CN103520776A - Medical titanium substrate material and manufacturing method thereof - Google Patents
Medical titanium substrate material and manufacturing method thereof Download PDFInfo
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- CN103520776A CN103520776A CN201210232397.8A CN201210232397A CN103520776A CN 103520776 A CN103520776 A CN 103520776A CN 201210232397 A CN201210232397 A CN 201210232397A CN 103520776 A CN103520776 A CN 103520776A
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Abstract
The invention provides a medical titanium substrate material, which comprises a titanium substrate and an anatase titanium dioxide film layer with a micron/nanometer multilevel composite pore structure formed on the surface of the titanium substrate. The invention also provides a manufacturing method of the medical titanium substrate material, which sequentially comprises the following steps: carrying out surface pretreatment on the titanium substrate, wherein the surface pretreatment comprises polishing and cleaning steps; performing acid etching treatment, wherein the acid etching solution is a mixed solution of sulfuric acid and hydrochloric acid, forming a micron-scale pore structure on the surface of the titanium substrate after the acid etching treatment, performing anodic oxidation treatment, and forming a nano-scale pore structure on the micron-scale structure after the anodic oxidation treatment, namely forming a micron/nano multi-scale composite pore structure; and carrying out heat treatment, and forming an anatase titanium dioxide film layer with a micron/nanometer multilevel composite pore structure on the surface of the titanium substrate material after the heat treatment.
Description
Technical field
The present invention relates to a kind of bio-based bottom material and manufacture method thereof, relate in particular to a kind of medical titanium base material and manufacture method thereof.
Background technology
In bio-based bottom material implantable bioartificial body, the very complicated physiological action of surperficial Hui Yu biological tissue's generation of base material, and the Surface Physical Chemistry character of bio-based bottom material, as the character such as surface topography, roughness and surface energy all can affect its biologically (G.Mendonca, D.Mendonca, Biomaterials, 2008,29:3822).Titanium and alloy thereof have advantages of that quality is light, elastic modelling quantity approaches with bone, biocompatibility and corrosion resistance good, form as widely used sclerous tissues replacement base material in biomedical sector.But the surface of titanio bottom material has biologically inert; after implant into body; between titanio bottom material and osseous tissue, often can form one deck fibers encapsulation tissue; finally cause the inefficacy of implant, be difficult to meet biological activity demand (X.Liu, P.K.Chu clinically; C.Ding; Mater.Sci.Eng.R, 2004,47:49).Therefore need to provide the titanium implant with high bioactivity and the compatibility, to reduce the difference in many performances between titanio bottom material and osseous tissue.
Summary of the invention
For solving titanio bottom material surface bioactive and the low problem of the compatibility, the invention provides a kind of manufacture method of medical titanium base material, comprise the following steps successively:
Titanio bottom material is carried out to surface preparation, comprise polishing step and cleaning step;
Carry out acid etch processing, acid etch solution is that volume ratio is (1-3): 1 weight ratio is 48% sulphuric acid (H
2sO
4) and weight ratio be 18% hydrochloric acid (HCl), etching temperature is 65-90 ℃, etch period is 1-3 hour, after acid etch is processed, at titanium substrate material surface, forms micrometer grade hole structure;
Carry out anodized, electrolyte is that weight ratio is the ammonium fluoride (NH of 0.3%-1%
4f) and weight ratio be 0.2%-1% hydrogen peroxide (H
2o
2) ethylene glycol solution or sodium hydroxide (NaOH) solution of 3-10mol/L, voltage is 10-50V, and temperature is room temperature, and the time is 30-180 minute, through anodized, in micrometer grade hole structure, form nanoscale titanium oxide pore structure, form micrometer/nanometer multistage composite pore structure;
Heat-treat, temperature is 400-500 ℃, and the time is 2-4 hour, forms the anatase titanium dioxide (TiO with micrometer/nanometer multistage composite pore structure through Overheating Treatment at titanium substrate material surface
2) rete.The pore diameter range of micrometer/nanometer multistage composite pore structure is 10 nanometers to 6 micron.
In surface preparation step, the polishing of titanio bottom material is to adopt carbonized carbonaceous silicon carbide paper to polish step by step to 1200#, and the cleaning of titanio bottom material is to adopt successively acetone, the ultrasonic cleaning of second alcohol and water, then dries standby.
After acid etch step, take out titanium metal substrate and carry out ultrasonic cleaning, dry standby.
In anodic oxidation step, anodised electrolyte is for containing the ammonium fluoride (NH that weight ratio is 0.3%-1%
4f) and weight ratio be 0.2%-1% hydrogen peroxide (H
2o
2) ethylene glycol solution, obtain micrometer/nanometer multistage network shape pore structure; Anodised electrolyte is sodium hydroxide (NaOH) solution of 3-10mo1/L, obtains the multistage spongy pore structure of micrometer/nanometer.
Heat treatment step carries out in Muffle furnace, in order to unbodied titanium dioxide film crystallization after anodic oxidation is become to anatase titanium dioxide rete.
At the bottom of the medical titanium base material of manufacturing by said method comprises titanio and the anatase titanium dioxide rete of the micrometer/nanometer multistage composite pore structure forming on this titanio basal surface.Micrometer/nanometer multistage composite pore structure is micrometer/nanometer multistage network shape pore structure or the multistage spongy pore structure of micrometer/nanometer.The pore diameter range of micrometer/nanometer multistage composite pore structure is 10 nanometers to 6 micron, and its surface texture makes it have high biological activity and biocompatibility.The method of above-mentioned manufacture medical titanium base material can be widely used in the surface modification to metal implantation body.
Accompanying drawing explanation
Fig. 1 is the SEM photo of resulting titanio bottom material in embodiment 1 and embodiment 2.
Fig. 2 is the Raman spectrum of resulting titanio bottom material in embodiment 1 and embodiment 2.
Fig. 3 be in embodiment 1, comparative example 2 and comparative example 3 resulting titanio bottom material SEM photo.
Fig. 4 is that MG63 cell is cultivated the SEM photo after 24 hours respectively on the resulting titanio bottom material of embodiment 1, comparative example 1, comparative example 2 and comparative example 3.
Fig. 5 is that MG63 cell is cultivated the MTT light absorption value after 1 day, 3 days and 7 days respectively on the resulting titanio bottom material of embodiment 1, comparative example 1, comparative example 2 and comparative example 3.
Fig. 6 is the SEM photo of resulting titanio bottom material in embodiment 2 and comparative example 4.
Fig. 7 is that MG63 cell is cultivated the fluorogram after 24 hours respectively on embodiment 2, comparative example 1, the resulting titanio bottom material of comparative example 4.
Fig. 8 is that MG63 cell is cultivated the MTT light absorption value after 1 day, 3 days and 7 days respectively on the resulting titanio bottom material of embodiment 2, comparative example 1 and comparative example 4.
Fig. 9 is that embodiment 1, embodiment 2, comparative example 1, comparative example 2 are soaked the SEM photo after 14 days in SBF solution.
Figure 10 is embodiment 1 and the EDS analysis of spectra of implementing the deposit rete of 2 resulting titanium substrate material surfaces.
Figure 11 is embodiment 1 and the infrared analysis spectrogram of implementing the deposit rete of 2 resulting titanium substrate material surfaces.
The specific embodiment
Embodiment 1:
Getting specification is the pure titanium plate of 10mm * 10mm * 2mm, and employing carbonized carbonaceous silicon carbide paper step by step sanding and polishing, to 1200#, is used acetone, the ultrasonic cleaning of second alcohol and water successively, dries standby.
Titanium plate through surface preparation is placed in to the 48%H that volume ratio is 2:1
2sO
4in 18%HCl acid etch solution, at the temperature of 75 ℃, etching is 1 hour, and ultrasonic cleaning after taking out forms micron order titanium pore structure on titanium plate surface.
Titanium plate through acid etch is placed in containing 0.3%NH
4f and 0.2%H
2o
2ethylene glycol electrolytic solution in carry out electrochemical anodic oxidation processing, voltage is 50V, the time is 30 minutes, dry again with pure water rinsing after taking-up, forms nanoscale titanium oxide pore structure in micrometer grade hole structure, forms micrometer/nanometer multistage composite pore structure.
To be placed in Muffle furnace through anodised titanium plate, and 450 ℃ of temperature lower calcinations 2 hours, after Overheating Treatment, at titanium substrate material surface, form anatase titanium dioxide rete, this titanium dioxide film has the multistage spongy pore structure of micrometer/nanometer.As Fig. 1 (a) and the demonstration of SEM photo (b), the pore diameter range of the multistage spongy pore structure of this micrometer/nanometer is 10nm-6 μ m.
Embodiment 2:
Getting specification is the pure titanium plate of 10mm * 10mm * 2mm, and employing carbonized carbonaceous silicon carbide paper step by step sanding and polishing, to 1200#, is used acetone, the ultrasonic cleaning of second alcohol and water successively, dries standby.
Titanium plate through surface preparation is placed in to 48%H2SO4 and the 18%HCl acid etch solution that volume ratio is 2:1, and at the temperature of 75 ℃, etching is 1 hour, and ultrasonic cleaning after taking out forms micron order titanium pore structure on titanium plate surface.
The NaOH electrolytic solution that titanium plate through acid etch is placed in to 5mol/L carries out electrochemical anodic oxidation processing, voltage is 15V, time is 120 minutes, dry again with pure water rinsing after taking-up, in micrometer grade hole structure, form nanoscale titanium oxide pore structure, form micrometer/nanometer multistage composite pore structure.
To be placed in Muffle furnace through anodised titanium plate, and 450 ℃ of temperature lower calcinations 2 hours, after Overheating Treatment, at titanium substrate material surface, form anatase titanium dioxide rete, this titanium dioxide film has micrometer/nanometer multistage network shape pore structure.As Fig. 1 (c) and the demonstration of SEM photo (d), the pore diameter range of this micrometer/nanometer multistage network shape pore structure is 10nm-6 μ m.
In the Raman of Fig. 2 spectrum, curve a is corresponding to the titanium dioxide film in embodiment 1 with micrometer/nanometer multistage network shape pore structure, and curve b is corresponding to the titanium dioxide film in embodiment 1 with micrometer/nanometer multistage network shape pore structure.Wavelength at Raman spectrum is 145cm
-1, 397cm
-1, 515cm
-1and 638cm
-1there is Detitanium-ore-type TiO in place
2characteristic spectrum peak, confirm that thus, in embodiment 1 and embodiment 2, the superficial film main component of titanio bottom material is Detitanium-ore-type TiO after Overheating Treatment
2.
Embodiment 3:
Getting specification is the pure titanium plate of 10mm * 10mm * 2mm, and employing carbonized carbonaceous silicon carbide paper step by step sanding and polishing, to 1200#, is used acetone, the ultrasonic cleaning of second alcohol and water successively, dries standby.
Titanium plate through surface preparation is placed in to the 48%H that volume ratio is 2:1
2sO
4in 18%HCl acid etch solution, at the temperature of 75 ℃, etching is 1 hour, and ultrasonic cleaning after taking out forms micron order titanium pore structure on titanium plate surface.
Titanium plate through acid etch is placed in containing 0.3%NH
4f and 0.2%H
2o
2ethylene glycol electrolytic solution in carry out electrochemical anodic oxidation processing, voltage is 40V, the time is 60 minutes, dry again with pure water rinsing after taking-up, forms nanoscale titanium oxide pore structure in micrometer grade hole structure, forms micrometer/nanometer multistage composite pore structure.
To be placed in Muffle furnace through anodised titanium plate, and 450 ℃ of temperature lower calcinations 2 hours, after Overheating Treatment, at titanium substrate material surface, form anatase titanium dioxide rete, this titanium dioxide film has the multistage spongy pore structure of micrometer/nanometer.This titanium dioxide film has the multistage spongy pore structure of micrometer/nanometer that pore diameter range is 40nm-6 μ m.
Embodiment 4:
Getting specification is the pure titanium plate of 10mm * 10mm * 2mm, and employing carbonized carbonaceous silicon carbide paper step by step sanding and polishing, to 1200#, is used acetone, the ultrasonic cleaning of second alcohol and water successively, dries standby.
Titanium plate through surface preparation is placed in to the 48%H that volume ratio is 2:1
2sO
4in 18%HCl acid etch solution, at the temperature of 75 ℃, etching is 1 hour, and ultrasonic cleaning after taking out forms micron order titanium pore structure on titanium plate surface.
The NaOH electrolytic solution that titanium plate through acid etch is placed in to 5mol/L carries out electrochemical anodic oxidation processing, voltage is 10V, time is 180 minutes, dry again with pure water rinsing after taking-up, in micrometer grade hole structure, form nanoscale titanium oxide pore structure, form micrometer/nanometer multistage composite pore structure.
To be placed in Muffle furnace through anodised titanium plate, 450 ℃ of temperature lower calcinations 2 hours, after Overheating Treatment, at titanium substrate material surface, form anatase titanium dioxide rete, this titanium dioxide film has the micrometer/nanometer multistage network shape pore structure that pore diameter range is 20nm-6 μ m.
Embodiment 5:
Getting specification is the pure titanium plate of 10mm * 10mm * 2mm, and employing carbonized carbonaceous silicon carbide paper step by step sanding and polishing, to 1200#, is used acetone, the ultrasonic cleaning of second alcohol and water successively, dries standby.
Titanium plate through surface preparation is placed in to the 48%H that volume ratio is 2:1
2sO
4in 18%HCl acid etch solution, at the temperature of 75 ℃, etching is 1 hour, and ultrasonic cleaning after taking out forms micron order titanium pore structure on titanium plate surface.
Titanium plate through acid etch is placed in containing 0.3%NH
4f and 0.2%H
2o
2ethylene glycol electrolytic solution in carry out electrochemical anodic oxidation processing, voltage is 35V, the time is 30 minutes, dry again with pure water rinsing after taking-up, forms nanoscale titanium oxide pore structure in micrometer grade hole structure, forms micrometer/nanometer multistage composite pore structure.
To be placed in Muffle furnace through anodised titanium plate, and 450 ℃ of temperature lower calcinations 2 hours, after Overheating Treatment, at titanium substrate material surface, form anatase titanium dioxide rete, this titanium dioxide film has the multistage spongy pore structure of micrometer/nanometer.This titanium dioxide film has the multistage spongy pore structure of micrometer/nanometer that pore diameter range is 50nm-6 μ m.
Embodiment 6:
Getting specification is the pure titanium plate of 10mm * 10mm * 2mm, and employing carbonized carbonaceous silicon carbide paper step by step sanding and polishing, to 1200#, is used acetone, the ultrasonic cleaning of second alcohol and water successively, dries standby.
Titanium plate through surface preparation is placed in to the 48%H that volume ratio is 2:1
2sO
4in 18%HCl acid etch solution, at the temperature of 75 ℃, etching is 1 hour, and ultrasonic cleaning after taking out forms micron order titanium pore structure on titanium plate surface.
The NaOH electrolytic solution that titanium plate through acid etch is placed in to 3mol/L carries out electrochemical anodic oxidation processing, voltage is 20V, time is 60 minutes, dry again with pure water rinsing after taking-up, in micrometer grade hole structure, form nanoscale titanium oxide pore structure, form micrometer/nanometer multistage composite pore structure.
To be placed in Muffle furnace through anodised titanium plate, 450 ℃ of temperature lower calcinations 2 hours, after Overheating Treatment, at titanium substrate material surface, form anatase titanium dioxide rete, this titanium dioxide film has the micrometer/nanometer multistage network shape pore structure that pore diameter range is 30nm-6 μ m.
Embodiment 7:
Getting specification is the pure titanium plate of 10mm * 10mm * 2mm, and employing carbonized carbonaceous silicon carbide paper step by step sanding and polishing, to 1200#, is used acetone, the ultrasonic cleaning of second alcohol and water successively, dries standby.
Titanium plate through surface preparation is placed in to the 48%H that volume ratio is 2:1
2sO
4in 18%HCl acid etch solution, at the temperature of 75 ℃, etching is 1 hour, and ultrasonic cleaning after taking out forms micron order titanium pore structure on titanium plate surface.
Titanium plate through acid etch is placed in containing 1%NH
4f and 1%H
2o
2ethylene glycol electrolytic solution in carry out electrochemical anodic oxidation processing, voltage is 50V, the time is 180 minutes, dry again with pure water rinsing after taking-up, forms nanoscale titanium oxide pore structure in micrometer grade hole structure, forms micrometer/nanometer multistage composite pore structure.
To be placed in Muffle furnace through anodised titanium plate, and 450 ℃ of temperature lower calcinations 2 hours, after Overheating Treatment, at titanium substrate material surface, form anatase titanium dioxide rete, this titanium dioxide film has the multistage spongy pore structure of micrometer/nanometer.This titanium dioxide film has the multistage spongy pore structure of micrometer/nanometer that pore diameter range is 30nm-6 μ m.
Embodiment 8:
Getting specification is the pure titanium plate of 10mm * 10mm * 2mm, and employing carbonized carbonaceous silicon carbide paper step by step sanding and polishing, to 1200#, is used acetone, the ultrasonic cleaning of second alcohol and water successively, dries standby.
Titanium plate through surface preparation is placed in to the 48%H that volume ratio is 2:1
2sO
4in 18%HCl acid etch solution, at the temperature of 75 ℃, etching is 1 hour, and ultrasonic cleaning after taking out forms micron order titanium pore structure on titanium plate surface.
The NaOH electrolytic solution that titanium plate through acid etch is placed in to 10mol/L carries out electrochemical anodic oxidation processing, voltage is 15V, time is 120 minutes, dry again with pure water rinsing after taking-up, in micrometer grade hole structure, form nanoscale titanium oxide pore structure, form micrometer/nanometer multistage composite pore structure.
To be placed in Muffle furnace through anodised titanium plate, 450 ℃ of temperature lower calcinations 2 hours, after Overheating Treatment, at titanium substrate material surface, form anatase titanium dioxide rete, this titanium dioxide film has the micrometer/nanometer multistage network shape pore structure that pore diameter range is 20nm-6 μ m.
Embodiment 9:
Getting specification is the pure titanium plate of 10mm * 10mm * 2mm, and employing carbonized carbonaceous silicon carbide paper step by step sanding and polishing, to 1200#, is used acetone, the ultrasonic cleaning of second alcohol and water successively, dries standby.
Titanium plate through surface preparation is placed in to the 48%H that volume ratio is 2:1
2sO
4in 18%HCl acid etch solution, at the temperature of 85 ℃, etching is 1 hour, and ultrasonic cleaning after taking out forms micron order titanium pore structure on titanium plate surface.
Titanium plate through acid etch is placed in to 0.3%NH
4f and 0.2%H
2o
2ethylene glycol electrolytic solution in carry out electrochemical anodic oxidation processing, voltage is 50V, the time is 30 minutes, dry again with pure water rinsing after taking-up, forms nanoscale titanium oxide pore structure in micrometer grade hole structure, forms micrometer/nanometer multistage composite pore structure.
To be placed in Muffle furnace through anodised titanium plate, and 450 ℃ of temperature lower calcinations 2 hours, after Overheating Treatment, at titanium substrate material surface, form anatase titanium dioxide rete, this titanium dioxide film has the multistage spongy pore structure of micrometer/nanometer.This titanium dioxide film has the multistage spongy pore structure of micrometer/nanometer that pore diameter range is 20nm-5 μ m.
Embodiment 10:
Getting specification is the pure titanium plate of 10mm * 10mm * 2mm, and employing carbonized carbonaceous silicon carbide paper step by step sanding and polishing, to 1200#, is used acetone, the ultrasonic cleaning of second alcohol and water successively, dries standby.
Titanium plate through surface preparation is placed in to the 48%H that volume ratio is 2:1
2sO
4in 18%HCl acid etch solution, at the temperature of 85 ℃, etching is 1 hour, and ultrasonic cleaning after taking out forms micron order titanium pore structure on titanium plate surface.
The NaOH electrolytic solution that titanium plate through acid etch is placed in to 5mol/L carries out electrochemical anodic oxidation processing, voltage is 15V, time is 180 minutes, dry again with pure water rinsing after taking-up, in micrometer grade hole structure, form nanoscale titanium oxide pore structure, form micrometer/nanometer multistage composite pore structure.
To be placed in Muffle furnace through anodised titanium plate, 450 ℃ of temperature lower calcinations 2 hours, after Overheating Treatment, at titanium substrate material surface, form anatase titanium dioxide rete, this titanium dioxide film has the micrometer/nanometer multistage network shape pore structure that pore diameter range is 15nm-5 μ m.
Comparative example 1:
Getting specification is the pure titanium plate of 10mm * 10mm * 2mm, and employing carbonized carbonaceous silicon carbide paper step by step sanding and polishing, to 1200#, is used acetone, the ultrasonic cleaning of second alcohol and water successively, dries standby.
Comparative example 2:
Getting specification is the pure titanium plate of 10mm * 10mm * 2mm, and employing carbonized carbonaceous silicon carbide paper step by step sanding and polishing, to 1200#, is used acetone, the ultrasonic cleaning of second alcohol and water successively, dries standby.
Titanium plate through surface preparation is placed in to the 48%H that volume ratio is 2:1
2sO
4in 18%HCl acid etch solution, at the temperature of 75 ℃, etching is 1 hour, and ultrasonic cleaning after taking out forms micrometer grade hole structure on titanium plate surface.
Titanium plate through acid etch is placed in to Muffle furnace, calcines 2 hours for 450 ℃.
Comparative example 3:
Getting specification is the pure titanium plate of 10mm * 10mm * 2mm, and employing carbonized carbonaceous silicon carbide paper step by step sanding and polishing, to 1200#, is used acetone, the ultrasonic cleaning of second alcohol and water successively, dries standby.
Titanium plate through surface preparation is placed in containing 0.3%NH
4f and 0.2%H
2o
2ethylene glycol electrolytic solution in carry out electrochemical anodic oxidation processing, voltage is 50V, the time is 30 minutes, dry again with pure water rinsing after taking-up, forms nano grade pore structure.
To be placed in Muffle furnace through anodised titanium plate, and 450 ℃ of temperature lower calcinations 2 hours, after Overheating Treatment, at titanium substrate material surface, form anatase titanium dioxide rete, this titanium dioxide film has the spongy pore structure of nanoscale.
Comparative example 4:
Getting specification is the pure titanium plate of 10mm * 10mm * 2mm, and employing carbonized carbonaceous silicon carbide paper step by step sanding and polishing, to 1200#, is used acetone, the ultrasonic cleaning of second alcohol and water successively, dries standby.
The NaOH electrolytic solution that titanium plate through surface preparation is placed in to 5mol/L carries out electrochemical anodic oxidation processing, and voltage is 15V, and the time is 120 minutes, dry again with pure water rinsing after taking-up, forms nano grade pore structure.
To be placed in Muffle furnace through anodised titanium plate, and 450 ℃ of temperature lower calcinations 2 hours, after Overheating Treatment, at titanium substrate material surface, form anatase titanium dioxide rete, this titanium dioxide film has the network-like pore structure of nanoscale.
The contrast of embodiment 1 and comparative example 1 to 3:
Fig. 3 is the SEM photo of embodiment 1, comparative example 2 and comparative example 3, wherein (a
1), (a
2), (a
3) corresponding to the SEM photo of comparative example 2, (b
1), (b
2), (b
3) corresponding to the SEM photo of comparative example 3, (c
1), (c
2), (c
3) corresponding to the SEM photo of embodiment 1.Fig. 4 is that MG63 cell is cultivated the SEM photo after 24 hours respectively on the resulting titanio bottom material of embodiment 1, comparative example 1, comparative example 2 and comparative example 3.Wherein, (a
1), (a
2) corresponding to the SEM photo of comparative example 1, (b
1), (b
2) corresponding to the SEM photo of comparative example 2, (c
1), (c
2) corresponding to the SEM photo of comparative example 3, (d
1), (d
2) corresponding to the SEM photo of embodiment 1.MG63 cell presents fusiformis on pure titanium plate surface, and the pseudopodium of cell stretches not obvious, there is no complete drawout.And the titanium substrate material surface obtaining at comparative example 2, comparative example 3, embodiment 1, relatively unfolding of Growth of Cells, presents the stretching, extension of many pseudopodium, and cell sticks better at material surface.
Fig. 5 is that MG63 cell is cultivated respectively the MTT light absorption value (OD) after 1 day, 3 days and 7 days on the resulting titanio bottom material of embodiment 1, comparative example 1, comparative example 2 and comparative example 3.As can be seen from the figure, cultivate after 1 day, MG63 cell on embodiment 1 and the resulting titanio bottom material of comparative example 3 cell quantity slightly more than the cell quantity in comparative example 1 and comparative example 2.Cultivate after 3 days, the cell quantity on embodiment 1, comparative example 2 and comparative example 3 surfaces is all more than comparative example 1 surface, but the cell quantity on the cell quantity on comparative example 3 surfaces and embodiment 1 surface there is no obvious difference, so cultivate the cell quantity on different materials surface after 3 days, present following rule: embodiment 1 ≈ comparative example 3 > comparative example 2 > comparative example 1.Continue to cultivate after 7 days, the growing state on cell embodiment 1, comparative example 2 and comparative example 3 surfaces is all better than comparative example 1 surface, wherein the cell quantity on embodiment 1 surface is maximum, and the cell quantity on different materials surface presents following relation: embodiment 1 > comparative example 3 > comparative example 2 > comparative example 1.
Table 1 is the water droplet contact angle numerical value of embodiment 1, comparative example 1, comparative example 2 and comparative example 3.
Table 1
| Comparative example 1 | Comparative example 2 | Comparative example 3 | |
| 52.6±1.26 | 26.2±1.63 | 5.5±1.13 | 1.2±0.87 |
From table 1, the surperficial water droplet contact angle of the resulting titanio bottom material of embodiment 1 is less than 5, illustrates that its surface is super hydrophilic.The surface wettability putting forward according to Wenzel and Cassie etc. is theoretical, and, if hydrophilic sample increases after roughness, sample surfaces is more hydrophilic; Otherwise if hydrophobic sample increases after roughness, sample surfaces is more hydrophobic.Above-mentioned surface wettability test result and this theory match, and illustrate that this is caused by factors such as surface topography, roughness.The surface hydrophilicity of the resulting titanio bottom material of embodiment 1 is strong, be conducive to cell in the sticking and growth of its surface, so its surperficial biological activity is the highest.
The contrast of embodiment 2 and comparative example 4:
Fig. 6 is the SEM photo of embodiment 2 and comparative example 4, and wherein (a1), (a2) be corresponding to comparative example 4, (b1), (b2) corresponding to embodiment 2.As can be seen here, there is the network-like cross-linked structure that differ in size of aperture in 10～100nm left and right in the surface of the resulting titanio bottom material of comparative example 4, there is micro-/ nano hierarchical porous structure in the surface of the resulting titanio bottom material of embodiment 2, do not affecting under the condition of micron loose structure, occurring the structure that nanoscale is network-like.
Fig. 7 is that MG63 cell is cultivated the fluorogram after 1 day respectively on embodiment 2, comparative example 1, the resulting titanio bottom material of comparative example 4.Wherein, (a1), (a2) corresponding to comparative example 1, (b1), (b2) corresponding to comparative example 4, (c1), (c2) corresponding to embodiment 2.As can be seen here, MG63 cell can not well be sprawled and come on comparative example 1 surface, presents certain fusiformis.And embodiment 2 after modification and the surface of comparative example 4, cell presents sprawling of star, and extended configuration is good, but there is no too large difference at embodiment 2 and the lip-deep cell attaching of the resulting titanio bottom material of comparative example 4 state.
Fig. 8 is that MG63 cell is cultivated respectively the MTT light absorption value (OD) after 1 day, 3 days and 7 days on the resulting titanio bottom material of embodiment 2, comparative example 1 and comparative example 4.As can be seen from the figure,, along with the prolongation of time, the cell quantity of every kind of titanium substrate material surface is all in increase gradually.Cultivate after 1 day, the cell quantity of each titanium substrate material surface is more or less the same, not too large difference; Cultivate after 3 days, the cell quantity on embodiment 2 and comparative example 4 surfaces is all more than comparative example 1 surface, and the cell quantity on embodiment 2 and comparative example 4 surfaces there is no significant difference; Cultivate after 7 days, on the resulting titanium substrate material surface of embodiment 2, have maximum cell quantities, the lip-deep cell quantity of the resulting titanio bottom material of comparative example 4 takes second place.Based on the above results, can find, aspect promotion cell proliferation, the excellent degree of the biological activity of material is as follows, and embodiment 2 > comparative example 4 > comparative example 1.
Table 2 is the water droplet contact angle numerical value of embodiment 2 and comparative example 4.
Table 2
| Comparative example 4 | |
| 9.8±1.37 | 1.8±1.02 |
From table 2, the surperficial water droplet contact angle of the resulting titanio bottom material of embodiment 2 is less than 5, illustrates that its surface is super hydrophilic.The surface hydrophilicity of the resulting titanio bottom material of embodiment 2 is strong, be conducive to cell in the sticking and growth of its surface, so its surperficial biological activity is the highest.
The contrast of embodiment 1-2 and comparative example 1-2:
For check biological activity of titanio bottom material after different disposal, embodiment 1, embodiment 2, comparative example 1, the resulting titanio bottom material of comparative example 2 are soaked in the SBF solution of 36.5 ℃ to 14 days.
Fig. 9 is that embodiment 1, embodiment 2, comparative example 1, comparative example 2 are soaked the SEM photo after 14 days in SBF solution, wherein (a) corresponding to embodiment 1, (b) corresponding to embodiment 2, (c) corresponding to comparative example 1, (d) corresponding to comparative example 2. Embodiment 1 and 2 resulting titanium substrate material surfaces form the deposit of one deck, the original surface topography of titanio bottom material is completely covered, sedimental rete is the hemispherical aperture structure being assembled into by nanometer thin lamellar crystal, present typical apatite pattern, the titanio bottom material that the titanium oxide film layer of the micro-/ nano composite construction having is described, its biological activity significantly strengthens.And the resulting titanium substrate material surface of comparative example 1 and comparative example 2 does not find that there is the formation of apatite rete on surface, its biological activity is poor.
Figure 10 is the EDS analysis of spectra of the deposit rete of embodiment 1 and the resulting titanium substrate material surface of embodiment 2.Result shows that this rete is mainly elementary composition by Ca, P and O, and calcium-phosphorus ratio is about 1.34, shows as the apatite of calcium deficiency, contains in addition C and Mg element, and this approaches the apatite composition in natural bone.
Figure 11 is the infrared spectrum analysis spectrogram of the deposit rete of embodiment 1 and the resulting titanium substrate material surface of embodiment 2.At 1038cm
-1there is PO in place
4 3-symmetrical stretching vibration (ν
3), at 602cm
-1and 561cm
-1there is the bending vibration (ν of O-P-O in place
4).At 1460cm
-1, 1420cm
-1and 875cm
-1there is CO
3 2-absworption peak, illustrate to soak in the apatite forming after SBF and contain CO
3 2-, and CO
3 2-part has replaced PO
4 3-.To sum up analyze, the apatite layer that titanium substrate material surface forms is the apatite that the carbonate of calcium deficiency partly replaces phosphate radical, also contains magnesium and carbon simultaneously, and the apatite composition in this component and natural bone is very similar, is called osteoid apatite.
In sum; although the present invention discloses as above with preferred embodiment; so it is not in order to limit the present invention; those skilled in the art should recognize in the situation that do not depart from change and the retouching that scope and spirit of the present invention that the appended claim of the present invention discloses are done, within all belonging to the protection domain of claim of the present invention.
Claims (8)
1. a medical titanium base material, is characterized in that, at the bottom of comprising titanio and the anatase titanium dioxide rete of the micrometer/nanometer multistage composite pore structure forming on this titanio basal surface.
2. medical titanium base material as claimed in claim 1, is characterized in that, micrometer/nanometer multistage composite pore structure is micrometer/nanometer multistage network shape pore structure or the multistage spongy pore structure of micrometer/nanometer.
3. medical titanium base material as claimed in claim 1 or 2, is characterized in that, the pore diameter range of micrometer/nanometer multistage composite pore structure is 10 nanometers to 6 micron.
4. a manufacture method for medical titanium base material, is characterized in that, comprises the following steps successively:
To carrying out surface preparation at the bottom of titanio, comprise polishing and cleaning;
Carry out acid etch processing, acid etch solution is sulphuric acid and hydrochloric acid mixed solution, after processing, acid etch forms micrometer grade hole structure at described titanio basal surface, described acid etch solution is that volume ratio is that the weight ratio of A:1 is that 48% sulfuric acid solution and weight ratio are that 18% hydrochloric acid solution mixes, etching temperature is 65-90 ℃, etch period is 1-3 hour, wherein 1≤A≤3;
Carry out anodized, after anodized, in micron order structure, form nano grade pore structure, form micrometer/nanometer multistage composite pore structure;
Heat-treat the anatase titanium dioxide rete of the micrometer/nanometer multistage composite pore structure forming at titanium substrate material surface after Overheating Treatment.
5. manufacture method as claimed in claim 4, is characterized in that, described anodised voltage is 10-50V, and temperature is room temperature, and the time is 30-180 minute.
6. manufacture method as claimed in claim 5, is characterized in that, described anodised electrolyte, for ammonium fluoride and the weight ratio that is 0.3%-1% containing weight ratio is the ethylene glycol solution of 0.2%-1% hydrogen peroxide, obtains the multistage spongy pore structure of micrometer/nanometer.
7. manufacture method as claimed in claim 5, is characterized in that, described anodised electrolyte is that concentration is the sodium hydroxide solution of 3-10mol/L, obtains micrometer/nanometer multistage network shape pore structure.
8. manufacture method as claimed in claim 4, is characterized in that, the temperature of described heat treatment step is 400-500 ℃, and the time is 2-4 hour.
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