CN111302785A - High-performance microwave dielectric ceramic and photocuring manufacturing method thereof - Google Patents
High-performance microwave dielectric ceramic and photocuring manufacturing method thereof Download PDFInfo
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Abstract
The invention belongs to the field of additive manufacturing, and discloses a high-performance microwave dielectric ceramic and a photocuring manufacturing method thereof. The method comprises the following steps: (a) preparing microwave dielectric ceramic powder by adopting a solid-phase reaction method; (b) dissolving a dispersing agent in photosensitive resin to obtain photosensitive premixed liquid, adding the microwave dielectric ceramic powder into the photosensitive premixed liquid, ball-milling, mixing and degassing to obtain high-solid-content microwave dielectric ceramic slurry; (c) taking the microwave dielectric ceramic slurry as a raw material, and carrying out photocuring forming by using photocuring forming equipment to prepare a microwave dielectric ceramic biscuit; (d) and drying, removing the glue and sintering the ceramic biscuit in sequence to obtain the high-performance microwave dielectric ceramic. The invention utilizes the photocuring technology to manufacture the high-performance microwave dielectric ceramic, can directly manufacture microwave dielectric ceramic devices with complex and precise structures, and has wide application prospect in the fields of electronic communication and the like.
Description
Technical Field
The invention belongs to the field of additive manufacturing, and particularly relates to a high-performance microwave dielectric ceramic and a photocuring manufacturing method thereof.
Background
As a key component of microwave devices such as filters, dielectric antennas and the like, the demand of microwave dielectric ceramic components is continuously rising, and simultaneously, higher requirements are provided for the complexity of the shapes and the structures of the components. The conventional ceramic forming method such as the dry pressing method has problems such as difficulty in manufacturing a complex structure ceramic depending on a mold, poor uniformity of components in manufacturing the ceramic, and the like. Therefore, a new ceramic manufacturing method is needed to manufacture high-performance microwave dielectric ceramics.
As one of mainstream ceramic 3D printing technologies, a technology of Stereolithography (SLA) is used, in which a resin monomer is initiated by ultraviolet light to generate a crosslinking reaction, so that a ceramic slurry containing photosensitive resin is rapidly cured to form a two-dimensional solid pattern, which is then stacked layer by layer to finally obtain a three-dimensional solid. Compared with other methods, the ceramic photocuring technology has great advantages in manufacturing high-compactness and complex-structure ceramics.
At present, the ceramic photocuring technology is mainly used for structural ceramics such as alumina, zirconia, silicon carbide and the like, but the application of the ceramic photocuring technology in functional ceramic forming is rare, and the research on the aspect is still blank.
Disclosure of Invention
Aiming at the defects or improvement requirements of the prior art, the invention provides a photocuring manufacturing method of high-performance microwave dielectric ceramic, which aims to obtain microwave dielectric ceramic powder by a solid-phase reaction method, obtain photocuring microwave dielectric ceramic slurry with high solid content and low viscosity by degassing after ball milling and mixing with photosensitive premixed liquid, form a ceramic biscuit by using a photocuring technology, and finally sequentially carry out drying, binder removal and sintering to obtain the ceramic biscuit with a complex and precise structure.
In order to achieve the above object, according to one aspect of the present invention, there is provided a photocuring method for manufacturing a high-performance microwave dielectric ceramic, comprising the steps of:
(a) preparing microwave dielectric ceramic powder by adopting a solid-phase reaction method;
(b) dissolving a dispersing agent in photosensitive resin to obtain photosensitive premixed liquid, adding the microwave dielectric ceramic powder into the photosensitive premixed liquid, ball-milling, mixing and degassing to obtain microwave dielectric ceramic slurry with the solid content of more than 40 vol% and the viscosity of less than 3Pa & s;
(c) carrying out photocuring forming on the microwave dielectric ceramic slurry serving as a raw material to prepare a microwave dielectric ceramic biscuit;
(d) and drying, removing the glue and sintering the microwave dielectric ceramic biscuit in sequence to obtain the high-performance microwave dielectric ceramic.
Further, in the step (a), the microwave dielectric ceramic powder is subjected to surface modification or surface coating treatment and then is sieved, and the average particle size after sieving is 0.8-1.6 μm.
Further, in the step (b), the photosensitive resin is one or more of trimethylolpropane triacrylate, 1, 6-hexanediol diacrylate and ethoxylated trimethylolpropane triacrylate.
Further, in the step (b), the photosensitive resin contains a photoinitiator, and the photoinitiator is one or more of 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide and 1-hydroxycyclohexyl phenyl ketone, wherein the concentration of the photoinitiator is 1 wt% to 3 wt% of the photosensitive resin.
Further, in the step (b), the dispersant is one or more of oleic acid, polyethylene glycol and polyvinylpyrrolidone, wherein the addition amount of the dispersant is 1 wt% -4 wt% of the microwave dielectric ceramic powder.
Further, in the step (b), the photocuring microwave dielectric ceramic slurry comprises the following components in percentage by volume: 45 vol% -55 vol% of microwave dielectric ceramic powder and 45 vol% -55 vol% of photosensitive premixed liquid.
Further, in the step (c), the light curing process parameters are as follows: the ultraviolet wavelength is 355nm or 405nm, the ultraviolet power is 300 mW-500 mW, the scanning speed is 1000 mm/s-3000 mm/s, and the scanning interval is 0.03 mm-0.05 mm.
Further, in the step (d), the glue discharging temperature adopted by the glue discharging process is 600-700 ℃, the heating rate is 0.2-1 ℃/min, and the heat preservation time is 6-12 h.
Further, in the step (d), the sintering temperature adopted by the sintering process is 1300-1650 ℃, the heating rate is 5-7 ℃/min, the heat preservation time is 3-5 h, and the temperature is naturally reduced.
In order to achieve the above object, according to another aspect of the present invention, there is provided a high performance microwave dielectric ceramic, which is prepared by using the photocuring manufacturing method of the high performance microwave dielectric ceramic as described in any one of the above.
In general, compared with the prior art, the technical scheme of the invention has the advantages that raw materials such as the ceramic slurry photosensitive resin for photocuring used for ceramic photocuring forming can be completely removed in the subsequent glue discharging process, and no extra impurities are introduced into the functional ceramic. Meanwhile, the ceramic slurry for photocuring has good stability, and can ensure that the microwave dielectric ceramic prepared by photocuring has uniform components and excellent electrical properties. The microwave dielectric ceramic is prepared by utilizing the photocuring technology, so that the production requirements of miniaturization and precision of microwave dielectric ceramic devices can be met, and the production period is shortened. More specifically, the photocuring manufacturing method of the high-performance microwave dielectric ceramic provided by the invention mainly has the following beneficial effects:
1. compared with the dry pressing and gel injection molding process, the microwave dielectric ceramic prepared by adopting the photocuring technology does not depend on a mold, has high forming precision, is not limited by the complexity of a ceramic structure, and overcomes the defect of preparing the microwave dielectric ceramic by adopting the traditional process;
2. the light-cured microwave dielectric ceramic slurry adopted in the manufacturing method mainly contains photosensitive resin and other raw materials, the photosensitive resin and the like can be completely removed through a glue removing process, other impurities cannot be introduced in the preparation process, the influence of the impurities on the microwave dielectric property of the microwave dielectric ceramic can be greatly reduced or even eliminated, and the microwave dielectric ceramic with excellent microwave dielectric property is finally obtained;
3. the microwave dielectric ceramic material often contains a plurality of ceramic materials, and the traditional process such as a dry pressing method is easy to cause non-uniform ceramic components, thereby influencing the microwave dielectric property of the microwave dielectric ceramic. The invention adopts the photocuring method to manufacture the microwave dielectric ceramic, and the photocuring microwave dielectric ceramic slurry has good stability and can manufacture the microwave dielectric ceramic with uniform components and excellent performance.
4. The invention utilizes the photocuring technology to manufacture the high-performance microwave dielectric ceramic, can directly manufacture microwave dielectric ceramic devices with complex and precise structures, and has wide application prospect in the fields of electronic communication and the like.
Drawings
FIG. 1 is a schematic flow chart of a photocuring manufacturing method of a high-performance microwave dielectric ceramic provided by the invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
As shown in FIG. 1, the present invention provides a photocuring method for manufacturing a high-performance microwave dielectric ceramic, which mainly comprises the following steps:
(a) preparing microwave dielectric ceramic powder by adopting a solid-phase reaction method;
preferably, the microwave dielectric ceramic powder prepared by the solid-phase reaction method is subjected to surface modification or surface coating treatment and then is sieved for later use, and the average particle size of the powder is 0.8-1.6 microns.
(b) Dissolving a dispersing agent in photosensitive resin to obtain photosensitive premixed liquid, adding the powder obtained in the step (a) into the photosensitive premixed liquid, ball-milling, mixing and degassing to obtain photocuring microwave dielectric ceramic slurry with high solid content; preferably, the solid content is more than 40 vol% and the viscosity is less than 3 pas.
Preferably, the photosensitive resin is one or more of trimethylolpropane triacrylate (TMPTA), 1, 6-hexanediol diacrylate (HDDA), and ethoxylated trimethylolpropane triacrylate (TMP3 EOTA).
Preferably, the photosensitive resin contains a photoinitiator, the photoinitiator is one or more of 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide (TPO) and 1-hydroxycyclohexyl phenyl ketone (184), and the concentration of the photoinitiator is 1 to 3 wt% of the photosensitive resin;
preferably, the dispersant is one or more of oleic acid, polyethylene glycol and polyvinylpyrrolidone, wherein the addition amount of the dispersant is 1 to 4 weight percent of the powder;
preferably, the photocuring microwave dielectric ceramic slurry comprises the following components in percentage by volume: 45 vol% -55 vol% of microwave dielectric ceramic powder and 45 vol% -55 vol% of photosensitive premixed liquid.
(c) Pouring the photocuring microwave dielectric ceramic slurry obtained in the step (b) into a trough of photocuring forming equipment, setting process parameters for photocuring forming, and preparing a microwave dielectric ceramic biscuit;
preferably, the ultraviolet wavelength of the photocuring forming equipment is 355nm or 405nm, the ultraviolet power is 300 mW-500 mW, the scanning speed is 1000 mm/s-3000 mm/s, and the scanning interval is 0.03 mm-0.05 mm.
(d) Drying, binder removal and sintering the ceramic biscuit obtained in the step (c) in sequence to obtain high-performance microwave dielectric ceramic;
preferably, the glue discharging temperature in the glue discharging process is 600-700 ℃, the heating rate is 0.2-1 ℃/min, and the heat preservation time is 6-12 h;
preferably, the sintering temperature in the sintering process is 1300-1650 ℃, the heating rate is 5-7 ℃/min, the heat preservation time is 3-5 h, and the temperature is naturally reduced.
The present invention is further described in detail below with reference to several specific examples.
Example 1
Step (a): ZnAl is weighed according to the mass ratio of 0.79:0.212O4Powder and TiO2Powder, using zirconia balls as ball milling media, using alcohol as dispersing agent, and ball milling the mixed material in a polyurethane ball milling tank by using a planetary ball mill. Ball-milling and drying, pre-burning at 1100 ℃ for 5h to obtain mixed powder, and performing TMPTA coating treatment on the powder by utilizing magnetic stirring and ultraviolet irradiation.
Step (b): the photosensitive resin is 1, 6-hexanediol diacrylate, the photoinitiator is 2, 2-dimethoxy-2-phenyl acetophenone, and the dispersant is polyvinylpyrrolidone. Uniformly mixing photosensitive resin and a dispersing agent in proportion to obtain a photosensitive premixed solution, then ball-milling and mixing the ceramic powder subjected to surface modification treatment and the photosensitive premixed solution in a planetary ball mill, degassing, and finally preparing the photocuring microwave dielectric ceramic slurry by adjusting the proportion of each component, wherein the photocuring microwave dielectric ceramic slurry comprises the following components in percentage by volume: 45 vol% of microwave dielectric ceramic powder and 55 vol% of photosensitive premixed liquid. Wherein, the content of the photoinitiator is 2 wt% of the photosensitive resin, and the content of the dispersant is 4 wt% of the powder. The solid content of the photocuring microwave dielectric ceramic slurry is more than 40 vol%, and the viscosity is less than 3Pa & s.
Step (c): and pouring the photocuring microwave dielectric ceramic slurry into a trough of photocuring forming equipment, scanning and superposing layer by layer to prepare the microwave dielectric ceramic biscuit, wherein the wavelength of ultraviolet light is 405nm, the power of the ultraviolet light is 300mW, the scanning speed is 1000mm/s, and the scanning interval is 0.05 mm.
Step (d): and (c) drying, binder removal and sintering the ceramic biscuit obtained in the step (c) in sequence to obtain the high-performance microwave dielectric ceramic. In the glue discharging process, the glue discharging temperature is 600 ℃, the heating rate is 0.2 ℃/min, and the heat preservation time is 12 h. In the sintering process, the sintering temperature is 1650 ℃, the heating rate is 6 ℃/min, the heat preservation time is 4h, the temperature is naturally reduced, and finally the high-performance 0.79ZnAl is prepared2O4-0.21TiO2Microwave dielectric ceramics. The microwave dielectric ceramic has less impurity content, can greatly reduce or even eliminate the influence of impurities on the microwave dielectric property of the microwave dielectric ceramic, and has excellent microwave dielectric property.
Example 2
Step (a): weighing Al according to the mass ratio of 1:1:22O3、SiO2And BaCO3Powder, using zirconia balls as ball milling media, using alcohol as dispersing agent, and ball milling the mixed material in a polyurethane ball milling tank by using a planetary ball mill. Ball-milling and drying, and presintering at 1175 ℃ for 3h to obtain BaAl2Si2O8And (3) performing surface modification treatment on the powder by using oleic acid immersion.
Step (b): the photosensitive resin is prepared by mixing 1, 6-hexanediol diacrylate and ethoxylated trimethylolpropane triacrylate according to the mass ratio of 9:1, wherein the photoinitiator is 1-hydroxycyclohexyl phenyl ketone, and the dispersant is polyethylene glycol. Uniformly mixing photosensitive resin and a dispersing agent in proportion to obtain a photosensitive premixed solution, then ball-milling and mixing ceramic powder and the photosensitive premixed solution in a planetary ball mill, degassing, and finally preparing the photocuring microwave dielectric ceramic slurry which comprises the following components in percentage by volume by adjusting the proportion of the components: 55 vol% of microwave dielectric ceramic powder and 45 vol% of photosensitive premixed liquid. Wherein, the content of the photoinitiator is 1 wt% of the photosensitive resin, and the content of the dispersant is 2 wt% of the powder. The solid content of the photocuring microwave dielectric ceramic slurry is more than 40 vol%, and the viscosity is less than 3Pa & s.
Step (c): and pouring the photocuring microwave dielectric ceramic slurry into a trough of photocuring forming equipment, scanning and superposing layer by layer to prepare the microwave dielectric ceramic biscuit, wherein the wavelength of ultraviolet light is 355nm, the power of the ultraviolet light is 500mW, the scanning speed is 3000mm/s, and the scanning interval is 0.03 mm.
Step (d): and (c) drying, binder removal and sintering the ceramic biscuit obtained in the step (c) in sequence to obtain the high-performance microwave dielectric ceramic. In the glue discharging process, the glue discharging temperature is 700 ℃, the heating rate is 0.5 ℃/min, and the heat preservation time is 10 h. In the sintering process, the sintering temperature is 1400 ℃, the heating rate is 7 ℃/min, the heat preservation time is 3h, the temperature is naturally reduced, and finally the high-performance BaAl is prepared2Si2O8Microwave dielectric ceramics. The microwave dielectric ceramic has less impurity content, can greatly reduce or even eliminate the influence of impurities on the microwave dielectric property of the microwave dielectric ceramic, and has excellent microwave dielectric property.
Example 3
Step (a): weighing Li according to the mass ratio of 1:1:32CO3ZnO and TiO2Powder, using zirconia balls as ball milling media, using alcohol as dispersing agent, and ball milling the mixed material in a polyurethane ball milling tank by using a planetary ball mill. Ball-milling, drying, and pre-sintering at 900 deg.C for 4h to obtain Li2ZnTi3O8And (3) coating the powder with nylon by using magnetic stirring.
Step (b): the photosensitive resin is prepared by mixing 1, 6-hexanediol diacrylate and trimethylolpropane triacrylate according to the mass ratio of 8:2, the photoinitiator is 2,4, 6-trimethylbenzoyl-diphenyl phosphine oxide, and the dispersant is oleic acid. Uniformly mixing photosensitive resin and a dispersing agent in proportion to obtain a photosensitive premixed solution, then ball-milling and mixing ceramic powder and the photosensitive premixed solution in a planetary ball mill, degassing, and finally preparing the photocuring microwave dielectric ceramic slurry which comprises the following components in percentage by volume by adjusting the proportion of the components: 50 vol% of microwave dielectric ceramic powder and 50 vol% of photosensitive premixed liquid. Wherein, the content of the photoinitiator is 3 wt% of the photosensitive resin, and the content of the dispersant is 1 wt% of the powder. The solid content of the photocuring microwave dielectric ceramic slurry is more than 40 vol%, and the viscosity is less than 3Pa & s.
Step (c): and pouring the photocuring microwave dielectric ceramic slurry into a trough of photocuring forming equipment, scanning and superposing layer by layer to prepare the microwave dielectric ceramic biscuit, wherein the wavelength of ultraviolet light is 405nm, the power of the ultraviolet light is 400mW, the scanning speed is 2000mm/s, and the scanning interval is 0.04 mm.
Step (d): and (c) drying, binder removal and sintering the ceramic biscuit obtained in the step (c) in sequence to obtain the high-performance microwave dielectric ceramic. In the glue discharging process, the glue discharging temperature is 650 ℃, the heating rate is 1 ℃/min, and the heat preservation time is 8 h. In the sintering process, the sintering temperature is 1300 ℃, the heating rate is 5 ℃/min, the heat preservation time is 5h, the temperature is naturally reduced, and finally the high-performance Li is prepared2ZnTi3O8Microwave dielectric ceramics. The microwave dielectric ceramic has less impurity content, can greatly reduce or even eliminate the influence of impurities on the microwave dielectric property of the microwave dielectric ceramic, and has excellent microwave dielectric property.
Example 4
Step (a): weighing Al according to the mass ratio of 9:12O3And TiO2Powder, using zirconia balls as ball milling media, using alcohol as dispersing agent, and ball milling the mixed material in a polyurethane ball milling tank by using a planetary ball mill. Presintering for 4h at 600 ℃ after ball milling and drying to obtain mixed powder, and performing HDDA coating treatment on the powder by utilizing magnetic stirring and ultraviolet irradiation.
Step (b): the photosensitive resin is prepared by mixing 1, 6-hexanediol diacrylate and trimethylolpropane triacrylate according to the mass ratio of 9:1, the photoinitiator is 2,4, 6-trimethylbenzoyl-diphenyl phosphine oxide, and the dispersant is polyvinylpyrrolidone. Uniformly mixing photosensitive resin and a dispersing agent in proportion to obtain a photosensitive premixed solution, then ball-milling and mixing ceramic powder and the photosensitive premixed solution in a planetary ball mill, degassing, and finally preparing the photocuring microwave dielectric ceramic slurry which comprises the following components in percentage by volume by adjusting the proportion of the components: 50 vol% of microwave dielectric ceramic powder and 50 vol% of photosensitive premixed liquid. Wherein, the content of the photoinitiator is 2 wt% of the photosensitive resin, and the content of the dispersant is 3 wt% of the powder. The solid content of the photocuring microwave dielectric ceramic slurry is more than 40 vol%, and the viscosity is less than 3Pa & s.
Step (c): and pouring the photocuring microwave dielectric ceramic slurry into a trough of photocuring forming equipment, scanning and superposing layer by layer to prepare the microwave dielectric ceramic biscuit, wherein the wavelength of ultraviolet light is 405nm, the power of the ultraviolet light is 350mW, the scanning speed is 1500mm/s, and the scanning interval is 0.05 mm.
Step (d): and (c) drying, binder removal and sintering the ceramic biscuit obtained in the step (c) in sequence to obtain the high-performance microwave dielectric ceramic. In the glue discharging process, the glue discharging temperature is 650 ℃, the heating rate is 1 ℃/min, and the heat preservation time is 6 h. In the sintering process, the sintering temperature is 1500 ℃, the heating rate is 5 ℃/min, the heat preservation time is 6h, the temperature is naturally reduced, and finally the high-performance 0.9Al is prepared2O3-0.1TiO2Microwave dielectric ceramics. The microwave dielectric ceramic has less impurity content, can greatly reduce or even eliminate the influence of impurities on the microwave dielectric property of the microwave dielectric ceramic, and has excellent microwave dielectric property.
It will be understood by those skilled in the art that the foregoing is only a preferred embodiment of the present invention, and is not intended to limit the invention, and that any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (10)
1. A photocuring manufacturing method of high-performance microwave dielectric ceramic is characterized by comprising the following steps:
(a) preparing microwave dielectric ceramic powder by adopting a solid-phase reaction method;
(b) dissolving a dispersing agent in photosensitive resin to obtain photosensitive premixed liquid, adding the microwave dielectric ceramic powder into the photosensitive premixed liquid, ball-milling, mixing and degassing to obtain microwave dielectric ceramic slurry with the solid content of more than 40 vol% and the viscosity of less than 3Pa & s;
(c) carrying out photocuring forming on the microwave dielectric ceramic slurry serving as a raw material to prepare a microwave dielectric ceramic biscuit;
(d) and drying, removing the glue and sintering the microwave dielectric ceramic biscuit in sequence to obtain the high-performance microwave dielectric ceramic.
2. The photocuring method of manufacturing a high-performance microwave dielectric ceramic as claimed in claim 1, wherein: in the step (a), the microwave dielectric ceramic powder is subjected to surface modification or surface coating treatment and then is sieved, and the average particle size after sieving is 0.8-1.6 microns.
3. The photocuring method of manufacturing a high-performance microwave dielectric ceramic as claimed in claim 1, wherein: in the step (b), the photosensitive resin is one or more of trimethylolpropane triacrylate, 1, 6-hexanediol diacrylate and ethoxylated trimethylolpropane triacrylate.
4. The photocuring method of manufacturing a high-performance microwave dielectric ceramic as claimed in claim 1, wherein: in the step (b), the photosensitive resin contains a photoinitiator, the photoinitiator is one or more of 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide and 1-hydroxycyclohexyl phenyl ketone, and the concentration of the photoinitiator is 1 wt% -3 wt% of the photosensitive resin.
5. The photocuring method of manufacturing a high-performance microwave dielectric ceramic as claimed in claim 1, wherein: in the step (b), the dispersant is one or more of oleic acid, polyethylene glycol and polyvinylpyrrolidone, wherein the addition amount of the dispersant is 1-4 wt% of the microwave dielectric ceramic powder.
6. The photocuring method of manufacturing a high-performance microwave dielectric ceramic as claimed in claim 1, wherein: in the step (b), the photocuring microwave dielectric ceramic slurry comprises the following components in percentage by volume: 45 vol% -55 vol% of microwave dielectric ceramic powder and 45 vol% -55 vol% of photosensitive premixed liquid.
7. The photocuring manufacturing method of a high-performance microwave dielectric ceramic as claimed in any one of claims 1 to 5, wherein in the step (c), the photocuring process parameters are as follows: the ultraviolet wavelength is 355nm or 405nm, the ultraviolet power is 300 mW-500 mW, the scanning speed is 1000 mm/s-3000 mm/s, and the scanning interval is 0.03 mm-0.05 mm.
8. The photocuring method for producing a high-performance microwave dielectric ceramic as claimed in any one of claims 1 to 5, wherein: in the step (d), the glue discharging temperature adopted by the glue discharging process is 600-700 ℃, the heating rate is 0.2-1 ℃/min, and the heat preservation time is 6-12 h.
9. The photocuring method for producing a high-performance microwave dielectric ceramic as claimed in any one of claims 1 to 5, wherein: in the step (d), the sintering temperature adopted by the sintering process is 1300-1650 ℃, the heating rate is 5-7 ℃/min, the heat preservation time is 3-5 h, and the temperature is naturally reduced.
10. A high-performance microwave dielectric ceramic is characterized in that: the high-performance microwave dielectric ceramic is prepared by adopting the photocuring manufacturing method of the high-performance microwave dielectric ceramic according to any one of claims 1 to 9.
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| CN116063064A (en) * | 2023-03-10 | 2023-05-05 | 河北工业大学 | Photocuring additive manufacturing method of ceramic |
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| CN113880559A (en) * | 2021-10-29 | 2022-01-04 | 华中科技大学 | Preparation method of hard-to-cure ceramic based on photocuring forming and product |
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