CN106365627A - Hydroxyapatite-carbon nanotube composite bioceramic - Google Patents

Hydroxyapatite-carbon nanotube composite bioceramic Download PDF

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CN106365627A
CN106365627A CN201610822313.4A CN201610822313A CN106365627A CN 106365627 A CN106365627 A CN 106365627A CN 201610822313 A CN201610822313 A CN 201610822313A CN 106365627 A CN106365627 A CN 106365627A
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hydroxyapatite
carbon nanotube
hydroxy apatite
nanotube composite
powder
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不公告发明人
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Abstract

The invention provides a hydroxyapatite-carbon nanotube composite bioceramic and relates to the field of biomedical materials. The composite bioceramic is formed by hydroxyapatite powder and carbon nanotubes, wherein the hydroxyapatite powder is coated with a silica nanoparticle layer, the mass ratio of the hydroxyapatite powder to the carbon nanotubes is (10-20):1, average particle size of the hydroxyapatite powder is 5 -20 micrometers, and thickness of the silica particle layer which coats the surface of the hydroxyapatite powder is 50-200nm. The preparation method for the hydroxyapatite-carbon nanotube composite bioceramic includes the following steps: preparing the hydroxyapatite powder by a hydrothermal method; conducting chemical vapor deposition reaction; conducting drying, cold pressing and molding; conducting high temperature calcinating and cooling. The hydroxyapatite-carbon nanotube composite bioceramic uses the hydroxyapatite as a base and has rather high bone repair performance through use of the carbon nanotubes, which have excellent mechanical property and have effect on bone cell proliferation, on the basis of the hydroxyapatite.

Description

A kind of hydroxyapatite-CNT composite boilogical ceramic
Technical field
The invention belongs to biomedical materials field, particularly to a kind of hydroxylapatite/carbon nanotube compound bio pottery Porcelain and the preparation method of this bioceramic.
Background technology
Bioceramic is the new ceramics relevant with organism, and bioceramic not only has the spy that plastic stainless-steel has Property, and there is hydrophilic, good affinity can be shown with biological tissues such as cells.
Bioceramic material is divided into bio-inert ceramic materials and biological active ceramic material, hydroxyl apatite bioceramic Belong to bioactive ceramicses, the structure of hydroxyapatite is similar to biological bone, therefore, the hydroxyl apatite bioceramic of synthesis is normal Replacement as skeleton or repair materials.
CNT, also known as Baji-tube, are a kind of One-dimensional Quantum materials with special construction, and having radial dimension is to receive Rice magnitude, axial dimension is micron dimension, and pipe two ends are substantially all the construction featuress of sealing.
CNT is as monodimension nanometer material, lightweight, and hexagonal structure connects perfection, has the power of many exceptions , electricity and chemical property.Goed deep into its wide application prospect with CNT and nano materials research also not in recent years Show disconnectedly.Biomedical material is the new field for CNT research and utilization.
In research with regard to the biological utilisation of CNT, there is scientist that osteoblast is inoculated on CNT, examine Examine its propagation and function, find CNT promote cell proliferation, increased alkaline phosphatase activitieses, intracellular protein synthesis and Extracellular Ca2＋ deposits.Although, CNT has certain cytotoxicity, its excellent performance, has still driven it giving birth to The application of thing material.
Patent documentation " the preparation of carbon nano-tube reinforced hydroxylapatite composite material of Application No. 201210555876.3 Method " discloses a kind of preparation method of hydroxylapatite/carbon nanotube composite, is synthesis in hydroxy apatite powder CNT, and carry out carbon nano tube surface modification using hydroxyapatite, and then prepare carbon nano-tube reinforced hydroxylapatite The method of composite, first prepares CNT-hydroxyapatite powder with nickelous carbonate and hydroxyapatite powder, then prepares hydroxyl CNT-hydroxyapatite powder that base apatite is modified, is finally obtained carbon nano-tube reinforced hydroxylapatite composite material.
It follows that the composite that this technical scheme provides, it is to carry out carbon nano tube surface using hydroxyapatite to repair Decorations, to improve wellability between CNT and hydroxyapatite matrix, and contribute to the molding of material, are a kind of effective Composite material and preparation method thereof.
Content of the invention
Present invention solves the technical problem that: for above-mentioned deficiency, overcome the defect of prior art, it is an object of the invention to provide one Plant hydroxylapatite/carbon nanotube composite boilogical ceramic and preparation method thereof.
Technical scheme: a kind of hydroxylapatite/carbon nanotube composite boilogical ceramic, composite boilogical ceramic is by wrapping Be covered with the hydroxy apatite powder of Nano particles of silicon dioxide layer and CNT constituted, wherein, hydroxy apatite powder flat All particle diameter is 5-20 μm, and the thickness of surface coated silicon dioxide granule layer is 50-200nm；
Wherein, the hydroxy apatite powder of nanoparticle layers that is coated with silicon oxide is 10- with the mass ratio example of CNT 20:1.
Preferably, described hydroxyapatite is prepared from according to hydro-thermal method.
A kind of preparation method of hydroxylapatite/carbon nanotube composite boilogical ceramic, preparation process is as follows:
(1) prepare hydroxy apatite powder: hydroxyapatite is prepared by hydro-thermal method, then drying and grinding is sieved；
(2) hydroxy apatite powder is put in chemical vapor deposition reaction chamber, carry out chemical vapour deposition reaction: be preheated to 600-800 DEG C, with tetraethyl orthosilicate as raw material, control the evaporating temperature of raw material to be 85-110 DEG C, be passed through argon protective gas, instead Answer the room speed of rotation to be 30-60r/min, response time 20-60min, after reaction terminates, be cooled to room temperature, take out；
(3) hydroxy apatite powder of the nanoparticle layers that are coated with silicon oxide and CNT are put into ball mill to be ground Dispersion, after mix homogeneously, vacuum drying；
(4) dried mixed powder is carried out cold moudling under 1.2-2gpa pressure；
(5) material after molding is carried out high-temperature calcination, temperature is 1100-1500 DEG C, pressure 2-5gpa, time 1-3h；
(6) after calcining, taking-up to be cooled, that is, obtain block hydroxylapatite/carbon nanotube composite boilogical ceramic.
Preferably, the gas flow that step (2) carries out argon in chemical vapour deposition reaction is 100-400ml/min.
Preferably, the temperature of step (5) high-temperature calcination is 1250-1400 DEG C.
Preferably, the pressure 2.5-4gpa of step (4) high temperature calcining.
Beneficial effect: the hydroxylapatite/carbon nanotube composite boilogical ceramic that the present invention provides, is to be with hydroxyapatite Basis, is made again for the proliferation function of bone cellses with it using the excellent mechanical performance of CNT on here basis Close bioceramic and there is higher bone injury repairing performance.
CNT is a kind of excellent material, but its dispersive property in solids is poor, can lead to because of gathering Hydraulic performance decline.Simply by high-temperature calcination after CNT and hydroxy apatite powder mixing, can be because CNT and hydroxyl phosphorus Between grey stone substrate, the wellability difference feature low with interface bond strength, leads to effect each other less, and can only be with list Only form exists, thus the reinforcement being unfavorable in performance, and the hydroxy apatite powder of area load CNT is difficult to into The feature of type, also leads to the mechanical performance of composite ceramic material not good.
Therefore, the present invention utilizes chemical vapour deposition technique, in one layer of tight titanium dioxide of hydroxy apatite powder Surface coating Silicon nano layer, by the effect in high temperature solid-state of silicon dioxide and CNT, and by CNT and hydroxy-apatite Stone powder body phase combines, and reaches the enhancing in performance, the composite ceramic material obtaining not only has preferable mechanical performance, and it is biological Feature is also preferable, and overcomes the not enough defect of biocompatibility.
Specific embodiment
For a further understanding of the present invention, with reference to embodiment, the preferred embodiment of the invention is described, but It should be appreciated that these descriptions are simply to further illustrate the features and advantages of the present invention, rather than to the claims in the present invention Limit.
Embodiment 1:
A kind of hydroxylapatite/carbon nanotube composite boilogical ceramic, composite boilogical ceramic is by the nanoparticle that is coated with silicon oxide The hydroxy apatite powder of layer and CNT composition, the hydroxy apatite powder of the nanoparticle layers that are coated with silicon oxide and carbon The mass ratio example of nanotube is 20:1.
Hydroxylapatite/carbon nanotube composite boilogical ceramic is prepared according to the preparation method that the present invention provides, step is as follows:
(1) prepare hydroxy apatite powder: by cahpo4With caco3Carry out dispensing by the ratio 6:4 of the amount of material；Then carry out wet Method ball milling, time 24h；The good slurry of ball milling is poured in container, adds distilled water, be stirred in the case of 90 DEG C of constant temperature, After completion of the reaction, place the precipitation of hydroxyapatite thing that precipitation obtains white, then drying and grinding is sieved；
(2) hydroxy apatite powder is put in chemical vapor deposition reaction chamber, carry out chemical vapour deposition reaction: be preheated to 735 DEG C, with tetraethyl orthosilicate as raw material, control the evaporating temperature of raw material to be 90 DEG C, be passed through argon protective gas, 200ml/min, The reative cell speed of rotation is 60r/min, response time 30min, after reaction terminates, is cooled to room temperature, takes out；
After testing, the mean diameter of hydroxy apatite powder is 10 μm, and the thickness of surface coated silicon dioxide granule layer is 70nm；
(3) hydroxy apatite powder of the nanoparticle layers that are coated with silicon oxide and CNT are put into ball mill to be ground Dispersion, after mix homogeneously, vacuum drying；
(4) dried mixed powder is carried out cold moudling under 1.5gpa pressure；
(5) material after molding is carried out high-temperature calcination, temperature is 1300 DEG C, pressure 3gpa, time 2h；
(6) after calcining, taking-up to be cooled, that is, obtain block hydroxylapatite/carbon nanotube composite boilogical ceramic.
Performance detection: density 3.12kg/ is carried out to the block hydroxylapatite/carbon nanotube composite boilogical ceramic obtaining m3；Comprcssive strength 450mpa；Bending strength 470mpa；Toughness 10mpa m1/2；Elastic modelling quantity 28gpa.
Embodiment 2:
A kind of hydroxylapatite/carbon nanotube composite boilogical ceramic, composite boilogical ceramic is by the nanoparticle that is coated with silicon oxide The hydroxy apatite powder of layer and CNT composition, the hydroxy apatite powder of the nanoparticle layers that are coated with silicon oxide and carbon The mass ratio example of nanotube is 10:1.
Hydroxylapatite/carbon nanotube composite boilogical ceramic is prepared according to the preparation method that the present invention provides, step is as follows:
(1) prepare hydroxy apatite powder: by cahpo4With caco3Carry out dispensing by the ratio 6:4 of the amount of material；Then carry out wet Method ball milling, time 24h；The good slurry of ball milling is poured in container, adds distilled water, be stirred in the case of 90 DEG C of constant temperature, After completion of the reaction, place the precipitation of hydroxyapatite thing that precipitation obtains white, then drying and grinding is sieved；
(2) hydroxy apatite powder is put in chemical vapor deposition reaction chamber, carry out chemical vapour deposition reaction: be preheated to 750 DEG C, with tetraethyl orthosilicate as raw material, control the evaporating temperature of raw material to be 95 DEG C, be passed through argon protective gas, 200ml/min, The reative cell speed of rotation is 30r/min, response time 45min, after reaction terminates, is cooled to room temperature, takes out；
After testing, the mean diameter of hydroxy apatite powder is 10 μm, and the thickness of surface coated silicon dioxide granule layer is 60nm；
(3) hydroxy apatite powder of the nanoparticle layers that are coated with silicon oxide and CNT are put into ball mill to be ground Dispersion, after mix homogeneously, vacuum drying；
(4) dried mixed powder is carried out cold moudling under 1.5gpa pressure；
(5) material after molding is carried out high-temperature calcination, temperature is 1300 DEG C, pressure 3gpa, time 2h；
(6) after calcining, taking-up to be cooled, that is, obtain block hydroxylapatite/carbon nanotube composite boilogical ceramic.
Performance detection: density 3.07kg/ is carried out to the block hydroxylapatite/carbon nanotube composite boilogical ceramic obtaining m3；Comprcssive strength 410mpa；Bending strength 420mpa；Toughness 11mpa m1/2；Elastic modelling quantity 23gpa.
Embodiment 3:
A kind of hydroxylapatite/carbon nanotube composite boilogical ceramic, composite boilogical ceramic is by the nanoparticle that is coated with silicon oxide The hydroxy apatite powder of layer and CNT composition, the hydroxy apatite powder of the nanoparticle layers that are coated with silicon oxide and carbon The mass ratio example of nanotube is 15:1.
Hydroxylapatite/carbon nanotube composite boilogical ceramic is prepared according to the preparation method that the present invention provides, step is as follows:
(1) prepare hydroxy apatite powder: by cahpo4With caco3Carry out dispensing by the ratio 6:4 of the amount of material；Then carry out wet Method ball milling, time 24h；The good slurry of ball milling is poured in container, adds distilled water, be stirred in the case of 90 DEG C of constant temperature, After completion of the reaction, place the precipitation of hydroxyapatite thing that precipitation obtains white, then drying and grinding is sieved；
(2) hydroxy apatite powder is put in chemical vapor deposition reaction chamber, carry out chemical vapour deposition reaction: be preheated to 800 DEG C, with tetraethyl orthosilicate as raw material, control the evaporating temperature of raw material to be 100 DEG C, be passed through argon protective gas, 300ml/ Min, the reative cell speed of rotation is 60r/min, response time 40min, after reaction terminates, is cooled to room temperature, takes out；
After testing, the mean diameter of hydroxy apatite powder is 10 μm, and the thickness of surface coated silicon dioxide granule layer is 150nm；
(3) hydroxy apatite powder of the nanoparticle layers that are coated with silicon oxide and CNT are put into ball mill to be ground Dispersion, after mix homogeneously, vacuum drying；
(4) dried mixed powder is carried out cold moudling under 1.5gpa pressure；
(5) material after molding is carried out high-temperature calcination, temperature is 1350 DEG C, pressure 3gpa, time 2h；
(6) after calcining, taking-up to be cooled, that is, obtain block hydroxylapatite/carbon nanotube composite boilogical ceramic.
Performance detection: density 3.13kg/ is carried out to the block hydroxylapatite/carbon nanotube composite boilogical ceramic obtaining m3；Comprcssive strength 450mpa；Bending strength 460mpa；Toughness 12mpa m1/2；Elastic modelling quantity 25gpa.
Embodiment 4:
A kind of hydroxylapatite/carbon nanotube composite boilogical ceramic, composite boilogical ceramic is by the nanoparticle that is coated with silicon oxide The hydroxy apatite powder of layer and CNT composition, the hydroxy apatite powder of the nanoparticle layers that are coated with silicon oxide and carbon The mass ratio example of nanotube is 12:1.
Hydroxylapatite/carbon nanotube composite boilogical ceramic is prepared according to the preparation method that the present invention provides, step is as follows:
(1) prepare hydroxy apatite powder: by cahpo4With caco3Carry out dispensing by the ratio 6:4 of the amount of material；Then carry out wet Method ball milling, time 24h；The good slurry of ball milling is poured in container, adds distilled water, be stirred in the case of 90 DEG C of constant temperature, After completion of the reaction, place the precipitation of hydroxyapatite thing that precipitation obtains white, then drying and grinding is sieved；
(2) hydroxy apatite powder is put in chemical vapor deposition reaction chamber, carry out chemical vapour deposition reaction: be preheated to 650 DEG C, with tetraethyl orthosilicate as raw material, control the evaporating temperature of raw material to be 90 DEG C, be passed through argon protective gas, 200ml/min, The reative cell speed of rotation is 30r/min, response time 60min, after reaction terminates, is cooled to room temperature, takes out；
After testing, the mean diameter of hydroxy apatite powder is 10 μm, and the thickness of surface coated silicon dioxide granule layer is 110nm；
(3) hydroxy apatite powder of the nanoparticle layers that are coated with silicon oxide and CNT are put into ball mill to be ground Dispersion, after mix homogeneously, vacuum drying；
(4) dried mixed powder is carried out cold moudling under 1.5gpa pressure；
(5) material after molding is carried out high-temperature calcination, temperature is 1350 DEG C, pressure 3.5gpa, time 2h；
(6) after calcining, taking-up to be cooled, that is, obtain block hydroxylapatite/carbon nanotube composite boilogical ceramic.
Performance detection: density 3.11kg/ is carried out to the block hydroxylapatite/carbon nanotube composite boilogical ceramic obtaining m3；Comprcssive strength 460mpa；Bending strength 480mpa；Toughness 11mpa m1/2；Elastic modelling quantity 24gpa.
Embodiment 5:
A kind of hydroxylapatite/carbon nanotube composite boilogical ceramic, composite boilogical ceramic is by the nanoparticle that is coated with silicon oxide The hydroxy apatite powder of layer and CNT composition, the hydroxy apatite powder of the nanoparticle layers that are coated with silicon oxide and carbon The mass ratio example of nanotube is 16:1.
Hydroxylapatite/carbon nanotube composite boilogical ceramic is prepared according to the preparation method that the present invention provides, step is as follows:
(1) prepare hydroxy apatite powder: by cahpo4With caco3Carry out dispensing by the ratio 6:4 of the amount of material；Then carry out wet Method ball milling, time 24h；The good slurry of ball milling is poured in container, adds distilled water, be stirred in the case of 90 DEG C of constant temperature, After completion of the reaction, place the precipitation of hydroxyapatite thing that precipitation obtains white, then drying and grinding is sieved；
(2) hydroxy apatite powder is put in chemical vapor deposition reaction chamber, carry out chemical vapour deposition reaction: be preheated to 728 DEG C, with tetraethyl orthosilicate as raw material, control the evaporating temperature of raw material to be 92 DEG C, be passed through argon protective gas, 300ml/min, The reative cell speed of rotation is 45r/min, response time 40min, after reaction terminates, is cooled to room temperature, takes out；
After testing, the mean diameter of hydroxy apatite powder is 10 μm, and the thickness of surface coated silicon dioxide granule layer is 120nm；
(3) hydroxy apatite powder of the nanoparticle layers that are coated with silicon oxide and CNT are put into ball mill to be ground Dispersion, after mix homogeneously, vacuum drying；
(4) dried mixed powder is carried out cold moudling under 1.5gpa pressure；
(5) material after molding is carried out high-temperature calcination, temperature is 1400 DEG C, pressure 4gpa, time 1.5h；
(6) after calcining, taking-up to be cooled, that is, obtain block hydroxylapatite/carbon nanotube composite boilogical ceramic.
Performance detection: density 3.10kg/ is carried out to the block hydroxylapatite/carbon nanotube composite boilogical ceramic obtaining m3；Comprcssive strength 420mpa；Bending strength 430mpa；Toughness 10mpa m1/2；Elastic modelling quantity 26gpa.
Described above to the disclosed embodiments, makes professional and technical personnel in the field be capable of or uses the present invention. Multiple modifications to these embodiments will be apparent from for those skilled in the art, as defined herein General Principle can be realized without departing from the spirit or scope of the present invention in other embodiments.Therefore, the present invention It is not intended to be limited to the embodiments shown herein, and be to fit to and principles disclosed herein and features of novelty phase one The scope the widest causing.

Claims (1)

1. a kind of hydroxylapatite/carbon nanotube composite boilogical ceramic it is characterised in that: composite boilogical ceramic is by being coated with dioxy The hydroxy apatite powder of SiClx nanoparticle layers and CNT, wherein, the mean diameter of hydroxy apatite powder is 5-20 μ M, the thickness of surface coated silicon dioxide granule layer is 50-200nm；
Wherein, the hydroxy apatite powder of nanoparticle layers that is coated with silicon oxide is 10-20 with the mass ratio of CNT: 1；Described hydroxyapatite is prepared from according to hydro-thermal method；
The preparation method of described hydroxylapatite/carbon nanotube composite boilogical ceramic is as follows:
(1) prepare hydroxy apatite powder: hydroxyapatite is prepared by hydro-thermal method, then drying and grinding is sieved；
(2) hydroxy apatite powder is put in chemical vapor deposition reaction chamber, carry out chemical vapour deposition reaction: be preheated to 600-800 DEG C, with tetraethyl orthosilicate as raw material, control the evaporating temperature of raw material to be 85-110 DEG C, be passed through argon protective gas, instead Answer the room speed of rotation to be 30-60r/min, response time 20-60min, after reaction terminates, be cooled to room temperature, take out；
(3) hydroxy apatite powder of the nanoparticle layers that are coated with silicon oxide and CNT are put into ball mill to be ground Dispersion, after mix homogeneously, vacuum drying；
(4) dried mixed powder is carried out cold moudling under 1.2-2gpa pressure；
(5) material after molding is carried out high-temperature calcination, temperature is 1100-1500 DEG C, pressure 2-5gpa, time 1-3h；
(6) after calcining, taking-up to be cooled, that is, obtain block hydroxylapatite/carbon nanotube composite boilogical ceramic.
CN201610822313.4A 2014-11-10 2014-11-10 Hydroxyapatite-carbon nanotube composite bioceramic Pending CN106365627A (en)

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