CN109161947A - High modulus carbon fiber surface treatment method and device and its application - Google Patents
High modulus carbon fiber surface treatment method and device and its application Download PDFInfo
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- CN109161947A CN109161947A CN201811005363.9A CN201811005363A CN109161947A CN 109161947 A CN109161947 A CN 109161947A CN 201811005363 A CN201811005363 A CN 201811005363A CN 109161947 A CN109161947 A CN 109161947A
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- deflector roll
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- rinsing bowl
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 166
- 229920000049 Carbon (fiber) Polymers 0.000 title claims abstract description 139
- 239000004917 carbon fiber Substances 0.000 title claims abstract description 139
- 238000000034 method Methods 0.000 title claims abstract description 35
- 238000004381 surface treatment Methods 0.000 title claims abstract description 24
- 239000003792 electrolyte Substances 0.000 claims abstract description 57
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 40
- 230000002378 acidificating effect Effects 0.000 claims abstract description 37
- 239000002131 composite material Substances 0.000 claims abstract description 24
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 17
- 238000010438 heat treatment Methods 0.000 claims description 17
- 239000007788 liquid Substances 0.000 claims description 12
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 9
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 9
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical group [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 8
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 8
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 8
- 239000001099 ammonium carbonate Substances 0.000 claims description 8
- 230000005611 electricity Effects 0.000 claims description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 8
- 125000004429 atom Chemical group 0.000 claims description 7
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 5
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 5
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 5
- 229910000990 Ni alloy Inorganic materials 0.000 claims description 4
- PCLURTMBFDTLSK-UHFFFAOYSA-N nickel platinum Chemical group [Ni].[Pt] PCLURTMBFDTLSK-UHFFFAOYSA-N 0.000 claims description 4
- 229910052697 platinum Inorganic materials 0.000 claims description 4
- -1 polytetrafluoroethylene Polymers 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims 2
- 230000007423 decrease Effects 0.000 abstract description 7
- 239000011229 interlayer Substances 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 24
- 230000003647 oxidation Effects 0.000 description 21
- 238000007254 oxidation reaction Methods 0.000 description 21
- 239000003822 epoxy resin Substances 0.000 description 18
- 229920000647 polyepoxide Polymers 0.000 description 18
- 238000005406 washing Methods 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 229910021642 ultra pure water Inorganic materials 0.000 description 13
- 239000012498 ultrapure water Substances 0.000 description 13
- 238000012360 testing method Methods 0.000 description 12
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 10
- 238000012545 processing Methods 0.000 description 10
- 230000008569 process Effects 0.000 description 9
- 229920005989 resin Polymers 0.000 description 8
- 239000011347 resin Substances 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- 229940058401 polytetrafluoroethylene Drugs 0.000 description 7
- 238000009955 starching Methods 0.000 description 6
- 230000010148 water-pollination Effects 0.000 description 6
- 239000000126 substance Substances 0.000 description 4
- WWILHZQYNPQALT-UHFFFAOYSA-N 2-methyl-2-morpholin-4-ylpropanal Chemical compound O=CC(C)(C)N1CCOCC1 WWILHZQYNPQALT-UHFFFAOYSA-N 0.000 description 3
- 238000007605 air drying Methods 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 238000003851 corona treatment Methods 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000001721 carbon Chemical class 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- BIGPRXCJEDHCLP-UHFFFAOYSA-N ammonium bisulfate Chemical compound [NH4+].OS([O-])(=O)=O BIGPRXCJEDHCLP-UHFFFAOYSA-N 0.000 description 1
- 238000007743 anodising Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000005586 carbonic acid group Chemical group 0.000 description 1
- 238000005255 carburizing Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- NZZFYRREKKOMAT-UHFFFAOYSA-N diiodomethane Chemical compound ICI NZZFYRREKKOMAT-UHFFFAOYSA-N 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/06—Elements
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/02—Ingredients treated with inorganic substances
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/005—Apparatus specially adapted for electrolytic conversion coating
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/51—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with sulfur, selenium, tellurium, polonium or compounds thereof
- D06M11/55—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with sulfur, selenium, tellurium, polonium or compounds thereof with sulfur trioxide; with sulfuric acid or thiosulfuric acid or their salts
- D06M11/56—Sulfates or thiosulfates other than of elements of Groups 3 or 13 of the Periodic Table
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/73—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof
- D06M11/76—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof with carbon oxides or carbonates
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/40—Fibres of carbon
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Textile Engineering (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
Abstract
The invention discloses high modulus carbon fiber surface treatment method and device and its applications, the described method includes: (1) carries out first segment anodized to high modulus carbon fiber using alkalescent electrolyte, to generate active atoms of carbon on the high modulus carbon fiber surface；(2) second segment anodized is carried out to the carbon fiber that step (1) obtains using acidic electrolysis bath, to form active group in the carbon fiber surface.Surface treatment to high modulus carbon fiber may be implemented using this method, and the tensile strength of treated carbon fiber and stretch modulus decline are lower, to solve the problems, such as that high modulus carbon fiber composite material interlayer shear strength is lower.
Description
Technical field
The present invention relates to high modulus carbon fiber surface treatment method and device and its applications.
Background technique
Carbon fiber be it is a kind of with high specific strength, high ratio modulus, light weight practical material, by the hair of decades
Exhibition, the production technology of carbon fiber improve constantly.Nowadays the trade mark of carbon fiber is broadly divided into two kinds of high-strength and high mould, high
The carbon fiber of modulus can be applied to space industry.For high modulus carbon fiber carburizing temperature at 2200 DEG C or more, graphite-like structure is completeer
Kind, chemical property is stablized.But with and the problem come be exactly high model carbon fiber surface inertness it is stronger, boundary with matrix resin
Face combination is weaker, leads to the interlaminar shear strength degradation of its composite material.It can be in carbon fiber surface by surface treatment
Oxygen-containing, nitrogenous active group is introduced, increases the surface energy of carbon fiber, improves the chemical bonding of carbon fiber and matrix resin, together
When can also increase the roughness of carbon fiber surface, improve the mechanical interlock of carbon fiber and matrix resin, finally improve carbon fiber
The interlaminar shear strength of reinforced resin.
Currently, it is a lot of to the Research on Surface Modification of carbon fiber both at home and abroad, it is related to electrochemical treatments, liquid phase oxidation, chemistry
Grafting, corona treatment etc..Liquid phase oxidation, chemical graft processing mode are flexible and changeable but maximum the disadvantage is that the processing time
It is long, it is difficult to realize industrialization online processing.Corona treatment is a kind of processing method emerging at present, has and realizes industrialization
Potential quality, but at present corona treatment Process Exploration it is also not overripened.
Anodizing is a kind of carbon fiber surface treatment method of current comparative maturity, when the advantages of this method is reaction
Between fast, oxidation uniformly, simple process and easily controllable.
For the carbon fiber of low modulus, current anode oxidation process and equipment all comparative maturities, by anodic oxidation
The carbon fiber of surface treatment can satisfy the demand of industry substantially.But for the carbon fiber of high-modulus, since its chemical property is steady
Fixed, surface inertness is stronger, it more difficult to be oxidized introducing active group, there is an urgent need to the further of anode oxidation process and equipment
It explores and perfect.
Summary of the invention
Technical problem to be solved by the invention is to provide a kind of high modulus carbon fiber surface treatment method and device and its
Using the surface treatment to high modulus carbon fiber may be implemented using this method, and the tensile strength of treated carbon fiber
It is lower with stretch modulus decline, to solve the problems, such as that high modulus carbon fiber composite material interlayer shear strength is lower.
In one aspect of the invention, the invention proposes a kind of high modulus carbon fiber surface treatment methods.According to this hair
Bright embodiment, which comprises (1) high modulus carbon fiber is carried out at first segment anodic oxidation using alkalescent electrolyte
Reason, to generate active atoms of carbon on the high modulus carbon fiber surface；(2) step (1) is obtained using acidic electrolysis bath
Carbon fiber carries out second segment anodized, to form active group in the carbon fiber surface.
Optional, in step (1), the modulus of the high modulus carbon fiber is 350~600GPa.
Optional, in step (1), the alkalescent electrolyte is ammonium hydrogen carbonate.
Optional, in step (1), the mass concentration of the alkalescent electrolyte is 5~10wt%.
Optional, in step (1), the temperature of the alkalescent electrolyte is 30~50 degrees Celsius.
Optional, in step (1), the current density of the first segment anodized is 5~10A/m2。
Optional, in step (2), the acidic electrolysis bath is selected from least one of ammonium sulfate and ammonium hydrogen sulfate.
Optional, in step (2), the concentration of the acidic electrolysis bath is 5~10wt%.
Optional, in step (2), the temperature of the acidic electrolysis bath is 30~50 degrees Celsius.
Optional, in step (2), the current density of the second segment anodized is 5~10A/m2。
Optional, the above method further comprises: the carbon fiber that step (2) obtains is washed and is dried by (3).
In another aspect of the invention, the invention proposes a kind of devices of high modulus carbon fiber surface treatment.According to
The embodiment of the present invention, described device include: the first electrolytic cell, and alkalescent electrolyte is filled in first electrolytic cell, described
Bottom in first electrolytic cell is equipped with the first cathode plate, and along wire direction, and the is successively arranged on first electrolytic cell
Described in one anode deflector roll, the first deflector roll, the second deflector roll and second plate deflector roll, first deflector roll and second deflector roll immerse
Alkalescent electrolyte；Second electrolytic cell, second electrolytic cell are connected with first electrolytic cell by third deflector roll, and described
Acidic electrolysis bath is filled in two electrolytic cells, the bottom in second electrolytic cell is equipped with the second cathode plate, and along wire side
To, third anode deflector roll, the 4th deflector roll, the 5th deflector roll and the 4th anode deflector roll are successively arranged on second electrolytic cell, it is described
4th deflector roll and the 5th deflector roll immerse the acidic electrolysis bath；First rinsing bowl, first rinsing bowl and described second
Electrolytic cell is connected, and first rinsing bowl is equipped with the first heating plate, and along wire direction, on first rinsing bowl successively
Equipped with the 6th deflector roll and the 7th deflector roll；Second rinsing bowl, the second rinsing bowl are connected with first rinsing bowl, second washing
Slot is equipped with the second heating plate, and along wire direction, be successively arranged on second rinsing bowl the 8th deflector roll, the 9th deflector roll,
Tenth deflector roll and the 11st deflector roll；Tube drier, the tube drier are connected with second rinsing bowl.
Optional, first cathode plate bottom moving up and down being located in first electrolytic cell, described second
The cathode plate bottom moving up and down being located in second electrolytic cell.
Optional, first cathode plate and second cathode plate are platinum electrode.
Optional, the first anode deflector roll, the second plate deflector roll, the third anode deflector roll and the 4th sun
Pole deflector roll is platinum-nickel alloy deflector roll.
Optional, first deflector roll, second deflector roll, the third deflector roll, the 4th deflector roll, the described 5th lead
Roller, the 6th deflector roll, the 7th deflector roll, the 8th deflector roll, the 9th deflector roll, the tenth deflector roll and the described tenth
One deflector roll is polytetrafluoroethylene (PTFE) deflector roll.
Optional, the first conductivity meter is equipped in first electrolytic cell, first conductivity meter is movably located at
In first electrolytic cell.
Optional, the second conductivity meter is equipped in second electrolytic cell, second conductivity meter is movably located at
In second electrolytic cell.
Optional, along wire direction, the tube drier is arranged obliquely.
Optional, in the height direction, second rinsing bowl is higher than first rinsing bowl.
Optional, device described above further comprises: alkalescent electrolyte circulator, the alkalescent electrolyte circulation
Machine is connected with first electrolytic cell.
Optional, device described above further comprises: acidic electrolysis liquid bath circulator, the acidic electrolysis liquid bath circulation
Machine is connected with second electrolytic cell.
In the third aspect of the invention, the invention proposes a kind of surface modified carbon fibers.Implementation according to the present invention
Example, the surface modified carbon fiber are to adopt with the aforedescribed process or above-mentioned system is prepared.
In the fourth aspect of the invention, the invention proposes a kind of composite materials.According to an embodiment of the invention, described
Composite material is prepared using above-mentioned surface modified carbon fiber.
The present invention makes carbon fiber surface by the way that high modulus carbon fiber is carried out anodized in alkalescent electrolyte
Active atoms of carbon is generated, then continues anodized in acidic electrolysis bath, carbon fiber surface can be significantly improved
Active group, make carbon fiber hydrophily, lyophily while enhancing, and surface can obviously increase, at the same pass through two sections of anodes
Tensile strength and the stretch modulus decline of carbon fiber ontology are lower after oxidation processes, then improve carbon fiber using hot water washing
The removal efficiency of electrolyte more than residual surface, low energy consumption for the heat radiation drying mode of tube drier, avoids traditional heated air drying pair
Damaged caused by carbon fiber, the interlaminar shear strength of gained surface modified carbon fiber and epoxy resin composite material promoted 2 times with
On.
Detailed description of the invention
Fig. 1 is the high modulus carbon fiber surface treatment method flow diagram of the embodiment of the present invention；
Fig. 2 is the high modulus carbon fiber surface processing device structural schematic diagram of the embodiment of the present invention；
Fig. 3 is the 2 full spectrogram of carbon fiber XPS of comparative example；
Fig. 4 is the full spectrogram of XPS for the surface modified carbon fiber that comparative example 1 obtains；
Fig. 5 is the full spectrogram of XPS for the surface modified carbon fiber that embodiment 1 obtains；
Fig. 6 is the full spectrogram of XPS for the surface modified carbon fiber that embodiment 2 obtains；
Fig. 7 is that the SEM of 2 carbon fiber of comparative example schemes；
Fig. 8 is the SEM figure for the surface modified carbon fiber that comparative example 1 obtains；
Fig. 9 is the SEM figure for the surface modified carbon fiber that embodiment 1 obtains；
Figure 10 is the SEM figure for the surface modified carbon fiber that embodiment 2 obtains；
Figure 11 is that 2 carbon fiber of comparative example is schemed with the SEM with epoxy resin composite material batten after compound；
Figure 12 is the SEM figure of the surface modified carbon fiber that comparative example 1 obtains and the compound rear composite material batten of epoxy resin；
Figure 13 is the SEM figure of the surface modified carbon fiber that embodiment 1 obtains and the compound rear composite material batten of epoxy resin；
Figure 14 is the SEM figure of the surface modified carbon fiber that embodiment 2 obtains and the compound rear composite material batten of epoxy resin.
Specific embodiment
The embodiments described below with reference to the accompanying drawings are exemplary, it is intended to be used to explain the present invention, and cannot understand
For limitation of the present invention.
In one aspect of the invention, the invention proposes a kind of high modulus carbon fiber surface treatment methods.According to this hair
Bright embodiment, with reference to Fig. 1, this method comprises:
S1: first segment anodized is carried out to high modulus carbon fiber using alkalescent electrolyte
In the step, the carbon fiber (modulus is 350~600GPa) of high-modulus is carried out first in alkalescent electrolyte
Section anodized, to generate active atoms of carbon on high modulus carbon fiber surface.Specifically, alkalescent electrolyte is carbonic acid
Hydrogen ammonium, and the mass concentration of alkalescent electrolyte is 5~10wt% (being configured using ultrapure water), preferably 7wt%, alkalescent electricity
The temperature for solving liquid is 30~50 degrees Celsius, and preferably 40 degrees Celsius, the current density of first segment anodized is 5~10A/
m2.Inventors have found that carbon fiber can be significantly improved by carrying out anodized to high modulus carbon fiber under the above conditions
The oxidation efficiency of dimension, to improve the active atoms of carbon on high modulus carbon fiber surface, and the stretching of carbon fiber under this condition is strong
Degree and the stretch modulus range of decrease are smaller.And the process monitors the temperature and concentration of the alkalescent electrolyte using conductivity meter,
When alkalescent concentration of electrolyte is lower, conductivity can be reduced, and fed electrolyte by circulator and kept the temperature of electrode solution steady
It is fixed.
S2: second segment anodized is carried out to the carbon fiber that step S1 is obtained using acidic electrolysis bath
In the step, second segment anodized is carried out to the carbon fiber that step S1 is obtained using acidic electrolysis bath, it can
To significantly improve the oxygen content of carbon fiber surface, that is, the active group of carbon fiber surface is improved, to enhance carbon fiber and resin
Between interface binding power, while the carbon fiber hydrophily, lyophily enhance simultaneously, and surface can obviously increase.Specifically, sour
Property electrolyte be selected from least one of ammonium sulfate and ammonium hydrogen sulfate, the concentration of acidic electrolysis bath is 5~10wt% (using super
Pure water configuration), preferably 7wt%, the temperature of acidic electrolysis bath is 30~50 degrees Celsius, preferably 40 degrees Celsius, second segment anodic oxygen
The current density for changing processing is 5~10A/m2.Inventors have found that by continuing to carry out anodic oxygen to carbon fiber under the above conditions
Change processing, can significantly improve the oxidation efficiency of carbon fiber, to improve the active function groups of carbon fiber surface, and then improve it
With the interface binding power between resin such as epoxy resin, while by the stretching of carbon fiber ontology under the conditions of the anodized
Intensity and stretch modulus decline are lower.And the process monitors the temperature and concentration of the acidic electrolysis bath using conductivity meter,
When acidic electrolysis bath concentration is lower, conductivity can be reduced, and fed electrolyte by circulator and kept the temperature of electrode solution steady
It is fixed.
According to an embodiment of the invention, the above method further comprises with reference to Fig. 1:
S3: the obtained carbon fiber of step S2 is washed and is dried
In the step, the carbon fiber that step S2 is obtained carries out two sections of washings, and two sections of water-washing process are all made of ultrapure water, and
And heating device is configured in two sections of water-washing process, washing temperature is improved, so that the electrolyte of carbon fiber surface remnants
Cleaned more thorough, first segment washing temperature is set as 60~80 degrees Celsius, preferably 70 degrees Celsius, and second segment washing temperature is set
It is set to 70~90 degrees Celsius, preferably 80 degrees Celsius, and water intake velocity is set as 450~550ml/min, preferably 500ml/min,
And drying temperature is set as 120~140 degrees Celsius, preferably 130 degrees Celsius, wherein drying process uses tube drier, and
And along wire direction, tube drier is arranged obliquely, the damage so as to avoid traditional heated air drying to carbon fiber ontology,
And then improve carbon fiber performance.
In another aspect of the invention, the invention proposes a kind of high modulus carbon fiber surface processing devices.According to this
The embodiment of invention, with reference to Fig. 2, which includes: the first electrolytic cell 100, the second electrolytic cell 200, the first rinsing bowl 300,
Two rinsing bowls 400 and tube drier 500.
According to an embodiment of the invention, filling alkalescent electrolyte, the first electrolytic cell in the first electrolytic cell 100 with reference to Fig. 2
Interior bottom is equipped with the first cathode plate 10, and along wire direction, is successively arranged first anode deflector roll on the first electrolytic cell 100
11, the first deflector roll 12, the second deflector roll 13 and second plate deflector roll 14, the first deflector roll 12 and the second deflector roll 13 immerse alkalescent electrolysis
Liquid.Specifically, by the carbon fiber (modulus is 350~600GPa) of high-modulus in the first electrolytic cell for filling alkalescent electrolyte
First segment anodized is carried out, to generate active atoms of carbon on high modulus carbon fiber surface.Specifically, alkalescent is electrolysed
Liquid is ammonium hydrogen carbonate, and the mass concentration of alkalescent electrolyte (is configured) for 5~10wt% using ultrapure water, preferably 7wt%,
The temperature of alkalescent electrolyte is 30~50 degrees Celsius, and preferably 40 degrees Celsius, the current density of first segment anodized is 5
~10A/m2.Inventors have found that can significantly be mentioned by carrying out anodized to high modulus carbon fiber under the above conditions
The oxidation efficiency of high carbon fiber, to improve the active atoms of carbon on high modulus carbon fiber surface, and carbon fiber under this condition
Tensile strength and the stretch modulus range of decrease are smaller.And first electrolytic cell 100 possesses the acid-alkali-corrosive-resisting electricity of independent constant-current supply
Solve slot, the bottom moving up and down being located in the first electrolytic cell 100 of the first cathode plate 10, so as to adjust the first sun in real time
The distance between pole deflector roll 11, second plate deflector roll 14 and first cathode plate 10 are improving carbon fiber oxidation efficiency while side
Just the cleaning of electrolytic cell, first cathode plate 10 are inert platinum electrode, and the first deflector roll 12 and the second deflector roll 13 are polytetrafluoroethyl-ne
Alkene deflector roll improves the oxidation efficiency of carbon fiber so as to avoid metal deflector roll band point from reacting but electrolyte is contaminated,
First anode deflector roll 11 and second plate deflector roll 14 are platinum-nickel alloy deflector roll, while the first electricity is equipped in the first electrolytic cell 100
Electrical conductivity instrument 15, which is movably located in the first electrolytic cell 100, so as to difference in a cell
Position is flexibly moved, and the temperature and concentration of alkalescent electrolyte in first electrolytic cell are monitored using conductivity meter, works as weak base
Property concentration of electrolyte when being lower conductivity can reduce, supply electrolyte and the temperature of electrode solution is kept to stablize.
According to an embodiment of the invention, the second electrolytic cell 200 and the first electrolytic cell 100 pass through third deflector roll 16 with reference to Fig. 2
It is connected, acidic electrolysis bath is filled in the second electrolytic cell 200, the bottom in the second electrolytic cell 200 is equipped with the second cathode plate 20, and
Along wire direction, third anode deflector roll 21, the 4th deflector roll 22, the 5th deflector roll 23 and are successively arranged on the second electrolytic cell 200
Four anode deflector rolls 24, the 4th deflector roll 22 and the 5th deflector roll 23 immerse acidic electrolysis bath.Specifically, by obtained in the first electrolytic cell
Carbon fiber, which is supplied into the second electrolytic cell for fill acidic electrolysis bath, carries out second segment anodized, can significantly improve carbon
The oxygen content of fiber surface improves the active group of carbon fiber surface, to enhance the interface cohesion between carbon fiber and resin
Power, while the carbon fiber hydrophily, lyophily enhance simultaneously, and surface can obviously increase.Specifically, acidic electrolysis bath is choosing
From at least one of ammonium sulfate and ammonium hydrogen sulfate, the concentration of acidic electrolysis bath is 5~10wt% (being configured using ultrapure water), excellent
Select 7wt%, the temperature of acidic electrolysis bath is 30~50 degrees Celsius, preferably 40 degrees Celsius, the electric current of second segment anodized
Density is 5~10A/m2.Inventors have found that by continuing to carry out anodized to carbon fiber under the above conditions, it can be with
The oxidation efficiency of carbon fiber is significantly improved, to improve the active function groups of carbon fiber surface, and then improves it with resin for example
Interface binding power between epoxy resin, while by the tensile strength and stretching of carbon fiber ontology under the conditions of the anodized
Modulus decline is lower.And second electrolytic cell 200 possesses the acid-alkali-corrosive-resisting electrolytic cell of independent constant-current supply, the second cathode plate
20 bottoms moving up and down being located in the second electrolytic cell 200, so as to adjust the 21, the 4th sun of third anode deflector roll in real time
The distance between pole deflector roll 24 and the second cathode plate 20 facilitate the cleaning of electrolytic cell while improving carbon fiber oxidation efficiency,
Second cathode plate 20 is inert platinum electrode, and the 4th deflector roll 22 and the 5th deflector roll 23 are polytetrafluoroethylene (PTFE) deflector roll, so as to
It avoids metal deflector roll band point from reacting but electrolyte is contaminated, improves the oxidation efficiency of carbon fiber, third anode deflector roll 21
It is platinum-nickel alloy deflector roll with the 4th anode deflector roll 24, while is equipped with the second conductivity meter 25 in the second electrolytic cell 200, this second
Conductivity meter 25 is movably located in the second electrolytic cell 200, is flexibly moved, is adopted so as to different location in a cell
The temperature and concentration that acidic electrolysis bath in second electrolytic cell is monitored with conductivity meter, it is electric when acidic electrolysis bath concentration is lower
Conductance can reduce, and the temperature of supply electrolyte and holding electrode solution is stablized.
According to an embodiment of the invention, the first rinsing bowl 300 is connected with the second electrolytic cell 200, the first rinsing bowl 300 is equipped with
First heating plate 30, and along wire direction, it is successively arranged the 6th deflector roll 31 and the 7th deflector roll 32 on the first rinsing bowl 300,
And it is suitable for carrying out washing process to carbon fiber obtained in above-mentioned second electrolytic cell.Specifically, water-washing process uses ultrapure water, and
And in the first rinsing bowl 300 washing temperature is improved by configuring the first heating plate 33, so that carbon fiber surface is remaining
Electrolyte is cleaned more thoroughly, and washing temperature is set as 60~80 degrees Celsius, preferably 70 degrees Celsius in the first rinsing bowl,
Water intake velocity is set as 450~550ml/min, preferably 500ml/min.And the 6th deflector roll 31 and the 7th deflector roll 32 are polytetrafluoro
Ethylene deflector roll.
According to an embodiment of the invention, the second rinsing bowl 400 is connected with the first rinsing bowl 300 with reference to Fig. 2, the second washing
Slot 400 is equipped with the second heating plate 40, and along wire direction, is successively arranged the 8th deflector roll the 41, the 9th on the second rinsing bowl 400
Deflector roll 42, the tenth deflector roll 43 and the 11st deflector roll 44, and be suitable for carrying out carbon fiber obtained in above-mentioned first rinsing bowl secondary
Washing process.Specifically, the water-washing process uses ultrapure water, and by configuring the second heating plate in the second rinsing bowl 400
40, washing temperature is improved, so that the electrolyte of carbon fiber surface remnants is cleaned more thoroughly, and in the second rinsing bowl
Washing temperature is set as 60~80 degrees Celsius, preferably 70 degrees Celsius, and in the height direction, and the second rinsing bowl 400 is higher than the
One rinsing bowl 300, the water after purification first flow into the second rinsing bowl, and liquid level is more than that the first rinsing bowl is flowed into after certain altitude, and first
Rinsing bowl is equipped with water outlet, will flow out from water outlet when the water in the first rinsing bowl reach a certain height.8th deflector roll 41,
Nine deflector rolls 42, the tenth deflector roll 43 and the 11st deflector roll 44 are polytetrafluoroethylene (PTFE) deflector roll.
According to an embodiment of the invention, tube drier 500 is connected with the second rinsing bowl 400 with reference to Fig. 2, and it is suitable for pair
Carbon fiber after the washing of the second rinsing bowl is dried.Drying temperature is set as 120~140 degrees Celsius, preferably 130
Degree Celsius, wherein along wire direction, tube drier 500 is arranged obliquely, so as to avoid traditional heated air drying to carbon fiber
The damage of ontology is tieed up, and then improves carbon fiber performance.
According to an embodiment of the invention, above-mentioned apparatus further comprises 600 He of alkalescent electrolyte circulator with reference to Fig. 2
Acidic electrolysis bath circulator 700, wherein alkalescent electrolyte circulator 600 is connected with the first electrolytic cell 100, so as to root
Electrolyte in the first electrolytic cell is supplemented according to the display of the first conductivity meter, keep the first electrolytic cell in electrolyte temperature and
Concentration it is constant；Acidic electrolysis bath circulator 700 is connected with the second electrolytic cell 200, so as to according to the second conductivity meter
Display supplements electrolyte in the second electrolytic cell, keeps the constant of electrolyte temperature and concentration in the second electrolytic cell.
It is carried out specifically, being surface-treated using above-mentioned apparatus to high modulus carbon fiber according to the following steps:
One, to the cleaning of equipment: will be miscellaneous in the first electrolytic cell, the second electrolytic cell, the first rinsing bowl and the second rinsing bowl
Matter is cleaned out and is rinsed 2~3 times with deionized water, with speckle with acetone first anode deflector roll of the cotton by surface treatment, the
One deflector roll, the second deflector roll, second plate deflector roll, third anode deflector roll, the 4th deflector roll, the 5th deflector roll and the 4th anode deflector roll,
Six deflector rolls, the 7th deflector roll, the 8th deflector roll, the 9th deflector roll, the tenth deflector roll and the 11st deflector roll scrub, wherein the first anode
Deflector roll to the 4th anode deflector roll diameter size is 99mm, remaining deflector roll is that roller diameter size is 99mm；
Two, the preparation of electrolyte: the acid-base property electrolyte that mass concentration is 5%~10% is prepared with ultrapure water and pours into first
In electrolytic cell and alkalescent electrolyte circulator, the temperature of circulator is set in 30~50 DEG C and is heated to electrolyte；It uses simultaneously
Ultrapure water is prepared the acidic electrolysis bath that mass concentration is 5%~10% and is poured into the second electrolytic cell and acidic electrolysis bath circulator,
The temperature of circulator is set in 30~50 DEG C to heat to electrolyte；
Three, the high modulus carbon fiber after graphite furnace being carbonized sequentially passes through the first electrolytic cell, the second electrolysis by as shown in Figure 2
(size of the first electrolytic cell and the second electrolytic cell is 125cm* for slot, the first rinsing bowl, the second rinsing bowl and tube drier
The size of 13cm*9cm, the first rinsing bowl and the second rinsing bowl is 140cm*15cm*10cm, and material is that plating nickel on surface chromium is stainless
Steel, tube drier, overall length 1.5m, internal diameter 6cm)；
Four, the deflector roll of starting surface treatment sets the output electric current of constant-current supply to regulate and control the first electrolytic cell and the second electricity
Cell current density is solved, the first rinsing bowl and the second rinsing bowl heater switch are opened, set tube drier heating temperature and is started
Heating；
Five, the first conductivity meter and the second conductivity meter are opened to monitor electrolyte in real time, starts to receive after stablizing 2 hours
Silk.
In the third aspect of the invention, the invention proposes a kind of surface modified carbon fibers.Implementation according to the present invention
Example, the surface modified carbon fiber are to adopt with the aforedescribed process or above-mentioned system is prepared.The carbon fiber surface as a result,
Active group with higher makes carbon fiber hydrophily, lyophily while enhancing, and surface can obviously increase, and the institute
The interlaminar shear strength for obtaining surface modified carbon fiber and epoxy resin composite material promotes 2 times or more.
In the fourth aspect of the invention, the invention proposes a kind of composite materials.According to an embodiment of the invention, described
Composite material is prepared using above-mentioned surface modified carbon fiber.Specifically, with surface modified carbon fiber obtained above with
For epoxy resin is compound, the interlaminar shear strength of the gained surface modified carbon fiber and epoxy resin composite material promotes 2 times
More than.
Below with reference to specific embodiment, present invention is described, it should be noted that these embodiments are only to describe
Property, without that should limit the invention in any way.
Embodiment 1
(1), the ammonium bicarbonate soln that mass concentration is 7% is prepared with ultrapure water pour into the first electrolytic cell and alkalescent electricity
In the liquid circulator of pole, the temperature of circulator is set in 40 DEG C and heats and circulates to electrolyte, while being prepared with ultrapure water
The ammonium bisulfate solution that mass concentration is 7% pours into the second electrolytic cell and acid electrode solution circulator, by the temperature of circulator
40 DEG C are set in heat and circulate to electrolyte；
(2), the first conductivity meter is switched on and starts to read, and opens when temperature reaches 40 DEG C and conductivity readings are stablized
DC power supply electric current is set as constant current mode, current density 10A/m by the DC power supply for opening the first electrolytic cell2, the second conductance
Rate instrument is switched on and starts to read, and the direct current of 40 DEG C and steady the second electrolytic cell of time opening of conductivity readings is reached to temperature
Second DC power supply electric current is set as constant current mode, current density 5A/m by source2；
(3), the water intake velocity of rinsing bowl is set as 500ml/min or so, and the first rinsing bowl heating temperature is 70 DEG C, the
Two rinsing bowl heating temperatures are set as 80 DEG C, and the drying temperature of tube drier is set as 130 DEG C；
(4), the carbon filament for collecting 1h not starching is used for the analysis of surface texture, collects carbon filament of the 5h Jing Guo starching for property
The test of energy.The full spectrogram of XPS of gained surface modified carbon fiber is as shown in figure 5, SEM schemes as shown in figure 9, it is multiple with epoxy resin
The SEM figure of composite material batten is as shown in figure 13 after conjunction.
Embodiment 2
(1), the ammonium bicarbonate soln that mass concentration is 7% is prepared with ultrapure water pour into the first electrolytic cell and alkalescent electricity
In the liquid circulator of pole, the temperature of circulator is set in 40 DEG C and heats and circulates to electrolyte, while being prepared with ultrapure water
The ammonium sulfate that mass concentration is 7% pours into the second electrolytic cell and acid electrode solution circulator, and the temperature of circulator is set
40 DEG C are scheduled on to heat and circulate to electrolyte；
(2), the first conductivity meter is switched on and starts to read, and opens when temperature reaches 40 DEG C and conductivity readings are stablized
DC power supply electric current is set as constant current mode, current density 10A/m by the DC power supply for opening the first electrolytic cell2, the second conductance
Rate instrument is switched on and starts to read, and the direct current of 40 DEG C and steady the second electrolytic cell of time opening of conductivity readings is reached to temperature
Second DC power supply electric current is set as constant current mode, current density 5A/m by source2；
(3), the water intake velocity of rinsing bowl is set as 500ml/min or so, and the first rinsing bowl heating temperature is 70 DEG C, the
Two rinsing bowl heating temperatures are set as 80 DEG C, and the drying temperature of tube drier is set as 130 DEG C；
(4), the carbon filament for collecting 1h not starching is used for the analysis of surface texture, collects carbon filament of the 5h Jing Guo starching for property
The test of energy.The full spectrogram of XPS of gained surface modified carbon fiber is as shown in fig. 6, SEM figure is as shown in Figure 10, with epoxy resin
The SEM figure of composite material batten is as shown in figure 14 after compound.
Comparative example 1
(1), the ammonium bicarbonate soln that mass concentration is 7% is prepared with ultrapure water pour into the first electrolytic cell and alkalescent electricity
In the liquid circulator of pole, the temperature of circulator is set in 40 DEG C and heats and circulates to electrolyte；
(2), the first conductivity meter is switched on and starts to read, and opens when temperature reaches 40 DEG C and conductivity readings are stablized
DC power supply electric current is set as constant current mode, current density 10A/m by the DC power supply for opening the first electrolytic cell2；
(3), the inlet valve of the first and second rinsing bowls is opened, water intake velocity is set as 500ml/min or so, starts
Heater switch sets the first rinsing bowl heating temperature as 70 DEG C, and the second rinsing bowl heating temperature is set as 80 DEG C；
(4), the heater switch for opening tube drier, is set as 130 DEG C for drying temperature；
(5), the carbon filament for collecting 1h not starching is used for the analysis of surface texture, collects carbon filament of the 5h Jing Guo starching for property
The test of energy.The full spectrogram of XPS of gained surface modified carbon fiber is as shown in figure 4, SEM schemes as shown in figure 8, it is multiple with epoxy resin
The SEM figure of composite material batten is as shown in figure 12 after conjunction.
Comparative example 2
The carbon fiber not being surface-treated in Examples 1 and 2 and comparative example 1.The full spectrogram of its XPS as shown in figure 3,
SEM figure is as shown in fig. 7, it is as shown in figure 11 with the SEM figure of epoxy resin composite material batten after compound.
In order to verify beneficial effects of the present invention, following tests has been done:
Test one: carbon fiber surface surface element relative amount changes high modulus carbon fiber surface treatment method before and after the processing, presses
Following steps are implemented: this test detects the element composition of carbon fiber surface using x-ray photoelectron spectroscopy (XPS), detection
As a result as shown in table 1 below.The oxygen content of carbon fiber surface mentions after one section of 1 ammonium hydrogen carbonate of comparative example oxidation as can be seen from Table 1
Liter is less obvious, and after embodiment 1 and the oxidation of 2 acidic electrolysis bath second segment of embodiment, oxygen content is promoted clearly, nitrogen
Content also increases one times or so, and it is preferable to the oxidation effectiveness of high modulus carbon fiber that this demonstrates the present invention.
The surface modified carbon fiber surface element relative amount and comparative example 2 that 1 embodiment 1,2 of table and comparative example 1 obtain
In unmodified carbon fiber surface surface element relative amount
| Sample | C1S | O1S | N1S | O1S/C1S | N1S/C1S |
| Embodiment 1 | 84.34 | 11.13 | 2.44 | 0.132 | 0.029 |
| Embodiment 2 | 81.28 | 14.32 | 1.97 | 0.176 | 0.024 |
| Comparative example 1 | 93.81 | 4.27 | 1.09 | 0.045 | 0.012 |
| Comparative example 2 | 98.06 | 1.65 | - | 0.017 | - |
Test two: high modulus carbon fiber surface treatment method before and after the processing carbon fiber contact angle and surface can variation, press
Following steps are implemented: moving for carbon fiber and water and diiodomethane is tested in this test using dynamic Contact angle tester (DCAT21)
State contact angle, then with OWRK formula go calculate carbon fiber surface can, as shown in table 2 below, it can be seen that by comparative example 1
After ammonium hydrogen carbonate first segment anodic oxidation, the contact angle of carbon fiber and water drops to 80.43 from 92.7, shows carbon fiber from hydrophobic
Property becomes hydrophily.And after Examples 1 and 2 second segment anodic oxidation, the hydrophily and lyophily of carbon fiber improve more
Add obviously, surface can also greatly increase.It is obvious that effect of the invention is demonstrated again.
Unmodified carbon fiber connects in the surface modified carbon fiber and comparative example 2 that 2 embodiment 1,2 of table and comparative example 1 obtain
Feeler and surface energy
Test three: the change of high modulus carbon fiber surface treatment method carbon fiber and its composite materials property before and after the processing
Change, implement according to the following steps: according to national standards, preparing the batten of tensile property of multi-filament, 8 battens of every group of sample preparation, and
It is tested under universal testing machine, obtains multifilament tensile strength and modulus such as the following table 3；Sample preparation and test are according to newest country
Carbon fiber and AG-80 epoxy resin are made a layer sample cutting item, and test carbon using 3 short beam methods by standard JC/T 773-2010
The interlaminar shear strength of fiber and AG-80 epoxy resin composite material is in the following table 3.
From table 3 it can be seen that the tensile strength of carbon fiber declines within 5% after surface treatment, illustrate the present invention to carbon
The damage of tensile strength of fiber is smaller；Carbon fiber multifilament stretch modulus is held essentially constant after surface treatment, is further demonstrated
The present invention damages carbon fiber mechanical property lower.And the interlayer shear from carbon fiber and AG-80 epoxy resin composite material is strong
It can be seen that, when the carbon fiber obtained using comparative example 1, interlaminar shear strength is promoted from 27MPa to 71MPa in degree variation,
Improve 1.63 times；When the carbon fiber obtained using Examples 1 and 2, gained carbon fiber and AG-80 epoxy resin composite material layer
Between shear strength compared to untreated sample improve 2 times or more, further demonstrate the present invention to high modulus carbon fiber
Surface treatment effect is fairly obvious.
Unmodified carbon fiber power in the surface modified carbon fiber and comparative example 2 that 3 embodiment 1,2 of table and comparative example 1 obtain
Learn performance
| Sample | Tensile strength/GPa | Stretch modulus/GPa | Interlaminar shear strength/MPa |
| Embodiment 1 | 3.88 | 415 | 85 |
| Embodiment 2 | 3.92 | 413 | 94 |
| Comparative example 1 | 3.95 | 415 | 71 |
| Comparative example 2 | 4.03 | 416 | 27 |
The above is only preferred embodiments of the invention, it is noted that for the ordinary skill people of the art
For member, without departing from the technical principles of the invention, several improvements and modifications can also be made, these improvements and modifications
Also it should be regarded as the protection scope that do not invent.
Claims (10)
1. a kind of high modulus carbon fiber surface treatment method, wherein include:
(1) first segment anodized is carried out to high modulus carbon fiber using alkalescent electrolyte, so as in the high-modulus
Carbon fiber surface generates active atoms of carbon；
(2) second segment anodized is carried out to the carbon fiber that step (1) obtains using acidic electrolysis bath, so as in the carbon
Fiber surface forms active group.
2. the method for claim 1, wherein in step (1), the modulus of the high modulus carbon fiber is 350~
600GPa。
Optional, the alkalescent electrolyte is ammonium hydrogen carbonate；
Optional, the mass concentration of the alkalescent electrolyte is 5~10wt%；
Optional, the temperature of the alkalescent electrolyte is 30~50 degrees Celsius；
Optional, the current density of the first segment anodized is 5~10A/m2。
3. the acidic electrolysis bath is selected from ammonium sulfate and sulfuric acid the method for claim 1, wherein in step (2)
At least one of hydrogen ammonium；
Optional, the concentration of the acidic electrolysis bath is 5~10wt%；
Optional, the temperature of the acidic electrolysis bath is 30~50 degrees Celsius；
Optional, the current density of the second segment anodized is 5~10A/m2。
4. the method for claim 1, wherein further comprising:
(3) carbon fiber that step (2) obtains is washed and is dried.
5. a kind of device of high modulus carbon fiber surface treatment, wherein include:
First electrolytic cell fills alkalescent electrolyte in first electrolytic cell, and the bottom in first electrolytic cell is equipped with the
One cathode plate, and along wire direction, first anode deflector roll, the first deflector roll, second are successively arranged on first electrolytic cell
Deflector roll and second plate deflector roll, first deflector roll and second deflector roll immerse the alkalescent electrolyte；
Second electrolytic cell, second electrolytic cell are connected with first electrolytic cell by third deflector roll, second electrolytic cell
Acidic electrolysis bath is inside filled, the bottom in second electrolytic cell is equipped with the second cathode plate, and along wire direction, and described the
Be successively arranged third anode deflector roll, the 4th deflector roll, the 5th deflector roll and the 4th anode deflector roll on two electrolytic cells, the 4th deflector roll and
5th deflector roll immerses the acidic electrolysis bath；
First rinsing bowl, first rinsing bowl are connected with second electrolytic cell, and first rinsing bowl is equipped with the first heating
Plate, and along wire direction, the 6th deflector roll and the 7th deflector roll are successively arranged on first rinsing bowl；
Second rinsing bowl, the second rinsing bowl are connected with first rinsing bowl, and second rinsing bowl is equipped with the second heating plate, and
And along wire direction, the 8th deflector roll, the 9th deflector roll, the tenth deflector roll and the 11st are successively arranged on second rinsing bowl and is led
Roller；
Tube drier, the tube drier are connected with second rinsing bowl.
6. device as claimed in claim 5, wherein first cathode plate is moving up and down to be located at first electrolytic cell
Interior bottom, second cathode plate bottom moving up and down being located in second electrolytic cell；
Optional, first cathode plate and second cathode plate are platinum electrode；
Optional, the first anode deflector roll, the second plate deflector roll, the third anode deflector roll and the 4th anode are led
Roller is platinum-nickel alloy deflector roll；
It is optional, first deflector roll, second deflector roll, the third deflector roll, the 4th deflector roll, the 5th deflector roll,
6th deflector roll, the 7th deflector roll, the 8th deflector roll, the 9th deflector roll, the tenth deflector roll and the described 11st
Deflector roll is polytetrafluoroethylene (PTFE) deflector roll.
7. device as claimed in claim 5, wherein be equipped with the first conductivity meter, first electricity in first electrolytic cell
Electrical conductivity instrument is movably located in first electrolytic cell；
Optional, the second conductivity meter is equipped in second electrolytic cell, second conductivity meter is movably located at described
In second electrolytic cell；
Optional, along wire direction, the tube drier is arranged obliquely；
Optional, in the height direction, second rinsing bowl is higher than first rinsing bowl.
8. device as claimed in claim 5, wherein further comprise: alkalescent electrolyte circulator, the alkalescent electrolysis
Liquid circulator is connected with first electrolytic cell；
Optional, described device further comprises: acidic electrolysis liquid bath circulator, the acidic electrolysis liquid bath circulator with it is described
Second electrolytic cell is connected.
9. a kind of surface modified carbon fiber, wherein the surface modified carbon fiber is using described in any one of claim 1-4
Method or any one of claim 5-8 described in system be prepared.
10. a kind of composite material, wherein the composite material is prepared into using surface modified carbon fiber as claimed in claim 9
It arrives.
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| CN114182453A (en) * | 2021-12-22 | 2022-03-15 | 张家港市港鹰实业有限公司 | Carbon fiber surface treatment device and use method thereof |
| CN114182453B (en) * | 2021-12-22 | 2023-12-05 | 张家港市港鹰实业有限公司 | Carbon fiber surface treatment device and application method thereof |
| CN114892393A (en) * | 2022-06-29 | 2022-08-12 | 北京化工大学 | Carbon fiber device based on MXene phase modification |
| CN114892393B (en) * | 2022-06-29 | 2023-01-20 | 北京化工大学 | Carbon fiber device based on MXene phase modification |
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