CN114524676B - Preparation method of photo-cured silicon nitride ceramic slurry and silicon nitride ceramic - Google Patents
Preparation method of photo-cured silicon nitride ceramic slurry and silicon nitride ceramic Download PDFInfo
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- CN114524676B CN114524676B CN202210179265.7A CN202210179265A CN114524676B CN 114524676 B CN114524676 B CN 114524676B CN 202210179265 A CN202210179265 A CN 202210179265A CN 114524676 B CN114524676 B CN 114524676B
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Abstract
The application discloses a preparation method of photo-curing silicon nitride ceramic slurry and silicon nitride ceramic, and relates to the technical field of ceramic materials. The application mixes the resin, the photoinitiator and the plasticizer to obtain the photosensitive resin; the resin comprises o-phenylphenoxyethyl acrylate and one or more of ethoxylated pentaerythritol tetraacrylate, trimethylolpropane triacrylate and tetrahydrofuran acrylate; the content of the o-phenylphenoxyethyl acrylate in the resin is 10-90 wt%. The preparation method can effectively solve the technical defects of low solid phase content and low single-layer curing thickness of the photo-curing molding of the traditional silicon nitride ceramic slurry.
Description
Technical Field
The application relates to the technical field of ceramic materials, in particular to a photo-curing silicon nitride ceramic slurry and a preparation method of silicon nitride ceramic.
Background
Silicon nitride (Si) 3 N 4 ) Ceramic has been one of the most attractive structural ceramics as an important structural ceramic material having excellent mechanical properties and thermal shock resistance. Because silicon nitride has excellent comprehensive properties, the silicon nitride has been widely applied to the fields of metallurgy, aerospace, energy, machinery, military technology, optics, glass industry and the like. Along with the development of scientific technology, the application field and the use requirement of the silicon nitride ceramics are also more and more severe. At present, the traditional manufacturing method is to mold silicon nitride powder or slurry, sinter and then machine the silicon nitride powder or slurry to obtain the required ceramic component, and the mold molding process makes the component have higher processing cost, is difficult to prepare parts with complex structures such as radians, hollows and the like, and severely limits the application and development of the silicon nitride ceramic.
The photo-curing molding technique is a net-size molding technique that molds the material without the need for a mold. The technology can prepare the silicon nitride ceramics with complex structures, so that the preparation cost is reduced, and the application field of the silicon nitride ceramics is widened. However, the conventional photo-curing molding technique has a technical disadvantage that the single-layer curing depth of photo-curing molding is low. According to Beer-Lambert model, scattering and absorption of powder affect the photo-curing characteristics of ceramic slurryThe main factors of the sex are as follows:C d -depth of cure; e-exposure energy; e (E) d -critical exposure energy; phi-powder volume fraction; the related parameters of the particle size of the beta-powder and the wavelength of the light source; n is n 1 -a light refractive index of silicon nitride powder; n is n 2 -optical refractive index of the resin. Silicon nitride powder has the characteristics of high absorbance and high refractive index (n is about 2.1), and is a main reason for low curing depth of silicon nitride slurry.
Disclosure of Invention
In view of the above, the present application provides a method for preparing a photo-cured silicon nitride ceramic slurry and a method for preparing silicon nitride ceramic using the same, which uses a resin with a high refractive index to reduce the difference between the refractive indexes of silicon nitride powder and resin, improves the curing depth of the silicon nitride ceramic slurry, and can effectively solve the technical defect of low single-layer curing thickness of the photo-cured molding of the traditional silicon nitride ceramic slurry. The specific scheme is as follows:
a preparation method of photo-curing silicon nitride ceramic slurry and silicon nitride ceramic comprises the following steps,
step one: ball-milling and dispersing silicon nitride powder and a sintering aid in an ethanol solution, and filtering and drying to obtain mixed powder; wherein, the mass ratio of the silicon nitride powder, the sintering aid and the ethanol solution is (6-12): 1: (18-22);
step two: stirring and mixing the resin, the photoinitiator and the plasticizer to obtain photosensitive resin; wherein, the mass ratio of the resin to the plasticizer is (5-10): 3, the photoinitiator accounts for 1-2wt% of the resin;
the resin comprises o-phenylphenoxyethyl acrylate (OPPEOA) and one or more of ethoxylated pentaerythritol tetraacrylate (PPTTA), trimethylolpropane triacrylate (TMPTA) and tetrahydrofuran acrylate (THFA); the content of the o-phenylphenoxyethyl acrylate (OPPEOA) in the resin is 10-90 wt%;
step three: mixing the mixed powder, photosensitive resin and dispersing agent at high speed to obtain silicon nitride ceramic slurry; wherein the mixed powder accounts for 65-71 wt% of the silicon nitride ceramic slurry, the photosensitive resin accounts for 35-29 wt% of the ceramic slurry, and the dispersing agent accounts for 2-3 wt% of the mixed powder.
Step four: placing the photo-cured silicon nitride ceramic slurry into photo-curing forming equipment, and preparing a blank by a photo-curing forming method;
step five: degreasing the formed green body in a degreasing furnace, heating to 500-700 ℃ at a speed of 0.2-0.5 ℃/min, and preserving heat for 3-5 h;
step six: and (3) placing the degreased blank body into an atmosphere sintering furnace, heating to 1800 ℃ at a speed of 5-15 ℃/min, preserving heat for 2-4h, and cooling to obtain the silicon nitride ceramic.
Preferably, in the first step, the particle size of the silicon nitride powder is 0.7-1.0 μm; the mass ratio of the silicon nitride powder, the sintering aid and the ethanol solution is 9:1:20. the sintering aid comprises at least one of non-rare earth oxide aluminum oxide and magnesium oxide, and one or more of rare earth oxide yttrium oxide, lanthanum oxide and ytterbium oxide; more preferably, the sintering aid consists of alumina and yttria in a mass ratio of 1:1.
Preferably, in the second step, the mass ratio of the resin to the plasticizer is 7:3. the content of the o-phenylphenoxyethyl acrylate (OPPEOA) in the resin is 40-70 wt%; more preferably, the resin is a mixed composition of o-phenylphenoxyethyl acrylate (OPPEOA) and ethoxylated pentaerythritol tetraacrylate (PPTTA).
The photoinitiator is at least one selected from 2-hydroxy-2-methyl-1-phenyl-1-acetone, diphenyl- (2, 4, 6-trimethyl benzoyl) phosphine oxide and 2-isopropyl thioxanthone.
The plasticizer is one or more selected from PEG-300, dioctyl phthalate and dibutyl phthalate. More preferably, the plasticizer is selected from dibutyl phthalate.
Preferably, in the third step, the dispersing agent is selected from one or more of BYK-9077, solsperse-85000 and Solsperse-88000. More preferably, the dispersant is selected from Solsperse-85000.
In the third step, the mixing speed of high-speed mixing is 2500-3000r/min, and the mixing time is 8-15min. More preferably, the mixing speed of the high-speed mixing is 2500r/min, and the mixing time is 10min.
Preferably, in the fourth step, the light source wavelength of the light curing molding is 350-450 nm, and the illumination intensity in the curing process is controlled at 20-26.3 mw/cm 2 The curing time is controlled to be 6-7 s. If the illumination intensity and the curing time are lower than the ranges, insufficient bonding force between the layers of the photo-cured blank can be caused, cracking can occur in the degreasing process, and if the illumination intensity and the curing time are higher than the ranges, overexposure can occur on the photo-cured blank, and the precision is reduced.
Preferably, in the fifth step, the atmosphere in the degreasing furnace is nitrogen.
Preferably, in the sixth step, the atmosphere in the atmosphere sintering furnace is nitrogen.
According to the application, the difference of the light refractive index between the silicon nitride powder and the resin is reduced by utilizing the high refractive index resin, so that the curing depth of the silicon nitride ceramic slurry is improved, and the technical defect of low curing thickness of a single layer formed by photocuring of the traditional silicon nitride ceramic slurry can be effectively overcome.
Detailed Description
The technical solutions of the present application will be clearly and completely described in conjunction with the embodiments of the present application, and it is apparent that the described embodiments are some embodiments of the present application, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the application without making any inventive effort, are intended to be within the scope of the application.
It should be understood that the terms "comprises" and "comprising," when used in this specification and the appended claims, specify the presence of stated features, integers, steps, operations, elements, and/or components, but do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components, and/or groups thereof.
It is also to be understood that the terminology used in the description of the application herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. As used in this specification and the appended claims, the singular forms "a," "an," and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise.
It should be further understood that the term "and/or" as used in the present specification and the appended claims refers to any and all possible combinations of one or more of the associated listed items, and includes such combinations.
Example 1
The preparation method of the silicon nitride ceramic comprises the following steps,
step one: ball-milling and dispersing silicon nitride powder and a sintering aid in an ethanol solution, and filtering and drying to obtain mixed powder; wherein, the mass ratio of the silicon nitride powder, the sintering aid and the ethanol solution is (6-12): 1: (18-22); the grain diameter of the silicon nitride powder is 0.7-1.0 mu m; the sintering aid comprises at least one of non-rare earth oxide aluminum oxide and magnesium oxide, and one or more of rare earth oxide yttrium oxide, lanthanum oxide and ytterbium oxide;
step two: stirring and mixing the resin, the photoinitiator and the plasticizer to obtain photosensitive resin; wherein, the mass ratio of the resin to the plasticizer is (5-10): 3, the photoinitiator accounts for 1-2wt% of the resin; the resin comprises o-phenylphenoxyethyl acrylate (OPPEOA) and one or more of ethoxylated pentaerythritol tetraacrylate (PPTTA), trimethylolpropane triacrylate (TMPTA) and tetrahydrofuran acrylate (THFA); the content of the o-phenylphenoxyethyl acrylate (OPPEOA) in the resin is 10-90 wt%; the photoinitiator is at least one selected from 2-hydroxy-2-methyl-1-phenyl-1-acetone, diphenyl- (2, 4, 6-trimethyl benzoyl) phosphine oxide and 2-isopropyl thioxanthone; the plasticizer is one or more selected from PEG-300, dioctyl phthalate and dibutyl phthalate;
step three: mixing the mixed powder, the photosensitive resin and the dispersing agent at a high speed to obtain silicon nitride ceramic slurry, wherein the mixing speed of the high-speed mixing is 2500-3000r/min, and the mixing time is 8-15min; wherein, the mixed powder accounts for 65 to 71 weight percent of the silicon nitride ceramic slurry, the photosensitive resin accounts for 35 to 29 weight percent of the ceramic slurry, and the dispersing agent accounts for 2 to 3 weight percent of the mixed powder; the dispersing agent is selected from one or more of BYK-9077, solsperse-85000 and Solsperse-88000;
step four: placing the photo-cured silicon nitride ceramic slurry into photo-curing forming equipment, and preparing a blank by a photo-curing forming method; the light source wavelength of the light curing molding is 350-450 nm, and the illumination intensity in the curing process is controlled at 20-26.3 mw/cm 2 The curing time is controlled to be 6-7 s;
step five: degreasing the formed green body in a degreasing furnace, heating to 500-700 ℃ at a speed of 0.2-0.5 ℃/min, and preserving heat for 3-5 h; the atmosphere in the degreasing furnace is nitrogen;
step six: and (3) placing the degreased blank body in an atmosphere sintering furnace, heating to 1800 ℃ at a speed of 5-15 ℃/min, preserving heat for 2-4h, taking nitrogen as the atmosphere in the atmosphere sintering furnace, and cooling to obtain the silicon nitride ceramic.
Example 2
The preparation method of the silicon nitride ceramic comprises the following steps,
step one: ball-milling and dispersing silicon nitride powder and a sintering aid in an ethanol solution, and filtering and drying to obtain mixed powder; wherein, the mass ratio of the silicon nitride powder, the sintering aid and the ethanol solution is 9:1:20, a step of; the grain diameter of the silicon nitride powder is 0.7-1.0 mu m; the sintering aid consists of alumina and yttrium oxide, and the mass ratio is 1:1;
step two: stirring and mixing the resin, the photoinitiator and the plasticizer to obtain photosensitive resin; wherein, the mass ratio of the resin to the plasticizer is 7:3, the photoinitiator accounts for 1-2wt% of the resin; the resin is formed by mixing o-phenylphenoxyethyl acrylate (OPPEOA) and ethoxylated pentaerythritol tetraacrylate (PPTTA); the content of the o-phenylphenoxyethyl acrylate (OPPEOA) in the resin is 40-70 wt%; the photoinitiator is selected from diphenyl- (2, 4, 6-trimethyl benzoyl) phosphine oxide; the plasticizer is selected from dibutyl phthalate;
step three: mixing the mixed powder, the photosensitive resin and the dispersing agent at a high speed to obtain silicon nitride ceramic slurry, wherein the mixing speed of the high-speed mixing is 2500r/min, and the mixing time is 10min; wherein, the mixed powder accounts for 65 to 71 weight percent of the silicon nitride ceramic slurry, the photosensitive resin accounts for 35 to 29 weight percent of the ceramic slurry, and the dispersing agent accounts for 2 to 3 weight percent of the mixed powder; the dispersant is selected from Solsperse-85000;
step four: placing the photo-cured silicon nitride ceramic slurry into photo-curing forming equipment, and preparing a blank by a photo-curing forming method; the light source wavelength of the light curing molding is 350-450 nm, and the illumination intensity in the curing process is controlled at 20-26.3 mw/cm 2 The curing time is controlled to be 6-7 s;
step five: degreasing the formed green body in a degreasing furnace, heating to 500-700 ℃ at a speed of 0.2-0.5 ℃/min, and preserving heat for 3-5 h; the atmosphere in the degreasing furnace is nitrogen;
step six: and (3) placing the degreased blank body in an atmosphere sintering furnace, heating to 1800 ℃ at a speed of 5-15 ℃/min, preserving heat for 2-4h, taking nitrogen as the atmosphere in the atmosphere sintering furnace, and cooling to obtain the silicon nitride ceramic.
Example 3
The preparation method of the silicon nitride ceramic comprises the following steps,
step one: ball-milling and dispersing silicon nitride powder and a sintering aid in an ethanol solution, and filtering and drying to obtain mixed powder; wherein, the mass ratio of the silicon nitride powder, the sintering aid and the ethanol solution is 6:1:22; the grain diameter of the silicon nitride powder is 0.7-1.0 mu m; the sintering aid consists of alumina and yttrium oxide, and the mass ratio is 1:1;
step two: stirring and mixing the resin, the photoinitiator and the plasticizer to obtain photosensitive resin; wherein, the mass ratio of the resin to the plasticizer is 5:3, the photoinitiator accounts for 1wt% of the resin; the resin is formed by mixing o-phenylphenoxyethyl acrylate (OPPEOA) and ethoxylated pentaerythritol tetraacrylate (PPTTA); the content of o-phenylphenoxyethyl acrylate (OPPEOA) in the resin is 60wt%; the photoinitiator is selected from diphenyl- (2, 4, 6-trimethyl benzoyl) phosphine oxide; the plasticizer is selected from dibutyl phthalate;
step three: mixing the mixed powder, the photosensitive resin and the dispersing agent at a high speed to obtain silicon nitride ceramic slurry, wherein the mixing speed of the high-speed mixing is 2500r/min, and the mixing time is 10min; wherein, the mixed powder is 65wt%, the photosensitive resin is 33.7wt% and the dispersing agent is 1.3wt%; the dispersant is selected from Solsperse-85000;
step four: placing the photo-cured silicon nitride ceramic slurry into photo-curing forming equipment, and preparing a blank by a photo-curing forming method; the light source wavelength of the light curing molding is 350-450 nm, and the illumination intensity in the curing process is controlled at 20-26.3 mw/cm 2 The curing time is controlled to be 6-7 s;
step five: degreasing the formed green body in a degreasing furnace, heating to 500 ℃ at the speed of 0.2 ℃/min, and preserving heat for 5 hours; the atmosphere in the degreasing furnace is nitrogen;
step six: and (3) placing the degreased blank body in an atmosphere sintering furnace, heating to 1800 ℃ at a speed of 5 ℃/min, preserving heat for 4 hours, taking nitrogen as the atmosphere in the atmosphere sintering furnace, and cooling to obtain the silicon nitride ceramic.
Example 4
The preparation method of the silicon nitride ceramic comprises the following steps,
step one: ball-milling and dispersing silicon nitride powder and a sintering aid in an ethanol solution, and filtering and drying to obtain mixed powder; wherein, the mass ratio of the silicon nitride powder, the sintering aid and the ethanol solution is 12:1:18; the grain diameter of the silicon nitride powder is 0.7-1.0 mu m; the sintering aid consists of alumina and yttrium oxide, and the mass ratio is 1:1;
step two: stirring and mixing the resin, the photoinitiator and the plasticizer to obtain photosensitive resin; wherein, the mass ratio of the resin to the plasticizer is 10:3, the photoinitiator accounts for 2wt% of the resin; the resin is formed by mixing o-phenylphenoxyethyl acrylate (OPPEOA) and ethoxylated pentaerythritol tetraacrylate (PPTTA); the content of o-phenylphenoxyethyl acrylate (OPPEOA) in the resin is 80wt%; the photoinitiator is selected from diphenyl- (2, 4, 6-trimethyl benzoyl) phosphine oxide; the plasticizer is selected from dibutyl phthalate;
step three: mixing the mixed powder, the photosensitive resin and the dispersing agent at a high speed to obtain silicon nitride ceramic slurry, wherein the mixing speed of the high-speed mixing is 2500r/min, and the mixing time is 10min; wherein, 71 weight percent of mixed powder, 26.87 weight percent of photosensitive resin and 2.13 weight percent of dispersing agent; the dispersant is selected from Solsperse-85000;
step four: placing the photo-cured silicon nitride ceramic slurry into photo-curing forming equipment, and preparing a blank by a photo-curing forming method; the light source wavelength of the light curing molding is 350-450 nm, and the illumination intensity in the curing process is controlled at 20-26.3 mw/cm 2 The curing time is controlled to be 6-7 s;
step five: degreasing the formed green body in a degreasing furnace, heating to 700 ℃ at the speed of 0.5 ℃/min, and preserving heat for 3 hours; the atmosphere in the degreasing furnace is nitrogen;
step six: and (3) placing the degreased blank body in an atmosphere sintering furnace, heating to 1800 ℃ at a speed of 15 ℃/min, preserving heat for 2 hours, taking nitrogen as the atmosphere in the atmosphere sintering furnace, and cooling to obtain the silicon nitride ceramic. Test of the influence of a resin on the curing thickness of ceramic
Example 5
The preparation method of the silicon nitride ceramic comprises the following steps,
step one: 90g of silicon nitride powder with the particle size of 0.7-1.0 mu m, 5g of alumina powder and 5g of yttrium oxide powder are added into a ball milling tank, 200g of absolute ethyl alcohol is poured into the ball milling tank, and ball milling is carried out for 4-6 hours in a ball mill at the speed of 350r/min to obtain mixed powder.
Step two: mixing 60wt% of OPPEOA and 40wt% of PPTTA to prepare resin; stirring and mixing resin, a photoinitiator diphenyl- (2, 4, 6-trimethylbenzoyl) phosphine oxide and a plasticizer dibutyl phthalate to obtain photosensitive resin; wherein, the mass ratio of the resin to the plasticizer is 7:3, the photoinitiator comprises 1.5wt% of the resin.
Step three: mixing the mixed powder, photosensitive resin and a dispersing agent Solsperse-85000 in a homogenizer for 10min at a speed of 2500r/min to obtain silicon nitride ceramic slurry; 68.25wt% of mixed powder, 30wt% of photosensitive resin and 1.75wt% of dispersing agent in the ceramic slurry;
step four: nitriding the above photo-cured materialPlacing the silicon ceramic slurry in photo-curing forming equipment, and preparing a blank by a photo-curing forming method; the light source wavelength of the light curing molding is 350-450 nm, and the illumination intensity in the curing process is controlled at 20-26.3 mw/cm 2 The curing time is controlled to be 6-7 s;
step five: degreasing the formed green body in a degreasing furnace, heating to 600 ℃ at the speed of 0.5 ℃/min, and preserving heat for 3 hours; the atmosphere in the degreasing furnace is nitrogen;
step six: placing the degreased blank body in an atmosphere sintering furnace, heating to 1800 ℃ at a speed of 10 ℃/min, and then preserving heat for 3 hours, wherein the atmosphere in the atmosphere sintering furnace is nitrogen, and the air pressure is 0.1MPa; and cooling to obtain the silicon nitride ceramic.
Example 6
In the preparation method of the silicon nitride ceramic in the embodiment 6, in the second step, 60wt% of OPPEOA, 20wt% of PPTTA and 20wt% of TMPTA are mixed to prepare resin; the other steps were the same as those of example 5.
Example 7
In the preparation method of the silicon nitride ceramic in the embodiment 6, in the second step, 60wt% of OPPEOA, 10wt% of PPTTA, 10wt% of THFA and 20wt% of TMPTA are mixed to prepare resin; the other steps were the same as those of example 5.
Comparative example 1
In the preparation method of the silicon nitride ceramic of the comparative example 1, in the second step, 60 weight percent of TMPTA and 40 weight percent of PPTTA are mixed to prepare resin; the other steps were the same as those of example 5.
Comparative example 2
In the preparation method of the silicon nitride ceramic of the comparative example 2, in the second step, 60wt% of THFA and 40wt% of PPTTA are mixed to prepare resin; the other steps were the same as those of example 5.
Comparative example 3
In the preparation method of the silicon nitride ceramic of the comparative example 3, in the second step, 100wt% of THFA is adopted as the resin; the other steps were the same as those of example 5.
Comparative example 4
In the preparation method of the silicon nitride ceramic in the comparative example 4, in the second step, 100 weight percent of PPTTA is adopted as resin; the other steps were the same as those of example 5.
Comparative example 5
In the preparation method of the silicon nitride ceramic in the comparative example 5, in the second step, 100wt% of TMPTA is adopted as resin; the other steps were the same as those of example 5.
Comparative example 6
In the preparation method of the silicon nitride ceramic of the comparative example 6, in the second step, 100wt% of OPPEOA is adopted as the resin; the other steps were the same as those of example 5.
The refractive index of the above-mentioned resin used is shown in table 1.
TABLE 1 light refractive index of resins
| Resin composition | PPTTA | THFA | TMPTA | OPPEOA |
| Refractive index of light | 1.475 | 1.458 | 1.475 | 1.576 |
The single-layer cured thicknesses of the silicon nitride ceramics of examples 5 to 7 and comparative examples 1 to 6 were measured, and the results are shown in Table 2.
Table 2 single layer cured thickness test results for silicon nitride ceramics of examples 5 to 7, comparative examples 1 to 6
From the test results of table 2, it can be seen that the addition of the high refractive index resin OPPEOA to the photosensitive resin can effectively increase the curing depth of the silicon nitride ceramic slurry during the photo-curing process. Only PPTTA or TMPTA is added into the photosensitive resin, the curing depth of the silicon nitride ceramic slurry in the photo-curing process is low, and only THFA or OPPEOA is added, so that the silicon nitride ceramic slurry cannot be cured.
Test of effect of OPPEOA content in two photosensitive resins on curing thickness
Resins of test examples 1-12 were prepared using various amounts of OPPEOA and PPTTA blends as shown in Table 3.
TABLE 3 resin Components of test examples 1-12
Silicon nitride ceramics corresponding to test examples 1 to 12 were prepared using the resins of test examples 1 to 12, respectively, in the same manner as in example 5.
The single-layer cured thicknesses of the silicon nitride ceramics of test examples 1 to 12 were measured, and the results are shown in Table 4.
TABLE 4 Single layer cure thickness test results for silicon nitride ceramics of test examples 1-12
From the test results in Table 4, it is understood that the single-layer cured thickness of the silicon nitride ceramic can be increased when the OPPEOA content in the resin reaches 10%, more preferably, when the OPPEOA content in the resin is 40-70%, the single-layer cured thickness of the silicon nitride ceramic reaches more than 60 μm, and the OPPEOA content is 60%, the single-layer cured thickness effect is optimal; when the OPPEOA content in the resin reaches 95%, the silicon nitride ceramic slurry is difficult to cure. Test of influence of the content of the mixed powder and the photosensitive resin in the silicon nitride ceramic slurry on the preparation of silicon nitride ceramic
The photosensitive resin is a novel photosensitive resin containing at least one of OPPEOA and PPTTA, TMPTA, THFA, and the photosensitive resin and the mixed powder can meet the preparation requirement of silicon nitride ceramics within a specific proportioning range in combination with the silicon nitride ceramic slurry formed by the mixed powder.
Test examples 13-17 silicon nitride ceramic slurries were prepared using various contents of photosensitive resin and mixed powder as shown in table 5.
TABLE 5 Experimental examples 13-17 silicon nitride ceramic slurry compositions
| Ceramic slurry | Test 13 | Test 14 | Test 15 | Test 16 | Test 17 |
| Mixed powder | 78.25％ | 73.25％ | 68.25％ | 63.25％ | 58.25％ |
| Photosensitive resin | 20％ | 25％ | 30％ | 35％ | 40％ |
| Dispersing agent | 1.75％ | 1.75％ | 1.75％ | 1.75％ | 1.75％ |
Silicon nitride ceramics corresponding to test examples 13 to 17 were prepared using the silicon nitride ceramic slurries of test examples 13 to 17, respectively, in the same manner as in example 5.
The results of the production of the silicon nitride ceramics of test examples 13 to 17 were examined and are shown in Table 6.
TABLE 6 preparation results of silicon nitride ceramics of test examples 13 to 17
From the test results in Table 6, it is clear that if the content of the mixed powder is too high, the viscosity of the prepared slurry is high, and the photo-curing molding cannot be performed; if the content of the mixed powder is too low, cracking or mechanical property reduction after sintering easily occurs in the degreasing process. Therefore, the ceramic slurry of the present application preferably contains 65 to 71wt% of the mixed powder, 35 to 29wt% of the photosensitive resin, and 2 to 3wt% of the dispersant.
Other description
1. Influence of degreasing process on preparation of silicon nitride ceramics
In the preparation method of the silicon nitride ceramic, a formed blank is placed in a degreasing furnace for degreasing, is heated to 500-700 ℃ at the speed of 0.2-0.5 ℃/min, and is kept for 3-5 hours; the atmosphere in the degreasing furnace is nitrogen.
If the temperature rising rate and the heat preservation temperature are not adopted, the blank body is easy to generate layering cracking in the degreasing process; if the temperature and time are not adopted, organic matters in the green body cannot be completely removed, and carbon residues are not beneficial to sintering of the green body.
2. Influence of sintering Process on preparation of silicon nitride ceramics
According to the preparation method of the silicon nitride ceramic, the degreased blank is placed in an atmosphere sintering furnace, the temperature is raised to 1800 ℃ at the speed of 5-15 ℃/min, and the temperature is kept for 2-4h. If the temperature rising rate is higher than 15 ℃/min, the blank body can generate uneven internal and external temperatures in the sintering process, so that cracking is caused in the sintering process; the relative density of the silicon nitride ceramic prepared without the heat preservation time is less than 98 percent, and the mechanical property is reduced.
3. Influence of particle size of silicon nitride powder on preparation of silicon nitride ceramics
According to the preparation method of the silicon nitride ceramic, the particle size of the silicon nitride powder is 0.7-1.0 mu m, and if the particle size of the powder is smaller than 0.7 mu m, the viscosity of the prepared silicon nitride ceramic slurry is larger, so that the silicon nitride ceramic slurry is not beneficial to photo-curing molding; if the particle size of the powder is larger than 1.0 mu m, insufficient sintering driving force can occur in the sintering process, and the relative density of the sintered silicon nitride ceramic is less than 98%.
While the application has been described with reference to certain preferred embodiments, it will be understood by those skilled in the art that various changes and substitutions of equivalents may be made and equivalents will be apparent to those skilled in the art without departing from the scope of the application. Therefore, the protection scope of the application is subject to the protection scope of the claims.
Claims (9)
1. A preparation method of photo-curing silicon nitride ceramic slurry is characterized by comprising the following steps,
step one: ball-milling and dispersing silicon nitride powder and a sintering aid in an ethanol solution, and filtering and drying to obtain mixed powder; wherein, the mass ratio of the silicon nitride powder, the sintering aid and the ethanol solution is (6-12): 1: (18-22);
step two: stirring and mixing the resin, the photoinitiator and the plasticizer to obtain photosensitive resin; wherein, the mass ratio of the resin to the plasticizer is (5-10): 3, the photoinitiator accounts for 1-2wt% of the resin;
the resin comprises o-phenylphenoxyethyl acrylate and one or more of ethoxylated pentaerythritol tetraacrylate, trimethylolpropane triacrylate and tetrahydrofuran acrylate; the content of the o-phenylphenoxyethyl acrylate in the resin is 10-90 wt%;
step three: mixing the mixed powder, photosensitive resin and dispersing agent at high speed to obtain silicon nitride ceramic slurry; wherein, the mixed powder accounts for 65 to 71 weight percent of the silicon nitride ceramic slurry, the photosensitive resin accounts for 35 to 29 weight percent of the ceramic slurry, and the dispersing agent accounts for 2 to 3 weight percent of the mixed powder;
the grain diameter of the silicon nitride powder is 0.7-1.0 mu m.
2. The method of preparing a photocurable silicon nitride ceramic slurry according to claim 1, wherein said sintering aid comprises at least one of non-rare earth oxide alumina and magnesia, and one or more of rare earth oxide yttria, lanthana, and ytterbia.
3. The method for preparing a photo-cured silicon nitride ceramic slurry according to claim 1, wherein the photoinitiator is at least one selected from the group consisting of 2-hydroxy-2-methyl-1-phenyl-1-propanone, phenyl bis (2, 4, 6-trimethylbenzoyl) phosphine oxide and 2-isopropylthioxanthone.
4. The method for preparing a photocurable silicon nitride ceramic slurry according to claim 1, wherein said plasticizer is one or more selected from the group consisting of PEG-300, dioctyl phthalate and dibutyl phthalate.
5. The method of preparing a photocurable silicon nitride ceramic slurry according to claim 1, wherein said dispersant is selected from one or more of BYK-9077, solsperse-85000 and Solsperse-88000.
6. The method for preparing a photocurable silicon nitride ceramic slurry according to claim 1, wherein in the third step, the mixing speed of high-speed mixing is 2500-3000r/min and the mixing time is 8-15min.
7. The preparation method of the silicon nitride ceramic is characterized by comprising the following steps of:
placing the light-cured silicon nitride ceramic slurry in light-curing forming equipment to prepare a blank by a light-curing forming method;
degreasing the formed green body in a degreasing furnace, heating to 500-700 ℃ at a speed of 0.2-0.5 ℃/min, and preserving heat for 3-5 h;
and (3) placing the degreased blank body into an atmosphere sintering furnace, heating to 1800 ℃ at a speed of 5-15 ℃/min, preserving heat for 2-4h, and cooling to obtain the silicon nitride ceramic.
8. The method for preparing silicon nitride ceramics according to claim 7, wherein the light source wavelength of the photo-curing molding is 350-450 nm, and the illumination intensity in the curing process is controlled to be 20-26.3 mw/cm 2 The curing time is controlled to be 6-7 s.
9. The method for producing silicon nitride ceramics according to claim 8, wherein the atmosphere in the degreasing furnace is nitrogen; the atmosphere in the atmosphere sintering furnace is nitrogen.
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