CN103936425B - A kind of preparation method of ceramic plate - Google Patents
A kind of preparation method of ceramic plate Download PDFInfo
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- CN103936425B CN103936425B CN201410024496.6A CN201410024496A CN103936425B CN 103936425 B CN103936425 B CN 103936425B CN 201410024496 A CN201410024496 A CN 201410024496A CN 103936425 B CN103936425 B CN 103936425B
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Abstract
The present invention relates to a kind of preparation method of ceramic plate, it comprises the following steps: provide a ceramic size, and described ceramic size comprises ceramic powder, organic monomer, dispersion agent, linking agent, initiator and solvent; There is provided the metal alloy of a molten state, the density of the metal alloy of described molten state is greater than the density of described ceramic size, and the surface that described ceramic size is poured into the metal alloy of described molten state is obtained a ceramic slurry bed of material; By the metal alloy of described molten state and the insulation of the ceramic slurry bed of material, make described organic monomer polymerization reaction take place, form a Ceramic gel layer on the surface of the metal alloy of described molten state; Described Ceramic gel layer is continued insulation on the surface of the metal alloy of described molten state to carry out drying, obtain a ceramic body; And, sinter described ceramic body, obtain a ceramic plate.
Description
Technical field
The present invention relates to a kind of preparation method of ceramic plate, particularly relate to a kind of preparation method of large-sized ceramic plate.
Background technology
Along with high-performance ceramics is in the widespread use of engineering field, usually need large-sized fine ceramics sheet material of some different thickness, and the existing method preparing pottery cannot solve as casting method, dry pressure formed method, cold isostatic compaction method and gel form method etc.
Ordinary gel injection formation technology can prepare high-density, evenly, the ceramic body of complicated shape, but when shaping large size sheet-shaped blank, the volumetric shrinkage of gel, drying process easily causes subsurface defect and buckling deformation.
Summary of the invention
In view of this, the necessary preparation method that a kind of large-sized and smooth ceramic plate is provided.
A preparation method for ceramic plate, it comprises the following steps: provide a ceramic size, and described ceramic size comprises ceramic powder, organic monomer, dispersion agent, linking agent, initiator and solvent; There is provided the metal alloy of a molten state, the density of the metal alloy of described molten state is greater than the density of described ceramic size, and the surface that described ceramic size is poured into the metal alloy of described molten state is obtained a ceramic slurry bed of material; By the metal alloy of described molten state and the insulation of the ceramic slurry bed of material, make described organic monomer polymerization reaction take place, form a Ceramic gel layer on the surface of the metal alloy of described molten state; Described Ceramic gel layer is continued insulation on the surface of the metal alloy of described molten state to carry out drying, obtain a ceramic body; And, sinter described ceramic body, obtain a ceramic plate.
Compared with prior art, the preparation method of ceramic plate of the present invention has the following advantages: the process forming described Ceramic gel layer and dry described Ceramic gel layer due to polymerization is carried out on the surface of the metal alloy of molten state, the metal alloy of this molten state is in a liquid state, surface is extremely smooth, thus greatly reduce polymerization and form resistance when to there is volumetric shrinkage after described Ceramic gel layer and described Ceramic gel layer dry out, obtain smooth, indeformable ceramic body, and then make the ceramic plate defect that obtains little.Further, by the metal alloy in molten state, polyreaction and drying process are all carried out under levitated state, the method by the restriction of size, can not form large-sized ceramic plate.
Accompanying drawing explanation
Fig. 1 is the schema of the preparation method of ceramic plate described in the embodiment of the present invention.
Fig. 2 be in the preparation method of ceramic plate described in Fig. 1 each raw material schematic diagram is set.
Fig. 3 be ceramic plate described in the embodiment of the present invention sintering process graphic representation.
Main element nomenclature
| The ceramic slurry bed of material | 10 |
| The metal alloy of molten state | 20 |
| Isolated film | 30 |
| Container | 40 |
Following specific embodiment will further illustrate the present invention in conjunction with above-mentioned accompanying drawing.
Embodiment
Below with reference to accompanying drawing, the preparation method to the ceramic plate that the embodiment of the present invention provides is further described.
Refer to Fig. 1 and Fig. 2, be the preparation method of the ceramic plate that first embodiment of the invention provides, this preparation method comprises the following steps:
Step S1, provides a ceramic size, and described ceramic size comprises ceramic powder, organic monomer, dispersion agent, linking agent, initiator and solvent;
Step S2, provides the metal alloy 20 of a molten state, and the surface described ceramic size being poured into the metal alloy 20 of described molten state obtains a ceramic slurry bed of material 10, and the density of the metal alloy 20 of described molten state is greater than the density of described ceramic size;
Step S3, is incubated for some time by the metal alloy 20 of described molten state and the ceramic slurry bed of material 10, makes described organic monomer polymerization reaction take place, forms a Ceramic gel layer on the surface of the metal alloy 20 of described molten state;
Step S4, continues insulation for some time to carry out drying, obtains a ceramic body on the surface of the metal alloy 20 of described molten state by described Ceramic gel layer; And
Step S5, sinters described ceramic body, obtains a ceramic plate.
In step sl, described formation ceramic size carries out at low temperatures, and preferably, temperature is 2 degrees Celsius ~ 20 degrees Celsius, is polymerized in advance to avoid described organic monomer.Specifically comprising the following steps of described formation ceramic size:
Step S11, provides the monomer solution that comprises organic monomer, dispersion agent, linking agent and aqueous solvent, to be added by ceramic powder in described monomer solution and to be stirred by mill Jie ball;
Step S12, isolates mill Jie ball, obtains a monomer ceramic size; And
Step S13, adds initiator, and continues to stir for some time, obtains homodisperse ceramic size.
In step s 11, describedly ceramic powder added monomer solution and stir to be undertaken by a Ball-stirring mill by grinding Jie ball.Concrete, a certain amount of mill Jie ball first added in Ball-stirring mill, join in Ball-stirring mill by ready monomer solution, start Ball-stirring mill, its rotating speed controls at 80 ~ 150 revs/min; Then lentamente a certain amount of ceramic powder is joined abundant dispersed with stirring in Ball-stirring mill, in whipping process, suitably can supplement some solvent deionized water, to make up the moisture of vaporization losses; Finally form the mixed slurry of uniform ceramic powder and monomer.Described mill Jie ball plays and makes ceramic powder be well-dispersed in object in monomer solution.Because ceramic powder is of a size of micro/nano level, the surface free energy of described ceramic powder is comparatively large, and is difficult to realize dispersion, by adding mill Jie's ball and Keep agitation, ceramic powder can be made to be infiltrated gradually, and be dispersed in monomer solution.
Described monomer solution is configured than for 40vol% ~ 50vol% according to the solid volume of described ceramic powder, with the solid ensureing that the described ceramic plate finally obtained is densification.Described organic monomer can be acrylamide, dimethylaminoethyl methacrylate, vinylformic acid, dimethylamino-propyl Methacrylamide etc., as long as ensure can to carry out polyreaction at 60 degrees Celsius ~ 90 degrees Celsius.Described dispersion agent plays and makes the homodisperse effect of described ceramic powder.Described dispersion agent can be citric acid ammonia, ammonium polyacrylate, polymine, Tetramethylammonium hydroxide etc.Described linking agent can promote the formation of covalent linkage between linear molecule or ionic linkage, makes linear molecule that the crosslinked polymkeric substance obtaining network structure occur.Described linking agent can be methylene-bisacrylamide, Vinylstyrene or vulcabond etc.
Described ceramic powder can be oxide compound (as Al
2o
3, ZrO
2deng), nitride is (as Si
3n
4, AlN etc.), carbide (as BC, TiC etc.), refractory materials (as mullite, zircon etc.), or its matrix material.The particle diameter of described ceramic powder is 100 nanometer ~ 500 micron.
In the present embodiment, described mill Jie ball is zirconium white, and described ceramic powder is Al
2o
3, Al
2o
3purity be 99.5%, described organic monomer is acrylamide, and described dispersion agent is citric acid ammonia, and described linking agent is methylene-bisacrylamide, and in described ceramic size, the solid volume ratio of ceramic powder is about 50vol%.
In step s 12, described mill Jie ball is separated by a screen cloth by described separation mill Jie ball, obtains monomer ceramic size.This monomer ceramic size low temperature seal is preserved.In the present embodiment, by one 60 object screen clothes, described zirconium white (mill Jie ball) is separated.
In step s 13, by stirring, described initiator is dispersed in described monomer ceramic size.By adding initiator in described monomer ceramic size, to improve the reaction efficiency of the polyreaction of organic monomer.The easy decomposes of described initiator becomes the compound with free radical.Alkene class, the radical polymerization of two vinyl monomer and copolymerization should can be caused further with compound of free radical, and the crosslinking curing of unsaturated polyester and high molecular crosslink reaction.Described initiator can be ammonium persulfate, peroxidation toluoyl, tertbutyl peroxide, 2,2'-Azobis(2,4-dimethylvaleronitrile), ammonium persulfate/sodium bisulfite etc.In the present embodiment, described initiator can be ammonium persulfate.
Further, the step of a vacuum stripping bubble can be carried out after adding the initiator.By removing bubble under vacuo, making the solid phase in described ceramic size and even in liquid phase mixing, and existing without larger bubble, thus finally obtaining solid compact distribution in ceramic plate.Concrete, first described ceramic size is positioned in an airtight container, then while vacuumizing, stirs described ceramic size.
In step s 2, be positioned over by the metal alloy 20 of described molten state in a container 40, the size on the surface of the metal alloy 20 of described molten state is consistent with the size of the bottom of described container 40.Described container 40 plays the effect of mould, when ceramic size being poured into metal alloy surperficial of described molten state, described in the size of the ceramic slurry bed of material that obtains consistent with the size of the bottom of described container 40.Thus, can the shape and size of ceramic plate according to specific needs, select the shape and size of described container 40.In the present embodiment, the shape of the bottom of described container 40 is square, and the length of side of bottom is 1340 millimeters, and the height of described container is 50 millimeters.
The fusing point of the metal alloy 20 of described molten state is 60 degrees Celsius ~ 95 degrees Celsius.The material of the metal alloy 20 of described molten state can be tin-bismuth alloy electroplating, bismuth-Sn-In alloy or bismuth-lead-Xi-cadmium alloy etc.The density of ceramic size described in the density ratio of the metal alloy 20 of described molten state is large, to ensure that described ceramic size floats over the surface of the metal alloy 20 of the described molten state of molten state.Preferably, the density of the metal alloy 20 of described molten state can be 1.5 times ~ 5 times of the density of described ceramic size.In the present embodiment, the material of the metal alloy 20 of described molten state is tin-bismuth alloy electroplating, and its density is 9g/cm
3, the density of the metal alloy 20 of described molten state is about 4 times of the density of described ceramic size.
Be appreciated that, before the described ceramic size of cast, an isolated film 30 can be laid in advance, to avoid infiltrating through in ceramic size with the metal alloy 20 of the interface partial melting state of described ceramic size at the metal alloy 20 of described molten state on the surface of the metal alloy 20 of described molten state.Described isolated film 30 is a continuous print laminate structure, and the density of described isolated film 30 is less than the density of the metal alloy 20 of described molten state, thus described isolated film 30 is held on therebetween.The chemical property of described isolated film 30 is more stable, so that ensure can not with each component generation chemical reaction in the metal alloy 20 of described molten state and ceramic size.Be appreciated that described isolated film 30, on the surface of the metal alloy 20 of molten state, the change of physical condition can not occur, such as gasification or liquefaction.The material of described isolated film 30 can be flexible plastic film or silicone oil.The material of described flexible plastic film can be polycarbonate (PC), polymethylmethacrylate (PMMA), polyethersulfone (PES), cellulose ester, polyvinyl chloride (PVC), benzocyclobutene (BCB), acrylic resin, acrylonitrile-butadiene-styrene copolymer (ABS), polyethylene terephthalate (PET), polycarbonate/acrylonitrile-butadiene-phenylethene copolymer blend (PC/ABS), polycarbonate/polybutylene terephthalate blend (PC/PBT), polycarbonate/polyethylene terephthalate blend (PC/PET), polycarbonate/material such as polymethylmethacrylate blend (PC/PMMA) or polyamide (PA).In the present embodiment, the material of described isolated film 30 is a plastics film, and the material of described plastics film is PET.
In step s3, the described metal alloy of molten state and the insulation of the ceramic slurry bed of material being referred to provides certain heat to make metal alloy continue to keep molten state, thus the described ceramic slurry bed of material is also kept at such a temperature, so that the polymerization reaction take place under the effect of initiator of the organic monomer in the described ceramic slurry bed of material.Described organic monomer is polymerization reaction take place under the effect of initiator and catalyzer, obtains the polymkeric substance comprising side chain.Because this polymkeric substance is water insoluble, thus this polyreaction can be carried out on the ceramic powder of solid phase.When described initiator adds fashionable, organic monomer carries out pre-polymerization and obtains performed polymer, and performed polymer is polymerized further; After performed polymer aggregate size progressively increases, the surface of ceramic powder can be deposited on, thus ceramic powder is coated and form a stable three-dimensional net structure, to realize gelation.
Described polyreaction can be carried out under low vacuum environment or inert atmosphere.This is because oxygen has the unpaired electron that two spin directions are identical, this unpaired electron can be at war with the free radical that needs in polyreaction and consume the free radical of part, carries out the efficiency affecting polyreaction.Described low vacuum environment can be the environment with certain vacuum degree, and such as normal atmosphere is-0.1MPa, or passes into rare gas element, as nitrogen, argon gas, neon.
The temperature of reaction of described polyreaction can be 25 degrees Celsius ~ 95 degrees Celsius, preferably, and 60 degrees Celsius ~ 95 degrees Celsius.By the metal alloy 20 of described molten state and the ceramic slurry bed of material 10 being incubated, the temperature of reaction required for described polyreaction can be ensured.Owing to adopting the supply source of metal alloy 20 as heat of molten state, the metal alloy 20 of this molten state can evenly and fast transfer heat to the described ceramic slurry bed of material 10, thus ensures carrying out smoothly of polyreaction.Further, because the surface of described polyreaction at the metal alloy 20 of described molten state is carried out, the metal alloy 20 of this molten state is in a liquid state, and makes the surface of the metal alloy 20 of described molten state extremely smooth; When floating on the described ceramic slurry bed of material 10 polymerization reaction take place on metal alloy 20 surface of molten state, the deflation resistance of generation can become very little, makes the described Ceramic gel layer that obtains smooth and smooth surface.
In the present embodiment, under the environment of low vacuum, the metal alloy 20 of described molten state and the ceramic slurry bed of material 10 are kept 1 hour at 85 degrees centigrade.
In step s 4 which, described Ceramic gel layer continues insulation for some time on the surface of the metal alloy 20 of molten state, to remove moisture.Described insulation instigates the metal alloy 20 of molten state to continue to keep molten state.Because the moisture in described Ceramic gel layer volatilizees gradually, can there is the linear shrinkage of at least 2% in described Ceramic gel layer on its surface.And be in a liquid state due to the metal alloy 20 of molten state, make the surface of the metal alloy 20 of described molten state extremely smooth; When the described Ceramic gel layer on metal alloy 20 surface floating on molten state shrinks, the resistance run into can become very little, makes the described ceramic body that obtains smooth and smooth surface, avoids the cracking and distortion that cause because resistance when shrinking is excessive.
In the present embodiment, described Ceramic gel layer is continued insulation 72 hours under 85 degrees Celsius, obtains described ceramic body.
In step s 5, refer to Fig. 3, described ceramic body is transferred in a sintering oven and carries out high temperature sintering, obtain described ceramic plate.Concrete, along with temperature raises, have the powder that specific surface is large and surface energy is higher in described ceramic body, gradually to the direction change reducing surface energy, constantly carry out crystal boundary and move, pore is progressively got rid of, and finally obtains the ceramic plate of the densification with some strength.In the present embodiment, the length of described ceramic plate is 1000mm, and width is 1000mm, and thickness is 20mm.
In the preparation method of ceramic plate of the present invention, the process forming described Ceramic gel layer and dry described Ceramic gel layer due to polymerization is carried out on the surface of the metal alloy 20 of molten state, the metal alloy 20 of this molten state is in a liquid state, surface is extremely smooth, thus greatly reduce polymerization and form resistance when to there is volumetric shrinkage after described Ceramic gel layer and described Ceramic gel layer dry out, obtain smooth, indeformable ceramic body, and then make the ceramic plate defect that obtains little.Further, by the metal alloy 20 in molten state, polyreaction and drying process are all carried out under levitated state, this preparation method by the restriction of size, can not form large-sized ceramic plate.This preparation method is simple, is beneficial to industrialization.
In addition, those skilled in the art also can do other change in spirit of the present invention, and these changes done according to the present invention's spirit, all should be included in the present invention's scope required for protection certainly.
Claims (8)
1. a preparation method for ceramic plate, it comprises the following steps:
There is provided a ceramic size, described ceramic size comprises ceramic powder, organic monomer, dispersion agent, linking agent, initiator and solvent;
The metal alloy of one molten state is provided, the density of the metal alloy of described molten state is greater than the density of described ceramic size, the fusing point of the metal alloy of described molten state is 60 degrees Celsius ~ 95 degrees Celsius, lay an isolated film on the surface of the metal alloy of described molten state, the surface described ceramic size being poured into the metal alloy of described molten state obtains a ceramic slurry bed of material;
By the metal alloy of described molten state and the insulation of the ceramic slurry bed of material, make described organic monomer polymerization reaction take place, form a Ceramic gel layer on the surface of the metal alloy of described molten state;
Described Ceramic gel layer is continued insulation on the surface of the metal alloy of described molten state to carry out drying, obtain a ceramic body; And
Sinter described ceramic body, obtain a ceramic plate.
2. the preparation method of ceramic plate as claimed in claim 1, it is characterized in that, described ceramic size is prepared by following steps:
The monomer solution that one comprises organic monomer, dispersion agent, linking agent and aqueous solvent is provided, ceramic powder is added in described monomer solution and to be stirred by mill Jie ball;
Isolate mill Jie ball, obtain a monomer ceramic size; And
Add initiator, and continue to stir, obtain a ceramic size.
3. the preparation method of ceramic plate as claimed in claim 2, it is characterized in that, described formation ceramic size carries out under temperature is 2 degrees Celsius ~ 20 degrees Celsius.
4. the preparation method of ceramic plate as claimed in claim 2, is characterized in that, carries out the step of a vacuum stripping bubble further after being separated described mill Jie ball.
5. the preparation method of ceramic plate as claimed in claim 1, it is characterized in that, the material of described metal alloy is tin-bismuth alloy electroplating, bismuth-Sn-In alloy or bismuth-lead-Xi-cadmium alloy.
6. the preparation method of ceramic plate as claimed in claim 1, it is characterized in that, the density of the metal alloy of described molten state is 1.5 times ~ 5 times of the density of described ceramic size.
7. the preparation method of ceramic plate as claimed in claim 1, it is characterized in that, described polyreaction is carried out under low vacuum environment or inert atmosphere.
8. the preparation method of ceramic plate as claimed in claim 1, it is characterized in that, described isolated film is arranged between the described ceramic slurry bed of material and the alloyed metal of described molten state, and the material of described isolated film is flexible plastic film or silicone oil.
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| CN115321954B (en) * | 2022-08-09 | 2023-07-07 | 广东环波新材料有限责任公司 | Preparation method of ceramic substrate and low-temperature co-fired ceramic substrate |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102351526A (en) * | 2011-06-11 | 2012-02-15 | 江苏尚易新材料科技有限公司 | Method for preparing AZO target materials by adopting gel injection molding forming |
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| CN102351526A (en) * | 2011-06-11 | 2012-02-15 | 江苏尚易新材料科技有限公司 | Method for preparing AZO target materials by adopting gel injection molding forming |
Non-Patent Citations (1)
| Title |
|---|
| 钛酸铝陶瓷水基注凝成型工艺;张敏等;《材料科学与工程学报》;20070620;第25卷(第03期);第415-417页 * |
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