CN114276143A - SiC-SiO based on 3D printing2Two-step sintering method of ceramic green body - Google Patents
SiC-SiO based on 3D printing2Two-step sintering method of ceramic green body Download PDFInfo
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Abstract
The invention relates to SiC-SiO based on 3D printing2A two-step sintering process for a ceramic green body comprising: (1) printing SiC/SiO photosensitive resin slurry containing silicon carbide powder and silicon dioxide powder by DLP technology2De-bonding the ceramic green body to obtain a ceramic green body; (2) carrying out vacuum-pressure impregnation on the obtained ceramic blank in an organic carbon source solution, and then carrying out densification treatment through solidification, carbothermic reduction and reactive sintering to obtain silicon carbide ceramic; preferably, the organic carbon source solution is a phenolic resin solution or a glucose solution, preferably a phenolic resinAnd (3) solution.
Description
Technical Field
The invention relates to SiC/SiO based on 3D printing2A two-step sintering method of ceramic green bodies belongs to the field of structural ceramics.
Background
Silicon carbide ceramic is a ceramic material with excellent properties such as high strength, high hardness, high thermal conductivity, high chemical stability and the like, and is widely applied to the fields of aerospace, microelectronics, automobile industry, nuclear industry and the like. In recent years, in the fields of automobile industry, aerospace and the like, there is a strong demand for parts with large sizes and complex structures. The 3D printing technology can realize the rapid molding of large-size and complex components. Photocuring 3D printing is currently the most widely used printing technique in commercial use. But the parameters of the slurry, such as curing thickness, solid content and the like, are limited due to the high absorbance and high refractive index of the silicon carbide.
Disclosure of Invention
To solve the problem of SiC/SiO2The invention provides a SiC/SiO with high sintering density and good mechanical property2A two-step sintering process.
In particular, the 3D printing-based SiC/SiO2The two-step sintering method of the ceramic green body comprises the following steps:
(1) printing SiC/SiO photosensitive resin slurry containing silicon carbide powder and silicon dioxide powder by DLP technology2De-bonding the ceramic green body to obtain a ceramic green body;
(2) carrying out vacuum-pressure impregnation on the obtained ceramic blank in a phenol organic carbon source solution, and then carrying out densification treatment through solidification, carbothermic reduction and reactive sintering to obtain silicon carbide ceramic; preferably, the organic carbon source solution is a phenolic resin solution or a glucose solution, preferably a phenolic resin solution. Other organic carbon sources are also possible, but phenolic resins have a higher carbon residue rate, and other organic carbon sources such as glucose solutions have a lower carbon residue rate and require multiple impregnations, and thus phenolic resins are preferred.
In the invention, silicon carbide powder, graded silicon dioxide powder, a monomer, a photoinitiator and a dispersant are used as main raw materials, and the uniformly dispersed slurry is obtained by combining mechanical stirring and ball milling. Discharging air bubbles from the slurry under vacuum, and then setting appropriate printing parameters to print the green body. After printing is finished, the green body is taken off from the forming table, and the final SiC/SiO is obtained through the post-treatment process of ultrasonic cleaning and post-curing2And (4) green pressing. After the green body is debonded, a carbon source is introduced by dipping phenolic resin, and the carbothermic reduction reaction is carried out at a certain temperature after the phenolic resin in the green body is cured. After the reaction is finished, the blank is fully paved with silicon particles with certain mass, and the silicon particles are densified in a reaction sintering mode at high temperature, so that SiC ceramic with excellent mechanical property and high densification degree is obtained.
Preferably, the volume content of the silicon carbide powder in the photosensitive resin slurry is 25-40 vol%, and the volume content of the silicon dioxide powder is not more than 20 vol%.
Preferably, the average grain diameter D of the silicon carbide powder 5020 to 50 μm; the silicon dioxide powder comprises silicon dioxide powder with a coarse particle size and silicon dioxide powder with a fine particle size; preferably, the coarse-grained silica powder has an average particle diameter D 5020 to 40 mu m, the average particle diameter D of the fine particle size silicon dioxide powder500.5 to 3 μm; more preferably, the mass ratio of the coarse-particle-size silica powder to the fine-particle-size silica powder is 1: (1.5-4). Wherein, the coarse/fine silicon oxide gradation can well improve the dispersion stability of the slurry. The SiC ceramic can be prepared only by using the silicon dioxide powder with the coarse particle size or the fine particle size, but the silicon dioxide powder with the coarse particle size is more precipitated, so that the components of a green body are not uniform in the printing process, and the preparation of large size and complex shape is not facilitated; only the silicon oxide powder with fine particle size is used, the viscosity of the slurry is high, and the slurry is difficult to be strickleed off by a scraper in the printing process, so that holes are generated in a green body, and the mechanical property is influenced.
Preferably, the curing thickness of the photosensitive resin slurry containing the silicon carbide powder and the silicon dioxide powder is 110-179 mu m, the dynamic viscosity is 1.5-4 Pa.s, and the 24h sedimentation height is 6%.
Preferably, the photosensitive resin is at least one selected from 1, 6-hexanediol diacrylate (HDDA), trimethylolpropane triacrylate (TMPTA), and polyethylene glycol diacrylate (PEGDA).
Preferably, the photosensitive resin paste containing silicon carbide powder and silicon dioxide powder further comprises a photocatalyst and a dispersing agent; the photocatalyst is phenyl bis (2,4, 6-trimethylbenzoyl) phosphine oxide (BAPO); the dispersing agent is polyethylene glycol (PEG).
Preferably, the photosensitizer accounts for 0.2-5 wt% of the total mass of the photosensitive resin slurry containing silicon carbide powder and silicon dioxide powder; preferably, the molecular weight of the PEG is 200-1000, and the PEG accounts for 5-30 vol% of the total mass of the photosensitive resin slurry containing the silicon carbide powder and the silicon dioxide powder.
Preferably, the molecular weight of the polyethylene glycol diacrylate PEGDA is 200-1000;
the volume ratio of the 1, 6-hexanediol diacrylate HDDA to the trimethylolpropane triacrylate TMPTA is (0.1-10): 1;
the polyethylene glycol diacrylate PEGDA: the volume ratio of the 1, 6-hexanediol diacrylate HDDA to the trimethylolpropane triacrylate TMPTA is (0.05-0.25): 1.
preferably, the photosensitive resin, the silicon carbide powder and the silicon dioxide powder are uniformly stirred and then degassed in a vacuum environment to obtain the photosensitive resin slurry containing the silicon carbide powder and the silicon dioxide powder.
Preferably, the solvent of the phenolic resin solution is absolute ethyl alcohol; the mass ratio of the phenolic resin to the absolute ethyl alcohol is (0.5-1.2): 1.
preferably, the parameters of the vacuum-pressure impregnation include: the vacuum degree is-0.1 to-0.09 Mpa, and the vacuum pressure maintaining time is 10 to 30 minutes; the inflation pressure is 1.5-2.5 Mpa, and the pressure maintaining time is 20-40 minutes;
the curing temperature is 100-200 ℃, and the curing time is 1-2 hours.
Preferably, the temperature raising system for carbothermic reduction comprises: the heating rate is 1-3 ℃/min at 0-200 ℃; the heating rate is 1-2 ℃/min at 200-600 ℃; the heating rate is 1-3 ℃/min at 600-900 ℃, and the temperature is kept for 30-60 min at 900 ℃; the temperature rise rate is 4-10 ℃/min at 900-1400 ℃, and the temperature is kept for 5-7 hours at 1400 ℃.
Preferably, the temperature raising system of the reaction sintering includes: the heating rate is 5-10 ℃/min at 0-1200 ℃; the heating rate is 3-5 ℃/min at 1200-1400 ℃; the temperature rise rate is 1-3 ℃/min at 1400-1550 ℃, and the temperature is kept for 30-60 min at 1550 ℃. Aiming at the green body of the 3D printing, the density of the green body is relatively low due to the fact that the solid content in the photocuring printing slurry is low, the selective reaction sintering is a good sintering method aiming at the 3D printing green body, and the reaction sintering can be sintered to be compact only at the temperature of about 1500 ℃.
In addition, the invention also provides SiC/SiO printed based on 3D printing according to the method2The silicon carbide ceramic prepared by the two-step sintering method of the ceramic green body has the bending strength average value of 268.66MPa and the density average value of 2.759g/cm3The average value of the fracture toughness is 3.08 Mpa.m1/2。
Has the advantages that:
in the invention, because the silicon oxide is added into the silicon carbide photocuring printing slurry, the effects of reducing the absorbance, improving the solid content, the printing efficiency, the printing precision and the like can be achieved, but the SiC/SiO printed slurry has the advantages of reducing the absorbance, improving the solid content, improving the printing efficiency, improving the printing precision and the like2Densification of ceramic green bodies has been studied only rarely. The carbon source is provided by impregnating phenolic aldehyde, and the densification can be well realized by combining a two-step sintering process of carbothermic reduction and reactive sintering, and good mechanical properties can be obtained. This facilitates photocuring printing of silicon carbide ceramics for large, complex components.
Drawings
FIG. 1 illustrates a complex piece of mirrors, lattice structures, etc. printed by a dispensed paste;
FIG. 2 shows a scanning electron micrograph of a cross-section of the bar after a five hour incubation at 1400 deg.C, from FIG. 2 it can be seen that there is some residual carbon and the particles are more tightly connected after impregnation with phenol;
FIG. 3 shows a scanning electron micrograph of the SiC ceramic after polishing after completion of reaction sintering in example 1; it can be seen from fig. 3 that the ceramic has higher compactness under the infiltration of silicon;
fig. 4 shows the sintered bar of comparative example 1, and it can be seen from fig. 4 that after reaction sintering, silicon is not infiltrated into the interior of the green body, silicon is only present at the surface of the green body, and the green body is not densified;
FIG. 5 shows a scanning electron microscope image of a cross section of the sintered test strip in comparative example 1, and it can be seen from FIG. 5 that only a few tens to a few hundreds of nanometers are infiltrated with silicon, and a large number of pores exist inside the green body, indicating that carbothermic treatment is essential before reactive sintering;
FIG. 6 shows XRD analysis of the sample composition after carbothermic reduction at different temperatures in example 4. from FIG. 6, diffraction peaks are seen for no silica after incubation at 1400 deg.C for five hours and 1500 deg.C for five hours, indicating that the silica has been fully reacted;
FIG. 7 shows XRD analysis of the sample composition after carbothermic reduction at different holding times in example 3. from FIG. 7, it can be seen that the diffraction peaks of silica are absent after 5 and 6 hours of holding at 1400 deg.C, indicating that the silica has been fully reacted;
figure 8 shows a front and back image of a silicon carbide mirror sintered in example 1.
Detailed Description
The present invention is further illustrated by the following examples, which are to be understood as merely illustrative and not restrictive.
In the present disclosure, by adding graded SiO to the printing paste2Thereby achieving the effects of improving solid content, increasing curing thickness and improving printing precision. However, the printed SiC/SiO film has not been treated so far2Green sintering was carefully studied, and SiC/SiO printed with this type of printing paste was therefore explored2The process of sintering densification of green articles is extremely important.
In particular, SiC/SiO prepared by DLP-3D printer2Vacuum-pressure impregnation of phenolic resin into ceramic body, and combined carbothermic reduction and reaction firingThe SiC ceramic with good mechanical property and high density is obtained by a two-step sintering process system.
The following exemplary description is given of SiC/SiO2A two-step sintering method of ceramic green bodies.
And placing the silicon oxide powder, the silicon carbide powder and the photosensitive resin which are graded according to a specific mass ratio in a beaker according to a certain proportion, and mechanically stirring to obtain the premixed slurry. Placing the premixed slurry and a silicon carbide ball milling medium in a ball milling tank for ball milling, and then performing vacuum air extraction treatment on the uniformly mixed printing slurry; the purpose of the vacuum treatment (degassing treatment in a vacuum environment) is to reduce fine bubbles generated by ball milling in the slurry and to prevent bubbles from remaining in the printed material. The SiC ceramic photosensitive slurry for photocuring 3D printing has the curing thickness of 110-179 mu m, the dynamic viscosity of 1.5-4 Pa.s and the 24-hour sedimentation height of 6%. Preferably, the cured thickness of the SiC ceramic photosensitive slurry for photocuring 3D printing is 135-179 mu m, the dynamic viscosity is 1.66-2.39 Pa.s, and the 24h sedimentation height is less than 5%. For example, the photosensitive resin is one or more of 1, 6-hexanediol diacrylate (HDDA), trimethylolpropane triacrylate (TMPTA), and polyethylene glycol diacrylate (PEGDA). As an example, the photosensitive resin paste may have a raw material composition including: 1, 6-hexanediol diacrylate (HDDA), trimethylolpropane triacrylate (TMPTA), polyethylene glycol diacrylate (PEGDA), phenyl bis (2,4, 6-trimethylbenzoyl) phosphine oxide (BAPO), polyethylene glycol (PEG). The molecular weight Mn of the PEGDA is 200-1000; the volume ratio of HDDA to TMPTA is (0.1-10): 1; the volume ratio of the PEGDA to the HDDA + TMPTA is (0.05-0.25): 1. the BAPO accounts for 0.2-5 wt% of the photosensitive resin. The molecular weight Mn of the PEG is 200-1000; the PEG accounts for 5-30 vol% of the photosensitive resin.
And (3) performing debonding treatment on the printed green body in a vacuum environment, and removing the polymerized photosensitive resin in the photocuring forming process. Wherein the temperature of the de-bonding treatment can be 700-1100 ℃, and the time can be 0.5-1.5 hours.
And (3) soaking the green body subjected to the de-bonding treatment in a phenolic resin solution, putting the green body into an impregnation tank to enable the phenolic resin to permeate into pores of the green body, and putting the green body into an oven to enable the phenolic resin to be cured after the impregnation is finished.
Wherein the phenolic resin solution is obtained by diluting with absolute ethyl alcohol. The proportion of the phenolic resin to the absolute ethyl alcohol is (0.5-1.2): 1, preferably 1: 1. higher concentrations of phenolic resin also have greater viscosity, which is detrimental to its impregnation into the pores of the green body; the lower concentration of phenolic resin, although of lower viscosity, does not have sufficient carbon residue to reduce the silicon oxide to silicon carbide, which is detrimental to the subsequent densification operation.
Wherein the impregnated phenolic aldehyde adopts vacuum-pressure impregnation. The vacuum degree is-0.1 to-0.09 Mpa, the vacuum pressure maintaining time is 10 to 30 minutes, and the preferred vacuum degree is-0.1 Mpa, and the pressure maintaining time is 20 minutes; the inflation pressure is 1.5-2.5 Mpa, the pressure maintaining time is 20-40 minutes, and the preferable inflation pressure is 2Mpa, and the pressure maintaining time is 30 minutes. The long-term vacuum environment can cause the rapid volatilization of alcohol. Considering that the viscosity of the diluted phenolic resin is small, the phenolic resin can fully permeate into the green body by adopting the inflation pressure of 2Mpa and the pressure maintaining time of 30 minutes.
And placing the impregnated green body into an oven to cure the phenolic aldehyde at the temperature of 100-200 ℃ for 1-2 hours, preferably 150 ℃, and keeping the temperature for 1 hour.
After the solidification is finished, the blank is placed into a debonding furnace for carbothermic reduction reaction, and silicon grains are fully paved after the carbothermic reduction reaction and are placed into the debonding furnace for reaction sintering to realize the final densification.
Wherein the carbon thermal reduction heating system is 1-3 ℃/min at the temperature of 0-200 ℃; 200 ℃ and 600 ℃ at 1-2 ℃/min; 600-; 900 ℃ and 1400 ℃ for 4-10 ℃/min, and preserving the heat at 1400 ℃ for 5-7 hours. Preferably: 3 ℃/min at the temperature of 0-200 ℃; 200 ℃ and 600 ℃ at 1 ℃/min; 600-; 900 ℃ and 1400 ℃ for 4 ℃/min, and preserving the heat at 1400 ℃ for 5 hours. The carbothermic reduction system is a phenolic resin cracking process before 900 ℃, and a carbon source is introduced through the phenolic resin to perform reduction reaction with the silicon dioxide. The carbothermic reaction temperature and time was finally determined to be 1400 deg.C/5 hours by orthogonal experiments, and the sample at this temperature was analyzed by XRD and had no diffraction peak of silicon oxide.
Wherein, the reaction sintering system is as follows: 5-10 ℃/min at 0-1200 ℃; 1200 ℃ and 1400 ℃ at a speed of 3-5 ℃/min; 1400 ℃ and 1550 ℃ for 1-3 ℃/min and the temperature is kept at 1550 ℃ for 30-60 minutes. Preferably: 10 ℃/min at 0-1200 ℃; 1200 ℃ and 1400 ℃ at a speed of 5 ℃/min; 1400 ℃ and 1550 ℃ for 3 ℃/min and the temperature is kept for 30-min at 1550 ℃.
In the invention, the three-point bending strength average value of the SiC ceramic is 268.66MPa according to the national standard GBT-6569-2006/ISO 14704:2000 fine ceramic bending strength test method. The density of the SiC ceramic measured by an Archimedes drainage method is 2.7-2.9g/cm3. The fracture toughness of SiC ceramic is 2.8-3.6 Mpa.m by adopting an Instron-5566 material universal tester1/2。
The present invention will be described in detail by way of examples. It is also to be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the invention, and that certain insubstantial modifications and adaptations of the invention by those skilled in the art may be made in light of the above teachings. The specific process parameters and the like of the following examples are also only one example of suitable ranges, i.e., those skilled in the art can select the appropriate ranges through the description herein, and are not limited to the specific values exemplified below.
Example 1
Silicon carbide powder (105.56g, average particle size of 30 μm), crude silicon oxide powder (7.94g, average particle size of 46 μm), fine silicon oxide powder (18.54g, average particle size of 2 μm, crude silicon oxide powder: fine silicon oxide powder ═ 1:2.34), photoinitiator BAPO (1.12g), HDDA (36g), TMPTA (11g), PEGDA (5.6g), PEG (8.7g) were placed in a beaker and mechanically stirred for 5 minutes, then placed in a ball mill and ball milled for 10 minutes by adding a silicon carbide ball milling medium until the slurry was uniformly dispersed. And then pouring the slurry into a spreading pool of a DLP-3D printer, adjusting the spreading thickness to 75 microns by a scraper, setting the printing parameters to be exposure power of 12.8mw/cm2 and the exposure time to be 6s, and introducing a model of a printed material to carry out printing. Taking out the green body from the forming table after printing, performing ultrasonic and post-curing treatment, performing debonding treatment (900 ℃/0.5h), and putting the green body into prepared phenolic resin (the phenolic resin and the anhydrous ethyl acetate) after the debonding treatmentThe mass ratio of alcohol is 1: 1) and putting the mixture into an impregnation tank, vacuumizing the impregnation tank to-0.1 Mpa, maintaining the pressure for 20 minutes, then filling nitrogen into the impregnation tank until the pressure is 2Mpa, and maintaining the pressure for 30 minutes. Taking out, curing for 1 hour in a drying oven at 150 ℃, then putting into a debonding furnace, raising the temperature to 1400 ℃ at a certain heating rate, preserving the heat for 5 hours, taking out, and then fully spreading silicon particles on a sample, wherein the mass ratio of the silicon particles to the sample is 1.2: 1. and then putting the SiC ceramic into a debonding furnace, raising the temperature to 1550 ℃ at a certain heating rate, and keeping the temperature for half an hour to obtain the sintered compact SiC ceramic. The average value of the three-point bending strength of the obtained silicon carbide ceramic is 268.66MPa, and the average value of the density is 2.759g/cm3The average value of the fracture toughness is 3.08 Mpa.m1/2。
Example 2
This example 2 is prepared identically to example 1, except that: the mass ratio of the phenolic aldehyde to the absolute ethyl alcohol in the phenolic resin is 0.5: 1. the obtained silicon carbide ceramic had an average flexural strength of 225.6MPa and an average density of 2.59g/cm3The average value of the fracture toughness is 2.52 Mpa.m1/2The reason is that the residual carbon content of the phenolic aldehyde is insufficient to completely reduce the silicon oxide in the green body, and the diffraction peak of the silicon oxide still exists in the XRD pattern of the sample after carbothermic reduction.
Example 3
This example 3 is the same as the preparation of example 1, except that: the thermal insulation time of the carbothermic reduction reaction is 6 h. The obtained silicon carbide ceramic has an average flexural strength of 252MPa and an average density of 2.705g/cm3The average value of the fracture toughness is 2.81 Mpa.m1/2The reason may be that prolonged holding may cause grain growth, thereby affecting the mechanical properties of the sintered body.
Example 4
This example 4 is the same as the preparation of example 1, except that: the carbothermic reaction temperature was 1500 ℃. The obtained silicon carbide ceramic had an average flexural strength of 256.7MPa and an average density of 2.68g/cm3The average value of the fracture toughness is 2.75 Mpa.m1/2The reason is that the long-term heat preservation at an excessively high temperature may cause grain growth, thereby affecting the mechanical properties of the sintered body.
Example 5
This example 5 is the same as the preparation of example 1, except that: the total mass of the coarse silica powder and the fine silica powder is 19.48g, wherein the mass ratio of the coarse silica powder (the average particle size is 46 mu m) to the fine silica powder (the average particle size is 2 mu m) is 1: 1.5. the average flexural strength and density of the obtained silicon carbide ceramic were 205.8MPa and 2.59g/cm, respectively3The average value of the fracture toughness is 2.46 Mpa.m1/2。
Example 6
This example 6 is the same as the preparation of example 1, except that: the total mass of the coarse silica powder and the fine silica powder is 19.48g, wherein the mass ratio of the coarse silica powder (the average particle size is 46 mu m) to the fine silica powder (the average particle size is 2 mu m) is 1: 4. the average bending strength of the obtained silicon carbide ceramic is 232.7MPa, and the density is 2.65g/cm3The average value of the fracture toughness is 2.74 Mpa.m1/2。
Example 7
This example 4 is the same as the preparation of example 1, except that: the total mass of fine silica powder (average particle size 2 μm) was 19.48g, and no coarse silica powder was present. The average flexural strength and density of the obtained silicon carbide ceramic were 205.6MPa and 2.57g/cm, respectively3The average value of the fracture toughness is 2.61 Mpa.m1/2。
Example 8
This example 8 was prepared identically to example 1, except that: the total mass of the coarse silica powder (average particle size 46 μm) was 19.48g, and no fine silica powder was present. The obtained silicon carbide ceramic had an average flexural strength of 196.5MPa and an average density of 2.66g/cm3The average value of the fracture toughness is 2.53 Mpa.m1/2。
Comparative example 1
Comparative example 1 is prepared identically to example 1, except that: the debinded green body is not impregnated with phenolic aldehyde and is not subjected to carbothermic reduction reaction, the debinded green body is directly subjected to reaction sintering, the green body is not sintered and compact, and silicon is not impregnated into the green body. The average bending strength of the obtained silicon carbide is only 40.6 MPa.
Claims (13)
1. SiC/SiO based on 3D printing2A two-step sintering method of a ceramic green body, characterized by comprising:
(1) printing SiC/SiO photosensitive resin slurry containing silicon carbide powder and silicon dioxide powder by DLP technology2De-bonding the ceramic green body to obtain a ceramic green body;
(2) carrying out vacuum-pressure impregnation on the obtained ceramic blank in an organic carbon source solution, and then carrying out densification treatment through solidification, carbothermic reduction and reactive sintering to obtain silicon carbide ceramic; preferably, the organic carbon source solution is a phenolic resin solution or a glucose solution, preferably a phenolic resin solution.
2. The two-step sintering method according to claim 1, wherein the photosensitive resin paste contains silicon carbide powder in an amount of 25 to 40vol% and silica powder in an amount of not more than 20 vol%.
3. The two-step sintering process according to claim 1, wherein the silicon carbide powder has an average particle diameter D50 20 to 50 μm;
the silicon dioxide powder comprises silicon dioxide powder with a coarse particle size and silicon dioxide powder with a fine particle size; preferably, the coarse-grained silica powder has an average particle diameter D50 20 to 40 mu m, and the average particle diameter D of the fine particle size silicon dioxide powder50 0.5 to 3 μm; more preferably, the mass ratio of the coarse-particle-size silica powder to the fine-particle-size silica powder is 1: (1.5-4).
4. The two-step sintering method according to claim 1, wherein the cured thickness of the photosensitive resin paste containing silicon carbide powder and silica powder is 110 to 179 μm, the dynamic viscosity is 1.5 to 4 Pa-s, and the 24-hour sedimentation height is 6%.
5. The two-step sintering method according to claim 1, wherein the photosensitive resin is selected from at least one of 1, 6-hexanediol diacrylate (HDDA), trimethylolpropane triacrylate (TMPTA), and polyethylene glycol diacrylate (PEGDA).
6. The two-step sintering method according to claim 1, wherein the photosensitive resin paste containing silicon carbide powder and silica powder further comprises a photocatalyst and a dispersant; the photocatalyst is phenyl bis (2,4, 6-trimethylbenzoyl) phosphine oxide (BAPO); the dispersing agent is polyethylene glycol (PEG);
preferably, the photosensitizer accounts for 0.2-5 wt% of the total mass of the photosensitive resin slurry containing silicon carbide powder and silicon dioxide powder;
preferably, the molecular weight of the PEG is 200-1000, and the PEG accounts for 5-30 vol% of the total mass of the photosensitive resin slurry containing the silicon carbide powder and the silicon dioxide powder.
7. The two-step sintering method according to claim 5 or 6, wherein the polyethylene glycol diacrylate PEGDA has a molecular weight of 200 to 1000;
the volume ratio of the 1, 6-hexanediol diacrylate HDDA to the trimethylolpropane triacrylate TMPTA is (0.1-10): 1;
the polyethylene glycol diacrylate PEGDA: the volume ratio of the 1, 6-hexanediol diacrylate HDDA to the trimethylolpropane triacrylate TMPTA is (0.05-0.25): 1.
8. the two-step sintering method according to any one of claims 1 to 7, wherein the photosensitive resin, the silicon carbide powder, and the silica powder are uniformly stirred and then degassed in a vacuum environment to obtain a photosensitive resin slurry containing the silicon carbide powder and the silica powder.
9. The two-step sintering process according to any one of claims 1 to 8, wherein the solvent of the phenolic resin solution is absolute ethanol; the mass ratio of the phenolic resin to the absolute ethyl alcohol is (0.5-1.2): 1.
10. the two-step sintering process according to any of claims 1 to 9, wherein the parameters of the vacuum-pressure impregnation comprise: the vacuum degree is-0.1 to-0.09 Mpa, and the vacuum pressure maintaining time is 10 to 30 minutes; the inflation pressure is 1.5-2.5 Mpa, and the pressure maintaining time is 20-40 minutes;
the curing temperature is 100-200 ℃, and the curing time is 1-2 hours.
11. The two-step sintering method according to any one of claims 1 to 10, wherein the temperature-raising regime of carbothermic reduction comprises: the heating rate is 1-3 ℃/min at 0-200 ℃; the heating rate is 1-2 ℃/min at 200-600 ℃; the heating rate is 1-3 ℃/min at 600-900 ℃, and the temperature is kept for 30-60 min at 900 ℃; the temperature rise rate is 4-10 ℃/min at 900-1400 ℃, and the temperature is kept for 5-7 hours at 1400 ℃.
12. The two-step sintering method according to any one of claims 1 to 11, wherein the temperature-raising regime of reaction sintering comprises: the heating rate is 5-10 ℃/min at 0-1200 ℃; the heating rate is 3-5 ℃/min at 1200-1400 ℃; the temperature rise rate is 1-3 ℃/min at 1400-1550 ℃, and the temperature is kept for 30-60 min at 1550 ℃.
13. 3D printing based SiC/SiO according to any of claims 1-122The silicon carbide ceramic prepared by the two-step sintering method of the ceramic green body is characterized in that the average bending strength value of the silicon carbide ceramic is 268.66MPa, and the average density value is 2.759g/cm3The average value of the fracture toughness is 3.08 Mpa.m1/2。
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| CN115010877A (en) * | 2022-05-27 | 2022-09-06 | 深圳大学 | Carbon-oxygen-silicon ceramic precursor, thick and compact ceramic part and 3D printing preparation method thereof |
| CN115894041A (en) * | 2022-10-14 | 2023-04-04 | 中国科学院上海硅酸盐研究所 | Preparation method of powder extrusion 3D printing molding reaction sintering silicon carbide ceramic |
| CN116730736A (en) * | 2023-06-09 | 2023-09-12 | 中国科学院上海硅酸盐研究所 | Preparation method of SiC composite material based on laser printing and vacuum-pressure assisted in-situ infiltration resin pre-densification |
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