CN103806281B - Carbon fiber surface grafting hyperbranched poly glycerine improves the method for composite material interface performance - Google Patents
Carbon fiber surface grafting hyperbranched poly glycerine improves the method for composite material interface performance Download PDFInfo
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- CN103806281B CN103806281B CN201410071232.6A CN201410071232A CN103806281B CN 103806281 B CN103806281 B CN 103806281B CN 201410071232 A CN201410071232 A CN 201410071232A CN 103806281 B CN103806281 B CN 103806281B
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Abstract
Carbon fiber surface grafting hyperbranched poly glycerine improves a method for composite material interface performance, belongs to carbon fiber surface modification field.Described method step is as follows: the first step is by the process of carbon fiber acid oxidase, and second step is by the carbon fiber chloride process of oxidation, and the 3rd step is by the carbon fiber grafting hyperbranched poly glycerine of chloride process.Because hyperbranched poly glycerine has a large amount of reactable group terminal hydroxy groups, after being grafted to carbon fiber surface, the polarity of carbon fiber surface can increase greatly, and the wettability between resin improves, simultaneously hydroxyl can and epoxy resin between react, form chemical bond at interface, this will increase the interface bond strength of composite greatly, improves the interface performance of composite.
Description
Technical field
The invention belongs to carbon fiber surface modification field, relate to a kind of method adopting carbon fiber surface grafting hyperbranched poly glycerine (HBPG) to improve Interface Properties of Carbon Fibers Reinforced Composites.
Background technology
Carbon fiber has high specific strength, high ratio modulus, high temperature resistant, anticorrosive, creep-resistant property is good, conduction, heat conduction and the series of advantages such as thermal coefficient of expansion is little, is thus widely used in preparing polymer matrix composites and is applied to a series of high-grade, precision and advanced fields such as space flight and aviation, automobile and high-grade sports equipment.But because carbon fiber surface is smooth and inertia, this causes carbon fiber interfacial combined function between matrix bad, it reduce the performance of carbon fibre composite, so composite material interface performance should be improved to carbon fiber surface modification before application of carbon fibres prepares composite.
The current process for modifying surface to carbon fiber mainly contains plasma treatment, chemical graft, oxidation processes and face coat method etc., but said method is fewer in the functional group of the increase of carbon fiber surface, improves limited to composite material interface performance.
Summary of the invention
In order to overcome above-mentioned the deficiencies in the prior art, the invention provides a kind of method that carbon fiber surface grafting hyperbranched poly glycerine improves composite material interface performance, namely by grafting hyperbranched poly glycerine after carbon fiber oxidation processes.
The object of the invention is to be achieved through the following technical solutions:
The oxidation processes of the first step, carbon fiber:
Mixed acid solution carbon fiber being put into the concentrated sulfuric acid and red fuming nitric acid (RFNA) carries out oxidation processes, is then adopted by the carbon fiber of oxidation processes distilled water extracting washing to neutral, dries;
In this step, in described mixed acid solution, the volume ratio of the concentrated sulfuric acid and red fuming nitric acid (RFNA) is 3:1;
In this step, described oxidation processes condition is: oxidation processes 4h under 60 DEG C of conditions.
The chloride process of second step, carbon fiber:
The carbon fiber first step obtained carries out chloride process in thionyl chloride solution, then dries stand-by by the carbon fiber of chloride process;
In this step, described chloride treatment conditions are: chloride process 72h under 76 DEG C of conditions.
3rd step, carbon fiber grafting hyperbranched poly glycerine:
The DMF solution that the carbon fiber obtained by second step is placed in containing hyperbranched poly glycerine carries out grafting process, then adopts acetone extraction out to the carbon fiber of grafting process, dries;
In this step, the mass concentration of described hyperbranched poly glycerine is 0.5%;
In this step, described grafting treatment conditions are: grafting process 24h under 100 DEG C of conditions;
In this step, described extraction times is 24h.
In the present invention, raw materials is existing product, and such as hyperbranched poly glycerine is obtained by Shanghai Communications University or purchased from the special resin Science and Technology Ltd. of Suzhou hypo.
Compared with prior art, the invention has the beneficial effects as follows: because hyperbranched poly glycerine has a large amount of reactable group terminal hydroxy groups, after being grafted to carbon fiber surface, the polarity of carbon fiber surface can increase greatly, and the wettability between resin improves, simultaneously hydroxyl can and epoxy resin between react, form chemical bond at interface, this will increase the interface bond strength of composite greatly, improves the interface performance of composite.
Accompanying drawing explanation
Fig. 1 is carbon fiber surface modification process;
Fig. 2 is carbon fiber SEM surface topography before modified;
Fig. 3 is modified carbon fiber SEM surface topography;
Fig. 4 is that before and after carbon fiber process, TG is weightless figure;
Fig. 5 is composite material interface performance before and after Treatment of Carbon process.
Detailed description of the invention
Below in conjunction with accompanying drawing, technical scheme of the present invention is further described; but be not limited thereto; everyly technical solution of the present invention modified or equivalent to replace, and not departing from the spirit and scope of technical solution of the present invention, all should be encompassed in protection scope of the present invention.
The invention provides a kind of by the method at the improvement Interface Properties of Carbon Fibers Reinforced Composites of carbon fiber surface grafting hyperbranched poly glycerine, as shown in Figure 1, concrete steps are as follows for its modifying process:
The oxidation processes of the first step, carbon fiber:
Configuration volume ratio is the concentrated sulfuric acid: the mixed acid solution of red fuming nitric acid (RFNA)=3:1, carbon fiber is put into mixed acid solution oxidation processes 4h under 60 DEG C of conditions, is then adopted by the carbon fiber of oxidation processes distilled water extracting washing to neutral, dries;
The chloride process of second step, carbon fiber:
The carbon fiber first step obtained chloride process 72h under 76 DEG C of conditions in thionyl chloride solution, then dries stand-by by the carbon fiber of chloride process;
3rd step, carbon fiber grafting hyperbranched poly glycerine:
Configuration quality concentration is the N of the hyperbranched poly glycerine of 0.5%, dinethylformamide solution, the carbon fiber obtained by second step is placed in hyperbranched poly glycerite, grafting process 24h under 100 DEG C of conditions, then acetone extraction is adopted out to the carbon fiber of grafting process, extraction times is 24h, dries.
Fig. 2 and Fig. 3 two photos are the SEM picture of carbon fiber before and after the process of hyperbranched poly glycerine respectively.As can be seen from Fig., after surface treatment, carbon fiber surface has obvious white attachment, and this illustrates that hyperbranched poly glycerine is successfully grafted to carbon fiber surface.
Fig. 4 is the carbon fiber hot weightless picture under nitrogen atmosphere before and after grafting, as can be seen from the figure, carbon fiber weight-loss ratio without grafting is 1.50%, and after grafting process, carbon fiber weight-loss ratio is 10.08%, and this shows that the hyperbranched poly glycerine percent grafting of carbon fiber surface is 8.58%.
Table 1, table 2 are carbon fiber XPS characterization result.Table 1 is surface treatment of carbon fibers front and rear surfaces constituent content, and as can be seen from the table after surface treatment of carbon fibers, its surface carbon constituent content drops to 73.01% from 84.82%, and oxygen element content is increased to 24.2%, O/C from 13.3% and is increased to 0.3315 from 0.1568.Table 2 is the chemical bond content of carbon fiber surface carbon, after process, C-C, C-O, C=O and
59.5%, 33.6%, 4.4%, 2.5% is become respectively from 70.3%, 24.7%, 2.7%, 2.3%.Can know that the oxygen polar functional group number that contains of carbon fiber surface increases greatly after surface treatment from table 1, table 2, this will be conducive to the interface performance improving composite.
Table 3 is carbon fiber advancing angle and surface energy characterization result before and after carbon fiber process, and as can be seen from Table 3 after grafting process, the surface energy of carbon fiber is from 18.54mJ.m
-2-be increased to 23.95mJ.m
-2-, can find out after surface treatment, the surface energy of carbon fiber has had and has improved by a relatively large margin, and this will be conducive to carbon fiber infiltrating raising between matrix, is conducive to the interface performance improving composite.
Fig. 5 is composite material interface performance characterization result, before modified, the interface shear strength of carbon fibre composite and interlayer are cut intensity and are increased to 110.16MPa and 105.29MPa from 59.86MPa and 57.57MPa respectively, increasing degree is respectively 84.03% and 82.89%, can find out that modified composite material interface performance improvement is obvious.
Table 1 carbon fiber process front and rear surfaces constituent content table
Table 2 carbon fiber process front and rear surfaces carbon chemical bond is containing scale
Advancing angle and surface energy table before and after the process of table 3 carbon fiber
Claims (5)
1. carbon fiber surface grafting hyperbranched poly glycerine improves the method for composite material interface performance, it is characterized in that described method step is as follows:
The oxidation processes of the first step, carbon fiber:
Mixed acid solution carbon fiber being put into the concentrated sulfuric acid and red fuming nitric acid (RFNA) carries out oxidation processes, is then adopted by the carbon fiber of oxidation processes distilled water extracting washing to neutral, dries;
The chloride process of second step, carbon fiber:
The carbon fiber first step obtained carries out chloride process in thionyl chloride solution, then dries stand-by by the carbon fiber of chloride process;
3rd step, carbon fiber grafting hyperbranched poly glycerine:
It is DMF solution grafting process 24h under 100 DEG C of conditions of 0.5% hyperbranched poly glycerine that the carbon fiber obtained by second step is placed in containing mass concentration, then adopts acetone extraction out to the carbon fiber of grafting process, dries.
2. carbon fiber surface grafting hyperbranched poly glycerine according to claim 1 improves the method for composite material interface performance, it is characterized in that the volume ratio of the concentrated sulfuric acid and red fuming nitric acid (RFNA) in described mixed acid solution is 3:1.
3. carbon fiber surface grafting hyperbranched poly glycerine according to claim 1 improves the method for composite material interface performance, it is characterized in that described oxidation processes condition is: oxidation processes 4h under 60 DEG C of conditions.
4. carbon fiber surface grafting hyperbranched poly glycerine according to claim 1 improves the method for composite material interface performance, it is characterized in that described chloride treatment conditions are: chloride process 72h under 76 DEG C of conditions.
5. carbon fiber surface grafting hyperbranched poly glycerine according to claim 1 improves the method for composite material interface performance, it is characterized in that described extraction times is 24h.
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| CN104195824B (en) * | 2014-09-15 | 2016-04-27 | 哈尔滨工业大学 | A kind of carbon fiber surface modification method |
| CN104480707B (en) * | 2014-12-26 | 2016-08-24 | 哈尔滨工业大学 | A kind of method of carbon fiber surface grafting hexa in supercritical methanol |
| CN105063999A (en) * | 2015-07-31 | 2015-11-18 | 山东科技大学 | Method for in situ growth of polyamide on surface of carbon fiber, and controllable hyperbranching of iteration number |
| CN106245319A (en) * | 2016-08-11 | 2016-12-21 | 西北工业大学 | A kind of surface modifying method of carbon fiber |
| CN107761375B (en) * | 2017-11-10 | 2020-04-24 | 青岛大学 | Method for grafting branched molecular tannic acid on surface of carbon fiber |
| CN109468842A (en) * | 2018-09-27 | 2019-03-15 | 深圳市富恒新材料股份有限公司 | A method of the carbon fiber surface based on plasma technology is grafted hyperbranched poly glycerol |
| CN109853089B (en) * | 2019-03-11 | 2021-10-12 | 施默尔(青岛)纤维复合材料有限公司 | High-performance carbon fiber and graphitization method thereof |
| CN110863341A (en) * | 2019-12-03 | 2020-03-06 | 深圳市富恒新材料股份有限公司 | Preparation method of PA66 grafted carbon fiber |
| CN113788930A (en) * | 2021-09-15 | 2021-12-14 | 安徽誉林新材料科技有限公司 | Production process of environment-friendly polyurethane elastomer for ground washing machine wheel |
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| CN103469534B (en) * | 2013-09-30 | 2015-05-13 | 哈尔滨工业大学 | Method for chemical grafting modification for surfaces of carbon fibers |
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