CN103806274A - Polymer surface grafting method for carbon fiber - Google Patents
Polymer surface grafting method for carbon fiber Download PDFInfo
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- CN103806274A CN103806274A CN201410074498.6A CN201410074498A CN103806274A CN 103806274 A CN103806274 A CN 103806274A CN 201410074498 A CN201410074498 A CN 201410074498A CN 103806274 A CN103806274 A CN 103806274A
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Abstract
The invention relates to a polymer surface grafting method for a carbon fiber, and aims to overcome the defects of high system temperature, difficulty in control over conditions, solvent environment unfriendliness and limited monomer selection of an existing grafting from method. The method comprises the following steps: (1) removing an epoxy coating; (2) oxidizing the carbon fiber; (3) acylating and chlorinating the carbon fiber to obtain the acylated and chlorinated carbon fiber; (4) performing alcoholysis on the carbon fiber; and (5) grafting a polymer under a Ce<4+> initiating system of the carbon fiber to complete the operation. According to the method, reaction conditions of a Ce<4+> oxidation-reduction initiating system are mild, the operation is simple, monomers with different characteristics can be selected, and different performances are provided; the polymer can carry a great number of polar groups, so that the surface activity of the carbon fiber is improved, and the interfacial bonding quality of the carbon fiber and resin is further improved. The invention relates to the field of carbon fiber modification.
Description
Technical field
The present invention relates to a kind of method of carbon fiber surface graft polymers.
Background technology
Carbon fiber is the reinforcement material often using in current high performance resin based composites, there is high specific strength and specific modulus, coefficient of thermal expansion is low, good stability of the dimension, thermal conductivity is good, the features such as the good and Heat stability is good of weatherability, are widely used in the various fields such as Aeronautics and Astronautics, defence and military, building, machinery, electronics, medical treatment, bioengineering.Carbon fiber is due to its smooth surface, and the content of active function groups is few, and surface is the features such as inertia and has had influence on the interfacial combined function between carbon fiber and resin matrix, thereby has affected the performance of carbon fibre composite entirety excellent properties.
Conventional carbon fiber surface modification method has oxidizing process, cladding process and radiation method etc.Oxidizing process is divided into gaseous oxidation, liquid phase oxidation, electrochemicial oxidation, in increasing carbon fiber surface activity group number, has the problem of the oxidation limit.Cladding process is divided into the methods such as electrochemical deposition and chemical plating, vapour deposition, surface electrical polymerization, sol-gel process, particle beams spraying; can avoid being oxidized the limit; little molecule applicator can better improve surface-activity point utilization rate; can play a protective role to carbon fiber, but interface binding power is not high simultaneously.Radiation method refers to that methods such as adopting gamma-rays, laser, ion beam injection, ultra-violet radiation, plasma processes carbon fiber, realizes etching and cleaning to carbon fiber surface, increases specific area, introduces active group, but easily causes the damage of fiber.
" grafting from " method in chemical graft is to realize a kind of the most effective method of high percent grafting.The method is on carbon fiber surface, to introduce active site, and under certain initiation conditions, on active site, produce initial free radical, trigger monomer carries out chain propagation reaction on carbon fiber surface, finally realize carbon fiber surface graft polymers, improve the activity of carbon fiber surface, increase the binding ability of carbon fiber and resin boundary surface.But existing employing " grafting from " method realizes carbon fiber surface glycerol polymerization, exists temperature of reaction system higher, and condition is wayward, the not environmental protection of system solvent, monomer is selected the shortcomings such as restricted.
Summary of the invention
The system temperature that the object of the invention is existing in order to solve " grafting from " method is high, and condition is wayward, and not environmental protection of solvent and monomer are selected restricted shortcoming, and a kind of method of carbon fiber surface graft polymers is provided.
The method of a kind of carbon fiber surface graft polymers of the present invention is to be undertaken by following steps:
One, remove epoxy coating;
Two, carbon oxide fiber: at normal temperatures, mixed solution 35～the 50ml of preparation potassium permanganate and sulfuric acid, wherein, the consumption of potassium permanganate is 0.35～0.60g, the concentration of sulfuric acid is 1～2mol/L, then the carbon fiber that is 0.35～0.70g by quality is put into the mixed solution of potassium permanganate and sulfuric acid, pour into after teat glass, put into overcritical device, it is 320～340 ℃ in temperature, pressure is the interior reaction of system 15～25min of 2～5MPa, then after carbon fiber being taken out, put into the beaker that mass concentration is 37.5% hydrochloric acid is housed, after good seal, put into the water-bath of 55～65 ℃, soak 2～4h, again put into apparatus,Soxhlet's, at 80 ℃, with ethanol cleaning carbon fiber 2～3h, then carbon fiber is taken out, be placed in the dry 2～4h of 70～80 ℃ of baking ovens, carbon fiber after being oxidized,
Three, the chloride of carbon fiber: the carbon fiber after step 2 oxidation is carried out to chloride, obtain the carbon fiber after chloride;
Four, the alcoholysis of carbon fiber: will add glycol and the 2-7ml triethylamine of 30-50ml in dry reaction bulb, after mixing, then add the carbon fiber after step 3 chloride, sealing, puts into water-bath by reaction bulb, constant temperature 24-72h at 60-80 ℃; Then put into apparatus,Soxhlet's, clean 1-4h with absolute ethyl alcohol extracting, then put into air dry oven, dry 2-5h at 70-90 ℃; Obtain the carbon fiber after alcoholysis; Wherein glycol is ethylene glycol, Macrogol 200, PEG400 or Macrogol 600;
Five, the Ce of carbon fiber
4+inducing Graft Polymerization thing:
A, take the acrylamide of 0.7108-4.9756g, be dissolved in the water of 50-80ml, be mixed with the aqueous solution of acrylamide;
B, measure the concentrated nitric acid solution of 1～2ml, be dissolved in the water of 20-50ml, be mixed with dilute nitric acid solution;
C, take the ammonium ceric nitrate of 0.05～1.10g, be dissolved in the dilute nitric acid solution of step b preparation the acidic aqueous solution of preparation ammonium ceric nitrate;
D, be placed in there-necked flask being tied with bezel and the magnet rotor of carbon fiber after alcoholysis, in there-necked flask, add the acrylamide monomer aqueous solution of preparing in step a, be then filled with nitrogen, drip the acidic aqueous solution of the ammonium ceric nitrate of step c simultaneously, after 15-30min, stop being filled with nitrogen, sealing;
E, the there-necked flask after steps d sealing is entered in constant temperature magnetic force heating stirrer, at 25～65 ℃, react 2.5～10h, then take out and put into apparatus,Soxhlet's, with the water cleaning 3～4h of 100 ℃, put into again air dry oven, dry at 80 ℃, to constant weight, complete the method for carbon fiber surface graft polymers.
The inventive method is except having the advantage of " grafting from " the high percent grafting of method, system Ce
4+redox initiation reaction mild condition, simple to operate, and can select the monomer of different qualities, provide different performance, and polymer can be with a large amount of polar groups, improve the activity of carbon fiber surface, improve to the greatest extent the interface quality of carbon fiber and resin.
Accompanying drawing explanation
Fig. 1 is the flow chart of test 1;
Fig. 2 is the full spectrogram of XPS of (Cleaned CF) carbon fiber after the destarch prepared of test 1 step 1;
Fig. 3 is the full spectrogram of XPS of rear (Oxidized CF) carbon fiber of test 1 step 2 oxidation;
Fig. 4 is the full spectrogram of XPS of the carbon fiber of (CF-EG) after the grafting ethylene glycol prepared of test 1 step 4;
Fig. 5 is the full spectrogram of (CF-EG-PAM) carbon fiber XPS after the grafted polyacrylamide homopolymers prepared of test 1 step 5;
Fig. 6 is the full spectrogram of XPS of (CF-PEG400-PAM) carbon fiber after the grafting PEG400 prepared of test 2 step 4;
Fig. 7 is the full spectrogram of (CF-PEG400-PAM) carbon fiber after the test grafting PEG400 prepared of 2 step 5 and polyacrylamide block copolymer;
Fig. 8 is (Cleaned CF) carbon fiber N1s peak matched curve figure after the destarch prepared of test 1 step 1;
Fig. 9 is (CF-EG-PAM) the carbon fiber N1s peak matched curve figure testing after the 1 grafted polyacrylamide homopolymers of preparing;
Figure 10 be test 2 preparation grafting PEG400s and polyacrylamide block copolymer after (CF-PEG400-PAM) carbon fiber N1s peak matched curve figure;
Figure 11 is the surface topography map of (Cleaned CF) carbon fiber after the destarch prepared of test 1 step 1;
Figure 12 for test 1 step 2 oxidation after Oxidized CF) surface topography map of carbon fiber;
Figure 13 is (CF-EG) carbon fiber surface shape appearance figure after the grafting ethylene glycol prepared of test 1 step 4;
Figure 14 is the carbon fiber surface shape appearance figure of (CF-EG-PAM) after the grafted polyacrylamide homopolymers of test 1 preparation;
Figure 15 is (CF-PEG400) carbon fiber surface shape appearance figure after the grafting PEG400 prepared of test 2 step 4;
Figure 16 is (CF-PEG400-PAM) carbon fiber surface shape appearance figure after the test grafting PEG400 prepared of 2 step 5 and polyacrylamide block copolymer;
Figure 17 is the carbon fiber of test 1 preparation and the interface shear strength figure of epoxy resin.
The specific embodiment
The specific embodiment one: the method for a kind of carbon fiber surface graft polymers of present embodiment is to be undertaken by following steps:
One, remove epoxy coating;
Two, carbon oxide fiber: at normal temperatures, mixed solution 35～the 50ml of preparation potassium permanganate and sulfuric acid, wherein, the consumption of potassium permanganate is 0.35～0.60g, the concentration of sulfuric acid is 1～2mol/L, then the carbon fiber that is 0.35～0.70g by quality is put into the mixed solution of potassium permanganate and sulfuric acid, pour into after teat glass, put into overcritical device, it is 320～340 ℃ in temperature, pressure is the interior reaction of system 15～25min of 2～5MPa, then after carbon fiber being taken out, put into the beaker that mass concentration is 37.5% hydrochloric acid is housed, after good seal, put into the water-bath of 55～65 ℃, soak 2～4h, again put into apparatus,Soxhlet's, at 80 ℃, with ethanol cleaning carbon fiber 2～3h, then carbon fiber is taken out, be placed in the dry 2～4h of 70～80 ℃ of baking ovens, carbon fiber after being oxidized,
Three, the chloride of carbon fiber: the carbon fiber after step 2 oxidation is carried out to chloride, obtain the carbon fiber after chloride:
Four, the alcoholysis of carbon fiber: will add glycol and the 2-7ml triethylamine of 30-50ml in dry reaction bulb, after mixing, then add the carbon fiber after step 3 chloride, sealing, puts into water-bath by reaction bulb, constant temperature 24-72h at 60-80 ℃; Then put into apparatus,Soxhlet's, clean 1-4h with absolute ethyl alcohol extracting, then put into air dry oven, dry 2-5h at 70-90 ℃; Obtain the carbon fiber after alcoholysis; Wherein glycol is ethylene glycol, Macrogol 200, PEG400 or Macrogol 600;
Five, the Ce of carbon fiber
4+inducing Graft Polymerization thing:
A, take the acrylamide of 0.7108-4.9756g, be dissolved in the water of 50-80ml, be mixed with the aqueous solution of acrylamide;
B, measure the concentrated nitric acid solution of 1～2ml, be dissolved in the water of 20-50ml, be mixed with dilute nitric acid solution;
C, take the ammonium ceric nitrate of 0.05～1.10g, be dissolved in the dilute nitric acid solution of step b preparation the acidic aqueous solution of preparation ammonium ceric nitrate;
D, be placed in there-necked flask being tied with bezel and the magnet rotor of carbon fiber after step 4 alcoholysis, in there-necked flask, add the acrylamide monomer aqueous solution of preparing in step a, then be filled with nitrogen, drip the acidic aqueous solution of the ammonium ceric nitrate of step c simultaneously, after 15-30min, stop being filled with nitrogen, sealing;
E, the there-necked flask after steps d sealing is entered in constant temperature magnetic force heating stirrer, at 25～65 ℃, react 2.5～10h, then take out and put into apparatus,Soxhlet's, with the water cleaning 3～4h of 100 ℃, put into again air dry oven, dry at 80 ℃, to constant weight, complete the method for carbon fiber surface graft polymers.
The method of present embodiment is except having the advantage of " grafting from " the high percent grafting of method, system Ce
4+redox initiation reaction mild condition, simple to operate, and can select the monomer of different qualities, provide different performance, and polymer can be with a large amount of polar groups, improve the activity of carbon fiber surface, improve to the greatest extent the interface quality of carbon fiber and resin.
The specific embodiment two: present embodiment is different from the specific embodiment one: the method for the removal epoxy coating described in step 1 is: carbon fiber bundle is put into apparatus,Soxhlet's, acetone to 75～85 ℃ in heating apparatus,Soxhlet's, maintain 2～8h, then put into overcritical device, it is 350～370 ℃ in temperature, pressure is to soak 20～30min in overcritical acetone～aqueous systems of 8～14MPa, and then put into apparatus,Soxhlet's, in the acetone of 75～85 ℃, clean carbon fiber 2～4h, again carbon fiber is taken out, be placed in the dry 2～4h of 70～80 ℃ of baking ovens, complete.Other are identical with the specific embodiment one.
The specific embodiment three: present embodiment is different from the specific embodiment one or two: described overcritical acetone～aqueous systems is made up of 25mL acetone and 5mL water.Other are identical with the specific embodiment one or two.
The specific embodiment four: present embodiment is different from one of specific embodiment one to three: the method for the carbon oxide fiber described in step 2 is: at normal temperatures, the mixed solution 50ml of preparation potassium permanganate and sulfuric acid, wherein, the consumption of potassium permanganate is 0.5g, the concentration of sulfuric acid is 1mol/L, then the carbon fiber that is 0.5g by quality is put into the mixed solution of potassium permanganate and sulfuric acid, pour into after teat glass, put into overcritical device, it is 320 ℃ in temperature, pressure is the interior reaction of the system 20min of 2MPa, then after carbon fiber being taken out, put into the beaker that mass concentration is 37.5% hydrochloric acid is housed, after good seal, put into the water-bath of 65 ℃, soak 6h, again put into apparatus,Soxhlet's, at 80 ℃, with ethanol cleaning carbon fiber 2h, then carbon fiber is taken out, being placed in the dry 4h of 80 ℃ of baking ovens completes.Other are identical with one of specific embodiment one to three.
The specific embodiment five: present embodiment is different from one of specific embodiment one to four: the method for the carbon fiber chloride described in step 3 is: pack the thionyl chloride of 80mL and the N of 5mL in dry reaction bulb into, N～dimethyl formamide, mix the carbon fiber of then putting into after oxidation processes, at 75 ℃, add hot reflux 48h and take out again carbon fiber, and at 80 ℃, dry 2h in air dry oven, complete.Other are identical with one of specific embodiment one to four.
By following verification experimental verification beneficial effect of the present invention:
One, remove epoxy coating;
Two, carbon oxide fiber: at normal temperatures, the mixed solution 50ml of preparation potassium permanganate and sulfuric acid, wherein, the consumption of potassium permanganate is 0.5g, the concentration of sulfuric acid is 1mol/L, then the carbon fiber that is 0.5g by quality is put into the mixed solution of potassium permanganate and sulfuric acid, pour into after teat glass, put into overcritical device, it is 320 ℃ in temperature, pressure is the interior reaction of the system 20min of 2MPa, then after carbon fiber being taken out, put into the beaker that mass concentration is 37.5% hydrochloric acid is housed, after good seal, put into the water-bath of 65 ℃, soak 6h, again put into apparatus,Soxhlet's, at 80 ℃, with ethanol cleaning carbon fiber 2h, then carbon fiber is taken out, be placed in the dry 4h of 80 ℃ of baking ovens, carbon fiber after being oxidized,
Three, the chloride of carbon fiber: the carbon fiber after step 2 oxidation is carried out to chloride, obtain the carbon fiber after chloride;
Four, the alcoholysis of carbon fiber: will add glycol and the 5ml triethylamine of 40ml in dry reaction bulb, after mixing, then add the carbon fiber after step 3 chloride, sealing, puts into water-bath by reaction bulb, constant temperature 48h at 75 ℃; Then put into apparatus,Soxhlet's, at 80 ℃, clean 2h with ethanol, then put into air dry oven, dry 3h at 80 ℃; Obtain the carbon fiber after alcoholysis; Wherein glycol is ethylene glycol;
Five, the Ce of carbon fiber
4+inducing Graft Polymerization thing:
A, take the acrylamide of 3.554g, be dissolved in the water of 75ml, be mixed with the aqueous solution of acrylamide;
B, measure the concentrated nitric acid solution of 1～2ml, be dissolved in the water of 25ml, be mixed with dilute nitric acid solution;
C, take the ammonium ceric nitrate of 1.0964g, be dissolved in the dilute nitric acid solution of step b preparation the acidic aqueous solution of preparation ammonium ceric nitrate;
D, be placed in there-necked flask being tied with bezel and the magnet rotor of carbon fiber after step 4 alcoholysis, in there-necked flask, add the acrylamide aqueous solution of preparing in step a, be then filled with nitrogen, drip the acidic aqueous solution of the ammonium ceric nitrate of step c simultaneously, after 20min, stop being filled with nitrogen, sealing;
E, the there-necked flask after steps d sealing is entered in constant temperature magnetic force heating stirrer, at 45 ℃, react 5h, then take out and put into apparatus,Soxhlet's, with the water cleaning 3～4h of 100 ℃, put into again air dry oven, dry at 80 ℃, to constant weight, complete a kind of method of carbon fiber surface graft polymers.
The flow chart of this test as shown in Figure 1.
One, remove epoxy coating;
Two, carbon oxide fiber: at normal temperatures, the mixed solution 50ml of preparation potassium permanganate and sulfuric acid, wherein, the consumption of potassium permanganate is 0.5g, the concentration of sulfuric acid is 1mol/L, then the carbon fiber that is 0.5g by quality is put into the mixed solution of potassium permanganate and sulfuric acid, pour into after teat glass, put into overcritical device, it is 320 ℃ in temperature, pressure is the interior reaction of the system 20min of 2MPa, then after carbon fiber being taken out, put into the beaker that mass concentration is 37.5% hydrochloric acid is housed, after good seal, put into the water-bath of 65 ℃, soak 6h, again put into apparatus,Soxhlet's, at 80 ℃, with ethanol cleaning carbon fiber 2h, then carbon fiber is taken out, be placed in the dry 4h of 80 ℃ of baking ovens, carbon fiber after being oxidized,
Three, the chloride of carbon fiber: the carbon fiber after step 2 oxidation is carried out to chloride, obtain the carbon fiber after chloride;
Four, the alcoholysis of carbon fiber: will add glycol and the 5ml triethylamine of 40ml in dry reaction bulb, after mixing, then add the carbon fiber after step 3 chloride, sealing, puts into water-bath by reaction bulb, constant temperature 48h at 75 ℃; Then put into apparatus,Soxhlet's, at 80 ℃, clean 2h with ethanol, then put into air dry oven, dry 3h, obtains the carbon fiber after alcoholysis at 80 ℃; Wherein glycol is PEG400;
Five, the Ce of carbon fiber
4+inducing Graft Polymerization thing:
A, take the acrylamide of 3.554g, be dissolved in the water of 75ml, be mixed with the aqueous solution of acrylamide;
B, measure the concentrated nitric acid solution of 1～2ml, be dissolved in the water of 25ml, be mixed with dilute nitric acid solution;
C, take the ammonium ceric nitrate of 1.0964g, be dissolved in the dilute nitric acid solution of step b preparation the acidic aqueous solution of preparation ammonium ceric nitrate;
D, be placed in there-necked flask being tied with bezel and the magnet rotor of carbon fiber after step 4 alcoholysis, in there-necked flask, add the acrylamide aqueous solution of preparing in step a, be then filled with nitrogen, drip the acidic aqueous solution of the ammonium ceric nitrate of step c simultaneously, after 20min, stop being filled with nitrogen, sealing;
E, the there-necked flask after steps d sealing is entered in constant temperature magnetic force heating stirrer, at 45 ℃, react 5h, then take out and put into apparatus,Soxhlet's, with the water cleaning 3～4h of 100 ℃, put into again air dry oven, dry at 80 ℃, to constant weight, complete a kind of method of carbon fiber surface graft polymers.
The method of the removal epoxy coating described in test 1 and test 2 step 1 is: carbon fiber bundle is put into apparatus,Soxhlet's, acetone to 75～85 ℃ in heating apparatus,Soxhlet's, maintain 2～8h, then put into overcritical device, it is 350～370 ℃ in temperature, pressure is to soak 20～30min in the overcritical acetone-water system of 8～14MPa, and then put into apparatus,Soxhlet's, in the acetone of 75～85 ℃, clean carbon fiber 2～4h, again carbon fiber is taken out, be placed in the dry 2～4h of 70～80 ℃ of baking ovens, complete; Wherein overcritical acetone-water system is made up of 25mL acetone and 5mL water.
The method of the carbon oxide fiber described in test 1 and test 2 step 2 is: the method for the carbon oxide fiber described in step 2 is: at normal temperatures, the mixed solution 50ml of preparation potassium permanganate and sulfuric acid, wherein, the consumption of potassium permanganate is 0.5g, the concentration of sulfuric acid is 1mol/L, then the carbon fiber that is 0.5g by quality is put into the mixed solution of potassium permanganate and sulfuric acid, pour into after teat glass, put into overcritical device, it is 320 ℃ in temperature, pressure is the interior reaction of the system 20min of 2MPa, then after carbon fiber being taken out, put into the beaker that mass concentration is 37.5% hydrochloric acid is housed, after good seal, put into the water-bath of 65 ℃, soak 6h, again put into apparatus,Soxhlet's, at 80 ℃, with ethanol cleaning carbon fiber 2h, then carbon fiber is taken out, being placed in the dry 4h of 80 ℃ of baking ovens completes.
The method of the carbon fiber chloride described in test 1 and test 2 step 3 is: in dry reaction bulb, pack the thionyl chloride of 80mL and the N of 5mL into, N～dimethyl formamide, mix the carbon fiber of then putting into after oxidation processes, at 75 ℃, add hot reflux 48h and take out again carbon fiber, and at 80 ℃, dry 2h in air dry oven, complete.
By XPS to through overtesting 1, test 2 carbon fibers after treatment, comprise the carbon fiber of destarch, oxidation, grafting ethylene glycol, grafted polyacrylamide homopolymers, grafting PEG400 and polyacrylamide copolymer, carry out surface-element and constituent content analysis, specifically see Fig. 2～Fig. 7 and table 1.From Fig. 2～7, the carbon fiber surface of destarch, oxidation and grafting ethylene glycol mainly contains C and two kinds of elements of O, N constituent content is less, in the full spectrogram of XPS without obvious characteristic peak, and after grafted polyacrylamide, in the XPS collection of illustrative plates of CF-EG-PAM and CF-PEG400-PAM, there is the characteristic peak of obvious N element.As shown in Table 1, the N constituent content of CF-EG-PAM is increased to 9.05% from the 3.81% N constituent content that is increased to 10.69%, CF-PEG400-PAM from 3.81%.
Table 1 test 1 and test 2 each step process after the surface-element content of carbon fiber
| Sample | C(%) | O(%) | N(%) | Ce(%) | N/C | O/C |
| CleanedCF | 93.24 | 3.95 | 3.81 | - | 0.041 | 0.042 |
| OxidizedCF | 78.96 | 15.98 | 4.47 | - | 0.057 | 0.202 |
| CF-EG | 78.08 | 20.64 | 1.08 | - | 0.014 | 0.264 |
| CF-PEG-PAM | 78.13 | 21.25 | 0.62 | ? | 0.008 | 0.272 |
| CF-EG-PAM | 64.31 | 24.70 | 10.69 | 0.30 | 0.166 | 0.384 |
| CF-PEG400-PAM | 64.67 | 25.48 | 9.05 | 0.80 | 0.140 | 0.394 |
Fig. 8～Figure 10 is respectively carbon fiber after destarch, the carbon fiber surface N1s peak matched curve of grafted polyacrylamide homopolymers carbon fiber and grafting PEG400 and polyacrylamide copolymer.The relative amount that table 2 is the different carbon fiber N1s matching Hou Ge functional group of answering in contrast.As can be seen from Figure 8, in the carbon fiber N1s matched curve after destarch, only have a curve, in conjunction with being 400.5eV, corresponding carbon fiber surface-nitrogen element in CN key, illustrate that now carbon fiber surface is without the nitrogen element of other combining forms.From Fig. 9 and Figure 10, can find out there are two curves in the carbon fiber N1s matched curve after grafted polyacrylamide, in conjunction with being respectively 400.5eV and 399.5eV, correspondence-CN key and O=C-NH
2in nitrogen element.As can be seen from Table 2, the carbon fiber surface O=C-NH after destarch
2in nitrogen element relative amount be 0%, and carbon fiber surface O=C-NH after grafted polyacrylamide
2in nitrogen element relative amount greatly increase, the wherein carbon fiber surface O=C-NH of grafted polyacrylamide homopolymers (CF-EG-PAM)
2in nitrogen element relative amount be increased to 87.80%, the carbon fiber surface O=C-NH of grafting PVOH 400 and polyacrylamide copolymer (CF-PEG400-PAM)
2in nitrogen element relative amount be increased to 82.50%.Carbon fiber surface O=C-NH
2in the obvious increase of nitrogen element relative amount, the remarkable reduction of nitrogen element relative amount in-CN, illustrates that polyacrylamide has been grafted to carbon fiber surface.
Table 2 test 1 and test 2 preparation carbon fiber N1s curve data
Table 3 is that the carbon fiber dynamic contact angle of destarch, grafted polyacrylamide homopolymers (CF-EG-PAM) and grafting polyethylene glycol and polyacrylamide block copolymer (CF-PEG400-PAM) can data with surface.Compared with carbon fiber after destarch, the carbon fibre surface energy after grafted polyacrylamide just increases substantially, and wherein polar component improves significantly.The polar component of CF-EG-PAM is from 29.84mNm
-1be increased to 94.13mNm
-1, surface can be from 37.45mNm
-1be increased to 100.65mNm
-1, increase rate is 168.75%.The polar component of CF-PEG400-PAM is from 29.84mNm
-1be increased to 101.55mNm
-1, surface can be from 37.45mNm
-1be increased to 110.16mNm
-1, increase rate is 190.15%.Increasing substantially of carbon fibre surface energy after grafted polyacrylamide, proves after reason, to have increased after grafting the active functional group content of carbon fiber surface, and preparation reinforcement and resin matrix have good wettability, and this result is consistent with XPS analysis above.
Figure 11～Figure 16 is the micromorphology figure of carbon fiber after treatment.As can be seen from Figure 11, de-by after carbon fiber surface smooth, prolonging longitudinal direction has groove clearly.As can be seen from Figure 12, the carbon fiber surface after oxidation is more coarse, and groove significant degree reduces, and illustrates when oxidation system improves carbon fiber surface polar group, carbon fiber surface has been carried out to corrasion simultaneously, has improved the roughness of carbon fiber surface.From Figure 13 and Figure 15, can find out, the carbon fiber surface groove after grafting ethylene glycol and PEG400 becomes not obvious, and ethylene glycol and polyethylene glycol are more evenly grafted on carbon fiber surface.As can be seen from Figure 14, the carbon fiber surface that grafted polyacrylamide homopolymers closes has obvious material to exist, and the material that groove place exists is more, has curling shape, and meanwhile, carbon fiber surface surface roughness increases, and presents scraggly surface.These explanations, Polyacrylamide Grafted has arrived on carbon fiber surface, has improved carbon fiber surface polarity, has increased the surface roughness of carbon fiber simultaneously.As can be seen from Figure 16, the carbon fiber surface after grafting PEG400 and polyacrylamide block copolymer has obvious particulate material, and some particle presents reunion state, and the distribution uniform of particle does not exist groove and non-groove place distributional difference.
Table 3 test 1 and test 2 each phase process after carbon fibre surface energy data
Figure 17 is the interface shear strength figure of carbon fiber and epoxy resin after above-mentioned processing.As can be seen from Figure 17, the carbon fiber of destarch and the interface shear strength of epoxy resin are not increased to 62.31MPa from 56.35MPa, and increase rate is 10.57%; The shear strength of CF-EG-PAM is increased to 70.52MPa from 56.35MPa, and increase rate is 24.37%; The shear strength of CF-PEG400-PAM is increased to 95.54MPa from 56.35MPa, and increase rate is 69.50%.The carbon fiber of CF-EG-PAM and CF-PEG-PAM and the interface shear strength of epoxy resin are all higher than the not carbon fiber of destarch and the interface shear strength of epoxy resin, after proof graft polymers, having improved the polarity of carbon fiber sees and can roll into a ball, the surface that has increased carbon fiber can, improve the wettability of carbon fiber and resin, analyzed consistent with above-mentioned XPS and DAA.
Claims (5)
1. a method for carbon fiber surface graft polymers, the method that it is characterized in that carbon fiber surface graft polymers is to be undertaken by following steps:
One, remove epoxy coating;
Two, carbon oxide fiber: at normal temperatures, mixed solution 35～the 50ml of preparation potassium permanganate and sulfuric acid, wherein, the consumption of potassium permanganate is 0.35～0.60g, the concentration of sulfuric acid is 1～2mol/L, then the carbon fiber that is 0.35～0.70g by quality is put into the mixed solution of potassium permanganate and sulfuric acid, pour into after teat glass, put into overcritical device, it is 320～340 ℃ in temperature, pressure is the interior reaction of system 15～25min of 2～5MPa, then after carbon fiber being taken out, put into the beaker that mass concentration is 37.5% hydrochloric acid is housed, after good seal, put into the water-bath of 55～65 ℃, soak 2～4h, again put into apparatus,Soxhlet's, at 80 ℃, with ethanol cleaning carbon fiber 2～3h, then carbon fiber is taken out, be placed in the dry 2～4h of 70～80 ℃ of baking ovens, carbon fiber after being oxidized,
Three, the chloride of carbon fiber: the carbon fiber after step 2 oxidation is carried out to chloride, obtain the carbon fiber after chloride;
Four, the alcoholysis of carbon fiber: will add glycol and the 2～7ml triethylamine of 30～50ml in dry reaction bulb, after mixing, then add the carbon fiber after step 3 chloride, sealing, puts into water-bath by reaction bulb, constant temperature 24～72h at 60～80 ℃; Then put into apparatus,Soxhlet's, clean 1～4h with absolute ethyl alcohol extracting, then put into air dry oven, dry 2～5h at 70～90 ℃; Obtain the carbon fiber after alcoholysis; Wherein glycol is ethylene glycol, Macrogol 200, PEG400 or Macrogol 600;
Five, the Ce of carbon fiber
4+inducing Graft Polymerization thing:
A, take the acrylamide of 0.7108～4.9756g, be dissolved in the water of 50～80ml, be mixed with the aqueous solution of acrylamide;
B, measure the concentrated nitric acid solution of 1～2ml, be dissolved in the water of 20～50ml, be mixed with dilute nitric acid solution;
C, take the ammonium ceric nitrate of 0.05～1.10g, be dissolved in the dilute nitric acid solution of step b preparation the acidic aqueous solution of preparation ammonium ceric nitrate;
D, be placed in there-necked flask being tied with bezel and the magnet rotor of carbon fiber after alcoholysis, in there-necked flask, add the acrylamide monomer aqueous solution of preparing in step a, be then filled with nitrogen, drip the acidic aqueous solution of the ammonium ceric nitrate of step c simultaneously, after 15～30min, stop being filled with nitrogen, sealing;
E, the there-necked flask after steps d sealing is entered in constant temperature magnetic force heating stirrer, at 25～65 ℃, react 2.5～10h, then take out and put into apparatus,Soxhlet's, with the water cleaning 3～4h of 100 ℃, put into again air dry oven, dry at 80 ℃, to constant weight, complete the method for carbon fiber surface graft polymers.
2. the method for a kind of carbon fiber surface graft polymers according to claim 1, the method that it is characterized in that the removal epoxy coating described in step 1 is: carbon fiber bundle is put into apparatus,Soxhlet's, acetone to 75～85 ℃ in heating apparatus,Soxhlet's, maintain 2～8h, then put into overcritical device, it is 350～370 ℃ in temperature, pressure is to soak 20～30min in overcritical acetone～aqueous systems of 8～14MPa, and then put into apparatus,Soxhlet's, in the acetone of 75～85 ℃, clean carbon fiber 2～4h, again carbon fiber is taken out, be placed in the dry 2～4h of 70～80 ℃ of baking ovens, complete.
3. the method for a kind of carbon fiber surface graft polymers according to claim 1 and 2, is characterized in that described overcritical acetone～aqueous systems is made up of 25mL acetone and 5mL water.
4. the method for a kind of carbon fiber surface graft polymers according to claim 1, the method that it is characterized in that the carbon oxide fiber described in step 2 is: at normal temperatures, the mixed solution 50ml of preparation potassium permanganate and sulfuric acid, wherein, the consumption of potassium permanganate is 0.5g, the concentration of sulfuric acid is 1mol/L, then the carbon fiber that is 0.5g by quality is put into the mixed solution of potassium permanganate and sulfuric acid, pour into after teat glass, put into overcritical device, it is 320 ℃ in temperature, pressure is the interior reaction of the system 20min of 2MPa, then after carbon fiber being taken out, put into the beaker that mass concentration is 37.5% hydrochloric acid is housed, after good seal, put into the water-bath of 65 ℃, soak 6h, again put into apparatus,Soxhlet's, at 80 ℃, with ethanol cleaning carbon fiber 2h, then carbon fiber is taken out, being placed in the dry 4h of 80 ℃ of baking ovens completes.
5. the method for a kind of carbon fiber surface graft polymers according to claim 1, the method that it is characterized in that the carbon fiber chloride described in step 3 is: in dry reaction bulb, pack the thionyl chloride of 80mL and the N of 5mL into, N～dimethyl formamide, mix the carbon fiber of then putting into after oxidation processes, at 75 ℃, add hot reflux 48h and take out again carbon fiber, and at 80 ℃, dry 2h in air dry oven, complete.
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| CN104987532B (en) * | 2015-07-16 | 2017-11-03 | 哈尔滨工业大学 | A kind of carbon fiber surface grafting method based on supercritical fluid technique |
| TWI699466B (en) * | 2015-12-22 | 2020-07-21 | 美商塞特工業公司 | Process for gas phase surface treatment |
| CN107141777A (en) * | 2017-04-20 | 2017-09-08 | 常州可赛成功塑胶材料有限公司 | A kind of preparation method of composite conducting engineering plastics |
| CN107476055A (en) * | 2017-09-07 | 2017-12-15 | 青岛大学 | A kind of method of carbon fiber surface directly green grafting carbon nano-fiber |
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