CN100525729C - Permanent implanted artificial bone and its preparation method - Google Patents
Permanent implanted artificial bone and its preparation method Download PDFInfo
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- CN100525729C CN100525729C CNB2006100456382A CN200610045638A CN100525729C CN 100525729 C CN100525729 C CN 100525729C CN B2006100456382 A CNB2006100456382 A CN B2006100456382A CN 200610045638 A CN200610045638 A CN 200610045638A CN 100525729 C CN100525729 C CN 100525729C
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Abstract
An artificial bone for permanent replanting, employing the memorable alloy of solid NiTi shape as base material, with porous coating on the surface, and the characteristics are in that: the said porous coating is prepared through laser reaction, the coating and the base material are combined in alloy. The artificial bone not only possesses the strength and modulus of the solid NiTi, but also possesses good bioavailability.
Description
Technical field:
The present invention relates to a kind of permanent novel artificial bone material technology of preparing, the synthesizing porous biomimetic features coating of a kind of laser reactive powder technology and prescription are provided especially, can significantly improve the biocompatibility of NiTi marmem at the porous coating of NiTi marmem surface preparation, help the fixing and steady in a long-term existence of implant in tissue.
Background technology:
Bone and articular system are tissue and the organs that human body bears load, reparation after they are damaged and alternate material should have higher mechanical strength, thereby metallic biomaterial is orthopaedic main material always, and in the fields such as manufacturing that medically are widely used in the substituting of sclerous tissues, reparation and medical apparatus and instruments.For the surgery graft materials, owing to have special mechanical performance and corrosion resistance, be most important up to now bio-medical material as biocompatibility metal or alloy Ti, Ti6A14V, Co-Cr, NiTi marmem.The most attractive in these materials is the NiTi marmem, its shape memory effect, super-elasticity, damping capacity and excellent anticorrosive and mechanical property, be acknowledged as a kind of ideal, promising surgery embedded material, and obtained to use widely.Yet, metal material and osseous tissue are being formed with widely different in nature, usually can not as bioactive materials, combine with osseous tissue generation chemical bond, often form the fibrous tissue film after making in the metal implant, metal-bone interface can not stable bond, causes implant loosening and come off easily.Simultaneously as implant, the Young's modulus of metal material is far above skeleton, be respectively 115,110 and 23GPa as the Young's modulus of Ti6A14V, NiTi marmem and skeleton, the high elastic modulus of alloy, high rigidity can cause the mechanical compatibility between implant and the bone not good enough, the mechanics mismatch of this alloy and skeleton will cause stress shielding, generation is to disadvantageous stress concentration of human body and bone resorption, be difficult to integrate, limited the transmission of the fixing and human motion of implanting tissue and tissue so inevitably with bone.
In order to alleviate the deficiency of the top entity metal implant material of being mentioned, the research of porous metals embedded material has obtained the attention of height, opening porous organization makes skeletal tissue be grown to serve as possibility in porous material, can strengthen the strong bonded between embedded material and skeleton.Because its biocompatibility and shape memory effect, porous NiTi shape memory alloy has obtained paying close attention to widely as a kind of promising synthetic bone material, and might substitute oral cavity, last jawbone and tiny skeleton.The method for preparing at present porous NiTi shape memory alloy mainly contains powder metallurgic method, self propagating high temperature synthetic method etc., because this is a new field, the article of achievement of having delivered and report porous NiTi shape memory alloy performance is less.People such as Li Bingyun, Li Yonghua adopts Ni, Ti, TiH
2The agglomerating method of mixed-powder has prepared porous NiTi shape memory alloy, and the pore-size of the porous material 60% of preparation is more than the 400 μ m, and the optimum size range of growth hole is 100-400 μ m in the sclerous tissueses such as skeleton.The tissue of porous material depends on synthetic preheat temperature and ignition temperature, can Os Elephatis bone system carry like that in order to make the porous NiTi alloy material, and porous NiTi alloy must have rational strength and the Young's modulus that approaches skeleton.Though the porous of porous NiTi alloy material and mechanical performance may be controlled, the research of relevant this respect yet there are no report.
Thieme has prepared porous coating with powder metallurgy method at conventional Ti surface sintering, this coating is by the Ti powder constituent of multilamellar varying particle size, the direction of growth is perpendicular to major axis, the Young's modulus that makes coating with this process is reduced to the level of skeleton by the solid material value, this gradient Ti alloy coat has improved the compatibility of material structure, makes it might become the permanent graft materials that substitutes skeleton.Yang etc. have preset gradient Ti coating at Ti alloy implantation material surface with the method for plasma spraying, powder with three kinds of different sizes is set up three layers of coating on the Ti surface, obtain gradient porous coating, but the subject matter of these coatings and plasma spraying technology is the combination of matrix and coating is physical bond, rather than metallurgical binding.
Have the elementary composition pottery of Ca, P in the natural bone, (HA) accounts for 60% of bone component as hydroxyapatite, thereby people adopt hydroxyapatite to carry out plasma spraying as coating material.The in-vivo embed evidence, hydroxyapatite coating layer can promote the chemical bond of bone forcefully, has quite high biocompatibility, can accelerate the growth of new bone, and be applied to clinical, but people's bone of hydroxyl apatite coating and artificial joint on mechanical property still existing problems.Thermal coefficient of expansion (15 * 10 as HA
-6K
-1) than titanium alloy (8.8 * 10
-6K
-1) much bigger, and the intensity of coating and fracture toughness are relatively poor, and the adhesion of coating and matrix is not high enough, unsatisfactory as its long-term clinical effectiveness of embedded material, especially to younger patient and the bigger patient of activity, crash rate is higher, and often several Nian Houxu perform the operation once more.
Summary of the invention:
The object of the present invention is to provide a kind of permanent novel artificial bone and technology of preparing thereof, the prepared artificial bone that goes out had both had the intensity and the modulus of entity NiTi alloy artificial bone, possessed excellent biological compatibility again.
Another object of the present invention provides a kind of coating of preparing porous material by laser synthesis reaction, utilizes this coating can realize the preparation of porous NiTi alloy material, and the described porous NiTi alloy material property of preparing is good.
The present invention specifically provides a kind of permanent implanted artificial bone, with entity NiTi marmem is base material, the surface has porous coating, it is characterized in that: described porous coating is by the synthetic preparation of laser reactive, and coating is excellent metallurgical with matrix and combines.
In the permanent implanted artificial bone of the present invention, the structure of described porous coating is to be made of the support frame of coating coralliform Ti-Ni intermetallic compound, be distributed with the hole of reduced size and disperse distribution, the Flos Mume shape TiN wild phase of size between 0.5～1 μ m on the skeleton, and around skeleton, be evenly distributed with size interconnected pore in 4～20 mu m ranges.
In the permanent implanted artificial bone of the present invention, the thickness of described porous coating is 250～400 μ m, and the coating composition distribution gradient is promptly increased progressively to coating surface element ti/Ni gradually by matrix.
The present invention also provides the preparation method of above-mentioned permanent implanted artificial bone, it is characterized in that the synthetic technological parameter of laser reactive is:
Handle early stage: matrix material NiTi marmem base material is standby after polishing, sandblast, acetone cleaning, sample surfaces roughness R
a=0.2 μ m;
Alloy powder: percentage by weight is 20～80% NiTi marmem powder, Ni-49.6at% wherein, and Ti-50.4at%, granularity is 43 μ m, surplus is the TiH2 powder; This powder is commercial purity, and its granularity is 38 μ m;
To be modulated into pasty state through the alloy powder of batch mixing and be preset in the NiTi alloy surface, the fore-put powder layer thickness is 0.7mm, through 80 ℃ of oven dry 4h;
The sample of oven dry is placed the controlled atmosphere reative cell, and Laser Surface Treatment adopts 2KW continuous wave Nd-YAG laser instrument, laser beam wavelength 1.06 μ m, the ZnSe lens focus, focal length 100mm, the minimum movement amplitude of laser works platform is 0.01mm, it is 50% that large-area laser is handled the scanning overlapping rate;
Laser power density scope: 10～25MJmm
-2
Under nitrogen protection, carry out reaction protection gas N
2(purity is 99.95%) flow 15～35L/min.
In the preparation method of the permanent implanted artificial bone of the present invention, the laser power density scope is preferably: 16～20MJmm
-2
In the preparation method of the permanent implanted artificial bone of the present invention, reaction protection gas N
2Flow is preferably 25～301/min.
In the permanent implanted artificial bone preparation method of the present invention, the percentage by weight of described NiTi marmem powder is preferably 40～60%.
In addition, the present invention also provides a kind of powder of preparing porous material by laser synthesis reaction, and described powder is 20～80% the NiTi marmem powder and the TiH of surplus by percentage by weight
2Powder constituent;
In the powder of preparing porous material by laser synthesis reaction of the present invention, the percentage by weight of NiTi marmem powder is preferably 40～60%.
In the powder of preparing porous material by laser synthesis reaction of the present invention,, can add 2～10% high molecular polymer during use in addition as binding agent in order to prevent splash.Described high molecular polymer is preferably polyvinyl alcohol.
The present invention uses for reference the successful experience of powder metallurgy and plasma spraying, adopt the laser irradiation reactive synthesis technique, in the bionical coating of NiTi marmem surface preparation porous NiTi, make the inert metal material surface realize the biological activity modification, can make the metal bone substitution material both keep the high mechanical strength of metal material, biological activity is arranged again, and the elastic modelling quantity of metal activation modified layer adjusted to the natural bone level, make load in osseous tissue and the metal material via this activation gradient layer transmission, more help reducing the stress shielding effect, solve the long-standing mechanical compatibility problem of bone substitution material, thereby help building again of bone and stablizing of implant.Preparation by the bionical coating of porous, improve the structure compatible of embedded material and skeleton, make it can adhere to and hold bone and its cells such as chondrocyte, osteoprogenitor cell, osteoblast, has the osteoblastic ability of regulation and control, provide active somatic cell existence essential nutrition channel, the final reconstruction bone that has vitality as support that forms is in vivo realized the permanent reparation of pathological changes and defective bone, the new way of a bone tissue engineer of developing.No matter this research is in theory, still all is significant in the clinical medicine application facet.Compare with existing medical embedded metal material, the present invention both can remedy the adverse effect that whole porous NiTi shape memory alloy is difficult to bear bigger load and fatigue behaviour is produced, the intensity and the fracture toughness that can overcome hydroxyapatite bioactive coating again are relatively poor, the drawback that coating and basal body binding force are not high enough.When giving material high strength osteogenic activity, make it to have good pore structure and certain mechanical strength, can develop a kind of novel artificial bone embedded material.
Description of drawings:
Fig. 1 is the synthesizing porous plater schematic diagram of laser reactive, and 1 can conduct laser glass among the figure, 2 laser heads, 3 gas outlets, protection chambers 4,5 samples, 6 laser beams, 7 nitration cases, 8 air inlets;
Fig. 2 is the porous coating optical microscope photograph, (a) sample B wall scroll, (b) sample C wall scroll, (c) scanning of sample B overlap joint.;
Fig. 3 is B, C sample overlap joint scanning porous coating surface OM pattern, (a) B sample, (b) C sample;
Fig. 4 is the alloy powder x-ray diffraction pattern, (a) NiTi alloy powder, (b) B sample powder;
Fig. 5 is the laser modified layer of A, B, three kinds of samples of a C X-ray diffraction spectrum;
Fig. 6 is the laser modified layer cross section SEM of a porous pattern;
Fig. 7 is the local enlarged photograph of Ni-Ti intermetallic compound;
Fig. 8 is a porous material pore appearance structure, (a) opening hole, (b) enclosed type hole;
Fig. 9 is a sample B surface pore structure SEM photo;
Figure 10 is two kinds of sample surfaces roughness, (a) laser surface modification sample, (b) NiTi substrate alloy;
Figure 11 base material and porous coating sample surfaces EDX analysis result, (a) NiTi base material, (b) the laser modified laminar surface of B sample;
Figure 12 is the electrochemistry anodic polarization curves of sample in 310KHank ' s solution;
Figure 13 is laser melting coating TiH
2The alloy coat tissue;
Figure 14 is the Bode figure and the phase angle frequency diagram of ac impedance spectroscopy sample leaves standstill 1h in 37 ℃ of Hank ' s solution after;
Figure 15 is the Nyqusit figure of ac impedance spectroscopy sample leaves standstill 1h in 37 ℃ of Hank ' s solution after;
Figure 16 is that sample soaks back SEM surface topography in SBF solution, and (a) base material soaked 20 days, and (b) base material soaked 30 days, and (c) laser modified sample soaked 20 days, and (d) laser modified sample soaked 30 days;
Figure 17 is that laser modified sample soaks FTIR diffuse reflection spectrum after 30 days in SBF solution;
Figure 18 is a sample implant site X-ray plain film verification film;
Figure 19 implants in the rabbit body nearly sample place animal tissue section optical microscope photograph after 21 days for the porous coating sample;
Figure 20 is that NiTi alloy substrate sample is implanted in the rabbit body nearly sample place animal tissue section optical microscope photograph after 21 days.
The specific embodiment:
Ni-49.6at% in the wherein related NiTi marmem alloy powder of NiTi marmem powder, Ti-50.4at%, granularity is 43 μ m; TiH
2Powder is commercial purity, and its granularity is 38 μ m;
With TiH
2Powder and NiTi marmem powder are prepared in proportion; mix homogeneously in Ar gas shiled planetary ball mill; adopt polyvinyl alcohol adhesive to be modulated into pasty state through the alloy powder of batch mixing and be preset in the NiTi alloy surface, the fore-put powder layer thickness is 0.7mm, through 80 ℃ of oven dry 4h.
Matrix material NiTi marmem base material is standby after polishing, sandblast, acetone cleaning, sample surfaces roughness R
a=0.2 μ m.
The sample of oven dry is placed the controlled atmosphere reative cell, Laser Surface Treatment adopts 2KW continuous wave Nd-YAG laser instrument, laser beam wavelength 1.06 μ m, the ZnSe lens focus, focal length 100mm, the laser works platform is by computer control, X, Y, Z three-dimensional motion, and the minimum movement amplitude of each direction of workbench is 0.01mm.Fig. 1 is the synthesizing porous plater schematic diagram of laser reactive.Reaction protection gas N
2Purity is 99.95%, and it is 50% that large-area laser is handled the scanning overlapping rate.
Test used alloy powder composition such as table 1.
Table 1 test alloy powder composition
Investigate by the experimentation that different powder formulations are carried out, found that TiH in laser irradiation density and the powder
2Content bigger to the formation of porous coating tissue influence.Fig. 2 is the laser modified layer of two kinds of compositions of B, a C section OM macro morphology.The OM observed result shows that similar to other material laser cladding layer, the laser modified layer of porous cross section also shows as half elliptic, and modified layer combines well with the NiTi alloy base material.Under this experiment condition, oval-shaped depth-width ratio except that with the laser processing technique relating to parameters, also relevant with the composition of coated powder, with TiH in the increase of laser beam irradiation power density and the preset coating powder
2The increase of content, the radian of modified layer ellipse tends towards stability, and depth-width ratio reduces.
Fig. 3 is B, C composition sample overlap scanning samples through laser treatment a surface topography, under certain laser processing technique condition, the basic uniformity of width of laser modified layer, the surface is made of the tiny band of certain width, the convergence direction of band is the scanning direction of laser beam, in process of the test, find, at laser beam irradiation optimum power intensity 16MJmm
-2Condition under, A, B composition sample surfaces are smooth, flawless produces, and network-like crackle has all appearred in some zone of C, D, E composition sample surfaces, this with preset alloy powder in the content of TiH2 relevant.
Fig. 4 is the XRD diffraction spectra of NiTi alloy powder before the laser irradiation and B composition alloy powder, and the NiTi alloy powder is mainly by NiTi, Ti
2The Ni phase composition.Fig. 5 is the laser modified layer of A, B, three kinds of compositions of a C XRD diffraction spectra, and modified layer is by NiTi, Ti
2Ni, TiNi
3Deng the thing phase composition, because laser treatment adopts N
2Protection, thereby also contain the TiN wild phase in the coating.Test result shows, with TiH in the fore-put powder coating
2The increase of content, Ti in the modified layer
2The Ni diffraction peak intensity strengthens.
TiH
2Be the most stable phase in the hydride of Ti, it forms heat is-80.3kJ/mol that in the laser irradiation process, the minimizing of H atomic concentration in the hydride will produce the metastable transition phase.TiH
2Catabolic process be divided into two stages, that is: TiH
2→ TiH
X→
～Ti, 0.7＜X＜1.1 here.Because the interatomic bond relation of closing energy, the H atom should be preferentially and Ti atomic building Ti-H key, makes the reduction of system free energy.And at TiH
2Decompose in the evolution process, the Ti atom all constitutes the tetrahedron dot matrix, and difference depends on the quantity of H atom and fill the situation of position, 8 tetrahedral interstices in the unit cell that the H atom is from occupying 8 tetrahedral interstices to occupying the part tetrahedral interstice.TiH
2The newborn Ti that decompose to generate contains a large amount of defectives, has higher activity, very easily with reative cell in N
2The synthetic TiN wild phase of reaction.
Fig. 6 is the laser modified layer of a porous NiTi alloy section SEM pattern, as can be seen, depth direction along modified layer, hole is evenly distributed on the modified layer inner base, Fig. 7 is the local enlarged photograph of Ni-Ti intermetallic compound in the modified layer tissue, still there is more tiny hole on the intermetallic compound surface as can be seen, thereby constituted similar " coralliform skeleton ", in coating structure, will play the effect of load-bearing skeleton, and between coralliform Ni-Ti intermetallic compound, have the synthetic wild phase TiN of reaction of tiny Flos Mume shape.
The hole kind of medical porous material can be divided into two classes, and as shown in Figure 8, a class is that hole and extraneous material are interconnected, and a class is independent enclosed shape hole.The typical pattern of the laser modified laminar surface hole of porous NiTi alloy as shown in Figure 9.Hole more than 90% presents three-dimensional communication, opening pattern as can be seen.Alloy coat has good pore communication, TiH in this and the laser irradiation process
2The decomposition and the diffusion of Ni, Ti atom relevant.On biomedicine, the hole shape of porous implantation material surface modified layer is open intercommunicating pore, to help the flowing of human body material, the infiltration of body fluid, the transmission of nutritional labeling and the regeneration and the reparation of tissue, accelerated material combines with body tissue, and participate in normal vital movement, its medical effect will be than block NiTi alloy material for well, and performances such as its intensity, toughness and compression will be similar to block materials.
The laser modified layer of porous has improved the apparent condition of entity NiTi marmem, porous coating is present in the solid material surface, help strengthening the practicality of entity NiTi marmem as biological implantation material, be easy to bring out organism and plant bone grafting tooth cell fast, and promote growing into of tissue on its surface.Figure 10 is that porous laser surface modification layer and entity NiTi marmem sample adopt the measured surface roughness of AFM, as seen even substantially along its distribution of pores of modified layer sample surfaces direction, have tangible configuration of surface advantage than entity NiTi marmem, thereby be convenient to reach the purpose that combines with the organism surrounding tissue.
Figure 11 is NiTi marmem base material and the laser modified laminar surface composition of porous EDX analysis result, experimental result shows, the Ni content of laser modified laminar surface is 12.5at%, be starkly lower than the 49.2at% in the original NiTi alloy, thereby, under this experiment condition, on the NiTi marmem, realize the preparation of porous coating, when changing NiTi alloy surface pattern, reduced the content of the harmful element Ni of NiTi alloy surface effectively, thereby will further improve the surface property of NiTi marmem as bio-medical material.
Figure 12 is porous laser surface modification layer and the electrochemistry anodic polarization curves of NiTi entity alloy sample in 37 ℃ of simulated body fluid Hank ' s solution, as can be seen, different with the porous material that adopts other method preparation, the porous laser surface modification layer of this research preparation does not make the corrosion resistance on NiTi surface descend, opposite because the rich titanium of surface layer, and there is the splendid TiN wild phase of chemical stability simultaneously, make the electrochemical corrosion performance of porous coating improve, table 2 is the electrochemical corrosion performance index parameter of two kinds of samples.The corrosion potential of the laser modified layer of porous improves, and corrosion electric current density reduces.According to the ultimate principle of electrochemical corrosion, the corrosion rate of material in medium is proportional to its anodic attack electric current density, thereby modified layer
Table 2 sample is the electrochemical corrosion performance parameter in 37 ℃ of Hank ' s solution
Corrosion current reduces, and its electrochemical corrosion resistant performance strengthens.This specific character is significantly different with other whole porous NiTi shape memory alloy existence, and is relevant with the design of powder composition with the synthetic unique process characteristic of laser reactive of the present invention.
Powder involved in the present invention is NiTi marmem powder and TiH
2Powder, wherein TiH
2Powder shared ratio in powder influences bigger to forming porous coating.TiH in the mixed-powder
2Content is lower than at 20% o'clock, and it is lower that synthesizing porous coating mesopore rate is reacted in laser irradiation, and the hole that is produced mostly is the enclosed type hole; TiH in the mixed-powder
2Content is higher than at 50% o'clock, and synthetic reaction is violent under laser irradiation conditions, very easily cracks; Work as TiH
2Content is higher than at 80% o'clock, and the coating mesopore is minimizing trend, produces to be similar to laser melting coating TiH
2The alloy coat tissue.As shown in figure 13.
The optimal processing parameter of laser irradiation reaction synthesis technique involved in the present invention is: laser irradiation density is 18MJmm
-2, when power density is lower than 16MJmm
-2The time, synthetic reaction coating mesopore rate is low, and simultaneously because energy density is lower, deficiency is so that matrix material NiTi alloy is little molten, and so coating and high base strength are lower, coating very easily comes off, and this is extremely dangerous for the use that is applied to embedded material.When energy density is higher than 20MJmm
-2The time, easily produce following several situation: (1) laser irradiation synthetic reaction is violent, and coating very easily cracks; (2) the matrix material depth of fusion increases, and the base material deflection increases, and when the deflection of laser irradiation generation is higher than 8%, then is difficult in actual applications use; (3) the coating alloy composition is diluted, and the Ni constituent content increases, thereby easily produces the harmful ionic stripping of Ni in as the embedded material use, makes Ni ion release rate increase, and causes inflammatory reaction, even carcinogenic.N in the laser reactive building-up process
2Flow porous coating is influenced: N
2When flow was lower than 15L/min, the synthetic TiN amount of reaction was less in the coating, makes the corrosion resistance of coating and biocompatibility descend.Simultaneously, TiH
2Decomposing the active Ti atom that produces is easy to and O
2In conjunction with, coating is oxidized, easily produces reunion, dross phenomenon in the coating reaction building-up process, works as N
2Flow is during greater than 35L/min, because active Ti is bigger with the affinity of N, TiN content increases in the coating, causes coating porosity to descend, and the while, a large amount of TiN sharply reacted generation, had increased the tearing tendency of coating.
The AC impedance method is one of the main research means in electrochemical research field, be the important tool of research electrode process and electrode surface electrochemical reaction phenomenon, be widely used in the research of electrochmical power source, metal erosion, metal electrodeposition, superficial phenomenon (as passivation, absorption) and other various electrode processes.In the research process of AC impedance, equivalent circuit commonly used is described electrode process.
Figure 14, Figure 15 are Bode figure, phase angle frequency diagram and the Nyqusit figure of the ac impedance spectroscopy (EIS) that records NiTi alloy base material and two kinds of samples of porous coating leave standstill 1h in 37 ℃ of Hank ' s solution after.The EIS figure of two kinds of samples all presents a time constant, and the impedance that meets the electrode system of the most classical metal electrode and solution composition constitutes.The electric capacity behavior can obtain indirectly by the variation of impedance with frequency.As seen from Figure 14, in test specification, the resistance value of porous coating sample all is higher than matrix material.At low frequency range, what resistance value reflected is the reaction transfer resistance of tested sample in electrolyte, and the reaction transfer resistance is big more, and the carrying out of corrosion reaction is just difficult more.
Table 3 is the parameter value of analog circuit, as can be seen, compares its solution resistance of porous coating R with the NiTi alloy substrate
eAnd transmission resistance R
pIncrease, and electric double layer capacitance CPE obviously reduces, by
As can be known, capacitance is more little, and the modulus of impedance value is big more.So the synthesizing porous coating of laser reactive has been improved the corrosion resistance of NiTi alloy in Hank ' s solution.
Table 3 NiTi alloy base material and laser modified sample soak each parameter value of the equivalent circuit of impedance spectrum behind the 1h in 37 ℃ of Hank ' s solution
The NiTi base material of 10mm * 10mm * 5mm and the sightingpiston for the treatment of of porous coating sample are ground to metallographic sample, after the washed with de-ionized water drying, place 200mL is housed, soak in the reagent bottle of 37 ℃ of simulated body fluid SBF solution, SBF solution was changed once in 2 days in the bottle, to keep SBF soak composition substantially constant.Two kinds of samples that are immersed in the SBF solution are regularly taken out at one time, washed with de-ionized water, after 50 ℃ of dryings, adopt the deposition conditions and the composition of SEM-EDX observation analysis sample surfaces osteoid apatite, adopt Nicolet fourier transform infrared spectrometry (FTIR) to analyze sedimental chemical constitution.
The formation of osteoid apatite is its prerequisite with osteoinductive on the biomaterial, thereby research influences the factor that the embedded material osteoid apatite forms, and is to explore the effective way that the material bone is induced mechanism.
Figure 16 is after NiTi base material and the laser modified sample of porous soak in 37 ℃ of SBF solution, sample surfaces deposit SEM pattern.Observe and find that the NiTi base material soaked 20 days in solution, its surface topography does not have to change substantially, and " mushroom " shape growth-gen that disperse distributes has appearred being in a large number in laser modified sample surfaces.Soaked 30 days, the deposit that laser modified sample surfaces grows covers sample surfaces substantially fully.The EDX quantitative analysis results shows: the porous coating surface deposits is rich in Ca, P, O element, and Ca, P atomic ratio change between 1.5～1.8 in its deposit.Figure 17 is that laser modified sample soaks FTIR diffuse reflection spectrum after 30 days in SBF solution.Wherein, 3340cm
-1The place is OH
-1Characteristic peak, 2358cm
-1And 1600cm
-1The place is H
2The O peak, 1437cm
-1Be CO
3 2-Characteristic peak, 1100～1033cm
-1Ownership PO
4 3-Vibration peak, 875cm
-1The place is HPO
4 2-Absworption peak, and 701cm
-1Then be relevant with the vibration of P-O key.Studies show that, contain OH in the human body hydroxyapatite equally
-1, H
2O, CO
3 2-, PO
4 3-, HPO
4 2-Deng, illustrate and in SBF solution, soak after 30 days that the laser modified sample surfaces deposit of porous structure is an osteoid apatite.
Embodiment 2:
Animal is implanted experiment.Test selected animal and be 2 of 18 months male rabbits of birth, body weight is respectively 6.5Kg, 6.3Kg.Water was prohibited in animal surgery fasting in evening the previous day the same day.According to a conventional method through ear's injection pentobarbital sodium narcotics, routine disinfection.According to research experience in the past, the implant site of embedded material influences the formation of body internal skeleton, produces in order to induce osteocyte smoothly, selects the nearly vertebra muscle in back as implant site.Cut the long otch of about 8cm in the back of rabbit, cut skin and subcutaneous tissue, expose muscular tissue, spatium intermusculare separately is with NiTi alloy dense material and two kinds of samples of porous coating divide into groups to implant respectively vertebra place, back of rabbit.Every group of parallel sample of embedded material is 8, and every rabbit left-right symmetric in two separate ranks implanted 4, and layering is sewed up the incision then.Postoperative is with the rabbit sub-cage rearing, in 21 days deadly coherence checks of doing of postoperative.Figure 18 implants position X-ray plain film verification film in the rabbit body for sample.
Implantation material surface forms the process that the process of osteoid apatite is the new solid phase of growing from liquid phase in animal body.By the crystal nucleation theory as can be known, the formation of cenotype can be divided into two stages: nucleus forms and crystal growth.New nuclear forms in the position of some favourable nucleation of material surface usually, place as surface depression or hole, because these ground can keep the ion concentration of body fluid not diluted preferably, the intravital body fluid circulation of animal simultaneously is restricted, therefore, its ion concentration of these positions of material is higher, that is to say that the porous material of micropore can keep near the ion concentration of material surface and more nucleation active site is provided.So form new nucleus easily in surface depression or pertusate place, in a single day nucleus forms promptly grows up rapidly.NiTi alloy dense material is because of surperficial opposed flattened, densification, little to the intravital body fluid circulation resistance of animal, its ion concentration keeps the meansigma methods of body fluid substantially, and it is very difficult will reaching the nucleation value of cutting off from a short time, so under our experiment condition, do not form osteoid apatite in 21 days.And porous coating has increased the surface area of sample, in case the concentration in the microenvironment has reached the nucleation threshold value around the material, can form new nuclear at material surface.Therefore, porous coating material is implanted the existence that can detect Ca, P, O composition in the animal body on its surface.
Figure 19 implants in the rabbit body animal tissue's section light microscopic photo after 21 days for the porous coating sample, is growing chondrocyte near porous coating one side as can be seen.Figure 20 is near the rabbit in-vivo tissue section photo NiTi base material, has occurred inflammatory cell in the tissue, and has not found that chondrocyte generates, and illustrates that porous coating has good osteoinductive and biocompatibility.
Claims (8)
1, a kind of permanent implanted artificial bone is a base material with entity NiTi marmem, and the surface has porous coating, it is characterized in that: described porous coating is by the synthetic preparation of laser reactive, and coating is excellent metallurgical with matrix and combines; The structure of porous coating is to be made of the support frame of coating coralliform Ti-Ni intermetallic compound, be distributed with the hole of reduced size and disperse distribution, the Flos Mume shape TiN wild phase of size between 0.5～1 μ m on the skeleton, and around skeleton, be evenly distributed with size interconnected pore in 4～20 mu m ranges.
2, according to the permanent implanted artificial bone of claim 1, the thickness that it is characterized in that described porous coating is 250～400 μ m, and the coating composition distribution gradient is promptly increased progressively to elementary composition Ti of coating surface and Ni ratio gradually by matrix.
3, the preparation method of the described permanent implanted artificial bone of a kind of claim 1 is characterized in that the synthetic technological parameter of laser reactive is:
Handle early stage: matrix material NiTi marmem base material is standby after polishing, sandblast, acetone cleaning, sample surfaces roughness R
a=0.2 μ m;
Alloy powder: percentage by weight is 20～80% NiTi marmem powder, Ni-49.6at% wherein, and Ti-50.4at%, granularity is 43 μ m; Surplus is TiH
2Powder, this powder are commercial purity, and its granularity is 38 μ m;
To be modulated into pasty state through the alloy powder of batch mixing and be preset in the NiTi alloy surface, the fore-put powder layer thickness is 0.7mm, through 80 ℃ of oven dry 4h;
The sample of oven dry is placed the controlled atmosphere reative cell, and Laser Surface Treatment adopts 2KW continuous wave Nd-YAG laser instrument, laser beam wavelength 1.06 μ m, the ZnSe lens focus, focal length 100mm, the minimum movement amplitude of laser works platform is 0.01mm, it is 50% that large-area laser is handled the scanning overlapping rate;
Laser power density scope: 10～25MJmm
-2
Carry out under nitrogen protection, purity is 99.95% reaction protection gas N
2Flow 15～35L/min.
4, according to the preparation method of the described permanent implanted artificial bone of claim 3, it is characterized in that laser power density scope: 16～20MJmm
-2
5,, it is characterized in that reaction protection gas N according to the preparation method of the described permanent implanted artificial bone of claim 3
2Flow 25～30L/min.
6, according to the preparation method of the described permanent implanted artificial bone of claim 3, the percentage by weight that it is characterized in that NiTi marmem powder is 40～60%.
7,, it is characterized in that in described alloy powder, adding the polymer of alloy powder weight 2～10% as binding agent according to the preparation method of the described permanent implanted artificial bone of claim 3.
8, according to the preparation method of the described permanent implanted artificial bone of claim 7, it is characterized in that described polymer is a polyvinyl alcohol.
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Non-Patent Citations (4)
| Title |
|---|
| NiTi合金表面激光原位反应合成TiN增强金属基复合材料涂层. 张春华，张松，文效忠，刘常升，才庆魁.复合材料学报，第22卷第3期. 2005 |
| NiTi合金表面激光原位反应合成TiN增强金属基复合材料涂层. 张春华，张松，文效忠，刘常升，才庆魁.复合材料学报，第22卷第3期. 2005 * |
| NiTi形状记忆合金***体氮化层组织及磨损性能. 张松，张春华，王强，文效忠，朱圣龙，才庆魁.稀有金属材料与工程，第34卷第6期. 2005 |
| NiTi形状记忆合金***体氮化层组织及磨损性能. 张松，张春华，王强，文效忠，朱圣龙，才庆魁.稀有金属材料与工程，第34卷第6期. 2005 * |
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