CN1769527A - Preparation method of bioactive nanocomposite layer on medical metal surface - Google Patents
Preparation method of bioactive nanocomposite layer on medical metal surface Download PDFInfo
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- CN1769527A CN1769527A CN 200510114407 CN200510114407A CN1769527A CN 1769527 A CN1769527 A CN 1769527A CN 200510114407 CN200510114407 CN 200510114407 CN 200510114407 A CN200510114407 A CN 200510114407A CN 1769527 A CN1769527 A CN 1769527A
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 28
- 239000002184 metal Substances 0.000 title claims abstract description 28
- 230000000975 bioactive effect Effects 0.000 title claims description 12
- 239000002114 nanocomposite Substances 0.000 title claims 11
- 238000002360 preparation method Methods 0.000 title description 10
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000010936 titanium Substances 0.000 claims abstract description 44
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 43
- 230000003647 oxidation Effects 0.000 claims abstract description 26
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 22
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 230000004913 activation Effects 0.000 claims abstract description 16
- 229910052588 hydroxylapatite Inorganic materials 0.000 claims abstract description 13
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 claims abstract description 13
- 238000010438 heat treatment Methods 0.000 claims abstract description 11
- 239000002253 acid Substances 0.000 claims abstract description 7
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 7
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 32
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 26
- 229910001069 Ti alloy Inorganic materials 0.000 claims description 26
- 239000012890 simulated body fluid Substances 0.000 claims description 26
- 239000000243 solution Substances 0.000 claims description 23
- 239000000758 substrate Substances 0.000 claims description 22
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 239000008151 electrolyte solution Substances 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 9
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 8
- 239000011734 sodium Substances 0.000 claims description 8
- 239000010935 stainless steel Substances 0.000 claims description 7
- 229910001220 stainless steel Inorganic materials 0.000 claims description 7
- 230000015572 biosynthetic process Effects 0.000 claims description 5
- 238000004140 cleaning Methods 0.000 claims description 5
- 239000012895 dilution Substances 0.000 claims description 5
- 238000010790 dilution Methods 0.000 claims description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- 229910052697 platinum Inorganic materials 0.000 claims description 4
- -1 polytetrafluoroethylene Polymers 0.000 claims description 4
- 239000002071 nanotube Substances 0.000 claims description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 3
- 230000003628 erosive effect Effects 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 claims description 2
- 230000001939 inductive effect Effects 0.000 claims 3
- 229910017855 NH 4 F Inorganic materials 0.000 claims 2
- 239000012670 alkaline solution Substances 0.000 claims 2
- 238000007743 anodising Methods 0.000 claims 2
- 238000002791 soaking Methods 0.000 claims 2
- 239000007983 Tris buffer Substances 0.000 claims 1
- 238000001816 cooling Methods 0.000 claims 1
- 238000001035 drying Methods 0.000 claims 1
- 239000000203 mixture Substances 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 abstract description 5
- 239000003085 diluting agent Substances 0.000 abstract description 5
- 239000003513 alkali Substances 0.000 abstract description 4
- 239000007788 liquid Substances 0.000 abstract description 4
- 239000000956 alloy Substances 0.000 abstract 2
- 229910045601 alloy Inorganic materials 0.000 abstract 2
- 239000011159 matrix material Substances 0.000 description 23
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- 229910021641 deionized water Inorganic materials 0.000 description 10
- 230000006872 improvement Effects 0.000 description 9
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- 239000011575 calcium Substances 0.000 description 7
- 239000010410 layer Substances 0.000 description 7
- 230000008569 process Effects 0.000 description 6
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 6
- 239000008186 active pharmaceutical agent Substances 0.000 description 5
- 239000010839 body fluid Substances 0.000 description 5
- 210000001124 body fluid Anatomy 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 238000009413 insulation Methods 0.000 description 5
- 239000002086 nanomaterial Substances 0.000 description 5
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 5
- 239000003637 basic solution Substances 0.000 description 4
- 238000002203 pretreatment Methods 0.000 description 4
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- 238000012986 modification Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 229910001424 calcium ion Inorganic materials 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 239000007943 implant Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 238000007750 plasma spraying Methods 0.000 description 2
- 239000011435 rock Substances 0.000 description 2
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- 229910019142 PO4 Inorganic materials 0.000 description 1
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Abstract
This invention relates to a biological active nanometer compound layer making method for the medical metal surface, which includes the following steps: putting the medical metal titanium and its alloy radix into the diluent acid liquid to do corrad pretreatment; using the pretreated titanium and its alloy radix as the anode to do anode oxidation to create the compact titanium dioxide nanometer tube film on the surface of the metal; putting them into the alkali lye to do activation treatment, then doing heat treatment with them under 450 DEG C-650 DEG C for 0.5-3 hours; Then putting them into the simulate liquid to produce hydroxyl apatite. The charater of this invention is that it provides a method that combines the anode oxidation and alkali heat treatment, and this invention impoves the biological compatibility of the medical metal greatly.
Description
[technical field]
The present invention relates to a kind of preparation method of medical material surface bioactive nanometer composite layer, in particular combine, in the body fluid environment, prepare the method for biological activity composite bed with nanostructure by anonizing and chemical method.
[background technology]
Titanium and titanium alloy because have excellent mechanical strength, density is low, Young's modulus is low and under physiological environment corrosion-resistant good plurality of advantages, be human body hard tissue biomaterial commonly used in medical field.But titanium and titanium alloy are in the environment of human body for a long time, can occur that biological activity is low, the problem of metal ion stripping.In order to solve the above problems, be necessary control and improve metallic surface character, improve the biocompatibility and the erosion resistance of metal implant material by the technology of surface modification.At present, process for modifying surface mainly comprises sol-gel method, alkali heat treating process, hydrogen peroxide facture, self-assembled monolayer method, plasma spraying, chemical gaseous phase depositing process and laser cladding.Wherein, what be most widely used clinically is plasma spraying technology, but plasma spray is coated in the powder of hydroxyapatite in the pyroprocess can decompose, thereby causes adhesive force of coatings to descend, and can produce coating shedding, dissolved problem behind the implant into body.
In recent years, the nanostructure research of titanium dioxide has caused investigator's very big interest, and the titanium dioxide that excites by UV-light demonstrates superior photocatalysis performance, has had in fields such as photoelectrochemistry, air-sensitive and purifying airs widely and has used.The iso-electric point of titanium dioxide is lower, the electronegative calcium ion that under the body fluid environment, can adsorb in the body fluid in surface, phosphate anion and calcium ion codeposition then, phosphatic rock heterogeneous nucleation and crystalline growth form class phosphatic rock at metal titanium or titanium alloy-based surface.
By chemical process or electrochemical method medical metal is carried out surface modification at present, the metallic surface for preparing only has micron-sized pore structure, truly nanostructure successfully is not applied in the surface modification of medical metal.By go out the nanostructure that has fine bonding force with matrix at the medical metal surface construction, can under the simulated body fluid environment, induce the formation of hydroxyapatite more effectively, to improve the biocompatibility of metal, prevent the slow release of harmful ion in human body in the metal.
[summary of the invention]
Technical problem to be solved by this invention is: a kind of preparation method of biologically active nanometer composite layer on medical-use metal surface is provided, the special nanostructure of constructing in the metallic surface by anodic oxidation, under the body fluid environment, promoted the deposition of hydroxyapatite, biologically active nanometer composite layer of preparing and matrix bond degree are good, its preparation technology's program is simple, cycle is short, strong operability.
For solving the problems of the technologies described above, the present invention adopts following technical scheme: a kind of preparation method of biologically active nanometer composite layer on medical-use metal surface is provided, and it comprises the steps:
Pre-treatment step, the acid solution of medical pure titanium or titanium alloy substrate being put into dilution corrodes processing;
The anodic oxidation step, pretreated titanium or titanium alloy substrate as anode, are placed in the polytetrafluoroethylene beaker that contains electrolyte solution, and stainless steel or platinized platinum are as negative electrode, carry out anodic oxidation 0.5～6 hour, and generated fine and close titania nanotube shape structural membrane on the surface;
The activation treatment step, treat that anodic oxidation finishes after, water cleans titanium or titanium alloy substrate, the basic solution of putting into 40～80 ℃ carried out activation treatment 0.5～3 hour;
Heat treatment step, titanium after the processing or titanium alloy substrate are placed on and are heated to 450 ℃～650 ℃ in the process furnace, and 450 ℃～650 ℃ down insulations 0.5～3 hour, to be cooledly take out to room temperature;
Induce to form the hydroxyapatite step, will immerse in the simulated body fluid, take out cleaning, oven dry behind the immersion certain hour through heat treated titanium or titanium alloy substrate.
Further improvement in the technical proposal is: in the pre-treatment step, the acid solution of described dilution is the hydrofluoric acid of 1～5% hydrofluoric acid diluent or 1～5% and the mixed solution of 5～30% nitric acid.
Further improvement in the technical proposal is: in the anodic oxidation step, anodised voltage is 10～30V, and temperature is 5～30 ℃.
Further improvement in the technical proposal is: in the anodic oxidation step, described electrolyte solution is 0.1～0.6% hydrofluoric acid solution or 0.5～2mol/L (NH
4)
2SO
4With 0.1～2wt%NH
4The aqueous solution of F or 0.5～2mol/L NH
4H
2PO
4With 0.1～2wt%NH
4The aqueous solution of F or 0.5～2mol/LH
25O
4The aqueous solution with 0.05～0.5mol/L NaF.
Further improvement in the technical proposal is: in the activation treatment step, described basic solution is the sodium hydroxide solution of 1mol/L～10mol/L.
Further improvement in the technical proposal is: in the heat treatment step, heat-up rate is 1～20 ℃/min.
Further improvement in the technical proposal is: induce to form in the hydroxyapatite step, will immerse in the simulated body fluid through heat treated titanium or titanium alloy substrate, immersion is after 1～15 day down at 35 ℃～38 ℃, and taking-up is cleaned, oven dry.
Further improvement in the technical proposal is: induce to form in the hydroxyapatite step, each ionic concn is in the simulated body fluid that is adopted: [Na
+]=142mM, [K
+]=5mM, [Ca
2+]=2.5mM, [Mg
2+]=1.5mM, [Cl
-]=125mM, [SO
4 2-]=0.5mM, [HCO
3 -]=27mM, [HPO
4 2-]=1.0mM.
Further improvement in the technical proposal is: described simulated body fluid is 7.40 with hydrochloric acid and the 50mM Tutofusin tris regulator solution pH of 1M.
Further improvement in the technical proposal is: described process furnace is the temperature control chamber type electric resistance furnace.
Because adopt technique scheme, the present invention has following beneficial effect: by the titanium deoxid film with nano tubular structure that anonizing prepares, good with the combination degree of body material; Activation treatment and thermal treatment by alkali lye, further improved the biological activity of the nano tubular structure film of titanium dioxide, under the body fluid environment, can induce the formation nanometer hydroxyapatite rapidly, from using the chemical bonding that has improved between medical embedded metal and the osseous tissue, strengthened biocompatibility.The technological operation of adopting is strong, and program is simple, and equipment requirements is low, and the time cycle is short.
[description of drawings]
Fig. 1 is the process flow diagram of a kind of preparation method of biologically active nanometer composite layer on medical-use metal surface of the present invention.
[embodiment]
As shown in Figure 1, the invention provides a kind of preparation method of biologically active nanometer composite layer on medical-use metal surface, it comprises the steps:
Pre-treatment step, the acid solution of medical pure titanium or titanium alloy substrate being put into dilution corrodes processing;
The anodic oxidation step, pretreated titanium or titanium alloy substrate as anode, are placed in the polytetrafluoroethylene beaker that contains electrolyte solution, and stainless steel or platinized platinum are as negative electrode, carry out anodic oxidation 0.5～6 hour, and generated fine and close titania nanotube shape structural membrane on the surface;
The activation treatment step, treat that anodic oxidation finishes after, water cleans titanium or titanium alloy substrate, the basic solution of putting into 40～80 ℃ carried out activation treatment 0.5～3 hour;
Heat treatment step, titanium after the processing or titanium alloy substrate are placed on and are heated to 450 ℃～650 ℃ in the temperature control chamber type electric resistance furnace, and 450 ℃～650 ℃ down insulations 0.5～3 hour, to be cooledly take out to room temperature;
Induce to form the hydroxyapatite step, will immerse in the simulated body fluid through heat treated titanium or titanium alloy substrate, immersion is after 1～20 day down at 35 ℃～38 ℃, and taking-up is cleaned, oven dry.
Wherein, in the pre-treatment step, the acid solution of described dilution is the hydrofluoric acid of 1～5% hydrofluoric acid diluent or 1～5% and the mixed solution of 5～30% nitric acid.
In the anodic oxidation step, described electrolyte solution is that described electrolyte solution is 0.1～0.6% hydrofluoric acid solution or 0.5～2mol/L (NH
4)
2SO
4With 0.1～2wt%NH
4The aqueous solution of F or 0.5～2mol/L NH
4H
2PO
4With 0.1～2wt%NH
4The aqueous solution of F or 0.5～2mol/L H
2SO
4The aqueous solution with 0.05～0.5mol/L NaF.
In the anodic oxidation step, anodised voltage is 10～30V, and temperature is 5～30 ℃.
In the activation treatment step, described basic solution is the sodium hydroxide solution of 1mol/L～10mol/L.
In the heat treatment step, heat-up rate is 1～20 ℃/min.
Induce to form the hydroxyapatite step, each ionic concn is in the simulated body fluid that is adopted: [Na
+]=142mM, [K
+]=5mM, [Ca
2+]=2.5mM, [Mg
2+]=1.5mM, [Cl
-]=125mM, [SO
4 2-]=0.5mM, [HCO
3 -]=27mM, [HPO
4 2-]=1.0mM.
Below by several experimental examples the present invention is set forth in more detail.
Experimental example 1
With medical pure titanium TA2 matrix, put into and contain 3% dilute hydrofluoric acid liquid and corroded 60 seconds, remove the dirt and the oxide compound on surface, with deionized water rinsing, oven dry; Pretreated titanium matrix as anode, is put into the beaker of the tetrafluoroethylene that contains 0.4% hydrofluoric acid electrolytic solution, and stainless steel is 20V as negative electrode at volts DS, carries out anodic oxidation 0.5 hour under 15 ℃; The sodium hydroxide solution of titanium matrix after the oxidation being put into 60 ℃ 5mol/L carried out activation treatment 1 hour, with deionized water rinsing, oven dry; The titanium matrix is put into the temperature control chamber type electric resistance furnace again and be warming up to 500 ℃, heat-up rate is 5 ℃/min, and 500 ℃ of down insulations 2 hours, to be cooledly takes out to room temperature.After 7 days, take out cleaning, oven dry in immersion under 36.5 ℃ in the simulated body fluid with the titanium matrix immersion preparation in advance after handling.Wherein, each ionic concn is respectively in the described simulated body fluid: [Na
+]=142mM, [K
+]=5mM, [Ca
2+]=2.5mM, [Mg
2+]=1.5mM, [Cl
-]=125mM, [SO
4 2-]=0.5mM, [HCO
3 -]=27mM, [HPO
4 2-]=1.0mM, and described simulated body fluid is 7.40 with hydrochloric acid and the 50mM Tutofusin tris regulator solution pH of 1M.By scanning electronic microscope the titanium matrix after calcining is characterized, the metallic surface oxidation forms many domain structures, and the outer aperture of the titanium dioxide tubular structure that occurs in each domain structure is 50～100nm, and internal orifice dimension is 20～60nm.
Experimental example 2
With medical titanium alloy substrate, the mixed solution of putting into the nitric acid that contains 2% hydrofluoric acid and 15% corroded 60 seconds, removed the dirt and the oxide compound on surface, with deionized water rinsing, oven dry; Pretreated titanium alloy substrate as anode, is put into the beaker of the tetrafluoroethylene that contains 0.4% hydrofluoric acid electrolytic solution, and stainless steel is 20V as negative electrode at volts DS, carries out anodic oxidation 0.5 hour under 25 ℃; The sodium hydroxide solution of titanium alloy substrate after the oxidation being put into 60 ℃ 10mol/L carried out activation treatment 30 minutes, with deionized water rinsing, oven dry; Titanium alloy substrate is put into the temperature control chamber type electric resistance furnace again and be warming up to 600 ℃, heat-up rate is 10 ℃/min, and 600 ℃ of down insulations 1 hour, to be cooledly takes out to room temperature.After 10 days, take out cleaning, oven dry in immersion under 37 ℃ in the simulated body fluid with the titanium alloy substrate immersion preparation in advance after handling.Wherein, each ionic concn is respectively in the described simulated body fluid: [Na
+]=142mM, [K
+]=5mM, [Ca
2+]=2.5mM, [Mg
2+]=1.5mM, [Cl
-]=125mM, [SO
4 2-]=0.5mM, [HCO
3 -]=27mM, [HPO
4 2-]=1.0mM, above-mentioned simulated body fluid is 7.40 with hydrochloric acid and the 50mM Tutofusin tris regulator solution pH of 1M.
Experimental example 3
With medical pure titanium matrix, put into 3% dilute hydrofluoric acid liquid and corroded 60 seconds, remove the dirt and the oxide compound on surface, the back is with deionized water rinsing, oven dry; Pretreated titanium matrix as anode, is put into and contained 1mol/L (NH
4)
2SO
4And 1wt%NH
4In the beaker of the tetrafluoroethylene of F electrolytic solution, platinized platinum is 20V as negative electrode at volts DS, carries out anodic oxidation under the condition of room temperature 3 hours; The solution of titanium matrix after the oxidation being put into 50 ℃ 10mol/L sodium hydroxide carried out activation treatment 0.5 hour, with deionized water rinsing, oven dry; Then the titanium matrix is placed in the temperature control chamber type electric resistance furnace 600 ℃ of calcinings 1 hour down, heat-up rate is 10 ℃/min, to be cooledly takes out to room temperature.The titanium matrix handled well immersed in the simulated body fluid for preparing in advance 36.5 ℃ soak 10 days down after, take out clean, oven dry.Wherein, each ionic concn is respectively in the simulated body fluid: [Na
+]=142mM, [K
+]=5mM, [Ca
2+]=2.5mM, [Mg
2+]=1.5mM, [Cl
-]=125mM, [SO
4 2-]=0.5mM, [HCO
3 -]=27mM, [HPO
4 2-]=1.0mM, above-mentioned simulated body fluid is 7.40 with the hydrochloric acid of 1M and the Tutofusin tris regulator solution pH of 50mM.
Experimental example 4
With medical pure titanium matrix, the diluent of putting into 2% hydrofluoric acid corroded 3 minutes, and the back is with deionized water rinsing, oven dry; Pretreated titanium matrix as anode, is put into and contained 1mol/LH
2SO
4In the beaker of the tetrafluoroethylene of 0.2mol/L NaF electrolytic solution, stainless steel is 20V as negative electrode at volts DS, carries out anodic oxidation under 20 ℃ the condition 1 hour; The solution of titanium matrix after the oxidation being put into 60 ℃ 5mol/L sodium hydroxide carried out activation treatment 1 hour, with deionized water rinsing, oven dry; The titanium matrix is placed in the retort furnace 600 ℃ of insulations 1 hour down, and heat-up rate is 10 ℃/min, to be cooledly takes out to room temperature.With the titanium matrix of handling well, immerse in the simulated body fluid for preparing in advance and after 15 days, take out cleaning, oven dry in immersion under 36.5 ℃.Wherein, each ionic concn is respectively in the simulated body fluid: [Na
+]=142mM, [K
+]=5mM, [Ca
2+]=2.5mM, [Mg
2+]=1.5mM, [Cl
-]=125mM, [SO
4 2-]=0.5mM, [HCO
3 -]=27mM, [HPO
4 2-]=1.0mM, above-mentioned simulated body fluid is 7.40 with hydrochloric acid and the 50mM Tutofusin tris regulator solution pH of 1M.
Experimental example 5
With medical pure titanium TA2 matrix, the diluent of putting into 3% hydrofluoric acid corrodes, and removes the dirt and the oxide compound on surface, and the back is with deionized water rinsing, oven dry; Pretreated titanium matrix as anode, is put into and contained 1mol/LNH
4H
2PO
4And 0.5wt%NH
4In the beaker of the tetrafluoroethylene of F electrolytic solution, stainless steel is 20V as negative electrode at volts DS, carries out anodic oxidation under the condition of room temperature 3 hours; The solution of titanium matrix after the oxidation being put into 60 ℃ 5mol/L sodium hydroxide carried out activation treatment 1 hour, with deionized water rinsing, oven dry; Then the titanium matrix is placed in the retort furnace and calcined 1 hour down at 600 ℃, heat-up rate is 10 ℃/min.Titanium matrix after handling immersed in the simulated body fluid for preparing in advance 36.5 ℃ soak 15 days down after, take out clean, oven dry.Wherein, each ionic concn is respectively in the simulated body fluid: [Na
+]=142mM, [K
+]=5mM, [Ca
2+]=2.5mM, [Mg
2+]=1.5mM, [Cl
-]=125mM, [SO
4 2-]=0.5mM, [HCO
3 -]=27mM, [HPO
4 2-]=1.0mM, above-mentioned simulated body fluid is 7.40 with hydrochloric acid and the 50mM Tutofusin tris regulator solution pH of 1M.
Claims (10)
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| WO2008071047A1 (en) * | 2006-12-14 | 2008-06-19 | Lepu Medical Technology (Beijing) Co., Ltd | Nanoporous drug release structure for drug elute instruments and the preparation method thereof |
| CN101942688A (en) * | 2010-09-21 | 2011-01-12 | 上海大学 | Composite oxidation technology for medicinal titanium alloy |
| CN102071450A (en) * | 2011-01-19 | 2011-05-25 | 天津大学 | Method for preparing nanostructure oxide film on surface of Ti-25Nb-3Mo-2Sn-3Zr (TLM) titanium alloy |
| CN102747403A (en) * | 2012-07-03 | 2012-10-24 | 淮阴工学院 | Method of preparing magnesium-doped hydroxyapatite/titania active film on surface of medical titanium alloy |
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