CN113620717A - Preparation method of silicon nitride ceramic with gradient layered structure - Google Patents
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- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 title claims abstract description 82
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Abstract
The invention discloses a preparation method of silicon nitride ceramic with a gradient layered structure. The applicant compares the rheological property, the dynamic stability, the wetting property and the photocuring property of the silicon nitride ceramic slurry before and after modification, and discloses a photocuring forming mechanism of the modified silicon nitride ceramic slurry. The mechanism is utilized to improve the rheological property, the dynamic stability, the wetting property and the photocuring property of the silicon nitride ceramic slurry, and the silicon nitride ceramic with high density, hardness and fracture toughness can be prepared.
Description
Technical Field
The invention relates to the technical field of silicon nitride ceramic forming, in particular to a preparation method of silicon nitride ceramic with a gradient layered structure.
Background
Silicon nitride ceramics have high hardness, relatively low thermal expansion coefficient and high fracture toughness, so that silicon nitride ceramic components such as exhaust valves, valve springs, bucket lifters, rocker arm pads and the like have wide application in the industrial field. The silicon nitride ceramic has high wear resistance and thermal shock resistance, so that the silicon nitride ceramic is widely applied to the field of machining. Due to the excellent thermoelectric property and corrosion resistance, the material can be widely applied to the fields of electric machines such as heat conductors, valves, catalyst carriers, spark plugs and the like. In addition, the excellent comprehensive physical properties of the material make the material a candidate material for a high-temperature gas-cooled reactor nuclear fusion reactor.
Meanwhile, the silicon nitride ceramic sandwich structure is used as a missile radome, the guidance performance of a missile is directly influenced by the performance of the silicon nitride ceramic sandwich structure, and the radome wall structure with the broadband and high wave-transmitting performance mainly adopts the sandwich structure.
However, the traditional machining method for manufacturing ceramic parts with complex structures has the problems of long period, high machining cost, severe dependence on molds and the like. In contrast, additive manufacturing techniques can enable the preparation of complex ceramic parts without a die. Among them, photocuring has incomparable advantages in the preparation of high-precision and complex ceramic parts, and has been applied to the fields of medicine and biology (such as tooth and bone restoration), microtechnology (such as sensors, piezoelectric elements and photonic crystals), mechanical heat-resistant structures, and the like. The photo-curing forming technology is that slurry formed by mixing photosensitive resin and ceramic powder is irradiated by ultraviolet light beams to perform polymerization reaction to form a cured blank. Currently, photocuring has been successful in producing complex, dense oxide ceramics. Zhou et Al studied the photocuring of cylindrical Al2O3And (3) degreasing and sintering the blank to obtain a sample with the density of 99%. Bian et al created a porous β -TCP scaffold with SL, and the compressive strength of the part reached 30 MPa. Chartier et Al studied Al in a volume fraction of 60 vol.%2O3And (3) preparing the ceramic part with the porous structure, wherein the density of the ceramic part is 97%. He et al select the optimum light-curing process parameters to prepare ZrO with complex structure2The green body is sintered at 1400 ℃ to respectively obtain the density of 97.14 percent, the hardness and the fracture toughness of 13GPa and 6 MPa-m1/2The parts of (1).
However, relatively few reports are currently made on nitride ceramics, particularly on gray or dark nitride ceramics, photocuring forming techniques. This is because silicon nitride ceramics have high ultraviolet absorptivity, high refractive index, strong scattering, and low depth of curing of the slurry, which makes it difficult to form. At the same time, the strong covalent bonding properties of nitride ceramics also make it difficult to sinter densify. Huang et al aloneOxidizing the silicon nitride powder to generate nano SiO on the surface2The film reduces the refractive index difference with the premixed liquid, and prepares Si with the density of 97.84 percent3N4Ceramics, but SiO2Can lead to a significant reduction in its mechanical properties.
Disclosure of Invention
The technical problem to be solved by the invention is to overcome the defects of the prior art: the method effectively improves the rheological property, the dynamic stability, the wetting property and the photocuring property of the silicon nitride ceramic slurry, and can prepare the silicon nitride ceramic with high density, hardness and fracture toughness.
The technical solution of the invention is as follows: a preparation method of silicon nitride ceramics with a gradient layered structure comprises the following specific steps:
1) weighing a surface modifier and silicon nitride powder, mixing, ball-milling for 10-20min, and drying to obtain modified silicon nitride powder; wherein, the weight portion is: 2-5 parts of surface modifier and 60-100 parts of silicon nitride powder;
2) weighing a diluent and an initiator, mixing, and stirring at a high speed in vacuum to obtain a premixed liquid, wherein the stirring speed is 1000-1350r/min, and the stirring time is 10-30 min; wherein, the weight portion is: 30-100 parts of diluent and 1-10 parts of initiator;
3) stirring and mixing the modified silicon nitride powder prepared in the step 1) and the premixed liquid prepared in the step 2) to respectively prepare at least two photocuring silicon nitride slurries with solid contents, wherein the stirring speed is 2000-2300 r/min;
4) carrying out periodic lamination curing on the photocuring silicon nitride slurry with at least two solid contents prepared in the step 3) respectively according to the decreasing or increasing sequence of the solid contents to form a gradient laminated structure blank cured by silicon nitride slurry layers with different solid contents, wherein the exposure time of each layer is 3-8s, the thickness of each layer is 0.03-0.06mm, and the total layer number is determined according to the total thickness requirement of the gradient laminated structure blank; for example, a total of 1 vol.%, 2 vol.% and 3 vol.% of photo-curable silicon nitride paste with solid content, which is cured from the lower layer to the upper layer periodically in the ascending order of solid content to a material comprising 7 cured layers, the structure composition of the layer is 1 vol.% to 2 vol.% to 3 vol.% to 1 vol.%;
5) sequentially degreasing and sintering the obtained gradient laminated structure blank to obtain the gradient laminated structure silicon nitride ceramic; wherein the degreasing temperature is 500-800 ℃, and the temperature rise rate of the degreasing temperature is 0.1-0.5 ℃/min; the sintering pressure is 0.1-0.2MPa, the sintering temperature is 1700-1800 ℃, the sintering temperature rise rate is 1-5 ℃/min, and the sintering time is 18-24 h.
The preferable scheme of the preparation method of the silicon nitride ceramic with the gradient layered structure comprises the following specific steps:
1) weighing a surface modifier and silicon nitride powder, mixing, ball-milling for 10-20min, and drying to obtain modified silicon nitride powder; wherein, the weight portion is: 2-5 parts of surface modifier and 60-100 parts of silicon nitride powder;
2) weighing a diluent and an initiator, mixing, and stirring at a high speed in vacuum to obtain a premixed liquid, wherein the stirring speed is 1000-1350r/min, and the stirring time is 10-30 min; wherein, the weight portion is: 30-100 parts of diluent and 1-10 parts of initiator;
3) stirring and mixing the modified silicon nitride powder prepared in the step 1) and the premixed liquid prepared in the step 2) to respectively prepare photocuring silicon nitride slurry with solid contents of 25-35 vol.% and 40-45 vol.%, wherein the stirring speed is 2000-;
4) carrying out periodic lamination curing on the two photocuring silicon nitride slurries with solid contents of 25-35 vol.% and 40-45 vol.% prepared in the step 3) on a 405nm photocuring machine according to the decreasing or increasing order of the solid contents to form a gradient layered structure blank cured by two silicon nitride slurry layers with solid contents, wherein the exposure time of each layer is 3-8s, the thickness of each layer is 0.03-0.06mm, and the total number of layers is determined according to the total thickness requirement of the gradient layered structure blank;
5) sequentially degreasing and sintering the obtained gradient laminated structure blank to obtain the gradient laminated structure silicon nitride ceramic; wherein the degreasing temperature is 500-800 ℃, and the temperature rise rate of the degreasing temperature is 0.1-0.5 ℃/min; the sintering pressure is 0.1-0.2MPa, the sintering temperature is 1700-1800 ℃, the sintering temperature rise rate is 1-5 ℃/min, and the sintering time is 18-24 h.
Preferably, the surface modifier is one or more of KH550, KH560 and KH 570.
Preferably, the diluent is one or more of HEA, HDDA and TMPTA.
Preferably, the initiator is one or more of TPO, 819 and 184.
Preferably, the particle size of the silicon nitride powder is 200-800 nm.
Optimally, in the step 5), the degreasing temperature is 500 ℃, and the heating rate of the degreasing temperature is 0.1 ℃/min; the sintering pressure is 0.1MPa, the sintering temperature is 1750 ℃, the sintering temperature rise rate is 1 ℃/min, and the sintering time is 24 h.
The invention has the beneficial effects that: the invention firstly screens out the surface modifier which can effectively reduce the refractive index difference of the silicon nitride ceramic particles and increase the curing depth of the surface modifier. The applicant compares the rheological property, the dynamic stability, the wetting property and the photocuring property of the silicon nitride ceramic slurry before and after modification, and discloses a photocuring forming mechanism of the modified silicon nitride ceramic slurry. The result shows that the Y group in the surface modifier is epoxy group (-CH (O) CH-), can generate ring opening under certain temperature and pH conditions, and reacts with hydroxyl group (-OH) on the surface of the copolymer to form ether covalent bond (R-O-R). The surface modifier is bridged with the acrylic acid premix, so that the submicron silicon nitride particles can be more remarkably dispersed in the premix, and the rheological property and the dynamic stability of the ceramic slurry are remarkably improved. Meanwhile, the ether covalent bond formed between the surface modified silicon nitride particles and the diluent reduces the surface tension of the ceramic slurry and improves the wettability of the ceramic slurry on the cured layer. Finally, an EA thin shell is formed on the surfaces of the silicon nitride particles, so that the refractive index difference between the ceramic powder and the premixed liquid is remarkably reduced, and the photocuring performance of the ceramic slurry is improved. And then the silicon nitride ceramic with high density, hardness and fracture toughness can be prepared by taking the silicon nitride ceramic as a raw material and solidifying the silicon nitride ceramic with different solid contents into a gradient layered structure.
Drawings
In fig. 1, (a) is a morphology chart of the original powder before modification, and (b) is a powder particle size distribution chart of the modified original powder after the modification by using different surface modifiers with the mass fraction of 1 wt.%.
In FIG. 2, (a) shows the effect of different silane coupling agent types on the rheological properties of the slurry, and (b) shows the content of KH560 on Si3N4Ceramic slurry viscosity effects.
FIG. 3 is 1 wt.% KH560 modified Si3N4After the ceramic, solid content is to Si3N4Ceramic slurry rheology effects.
FIG. 4 is a graph showing that 1 wt.% of silane coupling agents KH550, KH560 and KH570 modify Si3N4And (5) comparing the stability of the ceramic slurry.
FIG. 5 is Si modified with 1 wt.% of different surface modifiers3N4Wetting properties of the powders were compared.
FIG. 6 shows modification with KH560 to extract Si3N4Infrared spectra of the ceramic particles.
FIG. 7 shows KH560 and EA-modified Si3N4The light curing mechanism of the ceramic slurry is schematically shown.
Detailed Description
The present invention will be described in further detail with reference to the following examples, but the present invention is not limited to the following examples.
Examples
The preparation method comprises the following steps of:
1) weighing a silane coupling agent KH570 and silicon nitride powder with the particle size of 200nm, mixing and ball-milling for 20min, and then drying in a drying oven at the drying temperature of 30 ℃ for 48h to obtain modified silicon nitride powder; wherein, the weight portion is: silane coupling agent KH 5703 and silicon nitride powder 100;
2) weighing a diluent HDDA and an initiator TPO, mixing, and stirring at high speed in vacuum to obtain a premixed liquid, wherein the stirring speed is 1350r/min, and the stirring time is 30 min; wherein, the weight portion is: 40 parts of diluent HDDA and 4 parts of initiator TPO;
3) stirring and mixing the modified silicon nitride powder prepared in the step 1) and the premixed liquid prepared in the step 2) to respectively prepare photocuring silicon nitride slurry with solid contents of 25 vol.% and 45 vol.%, wherein the stirring speed is 2300 r/min;
4) curing the two photo-curing silicon nitride slurries with the solid contents of 25 vol.% and 45 vol.% prepared in the step 3) into a material comprising 7 cured layers periodically and layer by layer from the lower layer to the upper layer in an increasing order of the solid contents on a 405nm photo-curing machine, wherein the slurry concentration of the gradient cured layers from the lower layer to the upper layer is 25 vol.% to 45 vol.% to 25 vol.%, and a gradient layered structure blank cured by the silicon nitride slurry layers with different solid contents is formed, wherein the exposure time of each layer is 5s, and the thickness of each layer is 0.05 mm;
5) sequentially degreasing and sintering the obtained gradient laminated structure blank to obtain the gradient laminated structure silicon nitride ceramic; wherein the degreasing temperature is 500 ℃, and the heating rate of the degreasing temperature is 0.1 ℃/min; the sintering pressure is 0.1MPa, the sintering temperature is 1750 ℃, the sintering temperature rise rate is 1 ℃/min, and the sintering time is 24 h.
The density, microhardness and fracture toughness of the silicon nitride ceramic with the gradient layered structure prepared by the embodiment are respectively 3.15g/cm314.43 +/-0.2 GPa and 7.95 +/-0.2 MPa.m1/2。
The above are merely characteristic embodiments of the present invention, and do not limit the scope of the present invention in any way. All technical solutions formed by equivalent exchanges or equivalent substitutions fall within the protection scope of the present invention.
Claims (8)
1. A preparation method of silicon nitride ceramics with a gradient layered structure is characterized by comprising the following specific steps:
1) weighing a surface modifier and silicon nitride powder, mixing, ball-milling for 10-20min, and drying to obtain modified silicon nitride powder; wherein, the weight portion is: 2-5 parts of surface modifier and 60-100 parts of silicon nitride powder;
2) weighing a diluent and an initiator, mixing, and stirring at a high speed in vacuum to obtain a premixed liquid, wherein the stirring speed is 1000-1350r/min, and the stirring time is 10-30 min; wherein, the weight portion is: 30-100 parts of diluent and 1-10 parts of initiator;
3) stirring and mixing the modified silicon nitride powder prepared in the step 1) and the premixed liquid prepared in the step 2) to respectively prepare at least two photocuring silicon nitride slurries with solid contents, wherein the stirring speed is 2000-2300 r/min;
4) carrying out periodic lamination curing on the photocuring silicon nitride slurry with at least two solid contents prepared in the step 3) respectively according to the decreasing or increasing sequence of the solid contents to form a gradient laminated structure blank cured by silicon nitride slurry layers with different solid contents, wherein the exposure time of each layer is 3-8s, the thickness of each layer is 0.03-0.06mm, and the total layer number is determined according to the total thickness requirement of the gradient laminated structure blank;
5) sequentially degreasing and sintering the obtained gradient laminated structure blank to obtain the gradient laminated structure silicon nitride ceramic; wherein the degreasing temperature is 500-800 ℃, and the temperature rise rate of the degreasing temperature is 0.1-0.5 ℃/min; the sintering pressure is 0.1-0.2MPa, the sintering temperature is 1700-1800 ℃, the sintering temperature rise rate is 1-5 ℃/min, and the sintering time is 18-24 h.
2. The method for preparing the silicon nitride ceramic with the gradient laminated structure according to claim 1, comprising the following specific steps:
1) weighing a surface modifier and silicon nitride powder, mixing, ball-milling for 10-20min, and drying to obtain modified silicon nitride powder; wherein, the weight portion is: 2-5 parts of surface modifier and 60-100 parts of silicon nitride powder;
2) weighing a diluent and an initiator, mixing, and stirring at a high speed in vacuum to obtain a premixed liquid, wherein the stirring speed is 1000-1350r/min, and the stirring time is 10-30 min; wherein, the weight portion is: 30-100 parts of diluent and 1-10 parts of initiator;
3) stirring and mixing the modified silicon nitride powder prepared in the step 1) and the premixed liquid prepared in the step 2) to respectively prepare photocuring silicon nitride slurry with solid contents of 25-35 vol.% and 40-45 vol.%, wherein the stirring speed is 2000-;
4) carrying out periodic lamination curing on the two photocuring silicon nitride slurries with solid contents of 25-35 vol.% and 40-45 vol.% prepared in the step 3) on a 405nm photocuring machine according to the decreasing or increasing order of the solid contents to form a gradient layered structure blank cured by two silicon nitride slurry layers with solid contents, wherein the exposure time of each layer is 3-8s, the thickness of each layer is 0.03-0.06mm, and the total number of layers is determined according to the total thickness requirement of the gradient layered structure blank;
5) sequentially degreasing and sintering the obtained gradient laminated structure blank to obtain the gradient laminated structure silicon nitride ceramic; wherein the degreasing temperature is 500-800 ℃, and the temperature rise rate of the degreasing temperature is 0.1-0.5 ℃/min; the sintering pressure is 0.1-0.2MPa, the sintering temperature is 1700-1800 ℃, the sintering temperature rise rate is 1-5 ℃/min, and the sintering time is 18-24 h.
3. The method for preparing silicon nitride ceramic with gradient layered structure according to claim 1 or 2, wherein the surface modifier is one or more of KH550, KH560 and KH 570.
4. The method for preparing silicon nitride ceramic with gradient laminated structure according to claim 1 or 2, wherein the diluent is one or more of HEA, HDDA and TMPTA.
5. The method for preparing silicon nitride ceramic with gradient laminated structure according to claim 1 or 2, wherein the initiator is one or more of TPO, 819 and 184.
6. The method for preparing a silicon nitride ceramic with a gradient layered structure as claimed in claim 1 or 2, wherein the particle size of the silicon nitride powder is 200-800 nm.
7. The method for preparing a silicon nitride ceramic having a gradient layered structure according to claim 1 or 2, wherein the temperature of degreasing in step 5) is 500 ℃, and the temperature rise rate of the degreasing temperature is 0.1 ℃/min.
8. The method for preparing a silicon nitride ceramic with a gradient layered structure according to claim 1 or 2, wherein in the step 5), the sintering pressure is 0.1MPa, the sintering temperature is 1750 ℃, the sintering temperature rise rate is 1 ℃/min, and the sintering time is 24 hours.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106965291A (en) * | 2017-04-07 | 2017-07-21 | 南京先临三维科技有限公司 | A kind of gel injection-moulding 3D printing preparation method of gradient ceramic |
| CN107417262A (en) * | 2017-09-20 | 2017-12-01 | 吴江中瑞机电科技有限公司 | 3D printing technique prepares material of graded ceramicses and preparation method thereof |
| CN108424149A (en) * | 2018-04-27 | 2018-08-21 | 中南大学 | Photocuring silicon nitride ceramics slurry |
| CN109795010A (en) * | 2019-01-30 | 2019-05-24 | 青岛理工大学 | A kind of continuous surface exposes ceramic 3D printing device and its working method |
| CN110357643A (en) * | 2019-07-25 | 2019-10-22 | 航天特种材料及工艺技术研究所 | Photocuring 3D printing silicon nitride ceramics slurry, preparation method and silicon nitride ceramics |
| CN110467475A (en) * | 2019-09-16 | 2019-11-19 | 广东工业大学 | A kind of preparation method of gradient function ceramics |
-
2021
- 2021-09-03 CN CN202111034657.6A patent/CN113620717A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106965291A (en) * | 2017-04-07 | 2017-07-21 | 南京先临三维科技有限公司 | A kind of gel injection-moulding 3D printing preparation method of gradient ceramic |
| CN107417262A (en) * | 2017-09-20 | 2017-12-01 | 吴江中瑞机电科技有限公司 | 3D printing technique prepares material of graded ceramicses and preparation method thereof |
| CN108424149A (en) * | 2018-04-27 | 2018-08-21 | 中南大学 | Photocuring silicon nitride ceramics slurry |
| CN109795010A (en) * | 2019-01-30 | 2019-05-24 | 青岛理工大学 | A kind of continuous surface exposes ceramic 3D printing device and its working method |
| CN110357643A (en) * | 2019-07-25 | 2019-10-22 | 航天特种材料及工艺技术研究所 | Photocuring 3D printing silicon nitride ceramics slurry, preparation method and silicon nitride ceramics |
| CN110467475A (en) * | 2019-09-16 | 2019-11-19 | 广东工业大学 | A kind of preparation method of gradient function ceramics |
Non-Patent Citations (2)
| Title |
|---|
| LIU YAO: "Stereolithographical fabrication of dense Si3N4 ceramics by slurry optimization and pressure sintering", 《CERAMICS INTERNETIONAL》 * |
| 占丽娜等: "高固相Si_3N_4坯体光固化用陶瓷浆料流变性研究", 《萍乡学院学报》 * |
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