CN101491698A - Preparation method of carbon nano-tube reinforced silicon-containing hydroxylapatite bone-cement biological material - Google Patents
Preparation method of carbon nano-tube reinforced silicon-containing hydroxylapatite bone-cement biological material Download PDFInfo
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Abstract
The invention relates to a method for preparing a nanotube-reinforced silicon-substituted hydroxyapatite and bone cement biomaterial, 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 a chemical pure tetraethyl orthosilicate solution into the solution D and placing the mixture in a microwave chemical reactor for reaction to obtain a white suspension; removing a supernatant of the suspension through filtration to obtain a sample E; drying, calcining and grinding the sample E to obtain silicon-substituted hydroxyapatite powder, adding a silane coupling agent and absolute ethanol into the silicon-substituted hydroxyapatite powder and subjecting to mixture to ultrasonic dispersion to obtain F; placing carbon fibers in deionized water, adding carboxymethylcellulose sodium, the sample F and potassium persulfate into the deionized water and subjecting the mixture to ultrasonic dispersion to obtain G; mixing acrylic acid and itaconic acid to obtain a mixed solution H1; adding sodium citrate into the mixed solution H1 to obtain a mixed solution H2; and placing a sample of K in a watch glass, adding the solution H2I into the watch glass, transferring the mixture into a mould for curing and obtaining the target product. In the composite prepared by the method, the carbon fibers distribute uniformly and are desirably combined with a substrate interface, so the composite is a biomedical composite with wide application prospect.
Description
Technical field
The present invention relates to a kind of enhancing bone-cement biological preparation methods, particularly a kind of preparation method of carbon nano-tube reinforced silicon-containing hydroxylapatite bone-cement biological material.
Background technology
Hydroxyapatite is the main inorganic composition of vertebrates skeleton and tooth, has good biocompatibility and biological activity.The human body osteocyte can be on hydroxyapatite directly forms chemical bond, and bond strength height, good stability, therefore is widely used as hard tissue substituting material.But the intensity of hydroxyapatite own is low, fragility is big, can only be used in that alveolar ridge increases, the ear ossiculum is replaced and non-bearing material aspect such as maxillofacial bone reparation, and is difficult to be applied to the load-bearing bone aspect, therefore need strengthen toughness reinforcing to hydroxyapatite.At present, hydroxyapatite is strengthened toughness reinforcing method mainly contains following approach both at home and abroad: other phases of introducing, single hydroxyapatite and organic-inorganic material carry out compound and add methods such as fiber, CNT in single hydroxyapatite matrixes in single hydroxyapatite matrix.People such as Tang Xiao love are with Ca (NO
3)
2, (NH
4)
3PO
4With ethyl orthosilicate be raw material, under certain pH conditions, adopt hydrothermal synthesis method to prepare the siliceous hydroxy apatite powder of nanometer [Tang Xiaolian, Xiao Xiufeng, Liu Rongfang, the hydro-thermal synthesis and structure of siliceous hydroxyapatite characterizes, Chinese Journal of Inorganic Chemistry, 2005,21 (10): 1500-1504].People such as Zhang Yumei are with (NH
4)
2HPO
4, Ca (NO
3)
2And Sr (NO
3)
2Be raw material, pH value to 10～11 with the ammonia regulator solution, 50 ℃ are reacted 24h down, adopt synthetic strontium containing hydroxyapatite [Zhang Yumei, Wang Qintao, pair great waves of having prepared of wet method, the wet method synthesis and structure stability of strontium containing hydroxyapatite, Rare Metals Materials and engineering, 2004,33 (10): 1049-1051].People such as Li Mingou are with Ca (NO
3)
2, (NH
4)
3PO
4And Zn (NO
3)
2Be reaction raw materials, adopt hydrothermal synthesis method, under the condition of pH＞11, control certain reaction temperature, time and heat treatment temperature have prepared zinc-containing hydroxyapatite [Li Mingou, Xiao Xiufeng, Liu Rongfang, the hydro-thermal synthesis and structure of zinc-containing hydroxyapatite characterizes, silicate journal, 2008,36 (3): 378-382].Though the used hydrothermal synthesis method of above-described preparation powder body is easier to obtain nano-grade hydroxy apatite, but the control to temperature and pressure is rather strict, under lower temperature and pressure, the powder body that obtains is generally other crystalline phases, and adopt the synthetic hydroxy apatite powder of wet method very easily to reunite, be difficult for obtaining dispersibility nano hydroxyapatite powder preferably.People such as Huang Fulong are matrix with synthetic poly-L-lactic acid (PDLLA), to adopt the synthetic hydroxyapatite superfine powder of liquid phase-sedimentation method serves as to add phase, adopt liquid phase adsorption method to prepare the HA/PDLLA composite then, by test to its bending strength, the mechanical strength of finding the PDLLA material that the HA/PDLLA composite the is more simple [Huang Fulong that increases, Dai Honglian, Fang Yuan, the preparation of HA/PDLLA composite and degradation property research thereof, Journal of Inorganic Materials, 2007,22 (2): 333-338].It is the n-HA/CS composite bone cement of coagulant with ZnO that people such as Zhang Li have prepared, when ZnO/ composite ratio is 1/8, consolidation liquid/(when the ratio of composite+ZnO) is 1.2ml/g, the comprcssive strength of bone cement can satisfy needs [Zhang Li, Li Yubao, the Zhou Gang of clinical manipulation, the curing mechanism research of nanometer hydroxyapatite/chitosan composite bone cement, Journal of Inorganic Materials, 2006,21 (5): 1197-1202].People such as Dong Hao adopt gelatin and calcium phosphate cement bracket to carry out compound, the gelatin of preparing/calcium phosphate bone cement compound support frame material compressive strength reaches 3.7MPa[Dong Hao, Ye Jiandong, Wang Xiupeng, the preparation of calcium phosphate bone cement/gelatin-compounded tissue engineering bracket material and structure thereof and performance, functional material, 2006,11 (37): 1805-1811].People such as Yan Yuhua have prepared glass fiber reinforced polyester methyl methacrylate (PMMA)/hydroxyapatite composite material, the hydroxyapatite micropowder of 5wt% is added in discovery in PMMA, can prepare the composite [Yan Yuhua of good biocompatibility, mechanical strength height, stable performance, Li Shipu, ten thousand great waves, PMMA/HA-GA composite, China YouSe Acta Metallurgica Sinica, 2002,12 (5): 935-939].Though with the organic material is that matrix, hydroxyapatite are that the mechanical property of adding the mutually prepared more single hydroxyapatite bone cement of its mechanical property of organic/hydroxyapatite composite material improves a lot, but Organic substance is difficult for degraded in human body, even can produce noxious substance.Human ultra-sonic dispersion such as Li Aimin in conjunction with the titration prepared silicon nitride/hydroxyapatite composite powder, through 1200 ℃, insulation 3h, pressureless sintering has prepared Hydroxyapatite and Nitride Silicon Composites [Li Aimin in air, Sun Kangning, Yin Yansheng, the preparation research of Hydroxyapatite and Nitride Silicon Composites, chemical industry progress, 2004,23 (1): 68-71].It is that wild phase is to improve the mechanical property of calcium phosphate bone cement that people such as Zhao Ping adopt carbon fiber, find that carbon fiber is after surface treatment, can improve the interface bond strength between itself and the bone cement greatly, effectively transmitted load makes the mechanical property of the composite of preparation significantly improve [Zhao Ping, Sun Kangning, Zhu Guangnan, carbon fiber strengthens calcium phosphate cement composite material, silicate journal, 2005,33 (1): 32-35].People such as Li Aimin are with homemade hydroxy apatite powder and the compound composite granule of preparing of CNT, through cold moudling and cold isostatic compaction and vacuum non-pressure sintering, obtain the composite of hydroxyapatite and CNT, by composite materials property is discovered, compare with pure ha, the bending strength and the fracture toughness of carbon nanometer tube/hydroxyapatite composite all increase, but the amplitude difference [Li Aimin that improves, Sun Kangning, Yin Yansheng, the mechanical property of carbon nanometer tube/hydroxyapatite composite and microstructure, composite journal, 2004,21 (5): 98-102].Though the mechanical property of the composite that the above method is prepared all increases, its complicated operation, reaction condition is wayward.
Summary of the invention
The object of the present invention is to provide the preparation method of the simple carbon nano-tube reinforced silicon-containing hydroxylapatite bone-cement biological material of a kind of preparation technology, prepared composite has higher rupture strength, can satisfy the requirement of clinical operation operation.
For achieving the above object, the technical solution used 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] be 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, 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: 2～2: 1: 5 volume ratio mix homogeneously;
After c, the D solution of getting 100ml place there-necked flask and add the chemical pure teos solution of 0.08ml～3.00ml at the microwave chemical reaction instrument in 60 ℃～100 ℃ reaction 1h～7h down;
After d, reaction finish,, get white suspension with taking out there-necked flask behind the microwave chemical reaction instrument natural cooling;
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, with sample E in 70 ℃～100 ℃ down oven dry;
H, the sample E after will drying put into alumina crucible in 700 ℃～1000 ℃ calcining 2h～5h down, treat to take out sample behind the body of heater natural cooling, promptly get siliceous hydroxy apatite powder grind 3min～5min in agate mortar after;
I, 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, under ultrasonic power 60w～100w, room temperature condition, ultra-sonic dispersion 15min～35min, the gained identified as samples is designated as F;
2): SURFACE TREATMENT OF CARBON FIBER and dispersion
A, be that 6mm, diameter are that the carbon fiber mass concentration of 7 μ m is 50%～63% HNO with average length
3Soak 10min～30min, the reuse mass concentration is 30% hydrogen peroxide pre-oxidation treatment 30min～60min, and is standby 80 ℃～100 ℃ down dry backs;
B, get the carbon fiber that 32g handled and place the there-necked flask that fills the 40ml deionized water, and then the sodium carboxymethyl cellulose dispersant that adds carbon fiber quality 1.0%～5.0% is to stir 15min～30min under 300rpm～400rpm at rotating speed, after treating that fiber dispersion fully, to the potassium peroxydisulfate initiator that wherein adds sample F and carbon fiber quality 0.5%～2.5%, under ultrasonic power 60w～100w, room temperature condition, ultra-sonic dispersion 15min～35min, the gained identified as samples is designated as G;
3): the preparation of bone-cement composite material
A, acrylic acid and itaconic acid are configured to the solution of 0.1mol/l～0.3mol/l and 0.1mol/l～0.3mol/l respectively, are labeled as L respectively
1And L
2
B, with L
1And L
2Volume ratio mix homogeneously with 1: 9～4: 6 gets mixed solution H
1
C, get 30ml～70ml Solution H
1, to Solution H
1The middle sodium citrate that adds its quality 0.1%～0.5% makes mixed solution H
2
D, get 5g～10g sample G in surface plate, add the Solution H of 10ml～20ml
2, at room temperature stir 3min～5min with Glass rod, leave standstill behind 3min～8min it is moved in mould, curing molding promptly obtains needed product under the pressure of 15MPa～40MPa.
The present invention adopts the microwave chemical reaction synthetic method to prepare the siliceous hydroxylapatite bone-cement composite material that rupture strength is 38.9～69.2MPa, can satisfy the requirement of clinical operation operation, and carbon fiber is uniformly dispersed in the prepared composite, fiber combines well with basal body interface, is the bio-medical composition that has application prospect.
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;
After c, the D solution of getting 100ml place there-necked flask and add the chemical pure teos solution of 0.15ml at the microwave chemical reaction instrument in 80 ℃ of reaction 4h down;
After d, reaction finish,, get white suspension with taking out there-necked flask behind the microwave chemical reaction instrument natural cooling;
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, with sample E in 100 ℃ of down oven dry;
H, the sample E after will drying put into alumina crucible in 800 ℃ of calcining 4h down, treat to take out sample behind the body of heater natural cooling, promptly get siliceous hydroxy apatite powder grind 3min in agate mortar after;
I, 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): SURFACE TREATMENT OF CARBON FIBER and dispersion
A, be that 6mm, diameter are that the carbon fiber mass concentration of 7 μ m is 50% HNO with average length
3Soak 10min, the reuse mass concentration is 30% hydrogen peroxide pre-oxidation treatment 60min, and is standby 92 ℃ of down dry backs;
B, get the carbon fiber that 32g handled and place the there-necked flask that fills the 40ml deionized water, and then the sodium carboxymethyl cellulose dispersant that adds carbon fiber quality 3.0% is to stir 20min under the 370rpm at rotating speed, after treating that fiber dispersion fully, to the potassium peroxydisulfate initiator that wherein adds sample F and carbon fiber quality 2.5%, under ultrasonic power 90w, room temperature condition, ultra-sonic dispersion 20min, the gained identified as samples is designated as G;
3): the preparation of bone-cement composite material
A, acrylic acid and itaconic acid are configured to the solution of 0.3mol/l and 0.25mol/l respectively, are labeled as L respectively
1And L
2
B, with L
1And L
2Volume ratio mix homogeneously with 4: 6 gets mixed solution H
1
C, get the 50ml Solution H
1, to Solution H
1The middle sodium citrate that adds its quality 0.3% makes mixed solution H
2
D, get 8g sample G in surface plate, add the Solution H of 20ml
2, at room temperature stir 5min with Glass rod, leave standstill behind the 8min it is moved in mould, curing molding promptly obtains 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 0.031mol/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;
After c, the D solution of getting 100ml place there-necked flask and add the chemical pure teos solution of 0.08ml at the microwave chemical reaction instrument in 60 ℃ of reaction 7h down;
After d, reaction finish,, get white suspension with taking out there-necked flask behind the microwave chemical reaction instrument natural cooling;
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, with sample E in 80 ℃ of down oven dry;
H, the sample E after will drying put into alumina crucible in 1000 ℃ of calcining 2h down, treat to take out sample behind the body of heater natural cooling, promptly get siliceous hydroxy apatite powder grind 5min in agate mortar after;
I, 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): SURFACE TREATMENT OF CARBON FIBER and dispersion
A, be that 6mm, diameter are that the carbon fiber mass concentration of 7 μ m is 60% HNO with average length
3Soak 18min, the reuse mass concentration is 30% hydrogen peroxide pre-oxidation treatment 40min, and is standby 80 ℃ of down dry backs;
B, get the carbon fiber that 32g handled and place the there-necked flask that fills the 40ml deionized water, and then the sodium carboxymethyl cellulose dispersant that adds carbon fiber quality 1.0% is to stir 30min under the 300rpm at rotating speed, after treating that fiber dispersion fully, to the potassium peroxydisulfate initiator that wherein adds sample F and carbon fiber quality 1.8%, under ultrasonic power 60w, room temperature condition, ultra-sonic dispersion 15min, the gained identified as samples is designated as G;
3): the preparation of bone-cement composite material
A, acrylic acid and itaconic acid are configured to the solution of 0.2mol/l and 0.1mol/l respectively, are labeled as L respectively
1And L
2
B, with L
1And L
2Volume ratio mix homogeneously with 1: 9 gets mixed solution H
1
C, get the 70ml Solution H
1, to Solution H
1The middle sodium citrate that adds its quality 0.1% makes mixed solution H
2
D, get 5g sample G in surface plate, add the Solution H of 16ml
2, at room temperature stir 3min with Glass rod, leave standstill behind the 5min it is moved in mould, curing molding promptly obtains needed product under the pressure of 32MPa.
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, 0.0lmol/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;
After c, the D solution of getting 100ml place there-necked flask and add the chemical pure teos solution of 3.00ml at the microwave chemical reaction instrument in 100 ℃ of reaction 1h down;
After d, reaction finish,, get white suspension with taking out there-necked flask behind the microwave chemical reaction instrument natural cooling;
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, with sample E in 70 ℃ of down oven dry;
H, the sample E after will drying put into alumina crucible in 700 ℃ of calcining 5h down, treat to take out sample behind the body of heater natural cooling, promptly get siliceous hydroxy apatite powder grind 4min in agate mortar after;
I, 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): SURFACE TREATMENT OF CARBON FIBER and dispersion
A, be that 6mm, diameter are that the carbon fiber mass concentration of 7 μ m is 55% HNO with average length
3Soak 24min, the reuse mass concentration is 30% hydrogen peroxide pre-oxidation treatment 30min, and is standby 100 ℃ of down dry backs;
B, get the carbon fiber that 32g handled and place the there-necked flask that fills the 40ml deionized water, and then the sodium carboxymethyl cellulose dispersant that adds carbon fiber quality 5.0% is to stir 15min under the 400rpm at rotating speed, after treating that fiber dispersion fully, to the potassium peroxydisulfate initiator that wherein adds sample F and carbon fiber quality 0.5%, under ultrasonic power 80w, room temperature condition, ultra-sonic dispersion 30min, the gained identified as samples is designated as G;
3): the preparation of bone-cement composite material
A, acrylic acid and itaconic acid are configured to the solution of 0.1mol/l and 0.3mol/l respectively, are labeled as L respectively
1And L
2
B, with L
1And L
2Volume ratio mix homogeneously with 1: 6 gets mixed solution H
1
C, get the 30ml Solution H
1, to Solution H
1The middle sodium citrate that adds its quality 0.5% makes mixed solution H
2
D, get 7g sample G in surface plate, add the Solution H of 10ml
2, at room temperature stir 4min with Glass rod, leave standstill behind the 3min it is moved in mould, curing molding promptly obtains needed product under the pressure of 25MPa.
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: 5 volume ratio mix homogeneously;
After c, the D solution of getting 100ml place there-necked flask and add the chemical pure teos solution of 0.25ml at the microwave chemical reaction instrument in 70 ℃ of reaction 5h down;
After d, reaction finish,, get white suspension with taking out there-necked flask behind the microwave chemical reaction instrument natural cooling;
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, with sample E in 90 ℃ of down oven dry;
H, the sample E after will drying put into alumina crucible in 900 ℃ of calcining 3h down, treat to take out sample behind the body of heater natural cooling, promptly get siliceous hydroxy apatite powder grind 3min in agate mortar after;
I, 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): SURFACE TREATMENT OF CARBON FIBER and dispersion
A, be that 6mm, diameter are that the carbon fiber mass concentration of 7 μ m is that 63% HNO3 soaks 30min with average length, the reuse mass concentration is 30% hydrogen peroxide pre-oxidation treatment 50min, and is standby 88 ℃ of dry down backs;
B, get the carbon fiber that 32g handled and place the there-necked flask that fills the 40ml deionized water, and then the sodium carboxymethyl cellulose dispersant that adds carbon fiber quality 2.0% is to stir 25min under the 320rpm at rotating speed, after treating that fiber dispersion fully, to the potassium peroxydisulfate initiator that wherein adds sample F and carbon fiber quality 1.5%, under ultrasonic power 100w, room temperature condition, ultra-sonic dispersion 35min, the gained identified as samples is designated as G;
3): the preparation of bone-cement composite material
A, acrylic acid and itaconic acid are configured to the solution of 0.25mol/l and 0.2mol/l respectively, are labeled as L respectively
1And L
2
B, with L
1And L
2Volume ratio mix homogeneously with 1: 3 gets mixed solution H
1
C, get the 60ml Solution H
1, to Solution H
1The middle sodium citrate that adds its quality 0.2% makes mixed solution H
2
D, get 10g sample G in surface plate, add the Solution H of 13ml
2, at room temperature stir 3min with Glass rod, leave standstill behind the 7min it is moved in mould, curing molding promptly obtains needed product under the pressure of 15MPa.
Claims (1)
1, the preparation method of carbon nano-tube reinforced silicon-containing hydroxylapatite bone-cement biological 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] be 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, 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: 2～2: 1: 5 volume ratio mix homogeneously;
After c, the D solution of getting 100ml place there-necked flask and add the chemical pure teos solution of 0.08ml～3.00ml at the microwave chemical reaction instrument in 60 ℃～100 ℃ reaction 1h～7h down;
After d, reaction finish,, get white suspension with taking out there-necked flask behind the microwave chemical reaction instrument natural cooling;
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, with sample E in 70 ℃～100 ℃ down oven dry;
H, the sample E after will drying put into alumina crucible in 700 ℃～1000 ℃ calcining 2h～5h down, treat to take out sample behind the body of heater natural cooling, promptly get siliceous hydroxy apatite powder grind 3min～5min in agate mortar after;
I, 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, under ultrasonic power 60w～100w, room temperature condition, ultra-sonic dispersion 15min～35min, the gained identified as samples is designated as F;
2): SURFACE TREATMENT OF CARBON FIBER and dispersion
A, be that 6mm, diameter are that the carbon fiber mass concentration of 7 μ m is 50%～63% HNO with average length
3Soak 10min～30min, the reuse mass concentration is 30% hydrogen peroxide pre-oxidation treatment 30min～60min, and is standby 80 ℃～100 ℃ down dry backs;
B, get the carbon fiber that 32g handled and place the there-necked flask that fills the 40ml deionized water, and then the sodium carboxymethyl cellulose dispersant that adds carbon fiber quality 1.0%～5.0% is to stir 15min～30min under 300rpm～400rpm at rotating speed, after treating that fiber dispersion fully, to the potassium peroxydisulfate initiator that wherein adds sample F and carbon fiber quality 0.5%～2.5%, under ultrasonic power 60w～100w, room temperature condition, ultra-sonic dispersion 15min～35min, the gained identified as samples is designated as G;
3): the preparation of bone-cement composite material
A, acrylic acid and itaconic acid are configured to the solution of 0.1mol/l～0.3mol/l and 0.1mol/l～0.3mol/l respectively, are labeled as L respectively
1And L
2
B, with L
1And L
2Volume ratio mix homogeneously with 1: 9～4: 6 gets mixed solution H
1
C, get 30ml～70ml Solution H
1, to Solution H
1The middle sodium citrate that adds its quality 0.1%～0.5% makes mixed solution H
2
D, get 5g～10g sample G in surface plate, add the Solution H of 10ml～20ml
2, at room temperature stir 3min～5min with Glass rod, leave standstill behind 3min～8min it is moved in mould, curing molding promptly obtains needed product under the pressure of 15MPa～40MPa.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009100213651A CN101491698B (en) | 2009-03-03 | 2009-03-03 | Preparation method of carbon nano-tube reinforced silicon-containing hydroxylapatite bone-cement biological material |
Applications Claiming Priority (1)
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103835117A (en) * | 2012-11-22 | 2014-06-04 | 浙江昱辉碳纤维材料有限公司 | Carbon fiber surface treatment method |
| CN105884274A (en) * | 2016-03-24 | 2016-08-24 | 陕西省建筑科学研究院 | Method for preparing HfC micron line and carbon fiber/Si3N4 micron band co-enhanced cement |
| CN109602948A (en) * | 2018-12-24 | 2019-04-12 | 深圳先进技术研究院 | The agent of bioactive bone cement solid phase and preparation method, bioactive bone cement slurry, solidified body and kit and application |
| US10369253B2 (en) | 2011-10-31 | 2019-08-06 | The University Of Toledo | Method for modifying surfaces for better osseointegration |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1217856C (en) * | 2003-11-21 | 2005-09-07 | 陕西科技大学 | Nanometer hydroxyapatite powder preparation method |
| CN101249282B (en) * | 2008-03-31 | 2011-05-18 | 陕西科技大学 | Preparation of biological compound material for bone repairing |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10369253B2 (en) | 2011-10-31 | 2019-08-06 | The University Of Toledo | Method for modifying surfaces for better osseointegration |
| CN103835117A (en) * | 2012-11-22 | 2014-06-04 | 浙江昱辉碳纤维材料有限公司 | Carbon fiber surface treatment method |
| CN105884274A (en) * | 2016-03-24 | 2016-08-24 | 陕西省建筑科学研究院 | Method for preparing HfC micron line and carbon fiber/Si3N4 micron band co-enhanced cement |
| CN105884274B (en) * | 2016-03-24 | 2018-05-25 | 陕西省建筑科学研究院 | A kind of HfC micro wires and carbon fiber/Si3N4Micro belt enhances the preparation method of cement altogether |
| CN109602948A (en) * | 2018-12-24 | 2019-04-12 | 深圳先进技术研究院 | The agent of bioactive bone cement solid phase and preparation method, bioactive bone cement slurry, solidified body and kit and application |
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