CN103272490A - Fiber reinforced flat carbon film and preparation method thereof - Google Patents
Fiber reinforced flat carbon film and preparation method thereof Download PDFInfo
- Publication number
- CN103272490A CN103272490A CN2013102275470A CN201310227547A CN103272490A CN 103272490 A CN103272490 A CN 103272490A CN 2013102275470 A CN2013102275470 A CN 2013102275470A CN 201310227547 A CN201310227547 A CN 201310227547A CN 103272490 A CN103272490 A CN 103272490A
- Authority
- CN
- China
- Prior art keywords
- preparation
- carbon
- fiber reinforced
- carbon membrane
- coal
- 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.)
- Granted
Links
Landscapes
- Ceramic Products (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention provides a fiber reinforced flat carbon film and a preparation method thereof. The fiber reinforced flat carbon film is formed by a carbon matrix and a fiber reinforced material fully filled in the carbon matrix, the carbon matrix is a continuous phase and has a developed pore structure, and the fiber reinforced material is a disperse phase and can be fused together with the carbon matrix. The fiber reinforced flat carbon film has a high strength and a strong corrosion resistance. The preparation method comprises the following technological steps: crushing a carbon-containing substance which is used as the precursor material of the flat carbon film, mixing the obtained crushed substance with an additive, ball-milling, screening, putting in a die having an inner side coated with a release agent, simultaneously adding the fiber reinforced material to the obtained material, molding, taking out the obtained film, drying, and charring to obtain the fiber reinforced flat carbon film. The method realizes the preparation of the high-strength flat carbon film through the direct compacting of a dry material, and has the advantages of simple preparation technology, low production cost, short production period and the like.
Description
Technical field
The invention belongs to the membrane separation technique field, relate in particular to a kind of fiber reinforcement tabular carbon membrane and preparation method thereof.
Background technology
Carbon membrane is a kind of novel charcoal basement membrane parting material, it organically blends the advantage (efficient, energy-conservation) of the excellent architectural characteristic of raw material of wood-charcoal material (abundant pore structure, the pore-size distribution of homogeneous) and membrane material and is one, shows good prospects for application at aspects such as gas separation, fluid separation applications.Carbon membrane normally by carbonaceous material under vacuum or inert gas shielding, be prepared from through high temperature pyrolysis.According to the difference of structure, carbon membrane can be divided into homogeneous carbon membrane and compound carbon membrane, and the homogeneous carbon membrane can be divided into tabular carbon membrane, tubulose carbon membrane, hollow fiber carbon membrane and capillary carbon membrane again.
Charing was prepared from (for example: CN1490076A, CN102527257A, CN101733001A, CN01147847A, CN1415406A and CN1569316A) after the homogeneous carbon membrane middle plateform of reporting at present and the preparation method of tubulose carbon membrane mainly adopted the wet method extrusion modling.In the moulding film-forming process, this method need be introduced solvent (as organic solvent or water) and binding agent, prepares former film through technologies such as mixing, refining, ageing and moulding, and former film need just can carry out charing and be prepared into carbon membrane after long-time drying at room temperature then.Therefore, adopt this legal system to be equipped with carbon membrane, not only need to spend very long drying time, simultaneously prevent the generation in former film bending or crack in the dry run temperature and humidity that will control environment meticulously, increase complexity and the control difficulty of preparation process, improved production cost.In addition, merge mutually and constitute because the charcoal skeleton structure of carbon membrane is mainly at high temperature passed through certain polycondensation reaction with the form of carbon and pulverized coal particle by undecomposed binding agent, its intensity is not very high usually, and in actual application, in the separation process as membrane module assembling and feed liquid, all to bear certain external force effect, and the circulation impact that will resist feed liquid with wash away, therefore, on mechanical strength, can't satisfy the requirement of large-scale commercial applicationsization according to the carbon membrane of this method preparation.
Fiber reinforcement tabular carbon membrane strengthens the mechanical strength that has carbon membrane now significantly by adding high-intensity fibrous material on the basis that guarantees the original excellent machinability of carbon membrane and hole structural property, can satisfy the application of multiple occasion.Therefore, development of new fiber reinforcement tabular carbon membrane will further be expanded the application of existing carbon membrane, accelerates the industrialization process of carbon membrane.
Summary of the invention
The present invention aims to provide simple, with low cost, the corrosion resistant high strength tabular of a kind of preparation technology carbon membrane and preparation method thereof, needs meticulous control, production cycle length, intensity to be difficult to satisfy deficiencies such as industrial production requirement in the existing carbon membrane material preparation process to solve and to remedy.
Fiber reinforcement tabular carbon membrane of the present invention is made of carbon matrix and the fibre reinforced materials that is full of carbon matrix, it is characterized in that carbon matrix is continuous phase, has flourishing pore structure; Fibre reinforced materials is decentralized photo, combines together with carbon matrix.The compression strength of fiber reinforcement tabular carbon membrane of the present invention is preferably 65-140kg/cm
2, the average pore size of pore structure is preferably 0.14 –, 0.60 μ m, and porosity is preferably 30-50%.
The present invention comprises following processing step for the preparation of the method for above-mentioned fiber reinforcement tabular carbon membrane: be the persursor material of tabular carbon membrane with the carbonaceous material, it is pulverized back and additive mix, after ball milling, screening, put into the mould that the inboard scribbles releasing agent, simultaneously fibre reinforced materials is added in the material, through moulding, open film, drying and charing step and obtain fiber reinforcement tabular carbon membrane.
Carbonaceous material is generally the coal of different degrees of metamorphism, as anthracite, coking coal, bottle coal, rich coal, lean coal, bituminous coal, brown coal, plant base charcoal, resin-based charcoal, petroleum coke, MCMB, phenolic resins etc., can use one or more mixture wherein.In addition, the carbonaceous material preferred powder is broken to 200-500 μ m.
Additive is generally selected one or more the mixture in carboxymethyl cellulose, starch, phenolic resins, polyvinyl alcohol, polyvinyl chloride, polyvinyl butyral resin, the polystyrene for use, and its addition is generally the 5%-40% of persursor material and additive gross mass.
Ball milling refers to that batch mixing is put into ball mill carries out milled processed, and the processing time is generally controlled at 0.5-4h.
Screening refers to screen cloth the large granular materials screening be removed, and the control raw meal particle size is at 5-50 μ m.
Releasing agent is generally selected one or more the mixture in oleic acid, silicone oil, methyl-silicone oil, paraffin, glycerine, the vaseline for use.
Fibre reinforced materials can use ceramic fibre net, short ceramic fibre, silicon carbide fibre net, boron fibre net, the Al of cutting
2O
3The mixture of one or more in fleece, carbon fibre web, short carbon fiber, stainless steel cloth, the nickel screen, the consumption of fibre reinforced materials is generally the 3-10% of persursor material quality.
Condition of molding is preferably as follows: briquetting pressure is controlled at 60-200MPa, and the dwell time is controlled at 10-20min.
Open film and refer to open mould film is taken out, the board-like carbon membrane that preferably will press this moment is clamped with plate jig, to prevent Flat Membrane malformation.
The Flat Membrane that preparation is finished is carried out drying and is handled, and baking temperature control usually is generally 1-12h drying time between room temperature to 100 ℃.
Dried former film is put into temperature programming control retort, under vacuum or inert gas shielding, heat up and carry out the charing processing, just prepare fiber reinforcement tabular carbon membrane.Wherein inert gas is selected nitrogen or argon gas usually for use, and heating rate is generally controlled at 0.5-10 ℃/min, and charing eventually temperature is selected 600-1000 ℃ usually, and general constant temperature 30-120min under this temperature.
The invention has the beneficial effects as follows:
Fiber reinforcement tabular carbon membrane intensity height of the present invention, resistance to corrosion are strong, have broad application prospects in gas, fluid separation applications field.In addition, the preparation method of the tabular carbon membrane that the present invention develops has realized the direct high strength tabular carbon membrane of preparing of siccative, have advantages such as preparation technology is simple, low production cost, and owing to need not to introduce liquid flux in the preparation process, thereby significantly shortened the production cycle.
The specific embodiment
Following non-limiting example can make those of ordinary skill in the art more fully understand the present invention, but does not limit the present invention in any way.
Embodiment 1
After anchracite duff is broken to 200-500 μ m, take by weighing the 100g anchracite duff respectively and 20g starch is put into grinding in ball grinder 2h, with screen cloth the large granular materials screening is removed, the control raw meal particle size is between 20-30 μ m.Material is put into the inboard scribble the mould of silicone oil and add 6g ceramic fibre net, pave back moulding press mold when briquetting pressure is 80MPa, behind the pressurize 10min, open mould, the board-like carbon membrane that presses is clamped dry 5h at room temperature with plate jig.Dried former film is put into temperature programming control retort, under argon shield, rise to 900 ℃ and constant temperature 30min with the heating rate of 3 ℃/min, treat that it is cooled to just can take out below 100 ℃.The carbon membrane performance is as shown in table 1.
Embodiment 2-9
According to the step of embodiment 1, but reinforcing material adds by the type that provides in the table 1, and the carbon membrane performance that obtains is as shown in table 1.
Table 1 uses the carbon membrane performance for preparing under the different reinforcing material conditions
Embodiment 10
After coking coal powder is broken to 200-500 μ m, take by weighing the 100g coking coal powder respectively and the 25g polyvinyl alcohol is put into grinding in ball grinder 3h, with screen cloth the large granular materials screening is removed, the control raw meal particle size is between 10-20 μ m.Material is put into the inboard scribble the mould of glycerine and add 3g boron fibre net, pave back moulding press mold when briquetting pressure is 100MPa, behind the pressurize 10min, open mould, the board-like carbon membrane that presses is clamped dry 3h at room temperature with plate jig.Dried former film is put into temperature programming control retort, under argon shield, rise to 800 ℃ and constant temperature 60min with the heating rate of 5 ℃/min, treat that it is cooled to just can take out below 100 ℃.The carbon membrane performance is shown in Table 2.
Embodiment 11-19
According to the step of embodiment 10, to add by the type that provides in the table 2 but contain carbon matrix precursor, the carbon membrane performance that obtains is as shown in table 2.
Table 2 uses the different carbon membrane performances that contain the carbon matrix precursor preparation
Embodiment 20
After bituminous coal powder is broken to 200-500 μ m, take by weighing 100g bituminous coal respectively and the 25g carboxymethyl cellulose is put into grinding in ball grinder 4h, with screen cloth the large granular materials screening is removed, the control raw meal particle size is between 5-15 μ m.Material is put into the inboard scribble the mould of vaseline and add 4g charcoal fleece, pave back moulding press mold when briquetting pressure is 120MPa, behind the pressurize 20min, open mould, the board-like carbon membrane that presses is clamped dry 2h at room temperature with plate jig.Dried former film is put into temperature programming control retort, under argon shield, rise to 950 ℃ and constant temperature 60min with the heating rate of 8 ℃/min, treat that it is cooled to just can take out below 100 ℃.The carbon membrane performance is shown in Table 3.
Embodiment 21-26
According to the step of embodiment 20, but additive adds by the type that provides in the table 3, and the carbon membrane performance that obtains is as shown in table 3.
Table 3 uses the carbon membrane performance of different additive preparation
Embodiment 27
After rich coal and lean coal be crushed to 200-500 μ m, take by weighing 70g rich coal, 30g lean coal and 15g polyvinyl alcohol respectively and put into grinding in ball grinder 1h, with screen cloth the large granular materials screening is removed, the control raw meal particle size is between 25-35 μ m.Material is put into the inboard scribble the mould of paraffin and add the 8g short carbon fiber, pave back moulding press mold when briquetting pressure is 150MPa, behind the pressurize 20min, open mould, the board-like carbon membrane that presses is clamped dry 2h at room temperature with plate jig.Dried former film is put into temperature programming control retort, under argon shield, rise to 850 ℃ and constant temperature 30min with the heating rate of 6 ℃/min, treat that it is cooled to just can take out below 100 ℃.The carbon membrane performance is shown in Table 4.
Embodiment 28-30
According to the step of embodiment 27, to add by the type that provides in the table 4 but contain carbon matrix precursor, the carbon membrane performance that obtains is as shown in table 4.
The carbon membrane performance that table 4 uses different presomas to be mixed and to prepare
Embodiment 31
After rich coal is crushed to 200-500 μ m, takes by weighing 100g rich coal, 15g phenolic resins and 5g polystyrene and put into grinding in ball grinder 1.5h, with screen cloth the large granular materials screening is removed, the control raw meal particle size is between 20-30 μ m.Material is put into the inboard to be scribbled the mould of paraffin and adds 10g Al
2O
3Fleece is paved back moulding press mold when briquetting pressure is 80MPa, behind the pressurize 10min, opens mould, and the board-like carbon membrane that presses is clamped dry 6h at room temperature with plate jig.Dried former film is put into temperature programming control retort, under argon shield, rise to 800 ℃ and constant temperature 60min with the heating rate of 5 ℃/min, treat that it is cooled to just can take out below 100 ℃.The carbon membrane performance is shown in Table 5.
Embodiment 32-35
According to the step of embodiment 31, but additive adds by the type that provides in the table 5, and the carbon membrane performance that obtains is as shown in table 5.
The carbon membrane performance that table 5 uses different additive to be mixed and to prepare
Claims (9)
1. a fiber reinforcement tabular carbon membrane is made of carbon matrix and the fibre reinforced materials that is full of carbon matrix, it is characterized in that carbon matrix is continuous phase, has flourishing pore structure; Fibre reinforced materials is decentralized photo, combines together with carbon matrix.
2. method for preparing the described fiber reinforcement tabular of claim 1 carbon membrane, it is characterized in that, comprise following processing step: be the persursor material of tabular carbon membrane with the carbonaceous material, it is pulverized back and additive mix, after ball milling, screening, put into the mould that the inboard scribbles releasing agent, simultaneously fibre reinforced materials is added in the material, through moulding, open film, drying and charing step and obtain fiber reinforcement tabular carbon membrane.
3. preparation method according to claim 2, it is characterized in that, carbonaceous material is one or more the mixture in anthracite, coking coal, bottle coal, rich coal, lean coal, bituminous coal, brown coal, plant base charcoal, resin-based charcoal, petroleum coke, MCMB, the phenolic resins, and carbonaceous material is crushed to 200-500 μ m.
4. preparation method according to claim 2, it is characterized in that, additive is one or more the mixture in carboxymethyl cellulose, starch, phenolic resins, polyvinyl alcohol, polyvinyl chloride, polyvinyl butyral resin, the polystyrene, and the additive addition is the 5%-40% of persursor material and additive gross mass.
5. preparation method according to claim 2 is characterized in that, the ball-milling treatment time is controlled at 0.5-4h, and screening control raw meal particle size is at 5-50 μ m.
6. preparation method according to claim 2, it is characterized in that, fibre reinforced materials is ceramic fibre net, short one or more the mixture of cutting in ceramic fibre, silicon carbide fibre net, boron fibre net, Al2O3 fleece, carbon fibre web, short carbon fiber, stainless steel cloth, the nickel screen, and the consumption of fibre reinforced materials is the 3-10% of persursor material quality.
7. preparation method according to claim 2 is characterized in that, briquetting pressure is controlled at 60-200MPa, and the dwell time is controlled at 10-20min.
8. preparation method according to claim 2 is characterized in that, dry carries out between room temperature to 100 ℃, and control at 1-12h drying time.
9. preparation method according to claim 2 is characterized in that, charing is carried out under vacuum or inert gas shielding; inert gas is selected nitrogen or argon gas for use; heating rate control is at 0.5-10 ℃/min, charing eventually temperature at 600-1000 ℃, and under this temperature constant temperature 30-120min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310227547.0A CN103272490B (en) | 2013-06-07 | 2013-06-07 | A kind of fiber reinforcement flat carbon film and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310227547.0A CN103272490B (en) | 2013-06-07 | 2013-06-07 | A kind of fiber reinforcement flat carbon film and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103272490A true CN103272490A (en) | 2013-09-04 |
| CN103272490B CN103272490B (en) | 2016-01-06 |
Family
ID=49055172
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310227547.0A Active CN103272490B (en) | 2013-06-07 | 2013-06-07 | A kind of fiber reinforcement flat carbon film and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103272490B (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105597560A (en) * | 2015-12-24 | 2016-05-25 | 鲁东大学 | Preparation method for biomass-based carbon membrane |
| CN105854629A (en) * | 2016-03-23 | 2016-08-17 | 成都易态科技有限公司 | Porous film and preparation method thereof |
| CN108043243A (en) * | 2017-12-13 | 2018-05-18 | 沈阳工业大学 | A kind of performance regulation and control method for purifying oily waste water carbon membrane |
| CN110448958A (en) * | 2019-07-25 | 2019-11-15 | 天津大学 | The preparation method of fiber reinforcement type porous charcoal base electro-catalysis filtrate |
| CN111960602A (en) * | 2020-08-04 | 2020-11-20 | 大连理工大学 | Method for treating electroplating wastewater by using electrocoagulation/electrochemical oxidation coupling process |
| CN114272758A (en) * | 2022-01-27 | 2022-04-05 | 南京新核复合材料有限公司 | Carbon fiber combined permeable membrane |
| CN114984766A (en) * | 2022-05-25 | 2022-09-02 | 天津工业大学 | Preparation method of carbon film with self-bonding performance and obtained carbon film |
| WO2022198583A1 (en) * | 2021-03-25 | 2022-09-29 | 宁德新能源科技有限公司 | Carbon current collector, electrochemical device comprising carbon current collector, and electronic device |
| CN115920665A (en) * | 2022-11-15 | 2023-04-07 | 大连理工大学 | Preparation method of composite carbon membrane |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0397611A (en) * | 1989-09-11 | 1991-04-23 | Osaka Gas Co Ltd | Pitch-based flat carbon fiber or carbon film |
| CN1490076A (en) * | 2003-08-30 | 2004-04-21 | 大连理工大学 | Preparation of coal based carbon film |
| CN101306327A (en) * | 2008-07-08 | 2008-11-19 | 大连理工大学 | Spiral carbon membrane and preparation method thereof |
| CN102527257A (en) * | 2011-12-31 | 2012-07-04 | 大连理工大学 | Preparation method of conductive carbon membrane |
-
2013
- 2013-06-07 CN CN201310227547.0A patent/CN103272490B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0397611A (en) * | 1989-09-11 | 1991-04-23 | Osaka Gas Co Ltd | Pitch-based flat carbon fiber or carbon film |
| CN1490076A (en) * | 2003-08-30 | 2004-04-21 | 大连理工大学 | Preparation of coal based carbon film |
| CN101306327A (en) * | 2008-07-08 | 2008-11-19 | 大连理工大学 | Spiral carbon membrane and preparation method thereof |
| CN102527257A (en) * | 2011-12-31 | 2012-07-04 | 大连理工大学 | Preparation method of conductive carbon membrane |
Non-Patent Citations (2)
| Title |
|---|
| 宋成文等: "炭膜制备技术的研究进展", 《化工进展》 * |
| 张万栋: "高强度煤基管状炭膜的制备及应用", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105597560A (en) * | 2015-12-24 | 2016-05-25 | 鲁东大学 | Preparation method for biomass-based carbon membrane |
| CN105854629A (en) * | 2016-03-23 | 2016-08-17 | 成都易态科技有限公司 | Porous film and preparation method thereof |
| CN105854629B (en) * | 2016-03-23 | 2019-10-08 | 成都易态科技有限公司 | Porous membrane and preparation method thereof |
| CN108043243A (en) * | 2017-12-13 | 2018-05-18 | 沈阳工业大学 | A kind of performance regulation and control method for purifying oily waste water carbon membrane |
| CN110448958A (en) * | 2019-07-25 | 2019-11-15 | 天津大学 | The preparation method of fiber reinforcement type porous charcoal base electro-catalysis filtrate |
| CN111960602A (en) * | 2020-08-04 | 2020-11-20 | 大连理工大学 | Method for treating electroplating wastewater by using electrocoagulation/electrochemical oxidation coupling process |
| CN111960602B (en) * | 2020-08-04 | 2022-11-22 | 大连理工大学 | Method for treating electroplating wastewater by using electrocoagulation/electrochemical oxidation coupling process |
| WO2022198583A1 (en) * | 2021-03-25 | 2022-09-29 | 宁德新能源科技有限公司 | Carbon current collector, electrochemical device comprising carbon current collector, and electronic device |
| CN114272758A (en) * | 2022-01-27 | 2022-04-05 | 南京新核复合材料有限公司 | Carbon fiber combined permeable membrane |
| CN114272758B (en) * | 2022-01-27 | 2022-10-28 | 南京新核复合材料有限公司 | Carbon fiber combined permeable membrane |
| CN114984766A (en) * | 2022-05-25 | 2022-09-02 | 天津工业大学 | Preparation method of carbon film with self-bonding performance and obtained carbon film |
| CN115920665A (en) * | 2022-11-15 | 2023-04-07 | 大连理工大学 | Preparation method of composite carbon membrane |
| CN115920665B (en) * | 2022-11-15 | 2024-05-10 | 大连理工大学 | Preparation method of composite carbon film |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103272490B (en) | 2016-01-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103272490B (en) | A kind of fiber reinforcement flat carbon film and preparation method thereof | |
| CN102464490B (en) | Method for preparing boron-carbide-based ceramic composite material | |
| CN106220996B (en) | Silicon carbon black/composite polyolefine material preparation method | |
| CN102351564B (en) | Method for preparing wood ceramics by sintering coal tar pitch and biomass materials | |
| CN102690525A (en) | Wood-plastic composite material using sweet sorghum slag as enhanced phase and preparation method for wood-plastic composite material | |
| CN102502594A (en) | Method for preparing isotropic graphite containing coal-based needle coke as aggregate | |
| CN102527257B (en) | Preparation method of conductive carbon membrane | |
| CN100589210C (en) | Conductance compound material and preparing process | |
| CN101817692B (en) | Method for preparing wood ceramics from solvent lignin modified resin | |
| CN107235489A (en) | A kind of preparation method of high-specific surface area Alveolate activated carbon | |
| CN103232664A (en) | Acrylic solid plate with characteristics of fire retardation, high strength and high toughness, and preparation method thereof | |
| CN107128914A (en) | The preparation method of petroleum coke pilum shaped activated carbon | |
| CN104033607B (en) | A kind of crystalline flake graphite compound seal plate and manufacture method | |
| CN107629828A (en) | A kind of method that forming charcoal is prepared using powdered carbon | |
| WO2015027529A1 (en) | Production method for lignite forming | |
| CN106590005A (en) | Plastic-wood composite floor and preparation method thereof | |
| CN101234502A (en) | Method for preparing bamboo base polyvinyl chloride composite board | |
| CN104031325B (en) | Polystyrene foam plate, its production method and the firming agent for it | |
| CN103043949A (en) | Method for manufacturing novel decorating material taking sodium chloride as base material | |
| CN103272561A (en) | Adsorbing material and preparation method thereof | |
| WO2012040932A1 (en) | Board made from powders of waste electronic circuit board and manufacturing process thereof | |
| CN108585874A (en) | A method of preparing silicon carbide woodceramics using Polycarbosilane and wood powder | |
| CN103419259A (en) | Manufacturing method for large format silicon carbide bamboo ceramic plate | |
| CN103540199A (en) | Method of preparing nano fire retardant coating by using wastes | |
| CN108976600B (en) | Charcoal/polypropylene composite material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |