CN106567283B - A kind of PVB phenol-formaldehyde resin modifieds enhancing carbon paper and its preparation technology and application - Google Patents
A kind of PVB phenol-formaldehyde resin modifieds enhancing carbon paper and its preparation technology and application Download PDFInfo
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- CN106567283B CN106567283B CN201611028405.1A CN201611028405A CN106567283B CN 106567283 B CN106567283 B CN 106567283B CN 201611028405 A CN201611028405 A CN 201611028405A CN 106567283 B CN106567283 B CN 106567283B
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/33—Synthetic macromolecular compounds
- D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D21H17/36—Polyalkenyalcohols; Polyalkenylethers; Polyalkenylesters
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/33—Synthetic macromolecular compounds
- D21H17/46—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D21H17/47—Condensation polymers of aldehydes or ketones
- D21H17/48—Condensation polymers of aldehydes or ketones with phenols
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8803—Supports for the deposition of the catalytic active composition
- H01M4/8807—Gas diffusion layers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8875—Methods for shaping the electrode into free-standing bodies, like sheets, films or grids, e.g. moulding, hot-pressing, casting without support, extrusion without support
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
- H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Inert Electrodes (AREA)
- Paper (AREA)
- Fuel Cell (AREA)
Abstract
The present invention relates to a kind of PVB phenol-formaldehyde resin modifieds enhancing carbon paper and its preparation technology and application；Belong to fuel battery diffusion layer technical field.The preparation method that the present invention designs includes：Carbon paper is immersed in PVB solution and impregnated, is taken out, obtains being impregnated with PVB carbon paper；Then gained is impregnated with PVB carbon paper immersion phenol resin solution and impregnated, taken out, dry, the carbon paper after being handled；Carbon paper after processing 160~220 DEG C, be pressurized to 10~30MPa, be incubated；Obtain the carbon paper of completion of cure；It is finally thermally treated to obtain the PVB phenol-formaldehyde resin modifieds enhancing carbon paper；The temperature of the heat treatment is 1800~2500 DEG C.Preparation technology of the present invention is simple, and prepared carbon paper has that pliability is good, the excellent performance such as intensity height, is easy to heavy industrialization application.
Description
Technical field
The present invention relates to a kind of PVB phenol-formaldehyde resin modifieds enhancing carbon paper and its preparation technology and application；Belong to fuel cell
Diffusion layer technical field.
Background technology
Because fossil energy is limited on the earth, seek the outlet that alternative clean energy resource is only the mankind.PEM fires
Material battery (PEMFC) is used as a kind of long-term continued power of energy, is easily carried, the high electric supply installation of generating efficiency, can be used as solid
Determine power station, it is also possible to make portable power source, the potential with huge market.Important set of the carbon paper as fuel battery diffusion layer
Into part, support catalyst, ventilative and draining, the effect of collector are shouldered, therefore carbon paper performance quality directly affects fuel
The performance of battery.
At present have some strengthen carbon papers technologies, as Application No. 201110169254.2 patent in disclose one kind
The technique that CTBN phenol-formaldehyde resin modifieds strengthen carbon fiber paper intensity；It impregnates after being blended using CTBN with phenolic resin；By
It can not be dissolved in phenol resin solution in CTBN, but be disperseed with molecule.Precipitation is can be easily separated in static environment
Solution bottom, so must be stirred using large scale process, add the difficulty of cost of equipment and control of product quality；CTBN
Phenol-formaldehyde resin modified enhancing carbon fiber paper intensity technique prepare carbon paper, carbon matrix be distributed on carbon paper it is less uniform.
Although being related at present, PVB modified phenolics resin improves adhesion strength, the method for resistance to vibration has been reported that, will
It is used as the presoma as matrix carbon on carbon paper, does not meet but.
The content of the invention
The present invention is directed to fuel battery diffusion layer the shortcomings of the prior art, there is provided a kind of PVB phenol-formaldehyde resin modifieds increase
Strong carbon paper and its preparation technology and application.
The present invention has attempted scheme of the independent phenolic resin as impregnating agent, but phenolic resin is compatible with carbon paper base substrate
Property is poor, and distributed effect is bad on carbon fiber, and it is mainly manifested in：Phenolic resin can not be formed well on carbon fiber after dipping
Conductive network structure and.
The present invention in heuristic process, it is not intended to find using first impregnate PVB solution, then again impregnated phenolic resin this
Technique serves unexpected effect.
A kind of PVB phenol-formaldehyde resin modifieds strengthen carbon paper；The carbon paper is strengthened through PVB phenol-formaldehyde resin modifieds.
A kind of preparation technology of PVB phenol-formaldehyde resin modifieds enhancing carbon paper of the present invention, comprises the steps：
Step 1
Carbon paper is immersed in PVB solution and impregnated, is taken out, obtains being impregnated with PVB carbon paper；
Step 2
The carbon paper that PVB is impregnated with obtained by step 1 is immersed in phenol resin solution and impregnated, is taken out, dries, obtains
Carbon paper after processing；
Step 3
Carbon paper after handling obtained by step 2 is placed in mould, 160~220 DEG C, be pressurized to 10~30MPa, be incubated；
Obtain the carbon paper of completion of cure；
Step 4
Under protective atmosphere, the carbon paper of completion of cure obtained by step 3 is heat-treated, obtains the PVB modified phenolics
Resin tooth carbon paper；The temperature of the heat treatment is 1800~2500 DEG C.
A kind of PVB phenol-formaldehyde resin modifieds of the present invention strengthen the preparation technology of carbon paper, and PVB solution is PVB ethanol in step 1
Solution；PVB concentration is 0.005g/ml~0.10g/ml in the PVB solution.Preferably 0.06g/ml.0.06g/ml's
The preferable of the combination property such as the carbon paper mechanical property impregnated in PVB solution, permeability, electric conductivity
In the present invention, if PVB excessive concentrations, the gas permeability of carbon paper is poor.Such as when PVB concentration is 0.15g/ml, phenolic aldehyde
The concentration 0.01g/ml of resin, carbon paper gas permeability only 841mlmmcm-2·hr-1mmAq-1。
A kind of preparation technology of present invention PVB phenol-formaldehyde resin modifieds enhancing carbon paper, phenol resin solution concentration in step 2
For 0.01~0.1g/ml.
In the present invention, phenolic resin excessive concentration, carbon paper gas permeability is poor.Such as when phenolic resin concentration is 0.105g/ml,
PVB concentration is 0.005g/ml, carbon paper gas permeability only 1097mlmmcm-2·hr-1mmAq-1。
A kind of preparation technology of present invention PVB phenol-formaldehyde resin modifieds enhancing carbon paper, in step 2, after impregnated phenolic resin,
Take out, 80 DEG C of freeze-day with constant temperature in drying box, the carbon paper after being handled.
A kind of preparation technology of PVB phenol-formaldehyde resin modifieds enhancing carbon paper of the present invention, carbon paper is through priority dipping PVB solution, phenol
What is finally given after urea formaldehyde solution is that PVB modified phenolic resins are adsorbed on the surface of carbon paper.
A kind of preparation technology of present invention PVB phenol-formaldehyde resin modifieds enhancing carbon paper, in step 3, mould is heated to 10~
130℃；Then the carbon paper after handling obtained by step 2 is placed in mould, 160~220 DEG C, be pressurized to 10~30MPa, protect
1~2.5h of temperature；Obtain the carbon paper of completion of cure.In industrial applications, mould is heated to 10~130 DEG C；Then by step
Carbon paper lamination after two gained are handled is positioned on vulcanizing press, and continue temperature to 160~220 DEG C and be pressurized to 10~
30MPa, it is incubated 1~2.5h.The mould is that vulcanizing press carries mould.
A kind of preparation technology of present invention PVB phenol-formaldehyde resin modifieds enhancing carbon paper, in step 4, the protective atmosphere is selected from
One kind in inert atmosphere.Preferably argon gas.
A kind of preparation technology of present invention PVB phenol-formaldehyde resin modifieds enhancing carbon paper, in step 4, during heat treatment, reach
1~3 hour is incubated after 1800~2500 DEG C.
Preferably, in step 4, it is heat-treated and per minute is warming up to 1800~2000 DEG C of insulation 1-3 hours with 5 DEG C.
PVB phenol-formaldehyde resin modifieds enhancing carbon paper provided by the invention has high-tensile, high-flexural strength, and with good
Good pliability.
Carbon paper base substrate is immersed in 0.06g/ml PVB ethanol solutions 3 minutes, taken out, again by dipped PVB carbon paper
Base substrate is immersed in 0.04g/ml phenolic resin ethanol solutions 20 seconds, is placed in 80 DEG C of baking ovens 5 hours, is being placed on after taking-up
In 180 DEG C of moulds, pressurize 20MPa, is incubated 2 hours, is put into high temperature furnace, and it is small to be warming up to 2000 DEG C of insulations 2 with 5 DEG C per minute
When；Obtain carbon paper, the bending strength of the carbon paper is 60.31MPa, tensile strength 30.10MPa, resistivity 3.27m
Ω·cm；Or
Carbon paper base substrate is immersed in 0.09g/ml PVB ethanol solutions 3 minutes, taken out, again by dipped PVB carbon paper
Base substrate is immersed in 0.07g/ml phenolic resin ethanol solutions 40 seconds, is placed in 80 DEG C of baking ovens 2 hours, is being placed on after taking-up
In 220 DEG C of moulds, pressurize 20MPa, is incubated 2 hours, is put into high temperature furnace, is warming up to 2200 DEG C and is incubated 2 hours；Obtain carbon paper,
The bending strength of the carbon paper be 65.55MPa, tensile strength 35.78MPa, resistivity are 2.89m Ω cm.
A kind of application of PVB phenol-formaldehyde resin modifieds enhancing carbon paper of the present invention, including the PVB phenol-formaldehyde resin modifieds are strengthened
Carbon paper is used for fuel battery diffusion layer.
The carbon paper characteristics test method GB/T 20042.7-2014 issued at present does not have carbon paper standard characteristic manner, root
According to document (Kim H, Lee Y J, Park G G, et al.Fabrication of carbon paper containing
PEDOT:PSS for use as a gas diffusion layer in proton exchange membrane fuel
cells[J].Carbon,2015,85:422-428.) report uses method, tests.Its result is as shown in Figure 4.
Polyvinyl butyral resin used in the present invention (Polyvinyl Butyral, PVB) possesses substantial amounts of activity hydroxy, and one
Aspect improves its solubility in alcohols, the adhesion strength on the other hand having had to phenolic resin and epoxy resin, while energy
Reacted with them.PVB can not only improve phenolic resin and is distributed on carbon paper, and can improve the boundary between Carbon fibe and matrix
Face bond strength.
Brief description of the drawings
Fig. 1 is the scanning electron microscope (SEM) photograph that PVB phenol-formaldehyde resin modifieds prepared by example 1 strengthen carbon paper.
Fig. 2 is the scanning electron microscope (SEM) photograph that PVB phenol-formaldehyde resin modifieds prepared by example 2 strengthen carbon paper.
Fig. 3 is the scanning electron microscope (SEM) photograph that PVB phenol-formaldehyde resin modifieds prepared by example 3 strengthen carbon paper.
Fig. 4 is the scanning electron microscope (SEM) photograph that comparative example 1 prepares the phenolic resin carbon paper for being not added with PVB
Fig. 5 is that PVB phenol-formaldehyde resin modifieds prepared by example 2 strengthen the actual pliability test chart of carbon paper.
It can find out that carbon matrix amounts are few from Fig. 1, be wrapped in very well on carbon paper carbon fiber, and on whole carbon paper uniformly.
It is more that matrix carbon amounts can be gone out from Fig. 2, and on whole carbon paper uniformly.
It can find out that matrix carbon is many from Fig. 3, and be uniformly distributed on whole carbon paper
It can find out that carbon matrix is poor in the uniformity of carbon paper surface distributed from Fig. 4.
As can be seen from Figure 5 the PVB phenol-formaldehyde resin modifieds enhancing carbon paper that prepared by example 2 shows good pliability.
The present invention is further exemplarily described in detail with reference to non-limiting specific embodiment.The embodiment of the present invention
Used in reagent commercially available obtain.
Example 1
(1) impregnate
PVB is configured to 0.02g/ml ethanol solution, carbon paper base substrate is impregnated in PVB solution and is immersed in again after 1 minute
20 seconds in 0.02g/ml phenolic resin ethanol solution, 80 DEG C of freeze-day with constant temperature are subsequently placed in drying box 1 hour.
(2) it is molded
When mold temperature is up to 110 DEG C, treated carbon paper is placed in vulcanizing press superimposed layer, and continue to be warming up to
200 DEG C and it is pressurised into 30MPa, is incubated 1~2.5h.
(3) it is heat-treated
The carbon paper molding sample of completion of cure, surfacing is passed through into charing, graphitization processing 2 hours at 2500 DEG C, system
Obtain used in proton exchange membrane fuel cell carbon paper.
It is 3.2g/cm that it, which provides the density of used in proton exchange membrane fuel cell carbon paper obtained by embodiment 1,3Bending strength is
49.78MPa, tensile strength 23.56MPa and resistivity 4.21m Ω cm correlation values.The gas permeability of carbon paper is：
2641ml·mm·cm-2·hr-1mmAq-1。
Example 2
(1) impregnate
PVB is configured to 0.06g/ml ethanol solution, carbon paper base substrate is impregnated in PVB solution and is immersed in again after 3 minutes
20 seconds in 0.04g/ml phenol resin solution, 80 DEG C of freeze-day with constant temperature are subsequently placed in drying box 1 hour.
(2) it is molded
When mold temperature is up to 120 DEG C, treated carbon paper is placed in vulcanizing press superimposed layer, and sets the temperature to be
180 DEG C and pressure are 20MPa, are incubated 1~2.5h.
(3) it is heat-treated
The carbon paper molding sample of completion of cure, surfacing is passed through into charing, graphitization processing 2 hours at 2500 DEG C, system
Obtain used in proton exchange membrane fuel cell carbon paper.
The density that used in proton exchange membrane fuel cell carbon paper is made is 3.8g/cm3, bending strength 60.31MPa, tension
Intensity is 30.10MPa and resistivity is 3.27m Ω cm.The gas permeability of carbon paper is：2611ml·mm·cm-2·hr-1mmAq-1
Example 3
(1) impregnate
PVB is configured to 0.09g/ml ethanol solution, carbon paper base substrate is impregnated in PVB solution and is immersed in again after 3 minutes
40 seconds in 0.07g/ml phenol resin solution, 80 DEG C of freeze-day with constant temperature are subsequently placed in drying box 2 hours.
(2) it is molded
When mold temperature is up to 130 DEG C, treated carbon paper is placed in vulcanizing press superimposed layer, and sets the temperature to be
220 DEG C and pressure are 10MPa, are incubated 1~2.5h.
(3) it is heat-treated
The carbon paper molding sample of completion of cure, surfacing is passed through and is incubated 3 hours at 2500 DEG C, PEM is made
Fuel cell carbon paper.
The density that used in proton exchange membrane fuel cell carbon paper is made is 4.5g/cm3Bending strength is 65.55MP, tension is strong
It is 2.89m Ω cm to spend for 35.78MPa and resistivity.The gas permeability of carbon paper is：1982ml·mm·cm-2·hr-1mmAq-1。
Example 4
(1) impregnate
PVB is configured to 0.09g/ml ethanol solution, is immersed in 0.09g/ml phenol resin solution 40 seconds, then
It is placed in drying box 80 DEG C of freeze-day with constant temperature 2 hours.
(2) it is molded
When mold temperature is up to 130 DEG C, treated carbon paper is placed in vulcanizing press superimposed layer, and sets the temperature to be
220 DEG C and pressure are 10MPa, are incubated 1~2.5h.
(3) it is heat-treated
The carbon paper molding sample of completion of cure, surfacing is passed through and is incubated 3 hours at 2200 DEG C, PEM is made
Fuel cell carbon paper.
The density that used in proton exchange membrane fuel cell carbon paper is made is 4.6g/cm3Bending strength is 70.55MP, tension is strong
It is 3.57m Ω cm to spend for 39.78MPa and resistivity.The gas permeability of carbon paper is：1946ml·mm·cm-2·hr-1mmAq-1。
Comparative example 1
Other conditions uniformly implement 4 unanimously, and difference is not impregnate PVB solution first, but directly using dipping phenolic aldehyde tree
Lipoprotein solution；
The density that used in proton exchange membrane fuel cell carbon paper is made is 4.6g/cm3Bending strength is 55.43MP, tension is strong
It is 6.85m Ω cm to spend for 30.45MPa and resistivity.
It can be seen that by comparative example 1 and embodiment 4：When carbon paper density is close, carbon paper intensity, electricity prepared by the present invention
Resistance rate has obvious advantage.
Comparative example 2
Other uniform embodiments 4 of condition are consistent, and difference is first to be mixed PVB solution with phenol resin solution
Close, then impregnated again；It was found that dipping can not be carried out.
Comparative example 3
Other according to condition consistent with embodiment 4, difference is PVB concentration for 0.15g/ml, the concentration of phenolic resin
0.09g/ml, gained carbon paper gas permeability only 841mlmmcm-2·hr-1mmAq-1。
Comparative example 4
Other according to condition consistent with embodiment 4, difference is that phenolic resin concentration is that 0.105g/ml, PVB concentration are
0.005g/ml, the gas permeability only 1097mlmmcm of gained carbon paper-2·hr-1mmAq-1。
Claims (2)
1. a kind of PVB phenol-formaldehyde resin modifieds strengthen carbon paper；It is characterized in that；Its preparation technology is；
Carbon paper base substrate is immersed in 0.06g/ml PVB ethanol solutions 3 minutes, taken out, then dipped PVB carbon paper base substrate is soaked
Stain is placed in 80 DEG C of baking ovens 5 hours after taking-up 20 seconds in 0.04g/ml phenolic resin ethanol solutions, is being placed on 180 DEG C of moulds
In tool, pressurize 20MPa, is incubated 2 hours, is put into high temperature furnace, and being warming up to 2500 DEG C with 5 DEG C per minute is incubated 2 hours；Obtain charcoal
Paper, the bending strength of the carbon paper is 60.31MPa, tensile strength 30.10MPa, resistivity are 3.27m Ω cm；Or
Carbon paper base substrate is immersed in 0.09g/ml PVB ethanol solutions 3 minutes, taken out, then dipped PVB carbon paper base substrate is soaked
Stain is placed in 80 DEG C of baking ovens 2 hours after taking-up 40 seconds in 0.07g/ml phenolic resin ethanol solutions, is being placed on 220 DEG C of moulds
In tool, pressurize 20MPa, is incubated 2 hours, is put into high temperature furnace, is warming up to 2500 DEG C and is incubated 2 hours；Obtain carbon paper, the carbon paper
Bending strength be 65.55MPa, tensile strength 35.78MPa, resistivity be 2.89m Ω cm；
Or
Carbon paper base substrate is immersed in 0.09g/ml PVB ethanol solutions 3 minutes, taken out, then dipped PVB carbon paper base substrate is soaked
Stain is placed in 80 DEG C of baking ovens 2 hours after taking-up 40 seconds in 0.09g/ml phenolic resin ethanol solutions, is being placed on 220 DEG C of moulds
In tool, pressurize 10MPa, is incubated 2.5 hours, is put into high temperature furnace, is warming up to 2200 DEG C and is incubated 3 hours；Obtain carbon paper, the charcoal
Paper density is 4.6g/cm3, bending strength 70.55MPa, tensile strength 39.78MPa, resistivity be 3.57m Ω cm, charcoal
The gas permeability of paper is 1946mlmmcm‐2·hr‐1mmAq‐1。
A kind of 2. application of PVB phenol-formaldehyde resin modifieds enhancing carbon paper according to claim 1, it is characterised in that：Including inciting somebody to action
The PVB phenol-formaldehyde resin modifieds enhancing carbon paper is used for fuel battery diffusion layer.
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| CN102061138A (en) * | 2009-11-17 | 2011-05-18 | 张维民 | Polyvinyl butyral (PVB) adhesive and preparation process thereof |
| CN101734940B (en) * | 2009-11-20 | 2012-07-25 | 中南大学 | Pressure difference-based method and device for improving properties of carbon paper of quick CVI coating |
| CN102230305B (en) * | 2011-06-22 | 2013-02-06 | 中南大学 | Technique for enhancing strength of carbon fibre paper by CTBN (Carboxy Terminal Butadiene-Acrylonitrile) modified phenolic resin |
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