CN103147280B - Biological activity modified method of carbon fiber surface - Google Patents
Biological activity modified method of carbon fiber surface Download PDFInfo
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- CN103147280B CN103147280B CN201310044978.3A CN201310044978A CN103147280B CN 103147280 B CN103147280 B CN 103147280B CN 201310044978 A CN201310044978 A CN 201310044978A CN 103147280 B CN103147280 B CN 103147280B
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Abstract
The invention discloses a biological activity modified method of a carbon fiber surface. The method is used for solving the technical problem of bad biological activity of the carbon fiber surface in the prior art. The technical scheme includes that the method comprises the steps of introducing an oxygenic functional group on the carbon fiber surface through an oxidizing reaction, and adopting electro-deposition to manufacture strontium hydroxyapatite coatings reinforced by carbon nano tubes and enable the biological activity coating to cover the carbon fiber surface and form a strong bonding with the carbon fiber. The method enhances mechanical performance of the pure hydroxyapatite coating through reinforcement of the carbon nano tubes, improves organization response behavior of the pure hydroxyapatite by introducing the microelement of strontium, and enhances the biological activity of the carbon fiber surface. In addition, the method is conducted under a condition of low temperature, is easy to operate and simple in equipment.
Description
Technical field
The present invention relates to a kind of bioactivation method of modifying, particularly relate to a kind of carbon fiber surface bioactivation method of modifying.
Background technology
Carbon fiber has high mechanical property, the feature that the burn into of resistance to body fluid endurance and quality are light, thereby have widely and quote in field of tissue engineering technology.Carbon fiber can directly apply to the reparation of ligament and tendon on the one hand, on the other hand can be as the reinforcement of medical composite material, and it is widely used in strengthening bioabsorbable polymer material, bioceramic material, biological carbon matrix material etc.But the surface of carbon fiber presents biologically inert, be difficult to form good bonding with body tissue.
Document 1 " I Rajzer; E Menaszek; L Bacakova; et al.In vitro and in vivo studies on biocompatibility of carbon fibres.J Mater Sci:Mater Med.2010; 21:2611～2622 " has been reported and has been adopted the method for simulated body fluid immersion to prepare hydroxyapatite bioactive coating on the surface of carbon fiber, this coating of research discovery has been improved the biologically inert of carbon fiber, has promoted the osteoblastic initial stage to adhere to and has improved bone tissue respondent behavior.
Document 2 " Cao Zhong; He Yinghe; Sun Lixian; et al.Nano-scale deposition of hydroxyapatite on bioactive and bioinert fibers using carbon nanofibers as templates.Advanced Materials Research.2011; 236～238:2122～2125 " has been reported the nano-grade hydroxy apatite of having grown in carbon fiber template, thereby has improved the biologically inert of carbon fiber.
Said method all adopts the method for preparing hydroxyapatite at carbon fiber surface to improve its biologically inert, but in human skeleton tissue outside hydroxyapatite, also contain various trace elements, this trace element has important effect for structure and the structural change of bone tissue.Therefore, in hydroxyapatite, add trace element and contribute to improve its biologically active and tissue response behavior, wherein the strontium element in trace element can promote the growth of osteoblastic propagation and inhibition osteoclast, and the calcium that the having of strontium element is beneficial in human body fluid exchange, so strontium containing hydroxyapatite is that the bioactivation of function admirable is material modified.In addition, for overcoming the problem of hydroxyl apatite bioceramic mechanical property deficiency, portion adds wild phase within it, wherein CNT have lightweight, specific area is large, mechanical property is excellent and the feature of stable chemical performance, is considered to the reinforcing material of excellent performance.Therefore the present invention proposes to prepare CNT enhancing strontium containing hydroxyapatite biologically active coating at carbon fiber surface, thereby develops a kind of method of carbon fiber being carried out to surface biological activation modification.
Summary of the invention
In order to overcome the poor deficiency of existing carbon fiber surface biologically active, the invention provides a kind of carbon fiber surface bioactivation method of modifying.First the method introduces oxygen-containing functional group by oxidation reaction on the surface of carbon fiber, then adopts electrodeposition technology on its surface, to prepare CNT and strengthens strontium containing hydroxyapatite coating.Thereby make bioactivity coatings coated carbon fiber surface also and between carbon fiber form strong bonding, can improve the biologically active of carbon fiber surface.
The technical solution adopted for the present invention to solve the technical problems is: a kind of carbon fiber surface bioactivation method of modifying, is characterized in comprising the following steps:
(1) carbon fiber is carried out to ultrasonic cleaning with acetone, absolute ethyl alcohol and distilled water successively, then put into vacuum drying chamber dry, obtain sample A;
(2) sample A is positioned in vessel, first adding mass percent concentration is 30% hydrogen peroxide, then add tungstophosphoric acid, wherein the quality of tungstophosphoric acid and the volume ratio of hydrogen peroxide are 5～20mg/ml, and it is under 60～90 degree conditions, to process 2～10h to obtain sample B in temperature that vessel are placed in to constant water bath box;
(3) strontium nitrate and calcium nitrate are added to evenly mixing in distilled water, wherein the concentration of strontium nitrate is 1～5mmol/L, the concentration of calcium nitrate is 8～50mmol/L, wherein the mol ratio of strontium nitrate and calcium nitrate is 1: 8～1: 10, gained solution is labeled as C, and wherein the molal quantity sum of strontium nitrate and calcium nitrate is designated as M1;
(4) in distilled water, add ammonium dihydrogen phosphate (ADP) uniform stirring, wherein the concentration of ammonium dihydrogen phosphate (ADP) is 6～55mmol/L, and gained solution is labeled as D, and wherein the molal quantity of ammonium dihydrogen phosphate (ADP) is counted M2;
(5) by solution C and solution D, according to M1:M2, being to mix for 3: 2～2: 1, is then 4～5 with the pH value of nitric acid and ammoniacal liquor adjustment solution, and gained solution is labeled as E;
(6) CNT is positioned in vessel, adding successively ferrous sulfate and concentration is 30% hydrogen peroxide, wherein the quality of ferrous sulfate and the volume ratio of hydrogen peroxide are 10～50mg/ml, at room temperature standing 1～5 hour, then use washed with de-ionized water, drying at room temperature obtains identified as samples and is designated as F;
(7) sample F is added in solution E, wherein the quality of F and the volume ratio of solution are 0.1～1mg/ml;
(8) take graphite material as anode, sample B are negative electrode, be placed in the solution of (7) step configuration, is 10～40mA at electric current, and temperature is that under 40～60 degree conditions, electro-deposition obtains sample G for 10～120 minutes;
(9) sample G is placed in to the strontium nitrate solution that concentration is 0.5～1.0mol/L, after temperature is to soak 24～48 hours under 40～60 degree conditions, obtains sample H;
(10) sample H is placed in to the sodium hydroxide solution that concentration is 0.5～1.0mol/L, after temperature is to soak 24～48 hours under 40～60 degree conditions, obtains bioactivation modified carbon fiber.
The invention has the beneficial effects as follows: because the method is introduced oxygen-containing functional group by oxidation reaction on the surface of carbon fiber, then adopt electrodeposition technology on its surface, to prepare CNT and strengthen strontium containing hydroxyapatite coating.Thereby make bioactivity coatings coated carbon fiber surface also and between carbon fiber form strong bonding, the method has improved the mechanical property of pure ha coating on the one hand by CNT wild phase, by introducing strontium trace element, improve on the other hand the tissue response behavior of pure ha, improved the biologically active of carbon fiber surface.In addition, the method is carried out under lower temperature conditions, and easy operating and equipment are simple.
Below in conjunction with drawings and Examples, the present invention is elaborated.
Accompanying drawing explanation
Fig. 1 is the stereoscan photograph of the surface active modified carbon fiber of the inventive method example 1 preparation.
The specific embodiment
The inventive method concrete steps are as follows:
Embodiment 1.
(1) carbon fiber is carried out to ultrasonic cleaning with acetone, absolute ethyl alcohol and distilled water successively, then put into vacuum drying chamber dry, obtain sample A;
(2) sample A is positioned in beaker, first adding mass percent concentration is 30% hydrogen peroxide, then add tungstophosphoric acid, wherein the quality of tungstophosphoric acid and the volume ratio of hydrogen peroxide are 5mg/ml, and it is under 60 degree conditions, to process 2h to obtain sample B in temperature that beaker is placed in to constant water bath box;
(3) strontium nitrate and calcium nitrate are added to evenly mixing in distilled water, wherein the concentration of strontium nitrate is 1mmol/L, and the concentration of calcium nitrate is 8mmol/L, and wherein the mol ratio of zinc nitrate and calcium nitrate is 1: 8, gained solution is labeled as C, and wherein the molal quantity sum of strontium nitrate and calcium nitrate is designated as M1;
(4) ammonium dihydrogen phosphate (ADP) uniform stirring in distilled water, wherein the concentration of ammonium dihydrogen phosphate (ADP) is 6mmol/L, and gained solution is labeled as D, and wherein the molal quantity of ammonium dihydrogen phosphate (ADP) is counted M2;
(5) by solution C and solution D, according to M1:M2, being to mix at 3: 2, is then 4 with the pH value of nitric acid and ammoniacal liquor adjustment solution, and gained solution is labeled as E;
(6) CNT is positioned in beaker, adding successively ferrous sulfate and concentration is 30% hydrogen peroxide, and wherein the quality of ferrous sulfate and the volume ratio of hydrogen peroxide are 10mg/ml, at room temperature standing 1 hour, then use washed with de-ionized water, drying at room temperature obtains identified as samples and is designated as F;
(7) sample F is added in solution E, wherein the quality of F and the volume ratio of solution are 0.1mg/ml;
(8) take graphite material as anode, sample B are negative electrode, be placed in the solution of (7) step configuration, is 10mA at electric current, and temperature is that under 40 degree conditions, electro-deposition obtains sample G for 10 minutes;
(9) sample G is placed in to the strontium nitrate solution that concentration is 0.5mol/L, after temperature is to soak 24 hours under 40 degree conditions, obtains sample H;
(10) sample H is placed in to the sodium hydroxide solution that concentration is 0.5mol/L, after temperature is to soak 24 hours under 40 degree conditions, obtains bioactivation modified carbon fiber.
The surface that can be found carbon fiber by Fig. 1 is covered completely by bioactive strontium containing hydroxyapatite, the even thickness of strontium containing hydroxyapatite and compact structure.
Embodiment 2.
(1) carbon fiber is carried out to ultrasonic cleaning with acetone, absolute ethyl alcohol and distilled water successively, then put into vacuum drying chamber dry, obtain sample A;
(2) sample A is positioned in beaker, first adding mass percent concentration is 30% hydrogen peroxide, then add tungstophosphoric acid, wherein the quality of tungstophosphoric acid and the volume ratio of hydrogen peroxide are 20mg/ml, and it is under 90 degree conditions, to process 10h to obtain sample B in temperature that beaker is placed in to constant water bath box;
(3) strontium nitrate and calcium nitrate are added to evenly mixing in distilled water, wherein the concentration of strontium nitrate is 5mmol/L, the concentration of calcium nitrate is 50mmol/L, wherein the mol ratio of zinc nitrate and calcium nitrate is 1: 10, gained solution is labeled as C, and wherein the molal quantity sum of strontium nitrate and calcium nitrate is designated as M1;
(4) ammonium dihydrogen phosphate (ADP) uniform stirring in distilled water, wherein the concentration of ammonium dihydrogen phosphate (ADP) is 55mmol/L, and gained solution is labeled as D, and wherein the molal quantity of ammonium dihydrogen phosphate (ADP) is counted M2;
(5) by solution C and solution D, according to M1:M2, being to mix at 2: 1, is then 5 with the pH value of nitric acid and ammoniacal liquor adjustment solution, and gained solution is labeled as E;
(6) CNT is positioned in beaker, adding successively ferrous sulfate and concentration is 30% hydrogen peroxide, and wherein the quality of ferrous sulfate and the volume ratio of hydrogen peroxide are 50mg/ml, at room temperature standing 5 hours, then use washed with de-ionized water, drying at room temperature obtains identified as samples and is designated as F;
(7) sample F is added in solution E, wherein the quality of F and the volume ratio of solution are 1mg/ml;
(8) take graphite material as anode, sample B are negative electrode, be placed in the solution of (7) step configuration, is 40mA at electric current, and temperature is that under 60 degree conditions, electro-deposition obtains sample G for 120 minutes;
(9) sample G is placed in to the strontium nitrate solution that concentration is 1.0mol/L, after temperature is to soak 48 hours under 60 degree conditions, obtains sample H;
(10) sample H is placed in to the sodium hydroxide solution that concentration is 1.0mol/L, after temperature is to soak 48 hours under 60 degree conditions, obtains bioactivation modified carbon fiber.
Embodiment 3.
(1) carbon fiber is carried out to ultrasonic cleaning with acetone, absolute ethyl alcohol and distilled water successively, then put into vacuum drying chamber dry, obtain sample A;
(2) sample A is positioned in beaker, first adding mass percent concentration is 30% hydrogen peroxide, then add tungstophosphoric acid, wherein the quality of tungstophosphoric acid and the volume ratio of hydrogen peroxide are 15mg/ml, and it is under 75 degree conditions, to process 6h to obtain sample B in temperature that beaker is placed in to constant water bath box;
(3) strontium nitrate and calcium nitrate are added to evenly mixing in distilled water, wherein the concentration of strontium nitrate is 3mmol/L, and the concentration of calcium nitrate is 30mmol/L, and wherein the mol ratio of zinc nitrate and calcium nitrate is 1: 9, gained solution is labeled as C, and wherein the molal quantity sum of strontium nitrate and calcium nitrate is designated as M1;
(4) ammonium dihydrogen phosphate (ADP) uniform stirring in distilled water, wherein the concentration of ammonium dihydrogen phosphate (ADP) is 30mmol/L, and gained solution is labeled as D, and wherein the molal quantity of ammonium dihydrogen phosphate (ADP) is counted M2;
(5) by solution C and solution D, according to M1:M2, being to mix at 9: 5, is then 4.5 with the pH value of nitric acid and ammoniacal liquor adjustment solution, and gained solution is labeled as E;
(6) CNT is positioned in beaker, adding successively ferrous sulfate and concentration is 30% hydrogen peroxide, and wherein the quality of ferrous sulfate and the volume ratio of hydrogen peroxide are 30mg/ml, at room temperature standing 3 hours, then use washed with de-ionized water, drying at room temperature obtains identified as samples and is designated as F;
(7) sample F is added in solution E, wherein the quality of F and the volume ratio of solution are 0.5mg/ml;
(8) take graphite material as anode, sample B are negative electrode, be placed in the solution of (7) step configuration, is 25mA at electric current, and temperature is that under 50 degree conditions, electro-deposition obtains sample G for 60 minutes;
(9) sample G is placed in to the strontium nitrate solution that concentration is 0.8mol/L, after temperature is to soak 36 hours under 50 degree conditions, obtains sample H;
(10) sample H is placed in to the sodium hydroxide solution that concentration is 0.8mol/L, after temperature is to soak 36 hours under 50 degree conditions, obtains bioactivation modified carbon fiber.
Embodiment 4.
(1) carbon fiber is carried out to ultrasonic cleaning with acetone, absolute ethyl alcohol and distilled water successively, then put into vacuum drying chamber dry, obtain sample A;
(2) sample A is positioned in beaker, first adding mass percent concentration is 30% hydrogen peroxide, then add tungstophosphoric acid, wherein the quality of tungstophosphoric acid and the volume ratio of hydrogen peroxide are 5mg/ml, and it is under 90 degree conditions, to process 5h to obtain sample B in temperature that beaker is placed in to constant water bath box;
(3) strontium nitrate and calcium nitrate are added to evenly mixing in distilled water, wherein the concentration of strontium nitrate is 3mmol/L, the concentration of calcium nitrate is 30mmol/L, wherein the mol ratio of zinc nitrate and calcium nitrate is 1: 10, gained solution is labeled as C, and wherein the molal quantity sum of strontium nitrate and calcium nitrate is designated as M1;
(4) ammonium dihydrogen phosphate (ADP) uniform stirring in distilled water, wherein the concentration of ammonium dihydrogen phosphate (ADP) is 40mmol/L, and gained solution is labeled as D, and wherein the molal quantity of ammonium dihydrogen phosphate (ADP) is counted M2;
(5) by solution C and solution D, according to M1:M2, being to mix at 2: 1, is then 4 with the pH value of nitric acid and ammoniacal liquor adjustment solution, and gained solution is labeled as E;
(6) CNT is positioned in beaker, adding successively ferrous sulfate and concentration is 30% hydrogen peroxide, and wherein the quality of ferrous sulfate and the volume ratio of hydrogen peroxide are 20mg/ml, at room temperature standing 4 hours, then use washed with de-ionized water, drying at room temperature obtains identified as samples and is designated as F;
(7) sample F is added in solution E, wherein the quality of F and the volume ratio of solution are 0.3mg/ml;
(8) take graphite material as anode, sample B are negative electrode, be placed in the solution of (7) step configuration, is 20mA at electric current, and temperature is that under 40 degree conditions, electro-deposition obtains sample G for 30 minutes;
(9) sample G is placed in to the strontium nitrate solution that concentration is 1.0mol/L, after temperature is to soak 48 hours under 40 degree conditions, obtains sample H;
(10) sample H is placed in to the sodium hydroxide solution that concentration is 0.5mol/L, after temperature is to soak 40 hours under 50 degree conditions, obtains bioactivation modified carbon fiber.
Claims (1)
1. a carbon fiber surface bioactivation method of modifying, is characterized in that comprising the following steps:
(1) carbon fiber is carried out to ultrasonic cleaning with acetone, absolute ethyl alcohol and distilled water successively, then put into vacuum drying chamber dry, obtain sample A;
(2) sample A is positioned in vessel, first adding mass percent concentration is 30% hydrogen peroxide, then add tungstophosphoric acid, wherein the quality of tungstophosphoric acid and the volume ratio of hydrogen peroxide are 5～20mg/ml, and it is under 60～90 degree conditions, to process 2～10h to obtain sample B in temperature that vessel are placed in to constant water bath box;
(3) strontium nitrate and calcium nitrate are added to evenly mixing in distilled water, wherein the concentration of strontium nitrate is 1～5mmol/L, the concentration of calcium nitrate is 8～50mmol/L, wherein the mol ratio of strontium nitrate and calcium nitrate is 1:8～1:10, gained solution is labeled as C, and wherein the molal quantity sum of strontium nitrate and calcium nitrate is designated as M1;
(4) in distilled water, add ammonium dihydrogen phosphate (ADP) uniform stirring, wherein the concentration of ammonium dihydrogen phosphate (ADP) is 6～55mmol/L, and gained solution is labeled as D, and wherein the molal quantity of ammonium dihydrogen phosphate (ADP) is counted M2;
(5) by solution C and solution D, according to M1:M2, being that 3:2～2:1 mixes, is then 4～5 by the pH value of nitric acid and ammoniacal liquor adjustment solution, and gained solution is labeled as E;
(6) CNT is positioned in vessel, adding successively ferrous sulfate and concentration is 30% hydrogen peroxide, wherein the quality of ferrous sulfate and the volume ratio of hydrogen peroxide are 10～50mg/ml, at room temperature standing 1～5 hour, then use washed with de-ionized water, drying at room temperature obtains identified as samples and is designated as F;
(7) sample F is added in solution E, wherein the quality of F and the volume ratio of solution are 0.1～1mg/ml;
(8) take graphite material as anode, sample B are negative electrode, be placed in the solution of (7) step configuration, is 10～40mA at electric current, and temperature is that under 40～60 degree conditions, electro-deposition obtains sample G for 10～120 minutes;
(9) sample G is placed in to the strontium nitrate solution that concentration is 0.5～1.0mol/L, after temperature is to soak 24～48 hours under 40～60 degree conditions, obtains sample H;
(10) sample H is placed in to the sodium hydroxide solution that concentration is 0.5～1.0mol/L, after temperature is to soak 24～48 hours under 40～60 degree conditions, obtains bioactivation modified carbon fiber.
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| CN107720796B (en) * | 2017-10-20 | 2019-04-05 | 西北工业大学 | A kind of preparation method of Bone Defect Repari tetra- constituent element Biocomposite material of C-Ca-P-Si |
| CN108118526B (en) * | 2017-12-13 | 2020-05-01 | 西北工业大学 | Preparation method of super-large calcium hydrogen phosphate dihydrate with surface in flower cluster shape |
| CN108570697A (en) * | 2018-04-26 | 2018-09-25 | 大同新成新材料股份有限公司 | A kind of Brush Plating composite technology |
| CN108546157B (en) * | 2018-05-31 | 2020-11-20 | 西北工业大学 | Surface modification method of carbon/carbon composite material |
| CN109750492B (en) * | 2018-12-20 | 2020-03-20 | 山东大学 | Surface treatment method for carbon cloth surface to grow carbon nano tube uniformly in early stage |
| CN112939631A (en) * | 2021-03-29 | 2021-06-11 | 西北工业大学 | High-unit-yield silicon carbide nanowire in carbon fiber preform and preparation method |
| CN114455921B (en) * | 2022-03-16 | 2023-01-17 | 天工俐德科技发展有限公司 | Biomass porous concrete sound-absorbing material and preparation method thereof |
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