CN110451986B - 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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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 invention relates to the technical field of 3D printing ceramic precursors, in particular to a photocuring 3D printing SiCN ceramic precursor material and application thereof.
Background
Nowadays, ceramic materials have high mechanical strength and hardness, good thermal stability, corrosion resistance and electromagnetic properties, and have wide application in the fields of aerospace, new energy, high-temperature camouflage stealth, biomedical treatment and the like. The traditional ceramic material processing technology mainly comprises injection molding, mould pressing and the like, and the molding process has high cost and long period, so that the excellent performance of the ceramic material is limited. Compared with other materials, the ceramic material has extremely high hardness and brittleness, so that the processing is extremely difficult, particularly high-precision special-shaped structures and periodic complex structures, and the difficulty of achieving good surface quality and dimensional precision is not to mention.
Much research has been devoted to the production of highly complex and precise ceramic structural parts and to the systems of new materials concerned, since they are of great significance in different fields of application. To date, various 3D printing technologies are applied to the preparation of ceramic materials, of which photo-curing 3D printing technologies (digital light processing (DLP) or Stereolithography (SLA)) have received most attention, and many studies have been made on the photo-curing 3D printing technologies based on ceramic powder slurry. Ceramic powder slurry is prepared by dispersing ceramic powder in photo-curable resin, wherein the filling rate of the powder can reach 60 vol%, obtaining ceramic green body by photo-curing, and then carrying out degumming and sintering. In order to obtain a dense ceramic part, the ceramic powder slurry needs to increase the loading of the powder to the maximum extent while maintaining suitable viscosity and optical characteristics, but still cannot avoid the residue of cracks and pores, resulting in poor strength and reliability of the ceramic part.
The Polymer Derived Ceramics (PDCs) are mainly used for preparing ceramic fibers and preparing compact composite materials by a Polymer Impregnation Pyrolysis (PIP) method, compared with the traditional powder sintering method, the PDCs can be pyrolyzed at a relatively low temperature (1000-1300 ℃), and in addition, the mechanical property, the electromagnetic property, the biocompatibility and other aspects of the PDCs can be regulated and controlled by adjusting the chemical composition and the molecular structure of a precursor polymer, thereby being beneficial to further application. In recent years, PDCs are increasingly applied to 3D printing.
The SiCN ceramic is a multifunctional material, has excellent thermodynamic performance, stable physicochemical performance and unique dielectric property, and can be regulated from an insulator to a conductor by adjusting the chemical composition of a precursor of PDCs, the cracking temperature and other parameters. By combining the production mode of photocuring 3D printing, the low-density high-strength mechanical part and the high-temperature wave-absorbing part which are composed of periodic microstructures can be obtained.
The photo-curable precursor system has high activity and sensitive light sensitivity, the curing thickness is difficult to control by fully exposing and crosslinking the liquid precursor in the 3D printing process, and weak light at the irradiation edge can also cause the photosensitive resin to be crosslinked and cured to a certain degree, so that the printing precision is reduced. Photocuring 3D printing generally uses pigment addition to improve printing accuracy, but the introduction of pigment causes impurity elements to appear in the ceramic, which affects various properties of the ceramic. The carbon nano tube has the light external absorption characteristic, and the carbon nano tube used as the light absorbent can effectively control the curing thickness, reduce the edge exposure intensity and improve the printing precision. Meanwhile, the carbon nano tube can improve the toughness of the ceramic green body, thereby improving the success rate of printing and not introducing impurity elements into the ceramic.
The photocuring 3D printing based on PDCs shows a huge application prospect in the field of ceramic processing. Suitable post-treatment processes (e.g. hot isostatic pressing and chemical vapour infiltration) offer the possibility of improved performance in all respects. The compact ceramic with the specific functional periodic three-dimensional structure is prepared by using a 3D printing technology, and the ultra-light and high-strength wave-absorbing part suitable for aerospace can be obtained by combining the unique dielectric property of SiCN ceramic.
Disclosure of Invention
The invention aims to overcome the defects and shortcomings in the background technology, and provides a photocuring 3D printing SiCN ceramic precursor material and a method for preparing a SiCN ceramic product with a high-precision special-shaped structure and a periodic complex structure by utilizing photocuring 3D printing of the SiCN ceramic precursor material.
The technical scheme of the invention is that a photocuring 3D printing SiCN ceramic precursor material 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.
The photocuring 3D printing SiCN ceramic precursor material disclosed by the invention is low in viscosity, does not contain solid components, so that no sedimentation occurs, the printed SiCN ceramic is compact, and the photocuring 3D printing SiCN ceramic precursor material has good mechanical properties and reliability. The invention adopts the carbon nano tube as the light absorber, the absorption of the carbon nano tube to ultraviolet light is from pi → pi < ANGSTROM transition generated by the pi free electron resonance absorption energy on the surface, and the absorbance of a material system can be effectively adjusted by regulating the addition amount of the carbon nano tube, thereby controlling the curing thickness in fixed exposure time and improving the printing precision. Meanwhile, the carbon nano tube can also improve the toughness of the ceramic green body, thereby improving the printing success rate and not containing impurity elements.
Further, the prepared liquid precursor comprises the following components in parts by weight: solid polysilazane ceramic precursor: liquid polycarbosilane precursor: n-hexane is (30-50): (5-20): (20-40); the preparation method of the prepared liquid precursor comprises the following steps: and mixing and stirring the solid polysilazane ceramic precursor, the liquid polycarbosilane precursor and the n-hexane in the weight ratio at room temperature for 4 hours until the solid polysilazane ceramic precursor is fully dissolved.
The solid polysilazane ceramic precursor has high molecular weight, can effectively form a cross-linked network, the normal hexane is used for dissolving the solid precursor, and the liquid polycarbosilane precursor has low molecular weight, high reaction activity and good fluidity, is used for adjusting viscosity and improving reaction rate. The higher the total precursor content, the higher the yield of the sintered ceramic.
Further, the acrylic acid reactive monomer comprises hexanediol diacrylate and pentaerythritol triacrylate, wherein the weight ratio of hexanediol diacrylate: pentaerythritol triacrylate is (5-15): (5-15).
The glycol diacrylate has low viscosity and high reaction activity. The pentaerythritol triacrylate has three reaction groups, and can effectively improve the crosslinking degree. According to the proportion of the precursor, the proper proportion is added to reduce the viscosity of the system and improve the reactivity and the crosslinking degree.
Further, the photoinitiator is at least one selected from TPO, ITX, 819, 184, and BDK.
The photoinitiator is selected according to the light source waveband of the printer and is used for initiating the free radical polymerization reaction under the exposure.
The invention also provides a preparation method of the photocuring 3D printing SiCN ceramic precursor material, which comprises the following steps:
and sequentially adding an acrylic acid active monomer, a photoinitiator, a light absorber, a flatting agent and a defoaming agent into the prepared modulated liquid precursor, and stirring at room temperature overnight to obtain the acrylic acid modified liquid precursor.
The invention also provides an application method of the photocuring 3D printing SiCN ceramic precursor material in photocuring 3D printing, namely a method for preparing SiCN ceramic by photocuring 3D printing, which comprises the steps of performing photocuring 3D printing by using the photocuring ceramic precursor as a consumable, performing exposure post-treatment and finally sintering.
Further, the method specifically comprises the following steps:
1) transferring the photocuring 3D printing SiCN ceramic precursor material to a resin tank of a photocuring 3D printer;
2) printing layer by layer at room temperature under the control of a pre-designed printing program to obtain a ceramic green body;
3) exposing the ceramic green body in an ultraviolet curing box for 20 minutes;
4) and drying the exposed ceramic green body in an oven at 60 ℃ for 4-10 hours, and sintering to obtain a ceramic finished product.
After printing and forming, the surface crosslinking degree of the ceramic green body is improved by exposure in an ultraviolet curing box, the ceramic green body is prevented from melting in the sintering process, n-hexane is fully volatilized after long-time drying in a 60 ℃ drying oven, and the content of a solvent in the ceramic green body is reduced.
Further, the sintering in the step 4) is carried out at 1500 ℃ of 800-.
The ceramic is transformed from amorphous to crystalline by increasing the sintering temperature and prolonging the holding time
The traditional photocuring 3D printing ceramic powder slurry material has the defects of high viscosity, easy powder sedimentation, and poor strength and reliability of ceramic parts caused by cracks and pores in the printed and sintered ceramic. Meanwhile, the traditional method improves the printing precision by adding colored pigment, and the addition of the pigment leads to the introduction of impurity elements in the ceramic, thereby influencing the performance of the ceramic in all aspects. Compared with the prior art, the invention has the advantages that:
1. the photocuring 3D printing SiCN ceramic precursor material disclosed by the invention is good in fluidity and free of the defect of sedimentation, and the printed SiCN ceramic is compact and has good mechanical property and reliability. The method is suitable for preparing SiCN ceramic products with high-precision special-shaped structures and periodic complex structures.
2. The photocuring 3D printing SiCN ceramic precursor material provided by the invention adopts the carbon nano tube as a light absorber, and the absorbance of a material system can be effectively adjusted by regulating the addition amount of the carbon nano tube, so that the curing thickness in a fixed exposure time is controlled, and the printing precision is improved. The carbon nano tube can also improve the toughness of the ceramic green body, thereby improving the printing success rate and not containing impurity elements.
3. In the technological process of the photocuring 3D printing SiCN ceramic precursor material, all components are uniformly mixed in proportion only by using a magnetic stirrer, and then the mixture is printed by using a photocuring 3D printer, so that the preparation process is simple and feasible, and the equipment requirement is low.
Drawings
These and/or other aspects and advantages of the present invention will become more apparent and more readily appreciated from the following detailed description of the embodiments of the invention, taken in conjunction with the accompanying drawings of which:
FIG. 1 is a photograph of a 3D printed ceramic green body in an embodiment of the invention;
FIG. 2 is a photograph of three 3D printed finished SiCN ceramic parts with complex structures in an embodiment of the present invention; wherein (a), (b) and (c) represent sintered finished products with different structures and sizes respectively
FIG. 3 is a scanning electron microscope photograph of three 3D printed SiCN ceramic parts with complex structures in the embodiment of the present invention; wherein (a) and (d) are scanning electron microscope micrographs of the unit structure of the periodic structure shown in FIG. 2 (a); (b) and (e) is a scanning electron micrograph of the unit structure of the periodic structure shown in FIG. 2 (b); (c) and (f) is a scanning electron micrograph of the unit structure of the periodic structure shown in FIG. 2 (c);
FIG. 4 is a photomicrograph of the interior polished surface of a 3D printed and sintered SiCN ceramic part in an embodiment of the invention;
FIG. 5 is a graph showing the effect of carbon nanotube content and exposure time on print thickness in an example of the present invention; wherein (a) is the effect of exposure time on print thickness in a component that does not contain a light absorber; (b) the influence curve of the exposure time on the printing thickness is shown when the content of the light absorbent is respectively 0.1%, 0.3%, 0.5% and 0.7% of the weight of the components;
FIG. 6 is a bar chart illustrating the effect of carbon nanotube content and exposure time on print accuracy variation in an embodiment of the present invention.
Detailed Description
In order that those skilled in the art will better understand the present invention, the following detailed description of the invention is provided in conjunction with the accompanying drawings and the detailed description of the invention.
Example 1:
mixing a solid polysilazane ceramic precursor, a liquid polycarbosilane precursor and n-hexane according to a weight ratio of 50: 15: 25, adding the mixture, and stirring the mixture for 4 hours at room temperature until the solid polysilazane precursor is fully dissolved to obtain a modulated liquid precursor; then the liquid precursor is prepared: adding acrylic acid active monomers in a weight ratio of 3:1 into the acrylic acid active monomers, wherein the weight ratio of hexanediol diacrylate to pentaerythritol triacrylate in the acrylic acid active monomers is 2:1, finally adding 1% of photoinitiator, 0.5% of carbon nanotube light absorber, 1% of leveling agent and defoaming agent according to the percentage of the total mass of all the added components, and stirring at room temperature overnight.
And transferring the prepared photo-curable precursor material to a resin tank of a photo-curing 3D printer, introducing a periodic lattice structure model, setting the thickness of a printing layer to be 50 micrometers, and printing layer by the printer at room temperature under the control of a designed printing program to obtain a ceramic green body. And exposing the ceramic green body in an ultraviolet curing oven for 20 minutes, finally drying the ceramic green body in an oven at the temperature of 60 ℃ for 4-10 hours, and sintering to obtain a ceramic finished product.
The ceramic green body is shown in fig. 1, and it can be seen that the periodic lattice structure is clearly intact and free of defects. The photo of the sintered finished ceramic is shown in FIG. 2, and it can be seen that after high temperature sintering, the finished ceramic retains the green structure, shrinks uniformly in all directions, has no defects in appearance, and tests show that the linear shrinkage, the apparent density, the porosity and the ceramic yield are respectively about 25.3% and 3.108g/cm36.9 percent and 62.9 percent. Fig. 3 is scanning electron micrographs of three 3D printed finished SiCN ceramic parts with complex structures in an embodiment of the present invention, wherein (a) and (D) are scanning electron micrographs of unit structures of the periodic structures shown in fig. 2 (a); (b) and (e) is a scanning electron micrograph of the unit structure of the periodic structure shown in FIG. 2 (b); (c) and (f) is a scanning electron microscope photomicrograph of the unit structure of the periodic structure shown in FIG. 2(c), and it can be seen that in the unit structure photograph magnified by 30 times, the finished ceramic product has a clear structure and no obvious defects. FIG. 4 is a microphotograph of the polished surface of the internal cross section of the ceramic part, which is enlarged by 100 times, and it can be seen that the polished surface is flat and compact, and has no defects such as voids and cracks.
Example 1 proves that the photocuring 3D printing SiCN ceramic precursor material can be used for preparing ceramic parts with complex structures, and the prepared ceramic has the advantages of small shrinkage, high yield, high density and good mechanical properties.
Example 2:
mixing a solid polysilazane ceramic precursor, a liquid polycarbosilane precursor and n-hexane according to a weight ratio of 50: 15: 25, adding the mixture, and stirring the mixture for 4 hours at room temperature until the solid polysilazane precursor is fully dissolved to obtain a modulated liquid precursor; then the liquid precursor is prepared: adding acrylic acid active monomers in a weight ratio of 3:1 into the acrylic acid active monomers, wherein the weight ratio of hexanediol diacrylate to pentaerythritol triacrylate in the acrylic acid active monomers is 2:1, finally adding 1% of photoinitiator, 0.1-0.7% of carbon nanotube light absorber, 1% of leveling agent and defoaming agent according to the percentage of the total mass of all the added components, and stirring at room temperature overnight.
Transferring the photo-curable precursor material added with different contents of carbon nanotube light absorbers into a resin tank of a photo-curing 3D printer, and respectively irradiating for 0-20s, wherein the thickness change is shown in figure 5, and (a) is the change trend of the photo-curable precursor material without the carbon nanotubes, and the thickness reaches the maximum value at 10s, and is about 1900 microns. (b) The photo-curable precursor material is added with carbon nano tubes with different contents, the curing thickness is obviously reduced within the same exposure time after the carbon nano tubes are added, and the curing thickness within the same exposure time is sequentially reduced along with the increase of the content of the light absorber of the carbon nano tubes. The printing precision (Δ XY is the difference between the actual size and the design size) changes as shown in fig. 6, after 6s of exposure, Δ XY of the photocurable precursor material without the carbon nanotube light absorber is increased from 100 microns to 300 microns, and Δ XY of the photocurable precursor material with the carbon nanotube light absorber is kept within 100 microns within 10 s.
The invention discloses a SiCN ceramic precursor material system suitable for photocuring 3D printing, and also discloses a method for effectively regulating and controlling the curing thickness of the material system and improving the printing precision by using a carbon nano tube as a light absorber without introducing impurity elements. The invention also provides a method for applying the photocuring 3D printing SiCN ceramic precursor material system to 3D printing SiCN ceramic material, and the photocuring 3D printing is adopted to obtain the ceramic with a complex structureAfter the green body is sintered, various complex-structure printed ceramic parts are completely and accurately stored and uniformly shrunk in all directions. The linear shrinkage, the apparent density, the porosity and the ceramic yield were about 25.3% and 3.108g/cm, respectively36.9 percent and 62.9 percent, and has good mechanical property.
Having described embodiments of the present invention, the foregoing description is intended to be exemplary, not exhaustive, and not limited to the embodiments disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the described embodiments. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (6)
1. A photocuring 3D printing SiCN ceramic precursor material is characterized by comprising the following components in percentage by weight:
preparing a liquid precursor of 40-75%,
20 to 65 percent of acrylic acid active monomer,
0.1 to 5 percent of photoinitiator,
0.1 to 1 percent of light absorbent,
0.1 to 2 percent of flatting agent,
0.1 to 2 percent of defoaming agent,
wherein the light absorber is a carbon nanotube;
the modulated liquid precursor comprises the following components in parts by weight: solid polysilazane ceramic precursor: liquid polycarbosilane precursor: n-hexane is (30-50): (5-20): (20-40);
the preparation method of the prepared liquid precursor comprises the following steps: mixing and stirring the solid polysilazane ceramic precursor, the liquid polycarbosilane precursor and the normal hexane in the weight ratio at room temperature for 4 hours until the solid polysilazane ceramic precursor is fully dissolved;
the acrylic acid active monomer comprises hexanediol diacrylate and pentaerythritol triacrylate, wherein the weight ratio of the hexanediol diacrylate to the pentaerythritol triacrylate is as follows: pentaerythritol triacrylate is (5-15): (5-15).
2. The photocurable 3D printed SiCN ceramic precursor material of claim 1 wherein the photoinitiator is selected from at least one of TPO, ITX, 819, 184, BDK.
3. The method for preparing a photocurable 3D printed SiCN ceramic precursor material according to claim 1 or 2, comprising the steps of:
and (3) sequentially adding an acrylic acid active monomer, a photoinitiator, a light absorber, a flatting agent and a defoaming agent into the prepared modulated liquid precursor, and stirring at room temperature overnight to obtain the acrylic acid active liquid precursor.
4. A method of applying the photocurable 3D printed SiCN ceramic precursor material in photocurable 3D printing as claimed in claim 1 or 2, which comprises photocuring 3D printing with a photocurable ceramic precursor as a consumable, followed by post-exposure treatment and final sintering.
5. The method for applying the photo-cured 3D printed SiCN ceramic precursor material in photo-cured 3D printing as claimed in claim 4, comprising the steps of:
1) transferring the photocuring 3D printing SiCN ceramic precursor material with uniformly mixed components into a resin tank of a photocuring 3D printer;
2) printing layer by layer at room temperature under the control of a pre-designed printing program to obtain a ceramic green body;
3) exposing the ceramic green body in an ultraviolet curing box for 20 minutes;
4) and drying the exposed ceramic green body in an oven at 60 ℃ for 4-10 hours, and sintering to obtain a ceramic finished product.
6. The method as claimed in claim 5, wherein the step 4) of sintering is performed at 800-1500 ℃ for 0.5-4 hours.
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