CN101491695A - Preparation method of carbon nano-tube reinforced chitosan/silicon-containing hydroxylapatite composite material - Google Patents
Preparation method of carbon nano-tube reinforced chitosan/silicon-containing hydroxylapatite composite material Download PDFInfo
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Abstract
The invention relates to a method for preparing carbon nanotube-reinforced chitosan and silicon-substituted hydroxyapatite composite, which comprises the following steps of: mixing a solution of calcium nitrate, a solution of ammonium dibasic phosphate and a solution of urea to obtain D; adding the solution D into a solution of tetraethyl orthosilicate, placing the mixture in a microwave chemical reactor till reaction finishes and removing a supernatant of the product of the reaction through filtration to obtain a sample E; calcining the sample in an alumina crucible and grinding the calcined sample in an agate mortar to obtain silicon-substituted hydroxyapatite powder; adding a lecithin coupling agent and absolute ethanol into the silicon-substituted hydroxyapatite powder and subjecting the mixture to ultrasonic dispersion to obtain F; placing nanotubes in the absolute ethanol, adding a sodium dodecylbenzebesuefonate dispersant into the absolute ethanol, placing the mixture in the microwave chemical reactor to disperse the nanotubes to obtain G, taking a sample of G, placing the sample in a hexanoic acid solution, and adding a sample F into the mixed solution, placing mixture in the microwave chemical reactor for reaction to obtained a sample K, adding chitosan into the K, placing the mixture into the microwave chemical reactor for reaction, and subjecting the product of the reaction to ultrasonic dispersion to obtain N; and placing a sample of N into a mould for curing and obtaining the target product.
Description
Technical field:
The present invention relates to a kind of method of CNT reinforced composite, the preparation method of particularly a kind of carbon nano-tube reinforced chitosan sugar/siliceous hydroxyapatite composite material.
Background technology
(Chitosan CS) has better biocompatibility and degradable absorbability to chitosan, and it is widely used in aspects such as post-operation adhesion preventing film, medicine sustained release carrier, poisonous substance adsorption separating agent, orthopaedics recovery support as bio-medical material.Zhang Jianxiang [Zhang Jianxiang, soup is built, Xu Bin, chitosan nail fixedly rabbit tibia dies and holds the experimentation of osteotomy, biomedical engineering's magazine, 1998,15 (2): 179-182] etc. the human Preparation of Chitosan diameter be that 4mm, length are the synthetism nail of 30mm～40mm, find that by test its tensile strength is 43.3MPa, shear strength is 46MPa.Hydroxyapatite is the important component part of natural bone tissue, has good biocompatibility and biological activity, therefore is widely used as bone and substitutes and bone grafting material.Studies show that in recent years, chitosan and the compound prepared composite of hydroxyapatite had stronger mechanical property, the mechanical property that all is higher than arbitrary homogenous material, simultaneously, the synosteosis ability and the biocompatibility of composite [the Itoh S. that all improves a lot, Kikuchi M., TakakudaK., The biocompatibility and osteoconductive activity of a novelhydroxyapatiite/collagen composite biomaterial, and its function asa carrier of rhBMP-2.Journal of Biomedical Materials Research, 2001,54:445-453.].Tu Xianyu [Tu Xianyu, Gao Lin, Deng Deming, the development of carbon fiber reinforced chitosan internal fixation bar and mechanical property evaluation, Changjiang University's journal, 2005,2 (12): 333-335] etc. the people adopts carbon fiber that chitosan is carried out enhancing modified, finds that the mechanical property of carbon fiber reinforced chitosan composite internal fixation bar obviously is better than simple chitosan internal fixation bar.People such as Zhao Ping [Zhao Ping, Sun Kangning, Zhu Guangnan, carbon fiber strengthens calcium phosphate cement composite material, silicate journal, 2005,33 (1): 32-35] adopting carbon fiber is that wild phase is to improve the mechanical property of calcium phosphate bone cement, after find adding the carbon fiber after handling with concentrated nitric acid liquid oxidatively method, can improve the interface bond strength between itself and the bone cement greatly, and the rupture strength of composite is 10.80MPa.Though this method can improve the rupture strength of calcium phosphate cement composite material to a certain extent, final result still can not satisfy the requirement of clinical operation operation.People such as Sun Kangning [Sun Kangning, Li Aimin, Yin Yansheng, the preparation research of carbon nanometer tube/hydroxyapatite composite, Chinese biological engineering in medicine journal, 2004,23 (6): 573-578] prepared the CNTs/HAP composite granule, after 111MPa cold moudling, 160MPa cold isostatic compaction, 600 ℃ of vacuum heat, find to add that the bending strength and the fracture toughness of CNTs/HAP composite all has raising behind the CNT, but the amplitude difference that improves.When content of carbon nanotubes was 2wt%, the bending strength of composite reached maximum 59.93MPa, and fracture toughness reaches 1.30MPam
1/2
At present, toughness reinforcing mainly the concentrating on of the enhancing of chitosan or this class biomaterial of hydroxyapatite added wild phase such as fiber (mainly being carbon fiber), CNT etc. both at home and abroad in single material.
Summary of the invention
The object of the present invention is to provide the preparation method of the simple carbon nano-tube reinforced chitosan sugar of a kind of preparation technology/siliceous hydroxyapatite composite material, prepared composite has higher rupture strength, can satisfy the requirement of clinical operation operation on rupture strength fully.
For achieving the above object, the technical solution adopted in the present invention is:
1): the preparation of siliceous hydroxy apatite powder
A, with analytically pure lime nitrate [Ca (NO
3)
24H
2O], diammonium phosphate [(NH
4)
2HPO
4] and carbamide [CO (NH
2)
2] being configured to the solution of 0.01mol/l～0.05mol/l, 0.01mol/l～0.05mol/l and 0.44mol/l～1.01mol/l respectively, solution is labeled as A, B, C respectively;
B. A, B, C three solution are got solution D with 2: 1: 2～2: 1: 6 volume ratio mix homogeneously;
C, get the D solution of 100ml and to the chemical pure teos solution that wherein adds 0.08ml～3.00ml, in the microwave chemical reaction instrument in 60 ℃～100 ℃ reaction 1h～7h down;
After d, reaction finished, solution got white suspension behind the natural cooling in the microwave chemical reaction instrument;
E. white suspension is poured in the beaker, left standstill 24h～96h in the room temperature lower open mouth, suspension is divided into two-layer up and down, and the upper strata is the stillness of night, and lower floor still is a suspension.
F, the elimination supernatant are cleaned lower floor's suspension 2 times with distilled water earlier behind the sucking filtration in the recirculated water vacuum pump, and the reuse dehydrated alcohol cleans 3～5 times, and the gained identified as samples is designated as E;
G. sample E is put into down alumina crucible after the oven dry in 700 ℃～1000 ℃ calcining 2h～5h down in 70 ℃～100 ℃, treat to take out sample behind the body of heater natural cooling, promptly get siliceous hydroxy apatite powder after in agate mortar, grinding 3min～5min;
H, the silicon hydroxy apatite powder put into beaker and add the lecithin coupling agent of its mass percent 0.5%～2.5%, the dehydrated alcohol that then splashes into 1ml～5ml is as solvent, at ultrasonic power is under 60w～100w, the room temperature condition, ultra-sonic dispersion 15min～35min, the gained identified as samples is designated as F;
2): the surface treatment of CNT and dispersion
A. be that 98% concentrated sulphuric acid and mass concentration are that 63% concentrated nitric acid fully mixes according to 2: 1～4: 1 volume ratio with mass concentration, mixed solution is labeled as M;
B. be that 0.8 μ m～450 μ m, diameter are that the CNT of 45nm～60nm soaks 30min～180min in solution M with length, the reuse mass concentration is 30% hydrogen peroxide pre-oxidation treatment 30min～90min, and is dry down at 80 ℃～100 ℃;
C. get processed carbon nanotubes and place dehydrated alcohol, the volume ratio of CNT and dehydrated alcohol is 90: 1～180: 1, the detergent alkylate semi-annular jade pendant acid sodium dispersant that adds CNT quality 0.05%～5.0% then under room temperature at the microwave chemical reaction instrument with 300rpm～400rpm microwave reaction 15min～30min, the gained identified as samples is designated as G;
D. with sample G in 40 ℃～70 ℃ following drying for standby;
3): the preparation of carbon nano-tube reinforced chitosan sugar/siliceous hydroxyapatite composite material
A. it is 2% acetic acid solution that the sample G that gets 32-96g places 40ml～120ml mass concentration, add 1g～10g sample F again, in under the room temperature in the microwave chemical reaction instrument with 300rpm～400rpm microwave reaction 30min～60min, the gained biased sample is labeled as K;
B. in biased sample K, add 4g～10g chitosan, in under the room temperature in the microwave chemical reaction instrument with 300rpm～400rpm microwave reaction 30min～60min, then under ultrasonic power 60w～100w, room temperature condition, 30min～240min is left standstill in deaeration behind ultra-sonic dispersion 15min～35min, and the gained identified as samples is designated as N;
C. sample N is moved in the mould, curing molding promptly gets needed product under the pressure of 15MPa～40MPa.
The present invention utilizes the microwave chemical reaction synthetic method can prepare siliceous hydroxy apatite powder, simultaneously, utilize Prepared by Solution Mixing Method to go out carbon nano-tube reinforced chitosan sugar/siliceous titanium/hydroxyl apatite biological composite material, prepared composite rupture strength is 70.5MPa～195.0MPa, can satisfy the requirement of clinical operation operation fully.
The specific embodiment
Embodiment 1:1): the preparation of siliceous hydroxy apatite powder
A, with analytically pure lime nitrate [Ca (NO
3)
24H
2O], diammonium phosphate [(NH
4)
2HPO
4] and carbamide [CO (NH
2)
2] be configured to the solution of 0.03mol/l, 0.05mol/l and 0.6mol/l respectively, be labeled as A, B, C solution respectively;
B, A, B, three kinds of solution of C are designated as solution D by 2: 1: 2 volume ratio mix homogeneously;
C, get the D solution of 100ml and behind the chemical pure teos solution that wherein adds 0.85ml in the microwave chemical reaction instrument in 80 ℃ of following reaction 4h;
After d, reaction finished, solution got white suspension behind the natural cooling in the microwave chemical reaction instrument;
E, white suspension is poured in the beaker, left standstill 24h～96h in the room temperature lower open mouth, suspension is divided into two-layer up and down, and the upper strata is the stillness of night, and lower floor still is a suspension;
F, the elimination supernatant are cleaned lower floor's suspension 2 times with distilled water earlier behind the sucking filtration in the recirculated water vacuum pump, and the reuse dehydrated alcohol cleans 3 times, and the gained identified as samples is designated as E;
G, sample E is put into down alumina crucible after the oven dry in 800 ℃ of calcining 4h down in 100 ℃, treat to take out sample behind the body of heater natural cooling, promptly get siliceous hydroxy apatite powder after in agate mortar, grinding 3min;
H, the silicon hydroxy apatite powder put into beaker and add the lecithin coupling agent of its mass percent 0.5%, the dehydrated alcohol that then splashes into 5ml is as solvent, under ultrasonic power 80w, room temperature condition, and ultra-sonic dispersion 20min, the gained identified as samples is designated as F;
2): the surface treatment of CNT and dispersion
A. be that 98% concentrated sulphuric acid and mass concentration are that 63% concentrated nitric acid fully mixes according to 2: 1 volume ratio with mass concentration, mixed solution is labeled as M;
B. be that 0.8 μ m～450 μ m, diameter are that the CNT of 45nm～60nm soaks 30min in solution M with length, the reuse mass concentration is 30% hydrogen peroxide pre-oxidation treatment 90min, and is dry down at 92 ℃.
C. get processed carbon nanotubes and place dehydrated alcohol, the volume ratio of CNT and dehydrated alcohol is 90: 1, and the detergent alkylate semi-annular jade pendant acid sodium dispersant that adds CNT quality 0.05% then is designated as G at the microwave chemical reaction instrument with 370rpm microwave reaction 20min gained identified as samples under room temperature;
D. sample G is standby in 50 ℃ of dry down backs;
3): the preparation of carbon nano-tube reinforced chitosan sugar/siliceous hydroxyapatite composite material
A. it is 2% acetic acid solution that the sample G that gets 32g places the 40ml mass concentration, adds the 1g sample F again, under the room temperature in the microwave chemical reaction instrument with 370rpm microwave reaction 30min, the gained biased sample is labeled as K;
B. in biased sample K, add the 10g chitosan, in under the room temperature in the microwave chemical reaction instrument with 300rpm microwave reaction 60min, then under ultrasonic power 80w, room temperature condition, 30min～240min is left standstill in deaeration behind the ultra-sonic dispersion 20min, and the gained identified as samples is designated as N;
C. sample N is moved in the mould, curing molding promptly gets needed product under the pressure of 40MPa.
Embodiment 2:1): the preparation of siliceous hydroxy apatite powder
A, with analytically pure lime nitrate [Ca (NO
3)
24H
2O], diammonium phosphate [(NH
4)
2HPO
4] and carbamide [CO (NH
2)
2] be configured to the solution of 0.01mol/l, 0.02mol/l and 0.44mol/l respectively, be labeled as A, B, C solution respectively;
B, A, B, three kinds of solution of C are designated as solution D by 2: 1: 4 volume ratio mix homogeneously;
C, get the D solution of 100ml and behind the chemical pure teos solution that wherein adds 0.08ml in the microwave chemical reaction instrument in 60 ℃ of following reaction 7h;
After d, reaction finished, solution got white suspension behind the natural cooling in the microwave chemical reaction instrument;
E, white suspension is poured in the beaker, left standstill 24h～96h in the room temperature lower open mouth, suspension is divided into two-layer up and down, and the upper strata is the stillness of night, and lower floor still is a suspension;
F, the elimination supernatant are cleaned lower floor's suspension 2 times with distilled water earlier behind the sucking filtration in the recirculated water vacuum pump, and the reuse dehydrated alcohol cleans 5 times, and the gained identified as samples is designated as E;
G, sample E is put into down alumina crucible after the oven dry in 1000 ℃ of calcining 2h down in 80 ℃, treat to take out sample behind the body of heater natural cooling, promptly get siliceous hydroxy apatite powder after in agate mortar, grinding 5min;
H, the silicon hydroxy apatite powder put into beaker and add the lecithin coupling agent of its mass percent 1.2%, the dehydrated alcohol that then splashes into 3ml is as solvent, under ultrasonic power 60w, room temperature condition, and ultra-sonic dispersion 30min, the gained identified as samples is designated as F;
2): the surface treatment of CNT and dispersion
A. be that 98% concentrated sulphuric acid and mass concentration are that 63% concentrated nitric acid fully mixes according to 3: 1 volume ratio with mass concentration, mixed solution is labeled as M;
B. be that 0.8 μ m～450 μ m, diameter are that the CNT of 45nm～60nm soaks 90min in solution M with length, the reuse mass concentration is 30% hydrogen peroxide pre-oxidation treatment 30min, and is dry down at 80 ℃.
C. get processed carbon nanotubes and place dehydrated alcohol, the volume ratio of CNT and dehydrated alcohol is 120: 1, and the detergent alkylate semi-annular jade pendant acid sodium dispersant that adds CNT quality 0.8% then is designated as G at the microwave chemical reaction instrument with 300rpm microwave reaction 30min gained identified as samples under room temperature;
D. sample G is standby in 70 ℃ of dry down backs;
3): the preparation of carbon nano-tube reinforced chitosan sugar/siliceous hydroxyapatite composite material
A. it is 2% acetic acid solution that the sample G that gets 50g places the 65ml mass concentration, adds the 4g sample F again, under the room temperature in the microwave chemical reaction instrument with 300rpm microwave reaction 40min, the gained biased sample is labeled as K;
B. in biased sample K, add the 6g chitosan, in under the room temperature in the microwave chemical reaction instrument with 400rpm microwave reaction 30min, then under ultrasonic power 100w, room temperature condition, 30min～240min is left standstill in deaeration behind the ultra-sonic dispersion 15min, and the gained identified as samples is designated as N;
C. sample N is moved in the mould, curing molding promptly gets needed product under the pressure of 30MPa.
Embodiment 3:1): the preparation of siliceous hydroxy apatite powder
A, with analytically pure lime nitrate [Ca (NO
3)
24H
2O], diammonium phosphate [(NH
4)
2HPO
4] and carbamide [CO (NH
2)
2] be configured to the solution of 0.04mol/l, 0.01mol/l and 0.8mol/l respectively, be labeled as A, B, C solution respectively;
B, A, B, three kinds of solution of C are designated as solution D by 2: 1: 3 volume ratio mix homogeneously;
C, get the D solution of 100ml and behind the chemical pure teos solution that wherein adds 3.00ml in the microwave chemical reaction instrument in 100 ℃ of following reaction 1h;
After d, reaction finished, solution got white suspension behind the natural cooling in the microwave chemical reaction instrument;
E, white suspension is poured in the beaker, left standstill 24h～96h in the room temperature lower open mouth, suspension is divided into two-layer up and down, and the upper strata is the stillness of night, and lower floor still is a suspension;
F, the elimination supernatant are cleaned lower floor's suspension 2 times with distilled water earlier behind the sucking filtration in the recirculated water vacuum pump, and the reuse dehydrated alcohol cleans 4 times, and the gained identified as samples is designated as E;
G, sample E is put into down alumina crucible after the oven dry in 700 ℃ of calcining 5h down in 70 ℃, treat to take out sample behind the body of heater natural cooling, promptly get siliceous hydroxy apatite powder after in agate mortar, grinding 4min;
H, the silicon hydroxy apatite powder put into beaker and add the lecithin coupling agent of its mass percent 2.0%, the dehydrated alcohol that then splashes into 1ml is as solvent, under ultrasonic power 90w, room temperature condition, and ultra-sonic dispersion 15min, the gained identified as samples is designated as F;
2): the surface treatment of CNT and dispersion
A. be that 98% concentrated sulphuric acid and mass concentration are that 63% concentrated nitric acid fully mixes according to 3: 1 volume ratio with mass concentration, mixed solution is labeled as M;
B. be that 0.8 μ m～450 μ m, diameter are that the CNT of 45nm～60nm soaks 150min in solution M with length, the reuse mass concentration is 30% hydrogen peroxide pre-oxidation treatment 70min, and is dry down at 100 ℃.
C. get processed carbon nanotubes and place dehydrated alcohol, the volume ratio of CNT and dehydrated alcohol is 150: 1, and the detergent alkylate semi-annular jade pendant acid sodium dispersant that adds CNT quality 3% then is designated as G at the microwave chemical reaction instrument with 400rpm microwave reaction 15min gained identified as samples under room temperature;
D. sample G is standby in 40 ℃ of dry down backs;
3): the preparation of carbon nano-tube reinforced chitosan sugar/siliceous hydroxyapatite composite material
A. it is 2% acetic acid solution that the sample G that gets 70g places the 90ml mass concentration, adds the 7g sample F again, under the room temperature in the microwave chemical reaction instrument with 400rpm microwave reaction 50min, the gained biased sample is labeled as K;
B. in biased sample K, add the 8g chitosan, in under the room temperature in the microwave chemical reaction instrument with 370rpm microwave reaction 50min, then under ultrasonic power 70w, room temperature condition, 30min～240min is left standstill in deaeration behind the ultra-sonic dispersion 30min, and the gained identified as samples is designated as N;
C. sample N is moved in the mould, curing molding promptly gets needed product under the pressure of 15MPa.
Embodiment 4:1): the preparation of siliceous hydroxy apatite powder
A, with analytically pure lime nitrate [Ca (NO
3)
24H
2O], diammonium phosphate [(NH
4)
2HPO
4] and carbamide [CO (NH
2)
2] be configured to the solution of 0.05mol/l, 0.04mol/l and 1.01mol/l respectively, be labeled as A, B, C solution respectively;
B, A, B, three kinds of solution of C are designated as solution D by 2: 1: 6 volume ratio mix homogeneously;
C, get the D solution of 100ml and behind the chemical pure teos solution that wherein adds 2.25ml in the microwave chemical reaction instrument in 70 ℃ of following reaction 5h;
After d, reaction finished, solution got white suspension behind the natural cooling in the microwave chemical reaction instrument;
E, white suspension is poured in the beaker, left standstill 24h～96h in the room temperature lower open mouth, suspension is divided into two-layer up and down, and the upper strata is the stillness of night, and lower floor still is a suspension;
F, the elimination supernatant are cleaned lower floor's suspension 2 times with distilled water earlier behind the sucking filtration in the recirculated water vacuum pump, and the reuse dehydrated alcohol cleans 5 times, and the gained identified as samples is designated as E;
G, sample E is put into down alumina crucible after the oven dry in 900 ℃ of calcining 3h down in 90 ℃, treat to take out sample behind the body of heater natural cooling, promptly get siliceous hydroxy apatite powder after in agate mortar, grinding 3min;
H, the silicon hydroxy apatite powder put into beaker and add the lecithin coupling agent of its mass percent 2.5%, the dehydrated alcohol that then splashes into 4ml is as solvent, under ultrasonic power 100w, room temperature condition, and ultra-sonic dispersion 35min, the gained identified as samples is designated as F;
2): the surface treatment of CNT and dispersion
A. be that 98% concentrated sulphuric acid and mass concentration are that 63% concentrated nitric acid fully mixes according to 4: 1 volume ratio with mass concentration, mixed solution is labeled as M;
B. be that 0.8 μ m～450 μ m, diameter are that the CNT of 45nm～60nm soaks 180min in solution M with length, the reuse mass concentration is 30% hydrogen peroxide pre-oxidation treatment 50min, and is dry down at 88 ℃.
C. get processed carbon nanotubes and place dehydrated alcohol, the volume ratio of CNT and dehydrated alcohol is 180: 1, and the detergent alkylate semi-annular jade pendant acid sodium dispersant that adds CNT quality 5.0% then is designated as G at the microwave chemical reaction instrument with 320rpm microwave reaction 25min gained identified as samples under room temperature;
D. sample G is standby in 60 ℃ of dry down backs;
3): the preparation of carbon nano-tube reinforced chitosan sugar/siliceous hydroxyapatite composite material
A. it is 2% acetic acid solution that the sample G that gets 96g places the 120ml mass concentration, adds the 10g sample F again, under the room temperature in the microwave chemical reaction instrument with 320rpm microwave reaction 60min, the gained biased sample is labeled as K;
B. in biased sample K, add the 4g chitosan, in under the room temperature in the microwave chemical reaction instrument with 320rpm microwave reaction 40min, then under ultrasonic power 60w, room temperature condition, 30min～240min is left standstill in deaeration behind the ultra-sonic dispersion 35min, and the gained identified as samples is designated as N;
C. sample N is moved in the mould, curing molding promptly gets needed product under the pressure of 20MPa.
Claims (1)
1, the preparation method of carbon nano-tube reinforced chitosan sugar/siliceous hydroxyapatite composite material is characterized in that:
1): the preparation of siliceous hydroxy apatite powder
A, with analytically pure lime nitrate [Ca (NO
3)
24H
2O], diammonium phosphate [(NH
4)
2HPO
4] and carbamide [CO (NH
2)
2] being configured to the solution of 0.01mol/l～0.05mol/l, 0.01mol/l～0.05mol/l and 0.44mol/l～1.01mol/l respectively, solution is labeled as A, B, C respectively;
B. A, B, C three solution are got solution D with 2: 1: 2～2: 1: 6 volume ratio mix homogeneously;
C, get the D solution of 100ml and to the chemical pure teos solution that wherein adds 0.08ml～3.00ml, in the microwave chemical reaction instrument in 60 ℃～100 ℃ reaction 1h～7h down;
After d, reaction finished, solution got white suspension behind the natural cooling in the microwave chemical reaction instrument;
E. white suspension is poured in the beaker, left standstill 24h～96h in the room temperature lower open mouth, suspension is divided into two-layer up and down, and the upper strata is the stillness of night, and lower floor still is a suspension.
F, the elimination supernatant are cleaned lower floor's suspension 2 times with distilled water earlier behind the sucking filtration in the recirculated water vacuum pump, and the reuse dehydrated alcohol cleans 3～5 times, and the gained identified as samples is designated as E;
G. sample E is put into down alumina crucible after the oven dry in 700 ℃～1000 ℃ calcining 2h～5h down in 70 ℃～100 ℃, treat to take out sample behind the body of heater natural cooling, promptly get siliceous hydroxy apatite powder after in agate mortar, grinding 3min～5min;
H, the silicon hydroxy apatite powder put into beaker and add the lecithin coupling agent of its mass percent 0.5%～2.5%, the dehydrated alcohol that then splashes into 1ml～5ml is as solvent, at ultrasonic power is under 60w～100w, the room temperature condition, ultra-sonic dispersion 15min～35min, the gained identified as samples is designated as F;
2): the surface treatment of CNT and dispersion
A. be that 98% concentrated sulphuric acid and mass concentration are that 63% concentrated nitric acid fully mixes according to 2: 1～4: 1 volume ratio with mass concentration, mixed solution is labeled as M;
B. be that 0.8 μ m～450 μ m, diameter are that the CNT of 45nm～60nm soaks 30min～180min in solution M with length, the reuse mass concentration is 30% hydrogen peroxide pre-oxidation treatment 30min～90min, and is dry down at 80 ℃～100 ℃;
C. get processed carbon nanotubes and place dehydrated alcohol, the volume ratio of CNT and dehydrated alcohol is 90: 1～180: 1, the detergent alkylate semi-annular jade pendant acid sodium dispersant that adds CNT quality 0.05%～5.0% then under room temperature at the microwave chemical reaction instrument with 300rpm～400rpm microwave reaction 15min～30min, the gained identified as samples is designated as G;
D. with sample G in 40 ℃～70 ℃ following drying for standby;
3): the preparation of carbon nano-tube reinforced chitosan sugar/siliceous hydroxyapatite composite material
A. it is 2% acetic acid solution that the sample G that gets 32-96g places 40ml～120ml mass concentration, add 1g～10g sample F again, in under the room temperature in the microwave chemical reaction instrument with 300rpm～400rpm microwave reaction 30min～60min, the gained biased sample is labeled as K;
B. in biased sample K, add 4g～10g chitosan, in under the room temperature in the microwave chemical reaction instrument with 300rpm～400rpm microwave reaction 30min～60min, then under ultrasonic power 60w～100w, room temperature condition, 30min～240min is left standstill in deaeration behind ultra-sonic dispersion 15min～35min, and the gained identified as samples is designated as N;
C. sample N is moved in the mould, curing molding promptly gets needed product under the pressure of 15MPa～40MPa.
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| CN101693131B (en) * | 2009-10-22 | 2012-12-26 | 浙江大学 | Method for reinforcing modified three-dimensional chitosan bar material by water soluble multi-wall carbon nano tubes |
| CN102000363A (en) * | 2010-11-10 | 2011-04-06 | 东华大学 | Preparation method of CA/CS/CNTs (cellulose acetate/chitosan/ carbon nano tubes) composite nano fiber with good biocompatibility |
| CN102000363B (en) * | 2010-11-10 | 2013-05-15 | 东华大学 | Preparation method of CA/CS/CNTs (cellulose acetate/chitosan/ carbon nano tubes) composite nano fiber with good biocompatibility |
| CN102430154A (en) * | 2011-12-07 | 2012-05-02 | 北京航空航天大学 | Preparation method of three-dimensional porous support frame material containing carbon nanometer tubes |
| CN107261206A (en) * | 2017-06-02 | 2017-10-20 | 华南师范大学 | A kind of biotic bone tissue engineering stent and preparation method and application |
| CN107261206B (en) * | 2017-06-02 | 2020-08-07 | 华南师范大学 | Bionic bone tissue engineering scaffold and preparation method and application thereof |
| CN107537063A (en) * | 2017-07-17 | 2018-01-05 | 大连理工大学 | A kind of complex stephanoporate bracket of carbon nanotubes and preparation method thereof |
| CN107537063B (en) * | 2017-07-17 | 2019-10-11 | 大连理工大学 | A kind of complex stephanoporate bracket of carbon nanotubes and preparation method thereof |
| CN107601913A (en) * | 2017-09-29 | 2018-01-19 | 重庆科技学院 | A kind of preparation method of the micro- pattern of material surface |
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