CN101982427A - Method for modifying composite surface of carbon fiber - Google Patents
Method for modifying composite surface of carbon fiber Download PDFInfo
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- CN101982427A CN101982427A CN 201010518017 CN201010518017A CN101982427A CN 101982427 A CN101982427 A CN 101982427A CN 201010518017 CN201010518017 CN 201010518017 CN 201010518017 A CN201010518017 A CN 201010518017A CN 101982427 A CN101982427 A CN 101982427A
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Abstract
The invention discloses a method for modifying the composite surface of a carbon fiber (CF), which relates to a double-surface processing method of the CF. The method comprises the following two steps: (1) carrying out nitric acid liquid-phase oxidization on the CF to improve the surface biocompatibility of the CF; and (2) immersing the oxidized CF in an iron chloride or calcium chloride solution to adsorb metal cations so as to improve the adhesion strength of microorganisms on the surface of the CF. The invention can effectively increase the adhesion quantity and the adhesion strength of microorganisms on the surface of the CF, thereby being beneficial to the CF as the biological film carrier used for sewage treatment based on a biological film method and other relevant fields.
Description
Technical field
The invention belongs to the surface modifying method of a kind of charcoal fiber (CF), the duplex surface that is specifically related to a kind of CF is handled to improve the bioaffinity of CF.
Background technology
At sewage treatment area, the biomembrance process sewage disposal technology is as one of high-efficiency sewage treatment process, has been widely used in during organic sewage such as sanitary sewage handles.The selection of microbial film biofilm carrier in this technology directly affects set and the biomembranous formation of microorganism on solid support material, be the biomembrance process sewage treatment process can be efficiently, one of the key factor of steady running.At present, domestic biofilm solid support material mainly can be divided into classifications such as hard packing, semi-soft packing and soft-filler, and wherein soft and material semi soft packing mainly is macromolecular materials such as polypropylene, polyethylene, but its anchor effect to microorganism is not good.
The preparation of biofilm carrier material and optimization are the gordian techniquies in the biomembrance process sewage treatment area.Because CF excellent biological compatibility, can make a large amount of microorganisms be anchored to its surface (Ojima Zhao fast, the assistant rattan is sincere. and the charcoal element is knitted the thing affinity The of supporting one's family and is applied flexibly the new い of water surrounding and save technology [J] from damage. Materials science, 1998,6 (35): 25-32), compared than remarkable advantages with the traditional biological membrane carrier materials.
Microbial film is the key factor of decision biomembrance process wastewater treatment efficiency in the fixed amount and the set intensity of carrier surface, and microorganism is anchored to carrier surface is biological film formed basis, and the material surface characteristic is (as surface energy, chemical constitution, wetting ability, electronegativity and roughness etc.) bacterium or cell there are influence (Jin Ho Lee significantly in its surperficial adhesion property, SangJin Lee, Gilson Khang, et al..The Effect of Fluid Shear Stress on Endothelial Cell Adhesiveness toPolymer Surfaces with Wettability Gradient[J] .Journal of Colloid and Interface Science, 2000,230 (1): 84-90).
Not surface treated CF surface is comparatively smooth, and the surfactivity carbon atom is less.If can select the method for suitable surface modification to optimize the CF condition of surface, then can improve the set ability of CF, thereby further improve wastewater treatment efficiency to microorganism in the water.So seek suitable surface modifying method is the subject matter of optimizing the CF carrier.
Summary of the invention
The purpose of this invention is to provide a kind of appropriate C F surface modifying method, thereby further improve the microorganism fixation performance performance of CF.
The technical solution adopted in the present invention may further comprise the steps: one, CF commercially available or preparation is carried out the nitric acid liquid phase oxidation; Two, will adsorb metallic cation in immersion iron(ic) chloride of the CF after the oxidation or the calcium chloride solution.The first step of the present invention introduces hydrophilic oxygen-containing functional group by surface oxidation treatment technology on the CF surface earlier and its wetting ability and surfaceness are improved in oxide etch CF surface.Because the increase of oxygen-containing functional group makes the CF surface present stronger electronegativity after the oxide treatment,, thereby weaken surperficial electronegativity so second step need be at CF surface adsorption metallic cation.
The nitric acid liquid phase oxidation step of CF comprises CF surface preparation and two steps of surface oxidation.The CF surface preparation is carried out according to the following steps: (1) removes CF surface sizing agent with CF; (2) CF that will remove sizing agent is with distilled water flushing and oven dry.The CF surface oxidation carries out according to the following steps: (1) is dipped to concentration with pretreated CF is 34-68% nitric acid, at 50-120 ℃ of following oxidation 0.5-5h; (2) repeatedly washing until scavenging solution pH value with distilled water the CF after the oxidation is 7, and oven dry.
CF absorption positively charged ion carries out according to the following steps: (1) CF concentration after with the nitric acid liquid phase oxidation is iron(ic) chloride or the calcium chloride solution soaking at room temperature 2-10h adsorbing metal ions of 0.1-1mol/L; (2) CF that will adsorb metal ion cleans up and dries with distilled water.
The duplex surface modification method of the present invention by the bond cation-adsorption further improves the microorganism fixation performance of CF after the liquid-phase oxidation, be the good method of modifying that improves CF carrier biofilm fixed amount, bigger development prospect arranged at the biomembrance process sewage treatment area.
Description of drawings
Fig. 1 is through the laser co-focusing microstructure figure of the CF of different surfaces modification
Embodiment
All adopt laser confocal microscope (LCM) to characterize the CF surface topography among the following embodiment; X-ray photoelectron power spectrum (XPS) characterizes CF surface oxygen functional group content; With equilibrium moisture content (Cen Zhenzhang wears gloss, Dong Lixin etc. surface treatment is to the influence of charcoal fiber carrier surface forming biofilm property research [J]. Chongqing Polytechnic College journal (natural science edition), 2007,21 (5): 18-20) characterize the CF wetting ability; With the microbial film fixed amount of CF (Liu Cunping wears gloss, Cen Zhenzhang etc. the anodic oxidation of charcoal fiber is to the influence [J] of active sludge fixation performance. developing material and application, 2007,22 (5): 32-35) characterize the microorganism fixation performance of CF carrier.
Embodiment 1
At room temperature (PAN-CF T300) is soaked in the surperficial Resins, epoxy sizing agent of removal in the acetone, with drying behind the distilled water flushing with high strong type PAN-based carbon fiber; The CF that will remove sizing agent again immerses and takes out after concentrated nitric acid constant temperature boiling water bath heats 0.5-2h, and washing until the pH of scavenging solution value repeatedly with distilled water is 7 back oven dry; At last the CF behind the nitric acid oxidation is immersed in the CaCl2 solution that concentration is 0.1-0.3mol/L and soak 5-6h, take out the back and clean up and dry with distilled water.
The CF test result of gained after surface modification is as follows: the surface oxygen functional group total amount is 24.13%, and equilibrium moisture content is 6.07%, and the microbial film fixed amount is 229.6%.Its LCM photo is shown in a among Fig. 1.
Embodiment 2
At room temperature (PAN-CF T300) is soaked in the surperficial Resins, epoxy sizing agent of removal in the acetone, with drying behind the distilled water flushing with high strong type PAN-based carbon fiber; The CF that will remove sizing agent again immerses and takes out after concentrated nitric acid constant temperature boiling water bath heats 1-3h, and washing until the pH of scavenging solution value repeatedly with distilled water is 7 back oven dry; At last the CF behind the nitric acid oxidation is immersed in the FeCl3 solution that concentration is 0.1-0.3mol/L and soak 4-5h, take out the back and clean up and dry with distilled water.
The CF test result of gained after surface modification is as follows: the surface oxygen functional group total amount is 20.85%, and equilibrium moisture content is 5.18%, and the microbial film fixed amount is 188.0%.Its LCM photo is shown in b among Fig. 1.
Comparative Examples
At room temperature (PAN-CF T300) is soaked in the surperficial Resins, epoxy sizing agent of removal in the acetone, with drying behind the distilled water flushing with high strong type PAN-based carbon fiber.Test result is as follows: the surface oxygen functional group total amount is 16.74%, and equilibrium moisture content is 1.20%, and the microbial film fixed amount is 117.1%.Its LCM photo is shown in c among Fig. 1.
Claims (5)
1. the duplex surface modification method of a charcoal fiber (CF) is characterized in that the CF duplex surface modification comprises two steps: (1) carries out the nitric acid liquid phase oxidation with CF commercially available or preparation; (2) will adsorb metallic cation in immersion iron(ic) chloride of the CF after the oxidation or the calcium chloride solution.
2. according to the described method of claim 1, it is characterized in that the phase oxidation of CF nitric acid liquid comprises CF surface preparation and two steps of CF surface oxidation.
3. according to the described method of claim 2, it is characterized in that the CF surface preparation carries out according to the following steps: (1) removes CF surface sizing agent; (2) will remove the CF of sizing agent with washing and oven dry.
4. according to the described method of claim 2, it is characterized in that the CF surface oxidation carries out according to the following steps: (1) is dipped to concentration with pretreated CF is 34-68% nitric acid, at 50-120 ℃ of following oxidation 0.5-5h; (2) repeatedly washing until scavenging solution pH value with distilled water the CF after the oxidation is 7, and oven dry.
5. method according to claim 1 is characterized in that step 2 CF absorption positively charged ion carries out according to the following steps: (1) CF concentration after with the nitric acid liquid phase oxidation is iron(ic) chloride or the calcium chloride solution soaking at room temperature 2-10h adsorbing metal ions of 0.1-1mol/L; (2) CF that will adsorb metal ion cleans up and dries with distilled water.
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| CN 201010518017 CN101982427A (en) | 2010-10-25 | 2010-10-25 | Method for modifying composite surface of carbon fiber |
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| CN 201010518017 CN101982427A (en) | 2010-10-25 | 2010-10-25 | Method for modifying composite surface of carbon fiber |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104803471A (en) * | 2015-04-14 | 2015-07-29 | 北京化工大学常州先进材料研究院 | Excellent and efficient carbon fiber biofilm carrier modification method |
| CN106148316A (en) * | 2015-04-20 | 2016-11-23 | 河南工业大学 | The ameliorative way of cell immobilization carrier surface hydrophilicity and application |
| CN109399788A (en) * | 2018-09-06 | 2019-03-01 | 浙江利欧环保科技有限公司 | The method of modifying and modified obtained Hdyrophilic polyurethane sponge filler of a kind of pair of polyurethane sponge filler |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104803471A (en) * | 2015-04-14 | 2015-07-29 | 北京化工大学常州先进材料研究院 | Excellent and efficient carbon fiber biofilm carrier modification method |
| CN106148316A (en) * | 2015-04-20 | 2016-11-23 | 河南工业大学 | The ameliorative way of cell immobilization carrier surface hydrophilicity and application |
| CN109399788A (en) * | 2018-09-06 | 2019-03-01 | 浙江利欧环保科技有限公司 | The method of modifying and modified obtained Hdyrophilic polyurethane sponge filler of a kind of pair of polyurethane sponge filler |
| CN109399788B (en) * | 2018-09-06 | 2021-10-26 | 浙江利欧环保科技有限公司 | Modification method of polyurethane sponge filler and hydrophilic polyurethane sponge filler obtained by modification |
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