CN1695744A - Biomedicine material of titanium or titanium alloy in use for artificial bones, and preparation method - Google Patents
Biomedicine material of titanium or titanium alloy in use for artificial bones, and preparation method Download PDFInfo
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- CN1695744A CN1695744A CN 200510013811 CN200510013811A CN1695744A CN 1695744 A CN1695744 A CN 1695744A CN 200510013811 CN200510013811 CN 200510013811 CN 200510013811 A CN200510013811 A CN 200510013811A CN 1695744 A CN1695744 A CN 1695744A
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Abstract
A biomedical Ti or Ti-alloy material used as artificial bone is composed of the nano-whiskers of hydroxyapatite, the autogenic potassium titanium film (K2Ti2O5.xH2O or K2Ti8O17), and Ti or Ti-alloy chosen from Ti-Mo, Ti-Mo-Nb, Ti-Mo-Zr-Fe, and Ti-Nb-Zr. Its preparing process includes preparing Ti or Ti-alloy substrate, pretreating, and chemical reaction to form said nano-whiskers-bioactive gradient autognic potassium titanium film on said substrate.
Description
Technical field
The present invention relates to be transplanted to the intravital prosthetic material of people, specifically a kind of titanium or titanium alloy biomedical material and preparation method thereof as artificial bone.
Background technology
Because titanium and titanium alloy fracture toughness property height and superior biocompatibility, some large hospital has begun with the material of its application as artificial bone in recent years.Although titanium and titanium alloy have advantages such as good biocompatibility, it can not combine with organism self skeleton, still shows as biologically inert.Therefore, titanium or titanium alloy are carried out the focus and emphasis that surface modification becomes people's research.
At present, utilize coating technologies such as plasma spraying both at home and abroad mostly, at titanium alloy surface spraying last layer hydroxyapatite, to reach the purpose of titanium or titanium alloy being carried out surface modification.CN 1487117, CN 03104100.0, CN 1042067, CN01106471.4 disclose the method at titanium alloy surface deposited hydroxyl apatite bioactive layer, and the shortcoming of these inventions is that the bond strength between hydroxyapatite bioactive layer and titanium alloy substrate is very low.CN 1487117 discloses the method and the goods thereof of a kind of titanium alloy surface cosputtering deposited hydroxyl apatite (HA)/titanium (Ti) bioactive gradient layer, though this invention has improved the bond strength between hydroxyapatite and titanium alloy substrate to a certain extent, but owing to relate to the use of pressure sintering that the ball milling of hydroxyapatite raw material mixes powder, rake thin, expensive magnetic control sputtering device equipment and follow-up a series of processing procedures such as high compressed steam processing, seeming, operation is miscellaneous, and cost strengthens.In a word, the fatal shortcoming that hydroxyapatite itself exists is: HA itself is very crisp, easily degraded in vivo, and the thermal coefficient of expansion of the thermal coefficient of expansion of HA and titanio body does not match, this has all had a strong impact on the interface bond strength between coating and the matrix, thereby has caused coating shedding to cause the medical care problem of prosthese graft failure; In addition, with the bioactive coating material of titanium-containing compound the method that titanium or titanium alloy carry out surface modification is also begun to obtain research.CN 1490058 has disclosed a kind of preparation method of biological activity titanium or titanium alloy hard tissue implanting material, adopt electrochemistry and chemically composited surface modification, at titanium or titanium alloy surface preparation biological activity thin film, at first adopt electrochemical method to prepare certain thickness oxide-film at Ti or Ti alloy surface, adopt the chemically treated method of aqueous slkali then, form the porous cancellated titanate gel layer of one deck on the oxide-film surface, again sample is heat-treated, make cancellated titanate gel layer crystalline stateization, to immerse through the material of above-mentioned processing in the simulation of human body liquid at last, will form the apatite layer close with sclerotin, wherein the aqueous slkali of Cai Yonging is NaOH, and the titanate gel layer of formation is the sodium titanate gel layer.The shortcoming of this method is that the sodium titanate coating of surface formation is very thin, and its intensity and less stable are easily degraded, and anti-wear performance is low, may cause prosthese implantation back to cause prosthetic loosening because of the existence of material surface degraded or wear particle.
Even to this day, bioactivity coatings combines problem and remains and use titanium clinically or the titanium alloy biomedical material is transplanted to distinct issues in the human body as artificial bone with interface between matrix, how the titanium or titanium alloy matrix surface of molding artificial bone generate not only with matrix bond firmly, but also with biocompatible and combine and itself have high-intensity thin layer bioactivity coatings, be the common urgency of a current material supply section scholar and medical science person difficult problem to be solved.New method for the surface modification of developing titanium-base biomedical material, the inventor has applied for following two relevant patent: CN 200510013523.0 " preparation method of the surface micropore titanium of titanium-base biomedical material " in phase nearby, and its main purpose is to improve bioactivity coatings and titanium high base strength by porous surfaceization; " there is TiO on the surface to CN 200510013527.9
2Biomedical composite of the titanium alloy of coating and preparation method thereof ", its main purpose is to have solved bioactivity coatings better to combine problem with the interface of titanium alloy substrate, has also further improved the wear resistance and corrosion resistance and the blood compatibility of titanium alloy surface.Yet,, also need to continually develop new titanium alloy biomedical material as artificial bone in order to satisfy clinical instructions for use.
Summary of the invention
Technical problem to be solved by this invention is: a kind of titanium or titanium alloy biomedical material that is used as artificial bone and preparation method thereof is provided, the self assembly calcium phosphorous compound nano whisker that this material has/spontaneous potassium titanate thin film bio material thin-layer itself not only with matrix bond firmly, but also have superior biocompatibility, and natural combination compatible with the biological tissue that is contacted is integral in organism.
The present invention solves this technical problem the technical scheme that is adopted:
Titanium or titanium alloy biomedical material as artificial bone of the present invention, be a kind ofly to have outerly, be expressed as self assembly calcium phosphorous compound nano whisker/spontaneous potassium titanate thin film/titanium or titanium alloy biomedical material for self assembly calcium phosphorous compound nano whisker, nexine are the titanium or the titanium alloy biomedical material of the bioactivity coatings of spontaneous potassium titanate thin film.
Titanium or titanium alloy biomedical material as artificial bone of the present invention, wherein the chemical composition of self assembly calcium phosphorous compound nano whisker is a hydroxyapatite, its crystal is a hexagonal crystal system, belongs to L
6PC symmetric form and P6
3/ m space group.
Titanium or titanium alloy biomedical material as artificial bone of the present invention, wherein the main component of potassium titanate thin film is K
2Ti
2O
5.xH
2O and K
2Ti
8O
17, thickness is uniform network structure at 3～20 μ m.
Titanium or titanium alloy biomedical material as artificial bone of the present invention, wherein titanium alloy is Ti-Mo, Ti-Mo-Nb, Ti-Mo-Zr-Fe or Ti-Nb-Zr series titanium alloy.
Titanium or titanium alloy biomedical material as artificial bone of the present invention, wherein preferably Ti-15Mo-3Nb beta-titanium alloy, Ti-13Nb-13Zr beta-titanium alloy, Ti-15Mo titanium alloy, Ti-12Mo-6Zr-2Fe beta-titanium alloy of titanium alloy.
Of the present invention as the titanium of artificial bone or the preparation method of titanium alloy biomedical material, the steps include:
(1) as the titanium of artificial bone or the preparation and the pretreatment of titanium alloy substrate
Melting titanium, Ti-Mo, Ti-Mo-Nb, Ti-Mo-Zr-Fe or Ti-Nb-Zr series titanium alloy are prepared the artificial bone prosthetic material under 1600～2000 ℃ of temperature, cut into the sample of required artificial bone then through forge hot annealing doubling, this sample is cleaned to removing oil stain with acetone on ultrasonic washing unit, use liquid honing afterwards, the sample of the artificial bone that polishing is good cleans respectively to greasy dirt and the abrasive dust of removing the surface with acetone, dehydrated alcohol, deionized water on ultrasonic washing unit successively, put into drying baker at last in 37 ℃ of dryings, standby;
(2) adopt chemical reaction method to handle, form self assembly calcium phosphorous compound nano whisker/spontaneous potassium titanate thin film bio active gradient thin layer at titanium or titanium alloy surface
Earlier that (1) step pretreatment is good titanium or titanium alloy substrate sample put into nitric acid or hydrochloric acid or sulphuric acid with deionized water according to volume ratio for sour: deionized water=1～3: 1 single acid or the mixed acid solution that is mixed with, handled 5～15 hours down at 60～80 ℃, take out back deionized water ultrasonic cleaning, then putting into concentration and be the KOH solution of 2～8mol/L handled 5～24 hours down in 60～110 ℃, use twice of deionized water ultrasonic cleaning to totally afterwards, afterwards in drying baker 37 ℃ of placements until drying, next sample is carried out pre-calcification and handle, be about to 0.5～1.5mol/L K that titanium behind the acid-alkali treatment or titanium alloy substrate sample are placed on 37～45 ℃
2HPO
4In the solution 10～20 hours, again at the saturated Ca of room temperature (OH)
2Soaked in the solution 5～10 hours, take out the back and use deionized water drip washing, put into 37 ℃ simulated body fluid at last and cultivate self assembly calcium phosphorous compound nano whisker/spontaneous potassium titanate thin film/titanium or titanium alloy biomedical material that 2～5 natural law promptly obtain being used as artificial bone.
The english abbreviation of simulated body fluid is SBF.
The invention has the beneficial effects as follows:
(1) have superior biocompatibility, and natural combination compatible with the biological tissue that is contacted is integral in organism.
The corrosion resistance that has not only increased substantially titanium or titanium alloy with the calcium phosphorous compound nano whisker/spontaneous potassium titanate thin film/titanium or the titanium alloy biomedical material of the inventive method preparation, and on the basis that guarantees the superior biocompatibility of this kind biomedical material, the self assembly of the nano calcium phosphorous compound whisker that forms in spontaneous potassium titanate thin film/titanium or the absorption of titanium alloy biomedical material surface deposition by the calcium in the biological fluid, phosphonium ion, make this material surface can be compatible in organism with the biological tissue that is contacted and natural combination be integral.This has obtained good confirmation by the cell in vitro culture experiment.The cell in vitro culture experiment shows: osteoblast is in material surface apposition growth rate, and calcium phosphorous compound nano whisker of the present invention/spontaneous potassium titanate thin film/titanium or titanium alloy biomedical material are pure titanium or titanium alloy substrate 2.3 times.The biocompatibility and the associativity of self-assembled nanometer calcium phosphorous compound whisker of the present invention/spontaneous potassium titanate thin film/titanium or titanium alloy biomedical material not only are better than pure titanium or titanium alloy itself, its biological associativity also is higher than the HA/Ti biomaterial, its major reason is that the calcium phosphorous compound in the biological fluid has produced the self-assembled structures of calcium phosphorous compound nano whisker on spontaneous potassium titanate thin film/titanium or titanium alloy biomaterial surface, make material surface bioactivity coatings of the present invention combine, thereby improved the biomechanics adaptability of this kind implantation prosthese greatly with giving birth to the biology that can form gradient transition between soma.
(2) combine firmly with titanium or titanium alloy substrate.
Because K
2Ti
2O
5.xH
2Potassium ion among the O has very high activity, can be from its interlayer structure stripping and calcium ion replace, have very strong calcium phosphorus absorbability, and a K
2Ti
8O
17Comparatively stable and its intensity is higher, thus make the potassium titanate biological activity thin film of formation have very high stability and intensity again.Because the oxide layer of titanium or titanium alloy surface provides the condition of in-situ authigenic for the formation of potassium titanate, so can form firm interface between potassium titanate thin film and matrix and combine.By measuring, potassium titanate thin film and titanium alloy-based body interface that the spontaneous reaction of titanium of the present invention or titanium alloy surface generates have formed firm chemical bonding, in addition, the thickness that records this thin layer by THICKNESS GAUGE FOR THE MEASUREMENT OF THIN FOILS is at 3～20 μ m, be uniform network structure, and have good intensity and stability, for the nano calcium phosphorous compound product must self assembly good chemical reaction condition and structural condition is provided, make the two can form firm chemical bond and structure gradient combination.
(3) has practicality.
Preparation method of the present invention can form the layer of even bioactive layer on the surface of complex-shaped prosthetic material, and it is low for equipment requirements, greatly reduce the preparation cost of this biomaterial, help its promotion and application as the material of hard tissue repair and replacement.
Except as mentioned above, beneficial effect of the present invention also is embodied in the following specific implementation method.
Description of drawings
The present invention is further described below in conjunction with drawings and Examples.
Fig. 1 is that titanium of the present invention or titanium alloy are handled the X-ray diffracting spectrum that the rear surface forms spontaneous potassium titanate thin film through chemical method.
Fig. 2 is the SEM pattern of titanium of the present invention or titanium alloy surface in-situ authigenic metatitanic acid potassium thin film.
Fig. 3 is the X-ray diffracting spectrum of material surface self-assembled nanometer calcium phosphorous compound whisker sedimentary deposit of the present invention.
Fig. 4 is the microstructure of material surface self-assembled nanometer calcium phosphorous compound whisker sedimentary deposit of the present invention under SEM and TEM.
Fig. 5 is the light microscopic photo that material surface cell in vitro of the present invention is cultivated.
The specific embodiment
From diffracting spectrum analysis shown in Figure 1 as can be known, the phase composition of spontaneous potassium titanate thin film mainly is K
2Ti
2O
5.xH
2O and K
2Ti
8O
17, contain a spot of Ti
2O.Because K
2Ti
2O
5.xH
2Potassium ion among the O has very high activity, can be from its interlayer structure stripping and calcium ion replace, have very strong calcium phosphorus absorbability, provide good chemical reaction condition for sclerotin apatite forms on its surface, and K
2Ti
8O
17Comparatively stable and intensity is higher, thus make the potassium titanate biological activity thin film of formation have very high stability and intensity again.Because the oxide layer of titanium or titanium alloy surface is the chemical reaction condition that in-situ authigenic was carried in the formation of potassium titanate, so has formed firm interface between potassium titanate thin film and matrix and combined.
(a) is titanio surface in-situ authigenic metatitanic acid potassium thin film among Fig. 2; (b) be Ti-13Nb-13Zr alloy surface in-situ authigenic metatitanic acid potassium thin film; (c～e) pass through the in-situ authigenic metatitanic acid potassium thin film that different chemical treatments obtains for the Ti-12Mo-6Zr-2Fe alloy surface; (f) be Ti-15Mo alloy surface in-situ authigenic metatitanic acid potassium thin film; (g～h) handle the in-situ authigenic metatitanic acid potassium thin film that obtains through different chemical for the Ti-15Mo-3Nb alloy surface; The potassium titanate thin film of observing visible titanium or titanium alloy surface formation from figure all is uniform network structure, and this porous netted gel layer is grown up at its surperficial forming core for sclerotin apatite provides good structural condition.
Know that from the X-ray diffracting spectrum analysis of self-assembled nanometer calcium phosphorous compound whisker sedimentary deposit shown in Figure 3 this calcium phosphorous compound is a hydroxyapatite.
(a) is the pattern that the high power of the SEM of calcium phosphorous compound whisker sedimentary deposit is amplified among Fig. 4, can be clearly seen that the nanometer self-assembled structures from figure, and hydroxide radical phosphorite nanocrystalline must be together interlaced; (b) be the TEM photo of hydroxyapatite, visible hydroxyapatite is the acicular whisker of nanometer, and this is typical hydroxyapatite structure.Because titanium or titanium alloy surface in-situ authigenic metatitanic acid potassium thin film have participated in the chemical reaction that nanometer hydroxyapatite forms, therefore can form a firm chemical gradient combination between the two, and structure gradient has improved the biomechanics adaptability of material of the present invention greatly.
(a) is the light microscopic photo of cell culture in the time of 2 days among Fig. 5; (b) be the light microscopic photo of cell culture in the time of 6 days.(b) two figure are as can be known from (a), the form of cell is normal, prolongation along with incubation time, osteoblast is in continuous propagation, and cell has formed good attached wall growth tendency at the edge of material, this shows that this kind material has the good cell compatibility, if the immediate union that implants and to help promoting between damaged bone tissue and implant.
Embodiment 1
(1) as the titanium of artificial bone or the preparation and the pretreatment of titanium alloy substrate
The melting titanium is prepared the artificial bone prosthetic material under 1600 ℃ of temperature, cut into the sample of required artificial bone then through the forge hot annealed wire, this sample was cleaned 20 minutes with acetone on ultrasonic washing unit, remove oil stain, use 80#, 280#, 400#, 600#, 800# liquid honing afterwards successively, the sample of the artificial bone that polishing is good cleaned respectively 20 minutes with acetone, dehydrated alcohol, deionized water on ultrasonic washing unit successively, remove the greasy dirt and the abrasive dust on surface, put into drying baker at last in 37 ℃ of dryings, standby;
(2) adopt chemical reaction method to handle, form self assembly calcium phosphorous compound nano whisker/spontaneous potassium titanate bio-active gradient thin layer at titanium or titanium alloy surface
The sample of earlier that (1) step pretreatment is good artificial bone is put into the acid solution that nitric acid and deionized water are mixed with according to 3: 1 volume ratio, handled 10 hours down at 60 ℃, take out back deionized water ultrasonic cleaning, then putting into concentration and be the KOH solution of 8mol/L handled 12 hours down in 65 ℃, used the deionized water ultrasonic cleaning afterwards 20 minutes, clean after twice 37 ℃ of dryings 24 hours, its pattern is shown in Fig. 2 (a), next sample is carried out pre-calcification and handle, soon the sample behind the acid-alkali treatment is placed on 45 ℃ 0.5mol/L K
2HPO
4In the solution 20 hours, again at the saturated Ca of room temperature (OH)
2Soaked 10 hours in the solution, take out the back and use deionized water drip washing, put into 37 ℃ simulated body fluid at last and cultivate self assembly calcium phosphorous compound nano whisker/spontaneous potassium titanate thin film/titanium or titanium alloy biomedical material that 2 natural law promptly obtain being used as artificial bone.
Embodiment 2
(1) as the titanium of artificial bone or the preparation and the pretreatment of titanium alloy substrate
Melting Ti-13Nb-13Zr beta-titanium alloy is prepared the artificial bone prosthetic material under 1700 ℃ of temperature, cut into the sample of required artificial bone then through the forge hot annealed wire, just this sample cleaned 20 minutes with acetone on ultrasonic washing unit, remove oil stain, use 80# afterwards successively, 280#, 400#, 600#, the 800# liquid honing, the sample of the artificial bone that polishing is good is used acetone successively on ultrasonic washing unit, dehydrated alcohol, deionized water cleaned respectively 20 minutes, remove the greasy dirt and the abrasive dust on surface, put into drying baker at last in 37 ℃ of dryings, standby;
(2) adopt chemical reaction method to handle, form self assembly calcium phosphorous compound nano whisker/spontaneous potassium titanate bio-active gradient thin layer at titanium or titanium alloy surface
The sample of earlier that (1) step pretreatment is good artificial bone is put into sulphuric acid and deionized water according to the acid solution that 1: 1 volume ratio is mixed with, and handles 7 hours down at 70 ℃, uses the deionized water ultrasonic cleaning after taking out.Then putting into concentration and be the KOH solution of 3mol/L handled 15 hours down in 80 ℃, used the deionized water ultrasonic cleaning afterwards 20 minutes, clean after twice 37 ℃ of dryings 24 hours, its pattern is shown in Fig. 2 (b), next sample is carried out pre-calcification and handle, soon the sample behind the acid-alkali treatment is placed on 43 ℃ 0.8mol/L K
2HPO
4In the solution 18 hours, again at the saturated Ca of room temperature (OH)
2Soaked 8 hours in the solution, take out the back and use deionized water drip washing, put into 37 ℃ simulated body fluid at last and cultivate self assembly calcium phosphorous compound nano whisker/spontaneous potassium titanate thin film/titanium or titanium alloy biomedical material that 3 natural law promptly obtain being used as artificial bone.
Embodiment 3
(1) as the titanium of artificial bone or the preparation and the pretreatment of titanium alloy substrate
Melting Ti-12Mo-6Zr-2Fe beta-titanium alloy is prepared the artificial bone prosthetic material under 1800 ℃ of temperature, cut into the sample of required artificial bone then through the forge hot annealed wire, just this sample cleaned 20 minutes with acetone on ultrasonic washing unit, remove oil stain, use 80# afterwards successively, 280#, 400#, 600#, the 800# liquid honing, the sample of the artificial bone that polishing is good is used acetone successively on ultrasonic washing unit, dehydrated alcohol, deionized water cleaned respectively 20 minutes, remove the greasy dirt and the abrasive dust on surface, put into drying baker at last in 37 ℃ of dryings, standby;
(2) adopt chemical reaction method to handle, form self assembly calcium phosphorous compound nano whisker/spontaneous potassium titanate bio-active gradient thin layer at titanium or titanium alloy surface
Earlier the good sample of (1) step pretreatment is put into hydrochloric acid, nitric acid, be respectively 1: 1 according to volume ratio with deionized water respectively with sulphuric acid, 2: 1, in the mixed acid solution that is mixed with at 1: 1, handled 15 hours down at 60 ℃, take out back deionized water ultrasonic cleaning, then putting into concentration and be the KOH solution of 2mol/L handled 5 hours down in 110 ℃, used the deionized water ultrasonic cleaning afterwards 20 minutes, clean after twice 37 ℃ of dryings 24 hours, its pattern is respectively as Fig. 2 (shown in the c～e), next sample is carried out pre-calcification and handle, soon the sample behind the acid-alkali treatment is placed on 40 ℃ 1.0mol/L K
2HPO
4In the solution 15 hours, again at the saturated Ca of room temperature (OH)
2Soaked 8 hours in the solution, take out back deionized water drip washing.Put into 37 ℃ simulated body fluid at last and cultivate self assembly calcium phosphorous compound nano whisker/spontaneous potassium titanate thin film/titanium or titanium alloy biomedical material that 3 natural law promptly obtain being used as artificial bone.
Embodiment 4
(1) as the titanium of artificial bone or the preparation and the pretreatment of titanium alloy substrate
Melting Ti-15Mo titanium alloy prepares the artificial bone prosthetic material under 1900 ℃ of temperature, cut into the sample of required artificial bone then through the forge hot annealed wire, just this sample cleaned 20 minutes with acetone on ultrasonic washing unit, remove oil stain, use 80#, 280#, 400#, 600#, 800# liquid honing afterwards successively, the sample of the artificial bone that polishing is good cleaned respectively 20 minutes with acetone, dehydrated alcohol, deionized water on ultrasonic washing unit successively, remove the greasy dirt and the abrasive dust on surface, put into drying baker at last in 37 ℃ of dryings, standby;
(2) adopt chemical reaction method to handle, form self assembly calcium phosphorous compound nano whisker/spontaneous potassium titanate bio-active gradient thin layer at titanium or titanium alloy surface
Earlier the good sample of (1) step pretreatment is put into nitric acid and deionized water according to the acid solution that 3: 1 volume ratio is mixed with, handled 5 hours down, use the deionized water ultrasonic cleaning after taking out at 80 ℃.Then putting into concentration and be the KOH solution of 2mol/L handled 24 hours down in 60 ℃, used the deionized water ultrasonic cleaning afterwards 20 minutes, clean after twice 37 ℃ of dryings 24 hours, its pattern is shown in Fig. 2 (f), next sample is carried out pre-calcification and handle, soon the sample behind the acid-alkali treatment is placed on 38 ℃ 1.2mol/L K
2HPO
4In the solution 12 hours, again at the saturated Ca of room temperature (OH)
2Soaked 6 hours in the solution, take out back deionized water drip washing.Put into 37 ℃ simulated body fluid at last and cultivate self assembly calcium phosphorous compound nano whisker/spontaneous potassium titanate thin film/titanium or titanium alloy biomedical material that 4 natural law promptly obtain being used as artificial bone.
Embodiment 5
(1) as the titanium of artificial bone or the preparation and the pretreatment of titanium alloy substrate
Melting Ti-15Mo-3Nb beta-titanium alloy is prepared the artificial bone prosthetic material under 2000 ℃ of temperature, cut into the sample of required artificial bone then through the forge hot annealed wire, just this sample cleaned 20 minutes with acetone on ultrasonic washing unit, remove oil stain, use 80#, 280#, 400#, 600#, 800# liquid honing afterwards successively, the sample of the artificial bone that polishing is good cleaned respectively 20 minutes with acetone, dehydrated alcohol, deionized water on ultrasonic washing unit successively, removed the greasy dirt and the abrasive dust on surface.Put into drying baker at last in 37 ℃ of drying for standby.
(2) adopt chemical reaction method to handle, form self assembly calcium phosphorous compound nano whisker/spontaneous potassium titanate bio-active gradient thin layer at titanium or titanium alloy surface
Earlier the good sample of (1) step pretreatment is put into the acid solution that nitric acid and deionized water are mixed with according to 3: 1 volume ratio, handled 10 hours down at 60 ℃, take out back deionized water ultrasonic cleaning, then putting into concentration respectively and be the KOH solution of 2mol/L and 4mol/L handled 5 hours down in 100 ℃, used the deionized water ultrasonic cleaning afterwards 20 minutes, clean after twice 37 ℃ of dryings 24 hours, its pattern respectively as Fig. 2 (g) (h) shown in, next sample is carried out pre-calcification and handle, soon the sample behind the acid-alkali treatment is placed on 37 ℃ 1.5mol/L K
2HPO
4In the solution 10 hours, in the saturated Ca of room temperature (OH) 2 solution, soaked 5 hours again, take out back deionized water drip washing.Put into 37 ℃ simulated body fluid at last and cultivate self assembly calcium phosphorous compound nano whisker/spontaneous potassium titanate thin film/titanium or the titanium alloy biomedical material that promptly obtained in 5 days as artificial bone.
Embodiment 6
The biocompatibility of nano calcium phosphorous compound whisker of the present invention/spontaneous potassium titanate thin film/titanium or titanium alloy bio-medical material and evaluated biological activity test.
Carry out external osteoblast (OCT-1 cells) culture experiment, original inoculum density is 1.5 * 10
4Individual/ml, cultivate after 6 days the superficial cell density of material of the present invention and breed nearly 9.3 times, reach 13.9 * 10
4Individual/ml, and living cells has intensive attached wall growth tendency thereon, and form stronger biology absorption with it, show the good cell compatibility, as shown in Figure 5.
Claims (6)
1. be used as the titanium or the titanium alloy biomedical material of artificial bone, it is characterized in that: be a kind ofly to have outerly, be expressed as self assembly calcium phosphorous compound nano whisker/spontaneous potassium titanate thin film/titanium or titanium alloy biomedical material for self assembly calcium phosphorous compound nano whisker, nexine are the titanium or the titanium alloy biomedical material of the bioactivity coatings of spontaneous potassium titanate thin film.
2. according to claim 1 described titanium or titanium alloy biomedical material as artificial bone, it is characterized in that: wherein the chemical composition of self assembly calcium phosphorous compound nano whisker is a hydroxyapatite, and its crystal is a hexagonal crystal system, belongs to L
6PC symmetric form and P6
3/ m space group.
3. according to claim 1 described titanium or titanium alloy biomedical material as artificial bone, it is characterized in that: wherein the main component of potassium titanate thin film is K
2Ti
2O
5.xH
2O and K
2Ti
8O
17, thickness is uniform network structure at 3～20 μ m.
4. according to claim 1 described titanium or titanium alloy biomedical material as artificial bone, it is characterized in that: wherein titanium alloy is Ti-Mo, Ti-Mo-Nb, Ti-Mo-Zr-Fe or Ti-Nb-Zr series titanium alloy.
5. according to claim 4 described titanium or titanium alloy biomedical material as artificial bone, it is characterized in that: wherein titanium alloy is Ti-15Mo-3Nb beta-titanium alloy, Ti-13Nb-13Zr beta-titanium alloy, Ti-15Mo titanium alloy, Ti-12Mo-6Zr-2Fe beta-titanium alloy.
6. claim 1 is described as the titanium of artificial bone or the preparation method of titanium alloy biomedical material, it is characterized in that step is:
(1) as the titanium of artificial bone or the preparation and the pretreatment of titanium alloy substrate
Melting titanium, Ti-Mo, Ti-Mo-Nb, Ti-Mo-Zr-Fe or Ti-Nb-Zr series titanium alloy are prepared the artificial bone prosthetic material under 1600～2000 ℃ of temperature, cut into the sample of required artificial bone then through forge hot annealing doubling, this sample is cleaned to removing oil stain with acetone on ultrasonic washing unit, use liquid honing afterwards, the sample of the artificial bone that polishing is good cleans respectively to greasy dirt and the abrasive dust of removing the surface with acetone, dehydrated alcohol, deionized water on ultrasonic washing unit successively, put into drying baker at last in 37 ℃ of dryings, standby;
(2) adopt chemical reaction method to handle, form self assembly calcium phosphorous compound nano whisker/spontaneous potassium titanate thin film bio active gradient thin layer at titanium or titanium alloy surface
Earlier that (1) step pretreatment is good titanium or titanium alloy substrate sample put into nitric acid or hydrochloric acid or sulphuric acid with deionized water according to volume ratio for sour: deionized water=1～3: 1 single acid or the mixed acid solution that is mixed with, handled 5～15 hours down at 60～80 ℃, take out back deionized water ultrasonic cleaning, then putting into concentration and be the KOH solution of 2～8mol/L handled 5～24 hours down in 60～110 ℃, use twice of deionized water ultrasonic cleaning to totally afterwards, afterwards in drying baker 37 ℃ of placements until drying, next sample is carried out pre-calcification and handle, be about to 0.5～1.5mol/L K that titanium behind the acid-alkali treatment or titanium alloy substrate sample are placed on 37～45 ℃
2HPO
4In the solution 10～20 hours, again at the saturated Ca of room temperature (OH)
2Soaked in the solution 5～10 hours, take out the back and use deionized water drip washing, put into 37 ℃ simulated body fluid at last and cultivate self assembly calcium phosphorous compound nano whisker/spontaneous potassium titanate thin film/titanium or titanium alloy biomedical material that 2～5 natural law promptly obtain being used as artificial bone.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104532213A (en) * | 2015-01-08 | 2015-04-22 | 吉林大学 | Preparation method of medical implant material surface function atom doped molecular sieve layer |
| CN106163580A (en) * | 2014-03-24 | 2016-11-23 | 混合金属股份公司 | For the method manufacturing the porous metal material for biomedical applications and the material obtained by described method |
| CN110438484A (en) * | 2019-07-11 | 2019-11-12 | 西安交通大学 | A kind of preparation method of HA nano-array bioactivity coatings |
| CN112451743A (en) * | 2020-12-07 | 2021-03-09 | 嘉兴海聚兴港新材料科技有限公司 | Bioactive coating material for surface of artificial bone |
| WO2022222996A1 (en) * | 2021-04-23 | 2022-10-27 | 李彦军 | Nano-titanate, nano-titanic acid, and nano-tio2 containing doping ag, preparation method therefor and use thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1490058A (en) * | 2002-10-18 | 2004-04-21 | 中国科学院金属研究所 | Preparing method for biological active peptide and titanium alloy hard tissue implanting material |
| CN2631510Y (en) * | 2003-01-20 | 2004-08-11 | 严伟祺 | Artificial bone made from titanium metal with high calcium and phosphorus composite layers thereon |
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2005
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106163580A (en) * | 2014-03-24 | 2016-11-23 | 混合金属股份公司 | For the method manufacturing the porous metal material for biomedical applications and the material obtained by described method |
| CN106163580B (en) * | 2014-03-24 | 2020-06-26 | 混合金属股份公司 | Method for manufacturing a porous metal material for biomedical applications and material obtained by said method |
| CN104532213A (en) * | 2015-01-08 | 2015-04-22 | 吉林大学 | Preparation method of medical implant material surface function atom doped molecular sieve layer |
| CN110438484A (en) * | 2019-07-11 | 2019-11-12 | 西安交通大学 | A kind of preparation method of HA nano-array bioactivity coatings |
| CN112451743A (en) * | 2020-12-07 | 2021-03-09 | 嘉兴海聚兴港新材料科技有限公司 | Bioactive coating material for surface of artificial bone |
| WO2022222996A1 (en) * | 2021-04-23 | 2022-10-27 | 李彦军 | Nano-titanate, nano-titanic acid, and nano-tio2 containing doping ag, preparation method therefor and use thereof |
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| CN100341587C (en) | 2007-10-10 |
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