CN104692348A - Double in-situ synthesis method for preparing carbon nano tube reinforced hydroxyapatite composite materials - Google Patents
Double in-situ synthesis method for preparing carbon nano tube reinforced hydroxyapatite composite materials Download PDFInfo
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Abstract
The invention relates to composite materials for prosthesis materials, in particular to a double in-situ synthesis method for preparing carbon nano tube reinforced hydroxyapatite composite materials. The method comprises the steps that 1, in-situ synthesis of carbon nano tube-hydroxyapatite in-situ mixed powder is carried out; 2, double in-situ synthesis of carbon nano tube-hydroxyapatite in-situ composite powder is carried out; 3, the carbon nano tube reinforced hydroxyapatite composite materials are prepared. On the basis of preparing the carbon nano tube-hydroxyapatite in-situ composite powder, a hydroxyapatite layer which is dense in coating and controllable in structure is synthesized on the surface of the carbon nano tube through a sol-gel process, the carbon nano tube reinforced hydroxyapatite composite materials are prepared, the prefect structure of a carbon nano tube and the good biocompatibility of the hydroxyapatite composite materials are both achieved, meanwhile, the dispersion effect of the carbon nano tube and the interface combination effect are obviously improved, the carbon nano tube reinforced hydroxyapatite composite materials with the excellent mechanical property and the biocompatibility are made, and the carbon nano tube reinforced hydroxyapatite composite materials are widely applied to the bio-medical field.
Description
Technical field
Technical scheme of the present invention relates to the matrix material for prosthetic material, specifically prepares two in-situ synthetic methods of carbon nano-tube reinforced hydroxylapatite composite material.
Background technology
Because hydroxyapatite has good biocompatibility, osteoconductive and biological activity, be therefore with a wide range of applications as sclerous tissues's implant, receive much attention.But mechanical property and the reliability of pure ha material are poor, particularly large, the bending strength of fragility and fracture toughness property low, be difficult to directly to be used as load-bearing implant and use.Since carbon nanotube is found by Iijima, due to the performance such as electricity, magnetics, calorifics of its high intensity, toughness and excellence, become a kind of generally acknowledged superpower one dimension strongthener.Use carbon nano-tube reinforced hydroxylapatite composite material, be expected to while alleviating hydroxyapatite material density further, improve intensity and the toughness of hydroxyapatite material, therefore, scientific research personnel has carried out a large amount of research work to carbon nano-tube reinforced hydroxylapatite composite material in recent years.
CN201210555876 discloses the preparation method of carbon nano-tube reinforced hydroxylapatite composite material, it is synthesizing carbon nanotubes in hydroxy apatite powder, and utilize hydroxyapatite to carry out carbon nano tube surface modification, and then prepare the method for carbon nano-tube reinforced hydroxylapatite composite material, first prepare carbon nanotube-hydroxyapatite powder with nickelous carbonate and hydroxyapatite powder, prepare carbon nanotube-hydroxyapatite powder that hydroxyapatite is modified again, finally obtained carbon nano-tube reinforced hydroxylapatite composite material.CN201210555876 is the technology that the present inventor team researches and develops previously, find that the prior art exists the following defect through practical application: all show through large quantity research, carbon nanotube toxicity main manifestations is in vivo for causing pneumonia and fibrosis, recycle system oxidative damage, atherosclerosis and systemic immune system extremely, so, in such matrix material preparation process, often need to take necessary technological measure to reduce the toxicity of carbon nanotube, improve the biocompatibility of matrix material.The processing method that CN201210555876 adopts is, after carbon nanotube-hydroxyapatite powder is put into deionized water, by sodium-chlor, the multiple starting material such as sodium bicarbonate dissolve in above-mentioned deionized water successively, hydroxyapatite is made to be formed in the solution and modify carbon nano tube surface, defect existing for it is: one, by above-mentioned various raw-material liquid-phase chemical reaction, the product formed is Nanoparticulate hydroxyapatite, and the hydroxyapatite of this form and granularity, only there is few quantity can be attached to carbon nano tube surface by the mode of physical adsorption, this patent specification accompanying drawing 3 has absolutely proved this point.From this figure, a small amount of hydroxyapatite nanoparticle is only had to be attached to carbon nano tube surface, and most bodys of carbon nanotube are in naked state, namely it is completely coated that the hydroxyapatite nanoparticle prepared by this patent cannot realize the larger carbon nanotube of length-to-diameter ratio, only can realize modifying the local of carbon nano tube surface.Matrix material prepared by the carbon nanotube dust using above-mentioned hydroxyapatite to modify, carbon nanotube must be avoided exposed at composite material surface, as this matrix material uses as bio-medical material, carbon nanotube will certainly contact with human body cell, tissue, blood, causes a series of toxicity problems caused by carbon nanotube toxicity.They are two years old, the catalyzer nickel that this patent synthesizing carbon nanotubes adopts is well-known toxic heavy metal element, nickel must remain and be present in prepared carbon nano-tube reinforced hydroxylapatite composite material, in matrix material use procedure, the existence of this element can cause chronic detrimentally affect to human immune system, hemopoietic system, reproductive system and skin.So, from biology performance and the consideration of use properties angle of prepared carbon nano-tube reinforced hydroxylapatite composite material, carbon nano-tube reinforced hydroxylapatite composite material prepared by this patent exists by carbon nanotube and nickel catalyzator initiation toxicity, poor biocompatibility, uses the defect having certain risk as bio-medical material.Its three, this patent adopt hydroxyapatite carry out carbon nano tube surface modification, be in fact that the nano-hydroapatite particles formed by liquid phase method is attached to carbon nano tube surface in the mode of physical adsorption.As everyone knows, this physisorption power between carbon nanotube and nano-hydroapatite particles belongs to the category of Van der Waals force, and therefore, interface binding power is between the two very little, is difficult to the effect reaching transmitted load and suppress crack propagation; Above-mentioned powder is made in the process of block composite material by compacting by this patent follow-up, Chemical bond can not be there is between carbon nanotube and hydroxyapatite, still keep original physical bond state, therefore, similar with traditional outer addition, there is not substantial change in the interface cohesion effect between carbon nanotube and hydroxyapatite.Cause thus as a result, though the standby matrix material mechanical property of this patent system increases, fracture toughness property is 1.4 ~ 3.6MPam
1/2, still with the fracture toughness property 4 ~ 12MPam of skeleton
1/2have larger gap, and lower fracture toughness property just hydroxyapatite composite material be difficult to the major cause of carrying out clinical application.As can be seen here, in the matrix material prepared by this patent, carbon nanotube-hydroxyapatite interface bond strength is low, causes composite materials property to be difficult to meet the service requirements of sclerous tissues's implant.
Although the art methods preparing carbon nano-tube reinforced hydroxylapatite composite material is numerous, but, the existing method preparing carbon nano-tube reinforced hydroxylapatite composite material, in obtained carbon nano-tube reinforced hydroxylapatite composite material, all may contact with tissue at material surface because part carbon nanotube is exposed, be difficult to avoid the toxicity caused because of carbon nanotube stripping to work the mischief to human body, thus exist and be difficult to take into account carbon nanotube perfect structure and hydroxyapatite based composites good biocompatibility, be difficult to the remarkable lifting realizing carbon nanotube dispersed effect and interface cohesion effect, thus have impact on the defect of this kind of material in biomedical sector widespread use.
Summary of the invention
Technical problem to be solved by this invention is: provide the two in-situ synthetic methods preparing carbon nano-tube reinforced hydroxylapatite composite material, preparing on carbon nanotube-hydroxyapatite in-situ composite powder basis, coated closely and the hydroxyapatite layer of structure-controllable in carbon nano tube surface synthesis by sol-gel technology, and then prepare carbon nano-tube reinforced hydroxylapatite composite material, both the perfect structure of carbon nanotube and the good biocompatibility of hydroxyapatite composite material had been taken into account, achieve again the remarkable lifting of carbon nanotube dispersed effect and interface cohesion effect simultaneously, prepare the carbon nano-tube reinforced hydroxylapatite composite material having excellent mechanical performance and biocompatibility concurrently, this kind of material is used widely at biomedical sector.
The present invention solves this technical problem adopted technical scheme: the two in-situ synthetic methods preparing carbon nano-tube reinforced hydroxylapatite composite material, and step is as follows:
The first step, the fabricated in situ of carbon nanotube-hydroxyapatite in-situ mixed powder:
It is nanometer ferric oxide in mass ratio: nanometer hydroxyapatite=0.026 ~ 0.176: the ratio of 1, take required nanometer ferric oxide and nanometer hydroxyapatite, agate mortar is adopted the two to be mixed, the quartzy Noah's ark that said mixture is housed is placed in horizontal pipe furnace flat-temperature zone, in this tube furnace, pass into nitrogen with the flow velocity of 90 ~ 130mL/min and be warming up to 600 ~ 800 DEG C, then close nitrogen, in this tube furnace, hydrogen is passed into the flow velocity of 90 ~ 130mL/min, insulation 0.5 ~ 2.5h, obtain iron-hydroxyapatite catalyzer, then close hydrogen, be nitrogen by volume ratio: propane=20 ~ 40: the gas mixture of 1 continues to pass into the flow velocity of 300 ~ 500mL/min, insulation 0.5 ~ 1h, close propane afterwards and adjust nitrogen flow, the quartzy Noah's ark that said mixture is housed in this tube furnace is made to be chilled to room temperature under the nitrogen atmosphere of 90 ~ 130mL/min flow velocity, obtained carbon nanotube-hydroxyapatite in-situ mixed powder, wherein the mass percentage of carbon nanotube is 2.0 ~ 15.6%,
Second step, two carbon nano-tube in situ-hydroxyapatite composite powder:
By calcium nitrate tetrahydrate and Vanadium Pentoxide in FLAKES in molar ratio 10: 3 ratio, take required weight respectively, being added by the Vanadium Pentoxide in FLAKES taken is equipped with in the beaker of dehydrated alcohol, the concentration of guarantee gained Vanadium Pentoxide in FLAKES solution is 0.1 ~ 0.2g/mL, and adopt magnetic stirrer 1 ~ 3h, the calcium nitrate tetrahydrate taken is added another to be equipped with in the beaker of dehydrated alcohol, the concentration of guarantee gained ca nitrate soln is 0.5 ~ 1g/mL, under whipped state, above-mentioned ca nitrate soln is added drop-wise in above-mentioned Vanadium Pentoxide in FLAKES solution by the flow velocity of 0.5 ~ 1mL/min, Keep agitation 1 ~ 3h after titration completes, leave standstill, binary colloidal is obtained after ageing 12 ~ 36h, carbon nanotube-hydroxyapatite in-situ the mixed powder taking the first step obtained by the concentration of 0.5 ~ 4.5g/L puts into above-mentioned binary colloidal, stir 1 ~ 4h, leave standstill 10 ~ 24h, then the mixed solution obtained is put into electric vacunm drying case and be dried to constant weight under vacuum tightness is-0.02 ~-0.1MPa and 60 ~ 90 DEG C condition, the dried powder obtained is placed in quartzy Noah's ark, this quartzy Noah's ark is placed in horizontal pipe furnace flat-temperature zone, in this tube furnace, pass into nitrogen with the flow velocity of 50 ~ 80mL/min and be warming up to 350 ~ 550 DEG C, after insulation 1.5 ~ 2.5h, the quartzy Noah's ark in this tube furnace is made to be chilled to room temperature under the nitrogen atmosphere of 50 ~ 80mL/min flow velocity, obtain two carbon nano-tube in situ-hydroxyapatite composite powder,
3rd step, prepared by carbon nano-tube reinforced hydroxylapatite composite material:
Use vacuum sintering funace, two carbon nano-tube in situ-hydroxyapatite composite powder obtained for second step is loaded in graphite jig, vacuum heating-press sintering 1 ~ 4h under the condition of 450 ~ 750MPa pressure and 900 ~ 1200 DEG C of temperature, the block of obtained carbon nano-tube reinforced hydroxylapatite composite material.
The above-mentioned two in-situ synthetic methods preparing carbon nano-tube reinforced hydroxylapatite composite material, wherein involved starting material and equipment obtain from known approach, and working method is that those skilled in the art can grasp.
The invention has the beneficial effects as follows: compared with prior art, the inventive method to have outstanding substantive distinguishing features as follows:
(1) the inventive method is in the design process of carbon nano-tube reinforced hydroxylapatite composite material structure, fully takes into account the biocompatibility requirement that such matrix material uses as bio-medical material.For overcoming in preparation process the difficult problem being difficult to thoroughly avoid carbon nanotube to contact with tissue, the mentality of designing proposing two carbon nano-tube in situ enhancing hydroxyapatite composite material of novelty.Carrying out on the basis of calcium/phosphorus than design, by the Design & preparation of a series of colloidal sol and gel, make the various ion needed for formation hydroxyapatite and functional group in the liquid phase fully coated, be gathered in around carbon nanotube, and eventually through calcining solid state reaction process formed hydroxyapatite.In this reaction process, the core that hydroxyapatite is nucleation and growth with carbon nanotube body, is closely wrapped in carbon nanotube wherein, defines the compound structure for new residence of hydroxyapatite layer in-stiu coating carbon nanotube; Carbon nano tube surface hydroxyapatite not with the form physical adsorption of nano particle in carbon nano tube surface, but form Chemical bond closely with the form of the hydroxyapatite layer of 5 ~ 20 nano thickness (see Figure of description 2,5) and carbon nanotube, thus carbon nanotube is coated in hydroxyapatite layer closely, completely, the existence of this airtight hydroxyapatite layer has thoroughly intercepted carbon nanotube and has contacted with the direct of tissue, while the enhancing of performance carbon nanotube, toughening effect, avoid the appearance of carbon nanotube toxicity.In addition, carry out in design process prepared by matrix material in the inventive method, also the harm how avoiding the required transition group metal catalyst of carbon nanotube synthesis to cause has been taken into full account, have employed the catalyzer that harmless iron synthesizes as carbon nanotube, farthest reduce the application risk of this matrix material, make prepared two carbon nano-tube in situ strengthen hydroxyapatite composite material and there is good biocompatibility.Therefore, carbon nano-tube reinforced hydroxylapatite composite material prepared by the inventive method, by the innovation of processing method, avoids the toxicity that carbon nanotube and catalyzer cause, achieve good biocompatibility, safe and reliable as bio-medical material.
(2) the inventive method is in the design process of carbon nano-tube reinforced hydroxylapatite composite material, fully takes into account the requirement of the mechanical property that such matrix material uses as bio-medical material, particularly fracture toughness property.In order to improve the comprehensive mechanical property of hydroxyapatite material, the interface cohesion effect improving carbon nanotube-hydroxyapatite is innovated as important outstanding technological core.By taking two fabricated in situ technique, completely coated to carbon nano tube surface of with the nanometer hydroxyapatite layer non-particulate form of achieving, both bonding interface areas are not only made to enlarge markedly, and to be grown up subsequently at carbon nanotube tube surfaces original position forming core by hydroxyapatite layer and define extremely strong Chemical bond, significantly improve the interface binding power of carbon nanotube-hydroxyapatite, the transmission of larger load can be realized by interface, suppress the formation of interface micro-flaw, thus improve the comprehensive mechanical property of hydroxyapatite material, the bending strength of material is made to reach 130 ~ 296MPa, fracture toughness property reaches 2.9 ~ 6.7MPam
1/2, substantially reach the fracture toughness property of skeleton.
(3) as a kind of new bio medical material having application potential, how to realize the comprehensive use properties of carbon nano-tube reinforced hydroxylapatite composite material, namely while this matrix material of guarantee has good biocompatibility, the mechanical property of combined with superior, the prerequisite that the combination of both realizations is carbon nano-tube reinforced hydroxylapatite composite material applies in biomedical materials field and technological difficulties.Based on above-mentioned consideration, the imagination proposing two carbon nano-tube in situ enhancing hydroxyapatite composite material of novelty of the present invention, namely by utilizing nanometer ferric oxide and nanometer hydroxyapatite to be starting material, first fabricated in situ had not only had superior bio consistency but also had had the carbon nanotube-hydroxyapatite composite powder of carbon nanotube-hydroxyapatite interface compatibility, then again nanometer hydroxyapatite layer is made to be coated on the surface of carbon nanotube and original nanometer hydroxyapatite by fabricated in situ technique, fundamentally completely cut off the chance that in the matrix material of follow-up preparation, carbon nanotube contacts with tissue, thoroughly avoid the appearance of carbon nanotube to human toxicity, achieve the Chemical bond of carbon nanotube and hydroxyapatite layer simultaneously, thus achieve the unification of carbon nano-tube reinforced hydroxylapatite composite material good biocompatibility and excellent mechanical performance (particularly fracture toughness property) simultaneously, the service requirements as human body hard tissue implant can be met.What the present invention was used is " two fabricated in situ " method, is a kind of method having outstanding substantive distinguishing features being different from existing in-situ synthetic method.Wherein, what fabricated in situ adopted for the first time is that chemical vapour deposition (CVD) technology realizes, and what second time fabricated in situ adopted is sol-gel technique realization.
Compared with prior art, the marked improvement that has of the inventive method is as follows:
(1) in the carbon nano-tube reinforced hydroxylapatite composite material prepared by the inventive method, carbon nanotube and hydroxyapatite interface bond strength are higher than the carbon nano-tube reinforced hydroxylapatite composite material prepared by all prior aries, and its mechanical property meets the service requirements of sclerous tissues's implant.
(2) carbon nano-tube reinforced hydroxylapatite composite material prepared by the inventive method achieves the unification of carbon nano-tube reinforced hydroxylapatite composite material good biocompatibility and excellent mechanical performance (particularly fracture toughness property) simultaneously, can meet the service requirements as human body hard tissue implant.
(3) the carbon nano-tube reinforced hydroxylapatite composite material nontoxicity prepared by the inventive method, has good biocompatibility, safe and reliable as bio-medical material.
Accompanying drawing explanation
Below in conjunction with drawings and Examples, the present invention is further described.
The electron scanning micrograph of the two carbon nano-tube in situ-hydroxyapatite composite powders of Fig. 1 obtained by the embodiment of the present invention 1.
The transmission electron microscope photo of the two carbon nano-tube in situ-hydroxyapatite composite powders of Fig. 2 obtained by example 1 of the present invention.
The electron scanning micrograph of the two carbon nano-tube in situ-hydroxyapatite composite material crimped section of Fig. 3 obtained by example 1 of the present invention.
The transmission electron microscope photo of the two carbon nano-tube in situ-hydroxyapatite composite material block of Fig. 4 obtained by example 1 of the present invention.
The transmission electron microscope photo of the two carbon nano-tube in situ-hydroxyapatite composite powders of Fig. 5 obtained by example 3 of the present invention.
Embodiment
Embodiment 1
The first step, the fabricated in situ of carbon nanotube-hydroxyapatite in-situ mixed powder:
It is nanometer ferric oxide in mass ratio: nanometer hydroxyapatite=0.026: the ratio of 1, take required nanometer ferric oxide and nanometer hydroxyapatite, agate mortar is adopted the two to be mixed, the quartzy Noah's ark that said mixture is housed is placed in horizontal pipe furnace flat-temperature zone, in this tube furnace, pass into nitrogen with the flow velocity of 90mL/min and be warming up to 600 DEG C, then close nitrogen, in this tube furnace, hydrogen is passed into the flow velocity of 90mL/min, insulation 0.5h, obtain iron-hydroxyapatite catalyzer, then close hydrogen, be nitrogen by volume ratio: propane=20: the gas mixture of 1 continues to pass into the flow velocity of 300mL/min, insulation 0.5h, close propane afterwards and adjust nitrogen flow, the quartzy Noah's ark that said mixture is housed in this tube furnace is made to be chilled to room temperature under the nitrogen atmosphere of 90mL/min flow velocity, obtained carbon nanotube-hydroxyapatite in-situ mixed powder, wherein the mass percentage of carbon nanotube is 2.0%.
Second step, two carbon nano-tube in situ-hydroxyapatite composite powder:
By calcium nitrate tetrahydrate and Vanadium Pentoxide in FLAKES in molar ratio 10: 3 ratio, take required weight respectively, being added by the Vanadium Pentoxide in FLAKES taken is equipped with in the beaker of dehydrated alcohol, the concentration of guarantee gained Vanadium Pentoxide in FLAKES solution is 0.1g/mL, and adopt magnetic stirrer 1h, the calcium nitrate tetrahydrate taken is added another to be equipped with in the beaker of dehydrated alcohol, the concentration of guarantee gained ca nitrate soln is 0.5g/mL, under whipped state, above-mentioned ca nitrate soln is added drop-wise in above-mentioned Vanadium Pentoxide in FLAKES solution by the flow velocity of 0.5mL/min, Keep agitation 1h after titration completes, leave standstill, binary colloidal is obtained after ageing 12h, carbon nanotube-hydroxyapatite in-situ the mixed powder taking the first step obtained by the concentration of 0.5g/L puts into above-mentioned binary colloidal, stir 1h, leave standstill 10h, then the mixed solution obtained is put into electric vacunm drying case and be dried to constant weight in vacuum tightness under-0.02MPa and 60 DEG C condition, the dried powder obtained is placed in quartzy Noah's ark, this quartzy Noah's ark is placed in horizontal pipe furnace flat-temperature zone, in this tube furnace, pass into nitrogen with the flow velocity of 50mL/min and be warming up to 350 DEG C, after insulation 1.5h, the quartzy Noah's ark in this tube furnace is made to be chilled to room temperature under the nitrogen atmosphere of 50mL/min flow velocity, obtain two carbon nano-tube in situ-hydroxyapatite composite powder,
The electron scanning micrograph of the two carbon nano-tube in situ-hydroxyapatite composite powders of Fig. 1 obtained by the present embodiment.From this figure, cylindric material elongated in figure is the coated carbon nanotube of hydroxyapatite layer, its length about 1 micron, caliber is in 70 ~ 80 nanometer range, hydroxyapatite layer is closely wrapped in outside carbon nanotube, carbon nanotube tube wall, without exposed region, has effectively been stopped carbon nanotube in follow-up matrix material and has been contacted with the direct of tissue, avoided the appearance of carbon nanotube toxicity.
The transmission electron microscope photo of the two carbon nano-tube in situ-hydroxyapatite composite powders of Fig. 2 obtained by the present embodiment.The aterrimus material of this figure core is carbon nanotube, and outside it, the material of indentation is Coated With Hydroxyapatite layer.From this figure, the hydroxyapatite layer in outside closely wraps the carbon nanotube of core, effectively can avoid the contact of carbon nanotube and tissue, carbon nanotube-hydroxyapatite interface is Chemical bond closely, is conducive to carbon nanotube and plays effective enhancement in final hydroxyapatite composite material.
3rd step, prepared by carbon nano-tube reinforced hydroxylapatite composite material:
Use vacuum sintering funace, two carbon nano-tube in situ-hydroxyapatite composite powder obtained for second step is loaded in graphite jig, vacuum heating-press sintering 1h under the condition of 450MPa pressure and 900 DEG C of temperature, the block of obtained carbon nano-tube reinforced hydroxylapatite composite material.
The electron scanning micrograph of the two carbon nano-tube in situ-hydroxyapatite composite material crimped section of Fig. 3 obtained by the present embodiment.Cylindrical bump in the middle part of picture is the carbon nanotube be pulled out after hydroxyapatite composite material bend fracture, this carbon nanotube is combined closely with the hydroxyapatite matrix of downside, in the process be pulled out, effectively deliver load, strengthening effect is played to matrix material.
The transmission electron microscope photo of the two carbon nano-tube in situ-hydroxyapatite composite material block of Fig. 4 obtained by the present embodiment.From this figure, in final hydroxyapatite composite material, the carbon nanotube dispersed indicated by black arrow is even, maintain original hollow tubular structure, and be combined closely with hydroxyapatite matrix, be desirable matrix-wild phase bonding state, can efficient hardening hydroxyapatite matrix.
Embodiment 2
The first step, the fabricated in situ of carbon nanotube-hydroxyapatite in-situ mixed powder:
It is nanometer ferric oxide in mass ratio: nanometer hydroxyapatite=0.1: the ratio of 1, take required nanometer ferric oxide and nanometer hydroxyapatite, agate mortar is adopted the two to be mixed, the quartzy Noah's ark that said mixture is housed is placed in horizontal pipe furnace flat-temperature zone, in this tube furnace, pass into nitrogen with the flow velocity of 110mL/min and be warming up to 700 DEG C, then close nitrogen, in this tube furnace, hydrogen is passed into the flow velocity of 110mL/min, insulation 1.5h, obtain iron-hydroxyapatite catalyzer, then close hydrogen, be nitrogen by volume ratio: propane=30: the gas mixture of 1 continues to pass into the flow velocity of 400mL/min, insulation 0.75h, close propane afterwards and adjust nitrogen flow, the quartzy Noah's ark that said mixture is housed in this tube furnace is made to be chilled to room temperature under the nitrogen atmosphere of 110mL/min flow velocity, obtained carbon nanotube-hydroxyapatite in-situ mixed powder, wherein the mass percentage of carbon nanotube is 9.4%.
Second step, two carbon nano-tube in situ-hydroxyapatite composite powder:
By calcium nitrate tetrahydrate and Vanadium Pentoxide in FLAKES in molar ratio 10: 3 ratio, take required weight respectively, being added by the Vanadium Pentoxide in FLAKES taken is equipped with in the beaker of dehydrated alcohol, the concentration of guarantee gained Vanadium Pentoxide in FLAKES solution is 0.15g/mL, and adopt magnetic stirrer 2h, the calcium nitrate tetrahydrate taken is added another to be equipped with in the beaker of dehydrated alcohol, the concentration of guarantee gained ca nitrate soln is 0.75g/mL, under whipped state, above-mentioned ca nitrate soln is added drop-wise in above-mentioned Vanadium Pentoxide in FLAKES solution by the flow velocity of 0.75mL/min, Keep agitation 2h after titration completes, leave standstill, binary colloidal is obtained after ageing 24h, carbon nanotube-hydroxyapatite in-situ the mixed powder taking the first step obtained by the concentration of 2.5g/L puts into above-mentioned binary colloidal, stir 2h, leave standstill 17h, then the mixed solution obtained is put into electric vacunm drying case and be dried to constant weight in vacuum tightness under-0.06MPa and 75 DEG C condition, the dried powder obtained is placed in quartzy Noah's ark, this quartzy Noah's ark is placed in horizontal pipe furnace flat-temperature zone, in this tube furnace, pass into nitrogen with the flow velocity of 65mL/min and be warming up to 450 DEG C, after insulation 2h, the quartzy Noah's ark in this tube furnace is made to be chilled to room temperature under the nitrogen atmosphere of 65mL/min flow velocity, obtain two carbon nano-tube in situ-hydroxyapatite composite powder,
3rd step, prepared by carbon nano-tube reinforced hydroxylapatite composite material:
Use vacuum sintering funace, two carbon nano-tube in situ-hydroxyapatite composite powder obtained for second step is loaded in graphite jig, vacuum heating-press sintering 2h under the condition of 600MPa pressure and 1100 DEG C of temperature, the block of obtained carbon nano-tube reinforced hydroxylapatite composite material.
Embodiment 3
The first step, the fabricated in situ of carbon nanotube-hydroxyapatite in-situ mixed powder:
It is nanometer ferric oxide in mass ratio: nanometer hydroxyapatite=0.176: the ratio of 1, take required nanometer ferric oxide and nanometer hydroxyapatite, agate mortar is adopted the two to be mixed, the quartzy Noah's ark that said mixture is housed is placed in horizontal pipe furnace flat-temperature zone, in this tube furnace, pass into nitrogen with the flow velocity of 130mL/min and be warming up to 800 DEG C, then close nitrogen, in this tube furnace, hydrogen is passed into the flow velocity of 130mL/min, insulation 2.5h, obtain iron-hydroxyapatite catalyzer, then close hydrogen, be nitrogen by volume ratio: propane=40: the gas mixture of 1 continues to pass into the flow velocity of 500mL/min, insulation 1h, close propane afterwards and adjust nitrogen flow, the quartzy Noah's ark that said mixture is housed in this tube furnace is made to be chilled to room temperature under the nitrogen atmosphere of 130mL/min flow velocity, obtained carbon nanotube-hydroxyapatite in-situ mixed powder, wherein the mass percentage of carbon nanotube is 15.6%.
Second step, two carbon nano-tube in situ-hydroxyapatite composite powder:
By calcium nitrate tetrahydrate and Vanadium Pentoxide in FLAKES in molar ratio 10: 3 ratio, take required weight respectively, being added by the Vanadium Pentoxide in FLAKES taken is equipped with in the beaker of dehydrated alcohol, the concentration of guarantee gained Vanadium Pentoxide in FLAKES solution is 0.2g/mL, and adopt magnetic stirrer 3h, the calcium nitrate tetrahydrate taken is added another to be equipped with in the beaker of dehydrated alcohol, the concentration of guarantee gained ca nitrate soln is 1g/mL, under whipped state, above-mentioned ca nitrate soln is added drop-wise in above-mentioned Vanadium Pentoxide in FLAKES solution by the flow velocity of 1mL/min, Keep agitation 3h after titration completes, leave standstill, binary colloidal is obtained after ageing 36h, carbon nanotube-hydroxyapatite in-situ the mixed powder taking the first step obtained by the concentration of 4.5g/L puts into above-mentioned binary colloidal, stir 4h, leave standstill 24h, then the mixed solution obtained is put into electric vacunm drying case and be dried to constant weight in vacuum tightness under-0.1MPa and 90 DEG C condition, the dried powder obtained is placed in quartzy Noah's ark, this quartzy Noah's ark is placed in horizontal pipe furnace flat-temperature zone, in this tube furnace, pass into nitrogen with the flow velocity of 80mL/min and be warming up to 550 DEG C, after insulation 2.5h, the quartzy Noah's ark in this tube furnace is made to be chilled to room temperature under the nitrogen atmosphere of 80mL/min flow velocity, obtain two carbon nano-tube in situ-hydroxyapatite composite powder,
The transmission electron microscope photo of the two carbon nano-tube in situ-hydroxyapatite composite powders of Fig. 5 obtained by the present embodiment.Compared with the Fig. 2 in embodiment 1, the present invention is by the regulation and control to two fabricated in situ technique, the control of hydroxyapatite layer thickness to closely coated outside carbon nanotube and structure can be realized, thus realize the regulation and control to carbon nano-tube reinforced hydroxylapatite composite material performance.
3rd step, prepared by carbon nano-tube reinforced hydroxylapatite composite material:
Use vacuum sintering funace, two carbon nano-tube in situ-hydroxyapatite composite powder obtained for second step is loaded in graphite jig, vacuum heating-press sintering 4h under the condition of 750MPa pressure and 1200 DEG C of temperature, the block of obtained carbon nano-tube reinforced hydroxylapatite composite material.
Starting material involved in above-described embodiment and equipment obtain from known approach, and working method is that those skilled in the art can grasp.
Claims (2)
1. prepare two in-situ synthetic methods of carbon nano-tube reinforced hydroxylapatite composite material, it is characterized in that step is as follows:
The first step, the fabricated in situ of carbon nanotube-hydroxyapatite in-situ mixed powder:
It is nanometer ferric oxide in mass ratio: nanometer hydroxyapatite=0.026 ~ 0.176: the ratio of 1, take required nanometer ferric oxide and nanometer hydroxyapatite, agate mortar is adopted the two to be mixed, the quartzy Noah's ark that said mixture is housed is placed in horizontal pipe furnace flat-temperature zone, in this tube furnace, pass into nitrogen with the flow velocity of 90 ~ 130mL/min and be warming up to 600 ~ 800 DEG C, then close nitrogen, in this tube furnace, hydrogen is passed into the flow velocity of 90 ~ 130mL/min, insulation 0.5 ~ 2.5h, obtain iron-hydroxyapatite catalyzer, then close hydrogen, be nitrogen by volume ratio: propane=20 ~ 40: the gas mixture of 1 continues to pass into the flow velocity of 300 ~ 500mL/min, insulation 0.5 ~ 1h, close propane afterwards and adjust nitrogen flow, the quartzy Noah's ark that said mixture is housed in this tube furnace is made to be chilled to room temperature under the nitrogen atmosphere of 90 ~ 130mL/min flow velocity, obtained carbon nanotube-hydroxyapatite in-situ mixed powder, wherein the mass percentage of carbon nanotube is 2.0 ~ 15.6%,
Second step, two carbon nano-tube in situ-hydroxyapatite composite powder:
By calcium nitrate tetrahydrate and Vanadium Pentoxide in FLAKES in molar ratio 10: 3 ratio, take required weight respectively, being added by the Vanadium Pentoxide in FLAKES taken is equipped with in the beaker of dehydrated alcohol, the concentration of guarantee gained Vanadium Pentoxide in FLAKES solution is 0.1 ~ 0.2g/mL, and adopt magnetic stirrer 1 ~ 3h, the calcium nitrate tetrahydrate taken is added another to be equipped with in the beaker of dehydrated alcohol, the concentration of guarantee gained ca nitrate soln is 0.5 ~ 1g/mL, under whipped state, above-mentioned ca nitrate soln is added drop-wise in above-mentioned Vanadium Pentoxide in FLAKES solution by the flow velocity of 0.5 ~ 1mL/min, Keep agitation 1 ~ 3h after titration completes, leave standstill, binary colloidal is obtained after ageing 12 ~ 36h, carbon nanotube-hydroxyapatite in-situ the mixed powder taking the first step obtained by the concentration of 0.5 ~ 4.5g/L puts into above-mentioned binary colloidal, stir 1 ~ 4h, leave standstill 10 ~ 24h, then the mixed solution obtained is put into electric vacunm drying case and be dried to constant weight under vacuum tightness is-0.02 ~-0.1MPa and 60 ~ 90 DEG C condition, the dried powder obtained is placed in quartzy Noah's ark, this quartzy Noah's ark is placed in horizontal pipe furnace flat-temperature zone, in this tube furnace, pass into nitrogen with the flow velocity of 50 ~ 80mL/min and be warming up to 350 ~ 550 DEG C, after insulation 1.5 ~ 2.5h, the quartzy Noah's ark in this tube furnace is made to be chilled to room temperature under the nitrogen atmosphere of 50 ~ 80mL/min flow velocity, obtain two carbon nano-tube in situ-hydroxyapatite composite powder,
3rd step, prepared by carbon nano-tube reinforced hydroxylapatite composite material:
Use vacuum sintering funace, two carbon nano-tube in situ-hydroxyapatite composite powder obtained for second step is loaded in graphite jig, vacuum heating-press sintering 1 ~ 4h under the condition of 450 ~ 750MPa pressure and 900 ~ 1200 DEG C of temperature, the block of obtained carbon nano-tube reinforced hydroxylapatite composite material.
2. prepare two in-situ synthetic methods of carbon nano-tube reinforced hydroxylapatite composite material according to claim 1, it is characterized in that: described quality is than nanometer ferric oxide: nanometer hydroxyapatite is 0.1: 1.
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| CN104998301A (en) * | 2015-08-12 | 2015-10-28 | 河北工业大学 | Preparation method of carbon nano tube reinforced mesoporous hydroxyapatite composite material |
| CN107117956A (en) * | 2017-04-05 | 2017-09-01 | 江苏大学 | It is a kind of for multiporous biological piezo-electricity composite material of Bone Defect Repari and preparation method thereof |
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| CN101156961A (en) * | 2007-11-12 | 2008-04-09 | 天津大学 | Method for preparing carbon nanometer tube/hydroxyapatite complex powder through vapour deposition reaction in-situ |
| WO2010072882A1 (en) * | 2008-12-24 | 2010-07-01 | Consejo Superior De Investigaciones Científicas (Csic) | Nanostructured calcium-silver phosphate composite powder, method for obtaining same, and bactericidal and fungicidal uses thereof |
| CN102976743A (en) * | 2012-12-19 | 2013-03-20 | 河北工业大学 | Preparation method of carbon nanotube reinforced hydroxyapatite composite material |
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| WO2010072882A1 (en) * | 2008-12-24 | 2010-07-01 | Consejo Superior De Investigaciones Científicas (Csic) | Nanostructured calcium-silver phosphate composite powder, method for obtaining same, and bactericidal and fungicidal uses thereof |
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| CN104998301B (en) * | 2015-08-12 | 2017-05-24 | 河北工业大学 | Preparation method of carbon nano tube reinforced mesoporous hydroxyapatite composite material |
| CN107117956A (en) * | 2017-04-05 | 2017-09-01 | 江苏大学 | It is a kind of for multiporous biological piezo-electricity composite material of Bone Defect Repari and preparation method thereof |
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