CN107137772A - The preparation method of carbon nano-tube reinforced hydroxylapatite composite material - Google Patents
The preparation method of carbon nano-tube reinforced hydroxylapatite composite material Download PDFInfo
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- CN107137772A CN107137772A CN201710350612.7A CN201710350612A CN107137772A CN 107137772 A CN107137772 A CN 107137772A CN 201710350612 A CN201710350612 A CN 201710350612A CN 107137772 A CN107137772 A CN 107137772A
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/40—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material
- A61L27/42—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material having an inorganic matrix
- A61L27/425—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material having an inorganic matrix of phosphorus containing material, e.g. apatite
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2430/00—Materials or treatment for tissue regeneration
- A61L2430/02—Materials or treatment for tissue regeneration for reconstruction of bones; weight-bearing implants
Abstract
The preparation method of carbon nano-tube reinforced hydroxylapatite composite material of the present invention, it is related to the composition using phosphate as base-material, it is one kind with chemical vapor deposition for carbon nanotubes and functionalization is carried out to it, the method being combined using magnetic force liquid phase paddling process with water-gel method prepares by dry state method for press forming the preparation method for the carbon nano-tube reinforced hydroxylapatite composite material that collagen is coated in the carbon nano tube surface in-stiu coating collagen layer through functionalization.The interface bond strength that the method overcome prior art generally existing carbon nano-tube reinforced hydroxylapatite composite material is low, and CNT bad dispersibility causes the comprehensive mechanical property of composite low；The poor biocompatibility of composite, or even there is toxicity, used as biomedical material and there is risk；The repairing effect for migrated to osteocyte, growing and breaking up is poor；And it is used as the not good defect of biomedical material using effect.
Description
Technical field
Technical scheme is related to the composition using phosphate as base-material, specifically CNT enhancing hydroxyl
The preparation method of apatite composite material.
Background technology
Hydroxyapatite accounts for the inanimate matter composition of human body hard tissue 70%, and structure is closely similar with body bone tissue, mirror
Have in it is nontoxic and without carcinogenic effect, and with excellent bioactivity, biological degradability, osteoconductive, bio-compatible
The characteristic of property and non-immunogenic, is widely used in biomedical sector, is especially used as the carrier of medicine and gene
And osseous tissue renovating material.But, the mechanical property and reliability of pure ha are poor, it is impossible to be directly used as load-bearing bone
Human body is implanted into, its extensive use in biomedical sector is constrained.Therefore, planted to meet hydroxyapatite as sclerous tissues
Enter the biological applications needs of thing, strengthen for hydroxyapatite and the research of toughness reinforcing has turned into promotion hydroxyapatite in biology
Medical domain vital link during.
In hydroxyapatite strengthens the R＆D work with toughness reinforcing, various enhancings are mutually attempted, such as titanium and its alloy, oxygen
Change aluminium, zirconium oxide, carborundum, polyethylene and CNT enhancing phase.Wherein, CNT has lightweight, draw ratio big, excellent
Mechanical property, high specific surface area, good electricity, calorifics and magnetic performance advantage, it is considered to be enhancing hydroxy-apatite
The preferable enhancing phase of stone composite material.The prior art for being related to CNT-hydroxyapatite composite material in recent years has
Some reports：CN104998301A, which reports CNT, strengthens the preparation method of mesoporous hydroxyapatite composite material, passes through
In-situ synthesis is prepared for CNT-hydroxyapatite complex powder, recycles sluggish precipitation to be received with water-gel method in carbon
The mesoporous hydroxyapatite of nanotube surface in-stiu coating, and then prepare the mesoporous hydroxyapatite composite material of CNT enhancing；
CN102976743A reports the preparation method of carbon nano-tube reinforced hydroxylapatite composite material, is in hydroxy apatite powder
Middle synthesizing carbon nanotubes, and carbon nano tube surface modification is carried out using hydroxyapatite, and then prepare CNT enhancing hydroxyl
The method of apatite composite material；CN201510125744, which is disclosed, prepares carbon nano-tube reinforced hydroxylapatite composite material
Double in-situ synthetic methods, on the basis of CNT-hydroxyapatite in-situ composite powder is prepared, further through sol-gel work
Skill hydroxyapatite layer in carbon nano tube surface fabricated in situ, and then prepare carbon nano-tube reinforced hydroxylapatite composite wood
Material；CN105523536A reports a kind of carbon nanotube hydroxyl apatite composite material preparation method, and the patent is first to many walls
CNT carries out surface oxidation treatment, is then dispersed in the aqueous solution, prepares carbon using the method for In-situ reaction and receive
Mitron-hydroxyapatite composite powder, and then prepare CNT-hydroxyapatite composite material；In addition, CN103100308A
The preparation method of a kind of gelatin film and gelatin single-walled carbon nanotube laminated film is disclosed, this method is with Cu (OH)2Nano wire
As sacrifice layer, gelatin is set to be deposited on Cu (OH) with filtration method2Nano wire gluing connection obtains gelatin film, then is made with filtration method bright
Glue is deposited on single-walled carbon nanotube substrate gluing connection and obtains gelatin single-walled carbon nanotube laminated film.Above-mentioned prior art is generally deposited
Low in the interface bond strength of carbon nano-tube reinforced hydroxylapatite composite material, CNT bad dispersibility causes composite wood
The comprehensive mechanical property of material is low；The poor biocompatibility of composite, or even there is toxicity, use and deposit as biomedical material
In risk；The repairing effect for migrated to osteocyte, growing and breaking up is poor；And it is good as biomedical material using effect
Defect.Therefore, there is still a need for further researching and developing the preparation method of the CNT-hydroxyapatite composite material updated, improve
Its performance, solves its pressing issues faced in biomedical sector application.
The content of the invention
The technical problems to be solved by the invention are：The preparation side of carbon nano-tube reinforced hydroxylapatite composite material is provided
Method, is one kind with chemical vapor deposition for carbon nanotubes and carries out functionalization to it, using magnetic force liquid phase paddling process
The method being combined with water-gel method passes through dry state in the carbon nano tube surface in-stiu coating collagen layer through functionalization
Method for press forming prepares the preparation method of the carbon nano-tube reinforced hydroxylapatite composite material of collagen cladding.This method overcomes
The interface bond strength of prior art generally existing carbon nano-tube reinforced hydroxylapatite composite material is low, and CNT disperses
Property is poor, causes the comprehensive mechanical property of composite low；The poor biocompatibility of composite, or even there is toxicity, it is used as life
Using there is risk in thing medical material；The repairing effect for migrated to osteocyte, growing and breaking up is poor；And it is used as biomedical material
Expect the not good defect of using effect.
The present invention solves the technical scheme that is used of the technical problem：Carbon nano-tube reinforced hydroxylapatite composite material
Preparation method, be that one kind with chemical vapor deposition for carbon nanotubes and carries out functionalization to it, using magnetic liquid
The method that phase paddling process is combined with water-gel method in the carbon nano tube surface in-stiu coating collagen layer through functionalization, and then
The preparation method for the carbon nano-tube reinforced hydroxylapatite composite material that collagen is coated, tool are prepared by dry state method for press forming
Body step is as follows：
The first step, prepares CNT-hydroxyapatite complex powder：
In mass ratio for needed for being weighed 0.55~1.75: 1 ratio the ferric chloride hexahydrate and granularity of quality be 10~
60nm hydroapatite particles, under conditions of using mechanical agitator with 100~400r/min rotating speed stirring, will be weighed
Hydroapatite particles be added in deionized water to formed molar concentration for 0.01~0.3mol/L hydroxyapatite hang
The ferric chloride hexahydrate weighed, is then added in above-mentioned hydroxyapatite suspensions by supernatant liquid, stirs 2~4h, makes iron chloride
It is uniformly impregnated within hydroxyapatite and obtains suspension I, is by volume suspension I: 25% (mass percent) ammoniacal liquor=20
~100: 1, the ammoniacal liquor of 25% (mass percent) is added in above-mentioned suspension I, and continue 1~4h of stirring and obtain suspension
II, the suspension II of formation is placed in ultrasonic disperse instrument, ultrasonic wave, which disperses 40~60min, under 20~40kHz frequency makes
Iron chloride fully reacts generation Fe (OH) with ammoniacal liquor3Colloid, is then aged 10~20h, obtains Fe (OH) at room temperature3- hydroxyl phosphorus
Lime stone binary colloidal mixture, is cleaned 2~4 time after using the filtering with microporous membrane binary colloidal and with deionized water, is put into electricity
5~10h is dried in 60~100 DEG C in heated drying case, by dry Fe (OH)3- hydroxyapatite binary colloidal mixture is placed in
In ball grinder, planetary ball mill is used with 800~1400r/min rotating speed 1~5h of ball milling, by the Fe after ball-milling treatment
(OH)3- hydroxyapatite binary colloidal mixture is laid in the quartzy Noah's ark for being placed in tube furnace flat-temperature zone, with 100~
200mL/min flow is passed through helium or argon gas into the tube furnace and is warming up to 400~800 DEG C, then closes helium or argon
Gas, while being passed through carbon monoxide into the tube furnace with 50~150mL/min flow and being warming up to 700~1000 DEG C, insulation
0.5~1.5h, is warming up to after 800~1200 DEG C again, is helium or argon gas: carbon monoxide=10~50 by volume ratio: 1 it is mixed
Close gas to be continually fed into tube furnace with 100~400mL/min flow and be incubated 0.5~1.5h, CO gas is closed afterwards
And it is 60~200mL/min to adjust helium or argon flow amount, tube furnace is naturally cooled to room temperature while stopping diamond heating,
CNT-hydroxyapatite complex powder that carbon nanotube mass percentage composition is 1.4~37.9% is made；
Second step, prepares the CNT of functionalization：
0.05~0.55g CNTs-hydroxyapatite complex powder made from the above-mentioned first step is placed in 10~50mL
In absolute ethyl alcohol, 1~10h is stirred with 300~600r/min rotating speed with machine mixer, and it is dense to add quality percentage thereto
20~60mL of liquor potassic permanganate of degree 3% and 2~20mL of nitric acid of mass percentage concentration 45%, then uses filtering with microporous membrane
Gained liquid, by obtained filtrate in the vacuum drying chamber that temperature is 40~90 DEG C, vacuum is -0.1~-0.05MPa
1~9h is dried, CNT-hydroxyapatite complex powder of functionalization is made；
3rd step, prepares CNT-hydroxyapatite complex powder of collagen cladding：
With magnetic force liquid phase paddling process CNT-hydroxyl that collagen is coated is prepared with the process that water-gel method is combined
Base apatite composite powder, concrete operation method is：Take the CNTs of 1~5g functionalizations made from above-mentioned second step-
Hydroxyapatite complex powder, which is added in 10~100mL deionized waters or absolute ethyl alcohol, obtains A, separately takes 0.5~2.5g collagens
Add in 10~100mL acetic acid, be heated to 40~90 DEG C and stirred on magnetic stirrer with 100~600r/min rotating speed
Mix 1~4h and obtain B, then above-mentioned B is added drop-wise in A with 1~20mL/min speed, during which adjust the mixing with urea or ammoniacal liquor
The pH value of liquid is continuing with magnetic stirrer between 9~15, after the completion of dropwise addition B and stirs 4~9h, obtains mixed liquor C, then will
Obtained mixed liquor C is warming up to 100~200 DEG C and is dried after being aged 1~4h in 40~90 DEG C in drying box, liquid to be mixed
When C becomes gel, drying box temperature is adjusted to 90~180 DEG C, until gel drying is fluffy block, that is, collagen cladding is made
The weight/mass percentage composition of CNT-hydroxyapatite complex powder, wherein CNT is 0.7~34.6%, the matter of collagen
It is 0.2~16.8% to measure percentage composition；
4th step, prepares the carbon nano-tube reinforced hydroxylapatite composite material of collagen cladding：
Using dry state method for press forming, the inner and outer tubes of degassing function are will be provided with as graphite compacting tool set, by
CNT-hydroxyapatite complex powder that collagen made from three steps is coated is placed in the compacting tool set, utilizes piston, inner tube
Enter line slip with outer tube, CNT-hydroxyapatite that annular space space between the inner and outer pipe sections is coated to collagen is combined
Powder applies 10~100MPa pressure, and progress is compressed axially and 1~3min of pressurize, by controlling discharge plasma agglomerant
Electric current during skill makes above-mentioned mould rise to 400~650 DEG C of sintering temperature with 40~190 DEG C/min programming rate, and protects
1~20min of the sintering temperature is held, the carbon nano-tube reinforced hydroxylapatite composite material of collagen cladding is made.
The preparation method of above-mentioned carbon nano-tube reinforced hydroxylapatite composite material, involved raw material are by commercially available
Obtain, equipment used and technique are known to those skilled in the art.
Beneficial effects of the present invention are as follows：
Compared with prior art, the inventive method has substantive distinguishing features prominent as follows：
(1) during the use of biomedical material, it is desirable to be used as the hydroxyapatite composite wood of sclerous tissues's implant
Material has good biocompatibility, bioadhesion performance and plasticity, and is required to meet the use requirement of sclerous tissues's implant.
In the design and implementation process of the present invention, in order to assign the biofacies that carbon nano-tube reinforced hydroxylapatite composite material is good
Capacitive, easily occurs to reunite and the virose problem of CNT, innovatively proposes and use magnetic while solving CNT
The method that power liquid phase paddling process is combined with water-gel method in the carbon nano tube surface in-stiu coating collagen layer through functionalization,
And then the new system for the carbon nano-tube reinforced hydroxylapatite composite material that collagen is coated is prepared by dry state method for press forming
Standby process.By functionalization by-CO2H and-OH functional groups are incorporated on CNT, are stirred by magnetic force liquid phase
Method makes the-NH of collagen with the method that water-gel method is combined2Functional group and the-CO of CNT2H functional groups, prepare plastic emitting
CNT-hydroxyapatite complex powder of original cladding, and then prepare the CNT enhancing that collagen is coated as raw material
Hydroxyapatite composite material.And the collagen for being coated on carbon nano tube surface is extracellular most important water-insoluble fiber egg
In vain, it is the skeleton of composition extracellular matrix, therefore, the CNT enhancing hydroxy-apatite of collagen cladding prepared by the inventive method
Stone composite material has excellent biocompatibility, good bioadhesion performance and plasticity, does not have toxic side effect to human body.
(2) as the enhancing phase of hydroxyapatite composite material, it is desirable to which it must have good dispersive property, so as to protect
Card enhancing plays good enhancing and toughening effect in hydroxyapatite composite material matrix, it is to avoid strengthen phase aggregate into
For the defect in matrices of composite material.In the design process of the present invention, collagen bag in hydroxyapatite matrix has been taken into full account
The CNT covered strengthens the scattering problem of phase, in design and implementation process, is realized by surface carboxylic's chemical industry skill and carbon is received
The surface modification of mitron so that it shows good dispersion in a solvent, it is to avoid agglomeration occurs for CNT；Together
When, pass through the fabricated in situ of CNT and collagen-modified in situ in hydroxyapatite matrix, it is to avoid what outer addition was caused
CNT enhancing is mutually reunited, and is realized the CNT of collagen cladding and is strengthened the Dispersed precipitate in hydroxyapatite matrix
The formation combined with enhancing phase-matrix good interface so that the good enhancing of CNT and toughening effect are given full play to.
Therefore, the carbon nano-tube reinforced hydroxylapatite composite material for the collagen cladding that prepared by the inventive method has excellent mechanical property
Energy.
(3) in the preparation process of carbon nano-tube reinforced hydroxylapatite composite material, to improve CNT enhancing phase
Dispersiveness and biocompatibility, it is necessary to prepare finishing coat to CNT, and between finishing coat and CNT
Interface cohesion, directly affect the enhancing effect of CNT in the composite.In order to solve carbon present in prior art
Interface cohesion is poor and easily peelable between nanotube and its finishing coat, so as to cause CNT in hydroxyapatite composite wood
The not good defect of activeness and quietness effect in material, in the design process of the present invention, will improve the interface cohesion of CNT-collagen
Effect is proposed by the method for functionalization as one of key technology, innovatively by-CO2H and-OH functional groups are incorporated into
On CNT, make-the NH of collagen with the method that water-gel method is combined further through magnetic force liquid phase paddling process2Functional group receives with carbon
- the CO of mitron2H functional groups, not only significantly increase the combination interface area of both collagen and CNT, and collagen
Extremely strong chemical bonds are formd with CNT, the interface binding power of CNT-collagen is significantly improved, and by excellent
Different interface fine structure improves enhancing and toughened ability of the CNT in hydroxyapatite composite material.Therefore, originally
The carbon nano-tube reinforced hydroxylapatite composite material of collagen cladding prepared by inventive method has excellent mechanical property.
(4) in design process of the invention, in order to solve carbon nano-tube reinforced hydroxylapatite present in prior art
The repairing effect difference of migration, growth and the differentiation of osteocyte after composite poor biocompatibility, composite implantation human body
Defect, innovatively proposes the new work for employing the CNT of collagen cladding as hydroxyapatite composite material enhancing phase
Process.Collagen is one of main component of vertebrate animal tissues structure, and the 25~33% of total protein are accounted in human body,
It is widely present in the histoorgans such as the skin of people, bone and cartilage, maintains the form and structure of skin and histoorgan, it is right
Each injury tissue plays repair；Meanwhile, collagen has good biocompatibility, can be greatly promoted new cell shape
Into, promote intercellular adhesion, with hemostatic function.Therefore, the present invention is coated by the innovation of process using collagen
CNT is as the enhancing phase of hydroxyapatite composite material, the CNT enhancing hydroxy-apatite that obtained collagen is coated
Stone composite material realizes good biocompatibility, significantly improves the repairing effect of the migration, growth and differentiation of osteocyte,
Cell adhesion can be improved, with hemostatic function, and the collagen needed for human body can also be supplemented in artificial bone degradation process,
It is notable as bio-medical material using effect.
Compared with prior art, the marked improvement of the inventive method is as follows：
(1) prior art CN103100308A is preparing gelatin film and gelatin single-walled carbon nanotube laminated film process
In, gelatin and CNT are combined together using glue crosslinking agent glutaraldehyde, and glue crosslinking agent glutaraldehyde has certain toxicity, can cause
Bronchitis and pulmonary edema, so that poor biocompatibility when mutually being used as composite enhancing, has toxicity and application risk
The problem of；Glue crosslinking agent can make linear molecule be cross-linked with each other, and intermolecular van der Waals interaction can cause CNT to reunite
Phenomenon, causes it to be difficult to disperse in hydroxyapatite composite material, the problem of activeness and quietness effect is not good；Glue crosslinking agent is substantial
It is by gelatin and CNT line style is intermolecular serves as a connection, so that collagen and CNT are cross-linked with each other and reticulated
Structure, gelatin is attached to carbon nano tube surface in the way of physical absorption, and interface binding power between the two is very small, so as to lead
Causing it, gelatin and CNT are easily peeling-off when strengthening phase as composite, do not only result in hydroxyapatite composite material
Poor mechanical property, and occur gelatin peel off after the toxicity that is triggered by CNT.Collagen bag made from the inventive method
The carbon nano-tube reinforced hydroxylapatite composite material covered overcomes above-mentioned present in prior art CN103100308A completely
Defect.
(2) prior art CN104998301A and CN105523536A use Coated With Hydroxyapatite CNT as hydroxyl
The enhancing phase of base apatite composite material, promotes neoblast to be formed and then promotes cytoadherence because hydroxyapatite does not possess
Ability, causes prepared hydroxyapatite composite material biocompatibility, the migration of osteocyte, growth, differentiation etc. to repair effect
It is really poor, as biomedical material using effect it is not good the problem of；The mesoporous hydroxyapatite structure of carbon nano tube surface cladding
Although being conducive to the growth of seeking connections with of cell, meso-hole structure is likely to become the micro-flaw inside hydroxyapatite composite material
Source, the problem of causing composite bending strength and poor fracture toughness.The CNT that collagen made from the inventive method is coated
Enhancing hydroxyapatite composite material overcomes upper present in prior art CN104998301A and CN105523536A completely
State defect.
(3) essential defect that prior art CN102976743A and CN201510125744 is present is：(a) hydroxy-apatite
The CNT of stone modification is substantially that nano-hydroapatite particles are attached to carbon nano tube surface in the way of physical absorption.
It is well known that this physisorption power between CNT and nano-hydroapatite particles belongs to Van der Waals force
Category, therefore, interface binding power between the two are very small, it is difficult to reach transmission load and suppress the effect of Crack Extension；Afterwards
The composite of continuous briquet still keeps original physical bond state, and it is only 1.4 thus to cause fracture of composite materials toughness
~3.6MPam1/2With 2.9~6.7MPam1/2, the fracture toughness 12MPam still with skeleton requirement1/2There is larger difference
Away from composite materials property is difficult to the use requirement for meeting sclerous tissues's implant；(b) using hydroxyapatite to CNT
Modified, because hydroxyapatite does not possess the ability for promoting neoblast formation and then promoting cytoadherence, caused prepared
The repairing effect such as hydroxyapatite composite material biocompatibility, the migration of osteocyte, growth, differentiation it is poor, be used as biological doctor
Learn materials'use effect not good；(c) in addition, the catalyst that CN102976743A is used is toxic heavy metal element nickel, nickel is inevitable
Residual in the composite, during composite use, the presence of the element can to human immune system, hemopoietic system,
Reproductive system, skin etc. cause chronic harmful effect, thus prepared composite used in the presence of safety as biomaterial
Risk.The carbon nano-tube reinforced hydroxylapatite composite material that collagen made from the inventive method is coated overcomes existing skill completely
Drawbacks described above present in art CN102976743A and CN201510125744.
(4) carbon nano-tube reinforced hydroxylapatite composite material prepared by the inventive method, is that the carbon coated with collagen is received
Mitron to be combined as mutually enhanced hydroxyapatite composite material, the CNT of innovative use collagen cladding is strengthened
Material has excellent biocompatibility, significantly improves the repairing effect of the migration, growth and differentiation of osteocyte, with good
Bioadhesion performance and plasticity, there is no toxic side effect to human body not only, and with hemostatic function, degraded in artificial bone
The collagen needed for human body can also be supplemented in journey；Pass through the innovation of process, collagen-carbon nanotube interface chemistry of realization
Cause composite that there is excellent mechanical property with reference to CNT fine dispersion；
(5) chemical vapor deposition for carbon nanotubes is used, is combined using magnetic force liquid phase paddling process with water-gel method
Method prepares glue in the carbon nano tube surface in-stiu coating collagen layer through functionalization by dry state method for press forming
The preparation method of the carbon nano-tube reinforced hydroxylapatite composite material of original cladding is carried out using mouse bone-forming cell MC3T3-E1
Vitro cytotoxicity experiment show, present invention chemical vapor deposition for carbon nanotubes, using magnetic force liquid phase paddling process
The method being combined with water-gel method passes through dry state in the carbon nano tube surface in-stiu coating collagen layer through functionalization
Method for press forming prepare collagen cladding carbon nano-tube reinforced hydroxylapatite composite material do not have cytotoxicity and with it is pure
Hydroxyapatite has similar biocompatibility；After cell contamination culture 72h, cellular morphology still keeps fusiformis or triangle, carefully
Intracellular growth is in good condition；Cell proliferation rate is 85% after being 90% after being 96% after cultivating 24h, cultivating 48h, cultivating 72h.Power
Performance test to be learned to show, the bending strength of the carbon nano-tube reinforced hydroxylapatite composite material of collagen cladding reaches 164~
366MPa, fracture toughness reaches 3.6~8.4MPam1/2, with the fracture toughness of skeleton closely, with excellent comprehensive
Mechanical property is closed, and is substantially better than hydroxy apatite-base composite property made from above-mentioned prior art.
Brief description of the drawings
The present invention is further described with reference to the accompanying drawings and examples.
Fig. 1 is that the X of CNT-hydroxyapatite complex powder of the collagen cladding obtained by the embodiment of the present invention 1 is penetrated
Ray diffraction diagram.
Fig. 2 is the scanning of CNT-hydroxyapatite complex powder of the collagen cladding obtained by the embodiment of the present invention 1
Electron micrograph.
Fig. 3 is the low power of CNT-hydroxyapatite complex powder of the collagen cladding obtained by the embodiment of the present invention 1
Transmission electron microscope photo.
Fig. 4 is the high power of CNT-hydroxyapatite complex powder of the collagen cladding obtained by the embodiment of the present invention 1
Transmission electron microscope photo.
Fig. 5 is the carbon nano-tube reinforced hydroxylapatite composite material of the collagen cladding obtained by the embodiment of the present invention 1
Tensile fracture electron scanning micrograph.
Embodiment
Embodiment 1
The first step, prepares CNT-hydroxyapatite complex powder：
The hydroxyl phosphorus that the ferric chloride hexahydrate and granularity of quality are 10nm in mass ratio for needed for being weighed 0.55: 1 ratio
Limestone particles, under conditions of using mechanical agitator with 100r/min rotating speed stirring, by the hydroapatite particles weighed
It is added to the hydroxyapatite suspensions that molar concentration is 0.01mol/L are formed in deionized water, then by six water weighed
Close iron chloride to be added in above-mentioned hydroxyapatite suspensions, stir 2h, iron chloride is uniformly impregnated within hydroxyapatite and obtain
It is by volume suspension I: 25% (mass percent) ammoniacal liquor=100 to suspension I: 1, added in above-mentioned suspension I
The ammoniacal liquor of 25% (mass percent), and continue stirring 1h obtain suspension II, the suspension II of formation is placed in ultrasonic disperse
In instrument, ultrasonic wave, which disperses 40min, under 20kHz frequency makes iron chloride fully react generation Fe (OH) with ammoniacal liquor3Colloid, then
10h is aged at room temperature, obtains Fe (OH)3- hydroxyapatite binary colloidal mixture, uses the filtering with microporous membrane binary glue
Body is simultaneously cleaned after 2 times with deionized water, is put into electrically heated drying cabinet and is dried 5h in 60 DEG C, by dry Fe (OH)3- hydroxy-apatite
Stone binary colloidal mixture is placed in ball grinder, planetary ball mill is used with 800r/min rotating speed ball milling 1h, at ball milling
Fe (OH) after reason3- hydroxyapatite binary colloidal mixture is laid in the quartzy Noah's ark for being placed in tube furnace flat-temperature zone, with
100mL/min flow is passed through helium or argon gas into the tube furnace and is warming up to 400 DEG C, then closes helium or argon gas, together
When carbon monoxide is passed through into the tube furnace with 50mL/min flow and 700 DEG C are warming up to, be incubated 0.5h, be warming up to again
It is helium or argon gas: carbon monoxide=50: 1 gaseous mixture is continually fed into 100mL/min flow by volume ratio after 800 DEG C
Tube furnace is simultaneously incubated 0.5h, and it is 60mL/min that CO gas is closed afterwards and helium or argon flow amount is adjusted, and is stopped simultaneously
Diamond heating makes tube furnace naturally cool to room temperature, that is, be made carbon nanotube mass percentage composition for 1.4% CNT-
Hydroxyapatite complex powder；
Second step, prepares the CNT of functionalization：
0.05g CNTs-hydroxyapatite complex powder made from the above-mentioned first step is placed in 10mL absolute ethyl alcohols,
1h is stirred with 300r/min rotating speed with machine mixer, and adds the liquor potassic permanganate of mass percentage concentration 3% thereto
Retain hydroxy-apatite while the 20mL and nitric acid 2mL of mass percentage concentration 45% is with to CNT progress oxidative functionalization
Stone, then with liquid obtained by filtering with microporous membrane, by obtained filtrate temperature be 40 DEG C, vacuum it is true for -0.05MPa's
1h is dried in empty drying box, CNT-hydroxyapatite complex powder of functionalization is made；
3rd step, prepares CNT-hydroxyapatite complex powder of collagen cladding：
With magnetic force liquid phase paddling process CNT-hydroxyl that collagen is coated is prepared with the process that water-gel method is combined
Base apatite composite powder, concrete operation method is：Take CNT-hydroxyl of 1g functionalizations made from above-mentioned second step
Apatite composite powder, which is added in 10mL deionized waters or absolute ethyl alcohol, obtains A, separately takes 2.5g collagens to add 100mL acetic acid
In, it is heated to 40 DEG C and B is obtained with 100r/min rotating speed stirring 1h on magnetic stirrer, then by above-mentioned B with 1mL/
Min speed is added drop-wise in A, and the pH value that the mixed liquor is during which adjusted with urea or ammoniacal liquor is 9, is continuing with after the completion of dropwise addition B
Magnetic stirrer stirs 4h, obtains mixed liquor C, is then aged after 1h obtained mixed liquor C in 40 DEG C in drying box and heats up
It is dried to 100 DEG C, when liquid C to be mixed becomes gel, drying box temperature is adjusted to 90 DEG C, until gel drying is fluffy piece
Body, that is, be made CNT-hydroxyapatite complex powder of collagen cladding, and the weight/mass percentage composition of wherein CNT is
0.7%, the weight/mass percentage composition of collagen is 16.8%；
Fig. 1 is the X-ray diffraction of CNT-hydroxyapatite complex powder of the collagen cladding obtained by the present embodiment
Figure.Respectively illustrated in figure collagen cladding CNT-hydroxyapatite complex powder in CNT (in figure ● shown),
The X ray diffracting spectrum of hydroxyapatite (in figure shown in ■) and collagen (in figure shown in ▼).It can be seen that collagen bag
Hydroxyapatite (in figure shown in ■) in the CNT-hydroxyapatite complex powder covered the angle of diffraction be 10.8 °,
26.2 °, 37.8 °, 45.1 °, there is obvious characteristic peak near the positions such as 53.8 °；CNT (in figure ● shown) is in the angle of diffraction
It is that 26.2 ° and 53.8 ° of positions characteristic peak occur, shows have CNT successfully to synthesize in the composite powder；Collagen (▼ in figure
It is shown) in the angle of diffraction it is that 7.2 ° and 22.3 ° of positions characteristic peak occur；The diffraction maximum of iron-less catalyst occurs in X-ray diffractogram,
This is due to that iron catalyst content is relatively low caused.It may be seen that in the base by chemical vapor deposition for carbon nanotubes
On plinth, the method being combined by magnetic force liquid phase paddling process with water-gel method in carbon nano tube surface in-stiu coating collagen layer, into
CNT-the hydroxyapatite complex powder for having obtained collagen cladding of work(.
Fig. 2 is the scanning electron of CNT-hydroxyapatite complex powder of the collagen cladding obtained by the present embodiment
Microphotograph.It can be seen that-the NH formed on collagen2Functional group and the-CO being incorporated on CNT2H functional groups
Generation chemical bond so that collagen is uniformly coated in carbon nano tube surface；CNT is uniformly dispersed and completely close by collagen
, there is not the exposed phenomenon of CNT, illustrates that collagen is successfully coated to CNT in cladding；Meanwhile, collagen
The CNT of cladding is uniformly dispersed in hydroxyapatite matrix powder, does not occur reunion, wrapping phenomena, after this is conducive to
CNT enhancing, the performance of toughening effect and matrix-enhancing mutually good boundary in the continuous hydroxyapatite based composites prepared
The formation that face is combined, it is ensured that composite has excellent comprehensive mechanical property.
Fig. 3 is the low power transmission of CNT-hydroxyapatite complex powder of the collagen cladding obtained by the present embodiment
Electron micrograph.It can be seen that CNT is coated by collagen layer completely, collagen is to be uniformly distributed in this clad
Thin layer, thickness can form fine and close cladding between 6~9nm to hollow CNT, thus impart composite tool
There is good biocompatibility；Meanwhile, hydroapatite particles closely link together with CNT, form good
With reference to.
Fig. 4 is the high power transmission of CNT-hydroxyapatite complex powder of the collagen cladding obtained by the present embodiment
Electron micrograph.It can be seen that the material of enveloped carbon nanometer tube tube wall is collagen, collagen distribution is than more uniform and thickness
Homogeneous, thickness is between 6~9nm；CNT remains in that the graphite clear-cut texture in good structural intergrity, tube wall
It can be seen that；Interface cohesion is close between CNT and collagen, can give full play to the CNT of collagen cladding good enhancing and
Toughening effect.
4th step, prepares the carbon nano-tube reinforced hydroxylapatite composite material of collagen cladding：
Using dry state method for press forming, the inner and outer tubes of degassing function are will be provided with as graphite compacting tool set, by
CNT-hydroxyapatite complex powder that collagen made from three steps is coated is placed in the mould, utilizes piston, inner tube and outer
Pipe enters line slip, CNT-hydroxyapatite complex powder that annular space space between the inner and outer pipe sections is coated to collagen
Apply 10MPa pressure, progress is compressed axially and pressurize 1min, by controlling the electricity during discharge plasma sintering process
Stream makes above-mentioned mould rise to 400 DEG C of sintering temperature with 40 DEG C/min programming rate, and keeps sintering temperature 1min, and glue is made
The carbon nano-tube reinforced hydroxylapatite composite material of original cladding.
Fig. 5 is that the stretching of the carbon nano-tube reinforced hydroxylapatite composite material of the collagen cladding obtained by the present embodiment is broken
Surface scan electron micrograph.It can be seen that obtained microstructure of composite is fine and close, do not have in matrix obvious hole or
Crackle is present；There are a large amount of tiny dimples in stretching fracture, illustrates that composite shows ductile fracture trend；Can in fracture surface
See what the CNT of the collagen cladding of embedded hydroxyapatite matrix and the CNT of collagen cladding left after being pulled out
Hole, the CNT enhancing of this explanation collagen cladding with the wetability of hydroxyapatite matrix is good, interface binding power is strong, tie
Close close, the CNT enhancing that collagen is coated in drawing process can mutually play bridging power transmission work between hydroxyapatite crystal grain
With playing the effect for sharing load and reinforcing interface, make the carbon nano-tube reinforced hydroxylapatite that obtained collagen coat multiple
Condensation material mechanical property is significantly improved.
Embodiment 2
The first step, prepares CNT-hydroxyapatite complex powder：
The hydroxy-apatite that the ferric chloride hexahydrate and granularity of quality are 40nm in mass ratio for needed for being weighed 1.2: 1 ratio
Stone particle, under conditions of using mechanical agitator with 250r/min rotating speed stirring, the hydroapatite particles weighed are added
Enter into deionized water to the hydroxyapatite suspensions that molar concentration is 0.15mol/L are formed, then by six hydrations weighed
Iron chloride is added in above-mentioned hydroxyapatite suspensions, is stirred 3h, iron chloride is uniformly impregnated within hydroxyapatite and obtain
Suspension I, is by volume suspension I: 25% (mass percent) ammoniacal liquor=60: 1, add 25% in above-mentioned suspension I
The ammoniacal liquor of (mass percent), and continue stirring 2.5h obtain suspension II, the suspension II of formation is placed in ultrasonic disperse instrument
In, ultrasonic wave, which disperses 50min, under 30kHz frequency makes iron chloride fully react generation Fe (OH) with ammoniacal liquor3Colloid, Ran Hou
15h is aged at room temperature, obtains Fe (OH)3- hydroxyapatite binary colloidal mixture, uses the filtering with microporous membrane binary colloidal
And cleaned with deionized water after 3 times, it is put into electrically heated drying cabinet and dries 7h in 80 DEG C, by dry Fe (OH)3- hydroxyapatite
Binary colloidal mixture is placed in ball grinder, planetary ball mill is used with 1000r/min rotating speed ball milling 3h, by ball-milling treatment
Fe (OH) afterwards3- hydroxyapatite binary colloidal mixture is laid in the quartzy Noah's ark for being placed in tube furnace flat-temperature zone, with
150mL/min flow is passed through helium or argon gas into the tube furnace and is warming up to 600 DEG C, then closes helium or argon gas, together
When carbon monoxide is passed through into the tube furnace with 100mL/min flow and 850 DEG C are warming up to, be incubated 1h, be warming up to again
It is helium or argon gas: carbon monoxide=30: 1 gaseous mixture is continually fed into 300mL/min flow by volume ratio after 1000 DEG C
Tube furnace is simultaneously incubated 1h, and it is 100mL/min that CO gas is closed afterwards and helium or argon flow amount is adjusted, while stopping pipe
Formula stove heat makes tube furnace naturally cool to room temperature, that is, be made carbon nanotube mass percentage composition for 23.7% CNT-
Hydroxyapatite complex powder；
Second step, prepares the CNT of functionalization：
0.3g CNTs-hydroxyapatite complex powder made from the above-mentioned first step is placed in 30mL absolute ethyl alcohols,
5h is stirred with 450r/min rotating speed with machine mixer, and adds the liquor potassic permanganate of mass percentage concentration 3% thereto
Retain hydroxy-apatite while the 40mL and nitric acid 10mL of mass percentage concentration 45% is with to CNT progress oxidative functionalization
Stone, then with liquid obtained by filtering with microporous membrane, by obtained filtrate temperature be 60 DEG C, vacuum it is true for -0.08MPa's
5h is dried in empty drying box, CNT-hydroxyapatite complex powder of functionalization is made；
3rd step, prepares CNT-hydroxyapatite complex powder of collagen cladding：
With magnetic force liquid phase paddling process CNT-hydroxyl that collagen is coated is prepared with the process that water-gel method is combined
Base apatite composite powder, concrete operation method is：Take CNT-hydroxyl of 3g functionalizations made from above-mentioned second step
Apatite composite powder, which is added in 50mL deionized waters or absolute ethyl alcohol, obtains A, separately takes 1.5g collagens to add in 50mL acetic acid,
It is heated to 65 DEG C and B is obtained with 300r/min rotating speed stirring 2.5h on magnetic stirrer, then by above-mentioned B with 10mL/
Min speed is added drop-wise in A, and the pH value that the mixed liquor is during which adjusted with urea or ammoniacal liquor is 12, is continuing with after the completion of dropwise addition B
Magnetic stirrer stirs 6h, obtains mixed liquor C, is then aged after 2.5h obtained mixed liquor C in 65 DEG C in drying box and rises
Warm to 150 DEG C are dried, and when liquid C to be mixed becomes gel, drying box temperature is adjusted into 130 DEG C, until gel drying is fluffy
Loose spot body, that is, be made the weight/mass percentage composition of the CNT-hydroxyapatite complex powder, wherein CNT of collagen cladding
For 17.4%, the weight/mass percentage composition of collagen is 8.3%；
4th step, prepares the carbon nano-tube reinforced hydroxylapatite composite material of collagen cladding：
Using dry state method for press forming, the inner and outer tubes of degassing function are will be provided with as graphite compacting tool set, by
CNT-hydroxyapatite complex powder that collagen made from three steps is coated is placed in the mould, utilizes piston, inner tube and outer
Pipe enters line slip, CNT-hydroxyapatite complex powder that annular space space between the inner and outer pipe sections is coated to collagen
Apply 50MPa pressure, progress is compressed axially and pressurize 2min, by controlling the electricity during discharge plasma sintering process
Stream makes above-mentioned mould rise to 500 DEG C of sintering temperature with 110 DEG C/min programming rate, and keeps sintering temperature 10min, is made
The carbon nano-tube reinforced hydroxylapatite composite material of collagen cladding.
Embodiment 3
The first step, prepares CNT-hydroxyapatite complex powder：
The hydroxyl phosphorus that the ferric chloride hexahydrate and granularity of quality are 60nm in mass ratio for needed for being weighed 1.75: 1 ratio
Limestone particles, under conditions of using mechanical agitator with 400r/min rotating speed stirring, by the hydroapatite particles weighed
It is added to the hydroxyapatite suspensions that molar concentration is 0.3mol/L are formed in deionized water, then by six hydrations weighed
Iron chloride is added in above-mentioned hydroxyapatite suspensions, is stirred 4h, iron chloride is uniformly impregnated within hydroxyapatite and obtain
Suspension I, is by volume suspension I: 25% (mass percent) ammoniacal liquor=20: 1, add 25% in above-mentioned suspension I
The ammoniacal liquor of (mass percent), and continue stirring 4h obtain suspension II, the suspension II of formation is placed in ultrasonic disperse instrument,
Ultrasonic wave, which disperses 60min, under 40kHz frequency makes iron chloride fully react generation Fe (OH) with ammoniacal liquor3Colloid, then in room
The lower ageing 20h of temperature, obtains Fe (OH)3- hydroxyapatite binary colloidal mixture, using the filtering with microporous membrane binary colloidal simultaneously
Cleaned with deionized water after 4 times, be put into electrically heated drying cabinet and dry 10h in 100 DEG C, by dry Fe (OH)3- hydroxyapatite
Binary colloidal mixture is placed in ball grinder, planetary ball mill is used with 1400r/min rotating speed ball milling 5h, by ball-milling treatment
Fe (OH) afterwards3- hydroxyapatite binary colloidal mixture is laid in the quartzy Noah's ark for being placed in tube furnace flat-temperature zone, with
200mL/min flow is passed through helium or argon gas into the tube furnace and is warming up to 800 DEG C, then closes helium or argon gas, together
When carbon monoxide is passed through into the tube furnace with 150mL/min flow and 1000 DEG C are warming up to, be incubated 1.5h, be warming up to again
It is helium or argon gas: carbon monoxide=10: 1 gaseous mixture is continually fed into 400mL/min flow by volume ratio after 1200 DEG C
Tube furnace is simultaneously incubated 1.5h, and it is 200mL/min that CO gas is closed afterwards and helium or argon flow amount is adjusted, and is stopped simultaneously
Diamond heating makes tube furnace naturally cool to room temperature, that is, it is 37.9% carbon nanometer that carbon nanotube mass percentage composition, which is made,
Pipe-hydroxyapatite complex powder；
Second step, prepares the CNT of functionalization：
0.55g CNTs-hydroxyapatite complex powder made from the above-mentioned first step is placed in 50mL absolute ethyl alcohols,
10h is stirred with 600r/min rotating speed with machine mixer, and adds the liquor potassic permanganate of mass percentage concentration 3% thereto
Retain hydroxy-apatite while the 60mL and nitric acid 20mL of mass percentage concentration 45% is with to CNT progress oxidative functionalization
Stone, then with liquid obtained by filtering with microporous membrane, by obtained filtrate temperature be 90 DEG C, vacuum it is true for -0.1MPa's
9h is dried in empty drying box, CNT-hydroxyapatite complex powder of functionalization is made；
3rd step, prepares CNT-hydroxyapatite complex powder of collagen cladding：
With magnetic force liquid phase paddling process CNT-hydroxyl that collagen is coated is prepared with the process that water-gel method is combined
Base apatite composite powder, concrete operation method is：Take CNT-hydroxyl of 5g functionalizations made from above-mentioned second step
Apatite composite powder, which is added in 100mL deionized waters or absolute ethyl alcohol, obtains A, separately takes 0.5g collagens to add 10mL acetic acid
In, it is heated to 90 DEG C and B is obtained with 600r/min rotating speed stirring 4h on magnetic stirrer, then by above-mentioned B with 20mL/
Min speed is added drop-wise in A, and the pH value that the mixed liquor is during which adjusted with urea or ammoniacal liquor is 15, is continuing with after the completion of dropwise addition B
Magnetic stirrer stirs 9h, obtains mixed liquor C, is then aged after 4h obtained mixed liquor C in 90 DEG C in drying box and heats up
It is dried to 200 DEG C, when liquid C to be mixed becomes gel, drying box temperature is adjusted to 180 DEG C, until gel drying is fluffy
Block, that is, be made CNT-hydroxyapatite complex powder of collagen cladding, and the weight/mass percentage composition of wherein CNT is
34.6%, the weight/mass percentage composition of collagen is 0.2%；
4th step, prepares the carbon nano-tube reinforced hydroxylapatite composite material of collagen cladding：
Using dry state method for press forming, the inner and outer tubes of degassing function are will be provided with as graphite compacting tool set, by
CNT-hydroxyapatite complex powder that collagen made from three steps is coated is placed in the mould, utilizes piston, inner tube and outer
Pipe enters line slip, CNT-hydroxyapatite complex powder that annular space space between the inner and outer pipe sections is coated to collagen
Apply 100MPa pressure, progress is compressed axially and pressurize 3min, by controlling discharge plasma sintering process during
Electric current makes above-mentioned mould rise to 650 DEG C of sintering temperature with 190 DEG C/min programming rate, and keeps sintering temperature 20min, system
Obtain the carbon nano-tube reinforced hydroxylapatite composite material of collagen cladding.
In above-described embodiment, involved raw material are this technologies by commercially available, used equipment and technique
Known to the technical staff in field.
Claims (1)
1. the preparation method of carbon nano-tube reinforced hydroxylapatite composite material, it is characterised in that：It is one kind chemical vapor deposition
Area method prepares CNT and carries out functionalization to it, the method being combined using magnetic force liquid phase paddling process with water-gel method
In the carbon nano tube surface in-stiu coating collagen layer through functionalization, and then collagen bag is prepared by dry state method for press forming
The preparation method of the carbon nano-tube reinforced hydroxylapatite composite material covered, is comprised the following steps that：
The first step, prepares CNT-hydroxyapatite complex powder：
The ferric chloride hexahydrate and granularity of quality are 10~60nm's in mass ratio for needed for being weighed 0.55~1.75: 1 ratio
Hydroapatite particles, under conditions of using mechanical agitator with 100~400r/min rotating speed stirring, by the hydroxyl weighed
The hydroxyapatite suspensions that it is 0.01~0.3mol/L to formation molar concentration in deionized water that apatite particle, which is added to, and
The ferric chloride hexahydrate weighed is added in above-mentioned hydroxyapatite suspensions afterwards, 2~4h is stirred, makes iron chloride homogeneous impregnation
Suspension I is obtained in hydroxyapatite, is by volume suspension I: 25% (mass percent) ammoniacal liquor=20~100: 1,
The ammoniacal liquor of 25% (mass percent) is added in above-mentioned suspension I, and continues 1~4h of stirring and obtains suspension II, will be formed
Suspension II be placed in ultrasonic disperse instrument, under 20~40kHz frequency ultrasonic wave disperse 40~60min makes iron chloride and ammonia
Water fully reacts generation Fe (OH)3Colloid, is then aged 10~20h, obtains Fe (OH) at room temperature3- hydroxyapatite binary glue
Body mixture, is cleaned 2~4 time after using the filtering with microporous membrane binary colloidal and with deionized water, is put into electrically heated drying cabinet
5~10h is dried in 60~100 DEG C, by dry Fe (OH)3- hydroxyapatite binary colloidal mixture is placed in ball grinder, is adopted
With planetary ball mill with 800~1400r/min rotating speed 1~5h of ball milling, by the Fe (OH) after ball-milling treatment3- hydroxy-apatite
Stone binary colloidal mixture is laid in the quartzy Noah's ark for being placed in tube furnace flat-temperature zone, with 100~200mL/min flow to this
Helium or argon gas are passed through in tube furnace and 400~800 DEG C are warming up to, helium or argon gas are then closed, while with 50~150mL/
Min flow is passed through carbon monoxide into the tube furnace and is warming up to 700~1000 DEG C, is incubated 0.5~1.5h, is warming up to again
It is helium or argon gas: carbon monoxide=10~50: 1 gaseous mixture is with 100~400mL/min by volume ratio after 800~1200 DEG C
Flow be continually fed into tube furnace and be incubated 0.5~1.5h, CO gas is closed afterwards and helium or argon flow amount is adjusted
For 60~200mL/min, tube furnace is naturally cooled to room temperature while stopping diamond heating, that is, carbon nanotube mass hundred is made
Divide CNT-hydroxyapatite complex powder that content is 1.4~37.9%；
Second step, prepares the CNT of functionalization：
0.05~0.55g CNTs made from the above-mentioned first step-hydroxyapatite complex powder is placed in 10~50mL is anhydrous
In ethanol, 1~10h is stirred with 300~600r/min rotating speed with machine mixer, and add mass percentage concentration thereto
3% 20~60mL of liquor potassic permanganate and 2~20mL of nitric acid of mass percentage concentration 45%, then uses filtering with microporous membrane institute
Liquid is obtained, obtained filtrate is dried in the vacuum drying chamber that temperature is 40~90 DEG C, vacuum is -0.1~-0.05MPa
Dry 1~9h, is made CNT-hydroxyapatite complex powder of functionalization；
3rd step, prepares CNT-hydroxyapatite complex powder of collagen cladding：
With magnetic force liquid phase paddling process CNT-hydroxyl phosphorus that collagen is coated is prepared with the process that water-gel method is combined
Lime stone composite powder, concrete operation method is：Take CNT-hydroxyl of 1~5g functionalizations made from above-mentioned second step
Apatite composite powder, which is added in 10~100mL deionized waters or absolute ethyl alcohol, obtains A, separately takes 0.5~2.5g collagens to add
In 10~100mL acetic acid, it is heated to 40~90 DEG C and stirs 1 on magnetic stirrer with 100~600r/min rotating speed
~4h obtains B, then above-mentioned B is added drop-wise in A with 1~20mL/min speed, during which adjusts the mixed liquor with urea or ammoniacal liquor
PH value between 9~15, be added dropwise B after the completion of be continuing with magnetic stirrer stir 4~9h, obtain mixed liquor C, then will
To mixed liquor C be aged 1~4h in 40~90 DEG C in drying box after be warming up to 100~200 DEG C and be dried, liquid C to be mixed
When becoming gel, drying box temperature is adjusted to 90~180 DEG C, until gel drying is fluffy block, that is, collagen cladding is made
The weight/mass percentage composition of CNT-hydroxyapatite complex powder, wherein CNT is 0.7~34.6%, the matter of collagen
It is 0.2~16.8% to measure percentage composition；
4th step, prepares the carbon nano-tube reinforced hydroxylapatite composite material of collagen cladding：
Using dry state method for press forming, the inner and outer tubes of degassing function are will be provided with as graphite compacting tool set, by the 3rd step
CNT-hydroxyapatite complex powder of obtained collagen cladding is placed in the compacting tool set, utilizes piston, inner tube and outer
Pipe enters line slip, CNT-hydroxyapatite complex powder that annular space space between the inner and outer pipe sections is coated to collagen
Apply 10~100MPa pressure, progress is compressed axially and 1~3min of pressurize, by controlling discharge plasma sintering process mistake
Electric current in journey makes above-mentioned mould rise to 400~650 DEG C of sintering temperature with 40~190 DEG C/min programming rate, and keeps being somebody's turn to do
1~20min of sintering temperature, is made the carbon nano-tube reinforced hydroxylapatite composite material of collagen cladding.
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