CN100458004C - Method for improving carbonfiber surface activity - Google Patents
Method for improving carbonfiber surface activity Download PDFInfo
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- CN100458004C CN100458004C CNB2006100100683A CN200610010068A CN100458004C CN 100458004 C CN100458004 C CN 100458004C CN B2006100100683 A CNB2006100100683 A CN B2006100100683A CN 200610010068 A CN200610010068 A CN 200610010068A CN 100458004 C CN100458004 C CN 100458004C
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Abstract
The invention is a carbon fiber surface activity improving method, relating to a composite reinforcer surface modification technique, adopting potassium permanganate/vitriol as initiating system, grafting crylic acid on the surface of the carbon fiber, leading in active functional groups, and improving carbon fiber surface inertia, and concretely comprising the steps of: 1. adopting crylic acid-vitriol mixed solution as grafting liquid, adding in to-be-modified carbon fiber, and keeping the carbon fiber fully immersed in the liquid; then slowly adding in potassium permanganate solution, and before and after adding, keeping the solution not change color, and making graft reaction; 2. taking out the carbon fiber from the solution after reaction, repeatedly washing several times with deionized water, then adding to boiling water to boil and finally drying. And the invention is simple to operate, low-cost and has no environmental pollution, and is convenient to industrialization. As compared with the unactivated carbon fiber surface, the O/C ratio of the activated carbon fiber surface is increased by 10-32%, and the layer-to-layer shear strength of its epoxy composite is increased by 5-18%.
Description
Technical field
The present invention relates to a kind of process for modifying surface of composite material reinforcement body, particularly a kind of method that improves carbon fiber surface activity by induced grafting.
Background technology
Carbon fiber is as a kind of high performance fiber, and it has advantages such as high specific strength, high ratio modulus, endurance, creep resistant and the coefficient of expansion are little, makes it become most important in recent years reinforcing material, and is used widely in the national economy every field.Carbon fiber is during as composite material reinforcement body, and is poor with the resin matrix wettability because surface smoothing presents chemical inertness, causes the interfacial adhesion performance poor, thereby seriously influenced the performance of the whole excellent properties of composite.That therefore, improves that carbon fiber surface activity become the research advanced composite material first develops one of direction.
Not surface treated carbon fiber surface is inertia, and specific area is little, and the edge active atoms of carbon is few, and surface energy is low, thus cause combining with the interface that strengthens matrix poor.The at present main method that improves carbon fiber surface activity that adopts has oxidizing process, plasma treatment, electro-deposition and voltolisation legal etc.Oxidizing process can be that gaseous oxidation also can be liquid phase oxidation, all can improve the oxygen-containing functional group of fiber surface, but its degree of oxidation is wayward, injures the body intensity of fiber easily; Obvious etc. the ex vivo treatment method to the fiber surface activation degree, but the harsh difficult industrialization that realizes of treatment conditions; The electropolymerization rule can't guarantee that fiber surface evenly applies high polymer, and fiber adheres to each other easily after handling.
Summary of the invention
The objective of the invention is to adopt potassium permanganate/sulfuric acid as initiator system,, introduce active function groups, improve the inertia of carbon fiber surface at the carbon fiber surface graft acrylic acid.Carbon fiber surface oxygen-containing functional group after the modification significantly improves, and surface-activity obviously increases, and the body intensity of fiber is unaffected.The present invention is simple to operate, and is with low cost, and environmentally safe, is convenient to industrialization.
Above-mentioned purpose of the present invention is achieved by following technical solution: one, adopting acrylic acid and sulfuric acid mixture liquid is grafting liquid, puts into the carbon fiber for the treatment of modification, guarantees that liquid is with the complete submergence of carbon fiber; Add liquor potassic permanganate then slowly, keep the solution nondiscolouring before and after adding, place under 30～90 ℃ the temperature and carry out graft reaction, about 2～6 hours of reaction time; Two: reacted carbon fiber is taken out from solution, wash repeatedly for several times, put into boiling water again and boiled 3～10 minutes, oven dry with deionized water; The mass ratio of wherein said acrylic acid and sulfuric acid is between 1000: 1～50: 1; The mass ratio of described sulfuric acid and adding potassium permanganate is between 1: 1～10: 1.
Acrylic acid is that a kind of activity is strong and contain the organic molecule of two keys and carboxyl, and its double bond structure helps taking place the free radical grafting reaction, and its carboxyl then can improve by the surface-activity of graft.Potassium permanganate and sulfuric acid react, and generation can form the MnO of free radical
2(4MnO
4 7-+ 4H
+→ 4MnO
2+ 2H
2O+3O
2), MnO
2Then further reaction generates Mn
4+, Mn
3+, Mn
2+And free radical (SO
4 -, OH, C).These free radicals can generate the activated centre by the attack carbon fiber surface, generate new free radical with the acrylic acid reaction simultaneously, make acrylic acid at fiber surface generation graft reaction.The present invention adopts potassium permanganate/sulfuric acid as initiator system, at the carbon fiber surface graft acrylic acid, introduces active function groups, improves the inertia of carbon fiber surface.Carbon fiber surface oxygen-containing functional group after the modification significantly improves, and surface-activity obviously increases, and the body intensity of fiber is unaffected.The present invention is simple to operate, and is with low cost, and environmentally safe, is convenient to industrialization.Carbon fiber surface O/C ratio after process the present invention activation not activated carbon fiber surface O/C has improved 10～32%, and the interlaminar shear strength of its epoxy composite material has improved 5～18%.
The specific embodiment
The specific embodiment one: present embodiment improves carbon fiber surface activity as follows:
One, adopting acrylic acid and sulfuric acid mixture liquid is grafting liquid, generates manganese dioxide initiation acrylic acid and carbon fiber graft reaction by adding potassium permanganate and sulfuric acid reaction.Concrete operation method is: after the solution mixing with acrylic acid and sulfuric acid, put into the carbon fiber for the treatment of modification, guarantee that liquid is with the complete submergence of carbon fiber.Add liquor potassic permanganate then slowly, keep the solution nondiscolouring before and after adding, prevent that potassium permanganate is excessive.The container that is placed with carbon fiber and reactant liquor placed under 30～90 ℃ the temperature and carry out graft reaction, about 2～6 hours of reaction time.
Two: reacted carbon fiber is taken out from solution, wash repeatedly for several times, put into boiling water again and boiled 3～10 minutes,, fiber is taken out put into the baking oven oven dry afterwards in order to using to remove the acrylic copolymer of fiber surface with deionized water.
In the present embodiment, the mass ratio of described acrylic acid and sulfuric acid is between 1000: 1～50: 1.Wherein acrylic acid concentration is 10～30wt%, and the concentration of sulfuric acid is 0.005～0.3mol/L.
In the present embodiment, the concentration of described potassium permanganate solution is 0.2～1wt%.
In the present embodiment, described graft copolymer solution is 100: 1～5: 1 with the fiber quality ratio.
In the present embodiment, the mass ratio of described sulfuric acid and adding potassium permanganate is between 1: 1～10: 1.
The specific embodiment two: the water of getting 1000g is put into the beaker of 2000mL, take by weighing 100g acrylic acid and put into beaker, the concentrated sulfuric acid that adds 1g again, put into the carbon fiber of 50g after mixing, make liquid with the complete submergence of fiber, place about 10min, the potassium permanganate that takes by weighing 0.8g is dissolved in the 50g deionized water, the liquor potassic permanganate for preparing is dropwise joined in the beaker, rock the potassium permanganate that beaker makes dropping in the dropping process gently and react the water white transparency that keeps solution in the beaker rapidly.Beaker is placed in the insulating box kept 70 ℃ of temperature 3 hours, take out beaker reactant liquor is poured out, wash fiber repeatedly 3 times, add deionized water again and boiled 5 minutes with deionized water.Took out in the baking oven that fiber is placed on 105 ℃ oven dry 1 hour.The gained fiber has improved 21% than untreated fibers surface oxygen content, and prepared epoxy composite material interface shear strength has improved 16%, reaches 92MPa.
The specific embodiment three: the water of getting 70g is put into beaker, take by weighing 30g acrylic acid and put into beaker, the concentrated sulfuric acid that adds 1g again, put into the carbon fiber of 10g after mixing, make liquid with the complete submergence of fiber, place about 10min, the potassium permanganate that takes by weighing 0.6g is dissolved in the 10g deionized water, the liquor potassic permanganate for preparing is dropwise joined in the beaker, rock the potassium permanganate that beaker makes dropping in the dropping process gently and react the water white transparency that keeps solution in the beaker rapidly.Beaker is placed in the insulating box kept 60 ℃ of temperature 3 hours, take out beaker reactant liquor is poured out, wash fiber repeatedly 3 times, add deionized water again and boiled 5 minutes with deionized water.Take out in the baking oven that fiber is placed on 105 ℃ and dry half an hour.The gained fiber has improved 26% than untreated fibers surface oxygen content, and prepared epoxy composite material interface shear strength has improved 18%.
The specific embodiment four: the water of getting 500g is put into cup, take by weighing 100g acrylic acid and put into beaker, the concentrated sulfuric acid that adds 2g again, put into the carbon fiber of 30g after mixing, make liquid with the complete submergence of fiber, place about 8min, the potassium permanganate that takes by weighing 3g is dissolved in the 30g deionized water, the liquor potassic permanganate for preparing is dropwise joined in the beaker, rock the potassium permanganate that beaker makes dropping in the dropping process gently and react the water white transparency that keeps solution in the beaker rapidly.Beaker is placed in the insulating box kept 70 ℃ of temperature 3 hours, take out beaker reactant liquor is poured out, wash fiber repeatedly 2 times, add deionized water again and boiled 8 minutes with deionized water.Took out in the baking oven that fiber is placed on 106 ℃ oven dry 1 hour.The gained fiber has improved 23% than untreated fibers surface oxygen content, and prepared epoxy composite material interface shear strength has improved 15.8%.
Claims (4)
1, a kind of method that improves carbon fiber surface activity is characterized in that described method is: one, adopting acrylic acid and sulfuric acid mixture liquid is grafting liquid, puts into the carbon fiber for the treatment of modification, guarantees that liquid is with the complete submergence of carbon fiber; Add liquor potassic permanganate then slowly, keep the solution nondiscolouring before and after adding, place under 30～90 ℃ the temperature and carry out graft reaction, the reaction time is 2～6 hours; Two: reacted carbon fiber is taken out from solution, wash repeatedly for several times, put into boiling water again and boiled 3～10 minutes, oven dry with deionized water; The mass ratio of wherein said acrylic acid and sulfuric acid is between 1000: 1～50: 1; The mass ratio of described sulfuric acid and adding potassium permanganate is between 1: 1～10: 1.
2, a kind of method that improves carbon fiber surface activity according to claim 1 is characterized in that described acrylic acid concentration is 10～30wt%, and the concentration of sulfuric acid is 0.005～0.3mol/L.
3, a kind of method that improves carbon fiber surface activity according to claim 1, the concentration that it is characterized in that described potassium permanganate solution is 0.2～1wt%.
4, a kind of method that improves carbon fiber surface activity according to claim 1 is characterized in that described graft copolymer solution and fiber quality ratio are 100: 1～5: 1.
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| CNB2006100100683A CN100458004C (en) | 2006-05-23 | 2006-05-23 | Method for improving carbonfiber surface activity |
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|---|---|---|---|
| CNB2006100100683A CN100458004C (en) | 2006-05-23 | 2006-05-23 | Method for improving carbonfiber surface activity |
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| CN100458004C true CN100458004C (en) | 2009-02-04 |
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| CNB2006100100683A Active CN100458004C (en) | 2006-05-23 | 2006-05-23 | Method for improving carbonfiber surface activity |
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101597862B (en) * | 2009-06-18 | 2012-08-22 | 天华溢威特种纤维(新泰)有限公司 | Method for improving carbon fiber surface activity |
| CN102888750B (en) * | 2012-10-29 | 2014-03-12 | 哈尔滨工业大学 | Method for modifying surface of carbon fiber |
| CN103275282B (en) * | 2013-06-04 | 2015-05-13 | 南昌航空大学 | Preparation method of acrylic polymer grafted carbon fiber multi-scale reinforcement |
| CN106319924A (en) * | 2016-09-14 | 2017-01-11 | 郑州峰泰纳米材料有限公司 | Surface treatment method of middle-high-strength carbon fibers |
| CN113652018B (en) * | 2021-06-22 | 2023-05-30 | 浙江邦德管业有限公司 | High-strength polyethylene gas pipeline and preparation method thereof |
| CN115450047B (en) * | 2022-10-11 | 2023-09-08 | 中国科学院上海应用物理研究所 | Preparation method of high-modulus carbon fiber grafted glycidyl methacrylate |
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|---|---|---|---|---|
| DE1646828A1 (en) * | 1967-02-21 | 1971-08-05 | Nat Res Dev | Carbon fibers with increased adhesion and their production and use for fiber-reinforced composite materials |
| US3855174A (en) * | 1971-03-19 | 1974-12-17 | Commissariat Energie Atomique | Method of manufacture of composite materials consisting of carbon fibers and resin and materials thus obtained |
| CN1032042A (en) * | 1986-12-25 | 1989-03-29 | 中国科学院山西煤炭化学研究所 | Surface treatment of carbon fibers processing method and equipment thereof |
| JPH06166954A (en) * | 1992-11-25 | 1994-06-14 | Osaka Gas Co Ltd | Production of hydrophilic carbon fiber and carbon fiber produced thereby |
| CN1657408A (en) * | 2004-12-28 | 2005-08-24 | 华南理工大学 | Surface-activated carbon fiber and its preparation method |
-
2006
- 2006-05-23 CN CNB2006100100683A patent/CN100458004C/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1646828A1 (en) * | 1967-02-21 | 1971-08-05 | Nat Res Dev | Carbon fibers with increased adhesion and their production and use for fiber-reinforced composite materials |
| US3855174A (en) * | 1971-03-19 | 1974-12-17 | Commissariat Energie Atomique | Method of manufacture of composite materials consisting of carbon fibers and resin and materials thus obtained |
| CN1032042A (en) * | 1986-12-25 | 1989-03-29 | 中国科学院山西煤炭化学研究所 | Surface treatment of carbon fibers processing method and equipment thereof |
| JPH06166954A (en) * | 1992-11-25 | 1994-06-14 | Osaka Gas Co Ltd | Production of hydrophilic carbon fiber and carbon fiber produced thereby |
| CN1657408A (en) * | 2004-12-28 | 2005-08-24 | 华南理工大学 | Surface-activated carbon fiber and its preparation method |
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Application publication date: 20061025 Assignee: Harbin Hua Jianxin energy technology development materials Co. Ltd. Assignor: Harbin Institute of Technology Contract record no.: 2013230000356 Denomination of invention: Method for improving carbonfiber surface activity Granted publication date: 20090204 License type: Common License Record date: 20130401 |
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