CN101264550A - Application of femtosecond laser in titanium or titanium alloy implantation material surface treatment - Google Patents
Application of femtosecond laser in titanium or titanium alloy implantation material surface treatment Download PDFInfo
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- CN101264550A CN101264550A CN 200810052875 CN200810052875A CN101264550A CN 101264550 A CN101264550 A CN 101264550A CN 200810052875 CN200810052875 CN 200810052875 CN 200810052875 A CN200810052875 A CN 200810052875A CN 101264550 A CN101264550 A CN 101264550A
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Abstract
The invention relates to an application of a femto-second laser in the treatment of titanium or titanium alloy implanting material surface, belonging to the technical field of application of laser in the material surface treatment, which comprises the following steps: in the air, the femto-second laser pulses are arranged over the massive titanium or titanium alloy materials, are vertically focused on the surface to form a focal point, the laser spot radius of which is 5 Mum, the processing parameters of the femto-second laser are: the PRF is 1 kHz, the single pulse energy is 50 to 300 micro-joules, the pulse width is 50 femto-seconds, the pulse center wavelength is 800 nm, the laser processing line spacing is 10 to 100 Mum, and the laser scanning speed is 0.2 to 1.0mm/s; the polarization direction of the femto-second laser is adjusted to be parallel with the scanning direction of the femto-second laser, the femto-second laser is used to scan the entire surface of the massive titanium or titanium alloy materials which have been immersed in hydroxyl apatite suspension liquid for 5 minutes, so the surface of the titanium or titanium alloy materials present uniform rough peak-like protrusions and a pattern of porous cyclist regular structure, and is loaded with the titanium-based biomedical material of calcium and phosphate salt.
Description
Technical field
Technical scheme of the present invention relates to the application of laser in material surface is handled, the application of femtosecond laser in titanium or titanium alloy implantation material surface processing specifically.
Background technology
The metal planting technology is repaired bone or injury of teeth was risen in 20th century.Plant the important means of pure titanium or titanium alloy material operation,, adopted by clinical more and more in recent years owing to can take into account aesthetic property and functional requirement as bone and tooth reparation.Yet the adaptability of the huge change of the ambient stress that planting body causes after implanting and corresponding surrounding bone is rebuild and is usually caused the loosening and dislocation of planting body, causes operative failure.Therefore, how giving the planting body Biofunctional, improve its surface stability, anti-wear performance and mechanical compatibility, is the main research task of present stage, and its basic means then is to utilize the process for modifying surface of metal planting body.
Current, the process for modifying surface of metal planting body has aciding after the sandblast, ionic reaction etching method, electrochemical process, common laser processing method and plasma spraying method.The picture on surface roughness of aciding preparation is inhomogeneous after the sandblast, and the degree of depth and the diameter of the hole that obtains are uncontrollable; Ionic reaction etching method and electrochemical process are introduced foreign ion easily, influence the biologically active of planting body; Common laser processing can only obtain groove at sample surfaces, than simple structures such as macroscopic voids, the combination that can't obtain multiple structure is to adapt to the cell growth.Plasma spraying can provide rough surface in the preparation hydroxyapatite coating on surface, but spraying can only provide thicker coating, thickness is 30～150 μ m, and in the cooling procedure after pyrolytic coating, because material coefficient of thermal expansion coefficient difference, cause easily and produce big stress even coating shedding between face coat and matrix, this also causes the graft failure after material is implanted easily.In addition, plasma spraying is raw materials used to be pure HA powder, costs an arm and a leg the equipment manufacturing cost height.And above-mentioned complex technical process, operating difficulties, influence factor are many, are unfavorable for its extensive use.
Reported that being used for the document that titanium or titanium alloy implant surface handle to strengthen the surface modifying method that planting body combines with bone tissue has: CN1712566 discloses the application that electrochemical process is handled at titanium or titanium alloy implantation material surface, is the H of employing 0.5～3M
2SO
4Solution corrodes to obtain the certain roughness in surface titanium or titanium alloy implantation material surface; CN1392799 has disclosed the implant made with titanium and other materials and the surface treatment method of prosthese, is to come continuously and separately the implant section is carried out corrosion treatment with hydrofluoric acid, three kinds of different acid of sulfuric acid and hydrochloric acid.Yet, the method of applied chemistry acid corrosion is handled the surface of titanium or titanium alloy embedded material, be difficult to obtain uniform roughness, and can not obtain the picture on surface of rule, be unfavorable for the oriented growth of inducing cell and the wound healing after promotion titanium or the titanium alloy material implantation.
Utilize femtosecond laser that [femtosecond pulse two-photon micro-nano process technology and application thereof are mainly carried out in the processing of solid material at present on transparent material, Science Bulletin, 2008,53 (1)], reason is the restriction that the focusing of femtosecond laser on transparent material can not be subjected to the surface, can focus at material internal, just can process corresponding pattern as long as guarantee the relative position of focus.And to the research of opaque metal materials processing, mainly concentrate on cutting [An optimalprocess of femtosecond laser cutting of NiTi shape memory alloy for fabricationof miniature devices to material, Optics and Lasers in Engineering 44 (2006) 1078-1087], [femtosecond laser prepares array hole metal micro-filtration membrane in punching, Chinese laser, 2007,34 (8)], reach the processing [Tsukamoto of point, M., K.Asuka, H.Nakano, et al., Periodic microstructures produced by femtosecondlaser irradiation on titanium plate.Vacuum, 2006.80 (11-12)].When block titanium in using the femtosecond laser process solutions or titanium alloy material surface, because solution to the refraction and the effect of nonlinear of light, makes laser focus on the difficulty that becomes at block titanium or titanium alloy material surface.Yet there are no in liquid and to use femtosecond laser block titanium or titanium alloy material are carried out the surface-treated report.Particularly in the hydroxyapatite suspension, carry out block titanium or the titanium alloy material surface treatment adds man-hour, because suspended particle in liquid is to the scattering of light effect, when the suspension excessive concentration, cause the reduction of laser intensity, influence the effect of patterned surface processing; And suspension concentration is crossed when hanging down, and has influenced the load capacity of calcium microcosmic salt again.Also not seeing at present utilizes femtosecond laser with the report of particle deposition in the liquid to solid material surface.
Summary of the invention
Technical problem to be solved by this invention is: the application process of femtosecond laser in titanium or titanium alloy implantation material surface processing is provided, concentration by control femtosecond laser parameter and hydroxyapatite suspension, make the titanium-base biomedical material that has regular pattern structure and load calcium microcosmic salt on titanium or titanium alloy material surface, this material surface helps the oriented growth of inducing cell and the wound healing after promotion titanium or the implantation of titanium alloy embedded material, overcome aciding after existing electrochemical process and the sandblast, the ionic reaction etching method, the surface that common laser processing method and plasma spraying method are handled titanium or titanium alloy embedded material is difficult to obtain uniform roughness, and can not obtain the shortcoming of picture on surface of rule, also overcome the calcium-phosphate layer of biomimetic growth method preparation and the shortcoming of basal body binding force difference.
The present invention solves this technical problem the technical scheme that is adopted: the application of femtosecond laser in titanium or titanium alloy implantation material surface processing the steps include:
The first step behind the titanium or titanium alloy material polishing with bulk, is used the deionized water ultrasonic cleaning, places the cleaning open containers stand-by then;
Second step, in air, with femto-second laser pulse be arranged in handled block titanium of the first step or titanium alloy material directly over, vertically focus on its surface, forming the laser facula radius is the focus of 5 μ m;
The 3rd step added the hydroxyapatite suspension in the container of the first step, make liquid level exceed block titanium or titanium alloy material surface 2～3mm, the consisting of of used hydroxyapatite suspension:
Constituent concentration
Nanometer hydroxyapatite 5～20g/L
Polyvinylpyrrolidone 5～30g/L
Two hydration calcium chloride, 2～5g/L
Solvent is a water
The pH value of hydroxyapatite suspension is 4～5;
The 4th step, the container that the 3rd step was added the hydroxyapatite suspension 80～100 μ m that move up, make wherein block titanium or the titanium alloy material focus top that is positioned at airborne femtosecond laser, the machined parameters of setting femtosecond laser is: pulse recurrence frequency 1 KHz, 50～300 little joules of single pulse energies, pulse width 50 femtoseconds, pulse center wavelength 800 nanometers, the Laser Processing distance between centers of tracks is 10～100 μ m, laser scanning speed 0.2～1.0mm/ second, regulate femto-second laser polarized direction, make it parallel with the femtosecond laser scanning direction, this bulk titanium or titanium alloy material soak after 5 minutes in the hydroxyapatite suspension that is added, scan this with this femtosecond laser and be soaked in block titanium or the whole surface of titanium alloy material in the hydroxyapatite suspension, the block titanium after the radiation treatment or the surface of titanium alloy material are formed with regularly arranged peak shape raised structures, on these peak shape projections, be covered with the granule of submicron order, simultaneously this bulk titanium or titanium alloy material area load the calcium microcosmic salt, make the pattern of the periodic regular structure of the rough peak shape projection that has uniformity on block titanium or titanium alloy material surface and porous thus, uniform roughness is promptly arranged, and load the titanium-base biomedical material of calcium microcosmic salt.
The invention has the beneficial effects as follows:
(1) but femtosecond laser rapidoprint surface has the little instantaneously producing steam of ablation threshold and plasma, its thermal conductance almost can ignore and do not produce liquid phase and the characteristics little to the heat affecting of matrix.The present invention uses block titanium or the titanium alloy material in the femtosecond laser processing hydroxyapatite suspension, can be when block titanium or titanium alloy material Surface Machining go out the different pattern structure, small hydroapatite particles is loaded to block titanium or titanium alloy material surface, thereby obtain both biologically active layers, have the implant surface of the topological structure pattern of suitable cell growth again.CN1712566 and CN1392799 adopt strong acid that implantation material surface is corroded to obtain certain roughness.This class chemical method is difficult in implantation material surface and obtains uniform roughness, and picture on surface that can not formation rule, in addition, because the effect of strong acid causes the hydrogenation of implantation material surface easily in processing procedure, influences the biologically active of embedded material.The femtosecond laser processing method that the present invention adopts is a physical method, and operating process is controlled, obtains the pattern of the periodic regular structure of the rough peak shape projection of uniformity and porous easily at implantation material surface, and uniform roughness is promptly arranged.The pattern of the periodic regular structure of this rough peak shape projection with uniformity and porous helps the oriented growth of inducing cell, thereby promotes the wound healing after material is implanted.Though also used nitric acid or hydrochloric acid in the inventive method, it only is the pH value that is used for regulating hydroxyapatite suspension system, and consumption is few, can not cause the hydrogenation of implantation material surface.
(2) to prepare the method for surface apatite layer be the biomimetic growth method to CN1712566, and this method is subjected to the influence of implantation material surface state easily; CN1392799 has adopted the method at surface-coated blood plasma to improve block titanium or titanium alloy material surfaces for biocompatibility, the used applicator of this simple painting method adheres to for simple physics with only combining of matrix, behind embedded material implantable bioartificial body, in the middle of material surface and coat, still there is the biologically inert interface, after applicator consumption, can causes the biologically active of material to reduce.A little less than the defective of implantation material surface and the impure adhesion that causes grown layer easily, implant the back and under the effect of various power, causes embedded material to come off easily.The present invention adopts the physics method that the calcium microcosmic salt is loaded to block titanium or titanium alloy material surface, the high temperature action that in loading process, produces owing to femtosecond laser, partial melting takes place in block titanium or titanium alloy material surface, thereby make the calcium microcosmic salt be embedded into block titanium or titanium alloy material surface (seeing accompanying drawing 2 and accompanying drawing 7), thereby significantly improved its adhesion, make it to possess good biologically active, and improved block titanium or titanium alloy material short-term and the long-term biocompatibility of implanting simultaneously.
(3) with sandblast after aciding or plasma spraying method handle implantation material surface and compare, the prepared implantation material surface pattern of the inventive method rule, controlled, machining process is easy, prepared load layer does not have foreign ion to pollute, and the calcium microcosmic salt of institute's load is embedded into implantation material surface pattern middle (seeing accompanying drawing 2 and accompanying drawing 7), tight with matrix bond, increase planting body stability by machinery is sealed with chemical bond, can greatly improve the bond strength of planting body bone interface.From the cell cultivation results as seen, block titanium or titanium alloy material superficial cell growth population many (seeing accompanying drawing 4 and accompanying drawing 9) after the present invention handles, cell grows more pseudopodium (seeing accompanying drawing 5 and accompanying drawing 10), and is tight with matrix bond.And the block titanium of acid etching or titanium alloy material superficial cell quantity few (seeing accompanying drawing 11) after the sandblast, the pseudopodium of growth is also few.Emiocytosis alkaline phosphatase capability analysis result (seeing accompanying drawing 12) on the block titanium that makes with distinct methods or the titanium alloy material is shown, the block titanium of handling in the present invention or the ability of the lip-deep emiocytosis alkaline phosphatase of titanium alloy material are apparently higher than the ability through the emiocytosis alkaline phosphatase on the block titanium of sandblast acid etching or titanium alloy material surface, and the block titanium that this explanation the present invention processing obtains or the regular pattern on titanium alloy material surface help improving the mineralization ability of Gegenbaur's cell tissue.
Beneficial effect of the present invention is also fully proved in the following embodiments.
Description of drawings
The present invention is further described below in conjunction with drawings and Examples.
Fig. 1 is a scanned photograph behind the pure titanium material surface of the embodiment of the invention 1 prepared bulk pulse laser irradiation.
Fig. 2 is the pure titanium material surface of the embodiment of the invention 1 a prepared bulk calcium microcosmic salt scanned photograph.
Fig. 3 is the energy spectrogram of the pure titanium material surface of the embodiment of the invention 1 prepared bulk.
Fig. 4 is the scanning picture of the pure titanium material surface of the embodiment of the invention 1 prepared bulk cell cultivation results.
Fig. 5 is the enlarged photograph of cell among Fig. 4.
Fig. 6 is a scanned photograph behind the embodiment of the invention 2 prepared block titanium alloy material surface pulse laser irradiations.
Fig. 7 is the embodiment of the invention 2 prepared block titanium alloy material surface calcium microcosmic salt scanned photograph.
Fig. 8 is that the embodiment of the invention 2 prepared block titanium alloy material surface calcium microcosmic salts can spectrogram.
Fig. 9 is the scanned photograph of the embodiment of the invention 2 prepared block titanium alloy material superficial cell cultivation results.
Figure 10 is the enlarged photograph of cell among Fig. 9.
Figure 11 is the scanned photograph of block titanium of acid etching after the sandblast or titanium alloy material superficial cell cultivation results.
Figure 12 is prepared block titanium of distinct methods or titanium alloy material surface Gegenbaur's cell secreting alkaline phosphorus phytase ability block diagram.Wherein, A is the block pure titanium material surface Gegenbaur's cell secreting alkaline phosphorus phytase ability block diagram of acid etching after the sandblast, B is the block titanium alloy material surface Gegenbaur's cell secreting alkaline phosphorus phytase ability block diagram of acid etching after the sandblast, C is the pure titanium material surface of the embodiment of the invention 1 a prepared bulk Gegenbaur's cell secreting alkaline phosphorus phytase ability block diagram, and D is the embodiment of the invention 2 prepared block titanium alloy material surface Gegenbaur's cell secreting alkaline phosphorus phytase ability block diagrams.
The specific embodiment
The first step is with 10 * 10 * 3mm
3Block pure titanium material polish step by step with 400-800 waterproof abrasive paper after, use the deionized water ultrasonic cleaning, place then the cleaning open containers stand-by;
Second step, in air, with femto-second laser pulse be arranged in the pure titanium material of the handled bulk of the first step directly over, use 10 times of object lens to focus on vertically in fact on its surface, forming the laser facula radius is the focus of 5 μ m;
The 3rd step added the hydroxyapatite suspension in the container of the first step, make liquid level exceed block titanium or titanium alloy material surface 2mm, the consisting of of used hydroxyapatite suspension:
Constituent concentration
Nanometer hydroxyapatite 20g/L
Polyvinylpyrrolidone 30g/L
Trishydroxymethylaminomethane 10g/L
Two hydration calcium chloride 5g/L
Solvent is a water
Adopt 10% rare nitric acid or watery hydrochloric acid to regulate the pH value to 4.5 of hydroxyapatite suspension.
The 4th step, the container that the 3rd step the was added the hydroxyapatite suspension 100 μ m that move up, make block pure titanium material wherein be arranged in femtosecond laser air focus top, setting the femtosecond laser machined parameters is: pulse recurrence frequency 1 KHz, 300 little joules of single pulse energies, pulse width 50 femtoseconds, pulse center wavelength 800 nanometers, the Laser Processing distance between centers of tracks is 100 μ m, laser scanning speed 0.2mm/ second, regulate femto-second laser polarized direction, make it parallel with the femtosecond laser scanning direction, the pure titanium material of this bulk soaks after 5 minutes in the hydroxyapatite suspension that is added, scan this with this femtosecond laser and be soaked in the whole surface of block pure titanium material in the hydroxyapatite suspension, block pure titanium material after the radiation treatment forms the regularly arranged peak shape raised structures of 10～20 μ m sizes and the surface that the submicron order micropore is formed, on these peak shape projections, be covered with the granule of a large amount of submicron orders, simultaneously in the load of the pure titanium material surface of this bulk the calcium microcosmic salt, make the pattern that block pure titanium material surface has the periodic regular structure of the rough peak shape projection of uniformity and porous thus, uniform roughness is promptly arranged, and load the titanium-base biomedical material of calcium microcosmic salt.
Carrying out mouse bone-forming cell on the active layer of the pure titanium material surface of the prepared bulk of present embodiment cultivates to verify its biologically active.Employed cell and cultural method are: this tests employed cell is the animal Gegenbaur's cell, takes from the mouse cranium, called after OCT-1 cell.Cell is commissioned to train foster through just, by after the transfection of viral gene calcium phosphate precipitation technology, being immortalized property becomes continuity clone again.The basic goal of carrying out cell transfecting is to increase the cell rise time, guarantees that cell has identical base attribute and physiological function in effective passage number.The OCT-1 cell is used for experimentizing after 3 days in recovery.Generally speaking, if the experiment thing is toxic to cultured cell, can show in back 48 hours in cultivation.Cell culture medium employing DMEM culture medium+volume fraction is hyclone+80U/mL gentamicin of 0.10.Under aseptic condition, the pure titanium material of the prepared bulk of present embodiment is put into culture dish, with the gluing jail of mouse tail, pour the cell suspension that modulates into, the pure titanium material of the prepared bulk of present embodiment is covered fully.Culture dish is put under 37 ± 0.5 ℃ of temperature in incubator inherence and is left standstill cultivation.Cultivate after 4 days and to take out the pure titanium material of the prepared bulk of present embodiment and drop into 3% glutaraldehyde solution immediately and fix, with the pure titanium material surface of the prepared bulk of scanning electron microscopic observation present embodiment cell adhesion condition.One group of pure titanium material of the prepared bulk of present embodiment was cultivated respectively 2,7,12 days, analyzed the mineralization ability of organizing of cell on the pure titanium material of the prepared bulk of present embodiment then with alkaline phosphoric acid enzyme method.
Scanned photograph and Fig. 2 embodiment of the invention 1 prepared titanium surface calcium microcosmic salt scanned photograph are as can be seen behind the pure titanium material surface of Fig. 1 embodiment of the invention 1 prepared bulk pulse laser irradiation, the pure titanium material surface of the prepared bulk of present embodiment has obtained having the surface of the big small peak shape of 10～20 μ m projection, on these projections, be covered with the granule of a large amount of submicron orders, and on projection visible needle-like loaded article.From the pure titanium material surface of Fig. 3 embodiment of the invention 1 prepared bulk can spectrogram energy spectrum analysis show that the composition of loaded article is Ca and P, prove that the material of the pure titanium material surface of this bulk load is the calcium microcosmic salt.This calcium microcosmic salt will can be used as the seed that cell adheres to and organize mineralising behind the implantable bioartificial body, thereby will improve the growth and the mineralization ability of osteocyte.From the scanned photograph of the pure titanium material surface of Fig. 4 embodiment of the invention 1 prepared bulk cell cultivation results as can be seen, cell at the pure titanium material surface of this bulk along the growth of creeping of projection arrangement direction orientation, and it is good in pure titanium material surface attaching situation of this bulk and growthform, compare with the cell cultivation results on block titanium of acid etching after the sandblast or titanium alloy material surface (seeing the scanned photograph of the cell cultivation results on block titanium of acid etching after Figure 11 sandblast or titanium alloy material surface), cell is not only adherent, stretch better, and cell proliferation is vigorous, presents multiple layer growth state.Fig. 5 is the enlarged photograph of cell in the pure titanium material surface growth of this bulk, visible cell tightly wraps peak shape projection and grows a large amount of pseudopodium, these pseudopodium hold on to the particle of projection at the pure titanium material surface of this bulk, illustrate that the pure titanium material surface of cell and this bulk has good binding.C among Figure 12 is the block diagram of the pure titanium material surface of the embodiment of the invention 1 prepared bulk Gegenbaur's cell Alkaline Phosphatase ability, as can be seen from the figure, cell was cultivated after 12 days, the alkaline phosphatase amount of the pure titanium material surface of the prepared bulk of present embodiment Gegenbaur's cell secretion is obviously more than the alkaline phosphatase amount (the block pure titanium material surface Gegenbaur's cell secreting alkaline phosphorus phytase ability block diagram of acid etching after seeing the A sandblast among Figure 12) of secreting through the pure titanium surface of sandblast acid etching Gegenbaur's cell, promptly the ability of the Gegenbaur's cell secreting alkaline phosphorus phytase on the block pure titanium material surface that present embodiment is handled is apparently higher than the ability through the Gegenbaur's cell secreting alkaline phosphorus phytase of the block pure titanium material surface of sandblast acid etching, and the pattern of the rough peak shape projection of the uniformity of the block pure titanium material surface that this explanation present embodiment processing obtains and the periodic regular structure of porous and the calcium-phosphate layer of load help promoting the mineralization ability of Gegenbaur's cell tissue.
The first step is with 10 * 10 * 3mm
3Block titanium alloy material polish step by step with 400-800 waterproof abrasive paper after, use the deionized water ultrasonic cleaning, place then the cleaning open containers stand-by;
Second step, in air, with femto-second laser pulse be arranged in the handled block titanium alloy material of the first step directly over, vertically use 10 times of object lens to focus on its surface, forming the laser facula radius is the focus of 5 μ m;
The 3rd step added the hydroxyapatite suspension in the container of the first step, make liquid level exceed block titanium alloy material surface 3mm, the consisting of of used hydroxyapatite suspension:
Constituent concentration
Nanometer hydroxyapatite 8g/L
Polyvinylpyrrolidone 10g/L
Trishydroxymethylaminomethane 5g/L
Two hydration calcium chloride 2g/L
Solvent is a water
Adopt 10% rare nitric acid or watery hydrochloric acid to regulate the pH value to 4 of hydroxyapatite suspension;
The 4th step, the container that the 3rd step the was added the hydroxyapatite suspension 80 μ m that move up, make block titanium alloy material wherein be arranged in femtosecond laser air focus top, setting the femtosecond laser machined parameters is: pulse recurrence frequency 1 KHz, 100 little joules of single pulse energies, pulse width 50 femtoseconds, pulse center wavelength 800 nanometers, the Laser Processing distance between centers of tracks is 10 μ m, laser scanning speed 0.8mm/ second, regulate femto-second laser polarized direction, make it parallel with the femtosecond laser scanning direction, this bulk titanium alloy material soaks after 5 minutes in the hydroxyapatite suspension that is added, scan this with this femtosecond laser and be soaked in the whole surface of block titanium alloy material in the hydroxyapatite suspension, the surface that the peak shape raised structures of 2～5 μ m sizes that the block titanium alloy material formation rule after the radiation treatment is arranged and submicron order micropore are formed, on these projections, be covered with the granule of a large amount of submicron orders, simultaneously at this bulk titanium alloy material area load calcium microcosmic salt, make the pattern that block titanium alloy material surface has the periodic regular structure of the rough peak shape projection of uniformity and porous thus, uniform roughness is promptly arranged, and load the titanium-base biomedical material of calcium microcosmic salt.
Carry out mouse bone-forming cell and cultivate to verify its biologically active on the active layer on the resulting block titanium alloy material of present embodiment surface, employed cell and cultural method are: with embodiment 1.
Scanned photograph and Fig. 7 embodiment of the invention 2 prepared block titanium alloy materials surface calcium microcosmic salt scanned photograph are as can be seen behind the pulse laser irradiations of the prepared block titanium alloy materials of Fig. 6 embodiment of the invention 2 surface, this bulk titanium alloy material surface has obtained by the peak shape projection of 2～5 μ m sizes and the surface that the submicron order micropore is formed, form visible dark loaded article in the middle of projection on these peak shape projections again by tiny particle and striped.Show from the energy spectrum analysis of Fig. 8 embodiment of the invention 2 prepared block titanium alloy material surface calcium microcosmic salts energy spectrograms, the composition of loaded article is Ca and P, the material of assert this bulk titanium alloy material area load is the calcium microcosmic salt, this calcium microcosmic salt will can be used as the seed that cell adheres to and organize mineralising behind the implantable bioartificial body, thereby will improve the growth and the mineralization ability of osteocyte.From the scanned photograph of Fig. 9 embodiment of the invention 2 prepared block titanium alloy material superficial cell cultivation results as can be seen, cell is good in this bulk titanium alloy material surface attaching situation and growthform, compare with the cell cultivation results on the block titanium alloy material surface of acid etching after the sandblast (seeing the scanned photograph of the cell cultivation results on block titanium of acid etching after Figure 11 sandblast or titanium alloy material surface), cell is not only adherent, stretching, extension is better, and cell proliferation is vigorous, presents multiple layer growth state.Figure 10 be cell at the epontic enlarged photograph of this bulk titanium alloy material, visible cell grows a large amount of pseudopodium, these pseudopodium stretch into the surface micropore in, illustrate that cell and this bulk titanium alloy material surface have good binding.D among Figure 12 is the embodiment of the invention 2 prepared block titanium alloy material surface Gegenbaur's cell Alkaline Phosphatase ability block diagrams, as can be seen from the figure, cell was cultivated after 12 days, the alkaline phosphatase amount of the prepared block titanium alloy material of present embodiment surface Gegenbaur's cell secretion is obviously more than the alkaline phosphatase amount of secreting through the titanium alloy surface Gegenbaur's cell of sandblast acid etching (the block titanium alloy material surface Gegenbaur's cell secreting alkaline phosphorus phytase ability block diagram of acid etching after seeing the B sandblast among Figure 12), promptly the ability of the lip-deep Gegenbaur's cell secreting alkaline phosphorus phytase of handling at present embodiment of block titanium alloy material is apparently higher than the ability through the Gegenbaur's cell secreting alkaline phosphorus phytase on the titanium bulk material surface of sandblast acid etching, and the pattern of the rough peak shape projection of the uniformity on the block titanium alloy material surface that this explanation present embodiment processing obtains and the periodic regular structure of porous and the calcium-phosphate layer of load help promoting the mineralization ability of Gegenbaur's cell tissue.
Other steps are all identical with embodiment 1 with condition, and difference is that the setting laser single pulse energy is 150 little joules, and laser scanning speed is 1.0mm/ second, and the Laser Processing distance between centers of tracks is 50 microns, and used hydroxyapatite suspension prescription is:
Constituent concentration
Nanometer hydroxyapatite 15g/L
Polyvinylpyrrolidone 20g/L
Trishydroxymethylaminomethane 8g/L
Two hydration calcium chloride 3g/L
Solvent is a water
Adopt 10% rare nitric acid or watery hydrochloric acid to regulate the pH value to 5 of hydroxyapatite suspension.
The pure titanium material of this bulk after the radiation treatment forms the surface of being made up of regularly arranged peak shape raised structures of 5～10 μ m size and submicron order micropore, on these peak shape projections, be covered with the granule of a large amount of submicron orders, simultaneously in the load of the pure titanium material surface of this bulk the calcium microcosmic salt, make the pattern that block pure titanium material surface has the periodic regular structure of the rough peak shape projection of uniformity and porous thus, uniform roughness is promptly arranged, and load the titanium-base biomedical material of calcium microcosmic salt.
Embodiment 4
Other steps are all identical with embodiment 1 with condition, and difference is that the gained laser single-pulse energy is 200 little joules, and laser scanning speed is 1.0mm/ second, and the Laser Processing distance between centers of tracks is 80 microns, and used hydroxyapatite suspension prescription is:
Constituent concentration
Nanometer hydroxyapatite 20g/L
Polyvinylpyrrolidone 20g/L
Trishydroxymethylaminomethane 5g/L
Two hydration calcium chloride 2g/L
Solvent is a water
Adopt 10% rare nitric acid or watery hydrochloric acid to regulate the pH value to 4.5 of hydroxyapatite suspension.
Block pure titanium material after the radiation treatment forms the surface of being made up of regularly arranged peak shape raised structures of 8～15 μ m size and submicron order micropore, on these peak shape projections, be covered with the granule of a large amount of submicron orders, simultaneously in the load of the pure titanium material surface of this bulk the calcium microcosmic salt, make the pattern that block pure titanium material surface has the periodic regular structure of the rough peak shape projection of uniformity and porous thus, uniform roughness is promptly arranged, and load the titanium-base biomedical material of calcium microcosmic salt.
Embodiment 5
Other steps are all identical with embodiment 1 with condition, and difference is that the setting laser single pulse energy is 130 little joules, and laser scanning speed is 1.0mm/ second, and the Laser Processing distance between centers of tracks is 20 microns, and used hydroxyapatite suspension prescription is:
Constituent concentration
Nanometer hydroxyapatite 10g/L
Polyvinylpyrrolidone 15g/L
Trishydroxymethylaminomethane 5g/L
Two hydration calcium chloride 2g/L
Solvent is a water
Adopt 10% rare nitric acid or watery hydrochloric acid to regulate the pH value to 4.5 of hydroxyapatite suspension.
Block pure titanium material after the radiation treatment forms the surface of being made up of regularly arranged peak shape raised structures of 3～8 μ m size and submicron order micropore, on these peak shape projections, be covered with the granule of a large amount of submicron orders, simultaneously in the load of the pure titanium material surface of this bulk the calcium microcosmic salt, make the pattern that block pure titanium material surface has the periodic regular structure of the rough peak shape projection of uniformity and porous thus, uniform roughness is promptly arranged, and load the titanium-base biomedical material of calcium microcosmic salt.
Embodiment 6
Other steps are all identical with embodiment 1 with condition, and difference is that the setting laser single pulse energy is 50 little joules, and laser scanning speed is 1.0mm/ second, and the Laser Processing distance between centers of tracks is 20 microns, and used hydroxyapatite suspension prescription is:
Constituent concentration
Nanometer hydroxyapatite 5g/L
Polyvinylpyrrolidone 5g/L
Trishydroxymethylaminomethane 2g/L
Two hydration calcium chloride 2g/L
Solvent is a water
Adopt 10% rare nitric acid or watery hydrochloric acid to regulate the pH value to 4.5 of hydroxyapatite suspension.
Block pure titanium material after the radiation treatment forms the surface of being made up of regularly arranged peak shape raised structures of 1～4 μ m size and submicron order micropore, on these peak shape projections, be covered with the granule of a large amount of submicron orders, simultaneously in the load of the pure titanium material surface of this bulk the calcium microcosmic salt, make the pattern that block pure titanium material surface has the periodic regular structure of the rough peak shape projection of uniformity and porous thus, uniform roughness is promptly arranged, and load the titanium-base biomedical material of calcium microcosmic salt.
Other steps are all identical with embodiment 1 with condition, and difference is that the setting laser single pulse energy is 50 little joules, and laser scanning speed is 0.2mm/ second, and the Laser Processing distance between centers of tracks is 10 microns, and used hydroxyapatite suspension prescription is:
Constituent concentration
Nanometer hydroxyapatite 20g/L
Polyvinylpyrrolidone 15g/L
Trishydroxymethylaminomethane 15g/L
Two hydration calcium chloride 5g/L
Solvent is a water
Adopt 10% rare nitric acid or watery hydrochloric acid to regulate the pH value to 4.5 of hydroxyapatite suspension.
Block pure titanium material after the radiation treatment forms the surface of being made up of regularly arranged peak shape raised structures of 1～6 μ m size and submicron order micropore, on these peak shape projections, be covered with the granule of a large amount of submicron orders, simultaneously in the load of the pure titanium material surface of this bulk the calcium microcosmic salt, make the pattern that block pure titanium material surface has the periodic regular structure of the rough peak shape projection of uniformity and porous thus, uniform roughness is promptly arranged, and load the titanium-base biomedical material of calcium microcosmic salt.
Embodiment 8
Other steps are all identical with embodiment 2 with condition, and difference is that the setting laser single pulse energy is 100 little joules, and laser scanning speed is 0.5mm/ second, and the Laser Processing distance between centers of tracks is 50 microns, and used hydroxyapatite suspension prescription is:
Constituent concentration
Nanometer hydroxyapatite 10g/L
Polyvinylpyrrolidone 20g/L
Trishydroxymethylaminomethane 7g/L
Two hydration calcium chloride 4g/L
Solvent is a water
Adopt 10% rare nitric acid or watery hydrochloric acid to regulate the pH value to 4.5 of hydroxyapatite suspension.
The surface that the peak shape raised structures of 3～8 μ m sizes that the block titanium alloy material formation rule after the radiation treatment is arranged and submicron order micropore are formed, on these projections, be covered with the granule of a large amount of submicron orders, simultaneously at this bulk titanium alloy material area load calcium microcosmic salt, make the pattern that block titanium alloy material surface has the periodic regular structure of the rough peak shape projection of uniformity and porous thus, uniform roughness is promptly arranged, and load the titanium-base biomedical material of calcium microcosmic salt.
Embodiment 9
Other steps are all identical with embodiment 2 with condition, and difference is that the setting laser single pulse energy is 300 little joules, and laser scanning speed is 1.0mm/ second, and the Laser Processing distance between centers of tracks is 90 microns, and used hydroxyapatite suspension prescription is:
Constituent concentration
Nanometer hydroxyapatite 12g/L
Polyvinylpyrrolidone 30g/L
Trishydroxymethylaminomethane 9g/L
Two hydration calcium chloride 5g/L
Solvent is a water
Adopt 10% rare nitric acid or watery hydrochloric acid to regulate the pH value to 5 of hydroxyapatite suspension.
The surface that the peak shape raised structures of 8～15 μ m sizes that the block titanium alloy material formation rule after the radiation treatment is arranged and submicron order micropore are formed, on these projections, be covered with the granule of a large amount of submicron orders, simultaneously at this bulk titanium alloy material area load calcium microcosmic salt, make the pattern that block titanium alloy material surface has the periodic regular structure of the rough peak shape projection of uniformity and porous thus, uniform roughness is promptly arranged, and load the titanium-base biomedical material of calcium microcosmic salt.
Claims (4)
1. the application of femtosecond laser in titanium or titanium alloy implantation material surface processing the steps include:
The first step behind the titanium or titanium alloy material polishing with bulk, is used the deionized water ultrasonic cleaning, places the cleaning open containers stand-by then;
Second step, in air, with femto-second laser pulse be arranged in handled block titanium of the first step or titanium alloy material directly over, vertically focus on its surface, forming the laser facula radius is the focus of 5mm;
The 3rd step added the hydroxyapatite suspension in the container of the first step, make liquid level exceed block titanium or titanium alloy material surface 2～3mm, the consisting of of used hydroxyapatite suspension:
Constituent concentration
Nanometer hydroxyapatite 5～20g/L
Polyvinylpyrrolidone 5～30g/L
Trishydroxymethylaminomethane 2～10g/L
Two hydration calcium chloride, 2～5g/L
Solvent is a water
The pH value of hydroxyapatite suspension is 4～5;
The 4th step, the container that the 3rd step was added the hydroxyapatite suspension 80～100 μ m that move up, make wherein block titanium or the titanium alloy material focus top that is positioned at airborne femtosecond laser, the machined parameters of setting femtosecond laser is: pulse recurrence frequency 1 KHz, 50～300 little joules of single pulse energies, pulse width 50 femtoseconds, pulse center wavelength 800 nanometers, the Laser Processing distance between centers of tracks is 10～100 μ m, laser scanning speed 0.2～1.0mm/ second, regulate femto-second laser polarized direction, make it parallel with the femtosecond laser scanning direction, this bulk titanium or titanium alloy material soak after 5 minutes in the hydroxyapatite suspension that is added, scan this with this femtosecond laser and be soaked in block titanium or the whole surface of titanium alloy material in the hydroxyapatite suspension, the block titanium after the radiation treatment or the surface of titanium alloy material are formed with regularly arranged peak shape raised structures, on these peak shape projections, be covered with the granule of submicron order, simultaneously this bulk titanium or titanium alloy material area load the calcium microcosmic salt, make the pattern of the periodic regular structure of the rough peak shape projection that has uniformity on block titanium or titanium alloy material surface and porous thus, uniform roughness is promptly arranged, and load the titanium-base biomedical material of calcium microcosmic salt.
2. according to the application of the described femtosecond laser of claim 1 in titanium or titanium alloy implantation material surface processing, it is characterized in that: the size of block titanium described in the above-mentioned first step or titanium alloy material is 10 * 10 * 3mm
3, polish step by step with 400-800 waterproof abrasive paper.
3. according to the application of the described femtosecond laser of claim 1 in titanium or titanium alloy implantation material surface processing, it is characterized in that: the focusing described in above-mentioned second step is to use 10 times of object lens to focus on.
4. according to the application of the described femtosecond laser of claim 1 in titanium or titanium alloy implantation material surface processing, it is characterized in that: the pH value of the hydroxyapatite suspension described in above-mentioned the 3rd step is 4～5, adopts 10% rare nitric acid or watery hydrochloric acid to regulate.
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