CN101659761B - Method for reinforcing modified 3D chitosan bars through multi-wall carbon nano tube - Google Patents
Method for reinforcing modified 3D chitosan bars through multi-wall carbon nano tube Download PDFInfo
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- CN101659761B CN101659761B CN200910152870XA CN200910152870A CN101659761B CN 101659761 B CN101659761 B CN 101659761B CN 200910152870X A CN200910152870X A CN 200910152870XA CN 200910152870 A CN200910152870 A CN 200910152870A CN 101659761 B CN101659761 B CN 101659761B
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Abstract
The invention discloses a method for reinforcing modified 3D chitosan bars through a multi-wall carbon nano tube, which comprises the steps of adding the multi-wall carbon nano tube into dilute acetic acid aqueous liquid, adding chitosan powder, and stirring ultrasonically to obtain mixed liquid; stewing and defoaming; injecting the chitosan liquid into a die to form a layer of inner film at first, and then injecting the mixed liquid into the die; using basic coagulating liquid to infiltrate and disperse, then independently assembling to obtain the multi-wall carbon nano tube/chitosan compound gel bar; and using distilled water to wash to be neutral and then drying. The multi-wall carbon nano tube/chitosan compound bar prepared by the method for reinforcing the modified 3D chitosan bars through the multi-wall carbon nano tube has excellent mechanical property; and the multi-wall carbon nano tube can inhibit the growth of osteoclast, is beneficial to the healing of fracture, and can meet the clinic application requirements for the inner fixation of fracture.
Description
Technical field
The present invention relates to the method for reinforcing modified 3 D chitosan bars through multi-wall carbon nano tube.
Background technology
Multi-walled carbon nano-tubes is hollow cylindrical, and size is little, specific surface area is big, length-to-diameter ratio is big, light weight, has very high tensile strength (45 ± 7Gpa) and Young's modulus (1.0TPa).Multi-walled carbon nano-tubes can be used for biology, bio-medical system as a class nano material, although nonwoven carbon tube material surface can adhere to a large amount of Fibrinogens, it is very low to activate hematoblastic ability.In vitro study work shows, several dissimilar cells well-grown on carbon nanotube and matrix material thereof, and the material that contains carbon nanotube has the good cell adhesivity, is the ideal tissue engineering material.Multi-walled carbon nano-tubes has excellent mechanical property, is often used as nano-composite material, to improve the mechanical property of polymer materials.A spot of multi-walled carbon nano-tubes joins the mechanical strength that just can significantly improve material in the polymeric matrix.
Summary of the invention
The method that the purpose of this invention is to provide a kind of reinforcing modified 3 D chitosan bars through multi-wall carbon nano tube is to obtain high-intensity multi-walled carbon nano-tubes/chitosan composite bar, as clinical bone fracture internal fixation material.
The method of reinforcing modified 3 D chitosan bars through multi-wall carbon nano tube of the present invention may further comprise the steps:
1), joins the 400ml volume fraction and be in 2% the dilute acetic acid aqueous solution, ultrasonic agitation 2h by per 0.05～0.5g multi-walled carbon nano-tubes;
2) the chitosan powder being dissolved in volume fraction is in 2% the dilute acetic acid, is mixed with massfraction and is 4%～5% chitosan solution, standing and defoaming;
3) in step 1) solution, add 20g chitosan powder, add at twice, add 5g chitosan powder first by per 0.05～0.5g multi-walled carbon nano-tubes, add 15g chitosan powder behind the ultrasonic agitation 2h once more, ultrasonic agitation 2h obtains multi-walled carbon nano-tubes/chitosan mixing solutions, standing and defoaming;
4) step 2 that takes a morsel) chitosan solution injects mould and forms one deck inner membrance earlier, then multi-walled carbon nano-tubes/chitosan mixing solutions is injected mould, again mould is put into massfraction and is 5% alkaline solidification liquid, solidify 6～24h, the demoulding, obtain multi-walled carbon nano-tubes/chitosan plural gel bar, be washed with distilled water to neutrality;
5) multi-walled carbon nano-tubes/chitosan plural gel bar is dry under 60 ℃～80 ℃, get final product.
Above-mentioned alkaline solidification liquid is NaOH or KOH.
Beneficial effect of the present invention is:
" super fiber " multi-walled carbon nano-tubes original position is compound in the chitosan basal body, and chitosan is an external phase as matrix, can transmit stress; And the multi-walled carbon nano-tubes random dispersion can connect each layer of chitosan basal body in chitosan basal body, and plays the effect of bearing external stress; Multi-walled carbon nano-tubes has also played the effect of nucleator, has improved the degree of crystallinity of chitosan basal body, thereby has effectively improved the mechanical property of three-dimensional chitosan rod; Multi-walled carbon nano-tubes can suppress the growth of osteoclast, the healing that helps fracturing.When the multi-walled carbon nano-tubes when 0.5% joins in the chitosan basal body, the flexural strength of composite bar and modulus in flexure reach 130.7MPa, 4.4Gpa, compare with unmodified chitosan bar and to have improved 34.3%, 7.3% respectively, can satisfy the clinical service requirements of fracture internal fixing.
Embodiment
Further specify the present invention below in conjunction with specific embodiment.
Embodiment 1:
1) take by weighing the 0.05g multi-walled carbon nano-tubes, join the 400ml volume fraction and be in 2% the dilute acetic acid aqueous solution, 2h is stirred on limit ultra-sonic dispersion, limit;
2) the chitosan powder being dissolved in volume fraction is in 2% the dilute acetic acid, is mixed with massfraction and is 4% chitosan solution, standing and defoaming;
3) in step 1) solution, add the chitosan powder at twice, add 5g chitosan powder first, ultrasonic agitation 2h, make a spot of chitosan be coated on the multi-wall carbon nano-tube tube-surface, help multi-walled carbon nano-tubes and be dispersed in the chitosan solution, add 15g chitosan powder then, ultrasonic agitation 2h, obtain multi-walled carbon nano-tubes/chitosan mixing solutions, standing and defoaming;
4) the chitosan solution step 2 that takes a morsel) evenly is coated on die surface, and it is 5% NaOH solidification liquid that mould is placed massfraction, chitosan freezing film under the room temperature, and the demoulding obtains chitosan film; Then multi-walled carbon nano-tubes/chitosan mixing solutions is injected mould, mould is put into massfraction again and be 5% NaOH solidification liquid, solidify 6h, the demoulding obtains multi-walled carbon nano-tubes/chitosan plural gel bar, is washed with distilled water to neutrality;
5) be dry 72h in 60 ℃ the baking oven with multi-walled carbon nano-tubes/chitosan plural gel bar being placed on temperature, promptly obtain multi-walled carbon nano-tubes/chitosan three-dimensional composite rod material.The Mechanics Performance Testing result:
Flexural strength: 104.0MPa
Modulus in flexure: 4.3GPa
Embodiment 2:
1) take by weighing the 0.1g multi-walled carbon nano-tubes, join the 400ml volume fraction and be in 2% the dilute acetic acid aqueous solution, 2h is stirred on limit ultra-sonic dispersion, limit;
2) the chitosan powder being dissolved in volume fraction is in 2% the dilute acetic acid, is mixed with massfraction and is 4% chitosan solution, standing and defoaming;
3) add the chitosan powder at twice in step 1) solution, add 5g chitosan powder first, add 15g chitosan powder behind the ultrasonic agitation 2h once more, ultrasonic agitation 2h obtains multi-walled carbon nano-tubes/chitosan mixing solutions, standing and defoaming;
4) the chitosan solution step 2 that takes a morsel) evenly is coated on die surface, and it is 5% KOH solidification liquid that mould is placed massfraction, chitosan freezing film under the room temperature, and the demoulding obtains chitosan film; Then multi-walled carbon nano-tubes/chitosan mixing solutions is injected mould, mould is put into massfraction again and be 5% KOH solidification liquid, solidify 24h, the demoulding obtains multi-walled carbon nano-tubes/chitosan plural gel bar, is washed with distilled water to neutrality;
5) be dry 96h in 80 ℃ the baking oven with multi-walled carbon nano-tubes/chitosan plural gel bar being placed on temperature, promptly obtain multi-walled carbon nano-tubes/chitosan three-dimensional composite rod material.The Mechanics Performance Testing result:
Flexural strength: 130.7MPa
Modulus in flexure: 4.4GPa
Embodiment 3:
1) take by weighing the 0.5g multi-walled carbon nano-tubes, join the 400ml volume fraction and be in 2% the dilute acetic acid aqueous solution, 2h is stirred on limit ultra-sonic dispersion, limit;
2) the chitosan powder being dissolved in volume fraction is in 2% the dilute acetic acid, is mixed with massfraction and is 5% chitosan solution, standing and defoaming;
3) add the chitosan powder at twice in step 1) solution, add 5g chitosan powder first, add 15g chitosan powder behind the ultrasonic agitation 2h once more, ultrasonic agitation 2h obtains multi-walled carbon nano-tubes/chitosan mixing solutions, standing and defoaming;
4) the chitosan solution step 2 that takes a morsel) evenly is coated on die surface, and it is 5% KOH solidification liquid that mould is placed massfraction, chitosan freezing film under the room temperature, and the demoulding obtains chitosan film; Then multi-walled carbon nano-tubes/chitosan mixing solutions is injected mould, mould is put into massfraction again and be 5% KOH solidification liquid, solidify 12h, the demoulding obtains multi-walled carbon nano-tubes/chitosan plural gel bar, is washed with distilled water to neutrality;
5) be dry 120h in 70 ℃ the baking oven with multi-walled carbon nano-tubes/chitosan plural gel bar being placed on temperature, promptly obtain multi-walled carbon nano-tubes/chitosan three-dimensional composite rod material.The Mechanics Performance Testing result:
Flexural strength: 101.3MPa
Modulus in flexure: 4.4GPa
Claims (2)
1. the method for reinforcing modified 3 D chitosan bars through multi-wall carbon nano tube may further comprise the steps:
1), joins the 400mL volume fraction and be in 2% the dilute acetic acid aqueous solution, ultrasonic agitation 2h by per 0.05～0.5g multi-walled carbon nano-tubes;
2) the chitosan powder being dissolved in volume fraction is in 2% the dilute acetic acid, is mixed with massfraction and is 4%～5% chitosan solution, standing and defoaming;
3) in step 1) solution, add 20g chitosan powder, add at twice, add 5g chitosan powder first by per 0.05～0.5g multi-walled carbon nano-tubes, add 15g chitosan powder behind the ultrasonic agitation 2h once more, ultrasonic agitation 2h obtains multi-walled carbon nano-tubes/chitosan mixing solutions, standing and defoaming;
4) step 2 that takes a morsel) chitosan solution injects mould and forms one deck inner membrance earlier, then multi-walled carbon nano-tubes/chitosan mixing solutions is injected mould, again mould is put into massfraction and is 5% alkaline solidification liquid, solidify 6～24h, the demoulding, obtain multi-walled carbon nano-tubes/chitosan plural gel bar, be washed with distilled water to neutrality;
5) multi-walled carbon nano-tubes/chitosan plural gel bar is dry under 60 ℃～80 ℃, get final product.
2. the method for reinforcing modified 3 D chitosan bars through multi-wall carbon nano tube according to claim 1 is characterized in that alkaline solidification liquid is NaOH or KOH.
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| Application Number | Priority Date | Filing Date | Title |
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| CN200910152870XA CN101659761B (en) | 2009-09-18 | 2009-09-18 | Method for reinforcing modified 3D chitosan bars through multi-wall carbon nano tube |
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| CN200910152870XA CN101659761B (en) | 2009-09-18 | 2009-09-18 | Method for reinforcing modified 3D chitosan bars through multi-wall carbon nano tube |
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| CN101659761A CN101659761A (en) | 2010-03-03 |
| CN101659761B true CN101659761B (en) | 2011-08-24 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102219203B (en) * | 2011-04-15 | 2012-12-26 | 清华大学 | Three-dimensional nano-carbon material for composite strengthening, and preparation method thereof |
| CN106916323A (en) * | 2017-03-13 | 2017-07-04 | 哈尔滨工程大学 | A kind of process of preparing of the chitosan biological gel mould of the multi-walled carbon nano-tubes that adulterates |
| CN109266314B (en) * | 2018-11-16 | 2020-03-06 | 北京师范大学 | Flexible composite phase change material and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101366972A (en) * | 2008-09-28 | 2009-02-18 | 浙江大学 | Preparation method for three-dimensional ordered stephanoporate chitosan bone renovating bracket material |
| CN101376038A (en) * | 2008-10-07 | 2009-03-04 | 浙江大学 | Method for preparing composite bone repair stent material containing chitosan and hydroxylapatite |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101366972A (en) * | 2008-09-28 | 2009-02-18 | 浙江大学 | Preparation method for three-dimensional ordered stephanoporate chitosan bone renovating bracket material |
| CN101376038A (en) * | 2008-10-07 | 2009-03-04 | 浙江大学 | Method for preparing composite bone repair stent material containing chitosan and hydroxylapatite |
Non-Patent Citations (2)
| Title |
|---|
| Shao-Feng Wang et al.Preparation and Mechanical Properties of Chitosan/Carbon Nanotubes Composites.《Biomacromolecules》.2005,第6卷(第6期),第3067-3072页. * |
| 吴子刚等.碳纳米管/壳聚糖复合材料.《化学进展》.2006,第18卷(第9期),第1020-1027页. * |
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