CN103071396B - Substrate induction method used for preparing ordered porous carbon film - Google Patents
Substrate induction method used for preparing ordered porous carbon film Download PDFInfo
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Abstract
The invention relates to a substrate induction method used for preparing an ordered porous carbon film. The method is characterized in that: a precursor is prepared into a solution, and is stirred and mixed with an organic surfactant solution; under substrate induction, through wet film formation, solvent evaporation, and drying, a solid organic film is obtained; after carbonization, the ordered porous carbon film is obtained. The carbon film has an average pore size of 0.7-100nm. The method comprises the steps that: 1, a film forming solution or sol is prepared; 2, film forming is carried out on a solid substrate; and 3, carbonization is carried out. According to the invention, the organic substance is adopted as the surfactant, and is mixed with the precursor solution; under a certain substrate induction effect, through processes such as solvent evaporation, self-assembling, drying, and carbonization, and through the adjustments on preparation process parameters, the porous carbon film with ordered pore channel structure is prepared, and the control over ordered porous carbon film order degree or regularity is realized.
Description
Technical field
The present invention relates to a kind of preparation method of ordered porous Carbon Materials, particularly relate to a kind of matrix revulsion preparing ordered porous carbon membrane.The matrix revulsion of the ordered porous carbon membrane of the preparation that the present invention provides comprises the selection of organic precursor, the configuration of film forming solution, self assembly and matrix induction filming, drying and pyrolytic process and the Preparation of Carbon Membranes with regular loose structure obtained, and belongs to the technical field of porous charcoal preparation and application.
Background technology
The microstructure of material determines macro property, and performance then determines its application.Therefore, the structure and theory of research material be listed in one of 21st century four large chemical science difficult problem [Xu Guangxian. Science Bulletin, 2001,46 (24): 2086-2091.].Porous charcoal can be widely used in field [Francisco RR.Carbon.1998, the 36:159-175 such as purification, gas separaion, catalysis, chromatogram, energy storage of water and air; Petro M, Belliardo F, Novak I, et al.J.Chromatogr.B, 1998,718:187-192; Lu Anhui, Zheng Jingtang, Wang Maozhang. chemical industry is in progress, 2001,4:12-18].Control hole structural parameters index is the key problem of porous charcoal preparation and application.Specify according to IUPAC, porous charcoal can be divided into Microporous Carbon (aperture is less than 2nm), macropore carbon (aperture is greater than 50nm) and mesoporous carbon (aperture is between 2 ~ 50nm) [SingK S W, Everett DH, Haul R A W, et al.Pure Appl.Chem., 1985,57 (4): 603-619.].People are by physical activation method, chemical activation method, catalytic activation method, organogel charring, the technology such as chemical vapour deposition technique and template is to porous charcoal microstructure, performance and pattern are prepared and regulate and control [He HZ, Srinivasan MP, Yaming N.Carbon, 2001,39:877-886; Kyotani T.Carbon, 2000,38:269-286].But, the vermiform unordered pore passage structure pore-size distribution of conventional porous charcoal is wider, though gas absorption can be met and be separated and the requirement of the aspect such as catalyst carrier, but need the field possessing specific pore structural material to seem helpless [Mariwala R K to some, Acharya M, Foley H.Micropor.Mesopor.Mater., 1998,22:281-288; SteelK M, Koros W J.Carbon, 2003,41:253-266].Along with the appearance with regular pore passage structure ordered porous structural charcoal, it is found that by carrying out chemical modification to its hole wall, its specific function can be given; Also the research of Heterogeneous Composite body for function element can be prepared in its hole; In addition, be also Substance Interactions, energy trasfer, under extreme condition, the research of the basic problem such as behavior of material provides model thing.So, the research of ordered porous Carbon Materials for chemical industry, information communication, biotechnology, the fields such as environmental energy have meaning of crucial importance [Inagaki M, Radovic L R.Carbon, 2002,40:2263-2284; Kowalewski T, Tsarevsky N V, Matyjaszewski R.J.Am.Chem.Soc., 2002,124:10632-10633].
Success rate due to template synthesis ordered porous structural is high and effective, and this method has become the main method of the ordered porous Carbon Materials of current preparation.According to templating species, template can be divided into hard template method and soft template method.Hard template method normally adopt silicon class or zeolite etc. (as MCM-48, SBA-1, SBA-15, KIT-1, MSU-1, X-type zeolite, y-type zeolite, type A zeolite, ZSM-5 type zeolite, Beta type zeolite etc.) porous mass is as template, to introduce in template duct containing carbon matrix precursor or performed polymer, obtained compound, then through processes such as polymerization, drying, charing and stripper plates, obtain ordered porous Carbon Materials [Cai M, Hu Q, Lu Y, et al. United States Patent (USP), USP7824646,2010; Zhou Ying, Qiu Jieshan, Yu Guihong, etc. Chinese invention patent, application number 200610134271; What Jianping, Di Zhiyong, kingly way army, etc. Chinese invention patent, application number 200810236269; Zhao Dongyuan, Sun Jinyu, Zhou Yaming, etc. Chinese invention patent, ZL01126539.6].And soft template rule adopts organic matter as template, it carries out organic-organic self assembly form space IPN ordered structure with containing carbon matrix precursor, then the step such as drying and charing, obtain ordered porous charcoal [Dai S, Liang C. United States Patent (USP), USP20060057051,2006].Can adjusting hole structural parameters by changing preparation process condition, as aperture, pore wall thickness, specific area and pore volume etc. [Zhang Junyong, Deng Yonghui, Wei Jing, etc. Chinese invention patent, 200910047017,2009.].Compared with hard template method, the template in soft template method usually can fall or change into charcoal by disintegrate after charing, and saves and remove template step.Therefore, soft template method technique is relatively simple, and manufacturing cycle is short.But soft template method adopts expensive specific template agent (as triblock copolymer P123 and F127 etc.) usually, makes the actual building cost of this method still higher.
Ordered porous Carbon Materials, with its structural particularity, can be widely used in multiple fields, as catalysis, absorption etc.Zhou Jianhuas etc. adopt nickel chloride as additive, through soft template method synthesized there is better electrocatalysis characteristic containing metal ordered mesoporous carbon [Zhou Jianhua, what Jianping, etc. Chinese invention patent, 200810236273].Wan Ying etc. have invented a kind of ordered mesoporous carbon containing nitrogen, and aperture is 2.0-6.0nm, specific area 500-1200m
3/ g, and for the absorption of phenol compound in liquid waste study [ten thousand grain husk, Feng Cuimiao, Zhang Dieqing, etc. Chinese invention patent, 200610148374].Grandson's generation just etc. prepared containing metal ion (as Ru, Pd, Ir, Fe, Co, Mo and Ni) ordered mesoporous carbon, as redox reaction catalyst [Sun Shigang, Chen Shuru in fuel cell, Zhao Dongyuan, etc. Chinese invention patent, 200910111579].Song Shuqin etc. have invented a kind of preparation method of ordered mesoporous carbon/tungsten carbide composites, and be used as catalyst carrier [Song Shuqin, Wu Dingcai, Fu Ruowen, etc. Chinese invention patent, 201010190122].Gao Peng etc. are (pH=0.7-3) in acid condition, and prepared the order mesoporous Carbon composites containing high degree of dispersion Ir, it has higher catalytic activity [Gao Peng to hydrazine decomposition reaction, Zhang Tao, Wang Aiqin, etc. Chinese invention patent, 200710159034].
The ordered porous charcoal that usual people prepare is all Powdered.And from application point, there is macroscopical bar-shaped, block and membranaceous ordered porous charcoal then there is more wide application prospect.Therefore, in recent years, preparation was had the carbon membrane of large area uniform and ordered loose structure as a study hotspot by chemical industry and Material Field.Researcher is had to carry out the work of part research and probe.[Liang C, Hong K, the GuiochonG A such as Liang, et al.Angew.Chem.Int.Ed., 2004,43 (43): 5785-5789] adopt polystyrene-poly (4-vinylpridine) as phenolic resins monomer, obtaining area through in-situ polymerization is 6cm
2hexagonal shape perpendicular to the membranaceous charcoal channel array on surface.[the Kataoka S such as Kataoka, Yamamoto T, Inagi Y, et al.Carbon, 2008,46 (10): 1358-1367] resorcinol and surfactant are applied on silicon chip, in formaldehyde vapor, carry out self assembly, then carbonize, remove surfactant, obtain ordered porous carbon membrane.[the Wang little Xian such as Wang little Xian, Li Tiehu, Ji Yongbin, Deng. Northwestern Polytechnical University's journal, 2008,26 (6): 787-791] under non-aqueous system condition, adopt sol-gel technique and evaporation-induced self-assembly to prepare surfactant/silicon oxide composite unit, obtain mesoporous carbon membrane by in-situ oxidation charing.[Simanjuntak F H, Jin J, the Nishiyama N such as Simanjuntak, et al.Carbon, 2009,47:2531-2533] adopt 1,5-dihydroxy naphthlene and Formaldehyde-water solution reaction, and by obtain organic-the direct pyrolysis of organic nano compound prepared order mesoporous carbon membrane.[Lin M-L, Huang C-C, the LoM-Y such as Lin, et al.J.Phys.Chem.C, 2008,112 (3): 867-873] be template with mesoporous SBA-15, by the precipitation of PtRu nanocatalyst, synthesize the mesoporous carbon membrane of shortrange order be expected to for fuel cell anode materials.In addition, the Addiego of the U.S. etc. are by a kind of liquid precursor mixture of deposition (comprising the aqueous solution and the non-ionic surface active agent of carbon precursor), drying, crosslinked and charing, obtain order mesoporous carbon membrane [Addiego W P, Senaratne W. United States Patent (USP), US2009004597].
In bibliographical information, researcher is using the glass of smooth densification or silicon chip surface as film forming matrix, does not have researcher to propose or notices that the character of film forming matrix and microstructure are on the impact of final carbon-film pore structure.
Summary of the invention
Object of the present invention is just to overcome prior art above shortcomings, the present inventor is through the deep research work of system, find that film forming matrix has vital impact to the microscopic appearance of final carbon membrane and pore structure, thus propose and develop a kind of matrix revulsion preparing ordered porous carbon membrane.The present invention, using organic matter as surfactant, mixes with precursor solution, under the inducing action of certain substrate, through solvent evaporation and self assembly, and the process such as drying and charing, preparation has the porous carbon membrane of regular pore canal structure.This ordered porous carbon membrane can be used for chemical industry, information communication, biotechnology, the research model in the fields such as environmental energy, is expected to the separation aspect research for improving admixture of gas or liquid mixture especially.
The technical solution that the present invention provides is: the matrix revulsion of the ordered porous carbon membrane of this preparation, be characterized in after presoma wiring solution-forming, after being uniformly mixed with organic surface active agent solution, under matrix induction, after becoming the evaporation of wet film, solvent, drying, obtain SOLID ORGANIC film; After charing, obtain ordered porous carbon membrane again, the average pore size of carbon membrane is 0.7 nanometer ~ 100 nanometer, is made up of following step:
(1) configuration of film forming solution or colloidal sol, with phenolic resins or phenol and formaldehyde mixture for presoma or prepolymer, and mixes with surfactant.By surfactant F127 or P123, with alcohol solution-forming, then through mechanical agitation or magnetic agitation after presoma or pre-polymer solution being mixed with surfactant solution, make mixed solution;
(2) film forming on solid matrix, this solution adopted the stagnant or coating of leaching or to topple over or dropping mode is attached to stromal surface, matrix material is the one in plate glass or charcoal or pottery or silicon or stainless steel or aluminium oxide or polymer or metallic sieve, and matrix average pore size is 0 ~ 500 nanometer; Through solvent volatilization, obtain SOLID ORGANIC film.The organic film that matrix is formed can be taken off and obtain unsupported film, or does not peel and the film that is supported from matrix;
(3) carbonize, by SOLID ORGANIC film obtained above in vacuum atmosphere or inert atmosphere, be raised to set temperature with specific heating rate from room temperature, and at charing final temperature constant temperature, then cool taking-up, obtain ordered porous carbon membrane.
Object to better implement the present invention, described film forming solution or the configuration of colloidal sol are made up of following step:
(1) by the performed polymer of presoma or presoma, with surfactant, catalyst and auxiliary agent, be dissolved in solvent and make homogeneous solution or colloidal sol;
(2) by the performed polymer of presoma, the solution formed with surfactant, catalyst and auxiliary agent, temperature controls to carry out polymerisation at 25 ~ 90 degrees Celsius, and the reaction time is 0.25 ~ 80 hour, obtains film forming solution or colloidal sol;
Persursor material is phenolic resins, or the performed polymer of presoma is the mixture of formaldehyde and phenol or resorcinol, and wherein, the mol ratio of formaldehyde and phenols is 0.8: 1 ~ 2.5: 1;
The molar fraction ratio of used catalyst and phenol is 0.05: 1 ~ 1: 1, and catalyst is selected from one or more in NaOH or sodium carbonate or ammoniacal liquor or caustic alcohol or acetic acid or hydrochloric acid.
The molar fraction ratio of surfactant used and phenol is 0.003: 1 ~ 0.06: 1, and surfactant is selected from one or more in nonionic both sexes triblock copolymer polyoxyethylene-poly-oxypropylene polyoxyethylene F127 or P123.
Adjuvant used is 0: 1 ~ 0.8: 1 with the molar fraction ratio of phenol, selection of auxiliary triethly orthoacetate.
Solvent is selected from one or more in water or ethanol.
Course of dissolution: be selected from and leave standstill or one or more in mechanical agitation or magnetic agitation or ultrasonic wave dispersion.
Object to better implement the present invention, described is made up of following step in solid matrix film forming:
(1) to matrix pretreatment;
(2) wet film is become in stromal surface;
(3) dry film is solidified into;
Matrix feature: material is selected from dense non-porous or has the one in the glass of porous or charcoal or pottery or silicon or stainless steel or aluminium oxide or polymer or metallic sieve; Hole average diameter is 0 ~ 500 nanometer;
Matrix pretreatment: be selected from polishing polishing or cleaning in one or more;
Wet film build method: be selected from dipping or drip or topple over or brush or spray or one in liquid deposition or sol-gel process;
Film-forming temperature is 10 ~ 120 degrees Celsius, and the time is 0.25 ~ 90 hour, and environment is the one in still air or vacuum or moving air or slumpability gas.
Object to better implement the present invention, described charing is made up of following step:
(1) become solid film is put into the retort controlled with temperature programming;
(2) set the heating rate of carbonization process, final temperature and atmosphere, carbonize;
(3) cool;
The heating rate of carbonization process is 0.2 ~ 5 degrees celsius/minute, and final temperature is 400 ~ 1000 degrees Celsius, and final temperature Time constant is 0 ~ 6 hour, and atmosphere is vacuum environment or inert gas shielding.Wherein, the gaseous species of inert atmosphere is one or more in nitrogen or helium or argon gas, and inert gas flow is 0 ~ 500 cc/min.
Cooling: cooling scheme is the one during Temperature fall or programme-control are lowered the temperature, and treats that in-furnace temperature is down to less than 80 degrees Celsius and is taken out sample.
The present invention, by controlling the material of parameter, particularly film forming matrix in above-mentioned preparation process and aperture and hole rule degree, can prepare aperture difference, specific area difference, ordered porous carbon membrane that the regular degree of pore structure is different.These technological parameters have: formaldehyde and phenol mol ratio are 0.8: 1 ~ 2.5: 1; catalyst is 0.05: 1 ~ 1: 1 with the molar fraction ratio of phenol; surfactant is 0.003: 1 ~ 0.06: 1 with the molar fraction ratio of phenol; triethly orthoacetate is 0: 1 ~ 0.8: 1 with the molar fraction ratio of phenol; film-forming temperature is 10 ~ 120 degrees Celsius; time is 0.25 ~ 90 hour; the heating rate of carbonization process is 0.2 ~ 5 degrees celsius/minute; final temperature is 400 ~ 1000 degrees Celsius; final temperature Time constant is 0 ~ 6 hour, and atmosphere is vacuum environment or inert gas shielding.Wherein, the gaseous species of inert atmosphere is one or more in nitrogen or helium or argon gas, and inert gas flow is 0 ~ 500 cc/min.
Compared with prior art, beneficial effect of the present invention is: by regulating kind and the microstructure of preparation technology parameter, particularly matrix, achieving and controlling ordered porous carbon membrane order degree or systematicness; This ordered porous carbon membrane is research Substance Interactions, energy trasfer, quality transmission, under extreme condition, the research of the basic problem such as behavior of material provides model thing, the present invention for chemical industry, information communication, biotechnology, the development in the fields such as environmental energy is significant.
Accompanying drawing explanation
The scanning electron microscopic picture of Fig. 1 matrix nylon leaching film of the present invention.
The scanning electron microscopic picture of ordered porous carbon membrane in Fig. 2 nylon leaching film of the present invention matrix.
The field emission scanning electron microscope picture of ordered porous carbon membrane in Fig. 3 nylon leaching film of the present invention matrix.
The transmission electron microscope picture of ordered porous carbon membrane in Fig. 4 nylon leaching film of the present invention matrix.
The scanning electron microscopic picture of Fig. 5 supporter stainless (steel) wire of the present invention.
The scanning electron microscopic picture of ordered porous carbon membrane in Fig. 6 stainless steel of the present invention matrix.
The scanning electron microscopic picture of ordered porous carbon membrane in phenolic resins matrix prepared by Fig. 7 dropping of the present invention method.
The scanning electron microscopic picture of ordered porous carbon membrane in phenolic resins matrix prepared by the stagnant method of Fig. 8 leaching of the present invention.
The scanning electron microscopic picture of ordered porous carbon membrane in the dense glass matrix of Fig. 9 alkali as a catalyst of the present invention synthesis.
The transmission electron microscope picture of ordered porous carbon membrane in the dense glass matrix of Figure 10 alkali as a catalyst of the present invention synthesis.
Figure 11 scanning electron microscopic picture being attached to ordered porous carbon membrane in Kapton matrix of the present invention.
Figure 12 field emission scanning electron microscope picture being attached to ordered porous carbon membrane in Kapton matrix of the present invention.
Figure 13 average pore size of the present invention is the stereoscan photograph of the matrix porous anode di-aluminium trioxide film of 200nm.
The scanning electron microscopic picture of Figure 14 ordered porous carbon membrane be attached on the 200nm porous anode alundum (Al2O3) membrane matrix of aperture of the present invention.
The field emission scanning electron microscope picture of Figure 15 ordered porous carbon membrane be attached on the 200nm porous anode alundum (Al2O3) membrane matrix of aperture of the present invention.
The field emission scanning electron microscope picture of Figure 16 ordered porous carbon membrane be attached on the 5nm porous anode alundum (Al2O3) membrane matrix of aperture of the present invention.
The transmission electron microscope picture of Figure 17 ordered porous carbon membrane be attached on the 200nm porous anode alundum (Al2O3) membrane matrix of aperture of the present invention.
Figure 18 is the transmission electron microscope picture of the ordered porous carbon membrane be attached on the 80nm porous anode alundum (Al2O3) membrane matrix of aperture of the present invention.
The transmission electron microscope picture of Figure 19 ordered porous carbon membrane be attached on the 5nm porous anode alundum (Al2O3) membrane matrix of aperture of the present invention.
The synthesis of Figure 20 acid as catalyst of the present invention take dense glass as the transmission electron microscope picture of the ordered porous carbon membrane of non-supported of matrix.
In Figure 21 nylon leaching film of the present invention matrix, phenol is the transmission electron microscope picture of the ordered porous carbon membrane of performed polymer.
In Figure 22 acetate fiber of the present invention filter membrane matrix, phenol is the transmission electron microscope picture of the ordered porous carbon membrane of performed polymer.
The transmission electron microscope picture of ordered porous carbon membrane on Figure 23 novolak resin precursor of the present invention body ceramic substrate.
Detailed description of the invention
Below in conjunction with Figure of description illustrated embodiment, the present invention is illustrated in greater detail:
Embodiment 1
With phenol or resorcinol and formaldehyde mixture for presoma prepolymer, formaldehyde and phenol mol ratio are 0.8: 1 ~ 2.5: 1, auxiliary agent triethly orthoacetate is 0: 1 ~ 0.8: 1 with the molar fraction ratio of phenol, surfactant is 0.003: 1 ~ 0.06: 1 with the molar fraction ratio of phenol, under acidity or base catalyst condition, presoma pre-polymer solution is mixed with surfactant solution, then at 25 ~ 90 degrees Celsius, through mechanical agitation or magnetic agitation 0.25 ~ 80 hour, make mixed solution.
This solution adopted the stagnant or coating of leaching or to topple over or dropping mode is attached in stromal surface, matrix was the one in the glass of smooth densification or porous or silicon or SOLID ORGANIC film or charcoal or pottery or stainless steel or aluminium oxide or polymer, through 10 ~ 120 degrees Celsius of dryings 0.25 ~ 90 hour.Obtain SOLID ORGANIC film.The organic film that matrix is formed can be taken off and obtain unsupported film, or contains the support membrane of matrix.
By SOLID ORGANIC film obtained above in vacuum atmosphere or inert atmosphere, be raised to 400 ~ 1000 DEG C with the heating rate of 0.2 ~ 5 DEG C/min from room temperature, and carbonizing final temperature constant temperature 0 ~ 6 hour, then naturally drop to room temperature, finally obtaining ordered porous carbon membrane.
Embodiment 2
By phenolic resins and organic surface active agent, add etoh solvent and water wiring solution-forming, surfactant is 0.003: 1 ~ 0.06: 1 with the molar fraction ratio of phenol.At 25 ~ 90 degrees Celsius, through mechanical agitation or magnetic agitation 0.25 ~ 80 hour, make mixed solution.
This solution adopted the stagnant or coating of leaching or to topple over or dropping mode is attached in stromal surface, matrix was the one in the glass of smooth densification or porous or silicon or SOLID ORGANIC film or charcoal or pottery or stainless steel or aluminium oxide or polymer, through 10 ~ 100 degrees Celsius of dryings 0.25 ~ 90 hour.Obtain SOLID ORGANIC film.The organic film that matrix is formed can be taken off and obtain unsupported film, or contains the support film of matrix.
By SOLID ORGANIC film obtained above in vacuum atmosphere or inert atmosphere, be raised to 400 ~ 1000 DEG C with the heating rate of 0.2 ~ 5 DEG C/min from room temperature, and carbonizing final temperature constant temperature 0 ~ 6 hour, then naturally drop to room temperature, finally obtaining ordered porous carbon membrane.
Embodiment 1
By resorcinol, ethanol, hydrochloric (37%), surfactant F127 wiring solution-forming, the mixed solution of formulation aid triethly orthoacetate and formaldehyde (37%), and dropwise add above-mentioned containing in the mixed liquor of resorcinol, at room temperature stir 20 minutes.This solution is divided into two-layer up and down, after separation, loses the upper strata of clarification, leaves the lower floor's brown solution being rich in polymer phase.
This solution is become wet film on the surface of nylon leaching film as matrix, drying at room temperature 24 hours, put into vacuum drying chamber with 105 DEG C of solidifications 6 hours.Matrix obtains SOLID ORGANIC film.
By SOLID ORGANIC film obtained above in an inert atmosphere, nitrogen flow is 100mL/min, setting heating schedule: room temperature heats up to 400 DEG C with the speed of 2 DEG C/min, constant temperature 3 hours, 600 DEG C of constant temperature 6 hours are warmed up to the speed of 1 DEG C/min, Temperature fall, obtains the ordered porous carbon membrane that average pore size is 42 nanometers.
Table 1 summarizes part preparation technology, matrix feature and result and gathers.The microscopic appearance photo of the matrix adopted and prepared ordered porous carbon membrane is shown in Fig. 1, Fig. 2, Fig. 3 and Fig. 4 respectively.
Table 1 preparation technology, matrix feature and result gather
Embodiment 2
If it is identical with embodiment 1 to fix other conditions, only change thin film-forming method for the stagnant method of leaching, can obtain the ordered porous carbon membrane of similar cell morphology equally, its average pore size is 52 nanometers.
Embodiment 3
If it is identical with embodiment 1 to fix other conditions, only changing a carbonization temperature is 800 degrees Celsius or 800 degrees Celsius or 1000 degrees Celsius, can obtain the ordered porous carbon membrane of similar cell morphology equally, and its average pore size is respectively 66 nanometers or 48 nanometers or 45 nanometers.
Embodiment 4
If it is identical with embodiment 1 to fix other conditions, when only change triethly orthoacetate consumption and resorcinol mol ratio are 0: 1 or 0.8: 1, can obtain the ordered porous carbon membrane of similar cell morphology equally, its average pore size is respectively 53 nanometers and 56 nanometers.
Embodiment 5
If it is identical with embodiment 1 to fix other conditions, when only change kinds of surfactants is P123, can obtain the ordered porous carbon membrane of similar cell morphology equally, its average pore size is 61 nanometers.
Embodiment 6
If it is identical with embodiment 1 to fix other conditions, when only change catalyst is NaOH, the film forming solution obtained is not stratified, and through same steps, finally also can obtain the ordered porous carbon membrane of similar cell morphology equally, its average pore size is 50 nanometers.
Embodiment 7
If it is identical with embodiment 1 to fix other conditions, when only change surfactant is P123 and F127 mixture, can obtain the ordered porous carbon membrane of similar cell morphology equally, its average pore size is 58 nanometers.
Embodiment 8
If it is identical with embodiment 1 to fix other conditions, when only change formaldehyde and resorcinol mol ratio are 0.8: 1 or 2.5: 1, can obtain the ordered porous carbon membrane of similar cell morphology equally, its average pore size is 76 nanometers and 72 nanometers.
Embodiment 9
If it is identical with embodiment 1 to fix other conditions, when only change hydrochloric acid and resorcinol mol ratio are 0.08: 1 or 0.8: 1, can obtain the ordered porous carbon membrane of similar cell morphology equally, its average pore size is 50 nanometers and 63 nanometers.
Embodiment 10
If it is identical with embodiment 1 to fix other conditions, when only change F127 consumption and resorcinol mol ratio are 0.005: 1 or 0.06: 1, can obtain the ordered porous carbon membrane of similar cell morphology equally, its average pore size is 44 nanometers and 71 nanometers.
Embodiment 11
If it is identical with embodiment 1 to fix other conditions, only changing inert gas is helium or argon gas, and can obtain the ordered porous carbon membrane of similar cell morphology equally, its average pore size is respectively 50 nanometers and 52 nanometers.
Embodiment 12
By resorcinol, ethanol, hydrochloric (37%), surfactant F127 wiring solution-forming.The mixed solution of formulation aid triethly orthoacetate and formaldehyde (37%), and dropwise add above-mentioned containing in the mixed liquor of resorcinol, at room temperature stir 20 minutes.This solution is divided into two-layer up and down, after separation, loses the upper strata of clarification, leaves the lower floor's brown solution being rich in polymer phase.
This solution is become wet film at stainless steel metal screen cloth on the surface of matrix, drying at room temperature 24 hours, put into vacuum drying chamber with 105 DEG C of solidifications 6 hours.Matrix obtains SOLID ORGANIC film.
By SOLID ORGANIC film obtained above in an inert atmosphere, nitrogen flow is 500mL/min, setting heating schedule: room temperature heats up to 400 DEG C with the speed of 5 DEG C/min, constant temperature 3 hours, 600 DEG C of constant temperature 6 hours are warmed up to the speed of 1 DEG C/min, Temperature fall, obtains the ordered porous carbon membrane that average pore size is 105 nanometers.
Table 2 summarizes part preparation technology, matrix feature and result and gathers.The microscopic appearance photo of the matrix adopted and prepared ordered porous carbon membrane is shown in Fig. 5 and Fig. 6 respectively.
Table 2 preparation technology, matrix feature and result gather
Embodiment 13
By resorcinol, ethanol, hydrochloric (37%), surfactant F127 wiring solution-forming.The mixed solution of formulation aid triethly orthoacetate and formaldehyde (37%), and dropwise add above-mentioned containing in the mixed liquor of resorcinol, at room temperature stir 50 minutes.This solution is divided into two-layer up and down, after separation, loses the upper strata of clarification, leaves the lower floor's brown solution being rich in polymer phase.
This solution is become wet film at circular plate phenolic resin film on the surface of matrix, drying at room temperature 24 hours, put into vacuum drying chamber with 95 DEG C of solidifications 60 hours.Matrix obtains SOLID ORGANIC film.
By SOLID ORGANIC film obtained above in an inert atmosphere, nitrogen flow is 20mL/min, setting heating schedule: room temperature heats up to 400 DEG C with the speed of 4 DEG C/min, constant temperature 1 hour, 600 DEG C of constant temperature 1 hour is warmed up to the speed of 2 DEG C/min, Temperature fall, obtains the ordered porous carbon membrane that average pore size is 38 nanometers.
Table 3 summarizes part preparation technology, matrix feature and result and gathers.The microscopic appearance photo of the matrix adopted and prepared ordered porous carbon membrane is shown in Fig. 7 and Fig. 8 respectively.
Table 3 preparation technology, matrix feature and result gather
Embodiment 14
Getting resorcinol is dissolved in absolute ethyl alcohol, stirs, after it dissolves completely, more dropwise add the formalin that concentration is 37% at putting into magnetic stirring apparatus 25 DEG C.Gained mixed liquor adds catalyst n aOH subsequently, continues stir about 1h in magnetic stirring apparatus, obtains phenolic resins performed polymer colloidal sol.Get surfactant F127 again, be dissolved in absolute ethyl alcohol and be configured to solution, then phenolic resins prepolymer solution is dropwise added, continue to stir 1.5h until solution colour becomes lavender in the constant temperature waters agitator of 30 DEG C, then be transferred on glass surface by this solution, ambient temperatare puts 12h until ethanolic solution volatilizees completely and forms a clear dark purple film.Solidify 24h by the vacuum drying chamber of this film at 100 DEG C subsequently, make it be polymerized further, the color of film becomes dark-brown.Finally this diaphragm is taken off from glass, namely obtain surfactant/RF nano composite material.Above-mentioned sample is placed in retort, makes its charing under nitrogen atmosphere protection.With the heating rate of 1 DEG C/min from room temperature to 800 DEG C, to naturally cool to room temperature after the nitrogen flow of 80mL/min charing constant temperature 3h, obtain the ordered porous carbon membrane that average pore size is 11 nanometers.
The stereoscan photograph of concrete preparation process condition and prepared ordered porous carbon membrane and transmission electron microscope photo are as shown in Fig. 9 and Figure 10 and table 4.
Table 4 preparation technology, matrix feature and result gather
Embodiment 15
By resorcinol, ethanol, hydrochloric (37%), surfactant F127 wiring solution-forming.The mixed solution of formulation aid triethly orthoacetate and formaldehyde (37%), and dropwise add above-mentioned containing in the mixed liquor of resorcinol, at room temperature stir 100 minutes.This solution is divided into two-layer up and down, after separation, loses the upper strata of clarification, leaves the lower floor's brown solution being rich in polymer phase.
This solution is become wet film on the surface of polyimide polymer film as matrix, drying at room temperature 48 hours, put into vacuum drying chamber with 105 DEG C of solidifications 24 hours.Matrix obtains SOLID ORGANIC film.
By SOLID ORGANIC film obtained above in vacuum atmosphere, setting heating schedule: room temperature heats up to 400 DEG C with the speed of 2 DEG C/min, and constant temperature 3 hours, is warmed up to 600 DEG C of constant temperature 6 hours with the speed of 1 DEG C/min, Temperature fall, obtains the ordered porous carbon membrane that average pore size is 18 nanometers.
Concrete preparation process condition and result are as shown in table 5 and Figure 11 and Figure 12.
Table 5 preparation technology, matrix feature and result gather
Embodiment 16
By resorcinol, ethanol, hydrochloric (37%), surfactant F127 wiring solution-forming.The mixed solution of formulation aid triethly orthoacetate and formaldehyde (37%), and dropwise add above-mentioned containing in the mixed liquor of resorcinol, at room temperature stir 20 minutes.This solution is divided into two-layer up and down, after separation, loses the upper strata of clarification, leaves the lower floor's brown solution being rich in polymer phase.
Be 2.5 centimetres by this solution at diameter, aperture is that the porous alumina of 5 nanometers or 80 nanometers or 200 nanometers becomes wet film as on the surface of matrix, drying at room temperature 24 hours, puts into vacuum drying chamber with 105 DEG C of solidifications 6 hours.Matrix obtains SOLID ORGANIC film.
By SOLID ORGANIC film obtained above in an inert atmosphere, nitrogen flow is 100mL/min, setting heating schedule: room temperature heats up to 400 DEG C with the speed of 2 DEG C/min, constant temperature 3 hours, 600 DEG C of constant temperature 6 hours are warmed up to the speed of 1 DEG C/min, Temperature fall, must arrive the ordered porous carbon membrane that aperture is respectively 18 nanometers, 36 nanometers and 80 nanometers.
Concrete preparation process condition and result are as shown in table 6 and Figure 13, Figure 14, Figure 15, Figure 16, Figure 17, Figure 18, Figure 19.
Table 6 preparation technology, matrix feature and result gather
Embodiment 17
By resorcinol, ethanol, hydrochloric (37%), surfactant F127 wiring solution-forming.The mixed solution of formulation aid triethly orthoacetate and formaldehyde (37%), and dropwise add above-mentioned containing in the mixed liquor of resorcinol, at room temperature stir 20 minutes.This solution is divided into two-layer up and down, after separation, loses the upper strata of clarification, leaves the lower floor's brown solution being rich in polymer phase.
This solution is become wet film at the glass of smooth densification on the surface of matrix, drying at room temperature 24 hours, put into vacuum drying chamber with 105 DEG C of solidifications 6 hours.Matrix obtains SOLID ORGANIC film.
By SOLID ORGANIC film obtained above in an inert atmosphere, nitrogen flow is 100mL/min, setting heating schedule: room temperature heats up to 400 DEG C with the speed of 2 DEG C/min, constant temperature 3 hours, 600 DEG C of constant temperature 6 hours are warmed up to the speed of 1 DEG C/min, Temperature fall, obtains the ordered porous carbon membrane that average pore size is 45 nanometers.
Concrete preparation process condition and result are as shown in table 7 and Figure 20.
Table 7 preparation technology, matrix feature and result gather
Embodiment 18
Getting phenol is dissolved in absolute ethyl alcohol, after dissolving completely, more dropwise adds the formalin that concentration is 37%.Gained mixed liquor adds catalyst n aOH subsequently, continues stir about 1h in magnetic stirring apparatus, obtains phenolic resins performed polymer colloidal sol.Get surfactant F127 again, be dissolved in absolute ethyl alcohol and be configured to solution, then dropwise phenolic resins prepolymer solution is dripped, continue to stir 1.5h until solution colour becomes lavender in the constant temperature waters agitator of 30 DEG C, then this solution is transferred in the porous nylon filter membrane that average pore size is 0.45um or acetate fiber filter membrane matrix.Ambient temperatare puts about 12h until ethanolic solution volatilizees completely and forms a clear dark purple film.Solidify 24h by the vacuum drying chamber of this film at 100 DEG C subsequently, make it be polymerized further, the color of film becomes dark-brown.Finally this diaphragm is taken off from glass, namely obtain surfactant/RF nano composite material.Above-mentioned sample is placed in retort, makes its charing under nitrogen atmosphere protection.With the heating rate of 1 DEG C/min from room temperature to 800 DEG C, to naturally cool to room temperature after the nitrogen flow of 80mL/min charing constant temperature 3h, obtain the ordered porous carbon membrane that average pore size is 1.2 nanometers and 0.8 nanometer.
The stereoscan photograph of concrete preparation process condition and prepared ordered porous carbon membrane and transmission electron microscope photo are as shown in Fig. 9 and Figure 10 and table 4.
Table 8 preparation technology, matrix feature and result gather
Embodiment 19
Get Phenolic resin powder and be dissolved in absolute ethyl alcohol, configure certain density solution.Get the solution that F127 is configured to absolute ethyl alcohol.5g phenol resin solution is slowly instilled in the solution of F127, and stirs 30 minutes, form colloidal sol for subsequent use.This colloidal sol is slowly dripped in the porous ceramics piece matrix of average pore size 0.15um.Through air drying 15 hours, then 105 DEG C of freeze-day with constant temperature 6 hours.
By dried support membrane, put into retort, with the heating rate to 400 DEG C of 1 DEG C/min, constant temperature 3 hours; Be heated to 600 DEG C again, constant temperature 6 hours, then naturally cool.Obtain the ordered porous carbon membrane that average pore size is respectively 1.5 nanometers.
The transmission electron microscope photo of prepared ordered porous carbon membrane as shown in figure 23.
Table 9 preparation technology, matrix feature and result gather
Embodiment 20
If it is identical with embodiment 13 to fix other conditions, only changing over membrane matrix is the porous carbon membrane of surface through average pore size 150 nanometer of polishing, polishing and cleaning, and can obtain the ordered porous carbon membrane of similar cell morphology equally, its average pore size is 98 nanometers.
Claims (1)
1. prepare the matrix revulsion of ordered porous carbon membrane for one kind, after it is characterized in that presoma wiring solution-forming and organic surface active agent solution are uniformly mixed, after becoming the evaporation of wet film, solvent, drying, SOLID ORGANIC film is obtained under matrix induction, ordered porous carbon membrane is obtained again after charing, the average pore size of carbon membrane is 0.7 nanometer ~ 100 nanometer, is made up of following step:
(1) configuration of film forming solution or colloidal sol, with phenolic resins or phenol and formaldehyde mixture for presoma or prepolymer, and mix with surfactant, by surfactant F127 or P123, with alcohol solution-forming, through mechanical agitation or magnetic agitation after presoma or pre-polymer solution being mixed with surfactant solution, make mixed solution, the configuration of film forming solution or colloidal sol is made up of following step again:
(1-1) by the performed polymer of presoma or presoma, with surfactant, catalyst and auxiliary agent, be dissolved in solvent and make homogeneous solution or colloidal sol;
(1-2) by the performed polymer of presoma, the solution formed with surfactant, catalyst and auxiliary agent, temperature controls to carry out polymerisation at 25 ~ 90 degrees Celsius, and the reaction time is 0.25 ~ 80 hour, obtains film forming solution;
Persursor material is phenolic resins, or performed polymer is the mixture of formaldehyde and phenol or resorcinol, and wherein, the mol ratio of formaldehyde and phenol is 0.8:1 ~ 2.5:1;
The molar fraction ratio of used catalyst and phenol is 0.05:1 ~ 1:1, and catalyst is at least the one in NaOH or sodium carbonate or ammoniacal liquor or caustic alcohol or acetic acid or hydrochloric acid;
The molar fraction ratio of surfactant used and phenol is 0.003:1 ~ 0.06:1, and surfactant is at least the one in nonionic both sexes triblock copolymer polyoxyethylene-poly-oxypropylene polyoxyethylene F127 or P123;
Adjuvant used is 0:1 ~ 0.8:1 with the molar fraction ratio of phenol, selection of auxiliary triethly orthoacetate;
Solvent is at least the one in water or ethanol;
Course of dissolution: be at least the one left standstill or in mechanical agitation or magnetic agitation or ultrasonic wave dispersion;
(2) film forming on solid matrix, this solution adopted the stagnant or coating of leaching or to topple over or dropping mode is attached to stromal surface, matrix material is the one in plate glass or charcoal or pottery or silicon or stainless steel or aluminium oxide or polymer or metallic sieve, and matrix average pore size is 0 ~ 500 nanometer; Through solvent volatilization, obtain SOLID ORGANIC film, the organic film that matrix is formed is taken off and is obtained unsupported film, or does not peel and the film that is supported from matrix, is made up of following step in solid matrix film forming:
(2-1) to matrix pretreatment;
(2-2) wet film is become in stromal surface;
(2-3) dry film is solidified into;
Matrix feature: material is selected from dense non-porous or has the one in the glass of porous or charcoal or pottery or silicon or stainless steel or aluminium oxide or polymer or metallic sieve; Hole average diameter is 0 ~ 500 nanometer;
Matrix pretreatment: be selected from polishing polishing or cleaning in one or more;
Wet film build method: be selected from dipping or drip or topple over or brush or spray or one in liquid deposition or sol-gel process;
Film-forming temperature is 10 ~ 120 degrees Celsius, and the time is 0.25 ~ 90 hour, and environment is the one in still air or vacuum or moving air or slumpability gas;
(3) carbonize, by SOLID ORGANIC film obtained above in vacuum atmosphere or inert atmosphere, be raised to set temperature with specific heating rate from room temperature, and at charing final temperature constant temperature, then cool taking-up, obtain ordered porous carbon membrane, carbonize and be made up of following step:
(3-1) become solid film is put into the retort controlled with temperature programming;
(3-2) by the heating rate set, final temperature and atmosphere, carbonize;
(3-3) cool;
The heating rate of carbonization process is 0.2 ~ 5 degrees celsius/minute, final temperature is 400 ~ 1000 degrees Celsius, final temperature Time constant is 0 ~ 6 hour, atmosphere is vacuum environment or inert gas shielding, wherein, the gaseous species of inert atmosphere is at least the one in nitrogen or helium or argon gas, and inert gas flow is 0 ~ 500 cc/min;
Cooling: cooling scheme is the one during Temperature fall or programme-control are lowered the temperature, and treats that in-furnace temperature is down to less than 80 degrees Celsius and is taken out sample.
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| CN109351202A (en) * | 2018-12-19 | 2019-02-19 | 安徽工业大学 | It is a kind of based on ceramic tube be the compound carbon membrane of supporter preparation method |
| CN110368818B (en) * | 2019-08-11 | 2021-09-28 | 景德镇陶瓷大学 | Preparation method of high-flux flat ceramic membrane |
| CN112619442B (en) * | 2019-09-24 | 2022-11-04 | 中国石油化工股份有限公司 | Composite molecular sieve carbon film based on phenolic resin-based carbon tube as support body and preparation method and application thereof |
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| CN114425245A (en) * | 2020-09-23 | 2022-05-03 | 中国石油化工股份有限公司 | Phenolic resin-based composite carbon film and preparation method and application thereof |
| CN112980045B (en) * | 2021-03-26 | 2023-03-14 | 四川大学 | Redox-responsive ordered porous membrane material and preparation method thereof |
| CN113637462B (en) * | 2021-08-19 | 2023-10-10 | 中国科学院广州能源研究所 | Preparation method of chemical heat storage material based on ordered porous carbon base |
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