CN114436658A - Photocuring silicon carbide ceramic slurry and preparation method and application thereof - Google Patents
Photocuring silicon carbide ceramic slurry and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a photocuring silicon carbide ceramic slurry and a preparation method and application thereof, wherein the preparation method comprises the following steps: (1) modifying the silicon carbide powder to obtain modified silicon carbide powder with the surface coated with silicon dioxide; (2) mixing the modified silicon carbide powder, photosensitive resin and a dispersing agent, and then carrying out ball milling treatment to obtain the photocuring silicon carbide ceramic slurry; the mass fraction of the modified silicon carbide powder in the photocuring silicon carbide ceramic slurry is 70-72%. The photocuring silicon carbide ceramic slurry prepared by the invention has good fluidity and strong curing capability, realizes 3D printing of the silicon carbide ceramic green body with high solid content, and provides guarantee for the mechanical properties of the silicon carbide ceramic green body after degreasing and sintering. The invention realizes the printing of the silicon carbide with a complex structure, and has the advantages of high forming precision and high speed, and the silicon carbide ceramic component with a complex shape can be manufactured without a die.
Description
Technical Field
The invention relates to the technical field of 3D printing ceramics, in particular to photocuring silicon carbide ceramic slurry and a preparation method and application thereof.
Background
The silicon carbide ceramic has the excellent performances of stable chemical performance, high thermal conductivity, small thermal expansion coefficient, high hardness, good wear resistance and corrosion resistance, high-temperature strength, small creep, thermal shock resistance and the like, so that the silicon carbide ceramic is widely applied to the fields of petroleum, chemical industry, machinery, aerospace, electronics, nuclear industry and the like, and is particularly applied to harsh environments of high temperature, corrosion and the like. At present, the traditional preparation methods of the silicon carbide material comprise methods such as die forming, pressureless sintering, hot-pressing sintering, hot isostatic pressing sintering, reaction sintering, gel casting, precursor cracking and the like. Due to the hard and brittle characteristics of silicon carbide, the machining is difficult, so that the methods generally have the problems of complicated process, long construction period, difficulty in meeting the design requirements of parts with high precision and complex shapes and the like.
With the continuous expansion of the application range of silicon carbide ceramic material components, people have more and more extensive requirements on silicon carbide ceramic composite material products with complex structures. The 3D printing technology is used as an effective mode for preparing high-precision and specific complex structural components, and a new path is opened up for preparing high-performance ceramics. The ceramic photocuring molding technology has high molding precision and surface quality, and can form a specific complex structure. However, the technology is greatly limited by a printing material system, mainly focuses on the preparation of biological ceramics and structural ceramics, and is difficult to form by photocuring because of the high ultraviolet light absorption rate, strong scattering effect, large refractive index difference with photosensitive resin and the like of silicon carbide powder; and because the ceramic solid phase content in the existing silicon carbide ceramic slurry based on photocuring molding is low, the mechanical strength of the finally prepared silicon carbide ceramic material is poor.
Disclosure of Invention
The embodiment of the invention provides photocuring silicon carbide ceramic slurry and a preparation method and application thereof, and the photocuring silicon carbide ceramic slurry solves the problems of high ultraviolet light absorption rate, strong scattering effect and large refractive index difference between silicon carbide powder and photosensitive resin of silicon carbide powder, and simultaneously ensures that the ceramic solid phase content of the silicon carbide ceramic obtained by 3D printing by adopting the photocuring silicon carbide ceramic slurry is higher.
In a first aspect, the present invention provides a method for preparing a photocuring silicon carbide ceramic slurry, comprising the steps of:
(1) modifying the silicon carbide powder to obtain modified silicon carbide powder with the surface coated with silicon dioxide;
(2) mixing the modified silicon carbide powder, photosensitive resin and a dispersing agent, and then carrying out ball milling treatment to obtain the photocuring silicon carbide ceramic slurry; the mass fraction of the modified silicon carbide powder in the photocuring silicon carbide ceramic slurry is 70-72%.
Preferably, in the step (1), the modification treatment is to heat the silicon carbide powder to 800-1100 ℃ at a heating rate of 3-5 ℃/min and to keep the temperature for 0-1 h.
More preferably, in the step (1), the silicon carbide powder is heated to 900 ℃ at a heating rate of 5 ℃/min and is subjected to heat preservation for 0.5 h.
Preferably, in the step (1), the average particle diameter of the silicon carbide powder is 10 μm.
Preferably, in the step (2), the mass fraction of the photosensitive resin in the mixed slurry is 24.4-29.3%; more preferably 25.8 to 27.9 percent;
the mass ratio of the modified silicon carbide powder to the dispersing agent is 100 (1-5).
Preferably, in the step (2), the photosensitive resin includes ditrimethylolpropane acrylate, a diluent and a photoinitiator;
the diluent is 1, 6-hexanediol diacrylate, and the photoinitiator is (2,4, 6-trimethylbenzoyl) diphenyl phosphorus oxide;
the mass ratio of the ditrimethylolpropane acrylate to the diluent is 1 (0.67-1.5), preferably 1: 1;
the mass of the photoinitiator is 2% of the sum of the masses of the ditrimethylolpropane acrylate and the diluent.
Preferably, in step (2), the dispersant is KOS110 or BYK-103.
More preferably, in step (2), the dispersant is BYK-103.
Preferably, in the step (2), the ball-to-material ratio adopted by the ball milling treatment is (2-3): 1;
the rotation speed of the ball milling treatment is 150-200 rpm, and the ball milling time is 3-6 h.
Preferably, in the step (2), the ball milling treatment adopts a mode of alternating forward rotation and reverse rotation; wherein the forward rotation and the reverse rotation are performed at the same time;
the forward rotation time and the reverse rotation time are both 25-40 min.
More preferably, the ball milling treatment is to rotate forwards for 30min and stay for 4min, then rotate backwards for 30min and stay for 4min, and the steps are circulated until the ball milling time of the ball milling treatment is reached.
Preferably, the viscosity of the photocured silicon carbide ceramic slurry is lower than 3000mPa & s; preferably less than 1000 mPas.
In a second aspect, the present invention provides a photocurable silicon carbide ceramic slurry obtained by the preparation method according to the first aspect.
In a third aspect, the present invention provides an application of the photo-cured silicon carbide ceramic slurry obtained by the preparation method of the first aspect or the photo-cured silicon carbide ceramic slurry of the second aspect, including: carrying out photocuring molding on the photocuring silicon carbide ceramic slurry to obtain a silicon carbide ceramic green body; wherein the ceramic solid phase content in the silicon carbide ceramic green body is 70-72 wt%.
Preferably, before the photocuring and forming of the photocuring silicon carbide ceramic slurry, the method further comprises: carrying out defoaming treatment on the photocuring silicon carbide ceramic slurry;
the defoaming treatment adopts ultrasonic treatment, and the ultrasonic time of the ultrasonic treatment is 3-5 min.
More preferably, the ultrasonic power of the ultrasonic treatment is 360W, and the ultrasonic frequency is 40 kHz.
Compared with the prior art, the invention at least has the following beneficial effects:
(1) the invention is prepared by the carbonization ofModifying the silicon powder to ensure that the surface of the modified silicon carbide powder is coated with a trace amount of SiO2The ultraviolet absorption (especially at the wavelength of 405 nm) can be reduced, so that the ultraviolet light can be irradiated on the photosensitive resin in the photocuring silicon carbide ceramic slurry more; in addition, the refractive index of the modified silicon carbide powder is relatively low, and the refractive index difference between the modified silicon carbide powder and photosensitive resin is reduced, so that the photocuring capacity of the photocuring silicon carbide ceramic slurry is remarkably improved, and the photocuring forming of the photocuring silicon carbide ceramic slurry is more favorably realized.
(2) In the invention, the photocuring silicon carbide ceramic slurry has stronger photocuring capability, so that the solid content of silicon carbide in the slurry can be further improved, and the silicon carbide ceramic prepared by photocuring and forming has excellent mechanical properties.
(3) The photocuring silicon carbide ceramic slurry provided by the invention has good fluidity and strong curing capability, realizes 3D printing of a silicon carbide ceramic green body with high solid content, provides guarantee for mechanical properties of the silicon carbide ceramic green body after degreasing and sintering, realizes printing of a complex structure, and has the advantages of high forming precision, high speed and capability of manufacturing silicon carbide ceramic components with complex shapes without a mould.
Drawings
In order to more clearly illustrate the embodiments or technical solutions of the present invention, the drawings used in the embodiments or technical solutions in the prior art are briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and it is obvious for those skilled in the art that other drawings can be obtained according to these drawings without creative efforts.
FIG. 1 is a flow chart of a method for preparing a photocurable silicon carbide ceramic slurry according to an embodiment of the present invention;
fig. 2 is a graph of the ultraviolet absorption spectrum of the modified silicon carbide powder after being subjected to different modification treatment temperatures according to the embodiment of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer and more complete, the technical solutions in the embodiments of the present invention will be described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are some, but not all, embodiments of the present invention, and based on the embodiments of the present invention, all other embodiments obtained by a person of ordinary skill in the art without creative efforts belong to the scope of the present invention.
As shown in fig. 1, an embodiment of the present invention provides a preparation method of a photocuring silicon carbide ceramic slurry, including the following steps:
(1) modifying the silicon carbide powder to obtain modified silicon carbide powder with the surface coated with silicon dioxide;
(2) mixing the modified silicon carbide powder, photosensitive resin and a dispersing agent, and then carrying out ball milling treatment to obtain the photocuring silicon carbide ceramic slurry; wherein the modified silicon carbide powder accounts for 70-72% by mass (for example, 70%, 70.5%, 71%, 71.5% or 72%) of the photocurable silicon carbide ceramic slurry.
In the invention, silicon carbide powder is modified, so that the surface of the modified silicon carbide powder is coated with a trace amount of SiO2Further reducing the ultraviolet absorption of the silicon carbide ceramic slurry, so that more ultraviolet light can irradiate on the photosensitive resin in the photocuring silicon carbide ceramic slurry; in addition, the refractive index of the modified silicon carbide powder is relatively low, and the refractive index difference between the modified silicon carbide powder and photosensitive resin is reduced, so that the photocuring capacity of the photocuring silicon carbide ceramic slurry is remarkably improved, and the photocuring forming of the photocuring silicon carbide ceramic slurry is more favorably realized.
In the invention, the photocuring silicon carbide ceramic slurry has stronger photocuring capability, so that the solid content of silicon carbide in the slurry can be further improved, and the silicon carbide ceramic prepared by photocuring and forming has excellent mechanical properties.
The photocuring silicon carbide ceramic slurry provided by the invention has good fluidity and strong curing capability, realizes 3D printing of a silicon carbide ceramic green body with high solid content, provides guarantee for the mechanical property of the silicon carbide ceramic green body after degreasing and sintering, realizes printing of a complex structure, and has the advantages of high forming precision and high speed, and the silicon carbide ceramic component with a complex shape can be manufactured without a die.
According to some preferred embodiments, in the step (1), the silicon carbide powder is heated to 800 to 1100 ℃ (for example, 800 ℃, 850 ℃, 900 ℃, 950 ℃, 1000 ℃, 1050 ℃ or 1100 ℃) at a heating rate of 3 to 5 ℃/min (for example, 3 ℃/min, 3.5 ℃/min, 4 ℃/min, 4.5 ℃/min or 5 ℃/min) and is kept at the temperature for 0 to 1h (for example, 0h, 0.2h, 0.5h, 0.6h, 0.8h or 1 h).
In the invention, the silicon carbide powder is slightly oxidized to generate a trace amount of SiO on the surface of the silicon carbide powder2The light-sensitive resin is coated on the surface, so that the refractive index and the ultraviolet absorption degree of the light-sensitive resin on ultraviolet light are reduced, especially the ultraviolet absorption at the wavelength of 405nm, and the ultraviolet light can be more irradiated on the light-sensitive resin of the slurry due to the fact that the light-sensitive resin has stronger ultraviolet absorption at the wavelength of 405nm, and therefore the light curing capability of the light-cured silicon carbide ceramic slurry is improved.
According to some more preferred embodiments, in the step (1), the modification treatment is to heat the silicon carbide powder to 900 ℃ at a heating rate of 5 ℃/min and keep the temperature for 0.5 h.
More specifically, the silicon carbide powder is put into a high-temperature sintering furnace to be heated to 900 ℃ at the heating rate of 5 ℃/min, and the temperature is maintained for 0.5h and then the silicon carbide powder is directly cooled along with the furnace to obtain the modified silicon carbide powder.
It should be noted that the temperature of the modification treatment cannot be too high, and the holding time cannot be too long, otherwise, SiO is generated on the surface of the silicon carbide powder2More silicon carbide is contained, so that the high solid content of a ceramic phase in a silicon carbide ceramic green body cannot be ensured, and the mechanical strength of the finally prepared silicon carbide ceramic material is poor. Thus, the present application provides the above-described limitations for the modification treatment.
According to some preferred embodiments, in the step (1), the average particle diameter of the silicon carbide powder is 10 μm.
In the present invention, it is necessary to limit the particle size of the silicon carbide powder to ensure that the photocuring 3D printing is realized, because of the influence of the thickness of the photocuring 3D printer layer. When the particle size of the silicon carbide powder is too small, the difficulty of photocuring 3D printing is increased; when the particle size of the silicon carbide powder is too large, a situation that single-layer curing cannot be achieved may occur, and then the photocuring 3D printing cannot be completed. In the present invention, when the printer device layer thickness is 30 μm, the average particle diameter of the silicon carbide powder is preferably 10 μm.
According to some preferred embodiments, in the step (2), the mass fraction of the photosensitive resin in the mixed paste is 24.4 to 29.3% (e.g., may be 24.4%, 24.8%, 25.1%, 25.5%, 26%, 26.5%, 27%, 27.5%, 28%, 28.5%, 29%, or 29.3%);
the mass ratio of the modified silicon carbide powder to the dispersant is 100 (1-5) (for example, 100:1, 100:2, 100:2.5, 100:3, 100:3.5, 100:4, 100:4.5, or 100: 5).
According to some more preferred embodiments, in the step (2), the mass fraction of the photosensitive resin in the mixed paste is 25.8 to 27.9% (e.g., may be 25.8%, 26%, 26.5%, 27%, 27.5%, or 27.9%).
According to some preferred embodiments, the viscosity of the photocurable silicon carbide ceramic slurry is less than 3000 mPas (which may be 2500, 2000, 1500, 1000, 800, 700, 600, 500, 400, 300, or 200 mPas, for example); preferably less than 1000 mPas (for example, 800 mPas, 500 mPas, 300 mPas, 250 mPas or 200 mPas).
In the invention, the inventor finds that when the photosensitive resin, the modified silicon carbide powder and the dispersing agent meet the mixture ratio, the prepared photocuring silicon carbide ceramic slurry has good fluidity (the viscosity is lower than 1000mPa & s), high solid content of the ceramic phase and strong curing capability. When the dispersant meets the above proportion, if the content of the photosensitive resin in the mixed slurry is too low, the curing capability of the photocuring silicon carbide ceramic slurry is reduced; if the content of the photosensitive resin in the mixed slurry is too high, the content of the modified silicon carbide powder is reduced, the solid content of the ceramic phase cannot be increased, and the mechanical strength of the finally prepared silicon carbide ceramic material is poor.
According to some preferred embodiments, in the step (2), the photosensitive resin includes ditrimethylolpropane acrylate, a diluent and a photoinitiator;
the diluent is 1, 6-hexanediol diacrylate, and the photoinitiator is (2,4, 6-trimethylbenzoyl) diphenyl phosphorus oxide;
the mass ratio of the ditrimethylolpropane acrylate to the diluent is 1 (0.67-1.5) (for example, 1:0.67, 1:0.8, 1:1, 1:1.2, 1:1.3 or 1: 1.5);
the mass of the photoinitiator is 2% of the sum of the masses of the ditrimethylolpropane acrylate and the diluent.
In the invention, experiments prove that compared with 7210 (polyester acrylate oligomer) and U600 (difunctional aliphatic urethane acrylate), the ditrimethylolpropane acrylate has better fluidity and stronger curing capability, so that the prepolymer used as the photosensitive resin can further ensure the fluidity and the curing capability of the photocuring silicon carbide ceramic slurry and reduce the difficulty of photocuring 3D printing. Meanwhile, 1, 6-hexanediol diacrylate has a stronger diluting ability than tripropylene glycol diacrylate, and thus is selected as a diluent for reducing the viscosity of the prepolymer.
According to some more preferred embodiments, in step (2), the mass ratio of the ditrimethylolpropane acrylate to the diluent is 1:1.
According to some preferred embodiments, in step (2), the dispersant is KOS110 or BYK-103.
According to some more preferred embodiments, in step (2), the dispersant is BYK-103.
In the invention, in order to uniformly disperse the photocuring silicon carbide ceramic slurry and ensure that the flow property and the stability meet the requirements of photocuring 3D printing, a dispersing agent needs to be added into the mixed slurry. Experiments prove that BYK-103 is more effective in reducing the viscosity of the photocured silicon carbide ceramic slurry compared with KOS110, polyvinylpyrrolidone (PVP) and TX-100, but due to the poor stability of the slurry after 12h, photocured 3D printing needs to be completed within 12 h. The good stability means that the slurry is uniformly dispersed, and no obvious layering or other phenomena occur.
Specifically, experiments prove that when PVP and TX-100 are used as dispersing agents under the experimental setting conditions, the viscosity of the prepared photocuring silicon carbide ceramic slurry is higher than that of the slurry without the dispersing agents when the addition amount of the PVP and TX-100 is only 1 wt%; and with the increase of the addition amount, the viscosity of the prepared photocuring silicon carbide ceramic slurry is gradually increased, so that the high solid content cannot be achieved, and the PVP and TX-100 are not suitable for being used as the dispersing agent. However, with the addition of BYK-103 and KOS110, the viscosity of the prepared photocuring silicon carbide ceramic slurry is reduced, and with the gradual increase of the addition amount (within the range of 1-5 wt%) of the two dispersing agents, the viscosity of the photocuring silicon carbide ceramic slurry is firstly reduced and then increased; under the premise of ensuring low viscosity, the consideration of stability of the photocuring silicon carbide ceramic slurry is combined, and the finding shows that the photocuring silicon carbide ceramic slurry is uniformly dispersed, has low viscosity and good stability by using BYK-103 with the addition of 3 wt% and KOS110 with the addition of 5 wt% as dispersing agents.
When KOS110 is used as a dispersing agent, in order to uniformly disperse the photocuring silicon carbide ceramic slurry and ensure that the flow property and the stability meet the requirements of photocuring 3D printing, the mass ratio of the modified silicon carbide powder to the dispersing agent is required to be 100: 5; when BYK-103 is used as the dispersant, the mass ratio of the modified silicon carbide powder to the dispersant is required to be 100:3.
According to some preferred embodiments, in the step (2), the ball milling treatment adopts a ball-to-material ratio of (2-3): 1 (for example, 2:1, 2.5:1 or 3: 1);
the rotation speed of the ball milling treatment is 150-200 rpm (for example, 150rpm, 160rpm, 170rpm, 180rpm, 190rpm or 200rpm can be achieved), and the ball milling time is 3-6 h (for example, 3h, 3.5h, 4h, 4.5h, 5h, 5.5h or 6h can be achieved).
Zirconia balls were used for the ball milling treatment.
In the invention, the purpose of the ball milling treatment is to fully and uniformly mix the mixed slurry to obtain the uniformly dispersed photocuring silicon carbide ceramic slurry. And under the condition of ensuring the photocuring thickness, when the ball milling time is 5-6 hours, the viscosity of the slurry can be continuously reduced, and the solid content of the silicon carbide in the slurry can be further improved.
According to some preferred embodiments, in the step (2), the ball milling treatment adopts a forward rotation mode and a reverse rotation mode alternately; wherein the forward rotation and the reverse rotation are performed at the same time;
the forward rotation time and the reverse rotation time are both 25-40 min (for example, 25min, 30min, 35min or 40 min).
According to some more preferred embodiments, in the step (2), the ball milling treatment is performed by rotating forward for 30min and staying for 4min, then rotating backward for 30min and staying for 4min, and the above circulation is performed until the ball milling time of the ball milling treatment is reached.
In the invention, the ball milling treatment is carried out by adopting a forward rotation and reverse rotation alternating mode, which is more beneficial to uniformly dispersing the photocuring silicon carbide ceramic slurry. Note that the residence time was not counted in the ball milling time.
The invention also provides photocuring silicon carbide ceramic slurry which is prepared by the preparation method of the photocuring silicon carbide ceramic slurry.
The invention also provides an application of the photocuring silicon carbide ceramic slurry, wherein the photocuring silicon carbide ceramic slurry is subjected to photocuring molding to obtain a silicon carbide ceramic green body; wherein the ceramic solid phase content in the silicon carbide ceramic green body is 70-72 wt%.
According to some preferred embodiments, before the photocuring and forming of the photocuring silicon carbide ceramic slurry, the method further comprises: carrying out defoaming treatment on the photocuring silicon carbide ceramic slurry;
the defoaming treatment adopts ultrasonic treatment, and the ultrasonic time of the ultrasonic treatment is 3-5 min (for example, 3min, 3.5min, 4min, 4.5min or 5 min).
According to some more preferred embodiments, the ultrasonic power of the ultrasonic treatment is 360W and the ultrasonic frequency is 40 kHz.
In the invention, bubbles in the mixed slurry can be removed by ultrasonic, thereby being beneficial to preparing the silicon carbide ceramic green body which does not contain defects such as bubbles and has a good structure.
In the prior art, the ceramic solid phase content in the silicon carbide ceramic green body prepared by 3D printing is usually 30-40 vol% (namely 50-67 wt%), but the ceramic solid phase content in the silicon carbide ceramic green body is higher in the application and is 70-72 wt%, so that the silicon carbide ceramic with good mechanical strength can be obtained after later degreasing and sintering. It should be noted that, in the present invention, 3D printing is performed by using a digital light processing DLP photocuring device according to preset photocuring molding parameters to obtain a silicon carbide ceramic green body with a desired shape, and a user can set the photocuring molding parameters according to actual needs.
In order to more clearly illustrate the technical scheme and advantages of the present invention, a photocuring silicon carbide ceramic slurry, a preparation method thereof and an application thereof are described in detail through several embodiments.
The photocuring molding apparatus used in the following examples was a Rui-Yi 3D printer model DLP800D, which emitted ultraviolet light having a wavelength of 405 nm.
Example 1
Preparing photocuring silicon carbide ceramic slurry:
(1) placing silicon carbide powder (with particle size of 10 μm) in a high-temperature sintering furnace, heating to 900 ℃ at a heating rate of 5 ℃/min, keeping the temperature for 0.5h, and directly cooling with the furnace to obtain modified silicon carbide powder coated with silicon dioxide on the surface;
(2) selecting ditrimethylolpropane acrylate as a prepolymer, 1, 6-hexanediol diacrylate as a diluent, uniformly mixing the prepolymer and the diluent according to the mass ratio of 1:1, adding 2 wt% (relative to the total mass of the prepolymer and the diluent) of a photoinitiator TPO (namely (2,4, 6-trimethylbenzoyl) diphenyl phosphorus oxide), and uniformly mixing by using a magnetic stirrer to prepare the photosensitive resin;
placing 35g of modified silicon carbide powder obtained in the step (1), 13.95g of photosensitive resin and 1.05g of dispersant BYK-103 into a ball milling tank, rotating forward for 30min at the rotating speed of 150rpm, staying for 4min, then rotating backward for 30min, staying for 4min, and circulating the steps until the ball milling treatment is carried out for 3h in total to obtain photocuring silicon carbide ceramic slurry (the viscosity is 977.19mPa & s);
wherein the mass fractions of the modified silicon carbide powder and the photosensitive resin in the photocuring silicon carbide ceramic slurry are respectively 70% and 27.9%; the mass of the dispersing agent is 3 wt% of the mass of the modified silicon carbide powder.
The application of the photocuring silicon carbide ceramic slurry comprises the following steps:
pouring the obtained photocuring silicon carbide ceramic slurry into a beaker, placing the beaker in an ultrasonic instrument, and carrying out ultrasonic vibration for 5min under the conditions of 360W and 40kHz to complete defoaming treatment; and (4) carrying out photocuring forming on the photocuring silicon carbide ceramic slurry subjected to defoaming by adopting photocuring forming equipment to obtain a silicon carbide ceramic green body.
Example 2
Example 2 is essentially the same as example 1, except that:
in the preparation process of the photocuring silicon carbide ceramic slurry, the dispersing agent is KOS110, and specifically comprises the following steps:
in the step (2), 35g of the modified silicon carbide powder obtained in the step (1), 13.25g of photosensitive resin and 1.75g of a dispersing agent KOS110 are placed in a ball milling tank, and are rotated forward for 30min, kept for 4min, and then rotated backward for 30min and kept for 4min at the rotation speed of 150rpm, and the steps are circulated until the ball milling treatment is carried out for 3h in total to obtain photocuring silicon carbide ceramic slurry (the viscosity is 1052.31mPa & s);
wherein the mass fraction of the modified silicon carbide powder in the photocuring silicon carbide ceramic slurry is 70%; the mass of the dispersing agent is 5 wt% of the mass of the modified silicon carbide powder.
Example 3
Example 3 is essentially the same as example 1, except that:
in the preparation process of the photocuring silicon carbide ceramic slurry, the ball milling time is 5 hours, and the preparation method specifically comprises the following steps:
in the step (2), 35g of modified silicon carbide powder obtained in the step (1), 13.95g of photosensitive resin and 1.05g of dispersant BYK-103 are placed in a ball milling tank, and are rotated forward for 30min at the rotating speed of 150rpm, kept for 4min, then rotated reversely for 30min, kept for 4min, and circulated in the way until the ball milling treatment is carried out for 5h in total, so that photocuring silicon carbide ceramic slurry (with the viscosity of 811.78 mPas) is obtained.
Example 4
Example 4 is essentially the same as example 1, except that:
in the preparation process of the photocuring silicon carbide ceramic slurry, the mass fraction of the modified silicon carbide powder in the photocuring silicon carbide ceramic slurry is 72 percent, and the preparation method specifically comprises the following steps:
placing 36g of modified silicon carbide powder obtained in the step (1), 12.92g of photosensitive resin and 1.08g of dispersant BYK-103 into a ball milling tank, rotating forward for 30min at the rotating speed of 150rpm, staying for 4min, then rotating backward for 30min, staying for 4min, and circulating the steps until the ball milling treatment is carried out for 3h in total to obtain photocuring silicon carbide ceramic slurry (the viscosity is 985.60mPa & s);
wherein the mass fraction of the modified silicon carbide powder in the photocuring silicon carbide ceramic slurry is 72%; the mass of the dispersing agent is 3 wt% of the mass of the modified silicon carbide powder.
Example 5
Example 5 is essentially the same as example 1, except that:
in the preparation process of the photocuring silicon carbide ceramic slurry, the mass fraction of the modified silicon carbide powder in the photocuring silicon carbide ceramic slurry is 72%, and the addition amount of the dispersing agent is different, specifically:
placing 36g of modified silicon carbide powder obtained in the step (1), 12.56g of photosensitive resin and 1.44g of dispersant BYK-103 into a ball milling tank for ball milling treatment; the mass of the dispersing agent is 4 wt% of the mass of the modified silicon carbide powder.
Example 6
Example 6 is essentially the same as example 1, except that:
in the preparation process of the photocuring silicon carbide ceramic slurry, the preparation method specifically comprises the following steps:
in the modification treatment in the step (1), the silicon carbide powder is heated to 900 ℃ at the heating rate of 3 ℃/min and is kept warm for 1 h;
in the step (2), the rotation speed of the ball milling tank is 200rpm, the ball milling tank rotates forwards for 40min, stays for 4min, then rotates backwards for 40min, stays for 4min, and the process is circulated until the ball milling treatment is carried out for 3 h.
Example 7
Example 7 is essentially the same as example 1, except that: step (1) is omitted, namely, the silicon carbide powder is directly used in the step (2), and the steps are as follows:
33.5g of silicon carbide powder, 15.495g of photosensitive resin and 1.005g of dispersant BYK-103 are placed in a ball milling tank for ball milling treatment. Wherein the mass fraction of the silicon carbide powder in the photocuring silicon carbide ceramic slurry is 67%; the mass of the dispersing agent is 3 wt% of the mass of the silicon carbide powder.
Example 8 to example 11
Examples 8 to 11 are substantially the same as example 1, except that:
in the preparation process of the photocuring silicon carbide ceramic slurry, the modification treatment temperature is different, and the heat preservation time is 0h, which is shown in table 2.
The photo-curing silicon carbide ceramic slurries prepared in examples 1 to 7 were subjected to a viscosity test using a digital rotary viscometer at room temperature (25 ℃), respectively, and the test results are shown in table 1.
The modified silicon carbide powder obtained in step (1) in examples 7 to 11 was subjected to uv scanning spectroscopic test, and the obtained uv absorption spectrum was shown in fig. 2.
TABLE 1
In table 1, the addition amount/wt% of the dispersant means the mass of the dispersant in the modified silicon carbide powder.
As can be seen from Table 1, BYK-103 (example 1) with the addition of 3 wt% is used as a dispersing agent and is subjected to ball milling for 3 hours to obtain photocuring silicon carbide ceramic slurry which is uniformly dispersed, low in viscosity and strong in curing capability, and can print a silicon carbide ceramic green body with high solid content; KOS110 (example 2) added in an amount of 5 wt% as a dispersant hardly generates bubbles after ball-milling treatment, and the stability thereof is superior to that of the photo-cured silicon carbide ceramic slurry prepared in example 1, and is more suitable for printing large-sized silicon carbide ceramic green bodies. Furthermore, the photocurable silicon carbide ceramic slurries prepared in examples 1 to 6 were all able to form good silicon carbide ceramic green bodies when applied. Meanwhile, it should be noted that, when the photo-cured silicon carbide ceramic slurry is prepared by directly using the silicon carbide powder, the ceramic solid phase content in the prepared photo-cured silicon carbide ceramic slurry is up to 67 wt% (as shown in example 7), and the photo-cured silicon carbide ceramic slurry has poor curing capability and difficult photo-curing molding due to the reasons of high ultraviolet light absorption rate, strong scattering effect, large refractive index difference with the photosensitive resin, and the like of the silicon carbide powder.
TABLE 2
The non-high-temperature oxidation in fig. 2 corresponds to example 7.
Correspondingly, as can be seen from table 2 in conjunction with fig. 2, compared with the silicon carbide powder, the modified silicon carbide powder after modification has a significantly reduced absorption value in the ultraviolet wavelength range of 390-420nm, i.e., the modification solves the problem of high ultraviolet light absorption rate of the silicon carbide powder, thereby reducing the difficulty of photo-curing 3D printing of the silicon carbide ceramic.
Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (10)
1. The preparation method of the photocuring silicon carbide ceramic slurry is characterized by comprising the following steps of:
(1) modifying the silicon carbide powder to obtain modified silicon carbide powder with the surface coated with silicon dioxide;
(2) mixing the modified silicon carbide powder, photosensitive resin and a dispersing agent, and then carrying out ball milling treatment to obtain the photocuring silicon carbide ceramic slurry; the mass fraction of the modified silicon carbide powder in the photocuring silicon carbide ceramic slurry is 70-72%.
2. The production method according to claim 1, wherein in step (1):
the modification treatment is to heat the silicon carbide powder to 800-1100 ℃ at a heating rate of 3-5 ℃/min and keep the temperature for 0-1 h;
preferably, the modification treatment is to heat the silicon carbide powder to 900 ℃ at a heating rate of 5 ℃/min and keep the temperature for 0.5 h; and/or
The average grain diameter of the silicon carbide powder is 10 mu m.
3. The production method according to claim 1, wherein in step (2):
the mass fraction of the photosensitive resin in the mixed slurry is 24.4-29.3%; preferably 25.8-27.9%;
the mass ratio of the modified silicon carbide powder to the dispersing agent is 100 (1-5).
4. The production method according to claim 1, wherein in step (2):
the photosensitive resin comprises ditrimethylolpropane acrylate, a diluent and a photoinitiator;
the diluent is 1, 6-hexanediol diacrylate, and the photoinitiator is (2,4, 6-trimethylbenzoyl) diphenyl phosphorus oxide;
the mass ratio of the ditrimethylolpropane acrylate to the diluent is 1 (0.67-1.5), preferably 1: 1;
the mass of the photoinitiator is 2% of the sum of the mass of the ditrimethylolpropane acrylate and the diluent; and/or
The dispersant is KOS110 or BYK-103; BYK-103 is preferred.
5. The production method according to claim 1, wherein in step (2):
the ball-material ratio adopted in the ball milling treatment is (2-3) to 1;
the rotation speed of the ball milling treatment is 150-200 rpm, and the ball milling time is 3-6 h.
6. The production method according to claim 1 or 5, characterized in that, in step (2):
the ball milling treatment adopts a forward rotation and reverse rotation alternating mode; wherein the forward rotation and the reverse rotation are performed at the same time;
the forward rotation time and the reverse rotation time are both 25-40 min;
preferably, the ball milling treatment is to rotate forwards for 30min and stay for 4min, then rotate backwards for 30min and stay for 4min, and the steps are circulated until the ball milling time of the ball milling treatment is reached.
7. The method of claim 1, wherein:
the viscosity of the photocuring silicon carbide ceramic slurry is lower than 3000mPa & s; preferably less than 1000 mPas.
8. A photocurable silicon carbide ceramic slurry obtained by the production method according to any one of claims 1 to 7.
9. Use of the photo-cured silicon carbide ceramic slurry according to claim 8 or the photo-cured silicon carbide ceramic slurry prepared by the preparation method according to any one of claims 1 to 7, wherein the photo-cured silicon carbide ceramic slurry is subjected to photo-curing molding to obtain a silicon carbide ceramic green body; wherein the ceramic solid phase content in the silicon carbide ceramic green body is 70-72 wt%.
10. The use according to claim 9, further comprising, before said photocuring-molding said photocured silicon carbide ceramic slurry: carrying out defoaming treatment on the photocuring silicon carbide ceramic slurry;
the defoaming treatment adopts ultrasonic treatment, and the ultrasonic time of the ultrasonic treatment is 3-5 min;
preferably, the ultrasonic power of the ultrasonic treatment is 360W, and the ultrasonic frequency is 40 kHz.
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| CN114956828A (en) * | 2022-05-17 | 2022-08-30 | 合肥商德应用材料有限公司 | Silicon carbide ceramic and preparation method and application thereof |
| CN115010498A (en) * | 2022-06-15 | 2022-09-06 | 西安铂力特增材技术股份有限公司 | Forming method of SiC complex component |
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| CN112723890A (en) * | 2021-02-07 | 2021-04-30 | 深圳大学 | Preparation method of photocuring ceramic slurry and silicon carbide ceramic |
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| CN110451985A (en) * | 2019-08-26 | 2019-11-15 | 西安增材制造国家研究院有限公司 | A kind of photocuring silicon carbide ceramics creme and preparation method thereof |
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| CN114956828A (en) * | 2022-05-17 | 2022-08-30 | 合肥商德应用材料有限公司 | Silicon carbide ceramic and preparation method and application thereof |
| CN114956828B (en) * | 2022-05-17 | 2023-08-15 | 合肥商德应用材料有限公司 | Silicon carbide ceramic and preparation method and application thereof |
| CN115010498A (en) * | 2022-06-15 | 2022-09-06 | 西安铂力特增材技术股份有限公司 | Forming method of SiC complex component |
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