CN115959916A - Modified SiC whisker toughened alumina self-healing ceramic and preparation method thereof - Google Patents
Modified SiC whisker toughened alumina self-healing ceramic and preparation method thereof Download PDFInfo
- Publication number
- CN115959916A CN115959916A CN202310250886.4A CN202310250886A CN115959916A CN 115959916 A CN115959916 A CN 115959916A CN 202310250886 A CN202310250886 A CN 202310250886A CN 115959916 A CN115959916 A CN 115959916A
- Authority
- CN
- China
- Prior art keywords
- modified sic
- sic whisker
- preparation
- healing
- dispersion
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000000919 ceramic Substances 0.000 title claims abstract description 67
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title claims abstract description 42
- 239000000843 powder Substances 0.000 claims abstract description 30
- 238000005245 sintering Methods 0.000 claims abstract description 24
- 239000013078 crystal Substances 0.000 claims abstract description 10
- 239000013003 healing agent Substances 0.000 claims abstract description 10
- 239000002245 particle Substances 0.000 claims abstract description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 75
- 239000006185 dispersion Substances 0.000 claims description 42
- 238000003756 stirring Methods 0.000 claims description 41
- 238000010438 heat treatment Methods 0.000 claims description 36
- 239000000243 solution Substances 0.000 claims description 34
- 239000000047 product Substances 0.000 claims description 31
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 28
- 239000011575 calcium Substances 0.000 claims description 24
- 239000007788 liquid Substances 0.000 claims description 22
- 239000002243 precursor Substances 0.000 claims description 22
- 238000000498 ball milling Methods 0.000 claims description 20
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 claims description 20
- 239000000725 suspension Substances 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 229910004261 CaF 2 Inorganic materials 0.000 claims description 19
- 238000001035 drying Methods 0.000 claims description 19
- 229920005610 lignin Polymers 0.000 claims description 19
- 235000019441 ethanol Nutrition 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 16
- 239000007864 aqueous solution Substances 0.000 claims description 15
- 239000012153 distilled water Substances 0.000 claims description 14
- 238000002390 rotary evaporation Methods 0.000 claims description 12
- 238000001291 vacuum drying Methods 0.000 claims description 11
- 230000032683 aging Effects 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 238000007873 sieving Methods 0.000 claims description 8
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 7
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 7
- 239000000292 calcium oxide Substances 0.000 claims description 7
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 7
- 229910052804 chromium Inorganic materials 0.000 claims description 7
- 239000011651 chromium Substances 0.000 claims description 7
- 238000000227 grinding Methods 0.000 claims description 7
- 238000010533 azeotropic distillation Methods 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- 238000002490 spark plasma sintering Methods 0.000 claims description 4
- QYEXBYZXHDUPRC-UHFFFAOYSA-N B#[Ti]#B Chemical compound B#[Ti]#B QYEXBYZXHDUPRC-UHFFFAOYSA-N 0.000 claims description 2
- 229910052580 B4C Inorganic materials 0.000 claims description 2
- INAHAJYZKVIDIZ-UHFFFAOYSA-N boron carbide Chemical compound B12B3B4C32B41 INAHAJYZKVIDIZ-UHFFFAOYSA-N 0.000 claims description 2
- 238000005119 centrifugation Methods 0.000 claims description 2
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 2
- 239000012467 final product Substances 0.000 claims description 2
- 239000000395 magnesium oxide Substances 0.000 claims description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 2
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 claims description 2
- 238000012216 screening Methods 0.000 claims 1
- 229910010293 ceramic material Inorganic materials 0.000 abstract description 11
- 230000000694 effects Effects 0.000 abstract description 7
- 239000011159 matrix material Substances 0.000 abstract description 2
- 238000007670 refining Methods 0.000 abstract description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 15
- 229920001223 polyethylene glycol Polymers 0.000 description 15
- 230000008569 process Effects 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 12
- 239000000463 material Substances 0.000 description 12
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 6
- 238000005303 weighing Methods 0.000 description 5
- 229910017855 NH 4 F Inorganic materials 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 238000001132 ultrasonic dispersion Methods 0.000 description 4
- 238000011161 development Methods 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 2
- -1 automobiles Substances 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000003754 machining Methods 0.000 description 2
- 125000004151 quinonyl group Chemical group 0.000 description 2
- 230000035939 shock Effects 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229920001222 biopolymer Polymers 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000035876 healing Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003758 nuclear fuel Substances 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- ODLMAHJVESYWTB-UHFFFAOYSA-N propylbenzene Chemical group CCCC1=CC=CC=C1 ODLMAHJVESYWTB-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000009991 scouring Methods 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
Landscapes
- Compositions Of Oxide Ceramics (AREA)
- Crystals, And After-Treatments Of Crystals (AREA)
Abstract
The invention provides a modified SiC whisker toughened alumina self-healing ceramic and a preparation method thereof, wherein the self-healing ceramic comprises the following components in percentage by mass: 1-5:1-10:1-5:1-5 of alumina powder, healing agent, sintering aid, modified SiC whisker and nano CaF with sheet structure 2 . The modified SiC whisker toughened alumina self-healing ceramic has obvious toughening effect on ceramic materials by adopting the modified SiC whisker and has a nano CaF with a sheet structure 2 The addition of the particles enhances the interface bonding strength of the whiskers and the matrix material, plays a role in refining crystal grains and increasing compactness, and the modified SiC whiskers and the nano-coated particles play a role in synergistically toughening the materialThe ceramic material has excellent mechanical performance.
Description
Technical Field
The invention belongs to the field of ceramic materials, and particularly relates to a modified SiC whisker toughened alumina self-healing ceramic and a preparation method thereof.
Background
The alumina structural ceramic not only has excellent comprehensive properties of high mechanical strength, high hardness, chemical corrosion resistance, thermal shock resistance and the like, but also has wide raw material sources and relatively low price, and is widely applied to the fields of electronic machinery, textile, automobiles, chemical industry, metallurgy and the like. With the development of modern science and technology, high requirements are put forward on materials in the departments of industry, energy, traffic, space technology and the like. For example, the channel material for magnetohydrodynamic power generation is required to resist high temperature and resist scouring of high-temperature and high-speed airflow and corrosion of various chemical substances. The development of space technology has placed higher demands on the materials used in the nozzles, combustion liners, nose cones, tail nozzles, jet engine blades, etc. of spacecraft. Reaction devices, heat exchangers, and nuclear fuel devices used in petrochemical industry, energy development, and the like have increasingly strict requirements for high temperature resistance, corrosion resistance, wear resistance, and the like of materials. In these applications, metallic materials are attractive and ceramic materials are generally superior to metals in terms of thermal stability, corrosion resistance and wear resistance. However, the main problem of the single-phase alumina ceramic material is that the brittleness is large, which limits the use of the single-phase alumina ceramic material. Research on alumina-based ceramic composites has attracted extensive attention worldwide.
The alumina ceramic has a generally high sintering temperature due to its ionic bonding property, which makes its melting point as high as 2025 ℃. The high sintering temperature not only consumes a large amount of energy, but also obviously increases the requirements on technical equipment, thereby having high preparation cost. Therefore, effectively reducing the sintering temperature of the alumina ceramic on the premise of ensuring the service performance of the alumina ceramic is one of the hot spots of research of people.
As one of the common disadvantages of ceramic materials, the presence and propagation of cracks necessarily results in a reduction of the strength of the material. Ceramic materials are very sensitive to surface cracks initiated during manufacture and use, such as sinter cooling, machining, thermal shock, etc. The strength is greatly reduced, the reliability of the material is reduced, and the application range of the material is greatly limited. It is possible if the self-healing of the crack is achieved to restore not only partially but even completely the intensity of the attenuation caused by the crack.
And the reliability of the ceramic component can be greatly improved, and the machining and polishing cost is reduced, so that the service life of the structural ceramic component is prolonged. The theoretical and practical application values brought by the self-healing of cracks in the structural ceramic field are very huge.
In addition, if the toughness of the alumina ceramic is improved, the application field of the material can be greatly widened. In the existing research on whisker toughening self-healing ceramics, the toughening effect is not obvious, so that other properties of the ceramic material, such as bending strength and other comprehensive mechanical properties, are poor. Therefore, how to obtain the alumina ceramic with the self-healing function which can be used for a long time at relatively low cost and simple preparation process is still a problem to be solved urgently.
Disclosure of Invention
In view of the above, the invention provides a modified SiC whisker toughened alumina self-healing ceramic and a preparation method thereof, aiming at overcoming the defects in the prior art.
In order to achieve the purpose, the technical scheme of the invention is realized as follows:
a preparation method of modified SiC whisker toughened alumina self-healing ceramic comprises the following steps:
step 1: preparing modified SiC whiskers:
adding SiC crystal whiskers, lignin and polyvinyl butyral into an ethanol aqueous solution, and performing ultrasonic stirring, rotary evaporation and vacuum drying to obtain modified SiC crystal whiskers;
and 2, step: preparation of Nano CaF 2 Precursor:
mixing Ca (NO) 3 ) 2 The dispersion was slowly added to the NH 4 In the F dispersion liquid, ultrasonic stirring is carried out, standing and aging are carried out after the reaction is finished, and then the product is obtainedCentrifuging and cleaning to obtain the nano CaF 2 A precursor;
and step 3: preparation of Nano CaF having sheet Structure 2 ：
The nano CaF is added 2 Adding the precursor and n-butanol into distilled water, performing azeotropic distillation treatment after ultrasonic stirring, and drying to obtain the nano CaF with the sheet structure 2 ；
And 4, step 4: preparing the aluminum oxide self-healing ceramic:
adding alumina powder, a healing agent, a sintering aid and the modified SiC whiskers into absolute ethyl alcohol, performing ultrasonic stirring to obtain a mixed suspension, performing primary ball milling on the mixed suspension, and adding the nano CaF with a sheet structure into the mixed suspension 2 And after secondary ball milling, drying, sieving and SPS sintering the product to obtain the modified SiC whisker toughened alumina self-healing ceramic.
Further, the solid-to-liquid ratio of the SiC whiskers, the lignin, the polyvinyl butyral and the ethanol aqueous solution in the step 1 is 1-10g:0.1-10 g:0.1-10 g:50-200mL; the temperature of the ultrasonic stirring step in the step 1 is 40-80 ℃; the temperature of the rotary steaming step in the step 1 is 50-80 ℃; the concentration of the ethanol in the ethanol water solution in the step 1 is 50-80%.
Preferably, the solid-to-liquid ratio of the SiC whiskers, the lignin, the polyvinyl butyral, and the ethanol aqueous solution in step 1 is 1 to 10g:1-10g:0.1-1g:100-200mL.
The lignin is a biopolymer with a three-dimensional network structure formed by mutually connecting 3 phenylpropane units through ether bonds and carbon-carbon bonds, and contains abundant active groups such as aromatic ring structures, aliphatic and aromatic hydroxyl groups, quinonyl groups and the like. Polyvinyl butyral (PVB) molecules contain longer branched chains and have good flexibility. The SiC crystal whisker is a single crystal fiber with a certain length-diameter ratio, and has quite good high-temperature resistance and high strength.
The modified SiC whisker is modified by adopting lignin and PVB, and the hydroxyl group of the lignin, the quinone group, the PVB long branched chain and the SiC whisker single crystal fiber form a multiple three-dimensional network structure, so that the strength of the modified SiC whisker is obviously improved.
Further, ca (NO) in said step 2 3 ) 2 Dispersion with NH 4 The molar ratio of the F dispersion liquid is 1; ca (NO) in said step 2 3 ) 2 The concentration of the dispersion liquid is 0.01-0.5mol/L; NH in the step 2 4 The concentration of the F dispersion is 0.1-1mol/L.
Further, the time of the ultrasonic stirring step in the step 2 is 10-60 minutes; the time of the aging step in the step 2 is 1-5 hours; the time of the centrifugation step in the step 2 is 10-60 minutes.
Further, the volume ratio of the n-butanol to the distilled water in the step 3 is 1.1-1; the azeotropic distillation treatment step in the step 3 is specifically as follows: heating in oil bath at 90-95 deg.C to remove water, and heating in oil bath at 110-120 deg.C for drying.
Further, the alumina powder, the healing agent, the sintering aid, the modified SiC whisker and the nano CaF with the sheet structure in the step 4 2 The mass ratio of (A) to (B) is 10-50:1-10:1-10:1-10:1-10; the healing agent is at least one of titanium boride, boron carbide or chromium boride; the sintering aid is at least one of magnesium oxide, calcium oxide or yttrium oxide.
Preferably, the alumina powder, the healing agent, the sintering aid, the modified SiC whisker and the nano CaF with the sheet structure in the step 4 are 2 The mass ratio of (A) to (B) is 10-50:1-10:1-10:1-5:1-5.
Further, the mass ratio of the mixed suspension to the grinding balls in the primary ball milling step in the step 4 is 1; the time of the primary ball milling step in the step 4 is 1-10 hours; the time of the secondary ball milling step in the step 4 is 1-10 hours; the temperature of the drying step in the step 4 is 100-150 ℃, and the time is 20-40 hours; the particle size of the screen in the sieving step in the step 4 is 100-200 meshes; the SPS sintering step in the step 4 is specifically carried out under the following conditions: the sintering pressure is 20-40Mpa, the temperature is raised to 1000 ℃ at the heating rate of 200 ℃/min, then the temperature is raised to 1250-1500 ℃ at the heating rate of 50 ℃/min, and the pressure maintaining time is 10min.
The self-healing ceramic comprises the following components in percentage by mass: 1-10:1-10:1-10:1-10 of alumina powder, healing agent, sintering aid, modified SiC whisker and nano CaF with sheet structure 2 。
Further, the modified SiC crystal whisker is prepared by mixing the following components in a solid-to-liquid ratio of 1-10g:0.1-10 g:0.1-10 g:50-200mL of SiC whisker, lignin, polyvinyl butyral and ethanol aqueous solution are subjected to ultrasonic stirring, rotary evaporation and vacuum drying to obtain the product; the nano CaF with the sheet structure 2 The preparation method comprises the following steps: mixing Ca (NO) 3 ) 2 The dispersion was slowly added to the NH 4 Performing ultrasonic stirring in the F dispersion liquid, standing and aging after the reaction is finished, and then centrifuging and cleaning the product to obtain the nano CaF 2 Precursor, preparing the nano CaF 2 Adding the precursor and n-butanol into distilled water, performing azeotropic distillation treatment after ultrasonic stirring, and drying to obtain the final product; the Ca (NO) is 3 ) 2 Dispersion with NH 4 The molar ratio of the F dispersion liquid is 1; the Ca (NO) is 3 ) 2 The concentration of the dispersion liquid is 0.01-0.5mol/L; the NH 4 The concentration of the F dispersion is 0.1-1mol/L.
Compared with the prior art, the invention has the following advantages:
the preparation method of the modified SiC whisker toughened alumina self-healing ceramic has the advantages that the modified SiC whisker adopted by the preparation method has obvious toughening effect on the ceramic material, and the nano CaF with a sheet structure is adopted 2 The addition of the particles enhances the interface bonding strength of the whiskers and the matrix material, and plays a role in refining grains and increasing compactness; the modified SiC crystal whiskers and the nano-coated particles play a synergistic toughening effect on the material, and compared with a single toughening mode, the toughening effect is more remarkable, and meanwhile, the ceramic material product has excellent mechanical properties.
Detailed Description
Unless defined otherwise, technical terms used in the following examples have the same meanings as commonly understood by one of ordinary skill in the art to which the present invention belongs. The test reagents used in the following examples, unless otherwise specified, are all conventional biochemical reagents; the experimental methods are conventional methods unless otherwise specified.
The present invention will be described in detail with reference to examples.
Example 1
A preparation method of modified SiC whisker toughened alumina self-healing ceramic comprises the following steps:
step 1: preparing modified SiC whiskers:
adding 5g of SiC whisker, 1g of lignin and 0.1g of polyvinyl butyral into 100mL of 70% ethanol aqueous solution, and performing ultrasonic stirring at 50 ℃, rotary evaporation at 55 ℃ and vacuum drying to obtain the modified SiC whisker;
step 2: preparation of Nano CaF 2 Precursor:
equal volume of 1mol/L Ca (NO) is prepared 3 ) 2 Solution and 2.5mol/L NH 4 Adding polyethylene glycol into 100mL of absolute ethyl alcohol, performing ultrasonic dispersion for 40 minutes to obtain 1% absolute ethyl alcohol solution containing polyethylene glycol, dividing the absolute ethyl alcohol solution containing polyethylene glycol into 2 parts, and respectively adding the solution into Ca (NO) 3 ) 2 Solution and NH 4 In the solution F, the solution is stirred for 30 minutes by ultrasound, and the anhydrous ethanol solution Ca (NO) containing polyethylene glycol with the same quantity is prepared 3 ) 2 Dispersion and NH 4 F dispersion of Ca (NO) 3 ) 2 The dispersion was slowly added to the NH 4 In the F dispersion liquid, ultrasonic stirring is carried out for 30 minutes, standing and aging are carried out for 2 hours after the reaction is finished, and then the nano CaF is obtained after the product is centrifuged for 30 minutes and repeatedly cleaned for 3 times 2 A precursor;
and 3, step 3: preparation of Nano CaF having sheet Structure 2 ：
The obtained nano CaF 2 Adding the precursor and n-butanol into distilled water, wherein the volume ratio of n-butanol to distilled water is 6, ultrasonically stirring, heating in an oil bath at 95 ℃ to remove water in the solution, then heating in an oil bath at 118 ℃ to dry, and drying to obtain the nano CaF with the sheet structure 2 ；
And 4, step 4: preparing the aluminum oxide self-healing ceramic:
adding 20g of alumina powder, 2g of chromium boride, 2g of calcium oxide and 4g of modified SiC whiskers into 150mL of absolute ethyl alcohol, ultrasonically stirring to obtain a mixed suspension, carrying out primary ball milling on the mixed suspension for 4 hours, and then adding 2g of nano CaF with a sheet structure into the mixed suspension 2 After secondary ball milling for 4 hours, drying the product at 150 ℃ for 24 hours, and sieving the product with a 200-mesh sieve to obtain ceramic powder;
weighing 5g of ceramic powder, adding the ceramic powder into a mold, manually prepressing, then placing the mold into a furnace, placing a grinding tool, closing a cabin door, prepressing for three to five times, vacuumizing, prepressing once again when the vacuum degree reaches about 10Pa, adjusting process parameters, wherein the sintering pressure is 25Mpa, heating to 1000 ℃ at the heating rate of 200 ℃/min, heating to 1300 ℃ at the heating rate of 50 ℃/min, keeping the pressure for 10min, starting the process, and cooling the temperature in the cabin to be below 120 ℃ after the process is stopped to obtain the product.
Example 2
A preparation method of modified SiC whisker toughened alumina self-healing ceramic comprises the following steps:
step 1: preparing modified SiC whiskers:
adding 8g of SiC whisker, 1g of lignin and 2g of polyvinyl butyral into 100mL of 70% ethanol aqueous solution, and performing ultrasonic stirring at 50 ℃, rotary evaporation at 55 ℃ and vacuum drying to obtain the modified SiC whisker;
step 2: preparation of Nano CaF 2 Precursor:
equal volume of 1mol/L Ca (NO) is configured 3 ) 2 Solution and 2.5mol/L NH 4 Adding polyethylene glycol into 100mL of absolute ethyl alcohol, performing ultrasonic dispersion for 40 minutes to obtain 1% absolute ethyl alcohol solution containing polyethylene glycol, dividing the absolute ethyl alcohol solution containing polyethylene glycol into 2 parts, and respectively adding the solution into Ca (NO) 3 ) 2 Solution and NH 4 Stirring the solution F for 30 minutes by ultrasonic to prepare an anhydrous ethanol solution Ca (NO) containing polyethylene glycol with the same quantity 3 ) 2 Dispersion and NH 4 F dispersion of Ca (NO) 3 ) 2 The dispersion was slowly added to the NH 4 In the F dispersion liquid, ultrasonic stirring is carried out for 30 minutes, standing and aging are carried out for 2 hours after the reaction is finished, and then the nano CaF is obtained after the product is centrifuged for 30 minutes and repeatedly cleaned for 3 times 2 A precursor;
and step 3: preparation of nano CaF with sheet structure 2 ：
The obtained nano CaF 2 Adding the precursor and n-butanol into distilled water, wherein the volume ratio of n-butanol to distilled water is 6, ultrasonically stirring, heating in an oil bath at 95 ℃ to remove water in the solution, then heating in an oil bath at 118 ℃ to dry, and drying to obtain the nano CaF with the sheet structure 2 ；
And 4, step 4: preparing the aluminum oxide self-healing ceramic:
adding 20g of alumina powder, 2g of chromium boride, 2g of calcium oxide and 4g of modified SiC whiskers into 150mL of absolute ethanol, carrying out ultrasonic stirring to obtain a mixed suspension, carrying out primary ball milling on the mixed suspension for 4h, and then adding 2g of nano CaF with a sheet structure 2 After secondary ball milling for 4 hours, drying the product at 150 ℃ for 24 hours, and sieving the product with a 200-mesh sieve to obtain ceramic powder;
weighing 5g of ceramic powder, adding the ceramic powder into a mold, manually prepressing, then placing the mold into a furnace, placing a grinding tool, closing a cabin door, prepressing for three to five times, vacuumizing, prepressing once again when the vacuum degree reaches about 10Pa, adjusting process parameters, wherein the sintering pressure is 25Mpa, heating to 1000 ℃ at the heating rate of 200 ℃/min, heating to 1300 ℃ at the heating rate of 50 ℃/min, keeping the pressure for 10min, starting the process, and cooling the temperature in the cabin to be below 120 ℃ after the process is stopped to obtain the product.
Example 3
A preparation method of modified SiC whisker toughened alumina self-healing ceramic comprises the following steps:
step 1: preparing modified SiC whiskers:
adding 5g of SiC whisker, 1g of lignin and 0.1g of polyvinyl butyral into 100mL of 70% ethanol aqueous solution, and performing ultrasonic stirring at 50 ℃, rotary evaporation at 55 ℃ and vacuum drying to obtain the modified SiC whisker;
step 2: preparation of Nano CaF 2 Precursor:
equal volume of 1mol/L Ca (NO) is prepared 3 ) 2 Solution and 2.5mol/L NH 4 Adding polyethylene glycol into 100mL of absolute ethyl alcohol, performing ultrasonic dispersion for 40 minutes to obtain 1% absolute ethyl alcohol solution containing polyethylene glycol, dividing the absolute ethyl alcohol solution containing polyethylene glycol into 2 parts, and respectively adding the solution into Ca (NO) 3 ) 2 Solution and NH 4 Stirring the solution F for 30 minutes by ultrasonic to prepare an anhydrous ethanol solution Ca (NO) containing polyethylene glycol with the same quantity 3 ) 2 Dispersion with NH 4 F dispersion of Ca (NO) 3 ) 2 The dispersion was slowly added to the NH 4 Ultrasonically stirring the dispersion liquid for 30 minutes, standing and aging the dispersion liquid for 2 hours after the reaction is finished, centrifuging the product for 30 minutes, and repeatedly cleaning the product for 3 times to obtain the nano CaF 2 A precursor;
and step 3: preparation of nano CaF with sheet structure 2 ：
The obtained nano CaF 2 Adding the precursor and n-butanol into distilled water, wherein the volume ratio of n-butanol to distilled water is 6, ultrasonically stirring, heating in an oil bath at 95 ℃ to remove water in the solution, then heating in an oil bath at 118 ℃ to dry, and drying to obtain the nano CaF with the sheet structure 2 ；
And 4, step 4: preparing the aluminum oxide self-healing ceramic:
adding 20g of alumina powder, 2g of chromium boride, 2g of calcium oxide and 10g of modified SiC whiskers into 150mL of absolute ethanol, carrying out ultrasonic stirring to obtain a mixed suspension, carrying out primary ball milling on the mixed suspension for 4h, and then adding 6g of nano CaF with a sheet structure into the mixed suspension 2 After secondary ball milling for 4 hours, drying the product at 150 ℃ for 24 hours, and sieving the product with a 200-mesh sieve to obtain ceramic powder;
weighing 5g of ceramic powder, adding the ceramic powder into a mold, manually prepressing, then placing the mold into a furnace, placing a grinding tool, closing a cabin door, prepressing for three to five times, vacuumizing, prepressing once again when the vacuum degree reaches about 10Pa, adjusting process parameters, wherein the sintering pressure is 25Mpa, heating to 1000 ℃ at the heating rate of 200 ℃/min, heating to 1300 ℃ at the heating rate of 50 ℃/min, keeping the pressure for 10min, starting the process, and cooling the temperature in the cabin to be below 120 ℃ after the process is stopped to obtain the product.
Comparative example 1
The preparation method of the modified SiC whisker toughened alumina self-healing ceramic is only different from the preparation method of the modified SiC whisker toughened alumina self-healing ceramic in the embodiment 1:
step 1: preparing modified SiC whiskers:
adding 5g of SiC whisker, 1g of lignin and 0.1g of silane coupling agent KH-550 into 100mL of 70% ethanol aqueous solution, and performing ultrasonic stirring at 50 ℃, rotary evaporation at 55 ℃ and vacuum drying to obtain the modified SiC whisker.
Comparative example 2
The preparation method of the modified SiC whisker toughened alumina self-healing ceramic is only different from the preparation method of the modified SiC whisker toughened alumina self-healing ceramic in the embodiment 1:
step 1: preparing modified SiC whiskers:
and adding 5g of SiC whisker and 1g of lignin into 100mL of 70% ethanol aqueous solution, and performing ultrasonic stirring at 50 ℃, rotary evaporation at 55 ℃ and vacuum drying to obtain the modified SiC whisker.
Comparative example 3
The preparation method of the modified SiC whisker toughened alumina self-healing ceramic is only different from that of the ceramic in the embodiment 1 in that:
step 1: preparing modified SiC whiskers:
5g of SiC whiskers and 0.1g of polyvinyl butyral are added into 100mL of 70% ethanol aqueous solution, and the modified SiC whiskers are obtained after ultrasonic stirring at 50 ℃, rotary evaporation at 55 ℃ and vacuum drying.
Comparative example 4
A preparation method of SiC whisker toughened alumina self-healing ceramic comprises the following steps:
step 1: preparation of Nano CaF 2 Precursor:
equal volume of 1mol/L Ca (NO) is configured 3 ) 2 Solution and 2.5mol/L NH 4 Adding polyethylene glycol into 100mL of absolute ethanol, performing ultrasonic dispersion for 40 minutes to obtain 1% absolute ethanol solution containing polyethylene glycol, and adding polyethylene glycolThe absolute ethyl alcohol solution of alcohol is divided into 2 portions and respectively added into Ca (NO) 3 ) 2 Solution and NH 4 Stirring the solution F for 30 minutes by ultrasonic to prepare an anhydrous ethanol solution Ca (NO) containing polyethylene glycol with the same quantity 3 ) 2 Dispersion with NH 4 F dispersion of Ca (NO) 3 ) 2 The dispersion was slowly added to the NH 4 Ultrasonically stirring the dispersion liquid for 30 minutes, standing and aging the dispersion liquid for 2 hours after the reaction is finished, centrifuging the product for 30 minutes, and repeatedly cleaning the product for 3 times to obtain the nano CaF 2 A precursor;
step 2: preparation of Nano CaF having sheet Structure 2 ：
The obtained nano CaF 2 Adding the precursor and n-butanol into distilled water, wherein the volume ratio of n-butanol to distilled water is 6, ultrasonically stirring, heating in an oil bath at 95 ℃ to remove water in the solution, then heating in an oil bath at 118 ℃ to dry, and drying to obtain the nano CaF with the sheet structure 2 ；
And step 3: preparing the aluminum oxide self-healing ceramic:
adding 20g of alumina powder, 2g of chromium boride, 2g of calcium oxide and 4g of SiC whiskers into 150mL of absolute ethyl alcohol, performing ultrasonic stirring to obtain a mixed suspension, performing primary ball milling on the mixed suspension for 4 hours, and then adding 2g of nano CaF with a sheet structure 2 After secondary ball milling for 4 hours, drying the product at 150 ℃ for 24 hours, and sieving the product with a 200-mesh sieve to obtain ceramic powder;
weighing 5g of ceramic powder, adding the ceramic powder into a mold, manually prepressing, then placing the ceramic powder into a furnace, placing a grinding tool, closing a cabin door to perform prepressing, vacuumizing the furnace after three to five times of prepressing, prepressing once again when the vacuum degree reaches about 10Pa, adjusting process parameters, setting the sintering pressure to be 25Mpa, heating to 1000 ℃ at the heating rate of 200 ℃/min, heating to 1300 ℃ at the heating rate of 50 ℃/min, keeping the pressure for 10min, starting the process, and after the process is stopped, reducing the temperature in the cabin to be below 120 ℃ to obtain the product.
Comparative example 5
A preparation method of modified SiC whisker toughened alumina self-healing ceramic comprises the following steps:
step 1: preparing modified SiC whiskers:
adding 5g of SiC whisker, 1g of lignin and 0.1g of polyvinyl butyral into 100mL of 70% ethanol aqueous solution, and performing ultrasonic stirring at 50 ℃, rotary evaporation at 55 ℃ and vacuum drying to obtain the modified SiC whisker;
step 2: preparing the aluminum oxide self-healing ceramic:
adding 20g of alumina powder, 2g of chromium boride, 2g of calcium oxide and 4g of modified SiC whiskers into 150mL of absolute ethanol, carrying out ultrasonic stirring to obtain a mixed suspension, carrying out primary ball milling on the mixed suspension for 4 hours, and then adding 2g of nano CaF 2 After secondary ball milling for 4 hours, drying the product at 150 ℃ for 24 hours, and sieving the product with a 200-mesh sieve to obtain ceramic powder;
weighing 5g of ceramic powder, adding the ceramic powder into a mold, manually prepressing, then placing the ceramic powder into a furnace, placing a grinding tool, closing a cabin door to perform prepressing, vacuumizing the furnace after three to five times of prepressing, prepressing once again when the vacuum degree reaches about 10Pa, adjusting process parameters, setting the sintering pressure to be 25Mpa, heating to 1000 ℃ at the heating rate of 200 ℃/min, heating to 1300 ℃ at the heating rate of 50 ℃/min, keeping the pressure for 10min, starting the process, and after the process is stopped, reducing the temperature in the cabin to be below 120 ℃ to obtain the product.
The mechanical properties of the products obtained in examples 1 to 3 and comparative examples 1 to 5 are shown in Table 1, the flexural strength of the materials of examples 1 to 3 is significantly better than that of comparative examples 1 to 5, and comparative example 4 is not similar to that of nano CaF having a lamellar structure due to the use of SiC whiskers 2 Forming strong synergistic effect, thus the effect is extremely undesirable; compared with the embodiment 1, in the comparative example 3, no lignin is added, the SiC whiskers are directly bonded with the PVB, a multiple network structure is not formed, and the toughness of the material is influenced; compared with the embodiment 1, in the comparative example 2, PVB is not added, and the SiC whiskers are combined with lignin and lack of crosslinking effect, so that certain influence is generated on the toughness; in comparative example 1, the PVB was replaced with a conventional coupling agent and the resulting material did not achieve the desired properties.
TABLE 1 mechanical Properties of alumina ceramics
The alumina ceramics obtained in example 1 and comparative examples 4 to 5 were crack-prepared on a Vickers hardness tester and healed at 900 ℃ in a muffle furnace for 5 hours, and the change of the bending strength was shown in Table 2.
TABLE 2 healing Capacity of alumina ceramics
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. A preparation method of modified SiC whisker toughened alumina self-healing ceramic is characterized by comprising the following steps: the method comprises the following steps:
step 1: preparing modified SiC whiskers:
adding SiC crystal whiskers, lignin and polyvinyl butyral into an ethanol aqueous solution, and performing ultrasonic stirring, rotary evaporation and vacuum drying to obtain modified SiC crystal whiskers;
step 2: preparation of Nano CaF 2 Precursor:
mixing Ca (NO) 3 ) 2 The dispersion was slowly added to the NH 4 Performing ultrasonic stirring in the F dispersion liquid, standing and aging after the reaction is finished, and then centrifuging and cleaning the product to obtain the nano CaF 2 A precursor;
and step 3: preparation of Nano CaF having sheet Structure 2 ：
The nano CaF is added 2 Adding the precursor and n-butanol into distilled water, performing azeotropic distillation treatment after ultrasonic stirring, and drying to obtain the nano CaF with the sheet structure 2 ；
And 4, step 4: preparing the alumina self-healing ceramic:
adding alumina powder, a healing agent, a sintering aid and the modified SiC whiskers into absolute ethyl alcohol, performing ultrasonic stirring to obtain a mixed suspension, performing primary ball milling on the mixed suspension, and adding the nano CaF with a sheet structure into the mixed suspension 2 And after secondary ball milling, drying, sieving and SPS sintering the product to obtain the modified SiC whisker toughened alumina self-healing ceramic.
2. The preparation method of the modified SiC whisker toughened alumina self-healing ceramic according to claim 1, which is characterized in that: the solid-to-liquid ratio of the SiC whiskers, the lignin, the polyvinyl butyral and the ethanol aqueous solution in the step 1 is 1-10g:0.1-10 g:0.1-10 g:50-200mL; the temperature of the ultrasonic stirring step in the step 1 is 40-80 ℃; the temperature of the rotary evaporation step in the step 1 is 50-80 ℃; the concentration of the ethanol in the ethanol water solution in the step 1 is 50-80%.
3. The preparation method of the modified SiC whisker toughened alumina self-healing ceramic according to claim 2, which is characterized in that: the solid-to-liquid ratio of the SiC whiskers, the lignin, the polyvinyl butyral and the ethanol aqueous solution in the step 1 is 1-10g:1-10g:0.1-1g:100-200mL.
4. The preparation method of the modified SiC whisker toughened alumina self-healing ceramic according to claim 1, which is characterized in that: ca (NO) in said step 2 3 ) 2 Dispersion with NH 4 The molar ratio of the F dispersion is 1-5; ca (NO) in said step 2 3 ) 2 The concentration of the dispersion liquid is 0.01-0.5mol/L; NH in the step 2 4 The concentration of the F dispersion is 0.1-1mol/L.
5. The preparation method of the modified SiC whisker toughened alumina self-healing ceramic according to claim 1, which is characterized in that: the time of the ultrasonic stirring step in the step 2 is 10-60 minutes; the time of the aging step in the step 2 is 1-5 hours; the time of the centrifugation step in the step 2 is 10-60 minutes.
6. The preparation method of the modified SiC whisker toughened alumina self-healing ceramic according to claim 1, which is characterized in that: the volume ratio of the n-butanol to the distilled water in the step 3 is 1.1-1; the azeotropic distillation treatment step in the step 3 specifically comprises the following steps: heating in oil bath at 90-95 deg.C to remove water, and heating in oil bath at 110-120 deg.C for drying.
7. The preparation method of the modified SiC whisker toughened alumina self-healing ceramic according to claim 1, which is characterized in that: the alumina powder, the healing agent, the sintering aid, the modified SiC whisker and the nano CaF with the sheet structure in the step 4 2 The mass ratio of (A) to (B) is 10-50:1-10:1-10:1-10:1-10; the healing agent is at least one of titanium boride, boron carbide or chromium boride; the sintering aid is at least one of magnesium oxide, calcium oxide or yttrium oxide.
8. The preparation method of the modified SiC whisker toughened alumina self-healing ceramic according to claim 1, which is characterized in that: in the primary ball milling step in the step 4, the mass ratio of the mixed suspension to the grinding balls is 1; the time of the primary ball milling step in the step 4 is 1-10 hours; the time of the secondary ball milling step in the step 4 is 1-10 hours; the temperature of the drying step in the step 4 is 100-150 ℃, and the time is 20-40 hours; the particle size of the screen mesh in the screening step in the step 4 is 100-200 meshes; the SPS sintering step in the step 4 is specifically carried out under the following conditions: the sintering pressure is 20-40Mpa, the temperature is raised to 1000 ℃ at the heating rate of 200 ℃/min, then the temperature is raised to 1250-1500 ℃ at the heating rate of 50 ℃/min, and the pressure maintaining time is 10min.
9. A modified SiC whisker toughened alumina self-healing ceramic is characterized in that: the self-healing ceramic comprises the following components in a mass ratio of 10-50:1-10:1-10:1-10:1-10 oxidationAluminum powder, healing agent, sintering aid, modified SiC whisker and nano CaF with sheet structure 2 。
10. The modified SiC whisker toughened alumina self-healing ceramic according to claim 9, wherein: the solid-liquid ratio of the modified SiC whisker is 1-10g:0.1-10 g:0.1-10 g:50-200mL of SiC whisker, lignin, polyvinyl butyral and ethanol aqueous solution are subjected to ultrasonic stirring, rotary evaporation and vacuum drying to obtain the product; the nano CaF with the sheet structure 2 The preparation method comprises the following steps: mixing Ca (NO) 3 ) 2 The dispersion was slowly added to the NH 4 Performing ultrasonic stirring in the F dispersion liquid, standing and aging after the reaction is finished, and then centrifuging and cleaning the product to obtain the nano CaF 2 Precursor, preparing the nano CaF 2 Adding the precursor and n-butanol into distilled water, performing azeotropic distillation treatment after ultrasonic stirring, and drying to obtain the final product; the Ca (NO) is 3 ) 2 Dispersion and NH 4 The molar ratio of the F dispersion is 1-5; said Ca (NO) 3 ) 2 The concentration of the dispersion liquid is 0.01-0.5mol/L; the NH 4 The concentration of the F dispersion is 0.1-1mol/L.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310250886.4A CN115959916A (en) | 2023-03-16 | 2023-03-16 | Modified SiC whisker toughened alumina self-healing ceramic and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310250886.4A CN115959916A (en) | 2023-03-16 | 2023-03-16 | Modified SiC whisker toughened alumina self-healing ceramic and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115959916A true CN115959916A (en) | 2023-04-14 |
Family
ID=87360272
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310250886.4A Pending CN115959916A (en) | 2023-03-16 | 2023-03-16 | Modified SiC whisker toughened alumina self-healing ceramic and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115959916A (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050133963A1 (en) * | 2003-12-18 | 2005-06-23 | The Regents Of The University Of California, A California Corporation | Silicon carbide whisker-reinforced ceramics with low rate of grain size increase upon densification |
| CN111943706A (en) * | 2020-08-21 | 2020-11-17 | 齐鲁工业大学 | Self-lubricating ceramic cutter added with SiC whiskers as well as preparation method and application of self-lubricating ceramic cutter |
| CN113880597A (en) * | 2021-12-07 | 2022-01-04 | 天津爱思达新材料科技有限公司 | Preparation method of modified carbon fiber toughened alumina self-healing ceramic |
-
2023
- 2023-03-16 CN CN202310250886.4A patent/CN115959916A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050133963A1 (en) * | 2003-12-18 | 2005-06-23 | The Regents Of The University Of California, A California Corporation | Silicon carbide whisker-reinforced ceramics with low rate of grain size increase upon densification |
| CN111943706A (en) * | 2020-08-21 | 2020-11-17 | 齐鲁工业大学 | Self-lubricating ceramic cutter added with SiC whiskers as well as preparation method and application of self-lubricating ceramic cutter |
| CN113880597A (en) * | 2021-12-07 | 2022-01-04 | 天津爱思达新材料科技有限公司 | Preparation method of modified carbon fiber toughened alumina self-healing ceramic |
Non-Patent Citations (2)
| Title |
|---|
| 李凤生等: "《先进陶瓷力学性能评价方法与技术》", 中国建材工业出版社 * |
| 郭念升: "纳米包覆颗粒与碳化硅晶须协同增韧的自润滑陶瓷刀具研制", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110483085B (en) | Whisker reinforced alumina composite ceramic and preparation method and application thereof | |
| CN110683769B (en) | Reinforced calcium-boron-silicon glass-ceramic composite material and preparation method thereof | |
| CN110483052B (en) | Silicon carbide refractory material and preparation method thereof | |
| CN113277863B (en) | Ceramic composite material and preparation method thereof, bulletproof plate and armor protection equipment | |
| CN103979971B (en) | Liquid-phase sintered boron carbide bulletproof material and preparation method thereof | |
| CN112279653B (en) | Ceramic material with crack healing capability and preparation method thereof | |
| CN100436369C (en) | Method for preparing corundum bricks composite with Nano alpha-Al2O3 | |
| CN105418054A (en) | Novel special ceramic material preparing method | |
| CN111153688A (en) | Preparation method of high-strength semitransparent alumina ceramic | |
| CN111253889A (en) | Low-temperature curing high-temperature-resistant carbon graphite material binder and preparation and use methods thereof | |
| CN105481347A (en) | Novel special ceramic material and preparation method thereof | |
| CN104829255A (en) | Ceramic silicon carbide grinding wheel containing carbon reinforced fiber | |
| CN113563085B (en) | AlN electronic ceramic material with high dielectric property | |
| CN115417683A (en) | Preparation method of oxide continuous filament reinforced oxide ceramic matrix composite | |
| CN113295003A (en) | Ceramic kiln furniture with light weight and low cost | |
| CN115959916A (en) | Modified SiC whisker toughened alumina self-healing ceramic and preparation method thereof | |
| CN106565251B (en) | High-strength light refractory fiber and preparation method thereof | |
| CN1226234C (en) | Producing method for carbide ceramic bullet-proof board material and ceramic bullet-proof board | |
| CN107793138B (en) | Alumina ceramic | |
| CN104876582A (en) | Silicon carbide ceramic for abrasive medium and preparation method of silicon carbide ceramic | |
| CN113896538B (en) | Preparation method of alumina fiber reinforced silicon carbide ceramic material and prepared alumina fiber reinforced silicon carbide ceramic material | |
| CN106588063B (en) | A kind of high-intensitive, high explosion-proof aluminium oxide ceramics | |
| CN104446579A (en) | Three-dimensional ceramic acoustic panel absorber | |
| CN115959909B (en) | B (B) 4 C-mullite-NbB 2 Composite ceramic and preparation method thereof | |
| CN113354420B (en) | Silicon nitride-based ceramic welding sealing component and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20230414 |
|
| RJ01 | Rejection of invention patent application after publication |