CN108892515B - Photocuring silicon nitride ceramic slurry, silicon nitride ceramic and preparation method thereof - Google Patents
Photocuring silicon nitride ceramic slurry, silicon nitride ceramic and preparation method thereof Download PDFInfo
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Abstract
The application belongs to the technical field of ceramic materials, and particularly relates to photocuring silicon nitride ceramic slurry, silicon nitride ceramic and a preparation method thereof. The application provides photocuring silicon nitride ceramic slurry, silicon nitride ceramic and a preparation method thereof, which can effectively overcome the technical defects that the traditional silicon nitride ceramic slurry is low in solid content and the photocuring-formed single-layer curing thickness is low. The application provides a preparation method of photocuring silicon nitride ceramic slurry, which comprises the following steps: step one, mixing a silicon nitride powder solution, a sintering aid solution, a dispersing agent and a precipitating agent to obtain a precipitation solution, and filtering the precipitation solution to obtain a mixed solid; step two, after the mixed solid is cleaned, calcined and ball-milled, coating powder is obtained; and step three, mixing the coating powder, the light-cured resin, the photoinitiator and the dispersant to obtain the light-cured silicon nitride ceramic slurry.
Description
Technical Field
The application belongs to the technical field of ceramic materials, and particularly relates to photocuring silicon nitride ceramic slurry, silicon nitride ceramic and a preparation method thereof.
Background
Silicon nitride ceramics are one of the most potential structural ceramics at present, and have excellent high-temperature performance, chemical stability and other characteristics, so that the silicon nitride ceramics play an important role in the high-temperature field. With the development of science and technology, the application field and the use requirement of the silicon nitride ceramic are more and more strict. At present, the traditional manufacturing method is to process the silicon nitride powder or slurry into the required ceramic component by a mould forming machine and a post-processing matching machine such as sintering, and the mould forming process leads the component to have higher processing cost and to be difficult to prepare parts with complex structures such as radian and hollow, and the application and development of the silicon nitride ceramic are severely limited.
In order to solve this problem, many researchers have proposed a net-size forming method, in which a member having a desired shape is directly formed by an additive manufacturing method (solid mold-free forming technology), which enables the preparation of a silicon nitride ceramic having a complicated structure, thus reducing the preparation cost and widening the field of use of the silicon nitride ceramic. The current rapid forming methods for ceramics are: three-dimensional printing and forming (3DP), Selective Laser Melting (SLM) and photocuring and forming (SLA/DLP). Compared with other two mainstream methods, the photocuring forming method is easier to prepare compact ceramic parts. However, the photocuring forming method requires a suitable silicon nitride ceramic slurry. The researchers studied silicon nitride ceramic slurry for photocuring molding, and the following problems existed: (1) the traditional silicon nitride ceramic slurry has low solid content; (2) the single-layer curing thickness of the conventional silicon nitride ceramic slurry is low. These two main problems limit the formation of silicon nitride ceramics by photocuring forming techniques.
Content of application
In view of the above, the present application provides a photocuring silicon nitride ceramic slurry, a silicon nitride ceramic and a preparation method thereof, which can effectively solve the technical defects of low solid content of the conventional silicon nitride ceramic slurry and low photocuring-formed single-layer curing thickness of the conventional silicon nitride ceramic slurry.
The application provides a preparation method of photocuring silicon nitride ceramic slurry, which comprises the following steps:
step one, mixing a silicon nitride powder solution, a sintering aid solution, a first dispersing agent and a precipitating agent to obtain a precipitation solution, and filtering the precipitation solution to obtain a mixed solid;
step two, after the mixed solid is cleaned, calcined and ball-milled, coating powder is obtained;
and step three, mixing the coating powder, the light-cured resin, the photoinitiator and the second dispersing agent to obtain the light-cured silicon nitride ceramic slurry.
Preferably, the particle diameter of the silicon nitride powder in the silicon nitride powder solution is 0.2-1 μm.
Preferably, the concentration of the silicon nitride powder solution is 0.1-1 mol/L.
Preferably, the sintering aid solution comprises one or more of an aluminum chloride hexahydrate solution, an aluminum nitrate nonahydrate solution, an yttrium nitrate hexahydrate solution, a magnesium chloride hexahydrate solution, and a magnesium nitrate hexahydrate solution.
Preferably, the concentration of the sintering aid solution is 0.01-0.5 mol/L.
More preferably, the concentration of the sintering aid solution is 0.01-0.04 mol/L.
Preferably, the precipitant comprises NaOH, KOH, NH3·H2O and CO (NH)2)2One or more of (a).
Preferably, the precipitation solution has a pH of 8 to 12.
More preferably, the pH value of the precipitation solution is 9-11.
The application also discloses silicon nitride ceramic slurry which is prepared by the preparation method of the photocuring silicon nitride ceramic slurry.
The application also discloses a preparation method of the silicon nitride ceramic, which comprises the following steps:
step 1, taking the photocuring silicon nitride ceramic slurry prepared by the preparation method of the photocuring silicon nitride ceramic slurry or the photocuring silicon nitride ceramic slurry as a raw material, and carrying out layer-by-layer curing and stacking treatment according to the slice outline of a part drawing to obtain a molded blank;
and 2, carrying out glue removal and sintering on the molded blank to obtain the silicon nitride ceramic.
The application also discloses silicon nitride ceramic prepared by the preparation method of the silicon nitride ceramic.
The surface coating of the silicon nitride powder is realized by a chemical precipitation method for mixing the silicon nitride powder solution, the sintering aid solution, the dispersing agent and the precipitating agent, and the surface characteristic of the silicon nitride powder is changed. The application has the following advantages: (1) the surface characteristics of the silicon nitride powder are changed, the refractive index difference between the powder and resin is reduced, and the solid content and the curing depth of the photocuring silicon nitride ceramic slurry are improved; (2) the uniform dispersion of the sintering aid is realized. From experimental data, the curing depth of the silicon nitride ceramic prepared from the photocuring silicon nitride ceramic slurry obtained by coating the surface of the silicon nitride powder by chemical precipitation is obviously improved, and the compactness of the silicon nitride ceramic is within a qualified range. The application provides silicon nitride ceramic slurry suitable for photocuring molding and a method for preparing silicon nitride ceramic by using the same, further improves the feasibility of printing the silicon nitride ceramic by 3d, and widens the application field of the silicon nitride ceramic.
Detailed Description
The application provides silicon nitride ceramic slurry, silicon nitride ceramic and a preparation method and application thereof, which are used for solving the technical defects that the traditional silicon nitride ceramic slurry is low in solid content, long in exposure time of photocuring molding and easy to generate scattering phenomenon.
The technical solutions in the embodiments of the present application will be described clearly and completely below, and it should be understood that the described embodiments are only a part of the embodiments of the present application, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.
The application provides a specific implementation mode of a preparation method of photocuring silicon nitride ceramic slurry, which comprises the following preparation steps:
(a) preparing 0.1-1mol/L silicon nitride powder aqueous solution and 0.01-0.5 mol/L sintering aid solution, mixing the silicon nitride powder aqueous solution, the sintering aid solution, the first dispersing agent and a precipitating agent, performing chemical precipitation coating on the silicon nitride powder to obtain a precipitation solution, and performing solid-liquid filtration on the precipitation solution to obtain a mixed solid, wherein the PH of the precipitation solution is 8-12;
(b) cleaning the mixed solid for multiple times by using deionized water and alcohol to remove residual ions, separating to obtain powder, drying the powder, and calcining and ball-milling the powder, wherein the calcining method comprises the following steps: heating the powder to 500-;
(c) and mixing the coating powder, the light-cured resin, the photoinitiator and the second dispersing agent to obtain the light-cured silicon nitride ceramic slurry.
Wherein the particle diameter of the silicon nitride powder in the silicon nitride powder solution is 0.2-1 μm.
Wherein the concentration of the silicon nitride powder solution is 0.1-1 mol/L.
Wherein the silicon nitride powder solution is an aqueous solution of silicon nitride powder.
Wherein the sintering aid solution comprises aluminum chloride hexahydrate solution (AlCl)3·H2O), aluminum nitrate nonahydrate solution (Al (NO)3)3·9H2O), yttrium nitrate hexahydrate solution (Y (NO)3)3·6H2O), magnesium chloride hexahydrate solution (MgCl)2·6H2O) and magnesium nitrate hexahydrate solution (Mg (NO)3)2·6H2O) is used.
Wherein the concentration of each sintering aid solution is 0.01-0.5 mol/L.
More preferably, the concentration of each sintering aid solution is 0.01-0.04 mol/L.
Wherein the first dispersant comprises one or more of sodium polyacrylate, ammonium polyacrylate or methyl cellulose.
The first dispersing agent is added in an amount of 0.5-1.5 wt% of the silicon nitride powder, the silicon nitride powder is silicon nitride powder in a silicon nitride powder solution, and the first dispersing agent is used for dispersing the silicon nitride powder in water, is beneficial to coating and has different effects from the second dispersing agent.
Wherein the mixing conditions of step (a) are one or more of magnetic stirring, mechanical stirring or heating.
Wherein the rotating speed of the magnetic stirring is 0-1250 rpm, the rotating speed of the mechanical stirring is 0-2000 rpm, and the heating temperature is 50-80 ℃.
Wherein the precipitant is NaOH, KOH, NH3·H2O or CO (NH)2)2One kind of (1).
More preferably, the pH of the precipitating solution is 9 to 11.
Wherein, the filtering method in the step (a) is vacuum filtration or rotary centrifugation, the vacuum degree is 0.09MPa, and the rotating speed is 8000-12000 rpm.
Wherein, the calcining method in the step (b) comprises the following steps: the powder is heated to 500-.
Wherein the light-cured resin comprises one or more of 1, 6-hexanediol diacrylate (HDDA), pentaerythritol tetraacrylate (PETTA) and trimethylolpropane triacrylate (TMPTA).
Wherein the added mass percentage of the light-cured resin is 40-60% of the light-cured silicon nitride ceramic slurry.
Wherein the photoinitiator is selected from one or more of 2-hydroxy-2-methyl-1-phenyl-1-propanone (1173), phenyl bis (2,4, 6-trimethylbenzoyl) phosphine oxide (819), (2,4, 6-trimethylbenzoyl) diphenylphosphine oxide (TPO), and 2 Isopropyl Thioxanthone (ITX).
Wherein the addition mass of the photoinitiator is 1-2 wt% of the photocurable resin.
Specifically, the second dispersing agent comprises one or more of BYK-9076, BYK-163 and BYK-9077.
Specifically, the addition amount of the second dispersing agent is 1-2 wt% of the coating powder, and the second dispersing agent is used for fully dispersing the coating powder in the preparation of the slurry, so that the viscosity of the product is reduced.
The application provides a forming method of silicon nitride ceramics, which comprises the following preparation steps:
step 1, taking the photocuring silicon nitride ceramic slurry as a raw material, and carrying out layer-by-layer curing and stacking treatment according to the slice profile of a part drawing to obtain a molded blank;
and 2, carrying out glue removal and sintering on the molded blank to obtain the silicon nitride ceramic.
Specifically, the step 1 of molding comprises the following steps: and cutting the model three-dimensional part drawing into a photocuring forming machine by using software, adding the prepared photocuring silicon nitride ceramic slurry into the photocuring forming machine, curing the ceramic slurry layer by layer and accumulating layer by layer according to program setting, and finally obtaining a formed blank.
Specifically, the glue discharging method comprises the following steps: and heating the formed blank body to 300 ℃ at the speed of 0.5-2 ℃/min in vacuum or air, preserving heat for 1-3 h, and heating to 600 ℃ at the speed of 0.5-2 ℃/min, and preserving heat for 1-3 h.
Specifically, the sintering method comprises the following steps: and heating the blank after the glue is removed to 1700-1850 ℃ at the speed of 0.5-3 ℃/min in the nitrogen or vacuum atmosphere, and preserving the heat for 1-3 h, wherein the air pressure is 0.1-10 MPa.
The raw materials used in the following examples are all commercially available or self-made.
Example 1
The embodiment of the application provides a first preparation method of photocuring silicon nitride ceramic slurry, which comprises the following steps:
(a) 0.8 wt% of sodium polyacrylate (sodium polyacrylate is 0.8 wt% of silicon nitride powder) was added to 0.1mol/L of deionized water solution of silicon nitride using a magnetic stirrer (rotation speed is 1250rpm) and 0.03mol/L of aluminum nitrate nonahydrate aqueous solution Al (NO)3)3·9H2O、NH3·H2O and 0.01mol/L aqueous yttrium nitrate hexahydrate Y (NO)3)3·6H2Dripping O into the deionized water solution of silicon nitride, and stirring and mixing to obtain a precipitation solution; adjusting the pH value of the precipitation solution to 10.5, and standing;
(b) separating powder from liquid by using a centrifugal machine on the precipitated solution, washing the separated powder for 3 times by using deionized water, washing the powder for 1 time by using alcohol, drying the powder for 24 hours, calcining the powder in the air, heating the powder to 500 ℃ at the speed of 1 ℃/min under the calcining condition, keeping the temperature for 3 hours, ball-milling the powder for 6 hours after calcining, and sieving the powder by using a 100-mesh sieve to obtain coated powder;
(c) and mixing 50g of the sieved coated powder with 23g of 1, 6-hexanediol diacrylate (HDDA), 0.4g of phenyl bis (2,4, 6-trimethylbenzoyl) phosphine oxide (819) and 0.5g of BYK-9076 to obtain the photocuring silicon nitride ceramic slurry.
The embodiment of the application provides a first method for forming silicon nitride ceramics, which comprises the following steps:
step one, forming: cutting the model three-dimensional part drawing into a photocuring forming machine by using software, adding the prepared photocuring silicon nitride ceramic slurry into the photocuring forming machine, and curing the photocuring silicon nitride ceramic slurry layer by layer and accumulating the layers by layer according to program setting to obtain a formed blank;
the second step is that: and (3) post-treatment: removing glue from the molded blank in the first step in the air, heating to 300 ℃ at the speed of 0.5 ℃/min, preserving heat for 1h, heating to 600 ℃ at the speed of 1 ℃/min, and preserving heat for 3 h; and sintering the blank after the glue is removed under nitrogen, heating to 1820 ℃ at the speed of 3 ℃/min, and keeping the temperature for 2h, wherein the air pressure is 0.1MPa, so as to obtain the silicon nitride ceramic with a complex shape.
Example 2
The embodiment of the application provides a preparation method of a second silicon nitride ceramic slurry, which comprises the following steps:
(a) 0.8 wt% of sodium polyacrylate and 0.03mol/L of aluminum nitrate nonahydrate Al (NO) are added into 0.1mol/L silicon nitride deionized water solution3)3·9H2O, NaOH and 0.01mol/L Yttrium nitrate hexahydrate (Y (NO)3)3·6H2O) stirring and mixing the aqueous solution by using a mechanical stirrer (the rotating speed is 1500rpm) to obtain a precipitation solution; adjusting the pH value of the precipitation solution to 11.5, heating to 60 ℃, and standing;
(b) separating powder from liquid by using vacuum filtration (the vacuum degree is 0.09MPa) on the precipitated solution, washing the separated powder for 4 times by using deionized water, washing the powder for 1 time by using alcohol, drying the powder for 24 hours, heating the calcined powder to 500 ℃ at the speed of 2 ℃/min during vacuum calcination, preserving the temperature for 2 hours, carrying out ball milling for 6 hours after calcination, and sieving the calcined powder by using a 100-mesh sieve to obtain coated powder;
(c) and mixing 50g of the sieved coated powder with 23g of pentaerythritol tetraacrylate (PETTA), 0.4g of 2-hydroxy-2-methyl-1-phenyl-1-acetone (1173) and 0.5g of BYK-9077 to obtain the photocuring silicon nitride ceramic slurry.
The embodiment of the application provides a second method for forming silicon nitride ceramics, which comprises the following steps:
step one, forming: cutting the model three-dimensional part drawing into a photocuring forming machine by using software, adding the prepared photocuring silicon nitride ceramic slurry into the photocuring forming machine, and curing the photocuring silicon nitride ceramic slurry layer by layer and accumulating the layers by layer according to program setting to obtain a formed blank;
the second step is that: and (3) post-treatment: removing glue from the formed blank in the first step in vacuum, heating to 300 ℃ at the speed of 1 ℃/min, preserving heat for 1.5h, and heating to 600 ℃ at the speed of 1 ℃/min, preserving heat for 2 h; and sintering the blank after the glue is removed under nitrogen, heating to 1820 ℃ at the speed of 2 ℃/min, and keeping the temperature for 2h, wherein the air pressure is 8MPa, so as to obtain the silicon nitride ceramic with a complex shape.
Example 3
The embodiment of the application provides a preparation method of a third silicon nitride ceramic slurry, which comprises the following steps:
(a) 0.8 wt% of sodium polyacrylate and 0.05mol/L of aluminum nitrate nonahydrate Al (NO) are added into 0.2mol/L silicon nitride deionized water solution3)3·9H2O, KOH and 0.03mol/L MgCl hexahydrate2·6H2Stirring and mixing the O aqueous solution by using a mechanical stirrer (the rotating speed is 1800rpm) to obtain a precipitation solution; adjusting the pH value of the precipitation solution to 10.5, heating to 60 ℃, and standing;
(b) separating powder from liquid by using vacuum filtration (the vacuum degree is 0.09MPa) on the precipitated solution, washing the separated powder for 3 times by using deionized water, washing the powder for 1 time by using alcohol, drying the powder for 24 hours, heating the calcined powder to 500 ℃ at the speed of 2 ℃/min for heat preservation for 2 hours after calcination in the air, performing ball milling for 6 hours after calcination, and sieving the calcined powder by using a 100-mesh sieve to obtain coated powder;
(c) and mixing 50g of the sieved coated powder with 35g of trimethylolpropane triacrylate (TMPTA), 0.35g of 2-hydroxy-2-methyl-1-phenyl-1-acetone (1173) and 1g of BYK-9075 to obtain the photocuring silicon nitride ceramic slurry.
The embodiment of the application provides a third method for forming silicon nitride ceramics, which comprises the following steps:
step one, forming: cutting the model three-dimensional part drawing into a photocuring forming machine by using software, adding the prepared photocuring silicon nitride ceramic slurry into the photocuring forming machine, and curing the photocuring silicon nitride ceramic slurry layer by layer and accumulating the layers by layer according to program setting to obtain a formed blank;
the second step is that: and (3) post-treatment: removing glue from the formed blank in the first step in vacuum, heating to 300 ℃ at the speed of 0.5 ℃/min, preserving heat for 0.5h, and heating to 600 ℃ at the speed of 0.5 ℃/min, preserving heat for 3 h; and sintering the blank after the glue is removed under nitrogen, heating to 1820 ℃ at the speed of 2 ℃/min, and keeping the temperature for 2h, wherein the air pressure is 0.1MPa, so as to obtain the silicon nitride ceramic with a complex shape.
Example 4
The embodiment of the application provides a fourth preparation method of photocuring silicon nitride ceramic slurry, which comprises the following steps:
(a) adding 0.1mol/L silicon nitride deionized water solution into 1.2 wt% sodium polyacrylate and 0.5mol/L aluminum nitrate nonahydrate Al (NO)3)3·9H2O, KOH and 0.03mol/L magnesium nitrate hexahydrate Mg (NO)3)2·6H2Stirring and mixing the O aqueous solution by using a mechanical stirrer (the rotating speed is 1000rpm) to obtain a precipitation solution; adjusting the pH value of the precipitation solution to 9.5, heating to 50 ℃, and standing;
(b) separating powder from liquid by using a centrifugal machine (the rotating speed is 8000rpm) on the precipitation solution, washing the separated powder by using deionized water for 3 times, washing the powder by using alcohol for 1 time, drying the powder for 24 hours, calcining the powder in the air, raising the temperature to 500 ℃ at the speed of 2 ℃/min, keeping the temperature for 2 hours, ball-milling the calcined powder for 6 hours, and sieving the calcined powder by using a 100-mesh sieve to obtain coated powder;
(c) and mixing 50g of the sieved coated powder with 35g of trimethylolpropane triacrylate (TMPTA), 0.35g of 2-hydroxy-2-methyl-1-phenyl-1-acetone (1173) and 1.5g of BYK-9077 to obtain the photocuring silicon nitride ceramic slurry.
The embodiment of the application provides a fourth method for forming silicon nitride ceramics, which comprises the following steps:
step one, forming: cutting the model three-dimensional part drawing into a photocuring forming machine by using software, adding the prepared photocuring silicon nitride ceramic slurry into the photocuring forming machine, and curing the photocuring silicon nitride ceramic slurry layer by layer and accumulating the layers by layer according to program setting to obtain a formed blank;
the second step is that: and (3) post-treatment: removing glue from the formed blank in the first step in vacuum, heating to 300 ℃ at the speed of 0.5 ℃/min, preserving heat for 0.5h, and heating to 600 ℃ at the speed of 0.5 ℃/min, preserving heat for 3 h; and (3) sintering the blank after the glue is removed under nitrogen, heating to 1850 ℃ at the speed of 1 ℃/min, and preserving the heat for 2h, wherein the air pressure is 0.1MPa, so as to obtain the silicon nitride ceramic with a complex shape.
Example 5
The embodiment of the application provides a fifth preparation method of photocuring silicon nitride ceramic slurry, which comprises the following steps:
(a) 1.2 wt% of sodium polyacrylate and 0.5mol/L of aluminum nitrate nonahydrate Al (NO) are added into 1mol/L silicon nitride deionized water solution3)3·9H2O、CO(NH2)2And 0.2mol/L magnesium nitrate hexahydrate Mg (NO)3)2·6H2Stirring and mixing the O aqueous solution to obtain a precipitate solution; adjusting the pH value of the precipitation solution to 9.5, heating to 60 ℃, and standing;
(b) separating powder from liquid by using a centrifugal machine (the rotating speed is 10000rpm) on the precipitated solution, washing the separated powder for 3 times by using deionized water, washing the powder for 1 time by using alcohol, drying the powder for 24 hours, calcining the powder in the air, raising the temperature to 500 ℃ at the speed of 2 ℃/min, keeping the temperature for 2 hours, ball-milling the calcined powder for 6 hours, and sieving the calcined powder by using a 100-mesh sieve to obtain coated powder;
(c) and mixing 50g of the sieved coated powder with 40g of pentaerythritol tetraacrylate (PETTA), 0.4g of (2,4, 6-trimethylbenzoyl) diphenylphosphine oxide (TPO) and 1.5g of BYK-9077 to obtain the photocuring silicon nitride ceramic slurry.
The embodiment of the application provides a fifth method for forming silicon nitride ceramics, which comprises the following steps:
step one, forming: cutting the model three-dimensional part drawing into a photocuring forming machine by using software, adding the prepared photocuring silicon nitride ceramic slurry into the photocuring forming machine, and curing the photocuring silicon nitride ceramic slurry layer by layer and accumulating the layers by layer according to program setting to obtain a formed blank;
the second step is that: and (3) post-treatment: removing glue from the formed blank in the first step in vacuum, heating to 300 ℃ at the speed of 0.5 ℃/min, preserving heat for 0.5h, and heating to 600 ℃ at the speed of 0.5 ℃/min, preserving heat for 3 h; and sintering the blank after the glue is removed under nitrogen, heating to 1820 ℃ at the speed of 2 ℃/min, and keeping the temperature for 2h, wherein the air pressure is 0.1MPa, so as to obtain the silicon nitride ceramic with a complex shape.
Example 6
The embodiment of the application provides a sixth preparation method of photocuring silicon nitride ceramic slurry, which comprises the following steps:
(a) using a magnetic stirrer (1500 rpm), 0.2mol/L silicon nitride deionized water solution was added with 1.2 wt% sodium polyacrylate and 0.1mol/L aluminum nitrate nonahydrate Al (NO)3)3·9H2O、CO(NH2)2And 0.08mol/L magnesium nitrate hexahydrate Mg (NO)3)2·6H2Stirring and mixing the O aqueous solution to obtain a precipitate solution; adjusting the pH value of the precipitation solution to 9, and standing;
(b) separating powder from liquid by using a centrifugal machine (the rotating speed is 12000rpm) on the precipitation solution, washing the separated powder for 2 times by using deionized water, washing the powder for 2 times by using alcohol, drying the powder for 24 hours, calcining the powder in the air, raising the temperature to 500 ℃ at the speed of 1 ℃/min, keeping the temperature for 2 hours, ball-milling the calcined powder for 6 hours, and sieving the calcined powder by using a 100-mesh sieve to obtain coated powder;
(c) and mixing 50g of the sieved coated powder with 40g of pentaerythritol tetraacrylate (PETTA), 0.4g of (2,4, 6-trimethylbenzoyl) diphenylphosphine oxide (TPO) and 1g of BYK-9076 to obtain the photocuring silicon nitride ceramic slurry.
The embodiment of the application provides a sixth method for forming silicon nitride ceramics, which comprises the following steps:
step one, forming: cutting the model three-dimensional part drawing into a photocuring forming machine by using software, adding the prepared photocuring silicon nitride ceramic slurry into the photocuring forming machine, and curing the photocuring silicon nitride ceramic slurry layer by layer and accumulating the layers by layer according to program setting to obtain a formed blank;
the second step is that: and (3) post-treatment: removing glue from the formed blank in the first step in vacuum, heating to 300 ℃ at the speed of 0.5 ℃/min, preserving heat for 0.5h, and heating to 600 ℃ at the speed of 1 ℃/min, preserving heat for 2 h; and sintering the blank after the glue is removed under nitrogen, heating to 1850 ℃ at the speed of 2 ℃/min, and preserving the heat for 3h under the air pressure of 10MPa to obtain the silicon nitride ceramic with a complex shape.
Comparative example
The application also provides a comparative example, the comparative example is silicon nitride ceramic slurry prepared from uncoated silicon nitride powder, and the specific preparation method of the silicon nitride ceramic prepared from the silicon nitride ceramic slurry comprises the following steps:
(1) ball-milling and mixing aluminum oxide powder, yttrium oxide powder and silicon nitride powder according to the proportion of 4:6:90 to obtain mixed powder;
(2) and mixing 50g of the mixed powder with 40g of pentaerythritol tetraacrylate (PETTA), 0.4g of (2,4, 6-trimethylbenzoyl) diphenylphosphine oxide (TPO) and 1g of BYK-9076 to obtain the photocuring silicon nitride ceramic slurry.
A method of forming a silicon nitride ceramic of a comparative example is provided as follows:
step one, forming: cutting the model three-dimensional part drawing into a photocuring forming machine by using software, adding the prepared photocuring silicon nitride ceramic slurry into the photocuring forming machine, and curing the photocuring silicon nitride ceramic slurry layer by layer and accumulating the layers by layer according to program setting to obtain a formed blank;
the second step is that: and (3) post-treatment: removing glue from the formed blank in the first step in vacuum, heating to 300 ℃ at the speed of 0.5 ℃/min, preserving heat for 0.5h, and heating to 600 ℃ at the speed of 1 ℃/min, preserving heat for 2 h; and sintering the blank after the glue is removed under nitrogen, heating to 1820 ℃ at the speed of 2 ℃/min, and keeping the temperature for 2h, wherein the air pressure is 8MPa, so as to obtain the silicon nitride ceramic with a complex shape.
The curing depth and the densification of the silicon nitride ceramics of the above examples 1 to 6 and comparative example were measured, and the results are shown in table 1.
TABLE 1 test results of examples 1-6 and comparative examples
| Sample (I) | Depth of cure (micron) | Density (%) |
| Comparative example | 20 | 92 |
| Example 1 | 22 | 95 |
| Example 2 | 22 | 97 |
| Example 3 | 24 | 85 |
| Example 4 | 25 | 85 |
| Example 5 | 35 | 80 |
| Example 6 | 27 | 82 |
As can be seen from Table 1, in examples 1 to 6 and comparative examples, the sintering aid is coated on the surface of silicon nitride by a chemical precipitation method, so that the thickness of single-layer curing of the silicon nitride ceramic slurry in the photocuring process can be effectively increased, and the interlayer bonding force can be ensured. In addition, the proper coating process is beneficial to improving the density, and the dispersion of the sintering aid in the silicon nitride powder is effectively improved through the coating treatment; from examples 1 to 6, it is understood that the silicon nitride ceramics are superior in the depth of solidification and densification properties when the concentration of each sintering aid is 0.01 to 0.04 mol/L.
The foregoing is only a preferred embodiment of the present application and it should be noted that those skilled in the art can make several improvements and modifications without departing from the principle of the present application, and these improvements and modifications should also be considered as the protection scope of the present application.
Claims (6)
1. The preparation method of the photocuring silicon nitride ceramic slurry is characterized by comprising the following steps of:
step one, mixing a silicon nitride powder solution, a sintering aid solution, a first dispersing agent and a precipitating agent to obtain a precipitation solution, and filtering the precipitation solution to obtain a mixed solid; the sintering aid solution comprises one or more of an aluminum chloride hexahydrate solution, an aluminum nitrate nonahydrate solution, an yttrium nitrate hexahydrate solution, a magnesium chloride hexahydrate solution and a magnesium nitrate hexahydrate solution; the precipitant comprises NaOH, KOH and NH3·H2O and CO (NH)2)2One or more of; the pH value of the precipitation solution is 8-12; the first dispersant comprises one or more of sodium polyacrylate, ammonium polyacrylate or methyl cellulose; the concentration of the sintering aid solution is 0.01-0.5 mol/L;
step two, after the mixed solid is cleaned, calcined and ball-milled, coating powder is obtained; the calcining method comprises the following steps: heating the powder to 500-;
mixing the coating powder, the light-cured resin, the photoinitiator and the second dispersing agent to obtain light-cured silicon nitride ceramic slurry; the second dispersing agent comprises one or more of BYK-9076, BYK-163 and BYK-9077.
2. The method for preparing the photocuring silicon nitride ceramic slurry according to claim 1, wherein the particle size of the silicon nitride powder in the silicon nitride powder solution is 0.2-1 μm.
3. The method for preparing a photocurable silicon nitride ceramic slurry according to claim 1, wherein the concentration of the silicon nitride powder solution is 0.1-1 mol/L.
4. A silicon nitride ceramic slurry, characterized by comprising the photocurable silicon nitride ceramic slurry according to any one of claims 1 to 3.
5. A preparation method of silicon nitride ceramics is characterized by comprising the following steps:
step 1, using the photocuring silicon nitride ceramic slurry prepared by the preparation method of the photocuring silicon nitride ceramic slurry according to any one of claims 1 to 3 or the photocuring silicon nitride ceramic slurry according to claim 4 as a raw material, and carrying out layer-by-layer curing and stacking treatment according to the slice outline of a part drawing to obtain a molded blank;
and 2, carrying out glue removal and sintering on the molded blank to obtain the silicon nitride ceramic.
6. A silicon nitride ceramic produced by the method for producing a silicon nitride ceramic according to claim 5.
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| CN110395994A (en) * | 2019-08-30 | 2019-11-01 | 广东工业大学 | A kind of overlay film nitride ceramics composite granule and preparation method thereof, nitride ceramics component and preparation method thereof |
| CN110451936B (en) * | 2019-09-04 | 2022-06-24 | 广东工业大学 | Complex phase ceramic and preparation method and application thereof |
| CN113024263B (en) * | 2019-12-24 | 2022-11-29 | 新疆晶硕新材料有限公司 | Silicon nitride composite formula powder, preparation method and preparation device thereof |
| CN111348921B (en) * | 2020-01-17 | 2021-11-19 | 华中科技大学 | Ceramic material for photocuring forming and emulsion coating preparation method and application thereof |
| CN111269007B (en) * | 2020-02-12 | 2022-03-08 | 深圳市光韵达增材制造研究院 | Ceramic photocuring slurry and preparation method thereof |
| CN111320480A (en) * | 2020-03-02 | 2020-06-23 | 广东省新材料研究所 | 3D printing photocuring ceramic particle and preparation method thereof |
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| CN112341206A (en) * | 2020-11-05 | 2021-02-09 | 衡阳凯新特种材料科技有限公司 | Forming method of rare earth praseodymium-holmium-stabilized silicon nitride ceramic |
| CN113511901B (en) * | 2021-04-21 | 2022-12-02 | 广东工业大学 | Photocuring-formed silicon nitride ceramic with high solid content and preparation method and application thereof |
| CN113800943B (en) * | 2021-08-17 | 2023-06-20 | 航天特种材料及工艺技术研究所 | Preparation of pore gradient Si based on photo-curing technology 3 N 4 Method for producing ceramic-based materials |
| CN114105650B (en) * | 2022-01-26 | 2022-07-19 | 中国人民解放军国防科技大学 | Method for preparing silicon nitride ceramic through 3D printing by using sinking type DLP (digital light processing) photocuring technology |
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