CN1214823C - Rapid synthesize method for bone phosphorite film - Google Patents

Abstract

The present invention relates to a method for rapidly synthesizing a bone phosphorite biological active film on the surface of a medical titanium base implant, namely micro-arc oxidation and photocatalysis enhanced deposition technology. The synthesizing method comprises: an anatase titanium oxide film with certain pore diameters and porosity is firstly prepared by the micro-arc oxidation of titanium or titanium alloy and then is irradiated by ultraviolet light for a short time in simulated body fluid, and a bone phosphorite film with the thickness of 5 to 10 micrometers is rapidly synthesized on the titanium oxide transition film. The titanium oxide and bone phosphorite film on the surface of a medical titanium base implant has high biological activity and binding strength and can be uniformly formed on the surface of an implant with a complicated shape.

Description

The fast synthesis method of osteolith film

Technical field

The present invention relates to a kind of fast synthesis method of osteolith film, be applicable to the synthetic of the medical implant surface bioactive film of titanio, to construct human body hard tissue reparation and replacement device with good mechanics and biology performance.

Background technology

Titanium and titanium alloy are the usual materials that uses of tooth implant and load bone implant, have good obdurability, but lack biological activity, in early days can not be longer at implant into body with bone formation chemical bond and healing time, need carry out the bioactivation modification.At present, the titanium alloy surface bioactivation mostly is hydroxyapatite or osteolith with coating, i.e. the apatite that replaced by carbonate of part of hydroxyl and be the nanocrystal feature.Compare with hydroxyapatite, osteolith has better biocompatibility and biological activity.The technology of preparing of hydroxyapatite and osteolith has multiple, and (1) differential arc oxidation-hydro-thermal is synthesized complex technique; (2) titanium alloy chemical treatment-simulated body fluid mineralising deposition technique; (3) ultraviolet light irradiation-simulated body fluid mineralising deposition technique.The synthetic preparation of differential arc oxidation-hydro-thermal hydroxyapatite membrane technology in nineteen ninety-five by propositions such as Japanese H.Ishizawa, this technology is at first synthesized the titanium dioxide film that is rich in calcium and phosphorus by differential arc oxidation at titanium alloy surface, has then synthesized the hydroxyapatite film by 300 ℃, 4 hours hydrothermal treatment consists.Titanium alloy chemical treatment-simulated body fluid mineralising deposition preparation osteolith membrane technology in 1992 by propositions such as Japanese T.Kokubo, this technology is handled formation titanium oxide or sodium titanate gel film by titanium alloy being carried out hydrogen peroxide or alkali liquor, then mineralising formed the osteolith film of thick about 5 μ m in 7 days in simulated body fluid, but, the subsequent heat treatment of its reinforcement has then been caused the further prolongation of osteolith film formation time because of titanium oxide and sodium titanate gel film and high base strength are lower.Ultraviolet light irradiation-simulated body fluid mineralising deposition synthetic bone apatite membrane technology is by propositions such as Japanese T.Kasuga, this technology is by carrying out 5 hours ultraviolet light irradiations to two-phase titanium oxide (rutile and anatase) powder compacting block, then in simulated body fluid, soaked mineralising 10 days, synthesized the osteolith film in titanium oxide pressing block surface.Though the two kinds of technology in back all can synthetic bone apatite films, have all that generated time is long, a bond strength shortcoming of weak (being generally 22-25MPa).

Summary of the invention

The object of the present invention is to provide the fast synthesis method of the medical implantation body of a kind of titanio bioactivation with the osteolith film.

For achieving the above object, the present invention has adopted the mutually compound scheme of differential arc oxidation and ultraviolet catalytic, and is specific as follows:

1) differential arc oxidation of titanium or titanium alloy: with (CH ₃COO) ₂CaH ₂O and β-C ₃H ₇Na ₂O ₆P5H ₂The aqueous solution of O is made the (CH that contains 0.2-0.5mol/l ₃COO) ₂CaH ₂β-C of O and 0.02-0.06mol/l ₃H ₇Na ₂O ₆P5H ₂The electrolyte of O; With titanium or titanium alloy is that anode, metal rustless steel are that negative electrode places electrolyte, and adopting the bipolar pulse power supply is that 200-250V, negative voltage are that 100V, frequency are that 100Hz, dutycycle are that 3-30%, cathode-anode plate spacing are under the condition of 8-12cm titanium or titanium alloy to be carried out differential arc oxidation in positive phase voltage;

2) ultraviolet light irradiation: according to ion component identical and concentration preparation simulated body fluid with human body fluid, titanium or titanium alloy after the differential arc oxidation processing are placed simulated body fluid, in the ultraviolet synthesizer, titanium or titanium alloy are carried out photocatalysis treatment, used light source is the mercury lamp of power 500-1000W, irradiation distance 30-50cm, exposure time 1-2h.

Adopt preparation technology of the present invention to synthesize and titanium alloy substrate between be the apatite film of transition zone with the anatase titanium dioxide pottery, and can be in the even film forming in the screw thread position of complicated form implant surface such as tooth implant.The bond strength of titanium dioxide ceramic transition zone is up to 42MPa, its submicron porous morphological characteristic helps growing into of apatite, has strengthened combining between apatite film and transition zone, makes the bond strength of integral membrane system reach 33-35MPa.Simultaneously, this phosphorus ash film stone is nanocrystal, is rich in carbonate, and the apatite in its structure and the skeleton is very approaching, has good biological activity, can directly be used as the biological activity top layer of the medical implantation body of titanio.

The specific embodiment

Embodiment 1, with (CH ₃COO) ₂CaH ₂O and β-C ₃H ₇Na ₂O ₆P5H ₂The aqueous solution of O is made the (CH that contains 0.2mol/l ₃COO) ₂CaH ₂β-C of O and 0.02mol/l ₃H ₇Na ₂O ₆P5H ₂The electrolyte of O; With the titanium sheet is that anode, stainless steel substrates are that negative electrode places electrolyte, and adopting the bipolar pulse power supply is that 200V, negative voltage are that 100V, frequency are under the condition that 100Hz, dutycycle are 3%, the cathode-anode plate spacing is 8cm titanium to be carried out 5 minutes differential arc oxidations in positive phase voltage; According to ion component identical and concentration preparation simulated body fluid with human body fluid, the differential arc oxidation sample is placed the quartz beaker that the 100ml simulated body fluid is housed, in the ultraviolet synthesizer, adopt the 800W mercury lamp, it carried out the ultraviolet light irradiation of 2h in the 30cm irradiation distance, can form the osteolith film that thickness is about 5 μ m, its bond strength can reach 35MPa.

Embodiment 2, with (CH ₃COO) ₂CaH ₂O and β-C ₃H ₇Na ₂O ₆P5H ₂The aqueous solution of O is made the (CH that contains 0.5mol/l ₃COO) ₂CaH ₂β-C of O and 0.06mol/l ₃H ₇Na ₂O ₆P5H ₂The electrolyte of O; With the titanium sheet is that anode, stainless steel substrates are that negative electrode places electrolyte, and adopting the bipolar pulse power supply is being that 250V, negative voltage are that 100V, frequency are under the condition that 100Hz, dutycycle are 30%, the cathode-anode plate spacing is 12cm titanium to be carried out 3 minutes differential arc oxidations in positive phase voltage; According to ion component identical and concentration preparation simulated body fluid with human body fluid, the differential arc oxidation sample is placed the quartz beaker that the 100ml simulated body fluid is housed, in the ultraviolet synthesizer, adopt the 1000W mercury lamp, it carried out the ultraviolet light irradiation of 2h in the 50cm irradiation distance, can form the osteolith film that thickness is about 10 μ m, its bond strength can reach 33MPa.

Embodiment 3, with (CH ₃COO) ₂CaH ₂O and β-C ₃H ₇Na ₂O ₆P5H ₂The aqueous solution of O is made the (CH that contains 0.3mol/l ₃COO) ₂CaH ₂β-C of O and 0.05mol/l ₃H ₇Na ₂O ₆P5H ₂The electrolyte of O; With the titanium sheet is that anode, stainless steel substrates are that negative electrode places electrolyte, and adopting the bipolar pulse power supply is that 230V, negative voltage are that 100V, frequency are under the condition that 100Hz, dutycycle are 10%, the cathode-anode plate spacing is 10cm titanium to be carried out 5 minutes differential arc oxidations in positive phase voltage; According to ion component identical and concentration preparation simulated body fluid with human body fluid, the differential arc oxidation sample is placed the quartz beaker that the 100ml simulated body fluid is housed, in the ultraviolet synthesizer, adopt the 500W mercury lamp, it carried out the ultraviolet light irradiation of 2h in the 40cm irradiation distance, can form the osteolith film that thickness is about 5 μ m, its bond strength can reach 35MPa.

Embodiment 4, with (CH ₃COO) ₂CaH ₂O and β-C ₃H ₇Na ₂O ₆P5H ₂The aqueous solution of O is made the (CH that contains 0.4mol/l ₃COO) ₂CaH ₂β-C of O and 0.03mol/l ₃H ₇Na ₂O ₆P5H ₂The electrolyte of O; With the titanium sheet is that anode, stainless steel substrates are that negative electrode places electrolyte, and adopting the bipolar pulse power supply is that 220V, negative voltage are that 100V, frequency are under the condition that 100Hz, dutycycle are 15%, the cathode-anode plate spacing is 9cm titanium to be carried out 3 minutes differential arc oxidations in positive phase voltage; According to ion component identical and concentration preparation simulated body fluid with human body fluid, the differential arc oxidation sample is placed the quartz beaker that the 100ml simulated body fluid is housed, in the ultraviolet synthesizer, adopt the 900W mercury lamp, it carried out the ultraviolet light irradiation of 1.5h in the 35cm irradiation distance, can form the osteolith film that thickness is about 10 μ m, its bond strength can reach 33MPa.

Embodiment 5, with (CH ₃COO) ₂CaH ₂O and β-C ₃H ₇Na ₂O ₆P5H ₂The aqueous solution of O is made the (CH that contains 0.2mol/l ₃COO) ₂CaH ₂β-C of O and 0.04mol/l ₃H ₇Na ₂O ₆P5H ₂The electrolyte of O; With the titanium alloy sheet is that anode, stainless steel substrates are that negative electrode places electrolyte, and adopting the bipolar pulse power supply is that 210V, negative voltage are that 100V, frequency are under the condition that 100Hz, dutycycle are 20%, the cathode-anode plate spacing is 11cm titanium to be carried out 5 minutes differential arc oxidations in positive phase voltage; According to ion component identical and concentration preparation simulated body fluid with human body fluid, the differential arc oxidation sample is placed the quartz beaker that the 100ml simulated body fluid is housed, in the ultraviolet synthesizer, adopt the 600W mercury lamp, it carried out the ultraviolet light irradiation of 1h in the 45cm irradiation distance, can form the osteolith film that thickness is about 5 μ m, its bond strength can reach 35MPa.

Embodiment 6, with (CH ₃COO) ₂CaH ₂O and β-C ₃H ₇Na ₂O ₆P5H ₂The aqueous solution of O is made the (CH that contains 0.5mol/l ₃COO) ₂CaH ₂β-C of O and 0.06mol/l ₃H ₇Na ₂O ₆P5H ₂The electrolyte of O; With the titanium alloy sheet is that anode, stainless steel substrates are that negative electrode places electrolyte, and adopting the bipolar pulse power supply is being that 240V, negative voltage are that 100V, frequency are under the condition that 100Hz, dutycycle are 25%, the cathode-anode plate spacing is 12cm titanium to be carried out 5 minutes differential arc oxidations in positive phase voltage; According to ion component identical and concentration preparation simulated body fluid with human body fluid, the differential arc oxidation sample is placed the quartz beaker that the 100ml simulated body fluid is housed, in the ultraviolet synthesizer, adopt the 700W mercury lamp, it carried out the ultraviolet light irradiation of 1.5h in the 40cm irradiation distance, can form the osteolith film that thickness is about 7 μ m, its bond strength can reach 33MPa.

Embodiment 7, with (CH ₃COO) ₂CaH ₂O and β-C ₃H ₇Na ₂O ₆P5H ₂The aqueous solution of O is made the (CH that contains 0.3mol/l ₃COO) ₂CaH ₂β-C of O and 0.02mol/l ₃H ₇Na ₂O ₆P5H ₂The electrolyte of O; With the titanium alloy sheet is that anode, stainless steel substrates are that negative electrode places electrolyte, and adopting the bipolar pulse power supply is being that 250V, negative voltage are that 100V, frequency are under the condition that 100Hz, dutycycle are 30%, the cathode-anode plate spacing is 8cm titanium to be carried out 5 minutes differential arc oxidations in positive phase voltage; According to ion component identical and concentration preparation simulated body fluid with human body fluid, the differential arc oxidation sample is placed the quartz beaker that the 100ml simulated body fluid is housed, in the ultraviolet synthesizer, adopt the 1000W mercury lamp, it carried out the ultraviolet light irradiation of 1h in the 30cm irradiation distance, can form the osteolith film that thickness is about 5 μ m, its bond strength can reach 35MPa.

Embodiment 8, with (CH ₃COO) ₂CaH ₂O and β-C ₃H ₇Na ₂O ₆P5H ₂The aqueous solution of O is made the (CH that contains 0.4mol/l ₃COO) ₂CaH ₂β-C of O and 0.03mol/l ₃H ₇Na ₂O ₆P5H ₂The electrolyte of O; With the titanium alloy sheet is that anode, stainless steel substrates are that negative electrode places electrolyte, and adopting the bipolar pulse power supply is that 200V, negative voltage are that 100V, frequency are under the condition that 100Hz, dutycycle are 20%, the cathode-anode plate spacing is 10cm titanium to be carried out 5 minutes differential arc oxidations in positive phase voltage; According to ion component identical and concentration preparation simulated body fluid with human body fluid, the differential arc oxidation sample is placed the quartz beaker that the 100ml simulated body fluid is housed, in the ultraviolet synthesizer, adopt the 500W mercury lamp, it carried out the ultraviolet light irradiation of 2h in the 38cm irradiation distance, can form the osteolith film that thickness is about 10 μ m, its bond strength can reach 33MPa.

The innovation part of technology that the present invention carries is: differential arc oxidation and the ultraviolet catalytic in simulated body fluid are combined, the synthetic of osteolith film finished in the irradiation process in short-term at ultraviolet light, need not long time mineralising in simulated body fluid again, generated time is short, the bond strength height.Adopting preparation technology of the present invention to synthesize with the titanium oxide ceramics in the medical implant surface of the titanio of complicated form is the osteolith film of transition zone, and the bond strength of film system reaches 33-35MPa, has than the better biological activity of hydroxyapatite.

Claims (1)

1, the fast synthesis method of osteolith film is characterized in that:

1) differential arc oxidation of titanium or titanium alloy: with (CH ₃COO) ₂CaH ₂O and β-C ₃H ₇Na ₂O ₆P5H ₂The aqueous solution of O is made the (CH that contains 0.2-0.5mol/l ₃COO) ₂CaH ₂β-C of O and 0.02-0.06mol/l ₃H ₇Na ₂O ₆P5H ₂The electrolyte of O; With titanium or titanium alloy is that anode, metal rustless steel are that negative electrode places electrolyte, and adopting the bipolar pulse power supply is that 200-250V, negative voltage are that 100V, frequency are that 100Hz, dutycycle are that 3-30%, cathode-anode plate spacing are under the condition of 8-12cm titanium or titanium alloy to be carried out differential arc oxidation in positive phase voltage;

2) ultraviolet light irradiation: according to ion component identical and concentration preparation simulated body fluid with human body fluid, titanium or titanium alloy after the differential arc oxidation processing are placed simulated body fluid, in the ultraviolet synthesizer, titanium or titanium alloy are carried out photocatalysis treatment, used light source is the mercury lamp of power 500-1000W, irradiation distance 30-50cm, exposure time 1-2h.