CN102716514A - Nano composite biological coating and preparation method thereof - Google Patents
Nano composite biological coating and preparation method thereof Download PDFInfo
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- CN102716514A CN102716514A CN2012101705354A CN201210170535A CN102716514A CN 102716514 A CN102716514 A CN 102716514A CN 2012101705354 A CN2012101705354 A CN 2012101705354A CN 201210170535 A CN201210170535 A CN 201210170535A CN 102716514 A CN102716514 A CN 102716514A
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Abstract
The invention discloses a nano composite biological coating and a preparation method of the nano composite biological coating. The nano composite biological coating comprises nano hydroxyapatite and graphene. The preparation method comprises the following steps of: weighing raw materials in different mixing ratios, performing ultrasonic dispersion and mixing; spraying and granulating the mixed powder to obtain nano hydroxyapatite-graphene micro agglomerated particles; and performing plasma spraying, and thus obtaining the hydroxyapatite-graphene nano composite biological coating. The nano composite biological coating has good antibacterial performance, bone induction performance and capability of promoting attachment of bone cells on the surface. Plasma spraying is adopted in the preparation method for the nano composite biological coating; and compared with the conventional coating preparation method, the preparation method has the advantages of improving the preparation efficiency and greatly reducing the processing cost.
Description
Technical field
The present invention relates to material science and biomedical crossing domain, relate in particular to a kind of hydroxyapatite-graphene nano composite biological coating and preparation method thereof.
Background technology
Bio-medical material is the necessary that ensures human health, and the innovation and the development of contemporary medical skill and health care system had guiding function.Meanwhile, the bio-medical material industry plays a significant role in World Economics as the basis of medical apparatus industry.2,527 hundred million dollars of being expected to increase to 2014 in the market of bio-medical material from 1,154 hundred million dollars of 2008.Therefore, relevant with bio-medical material research also more and more obtains paying attention to.
Tradition has excellent performance with the human body implantable bone of metal material preparation on mechanical property, but these materials are biologically inerts.And ideal human body implantable bone material not only will satisfy the requirement of mechanical property, also will have excellent anti-microbial property, biological activity and biocompatibility.Hydroxyapatite is one of maximum bioactive ceramics of research at present; The extremely favor of biomedical engineering field researcher always, the apatite that hydroxyapatite excellent biological compatibility and biological activity come from its chemical constituent and crystal structure and the skeleton is quite similar.So, at metal human body implantable bone surface preparation one deck hydroxyapatite coating layer, can improve the biocompatibility of metallic matrix, give full play to the excellent mechanical property of metallic matrix.But the intrinsic fragility of hydroxyapatite has greatly limited its use as the load-bearing bone alternate material.Therefore, the research hydroxyapatite composite material biological coating that has both high-strength tenacity and excellent biological activity, biocompatibility has great importance undoubtedly.
In the hydroxyapatite matrix, adding second, to carry out tough processing mutually be a kind of the most suitable scheme.The tough phase of ideal hydroxyapatite coating layer at first need satisfy the mechanical property that under the prerequisite of less addition, improves hydroxyapatite to greatest extent; Simultaneously as body implant; Toughly want no cytotoxicity mutually and can inherit the excellent biological activity of matrix material, even toughly itself will have certain antibacterial ability, osteoinductive ability mutually.
Mainly adopt hard particles, high molecular polymer, fiber and CNT as tough phase at present in the research.The tough of the present invention's use is Graphene mutually, and Graphene is a kind of cellular two-dimentional carbon atom crystal of periodicity that is formed with hexagonal array by the carbon atom of sp2 hydridization, its light weight, the big (2630m of specific surface area
2g
-1) and excellent mechanical property (Young's modulus 1100GPa, fracture toughness 125GPa) be expected to make it to become a kind of new tough phase.There has been research to report that Graphene has the better inhibited ability to colibacillary growth, shown that it has certain antibacterial ability.In the process of the present invention, accomplished the immersion test of Graphene in simulated body fluid, found the calcium phosphate of mineralising on the Graphene surface, shown that Graphene has certain osteoinductive ability.Among the present invention simultaneously, the biological coating for preparing has been carried out osteoblastic attaching experiment, the result shows that Graphene has the osteoblast of promotion in the attaching ability of hydroxyapatite on the surface, and this has embodied the good biological activity of Graphene.This a series of excellent properties is expected to let Graphene become a kind of novel tough phase material of human body implantable bone.
The tough material that the present invention adopts is a Graphene, and similarly is to select CNT mutually tough as hydroxyapatite coating layer for use with this patent.Similarly patent has: patent CN101949046A, the method for preparing of a kind of carbonate type hydroxyapatite-CNT composite coating material.This invention deposits to metal base surface with electrophoretic deposition with calcium carbonate powder or the powder and the CNT that contain calcium carbonate; Obtain calcium carbonate powder-carbon nanotube coating, then calcium carbonate powder-carbon nanotube coating is changed into carbonate type hydroxyapatite-CNT composite coating after phosphate buffer solution is handled.
Patent CN1772969, nanometer hydroxyapatite-CNT preparation method of composite coating.What this invention was adopted is the composite of nanometer hydroxyapatite and CNT, adopts electrophoretic deposition to prepare hydroxyapatite-CNT composite coating.
Patent CN1440948, hydroxyapatite-carbon nano tube compound material and preparation technology thereof.The chemical precipitation method synthesizing hydroxylapatite is adopted in this invention, without the solid-liquid separation process, and the direct and compound hydroxyapatite-carbon nano tube compound material of preparing of CNT.
Patent CN101530633, antibacterial argentum-carried hydroxylapatite-carbon nanotube composite artificial bone and preparation thereof.This invention is a carrier with the hydroxyapatite-carbon nano-tube composite powder of in-situ synthesis preparation, obtains argentum-carried hydroxylapatite-carbon nano-tube composite powder through ion exchange and ion adsorption; With this powder body is raw material, adopts hot pressing sintering method to prepare antibacterial argentum-carried hydroxylapatite-carbon nanotube composite artificial bone.
From the improvement of mechanical property, CNT is a kind of reasonable tough phase, but as human body implantable bone material, only is that the improvement on the mechanical property is not enough, also will consider the problem of material on biocompatibility.Big quantity research also has dispute to the cytotoxicity of CNT, and wherein some researcher thinks that the cytotoxicity of CNT comes from mainly that beavy metal impurity residual in the made of carbon nanotubes process causes.Compare with CNT, need not use metal as catalyst in the preparation process of Graphene, and can obtain highly purified Graphene, avoided the adverse effect of impurity greatly.Patent CN101949046A, CN1772969 and CN1440948 need more rigorous this factor of consideration.This material system of argentum-carried hydroxylapatite-CNT can improve the mechanical property of material, and has certain antibacterial action.But the anti-microbial property of Ag-carried antibacterial material directly with material in silver ion separate out relevantly, silver is as a heavy metal species, to the toxic effect of histoorgan, so silver ion separates out concentration and needs control again, this is to need the place further studied on the material system; Next, whether such material system has excellent biological compatibility, whether can improve osteoblastic attaching all is unknown with propagation; It is complicated uploading this technology of silver at CNT in addition, and it is more complicated how to control the content that carries silver-colored particulate size and silver simultaneously, and this is the aspect that requires careful consideration in the material preparation.
Therefore,, be necessary to provide a kind of nano-composite coating material and preparation method thereof, to overcome above-mentioned defective to above-mentioned technical problem.
Summary of the invention
In view of this; The object of the present invention is to provide a kind of human loaded bone coating material system; Promptly adopt plasma spraying technology; Prepare hydroxyapatite-graphene nano composite biological coating at titanium alloy surface, be intended to make it to have excellent biological activity and biocompatibility, good mechanical performance and improve its anti-microbial property and mechanical property.
For realizing above-mentioned purpose, the present invention provides following technical scheme:
A kind of nano composite material biological coating, its raw material component comprises nano-hydroapatite particles and Graphene.
Preferably, in above-mentioned nano composite material biological coating, said Graphene percentage by weight is 0.1% ~ 2.0% of a nanometer hydroxyapatite, and nanometer hydroxyapatite is a corynebacterium.
A kind of method for preparing of nano composite material biological coating, this method for preparing comprises the steps:
A. analytical balance takes by weighing an amount of nanometer hydroxyapatite and Graphene respectively;
B. load weighted Graphene carries out ultra-sonic dispersion, adds the ultrasonic mixing of load weighted nano-hydroapatite particles then, and blended nanometer hydroxyapatite-graphene powder is carried out dried;
C. mixed-powder among the step B is carried out mist projection granulating and handles, make nanometer hydroxyapatite-Graphene micron agglomerated particle, and dry, screen this micron agglomerated particle;
D. plasma spraying preparation of hydroxyapatite-graphene nano composite biological coating.
Preferably, in the method for preparing of nano composite material biological coating, the Graphene percentage by weight is 0.1% ~ 2.0% of a nanometer hydroxyapatite in the said steps A, and nanometer hydroxyapatite is a corynebacterium.
Preferably; In the method for preparing of nano composite material biological coating; Ultra-sonic dispersion among the said step B, to mix all be in dehydrated alcohol, to carry out, and wherein adds an amount of dodecylbenzene sodium sulfonate as dispersant, ultra-sonic dispersion 30min during the Graphene ultra-sonic dispersion; Then add the ultrasonic mixing of nanometer hydroxyapatite 60min, the dried parameter is 120 ℃ of dry 120min.
Preferably, in the method for preparing of nano composite material biological coating, said employing spray granulation makes nanometer hydroxyapatite-Graphene micron agglomerated particle, specifically comprises step:
C1. add distilled water, Polyethylene Glycol dispersant and polyvinyl alcohol adhesive to fully ultrasonic mixed mixed-powder, mechanical agitation becomes the uniform mixing slip then;
C2. adopt the press atomization prilling granulator that the mixed slurry that forms among the C1 is handled, process nanometer hydroxyapatite-Graphene micron agglomerated particle;
C3. nanometer hydroxyapatite-Graphene micron agglomerated particle dried;
C4. filter out the micron agglomerated particle of special diameter scope, as the plasma spraying feeding.
Preferably, in the method for preparing of nano composite material biological coating, among the said step C2, the parameter of press atomization prilling granulator comprises atomizing pressure 0.3MPa, 300 ℃ of hothouse temperature.
Preferably, in the method for preparing of nano composite material biological coating, among the said step C3, the dried parameter is 120 ℃ of dry 120min.
Preferably, in the method for preparing of nano composite material biological coating, among the said step C4, the diameter range of the micron agglomerated particle that filters out is 40 ~ 70 μ m.
Preferably, in the method for preparing of nano composite material biological coating, said step D specifically comprises:
D1. to the Ti6Al4V substrate carry out sandblast, the cleaning of deoiling, then be fixed on the turntable of plasma spraying chamber and and carry out preheating it;
D2. the plasma spray coating process parameter is voltage 40 ~ 60V, electric current 600 ~ 800A, main gas (argon) 40 ~ 60L/min, auxilliary gas (hydrogen) 20 ~ 30L/min, carrier gas (argon) 40 ~ 60L/min, spray distance 80 ~ 100mm;
D3. in the Plasma Spraying Process Using, adopt Accuraspray-G3C plasma spraying on-line monitoring equipment, the average surface temperature of feeding and average flight speed are optimized the plasma spray coating process parameter with this in the on-line monitoring plasma flame.
Can find out from technique scheme; The nano composite material biological coating of the embodiment of the invention has good antibacterial performance, osteoinductive can and promote the ability that osteoblast attaches in hydroxyapatite surface; The method for preparing of the embodiment of the invention utilizes plasma spraying technology to prepare hydroxyapatite-Graphene composite coating; More traditional preparation technology of coating, this kind preparation technology has improved preparation efficiency, has greatly practiced thrift processing cost.
Compared with prior art, the invention has the beneficial effects as follows:
(1) material system design aspect; Hydroxyapatite-graphene nano composite biological coating material system that the present invention announces; The Graphene that promptly in nanometer hydroxyapatite, adds weight ratio 0.1%-2.0% is as tough phase; This nano composite material biological coating not only mechanical property is improved, and has good antibacterial performance, osteoinductive ability and promote the ability that osteoblast attaches at coating surface.
(2) technology of preparing aspect; The plasma spraying technology that utilizes that the present invention announces prepares the technology of hydroxyapatite-graphene nano composite biological coating; More traditional preparation technology of coating, this preparation technology has improved preparation efficiency, has greatly practiced thrift processing cost.
Description of drawings
In order to be illustrated more clearly in the embodiment of the invention or technical scheme of the prior art; To do to introduce simply to the accompanying drawing of required use in embodiment or the description of the Prior Art below; Obviously, the accompanying drawing relevant of the present invention in describing below only is some embodiments of the present invention, for those of ordinary skills; Under the prerequisite of not paying creative work, can also obtain other accompanying drawing according to these accompanying drawings.
Fig. 1 is hydroxyapatite of the present invention-graphene nano composite biological coating preparation flow figure;
Fig. 2 is the Raman spectrogram of the hydroxyapatite-graphene nano composite biological coating of Graphene and plasma spraying preparation; Wherein: label 1 is represented the Raman spectrogram of Graphene; On behalf of plasma spraying, label 2 do not add the Raman spectrogram of the nano hydroxyapatite coating of Graphene; It is the Raman spectrogram of 0.5% nano hydroxyapatite coating that label 3 is represented plasma spraying Graphene percentage by weight; It is the Raman spectrogram of 1.0% nano hydroxyapatite coating that label 4 is represented plasma spraying Graphene percentage by weight; Mark among the figure the 430,590,961,1047, the 3571st, the characteristic peak of hydroxyapatite, the 1347, the 1581st, the characteristic peak of Graphene;
Fig. 3 is the transmission electron microscope picture that Graphene soaked in simulated body fluid 10 days, and analysis result shows that wherein shaft is a calcium phosphate;
Fig. 4 a ~ 4f is an osteoblast at hydroxyapatite coating layer in plasma spraying (4a, 4d), plasma spraying Graphene percentage by weight is that 0.5% nano hydroxyapatite coating (4b, 4e), plasma spraying Graphene percentage by weight are that 0.5% nano hydroxyapatite coating (4c, 4f) surface attaches 6 hours fluorescence microscope photo; Wherein bright spot is osteoblastic nucleus; 4a, 4b, 4c amplification are 100 times, and 4d, 4e, 4f amplification are 200 times.
The specific embodiment
The invention discloses a kind of nano composite material biological coating and preparation method thereof, this nano composite material biological coating has good antibacterial performance, osteoinductive can and promote the ability that osteoblast attaches in hydroxyapatite surface; This method for preparing utilizes plasma spraying technology to prepare hydroxyapatite-graphene nano composite biological coating, more traditional preparation technology of coating, and this kind preparation technology has improved preparation efficiency, has greatly practiced thrift processing cost.
This nano composite material biological coating, its raw material component comprises nano-hydroapatite particles and Graphene.
Further, said Graphene percentage by weight is 0.1% ~ 2.0% of a nanometer hydroxyapatite, and nanometer hydroxyapatite is a corynebacterium.
The method for preparing of this nano composite material biological coating, this method for preparing comprises the steps:
A. analytical balance takes by weighing an amount of nanometer hydroxyapatite and Graphene respectively;
B. load weighted Graphene carries out ultra-sonic dispersion, adds the ultrasonic mixing of load weighted nano-hydroapatite particles then, and blended nanometer hydroxyapatite-graphene powder is carried out dried;
C. mixed-powder among the step B is carried out mist projection granulating and handles, make nanometer hydroxyapatite-Graphene micron agglomerated particle, and dry, screen this micron agglomerated particle;
D. plasma spraying preparation of hydroxyapatite-graphene nano composite biological coating.
Further, the Graphene percentage by weight is the 0.1%-2.0% of nanometer hydroxyapatite in the said steps A, and nanometer hydroxyapatite is a corynebacterium.
Further, ultra-sonic dispersion among the said step B, to mix all be in dehydrated alcohol, to carry out, and wherein adds an amount of dodecylbenzene sodium sulfonate as dispersant, ultra-sonic dispersion 30min during the Graphene ultra-sonic dispersion; Then add the ultrasonic mixing of nanometer hydroxyapatite 60min, the dried parameter is 120 ℃ of dry 120min.
Further, said employing spray granulation makes nanometer hydroxyapatite-Graphene micron agglomerated particle, specifically comprises step:
C1. add distilled water, Polyethylene Glycol dispersant and polyvinyl alcohol adhesive to fully ultrasonic mixed mixed-powder, mechanical agitation becomes the uniform mixing slip then;
C2. adopt the press atomization prilling granulator that the mixed slurry that forms among the C1 is handled, process nanometer hydroxyapatite-Graphene micron agglomerated particle;
C3. nanometer hydroxyapatite-Graphene micron agglomerated particle dried;
C4. filter out the micron agglomerated particle of special diameter scope, as the plasma spraying feeding.
Further, among the said step C2, the parameter of press atomization prilling granulator comprises atomizing pressure 0.3MPa, 300 ℃ of hothouse temperature.
Further, among the said step C3, the dried parameter is 120 ℃ of dry 120min.
Further, among the said step C4, the diameter range of the micron agglomerated particle that filters out is 40 ~ 70 μ m.
Further, said step D specifically comprises:
D1. to the Ti6Al4V substrate carry out sandblast, the cleaning of deoiling, then be fixed on the turntable of plasma spraying chamber and and carry out preheating it;
D2. the plasma spray coating process parameter is voltage 40 ~ 60V, electric current 600 ~ 800A, main gas (argon) 40 ~ 60L/min, auxilliary gas (hydrogen) 20 ~ 30L/min, carrier gas (argon) 40 ~ 60L/min, spray distance 80 ~ 100mm;
D3. in the Plasma Spraying Process Using, adopt Accuraspray-G3C plasma spraying on-line monitoring equipment, the average surface temperature of feeding and average flight speed are optimized the plasma spray coating process parameter with this in the on-line monitoring plasma flame.
To combine the accompanying drawing in the embodiment of the invention below, the technical scheme in the embodiment of the invention is carried out detailed description, obviously, described embodiment only is the present invention's part embodiment, rather than whole embodiment.Based on the embodiment among the present invention, the every other embodiment that those of ordinary skills are obtained under the prerequisite of not making creative work belongs to the scope that the present invention protects.
As shown in Figure 1, the present invention realizes that through following technical scheme step comprises:
(1) mixes starting powder
A. take by weighing nanometer hydroxyapatite and Graphene respectively with analytical balance, the Graphene percentage by weight is 0.1% ~ 2.0% of a hydroxyapatite;
B. load weighted Graphene is placed dehydrated alcohol ultra-sonic dispersion 30min, add an amount of dodecylbenzene sodium sulfonate, then add the ultrasonic mixing of nanometer hydroxyapatite 60min as dispersant;
C. mixed-powder among the step B is put into 120 ℃ of dry 120min of baking oven.
(2) spray granulation prepares nanometer hydroxyapatite-Graphene micron agglomerated particle
A. add distilled water, Polyethylene Glycol dispersant and polyvinyl alcohol adhesive to fully ultrasonic mixed mixed-powder, mechanical agitation becomes the uniform mixing slip then;
B. adopt the press atomization prilling granulator that mixed slurry is handled and process a micron agglomerated particle, the parameter of press atomization prilling granulator comprises atomizing pressure 0.3MPa, 300 ℃ of hothouse temperature;
C. micron agglomerated particle 120 ℃ of dry 120min in baking oven;
D. using screen cloth screening diameter is that the micron agglomerated particle of 40 ~ 70 μ m is as the plasma spraying starting powder.
(3) plasma spraying prepares nanometer hydroxyapatite-Graphene coating
A. to the Ti6Al4V substrate carry out sandblast, the cleaning of deoiling, then be fixed on the turntable of plasma spraying chamber and and carry out preheating it;
B. the plasma spraying parameter is voltage 40 ~ 60V, electric current 600 ~ 800A, main gas (argon) 40 ~ 60L/min, auxilliary gas (hydrogen) 20 ~ 30L/min, carrier gas (argon) 40 ~ 60L/min, spray distance 80 ~ 100mm (Fig. 1 is seen in technological process);
C. in the Plasma Spraying Process Using, adopt Accuraspray-G3C plasma spraying on-line monitoring equipment, the average surface temperature of feeding and average flight speed are optimized the plasma spray coating process parameter with this in the on-line monitoring plasma flame.
To combine concrete embodiment to further specify technical scheme of the present invention below:
Embodiment 1
Adopting nanometer hydroxyapatite, Graphene is raw material, is that 0.5% of nanometer hydroxyapatite takes by weighing raw material respectively by the Graphene percentage by weight; Load weighted Graphene adds an amount of dodecylbenzene sodium sulfonate as dispersant, ultra-sonic dispersion 30min in dehydrated alcohol; And then add the ultrasonic mixing of load weighted nanometer hydroxyapatite 60min; The powder that has mixed is put into 120 ℃ of dry 120min of baking oven.Mixed-powder behind ultra-sonic dispersion adds distilled water, Polyethylene Glycol dispersant and polyvinyl alcohol adhesive, and mechanical agitation becomes the uniform mixing slip then; Adopt the press atomization prilling granulator that mixed slurry is handled and process a micron agglomerated particle, the parameter of press atomization prilling granulator comprises atomizing pressure 0.3MPa, 300 ℃ of hothouse temperature; Micron agglomerated particle 120 ℃ of dry 120min in baking oven.Using screen cloth screening diameter is that the micron agglomerated particle of 40 ~ 70 μ m is as the plasma spraying starting powder.To the Ti6Al4V substrate carry out sandblast, the cleaning of deoiling, then be fixed on the turntable of plasma spraying chamber and and carry out preheating it.The plasma spraying parameter is voltage 45V, electric current 700A, main gas (argon) 40L/min; Auxilliary gas (hydrogen) 20L/min; Carrier gas (argon) 40L/min, spray distance 100mm adopts Accuraspray-G3C plasma spraying on-line monitoring equipment; The average surface temperature of feeding and average flight speed are optimized the plasma spray coating process parameter with this in the on-line monitoring plasma flame.
Adopting nanometer hydroxyapatite, Graphene is raw material, is that 1.0% of nanometer hydroxyapatite takes by weighing raw material respectively by the Graphene percentage by weight; Load weighted Graphene adds an amount of dodecylbenzene sodium sulfonate as dispersant, ultra-sonic dispersion 30min in dehydrated alcohol; And and then add the ultrasonic mixing of load weighted nanometer hydroxyapatite 60min; The powder that has mixed is put into 120 ℃ of dry 120min of baking oven.Mixed-powder behind ultra-sonic dispersion adds distilled water, Polyethylene Glycol dispersant and polyvinyl alcohol adhesive, and mechanical agitation becomes the uniform mixing slip then; Adopt the press atomization prilling granulator that mixed slurry is handled and process a micron agglomerated particle, the parameter of press atomization prilling granulator comprises atomizing pressure 0.3MPa, 300 ℃ of hothouse temperature; Micron agglomerated particle 120 ℃ of dry 120min in baking oven.Using screen cloth screening diameter is that the micron agglomerated particle of 40 ~ 70 μ m is as the plasma spraying starting powder.To the Ti6Al4V substrate carry out sandblast, the cleaning of deoiling, then be fixed on the turntable of plasma spraying chamber and and carry out preheating it.The plasma spraying parameter is voltage 45V, electric current 700A, main gas (argon) 40L/min; Auxilliary gas (hydrogen) 20L/min; Carrier gas (argon) 40L/min, spray distance 100mm adopts Accuraspray-G3C plasma spraying on-line monitoring equipment; The average surface temperature of feeding and average flight speed are optimized the plasma spray coating process parameter with this in the on-line monitoring plasma flame.
The employing nanometer hydroxyapatite is a raw material, does not add Graphene; Load weighted Graphene adds an amount of dodecylbenzene sodium sulfonate as dispersant, ultra-sonic dispersion 30min in dehydrated alcohol; Then add load weighted nanometer hydroxyapatite and continue ultra-sonic dispersion 60min; Divide the powder that clears to put into 120 ℃ of dry 120min of baking oven.Powder behind ultra-sonic dispersion adds distilled water, Polyethylene Glycol dispersant and polyvinyl alcohol adhesive, and mechanical agitation becomes the uniform mixing slip then; Adopt the press atomization prilling granulator that mixed slurry is handled and process a micron agglomerated particle, the parameter of press atomization prilling granulator comprises atomizing pressure 0.3MPa, 300 ℃ of hothouse temperature; Micron agglomerated particle 120 ℃ of dry 120min in baking oven.Using screen cloth screening diameter is that the micron agglomerated particle of 40 ~ 70 μ m is as the plasma spraying starting powder.To the Ti6Al4V substrate carry out sandblast, the cleaning of deoiling, then be fixed on the turntable of plasma spraying chamber and and carry out preheating it.The plasma spraying parameter is voltage 45V, electric current 700A, main gas (argon) 40L/min; Auxilliary gas (hydrogen) 20L/min; Carrier gas (argon) 40L/min, spray distance 100mm adopts Accuraspray-G3C plasma spraying on-line monitoring equipment; The average surface temperature of feeding and average flight speed are optimized the plasma spray coating process parameter with this in the on-line monitoring plasma flame.
Experiment effect
As shown in Figure 2; Label 1 is represented the Raman spectrogram of Graphene among the figure; On behalf of plasma spraying, label 2 do not add the Raman spectrogram of the nano hydroxyapatite coating of Graphene; It is the Raman spectrogram of 0.5% nano hydroxyapatite coating that label 3 is represented plasma spraying Graphene percentage by weight, and it is the Raman spectrogram of 1.0% nano hydroxyapatite coating that label 4 is represented plasma spraying Graphene percentage by weight.Mark among the figure the 430,590,961,1047, the 3571st, the characteristic peak of hydroxyapatite; 1347, the 1581st, the characteristic peak of Graphene.The preparation coating material is carried out the Raman spectrum experiment; Adopt the 514.5nm wavelength to experimentize; The characteristic peak of Graphene is obvious in the experimental result, explains that most of Graphene prototype structure has obtained reservation in the coating material, and this helps Graphene is brought into play its tough phase in coating effect.
As shown in Figure 3, be Graphene soaks 10 days sample in simulated body fluid transmission electron microscope picture.Graphene adds in the simulated body fluid Graphene and ultrasonic mixing in the simulated body fluid immersion test by a certain percentage, and blended sample places 37 ± 1 ℃ of 5%CO of temperature
2Incubator in 10 days, centrifugalize Graphene then, isolating Graphene is with washed with de-ionized water three times, the Graphene that obtains at last is at room temperature dry.The Graphene that soaks carries out the transmission electron microscope experiment, and there is shaft-like calcium phosphate (like Fig. 3) in the experiment proof on the Graphene surface, and the Ca in the simulated body fluid in the immersion process is described
2+And PO
4 3-Can be in the surperficial mineralising of Graphene, this shows that Graphene has certain bone inducibility.
Shown in Fig. 4 a ~ 4f; The osteoblast of fluorescence microscope is that 0.5% nano hydroxyapatite coating (4b, 4e), plasma spraying Graphene percentage by weight are that 1.0% nano hydroxyapatite coating (4c, 4f) surface attaches 6 hours fluorescence microscope photo at plasma spraying nano hydroxyapatite coating (4a, 4d), plasma spraying Graphene percentage by weight; Wherein bright spot is osteoblastic nucleus; 4a, 4b, 4c amplification are 100 times, and 4d, 4e, 4f amplification are 200 times.Osteoblast attaches in the experiment, is 1 * 10 in the sample surfaces planting density
5/ cm
2Osteoblast, the sample of having planted cell places 37 ± 1 ℃ of 5%CO of temperature
2Incubator in attached in 6 hours, the sample that has attached cell cleans, fixing and fluorescence staining, utilizes fluorescence microscope to observe at last.Fluorescence experiments shows that osteoblastic attaching amount in the experiment increases with the addition of Graphene, and this shows that adding Graphene helps osteoblastic attaching.
Utilizing the instrumentation micron to be pressed into technology tests the elastic modelling quantity and the hardness of material.Be pressed at the instrumentation micron that the loading velocity with 1633 μ N/s is loaded into maximum load 2.94N in the experiment, protect then and carry a 15s, unload with 1633 μ N/s at last.Experimental result shows that hydroxyapatite-graphene nano composite biological coating that the present invention prepares improves 40% ~ 50% than the hydroxyapatite coating layer elastic modelling quantity, and hardness improves 20% ~ 30%.
The fracture toughness of material is passed through computes:
Wherein P is a load, and E is an elastic modelling quantity, and H is a hardness, and C is the crackle radical length.Experimental result shows that hydroxyapatite-graphene nano composite biological coating that the present invention prepares improves 60% ~ 80% than the hydroxyapatite coating layer fracture toughness.
To those skilled in the art, obviously the invention is not restricted to the details of above-mentioned example embodiment, and under the situation that does not deviate from spirit of the present invention or basic feature, can realize the present invention with other concrete form.Therefore; No matter from which point; All should regard embodiment as exemplary; And be nonrestrictive, scope of the present invention is limited accompanying claims rather than above-mentioned explanation, therefore is intended to the implication of the equivalents that drops on claim and all changes in the scope are included in the present invention.Should any Reference numeral in the claim be regarded as limit related claim.
In addition; Describing according to embodiment though should be appreciated that this description, is not that each embodiment only comprises an independently technical scheme; This narrating mode of description only is for clarity sake; Those skilled in the art should make description as a whole, and the technical scheme among each embodiment also can form other embodiments that it will be appreciated by those skilled in the art that through appropriate combination.
Claims (10)
1. nano composite material biological coating, it is characterized in that: its raw material component comprises nanometer hydroxyapatite and Graphene.
2. nano composite material biological coating according to claim 1 is characterized in that: said Graphene percentage by weight is 0.1% ~ 2.0% of a nanometer hydroxyapatite, and nanometer hydroxyapatite is a corynebacterium.
3. the method for preparing of the described nano composite material biological coating of claim 1, it is characterized in that: this method for preparing comprises the steps:
A. analytical balance takes by weighing an amount of nanometer hydroxyapatite and Graphene respectively;
B. load weighted Graphene carries out ultra-sonic dispersion, adds the ultrasonic mixing of load weighted nanometer hydroxyapatite then, and blended nanometer hydroxyapatite-graphene powder is carried out dried;
C. mixed-powder among the step B is carried out mist projection granulating and handles, make nanometer hydroxyapatite-Graphene micron agglomerated particle, and dry, screen this micron agglomerated particle;
D. plasma spraying preparation of hydroxyapatite-graphene nano composite biological coating.
4. the method for preparing of nano composite material biological coating according to claim 3 is characterized in that: the Graphene percentage by weight is 0.1% ~ 2.0% of a nanometer hydroxyapatite in the said steps A, and nanometer hydroxyapatite is a corynebacterium.
5. the method for preparing of nano composite material biological coating according to claim 3; It is characterized in that: ultra-sonic dispersion, mixing all are in dehydrated alcohol, to carry out among the said step B; Wherein add an amount of dodecylbenzene sodium sulfonate during the Graphene ultra-sonic dispersion as dispersant, ultra-sonic dispersion 30min; Then add the ultrasonic mixing of nanometer hydroxyapatite 60min, the dried parameter is 120 ℃ of dry 120min.
6. the method for preparing of nano composite material biological coating according to claim 3 is characterized in that: adopt spray granulation to make nanometer hydroxyapatite-Graphene micron agglomerated particle, specifically comprise step:
C1. add distilled water, Polyethylene Glycol dispersant and polyvinyl alcohol adhesive to fully ultrasonic mixed mixed-powder, mechanical agitation becomes the uniform mixing slip then;
C2. adopt the press atomization prilling granulator that the mixed slurry that forms among the C1 is handled, process nanometer hydroxyapatite-Graphene micron agglomerated particle;
C3. nanometer hydroxyapatite-Graphene micron agglomerated particle dried;
C4. filter out the micron agglomerated particle of special diameter scope, as the plasma spraying feeding.
7. the method for preparing of nano composite material biological coating according to claim 6 is characterized in that: among the said step C2, the parameter of press atomization prilling granulator comprises atomizing pressure 0.3MPa, 300 ℃ of hothouse temperature.
8. the method for preparing of nano-composite coating material according to claim 6, it is characterized in that: among the said step C3, the dried parameter is 120 ℃ of dry 120min.
9. the method for preparing of nano composite material biological coating according to claim 6 is characterized in that: among the said step C4, the diameter range of the micron agglomerated particle that filters out is 40 ~ 70 μ m.
10. the method for preparing of nano composite material biological coating according to claim 3 is characterized in that: said step D specifically comprises:
D1. to the Ti6Al4V substrate carry out sandblast, the cleaning of deoiling, then be fixed on the turntable of plasma spraying chamber and and carry out preheating it;
D2. the plasma spray coating process parameter is voltage 40 ~ 60V, electric current 600 ~ 800A, main gas (argon) 40 ~ 60L/min, auxilliary gas (hydrogen) 20 ~ 30L/min, carrier gas (argon) 40 ~ 60L/min, spray distance 80 ~ 100mm;
D3. in the Plasma Spraying Process Using, adopt Accuraspray-G3C plasma spraying on-line monitoring equipment, the average surface temperature of feeding and average flight speed are optimized the plasma spray coating process parameter with this in the on-line monitoring plasma flame.
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