routine being pre-designed, is successively printed at room temperature, obtains ceramic green；
3) ceramic green is exposed 20 minutes in ultra-violet curing case；
4) ceramic green after exposure is 4-10 hours dry in 60 DEG C of baking ovens, then be sintered, ceramic product is made.
After printing shaping, exposure improves ceramic green surface-crosslinked degree in ultra-violet curing case, prevents in sintering process
Melt, drying makes n-hexane sufficiently volatilize for a long time in 60 DEG C of baking ovens, reduces the solvent content in ceramic green.
Further, above-mentioned steps 4) in be sintered to 800-1500 DEG C heat preservation 0.5-4 hours.
It improves sintering temperature and extends soaking time, ceramics can be made from amorphous to crystalline transformation
Viscosity existing for traditional photocuring 3D printing ceramic powder paste material is high, powder is easy sedimentation, prints and burns
The ceramics of knot are internal that crackle and hole cause the intensity of ceramic part and reliability poor.Meanwhile conventional method makes
Printing precision is improved with addition colored pigment, the addition of pigment makes to introduce impurity element in ceramics, to the various aspects of ceramics
Performance impacts.Compared with the prior art, the advantages of the present invention are as follows the followings:
1, the good fluidity of photocuring 3D printing SiCN pre-ceramic materials of the invention is beaten the shortcomings that sedimentation
The SiCN ceramic dense of print has good mechanical property and reliability.It is multiple suitable for preparing high-accuracy shaped structure, periodicity
The SiCN ceramic product of miscellaneous structure.
2, photocuring 3D printing SiCN pre-ceramic materials of the invention are passed through using carbon nanotube as light absorber
The additive amount for regulating and controlling carbon nanotube, can effectively adjust the absorbance of material system, to control consolidating in the fixed time for exposure
Change thickness, improves printing precision.Carbon nanotube can also improve ceramic green toughness, to improve printing success rate, and be free of
Impurity element.
3, it only needs to stir using magnetic force in the technical process of photocuring 3D printing SiCN pre-ceramic materials of the invention
It mixes device and uniformly mixes all components in proportion, then carrying out printing using photocuring 3D printer can be realized, therefore prepare work
Skill simple possible, equipment requirement are low.
Detailed description of the invention
From the detailed description with reference to the accompanying drawing to the embodiment of the present invention, these and/or other aspects of the invention and
Advantage will become clearer and be easier to understand, in which:
Fig. 1 is the 3D printing ceramic green photo in the embodiment of the present invention；
Fig. 2 is three kinds of 3D printing labyrinth SiCN ceramic part finished product photos in the embodiment of the present invention；Wherein (a),
(b), (c) respectively represents finished product after the sintering of different structure and size
Fig. 3 is that the scanning electron microscope of three kinds of 3D printing labyrinth SiCN ceramic part finished products in the embodiment of the present invention is shone
Piece；Wherein (a), the cellular construction surface sweeping Electronic Speculum micrograph that (d) is periodic structure shown in Fig. 2 (a)；(b), (e) is Fig. 2
(b) the cellular construction surface sweeping Electronic Speculum micrograph of periodic structure shown in；(c), (f) is the list of periodic structure shown in Fig. 2 (c)
Meta structure surface sweeping Electronic Speculum micrograph；
Fig. 4 is the inside burnishing surface micrograph of the 3D printing in the embodiment of the present invention and sintered sic N ceramic part；
Fig. 5 is content of carbon nanotubes in the embodiment of the present invention and time for exposure to the influence curve of print thickness；Wherein
It (a) is the time for exposure in the component without light absorber to the influence curve of print thickness；(b) it is respectively for light absorber content
In component weight 0.1%, 0.3%, 0.5%, 0.7% when, influence curve of the time for exposure to print thickness；
Fig. 6 is that the content of carbon nanotubes and time for exposure in the embodiment of the present invention change influence histogram to printing precision.
Specific embodiment
In order to make those skilled in the art more fully understand the present invention, with reference to the accompanying drawings and detailed description to this hair
It is bright to be described in further detail.
Embodiment 1:
It is by weight 50:15:25 by solid-state polysilazane ceramic precursor, liquid polycarbosilane precusor, n-hexane
Addition is stirred 4h at room temperature and is sufficiently dissolved to solid-state polysilazane precursor, obtains modulation liquid precursor；Then modulating liquid is pressed
Body precursor: the ratio that acrylic acid activated monomer weight ratio is 3:1 adds acrylic acid activated monomer, in acrylic acid activated monomer oneself
The weight ratio of glycol diacrylate and pentaerythritol triacrylate is 2:1, finally by the gross mass of all addO-on therapies
1% photoinitiator is added in percentages, and 0.5% carbon nanotube light absorber, 1% levelling agent and defoaming agent stir at room temperature
It mixes overnight.
Configured photocurable precursor material is transferred in photocuring 3D printer resin storage tank, periodic points are imported
Battle array structural model, setting printing thickness be 50 microns, printer under the control of the print routine of design, carry out at room temperature by
Layer printing, obtains ceramic green.Ceramic green is exposed 20 minutes in ultra-violet curing case, finally dries ceramic green at 60 DEG C
It is 4-10 hours dry in case, then be sintered, ceramic product is made.
Ceramic green is as shown in Figure 1, it can be seen that periodic lattice structure complete display, without defect.After sintering at
For product ceramics photo as shown in fig. 2, it can be seen that after high temperature sintering, finished product ceramics remain green structure, and all directions are uniformly received
Contracting, apparently without defect, after tested, straight line shrinking percentage, apparent density, porosity and ceramic yield respectively may be about 25.3%,
3.108g/cm3, 6.9%, 62.9%.Fig. 3 be the embodiment of the present invention in three kinds of 3D printing labyrinth SiCN ceramic parts at
The stereoscan photograph of product, wherein (a), the cellular construction surface sweeping Electronic Speculum micrograph that (d) is periodic structure shown in Fig. 2 (a)；
(b), (e) is the cellular construction surface sweeping Electronic Speculum micrograph of periodic structure shown in Fig. 2 (b)；(c), (f) is week shown in Fig. 2 (c)
The cellular construction surface sweeping Electronic Speculum micrograph of phase property structure, it can be seen that in 30 times of amplification of cellular construction photo, finished product pottery
Porcelain is clear in structure, without obvious shortcoming.Fig. 4 is the finished product ceramic part inner section burnishing surface micrograph for amplifying 100 times, can
To find out, the smooth densification of burnishing surface, the defects of without gap, crackle.
Embodiment 1 proves that photocuring 3D printing SiCN pre-ceramic materials of the invention can be prepared with labyrinth
Ceramic part, and prepare ceramic shrinkage it is small, yield is high, density is high, have good mechanical property.
Embodiment 2:
It is by weight 50:15:25 by solid-state polysilazane ceramic precursor, liquid polycarbosilane precusor, n-hexane
Addition is stirred 4h at room temperature and is sufficiently dissolved to solid-state polysilazane precursor, obtains modulation liquid precursor；Then modulating liquid is pressed
Body precursor: the ratio that acrylic acid activated monomer weight ratio is 3:1 adds acrylic acid activated monomer, in acrylic acid activated monomer oneself
The weight ratio of glycol diacrylate and pentaerythritol triacrylate is 2:1, finally by the gross mass of all addO-on therapies
The carbon nanotube light absorber of 1% photoinitiator, 0.1-0.7%, 1% levelling agent and defoaming agent, room temperature is added in percentages
Under be stirred overnight.
The photocurable precursor material that different content carbon nanotube light absorber is added is transferred to photocuring 3D printing
In machine resin storage tank, 0-20s is irradiated respectively, and thickness change is as shown in figure 5, (a) is the photocurable pioneer for not adding carbon nanotube
The variation tendency of body material, in 10s, thickness reaches maximum value, and about 1900 microns.It (b) is addition different content carbon nanotube
Photocurable precursor material, after carbon nanotube is added, in the identical time for exposure, cured thickness is obviously reduced, and is received with carbon
The increase of mitron light absorber content, the cured thickness in the identical time for exposure are sequentially reduced.(Δ XY is practical to its printing precision
Size subtracts the difference of design size) change as shown in fig. 6, not adding the photocurable precursor material of carbon nanotube light absorber
Δ XY increases to 300 microns by 100 microns after exposing 6s, and the photocurable precursor material of carbon nanotube light absorber is added
Material Δ XY in 10s is maintained within 100 microns.
Embodiment 2 proves that the present invention uses carbon nanotube as light absorber, is capable of consolidating for effective controlled material system
Change thickness, improves printing precision.
The invention discloses the SiCN pre-ceramic materials systems for being suitable for photocuring 3D printing, also disclose using carbon
Nanotube is capable of the cured thickness of effective controlled material system, improves printing precision, while not introducing miscellaneous as light absorber
Prime element.Photocuring 3D printing SiCN pre-ceramic materials system is used for 3D printing SiCN pottery the present invention also provides a kind of
The method of ceramic material obtains labyrinth ceramic green by photocuring 3D printing, after sintering, various labyrinth printings
Ceramic part saves complete accurate, all directions uniform shrinkage.Straight line shrinking percentage, apparent density, porosity and ceramic yield difference
About 25.3%, 3.108g/cm3, 6.9%, 62.9%, have good mechanical property.
Various embodiments of the present invention are described above, above description is exemplary, and non-exclusive, and
It is not limited to disclosed each embodiment.Without departing from the scope and spirit of illustrated each embodiment, for this skill
Many modifications and changes are obvious for the those of ordinary skill in art field.Therefore, protection scope of the present invention is answered
This is subject to the protection scope in claims.
Claims (8)
1. a kind of photocuring 3D printing SiCN pre-ceramic materials, which is characterized in that it includes the group of following weight percent
Point:
Liquid precursor 40-75% is modulated,
Acrylic acid activated monomer 20-65%,
Photoinitiator 0.1-5%,
Light absorber 0.1-1%,
Levelling agent 0.1-2%,
Defoaming agent 0.1-2%,
Wherein the light absorber is carbon nanotube.
2. photocuring 3D printing SiCN pre-ceramic materials as described in claim 1, which is characterized in that
The modulation liquid precursor includes the component of following weight ratio: solid-state polysilazane ceramic precursor: the poly- carbon silicon of liquid
Alkane precursor: n-hexane is (30-50): (5-20): (20-40)；
It is described modulation liquid precursor the preparation method comprises the following steps: taking the solid-state polysilazane ceramic precursor of above-mentioned weight ratio, liquid
Polycarbosilane precusor and n-hexane mix at room temperature, stirring 4h to solid-state polysilazane ceramic precursor sufficiently dissolves.
3. photocuring 3D printing SiCN pre-ceramic materials as described in claim 1, which is characterized in that the acrylic acid is living
Property monomer includes hexanediyl and pentaerythritol triacrylate, the weight ratio hexanediyl of the two: season penta
Tetrol triacrylate is (5-15): (5-15).
4. photocuring 3D printing SiCN pre-ceramic materials as described in claim 1, which is characterized in that the photoinitiator
Selected from least one of TPO, ITX, 819,184, BDK.
5. the preparation side of the photocuring 3D printing SiCN pre-ceramic materials as described in any claim in claim 1-4
Method, which is characterized in that it the following steps are included:
Acrylic acid activated monomer, photoinitiator, light absorber, levelling agent will be sequentially added in the modulation liquid precursor prepared
And defoaming agent, be stirred overnight at room temperature to get.
6. a kind of photocuring 3D printing SiCN pre-ceramic materials as described in any claim in claim 1-4 are in light
Solidify the application method in 3D printing, which is characterized in that it includes using photocurable ceramic precursor to carry out light as consumptive material to consolidate
Change 3D printing and then post-exposure processes, be finally sintered.
7. application side of the photocuring 3D printing SiCN pre-ceramic materials as claimed in claim 6 in photocuring 3D printing
Method, which is characterized in that it specifically includes the following steps:
1) the photocuring 3D printing SiCN pre-ceramic materials that each component is uniformly mixed are transferred to photocuring 3D printer
In resin storage tank；
2) it under the control for the print routine being pre-designed, is successively printed at room temperature, obtains ceramic green；
3) ceramic green is exposed 20 minutes in ultra-violet curing case；
4) ceramic green after exposure is 4-10 hours dry in 60 DEG C of baking ovens, then be sintered, ceramic product is made.
8. application side of the photocuring 3D printing SiCN pre-ceramic materials as claimed in claim 7 in photocuring 3D printing
Method, which is characterized in that in the step 4) be sintered to 800-1500 DEG C heat preservation 0.5-4 hours.
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|---|---|---|---|---|
| CN114083882A (en) * | 2021-11-17 | 2022-02-25 | 南京智能高端装备产业研究院有限公司 | Double-layer C6v lattice metamaterial sensor based on three-dimensional metal printing technology |
| FR3130271A1 (en) * | 2021-12-14 | 2023-06-16 | Centre National De La Recherche Scientifique | PHOTOCURING COMPOSITION FOR THREE-DIMENSIONAL PRINTING OF CERAMIC OBJECTS BASED ON POLYCRYSTALLINE SILICON CARBIDE |
| CN116444282A (en) * | 2023-03-14 | 2023-07-18 | 北京遥感设备研究所 | Fused quartz photocuring forming method based on introduction of ZrO2-B4C |
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