CN103357063B - The metallic composite of a kind of bootable osteogenesis and application thereof - Google Patents
The metallic composite of a kind of bootable osteogenesis and application thereof Download PDFInfo
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- CN103357063B CN103357063B CN201210103124.3A CN201210103124A CN103357063B CN 103357063 B CN103357063 B CN 103357063B CN 201210103124 A CN201210103124 A CN 201210103124A CN 103357063 B CN103357063 B CN 103357063B
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Abstract
The metallic composite of a kind of bootable osteogenesis and application thereof, this material is particularly well-suited to the biomedical engineering of human body hard tissue defect, including artificial joint, artificial bone, dental implant, shaping and beauty medical apparatus and instruments, medullary cavity implant etc., it is embodied in the double-phase composite of a kind of bootable osteogenesis: at the medical metal material (titanium or titanium alloy of clinical practice, rustless steel, cobalt-base alloys, niti-shaped memorial alloy etc.) on prepare loose structure, the magnesium of bootable osteogenesis or magnesium alloy are packed in loose structure, this structural composite material can be applied as solid material, also can as the surface of solid metal material or part-structure.This design of material can improve the biological activity of existing medical metal implantation instrument, along with magnesium or magnesium alloy constantly degrading and bone inductive effect in human body environment, progressively inducting osseous tissue is grown in loose structure, thus the bond strength that can increase between osseous tissue and implant, prevent implant from loosening, realize good biological fixation, make Integrated implant effect be greatly increased.
Description
Technical field
The invention belongs to biology medical material technical field, particularly to metallic composite and the application thereof of a kind of bootable osteogenesis.
Background technology
Clinical conventional medical metal material includes at present: pure titanium, titanium alloy, rustless steel, cobalt-base alloys, niti-shaped memorial alloy.Medical metal material is with its high-strength tenacity, endurance, easily shape and the premium properties such as the high reliability in Clinical practice, it is always up a consumption class bio-medical material greatly and widely clinically, is widely used in and needs to bear in the bone of high load, Chi Deng sclerous tissues medical field.The medical metal material of current clinical practice, with its metastable chemical property, meets certain biocompatibility requirement, bears specific load in vivo and forever or semi-permanently retains.These metal materials are typically in biological environment to show as biologically inert, poor with bone tissue interface cohesion, tend to produce to loosen, have impact on therapeutic effect after implant stress in vivo.
Owing to the elastic modelling quantity of medical metal material is higher than osseous tissue, produce stress shielding in vivo, it is easy to osteoporosis and secondary fracture occur.Adopt loose structure can regulate the elastic modelling quantity of metal material, thus matching with osseous tissue.It addition, loose structure is conducive to growing into of around area of new bone, it is possible to increase the bond strength of implant and osseous tissue.But this loose structure can not produce close contact with osseous tissue after implanting, but preferentially by some Soft-tissue operation, directly results in osteogenesis amount few, take length, bone depth of penetration is limited, it is impossible to make osseous tissue grow into deeper material internal.Additionally, loose structure reduces the mechanical property of metal material so that porous metals cannot bear big load, and application is restricted.
Summary of the invention
It is an object of the invention to aim to solve the problem that the problem that current medical metal implantation instrument biological activity is low, advantage in conjunction with the good biological activity of magnesium and magnesium alloy, good self-bone grafting performance and absorbable and degradable, it is provided that the metallic composite of a kind of bootable osteogenesis and application thereof.
The invention provides the metallic composite of a kind of bootable osteogenesis, this material, with the metal medical material of loose structure for matrix, is filled in loose structure and is had bioactive magnesium and magnesium alloy；Design on this composite construction and composition can effectively guide the growth of freshman bone tissue, particularly makes osseous tissue grow in the deeper of inside of implant, promotes the combination of osseous tissue and implant, and ensure that the mechanical property of implant.
The metallic composite of bootable osteogenesis provided by the invention, described metal medical material is one or more in pure titanium, titanium alloy, rustless steel, cobalt-base alloys, niti-shaped memorial alloy.
The metallic composite of bootable osteogenesis provided by the invention, the material of described magnesium and magnesium alloy is a kind of in pure magnesium system, magnalium series alloy, magnesium manganese series alloy, magnesium zinc series alloy, magnesium zirconium series alloy, magnesium rare earth metal alloy, magnesium lithium series alloy, magnesium calcium series alloy, magnesium Silver Alloys or by the ternary system of these system combinations or polynary system magnesium alloy.
The metallic composite of bootable osteogenesis provided by the invention, described magnesium and magnesium alloy are filled into the fill method in loose structure is molten liquid forming or casting method.
The metallic composite of bootable osteogenesis provided by the invention, the porosity of described loose structure is 10～80%, and aperture size is 100 μ～900 μm, percent opening > 60%.
The metallic composite of bootable osteogenesis provided by the invention, the preparation method of described loose structure includes quick shaping method, powder metallurgic method, plasma spraying method, laser boring method, electrochemistry micro Process method, gel casting forming method, self-propagating high-temperature synthesis, fiber sintering method, foaming, acid etching method, bead, blasting treatment.
Present invention also offers the application of the metallic composite of described bootable osteogenesis, this material is used for preparing sclerous tissues's implant (including artificial joint, artificial bone, dental implant, shaping and beauty medical apparatus and instruments, medullary cavity implant), it is particularly well-suited to the biomedical engineering that human body hard tissue defect is filled, can use as hardware, it is possible to as surface and the ingredient therein of device.
Magnesium and magnesium alloy are owing to having good biocompatibility and biodegradable absorbability, in recent years as degradable medical material by extensive concern and research.Research shows, magnesium elements is the important element that human metabolism is indispensable, and the magnesium demand being grown up every day is about 400mg, and therefore magnesium has very good safety basis as bio-medical material.Compared with existing medical metal material, magnesium alloy has more excellent biological activity.After magnesium alloy implants, surface has phosphate to generate, and has New born formation between phosphate and osseous tissue, and phosphate layer constantly changes to new bone tissue, and new bone tissue just grows on magnesium alloy implant.It addition, a big advantage of magnesium and magnesium alloy is its degradable absorbability, magnesium alloy implant is in-service gradually by human body degraded and absorbed.Therefore, magnesium alloy is packed into the composite implant that porous metal structure is formed, and ensure that the mechanical property of porous medical metal material on the one hand；On the other hand, along with degraded and the bone inductive effect of magnesium and magnesium alloy, inside progressively loose structure is grown into by guiding freshman bone tissue, enhance the bond strength between freshman bone tissue and implant, become bone amount to increase, it is achieved good biological fixation.
It is an advantage of the current invention that:
1. biological activity is high.Present invention introduces the magnesium alloy that biological activity is high, by the magnesium alloy good guiding function to osteogenesis, freshman bone tissue can be made to grow into inside loose structure, add the bond strength between osseous tissue and implant, become bone amount to increase, it is achieved good biological fixation.
2. good mechanical properties.The present invention is packed into magnesium metal and alloy material thereof in loose structure, loose structure become the metallic composite of entity, and mechanical property relatively loose structure is significantly improved.
3. applied widely.The composite of the present invention is mainly used in design sclerous tissues implant, is applied to the many aspects of medical field, including artificial joint, artificial bone, dental implant, shaping and beauty medical apparatus and instruments, medullary cavity implant etc..
Accompanying drawing explanation
Fig. 1 is the porous titanium alloy support that electron-beam melting Rapid Prototyping technique is prepared；
Fig. 2 is the interface cohesion microcosmic picture of porous titanium alloy and pure magnesium in above-mentioned composite；
Fig. 3 is the compression stress strain curve comparison diagram of porous titanium alloy, pure magnesium and POROUS TITANIUM/magnesium base composite material；
Fig. 4 is porous titanium alloy support zoopery embedded material macro morphology figure, wherein (a), (b), (c) be followed successively by untreated porous titanium alloy support, POROUS TITANIUM/magnesium base composite material, differential arc oxidation process after POROUS TITANIUM/magnesium base composite material.
Detailed description of the invention
The present invention will be further described by following example, but not thereby limiting the invention.
Embodiment 1:
The preparation of electron-beam melting Rapid Prototyping technique is adopted to be of a size ofCylindric porous titanium alloy (Ti6Al4V) support, its pattern is as shown in Figure 1.Above-mentioned support average pore size is 600 μm, and porosity is about 60%.This support has class alveolate texture, is interconnected and runs through the outer surface of support, have three-dimensional communication between Kong Yukong.Then, adopt infiltration process to be packed in the hole of above-mentioned porous titanium alloy support by pure magnesium (purity: 99.99%), form double-phase composite.Fig. 2 is the interface microscopic appearance of the double-phase composite formed, can be seen that pure magnesium and porous titanium alloy mount interface do not have the defects such as space, pure magnesium has been filled up completely with in the three-dimensional pore space of porous titanium alloy support and has defined good metallurgical binding, it is ensured that the mechanical property of this composite.
This composite is cut intoCompression sample be compressed experiment, Fig. 3 is the compression stress strain curve comparison diagram of above-mentioned composite (pTi/Mg), pure magnesium and porous titanium alloy matrix (pTi), as can be seen from the figure the filling of magnesium is greatly improved the comprcssive strength of porous titanium alloy support, the comprcssive strength of this composite is 275 ± 10MPa, meets the requirement to mechanical property of sclerous tissues's implant.
Fig. 4 is embedded material macro morphology figure needed for above-mentioned porous titanium alloy support zoopery, be followed successively by untreated porous titanium alloy support from left to right, POROUS TITANIUM/magnesium base composite material, differential arc oxidation process after POROUS TITANIUM/magnesium base composite material.The hard tissue slicing coloration result that animal is implanted after testing 4 weeks shows, the inner void of porous titanium alloy matched group implant is occupied by fibrous tissue, and implant circumferential surface is also coated with one layer of fibrous tissue, grows into almost without freshman bone tissue.By contrast, the fibrous tissue around composite implant that above-mentioned POROUS TITANIUM/magnesium base composite material and differential arc oxidation processed is less, and the pure magnesium being packed in hole is degraded, and neighbouring visible freshman bone tissue shows good biological activity.
Embodiment 2:
Adopt slurry foaming obtain porosity respectively 58% and 70% porous 317L rustless steel sample, above-mentioned porous stainless steel be tridimensional network, and connectivity is strong, and comparatively uniformly, aperture is 40-250 μm to distribution of pores, and comprcssive strength is 189MPa and 59MPa respectively.Mg-0.5Ca alloy is packed in the porous stainless steel sample of above two porosity by the method for melt infiltration to be formed the double-phase composite of two kinds of pore structures.189MPa and the 59MPa of the comprcssive strength of both composites porous stainless steel respectively increases respectively to 380MPa and 283MPa, it is seen that Mg-Ca alloy be filled with the lifting being beneficial to porous material mechanical property.After above-mentioned composite cultivates 5 days in simulated body fluid, surface finds the deposition having synthos material, shows good biological activity.In addition, in order to improve the decay resistance of above-mentioned composite, this composite has carried out differential arc oxidation process, and (rustless steel generally processes surface without differential arc oxidation, surface passivating treatment can be made into), the composite material exhibits that differential arc oxidation processed goes out the resistance to corrosion in body fluid performance of excellence, mtt assay detects that the cytotoxicity of above-mentioned composite is 0 grade, meets the instructions for use of embedded material.
Embodiment 3:
Laser drilling preparation is adopted to be of a size of: 5 × 5 × 5mm3, porosity be 75%, aperture be the cobalt-base alloys (Co62Cr28Mo6) of 400-600 μm, then adopt infiltration process to be packed into by Mg-6Zn alloy in the hole of above-mentioned porous cobalt-base alloys, form composite.The compressive strength of this composite is 232 ± 5MPa, more than human body natural's bone strength, also can meet the mechanical property requirements to implant.
Embodiment 4:
Adopt metal powder sintered method prepare porosity be 30%, aperture be niti-shaped memorial alloy (Ni50Ti50) skeleton of 200-300 μm.Then melted Mg-Sr alloy infiltration is made to enter in this stephanoporate framework under the combined effect of vacuum and high-pressure inert gas, thus preparing two-phase metallic composite.Scanning electron microscopic observation shows, in the hole that Mg-Sr alloy was uniformly distributed and was filled in porous nickel-titanium alloy, fully to infiltrate.Nickel porous titanium alloy framework compression experiment it is shown that reach maximal pressure contracting intensity when strain value is 18%, for 80MPa.And the compressive strength through infiltrating the two-phase metallic composite filled has reached 295 ± 10MPa, it is seen that the filling of Mg-Sr alloy is effectively improved this bone porous mechanical property.
Embodiment 5:
Adopt casting method to be packed into by pure magnesium in hollow Porous titanium and form two-phase metallic composite.Then this composite being implanted animal femur, after 2 months, sampling carries out histological observation discovery, and the pure magnesium filled in inlet hole has occurred and that there be growing into of new bone tissue in composite hole by Partial digestion.Compared with blank sample, the osteogenesis amount of composite material surface substantially increases, it is shown that the degraded of pure magnesium carries out with new bone tissue growth simultaneously.
Claims (3)
1. the metallic composite of a bootable osteogenesis, it is characterised in that: this material, with the metal medical material of loose structure for matrix, is filled in loose structure and is had bioactive magnesium and magnesium alloy；
Described metal medical material is one or more in pure titanium, titanium alloy, rustless steel, cobalt-base alloys；
The material of described magnesium and magnesium alloy is a kind of in pure magnesium system, magnalium series alloy, magnesium manganese series alloy, magnesium zinc series alloy, magnesium zirconium series alloy, magnesium rare earth metal alloy, magnesium lithium series alloy, magnesium calcium series alloy, magnesium Silver Alloys or by the ternary system of these system combinations or polynary system magnesium alloy；
It is described that magnesium and magnesium alloy are filled into the fill method in loose structure is molten liquid forming or casting method, make under the combined effect of vacuum and high-pressure inert gas the material of molten magnesium and magnesium alloy be impregnated into porosity be 30%, aperture be in the niti-shaped memorial alloy Ni50Ti50 skeleton of 200-300 μm；
The preparation method of described loose structure includes quick shaping method, powder metallurgic method, laser boring method, gel casting forming method, self-propagating high-temperature synthesis, fiber sintering method, foaming；
This material is used for preparing sclerous tissues's implant, it is adaptable to the biomedical engineering that human body hard tissue defect is filled, and can use as hardware, it is possible to as surface and the ingredient therein of device.
2. the metallic composite of bootable osteogenesis described in claim 1, it is characterised in that: the percent opening of described loose structure > 60%.
3. the metallic composite of bootable osteogenesis described in claim 1, it is characterised in that: sclerous tissues's implant includes artificial joint, artificial bone, dental implant, shaping and beauty medical apparatus and instruments, medullary cavity implant.
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| JP6917313B2 (en) | 2015-07-25 | 2021-08-11 | ローレンス・リバモア・ナショナル・セキュリティ・エルエルシーＬａｗｒｅｎｃｅ Ｌｉｖｅｒｍｏｒｅ Ｎａｔｉｏｎａｌ Ｓｅｃｕｒｉｔｙ， ＬＬＣ | Surface modification of polymer foam using plasma |
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