CN103357063A - Metal composite material capable of inducing bone growth and application thereof - Google Patents
Metal composite material capable of inducing bone growth and application thereof Download PDFInfo
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- CN103357063A CN103357063A CN2012101031243A CN201210103124A CN103357063A CN 103357063 A CN103357063 A CN 103357063A CN 2012101031243 A CN2012101031243 A CN 2012101031243A CN 201210103124 A CN201210103124 A CN 201210103124A CN 103357063 A CN103357063 A CN 103357063A
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Abstract
The invention discloses a metal composite material capable of inducing bone growth and an application thereof. The metal composite material is especially suitable for biomedical engineering for human hard tissue defect, comprising an artificial joint, artificial bone, a dental implant, a plastic surgery medical apparatus and instrument, a bone marrow cavity implant and the like. Specifically a double-phase composite material capable of inducing bone growth is provided, a cellular structure is prepared on a clinical medical metal material (titanium, titanium alloy, stainless steel, cobalt-base alloy, nickel-titanium shape memory alloy and the like), magnesium or a magnesium alloy capable of inducing bone growth is filled in the cellular structure, and the composite material in the structure can be used as a solid material, and as the surface/partial structure of a solid metal material. By virtue of the design of the composite material, the bioactivity of an existing medical metal implantable device can be improved; along with the continuous decomposition and bone induction effect of the magnesium or the magnesium alloy in a human body environment, and the bone structure is gradually induced to grow into the cellular structure to enhance the binding strength of the bone tissue with the implant so as to prevent the implant from getting separated, achieve good biological immobilization, and greatly improve the bone integration effect.
Description
Technical field
The invention belongs to the bio-medical material technical field, particularly a kind of metallic composite of bootable osteogenesis and application thereof.
Background technology
Clinical medical metal material commonly used comprises at present: pure titanium, titanium alloy, rustless steel, cobalt-base alloys, niti-shaped memorial alloy.Medical metal material with its high-strength tenacity, endurance, easily shape with clinical use in the premium properties such as high reliability, be the large and widely class bio-medical material of consumption clinically always, be widely used in sclerous tissues's medical fields such as the bone that need to bear high load, tooth.The medical metal material of at present clinical practice satisfies certain biocompatibility requirement with its metastable chemical property, bears in vivo specific load and permanent or semipermanent ground retention.These metal materials generally show as biologically inert in the organism environment, it is poor to be combined with surrounding bone organizational interface, often produce easily looseningly after implant is stressed in vivo, have affected therapeutic effect.
Because the elastic modelling quantity of medical metal material is higher than osseous tissue, produces in vivo stress shielding, osteoporosis and secondary fracture occurs easily.Adopt loose structure can regulate the elastic modelling quantity of metal material, thereby be complementary with osseous tissue.In addition, loose structure is conducive to growing into of area of new bone on every side, can increase the bond strength of implant and osseous tissue.Yet this loose structure can not produce close contact with osseous tissue after implanting, but is preferentially filled by some soft tissues, has directly caused the osteogenesis amount few, takes length, and the bone depth of penetration is limited, can't make the osseous tissue darker material internal of growing into.In addition, loose structure has reduced the mechanical property of metal material, so that porous metals can't bear large load, application is restricted.
Summary of the invention
The objective of the invention is to be intended to solve the low problem of present medical metal implantation instrument biological activity, in conjunction with the good biological activity of magnesium and magnesium alloy, the advantage of osteoinductive energy and absorbable and degradable preferably, provide a kind of metallic composite and application thereof of bootable osteogenesis.
The invention provides a kind of metallic composite of bootable osteogenesis, this material is take the metal medical material of loose structure as matrix, fills to have bioactive magnesium and magnesium alloy in loose structure; Design on this composite construction and the composition can effectively guide the growth of freshman bone tissue, and osseous tissue is grown in the darker inside of implant, promotes the combination of osseous tissue and implant, and has guaranteed the mechanical property of implant.
The metallic composite of bootable osteogenesis provided by the invention, described metal medical material are one or more in pure titanium, titanium alloy, rustless steel, cobalt-base alloys, the niti-shaped memorial alloy.
The metallic composite of bootable osteogenesis provided by the invention, the material of described magnesium and magnesium alloy are 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, the magnesium Silver Alloys or the ternary system or the polynary system magnesium alloy that are formed by these system combinations.
The metallic composite of bootable osteogenesis provided by the invention, the described fill method that magnesium and magnesium alloy are filled in the loose structure is melt infiltration method or casting method.
The metallic composite of bootable osteogenesis provided by the invention, the porosity of described loose structure are 10～80%, and aperture size is 100 μ～900 μ m, percent opening＞60%.
The metallic composite of bootable osteogenesis provided by the invention, the preparation method of described loose structure comprise quick shaping method, powder metallurgic method, plasma spraying method, laser boring method, the little processing method of electrochemistry, gel casting forming method, self propagating high temperature synthetic method, fiber sintering method, foaming, acid etching method, bead, blasting treatment.
The present invention also provides the application of the metallic composite of described bootable osteogenesis, this material is for the preparation of sclerous tissues's implant (comprising artificial joint, artificial bone, dental implant, shaping and beauty medical apparatus and instruments, medullary cavity implant), be specially adapted to the biomedical engineering that the human body hard tissue defective is filled, can be used as hardware and use, also can be used as the surface of device and ingredient wherein.
Magnesium and magnesium alloy be owing to have good biocompatibility and a biodegradable absorbability, in recent years as the degradable medical material by extensive concern and research.Studies show that magnesium elements is the indispensable important element of human body metabolism, the magnesium demand of per day for adults is about 400mg, so magnesium has very good safety basis as bio-medical material.Compare with existing medical metal material, magnesium alloy has more excellent biological activity.After magnesium alloy implanted, the surface had phosphate to generate, and new osteogenesis is arranged between phosphate and osseous tissue, and phosphate layer constantly changes to new bone tissue, and new bone tissue is just grown at the magnesium alloy implant.In addition, a large advantage of magnesium and magnesium alloy is its degradable absorbability, and the magnesium alloy implant is in-service gradually by the human body degraded and absorbed.Therefore, magnesium alloy is packed into the composite implant that porous metal structure forms, and has guaranteed on the one hand the mechanical property of porous medical metal material; On the other hand, along with degraded and the bone inductive effect of magnesium and magnesium alloy, progressively guide the freshman bone tissue loose structure inside of growing into, strengthened the bond strength between freshman bone tissue and the implant, the skeletonization amount increases, and realizes good biological fixation.
The invention has the advantages that:
1. biological activity is high.The present invention introduces the high magnesium alloy of biological activity, by the good guiding function of magnesium alloy to osteogenesis, can make the freshman bone tissue loose structure inside of growing into, and has increased the bond strength between osseous tissue and the implant, and the skeletonization amount increases, and realizes good biological fixation.
2. good mechanical properties.The present invention is packed into magnesium metal and alloy material thereof in loose structure, become the metallic composite of entity by loose structure, and mechanical property is significantly improved than loose structure.
3. applied widely.Composite of the present invention is mainly used in designing sclerous tissues's implant, is applied to the many aspects of medical field, comprises artificial joint, artificial bone, dental implant, shaping and beauty medical apparatus and instruments, medullary cavity implant etc.
Description of drawings
Fig. 1 is the porous titanium alloy support that the electron-beam melting Rapid Prototyping technique is prepared;
Fig. 2 is that porous titanium alloy is combined the microgram sheet in the above-mentioned composite with the interface of pure magnesium;
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, and wherein (a), (b), (c) are followed successively by the porous titanium alloy support that is untreated, POROUS TITANIUM/magnesium base composite material, the rear POROUS TITANIUM/magnesium base composite material of differential arc oxidation processing.
The specific embodiment
Following examples will be further described the present invention, but not thereby limiting the invention.
Embodiment 1:
Adopt electron-beam melting Rapid Prototyping technique preparation size to be
Cylindric porous titanium alloy (Ti6Al4V) support, its pattern is as shown in Figure 1.Above-mentioned support average pore size is 600 μ m, and porosity is about 60%.This support has the class alveolate texture, is interconnected between the Kong Yukong and runs through the outer surface of support, has three-dimensional communication.Then, adopt the infiltration method with pure magnesium (purity: 99.99%) be packed in the hole of above-mentioned porous titanium alloy support, form double-phase composite.Fig. 2 is the interface microscopic appearance of formed double-phase composite, can find out that pure magnesium and porous titanium alloy mount interface do not have the defectives such as space, pure magnesium has been filled in the three-dimensional pore space of porous titanium alloy support fully and has formed good metallurgical binding, has guaranteed the mechanical property of this composite.
This composite is cut into
The compression sample carry out compression 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 has promoted the comprcssive strength of porous titanium alloy support greatly, the comprcssive strength of this composite is 275 ± 10MPa, has satisfied the requirement of sclerous tissues's implant to mechanical property.
Fig. 4 is the required embedded material macro morphology of above-mentioned porous titanium alloy support zoopery figure, is followed successively by from left to right the porous titanium alloy support that is untreated, POROUS TITANIUM/magnesium base composite material, the rear POROUS TITANIUM/magnesium base composite material of differential arc oxidation processing.The section statining result of sclerous tissues that animal was implanted after 4 weeks of experiment shows that the inner void of porous titanium alloy matched group implant is occupied by fibrous tissue, and the implant circumferential surface also coats one deck fibrous tissue, does not almost have freshman bone tissue to grow into.By contrast, the fibrous tissue around the composite implant that above-mentioned POROUS TITANIUM/magnesium base composite material and differential arc oxidation were processed is less, and the pure magnesium that is packed in the hole is degraded, and near visible freshman bone tissue shows good biological activity.
Embodiment 2:
Employing slurry foaming acquisition porosity is respectively 58% and 70% porous 317L rustless steel sample, above-mentioned porous stainless steel is tridimensional network, and connectivity is strong, and distribution of pores is comparatively even, the aperture is 40-250 μ m, and comprcssive strength is respectively 189MPa and 59MPa.Method by melt infiltration is packed into the Mg-0.5Ca alloy double-phase composite that forms two kinds of pore structures in the porous stainless steel sample of above-mentioned two kinds of porositys.The comprcssive strength of these two kinds of composites respectively 189MPa and the 59MPa of porous stainless steel is increased to respectively 380MPa and 283MPa, visible Mg-Ca alloy be filled with the lifting that is beneficial to the porous material mechanical property.Above-mentioned composite is cultivated 5 days in simulated body fluid after, the deposition of synthos material is found to have in the surface, shows good biological activity.In addition, in order to improve the decay resistance of above-mentioned composite, this composite has been carried out the differential arc oxidation processing, and (rustless steel is generally without the differential arc oxidation treatment surface, can make surface passivating treatment into), the composite that differential arc oxidation was processed shows excellent anti-body fluid corrosive nature, the cytotoxicity that mtt assay detects above-mentioned composite is 0 grade, satisfies the instructions for use of embedded material.
Embodiment 3:
Adopt the laser drilling preparation size to be: 5 * 5 * 5mm
3, porosity is 75%, the aperture is the cobalt-base alloys (Co62Cr28Mo6) of 400-600 μ m, then adopts the infiltration method Mg-6Zn alloy to be packed in the hole of above-mentioned porous cobalt-base alloys, forms composite.The compressive strength of this composite is 232 ± 5MPa, greater than human body natural's bone strength, also can satisfy the mechanical property requirements to implant.
Embodiment 4:
Adopt that metal powder sintered legal system is standby to go out that porosity is 30%, the aperture is niti-shaped memorial alloy (Ni50Ti50) skeleton of 200-300 μ m.Melting Mg-Sr alloy infiltration is entered in this stephanoporate framework, thereby prepare the two-phase metallic composite.Scanning electron microscopic observation shows that the Mg-Sr alloy evenly distributes and is filled in the hole of porous nickel-titanium alloy, fully infiltration.Nickel porous titanium alloy framework compression experiment is the result show, reaches maximal pressure contracting intensity when strain value is 18%, is 80MPa.And the compressive strength of the two-phase metallic composite of filling through infiltrating has reached 295 ± 10MPa, and the filling of visible Mg-Sr alloy has improved this bone porous mechanical property effectively.
Embodiment 5:
Adopt casting method that pure magnesium is packed into and form the two-phase metallic composite in the hollow Porous titanium.Then this composite is implanted the animal femur, the histological observation discovery is carried out in sampling after 2 months, and Partial digestion has occured the pure magnesium of filling in the inlet hole, and growing into of new bone tissue arranged in the composite hole.Compare with blank contrast sample, the osteogenesis amount of composite material surface obviously increases, and the degraded and the new bone tissue growth that demonstrate pure magnesium are carried out simultaneously.
Claims (8)
1. the metallic composite of a bootable osteogenesis is characterized in that: this material is take the metal medical material of loose structure as matrix, fills to have bioactive magnesium and magnesium alloy in loose structure.
2. according to the metallic composite of the described bootable osteogenesis of claim 1, it is characterized in that: described metal medical material is one or more in pure titanium, titanium alloy, rustless steel, cobalt-base alloys, the niti-shaped memorial alloy.
3. according to the metallic composite of the described bootable osteogenesis of claim 1, it is characterized in that: 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, the magnesium Silver Alloys or the ternary system or the polynary system magnesium alloy that are formed by these system combinations.
4. according to the metallic composite of the described bootable osteogenesis of claim 1, it is characterized in that: the described fill method that magnesium and magnesium alloy are filled in the loose structure is melt infiltration method or casting method.
5. according to the metallic composite of the described bootable osteogenesis of claim 1, it is characterized in that: the porosity of described loose structure is 10～80%, and aperture size is 100 μ～900 μ m, percent opening＞60%.
6. according to the metallic composite of the described bootable osteogenesis of claim 1, it is characterized in that: the preparation method of described loose structure comprises quick shaping method, powder metallurgic method, plasma spraying method, laser boring method, the little processing method of electrochemistry, gel casting forming method, self propagating high temperature synthetic method, fiber sintering method, foaming, acid etching method, bead, blasting treatment.
7. the application of the metallic composite of the described bootable osteogenesis of claim 1, it is characterized in that: this material is for the preparation of sclerous tissues's implant, be specially adapted to the biomedical engineering that the human body hard tissue defective is filled, can be used as hardware and use, also can be used as the surface of device and ingredient wherein.
8. according to the application of the metallic composite of the described bootable osteogenesis of claim 7, it is characterized in that: sclerous tissues's implant comprises artificial joint, artificial bone, dental implant, shaping and beauty medical apparatus and instruments, medullary cavity implant.
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| CN104707182A (en) * | 2013-12-16 | 2015-06-17 | 财团法人金属工业研究发展中心 | Intervertebral implant |
| CN106667624A (en) * | 2016-11-03 | 2017-05-17 | 河北医科大学第三医院 | Absorbable internal implant for filling bone tunnel defect in minimally invasive surgery |
| CN106670464A (en) * | 2017-01-13 | 2017-05-17 | 哈尔滨工业大学 | Preparation method for titanium-magnesium double-metal composite of double-communication netted structure |
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| CN114833346A (en) * | 2022-05-17 | 2022-08-02 | 哈尔滨工业大学 | Titanium-based composite material with multi-level scale microstructure and preparation method thereof |
| CN115501386A (en) * | 2022-09-28 | 2022-12-23 | 北京科技大学 | Full-degradable high-toughness bionic gradient composite material and additive manufacturing method thereof |
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