CN107638591A - A kind of good ceria doped hydroxyapatite coating of biological antioxidant performance and its application - Google Patents
A kind of good ceria doped hydroxyapatite coating of biological antioxidant performance and its application Download PDFInfo
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- CN107638591A CN107638591A CN201610574196.4A CN201610574196A CN107638591A CN 107638591 A CN107638591 A CN 107638591A CN 201610574196 A CN201610574196 A CN 201610574196A CN 107638591 A CN107638591 A CN 107638591A
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Abstract
The present invention relates to a kind of good ceria doped hydroxyapatite coating of biological antioxidant performance and its application, ceria doped hydroxylapatite powder is sprayed on by matrix surface using plasma-spray technique, obtain the ceria doped hydroxyapatite coating, the mass fraction of ceria is 10~50wt%, preferably 10~30 wt% in the ceria doped hydroxylapatite powder.The coating of the present invention not only has excellent biocompatibility, and has inoxidizability, can effectively reduce damage of the oxidative stress to bone tissue in osteoporosis, can promote patients with osteoporosis Cranial defect position Bone Defect Repari.The preparation method of the present invention has the advantages that simple to operate, efficiency high, favorable repeatability, is adapted to large-scale production.
Description
Technical field
Biological antioxidant coating of oxidative stress and preparation method thereof in osteoporosis, tool are directed to the present invention relates to a kind of
Body says, is to be related to a kind of using plasma spraying technology and prepare ceria in metallic substrate surfaces such as pure titanium, titanium alloys to mix
Miscellaneous method for coating hydroxyapatite.
Background technology
With aging population, the incidence of disease and thing followed fracture complication of osteoporosis improve year by year.Bone
Containing the higher inflammatory factor of concentration and active oxygen radical in the environment of the loose patients with fractures's site of injury of matter, while because of postoperative patient
The decline of person's internal body anti-oxidative defense ability, causes oxidability to exceed oxidation resistance, oxidative stress finally occurs.Oxygen
Change stress be due to that oxidation-reduction system caused by active oxygen radical surplus is unbalance in body, can cause bone tissue oxygen
Change damage.Increasing evidence shows that oxidative stress can improve osteoclast activity, suppress osteoblast differentiation and mineralising
Effect, is unfavorable for knitting.Therefore, development can correct osteoporotic fracture part interior environment (such as oxidative stress status)
Bone is implanted into coating material, has important clinical significance for promoting Bone Defect Repari and improving bone mass.
Plasma spray coating hydroxyapatite (HA) coating is that clinically most widely used bone is implanted into coating material, so
And HA coatings do not possess biological antioxidant performance, it is impossible to protect Gegenbaur's cell from the damage of oxidative stress.
The content of the invention
In view of the above-mentioned problems, not only there is excellent bio-compatible performance it is an object of the invention to provide a kind of, and
Ceramic coating with good biological antioxygenic property.
On the one hand, invention provides a kind of ceria doped hydroxyapatite coating, using plasma-spray technique by two
Cerium oxide-doped hydroxy apatite powder is sprayed in matrix surface, obtains the ceria doped hydroxyapatite coating,
The mass fraction of ceria is 10~50wt% in the ceria doped hydroxylapatite powder.
Ceria (CeO2) there is excellent catalytic activity.Its catalytic property can be quick from surface cerium ion
Ground carries out Ce3+And Ce4+Transformation, can easily receive according to environment or lose electronics.Tax coexists in cerium ion mixed valence
Ceria antioxidation is given so that the excess activity oxygen radical in organism can be catalytically decomposed in it.Hydroxyl phosphorus
Lime stone has good bio-compatible performance.The ceria doped hydroxyapatite that the present invention is prepared using plasma-spray technique
Coating not only has excellent bio-compatible performance, and has good biological antioxygenic property.
It is preferred that the particle diameter of the ceria doped hydroxylapatite powder is 10~200 microns, preferably 60~
150 microns.
It is preferred that the thickness of the ceria doped hydroxyapatite coating is 50~200 microns.
It is preferred that described matrix is pure titanium, titanium alloy, stainless steel or vitallium.
It is preferred that the plasma-spray technique parameter includes：Plasma gas Ar flows are 30~50 standard liters per minutes
Clock；Plasma gas H2Flow is 6~18 standard liter/mins；Powder carrier gas Ar flows are 1.5~5 standard liter/mins；Spray
It is 80~330 millimeters to apply distance；Spray power is 30~55 kilowatts；Powder feeding rate is 8.0~30 gram/minutes；Spray time is 4
~15 minutes.
In the present invention, the preparation process of the ceria doped hydroxylapatite powder includes：
After cerium dioxide powder and hydroxy apatite powder are uniformly mixed in mass ratio, binding agent mixing and ball milling is added, is obtained
To mixed powder；
By gained mixed powder it is compressing after sinter 1~3 hour at 600~1300 DEG C, then after ground, sieving, drying
Obtain the ceria doped hydroxylapatite powder.
It is preferred that the binding agent is polyvinyl alcohol or/and polyurethane.
Also, it is preferred that cerium dioxide powder and the amount ratio of hydroxy apatite powder gross mass and binding agent be 10~
50g：1~5mL.
Present invention also offers a kind of reparation of ceria doped hydroxyapatite coating in sclerous tissues and alternate material
In application.
The coating of the present invention not only has excellent biocompatibility, and has inoxidizability, can effectively reduce sclerotin
Damage of the oxidative stress to bone tissue in osteoporosis, patients with osteoporosis Cranial defect position Bone Defect Repari can be promoted.The present invention's
Preparation method has the advantages that simple to operate, efficiency high, favorable repeatability, is adapted to large-scale production.
Brief description of the drawings
Fig. 1 is ceria doped hydroxyapatite coating (HA-CeO prepared by the embodiment of the present invention 12- 30wt%) cut
The scanning electron microscope (SEM) photograph in face；
Fig. 2 is ceria doped hydroxyapatite (HA-CeO prepared by the embodiment of the present invention 12- 30wt%) powder and dioxy
Change the XRD spectrum of cerium dopping hydroxyapatite coating layer, wherein, a is the ceria doped hydroxylapatite powder of the present invention
XRD spectrum, b are the XRD spectrums of the ceria doped hydroxyapatite coating of the present invention；
Fig. 3 is ceria doped hydroxyapatite (HA-CeO prepared by the embodiment of the present invention 12- 30wt%) coating scanning
Electron microscope；
Fig. 4 is the scanning electron microscope (SEM) photograph of hydroxyapatite coating layer prepared by comparative example 1 of the present invention；
Fig. 5 is that the ceria of Ti-6Al-4V alloys, HA coatings prepared by comparative example 1 and the preparation of embodiment 1 adulterates hydroxy-apatite
Stone (HA-CeO2- 30wt%) coating surface cell propagation Behavioral effect figure；
Fig. 6 is that the ceria of Ti-6Al-4V alloys, HA coatings prepared by comparative example 1 and the preparation of embodiment 1 adulterates hydroxy-apatite
Stone (HA-CeO2- 30wt%) cell is bred under the oxidative stress status simulated to hydrogen peroxide solution of coating protective effect effect
Figure；
Fig. 7 is ceria doped hydroxyapatite (HA-CeO prepared by the embodiment of the present invention 22- 10wt%) powder and dioxy
Change the XRD spectrum of cerium dopping hydroxyapatite coating layer, wherein, a is the ceria doped hydroxylapatite powder of the present invention
XRD spectrum, b are the XRD spectrums of the ceria doped hydroxyapatite coating of the present invention；
Fig. 8 is ceria doped hydroxyapatite (HA-CeO prepared by the embodiment of the present invention 22- 10wt%) coating scanning
Electron microscope；
Fig. 9 is that the ceria of Ti-6Al-4V alloys, HA coatings prepared by comparative example 1 and the preparation of embodiment 2 adulterates hydroxy-apatite
Stone (HA-CeO2- 10wt%) coating surface cell propagation Behavioral effect figure；
Figure 10 is that the ceria of Ti-6Al-4V alloys, HA coatings prepared by comparative example 1 and the preparation of embodiment 2 adulterates hydroxyl phosphorus
Lime stone (HA-CeO2- 10wt%) cell is bred under the oxidative stress status simulated to hydrogen peroxide solution of coating protective effect effect
Fruit is schemed；
Figure 11 is ceria doped hydroxyapatite (HA-CeO prepared by the embodiment of the present invention 32- 50wt%) powder and dioxy
Change the XRD spectrum of cerium dopping hydroxyapatite coating layer, wherein, a is the ceria doped hydroxylapatite powder of the present invention
XRD spectrum, b are the XRD spectrums of the ceria doped hydroxyapatite coating of the present invention；
Figure 12 is ceria doped hydroxyapatite (HA-CeO prepared by the embodiment of the present invention 32- 50wt%) coating scanning
Electron microscope；
Figure 13 is that the ceria of Ti-6Al-4V alloys, HA coatings prepared by comparative example 1 and the preparation of embodiment 3 adulterates hydroxyl phosphorus
Lime stone (HA-CeO2- 50wt%) coating surface cell propagation Behavioral effect figure；
Figure 14 is that the ceria of Ti-6Al-4V alloys, HA coatings prepared by comparative example 1 and the preparation of embodiment 3 adulterates hydroxyl phosphorus
Lime stone (HA-CeO2- 50wt%) cell is bred under the oxidative stress status simulated to hydrogen peroxide solution of coating protective effect effect
Fruit is schemed.
Embodiment
The present invention is further illustrated below by way of following embodiments, it should be appreciated that following embodiments are merely to illustrate this
Invention, is not intended to limit the present invention.
The present invention is directed to oxidative stress in osteoporosis, and using plasma spraying technology prepares ceria doping hydroxyl
Base apatite coating, obtain the coating of biological antioxidant function.The good titanium dioxide of biological antioxidant performance provided by the invention
Cerium dopping hydroxyapatite coating layer, refer on matrix (such as the base material such as pure titanium, titanium alloy, stainless steel or vitallium) surface
The coating formed by the hydroxy apatite powder spraying of ceria doping.In the ceria doped hydroxylapatite powder
The mass fraction of ceria can be 10~50wt%, preferably 10~30wt%.When the ceria adulterates hydroxy-apatite
When the mass fraction of ceria is more than 50wt% in stone flour body, coating and metallic matrix bond strength are relatively low.Less than 10wt%,
Coating biology antioxidant effect unobvious.
The preparation method of the ceria doped hydroxyapatite coating of we's offer is provided to following exemplary.
By cerium dioxide powder and hydroxy apatite powder (10-50) in mass ratio:(90-50) is uniformly after mixing, then add
Enter binding agent mixing and ball milling, obtain mixed powder.Wherein binding agent can be polyvinyl alcohol or/and polyurethane etc..Ceria powder
Body and the amount ratio of hydroxy apatite powder gross mass and binding agent can be 10~50g：1~5mL.
By mixed powder it is compressing after sinter 1~3 hour at 600~1300 DEG C, then sieve that is ground, crossing 80 mesh,
The ceria doped hydroxylapatite powder is obtained after drying.
Ceria doped hydroxylapatite powder provided by the invention is the powder after sintered crush.After sintering crushing
Powder fluidity improves, and avoids the generation that powder phenomenon is blocked up in spraying process, is so advantageous to improve spray efficiency and enhancing applies
Layer cohesive force.
Ceria doped hydroxylapatite powder is formed at by the present invention by ionomer spray technology is used as medical gold
The surface of the base material of category or medical alloy material is as the biological coating to improve the biological antioxidant performance of base material.The present invention
It by particle diameter can be 10~200 microns, more preferably 60~150 microns that the ceria doped hydroxylapatite powder of selection, which is,
Particle forms, and the particle in the size range has enough mobility, is advantageous to be deposited on matrix surface, improves the combination of coating
Intensity.
The present invention includes the plasma-spray technique parameter：Plasma gas Ar flows can be 30~50 standard liters/
Minute.Plasma gas H2Flow can be 6~18 standard liter/mins.Powder carrier gas Ar flows can be 1.5~5 standard liters per minutes
Clock.Spray distance can be 80~330 millimeters.Spray power can be 30~55 kilowatts.Powder feeding rate can be 8.0~30 gram/minutes.
Spray time can be 4~15 minutes.Suitable process conditions are selected, the bond strength of coating and base material can be improved, make coating
Surface has micron-sized rough surface.
Ceria doped hydroxyapatite coating (HA- prepared by the scanned electron microscope observation present invention of the present invention
CeO2- 30wt%) Cross Section Morphology (as shown in Figure 1), the thickness for measuring coating can be 150~200 microns.If coating layer thickness is too
It is thin, then undercoating can be degradable shorter in the period of, so as to realize being completely combined for coating and bone tissue.If apply
Thickness degree is too thick, then the bond strength of coating and base material can be reduced substantially, it may occur that the risk that coating peels off from substrate surface.
The coating of the present invention not only has excellent biocompatibility, and has antioxidation.The life of the present invention
Thing coating has significant protective effect to osteoblastic proliferation under oxidative stress status, can reduce active oxygen radical into
The adverse effect of bone cell proliferation.
Embodiment is enumerated further below to describe the present invention in detail.It will similarly be understood that following examples are served only for this
Invention is further described, it is impossible to is interpreted as limiting the scope of the invention, those skilled in the art is according to this hair
Some nonessential modifications and adaptations that bright the above is made belong to protection scope of the present invention.Following examples are specific
Technological parameter etc. is also only an example in OK range, i.e. those skilled in the art can be done properly by this paper explanation
In the range of select, and do not really want to be defined in the concrete numerical value of hereafter example.
Embodiment 1
Sintering crushing method prepares powder.By ceria powder, hydroxy apatite powder and zirconium oxide abrasive ball according to 30:70:200
Mass ratio altogether 600g mix, be put into the grinding pot of polytetrafluoroethylene (PTFE), ball milling, rotational speed of ball-mill carried out in planetary ball mill
For 400r/min, Ball-milling Time 300min.According to 10g：Mixed powder and polyvinyl alcohol are ground to epigranular by 1mL
Dry powder, then put it into compressing in steel grinding tool, formed blocks are placed in Muffle furnace 800 DEG C of dumpings and to sinter 1 small
When.Block after sintering is put into hand-ground in mortar, crosses 80 mesh sieves afterwards, ceria doping hydroxyl is dried to obtain at 110 DEG C
Base apatite powder, it is standby.
Plasma spray process prepares ceramic coating：
After Ti-6Al-4V alloy surfaces are carried out into blasting treatment (pressure 0.3MPa), 2 are cleaned by ultrasonic in ethanol solution
It is secondary, 4 minutes every time, then dried 1 hour at 110 DEG C, it is standby；
Using plasma spraying coating process, the titanium alloy surface that ceria doped hydroxylapatite powder is sprayed to after processing
Obtain HA-CeO2- 30wt% ceramic coatings, thickness are 150 microns.Wherein, plasma spray process parameter is as follows：Plasma
Body gas Ar flows are 40slpm, plasma gas H2Flow is 10slpm, and mixed powder carrier gas Ar flows are 3.5slpm,
Spray distance is 100mm, spray power 42kW, powder feeding rate 18gmin-1, spray time is 12 minutes.
Ceria doped hydroxylapatite powder as shown in Figure 2 is visible with the XRD spectrum of coating：Coating and powder
Significant change does not occur for composition structure, but partial amorphization phenomenon occurs in coating after spraying, and this is due to quick cooling
During, caused by partial melting does not crystallize mutually in time.Coating has coarse surface topography, rough surface as seen from Figure 3
Coating material be advantageous to be combined with bone tissue in human body.
Comparative example 1 (only spraying hydroxyapatite powder)
Plasma spray process prepares pure ha coating
After Ti-6Al-4V alloy surfaces are carried out into blasting treatment (pressure 0.3MPa), 2 are cleaned by ultrasonic in ethanol solution
It is secondary, 4 minutes every time, then dried 1 hour at 110 DEG C, it is standby；
Using plasma spraying coating process, the titanium alloy surface that pure ha powder is sprayed to after processing is obtained into pure HA and made pottery
Porcelain coating, thickness are about 100 microns.Wherein, plasma spray process parameter is as follows：Plasma gas Ar flows are
40slpm, plasma gas H2Flow is 10slpm, and mixed powder carrier gas Ar flows are 3.5slpm, and spray distance is
100mm, spray power 42kW, powder feeding rate 18gmin-1, spray time is 10 minutes.
Coating cell compatibility is tested
Sterilization is carried out to coating material using steam sterilizer (121 DEG C, 30min), is subsequently placed at 48 hole cell trainings
Support in plate.The good MC3T3-E1 Gegenbaur's cells of growth conditions are collected, digests and adjusts concentration of cell suspension to 104Individual cell/
ml.The mixed solution of 1ml cell suspending liquids is seeded in HA-CeO2In coating material surface and control group titanium sheet and HA coatings.Will
Tissue Culture Plate is placed in 37 DEG C, 5%CO2Cultivated respectively in cell culture incubator 4 and 7 days.After acting on the corresponding time, culture is discarded
Liquid, often it is separately added into 0.5ml fresh mediums and 0.05ml CCK-8 solution in hole.Continue culture 3 hours in cell culture incubator
Afterwards, carefully each hole solution is suctioned out and added in 96 orifice plates.By the OD values that each hole is measured at ELIASA 450nm.
HA-CeO as seen from Figure 52Cell proliferation rate is substantially better than titanium sheet group in -30wt% and HA coating groups, and
And HA-CeO2Cell proliferation rate highest in -30wt% coating groups, it is good to show that cerium oxide-doped hydroxyapatite coating layer has
Cell compatibility.
Coating anti-oxidation stress performance test
Sterilization is carried out to coating material using steam sterilizer (121 DEG C, 30min), is subsequently placed at 48 hole cell trainings
Support in plate.The good MC3T3-E1 Gegenbaur's cells of growth conditions are collected, digests and adjusts concentration of cell suspension to 104Individual cell/
ml.Using PBS cushioning liquid by the hydrogen peroxide (H of 30% concentration2O2) reagent dilutions to 0.5mM, take 0.1ml H2O2And 0.9ml
The mixed solution of cell suspending liquid is seeded in HA-CeO2In coating material surface and control group titanium sheet and HA coatings, it will be not added with
The groups of cells of hydrogen peroxide is as blank control group culture.Pass through H2O2Intervene the MC3T3-E1 cells of in vitro culture, simulation oxidation should
Swash state.Tissue Culture Plate is placed in 37 DEG C, 5%CO2Cultivated respectively in cell culture incubator 4 and 7 days and (continue to add when changing liquid every time
Add the H of same concentrations2O2).After acting on the corresponding time, discard nutrient solution, per be separately added into hole 0.5ml fresh mediums and
0.05ml CCK-8 solution.After continuing culture in cell culture incubator 3 hours, carefully each hole solution is suctioned out and adds 96 orifice plates
In.By the OD values that each hole is measured at ELIASA 450nm.Versus cell appreciation rate (%)=(sample sets absorbance/blank group
Absorbance) * 100.
Fig. 6 shows that cell propagation is substantially suppressed under oxidative stress status, meanwhile, HA-CeO2In -30wt% coating groups
Cell propagation is better than titanium sheet group and HA coating groups, shows CeO2Incorporation can reduce H2O2The damage of solution cell proliferation,
HA-CeO2- 30wt% coatings have protective effect to cell propagation under oxidative stress status.
Embodiment 2
Sintering crushing method prepares powder.By ceria powder, hydroxy apatite powder and zirconium oxide abrasive ball according to 10:90:200
Mass ratio altogether 600g mix, be put into the grinding pot of polytetrafluoroethylene (PTFE), ball milling, rotational speed of ball-mill carried out in planetary ball mill
For 400r/min, Ball-milling Time 300min.According to 10g：Mixed powder and polyvinyl alcohol are ground to epigranular by 1mL
Dry powder, then put it into compressing in steel grinding tool, formed blocks are placed in Muffle furnace 800 DEG C of dumpings and to sinter 1 small
When.Block after sintering is put into hand-ground in mortar, crosses 80 mesh sieves afterwards, ceria doping hydroxyl is dried to obtain at 110 DEG C
Base apatite powder, it is standby.
Plasma spray process prepares ceramic coating：
After Ti-6Al-4V alloy surfaces are carried out into blasting treatment (pressure 0.3MPa), 2 are cleaned by ultrasonic in ethanol solution
It is secondary, 4 minutes every time, then dried 1 hour at 110 DEG C, it is standby；
Using plasma spraying coating process, the titanium alloy surface that ceria doped hydroxylapatite powder is sprayed to after processing
Obtain HA-CeO2- 10wt% ceramic coatings, thickness are 120 microns.Wherein, plasma spray process parameter is as follows：Plasma
Body gas Ar flows are 40slpm, plasma gas H2Flow is 10slpm, and mixed powder carrier gas Ar flows are 3.5slpm,
Spray distance is 100mm, spray power 42kW, powder feeding rate 18gmin-1, spray time is 11 minutes.
Ceria doped hydroxylapatite powder as shown in Figure 7 is visible with the XRD spectrum of coating：Coating and powder
Significant change does not occur for composition structure, but partial amorphization phenomenon occurs in coating after spraying, and this is due to quick cooling
During, caused by partial melting does not crystallize mutually in time.By, it can be seen that coating has a coarse surface topography, surface is thick in Fig. 8
Rough coating material is advantageous to be combined with bone tissue in human body.
Coating cell compatibility is tested
Sterilization is carried out to coating material using steam sterilizer (121 DEG C, 30min), is subsequently placed at 48 hole cell trainings
Support in plate.The good MC3T3-E1 Gegenbaur's cells of growth conditions are collected, digests and adjusts concentration of cell suspension to 104Individual cell/
ml.The mixed solution of 1ml cell suspending liquids is seeded in HA-CeO2In coating material surface and control group titanium sheet and HA coatings.Will
Tissue Culture Plate is placed in 37 DEG C, 5%CO2Cultivated respectively in cell culture incubator 4 and 7 days.After acting on the corresponding time, culture is discarded
Liquid, often it is separately added into 0.5ml fresh mediums and 0.05ml CCK-8 solution in hole.Continue culture 3 hours in cell culture incubator
Afterwards, carefully each hole solution is suctioned out and added in 96 orifice plates.By the OD values that each hole is measured at ELIASA 450nm.
HA-CeO as seen from Figure 92Cell proliferation rate is substantially better than titanium sheet group in -10wt% and HA coating groups, and
The HA-CeO at the 7th day2- 10wt% coatings have highest cell proliferation rate, show cerium oxide-doped hydroxyapatite coat
Layer has good cell compatibility.
Coating anti-oxidation stress performance test
Sterilization is carried out to coating material using steam sterilizer (121 DEG C, 30min), is subsequently placed at 48 hole cell trainings
Support in plate.The good MC3T3-E1 Gegenbaur's cells of growth conditions are collected, digests and adjusts concentration of cell suspension to 104Individual cell/
ml.Using PBS cushioning liquid by the hydrogen peroxide (H of 30% concentration2O2) reagent dilutions to 0.5mM, take 0.1ml H2O2And 0.9ml
The mixed solution of cell suspending liquid is seeded in HA-CeO2In coating material surface and control group titanium sheet and HA coatings, it will be not added with
The groups of cells of hydrogen peroxide is as blank control group culture.Pass through H2O2Intervene the MC3T3-E1 cells of in vitro culture, simulation oxidation should
Swash state.Tissue Culture Plate is placed in 37 DEG C, 5%CO2Cultivated respectively in cell culture incubator 4 and 7 days and (continue to add when changing liquid every time
Add the H of same concentrations2O2).After acting on the corresponding time, discard nutrient solution, per be separately added into hole 0.5ml fresh mediums and
0.05ml CCK-8 solution.After continuing culture in cell culture incubator 3 hours, carefully each hole solution is suctioned out and adds 96 orifice plates
In.By the OD values that each hole is measured at ELIASA 450nm.Versus cell appreciation rate (%)=(sample sets absorbance/blank group
Absorbance) * 100.
Figure 10 shows that cell propagation is substantially suppressed under oxidative stress status, meanwhile, HA-CeO2- 10wt% coating groups
Middle cell propagation is better than titanium sheet group and HA coating groups, shows CeO2Incorporation can reduce H2O2The damage of solution cell proliferation
Wound, HA-CeO2- 10wt% coatings have protective effect to cell propagation under oxidative stress status.
Embodiment 3
Sintering crushing method prepares powder.By ceria powder, hydroxy apatite powder and zirconium oxide abrasive ball according to 50:50:200
Mass ratio altogether 600g mix, be put into the grinding pot of polytetrafluoroethylene (PTFE), ball milling, rotational speed of ball-mill carried out in planetary ball mill
For 400r/min, Ball-milling Time 300min.According to 10g：Mixed powder and polyvinyl alcohol are ground to epigranular by 1mL
Dry powder, then put it into compressing in steel grinding tool, formed blocks are placed in Muffle furnace 800 DEG C of dumpings and to sinter 1 small
When.Block after sintering is put into hand-ground in mortar, crosses 80 mesh sieves afterwards, ceria doping hydroxyl is dried to obtain at 110 DEG C
Base apatite powder, it is standby.
Plasma spray process prepares ceramic coating：
After Ti-6Al-4V alloy surfaces are carried out into blasting treatment (pressure 0.3MPa), 2 are cleaned by ultrasonic in ethanol solution
It is secondary, 4 minutes every time, then dried 1 hour at 110 DEG C, it is standby；
Using plasma spraying coating process, the titanium alloy surface that ceria doped hydroxylapatite powder is sprayed to after processing
Obtain HA-CeO2- 50wt% ceramic coatings, thickness are 170 microns.Wherein, plasma spray process parameter is as follows：Plasma
Body gas Ar flows are 40slpm, plasma gas H2Flow is 10slpm, and mixed powder carrier gas Ar flows are 3.5slpm,
Spray distance is 100mm, spray power 42kW, powder feeding rate 18gmin-1, spray time is 13 minutes.
Ceria doped hydroxylapatite powder as shown in Figure 11 is visible with the XRD spectrum of coating：Coating and powder
Composition structure do not occur significant change, but there is partial amorphization phenomenon in coating after spraying, this is due to fast quickly cooling
But during, caused by partial melting does not crystallize mutually in time.By can be seen that coating has coarse surface topography, surface in Figure 12
Coarse coating material is advantageous to be combined with bone tissue in human body.
Coating cell compatibility is tested
Sterilization is carried out to coating material using steam sterilizer (121 DEG C, 30min), is subsequently placed at 48 hole cell trainings
Support in plate.The good MC3T3-E1 Gegenbaur's cells of growth conditions are collected, digests and adjusts concentration of cell suspension to 104Individual cell/
ml.The mixed solution of 1ml cell suspending liquids is seeded in HA-CeO2In coating material surface and control group titanium sheet and HA coatings.Will
Tissue Culture Plate is placed in 37 DEG C, 5%CO2Cultivated respectively in cell culture incubator 4 and 7 days.After acting on the corresponding time, culture is discarded
Liquid, often it is separately added into 0.5ml fresh mediums and 0.05ml CCK-8 solution in hole.Continue culture 3 hours in cell culture incubator
Afterwards, carefully each hole solution is suctioned out and added in 96 orifice plates.By the OD values that each hole is measured at ELIASA 450nm.
HA-CeO as seen from Figure 132Cell proliferation rate is substantially better than titanium sheet group, table in -50wt% and HA coating groups
Bright cerium oxide-doped hydroxyapatite coating layer has good cell compatibility.
Coating anti-oxidation stress performance test
Sterilization is carried out to coating material using steam sterilizer (121 DEG C, 30min), is subsequently placed at 48 hole cell trainings
Support in plate.The good MC3T3-E1 Gegenbaur's cells of growth conditions are collected, digests and adjusts concentration of cell suspension to 104Individual cell/
ml.Using PBS cushioning liquid by the hydrogen peroxide (H of 30% concentration2O2) reagent dilutions to 0.5mM, take 0.1ml H2O2And 0.9ml
The mixed solution of cell suspending liquid is seeded in HA-CeO2In coating material surface and control group titanium sheet and HA coatings, it will be not added with
The groups of cells of hydrogen peroxide is as blank control group culture.Pass through H2O2Intervene the MC3T3-E1 cells of in vitro culture, simulation oxidation should
Swash state.Tissue Culture Plate is placed in 37 DEG C, 5%CO2Cultivated respectively in cell culture incubator 4 and 7 days and (continue to add when changing liquid every time
Add the H of same concentrations2O2).After acting on the corresponding time, discard nutrient solution, per be separately added into hole 0.5ml fresh mediums and
0.05ml CCK-8 solution.After continuing culture in cell culture incubator 3 hours, carefully each hole solution is suctioned out and adds 96 orifice plates
In.By the OD values that each hole is measured at ELIASA 450nm.Versus cell appreciation rate (%)=(sample sets absorbance/blank group
Absorbance) * 100.
Figure 14 shows that cell propagation is substantially suppressed under oxidative stress status, meanwhile, HA-CeO2- 50wt% coating groups
Middle cell propagation is better than titanium sheet group and HA coating groups, shows CeO2Incorporation can reduce H2O2The damage of solution cell proliferation
Wound, HA-CeO2- 50wt% coatings have protective effect to cell propagation under oxidative stress status.
Claims (9)
1. a kind of ceria doped hydroxyapatite coating, it is characterised in that mixed ceria using plasma-spray technique
Miscellaneous hydroxy apatite powder is sprayed in matrix surface, obtains the ceria doped hydroxyapatite coating, the dioxy
The mass fraction for changing ceria in cerium dopping hydroxy apatite powder is 10~50wt%, preferably 10~30 wt%.
2. ceria doped hydroxyapatite coating according to claim 1, it is characterised in that the ceria is mixed
The particle diameter of miscellaneous hydroxy apatite powder is 10~200 microns, preferably 60~150 microns.
3. ceria doped hydroxyapatite coating according to claim 1 or 2, it is characterised in that the titanium dioxide
The thickness of cerium dopping hydroxyapatite coating layer is 50~200 microns.
4. the ceria doped hydroxyapatite coating according to any one of claim 1-3, it is characterised in that described
Matrix is pure titanium, titanium alloy, stainless steel or vitallium.
5. the ceria doped hydroxyapatite coating according to any one of claim 1-4, it is characterised in that described
Plasma-spray technique parameter includes：Plasma gas Ar flows are 30~50 standard liter/mins；Plasma gas H2
Flow is 6~18 standard liter/mins；Powder carrier gas Ar flows are 1.5~5 standard liter/mins；Spray distance is 80~330 millis
Rice；Spray power is 30~55 kilowatts；Powder feeding rate is 8.0~30 gram/minutes；Spray time is 4~15 minutes.
6. the ceria doped hydroxyapatite coating according to any one of claim 1-5, it is characterised in that described
The preparation process of ceria doped hydroxylapatite powder includes：
After cerium dioxide powder and hydroxy apatite powder are uniformly mixed in mass ratio, binding agent mixing and ball milling is added, is obtained
To mixed powder；
By gained mixed powder it is compressing after sinter 1~3 hour at 600~1300 DEG C, then after ground, sieving, drying
Obtain the ceria doped hydroxylapatite powder.
7. ceria doped hydroxyapatite coating according to claim 6, it is characterised in that the binding agent is poly-
Vinyl alcohol or/and polyurethane.
8. ceria doped hydroxyapatite coating according to claim 7, it is characterised in that cerium dioxide powder and
The amount ratio of hydroxy apatite powder gross mass and binding agent is 10~50g：1~5mL.
9. a kind of ceria doped hydroxyapatite coating as any one of claim 1-8 is in the reparation of sclerous tissues
With the application in alternate material.
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