CN104096267A - Medical gradient composite material - Google Patents
Medical gradient composite material Download PDFInfo
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- CN104096267A CN104096267A CN201410325163.7A CN201410325163A CN104096267A CN 104096267 A CN104096267 A CN 104096267A CN 201410325163 A CN201410325163 A CN 201410325163A CN 104096267 A CN104096267 A CN 104096267A
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Abstract
The invention discloses a medical gradient composite material. The medical gradient composite material comprises a base body adopting a uniform porous structure or a gradient porous structure as well as a strengthening phase infiltrating the base body, wherein the base body is formed by weaving of medical metal wires; the strengthening phase is metal with the melting point lower than those of the metal wires; the strengthening phase infiltrates the porous structure of the base body with a pressure cast-infiltration, pressureless infiltration or suction casting technology and then is partially removed through selective corrosion by a chemical corrosive agent, so that the medical gradient composite material which is solid inside and porous outside is formed. The medical gradient composite material is excellent in performance, reasonable in structure, low in preparation cost, excellent in mechanical property, bone transmission characteristic and bone induction characteristic and capable of meeting most of requirements of bone filling, bone repair and bone transplantation applications.
Description
Technical field
The present invention relates to a kind of medical bio composite, be specifically related to a kind of medical gradient composites that is applicable to bone reparation and bone transplanting, belong to bio-medical material technical field.
Background technology
People's osseous tissue is a kind of functionally gradient material (FGM), and bone implant material requires its structure and people's bone photo together, has both required bone material to have good bone transmission and bone inducing properties, requires its performance to mate with people's bone simultaneously.Traditional bone material mainly contains solid material and porous material, but modular ratio people's bone of solid material is much higher, can cause " stress shielding " phenomenon and causes the failure of operation, and solid material bone inducing properties is lower; Although porous material has good bone transmission and bone inducing properties, its mechanical property is often lower, can not be applied in the higher bone of requirement of strength is implanted.No matter be in addition traditional solid material or porous material, its structure is different from people's bone, and this implants bone is disadvantageous.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, a kind of medical gradient composites is provided, this composite property mates with people's bone photo, structure and people's bone photo are near, to meet the bone of all kinds of artificial jointes (hip joint, knee joint etc.), spinal fusion material, bone support repair materials etc., implant needs.
The technical scheme that the present invention solves its technical problem is:
A kind of medical gradient composites, the hardening constituent that it comprises the matrix of the loose structure that has uniform loose structure or change in gradient and infiltrates this matrix, described matrix is formed by medical metal wire knitted, described hardening constituent is that fusing point is than this low-melting metal wiry, its by pressure, cast ooze, pressure-free impregnation or inhale casting process and infiltrate in the loose structure of described matrix, then with chemical mordant, carry out selective corrosion and partly remove this hardening constituent, form internal entity and the medical gradient composites of outside porous.
As further improvement, by changing described string diameter wiry or weaving method, control aperture and the porosity of described matrix, the porosity of this matrix is adjustable within the scope of 10%-90%.
As further improvement, described tinsel is medical titanium silk, tantalum wire, zirconium silk or stainless steel silk, and diameter is 0.005mm-3mm.
As further improvement, described hardening constituent is magnesium, magnesium alloy, titanium, titanium alloy, zirconium, zircaloy, zinc or kirsite.
As further improvement, by controlling etching time, regulate the removal volume of hardening constituent, regulate and control the volume fraction of described matrix and hardening constituent, to regulate and control structure and the mechanical property of described medical gradient composites, meet the instructions for use under different situations.
As further improvement, described etching time is 3-45 minute, and the volume fraction of described hardening constituent is adjustable within the scope of 0%-90%.
As further improvement, described chemical mordant is hydrochloric acid, sulphuric acid, dilute sulfuric acid or rare nitric acid.
As further improvement, the porosity ranges of described gradient composites is 0% to 90%, and comprcssive strength scope is 5.0MPa-300MPa, and modulus of elasticity in comperssion scope is 100MPa-120GPa.
As further improvement, described gradient composites adds Ag, Ca or Sr element in preparation process, carries out differential arc oxidation or anodized surface and process after having prepared.
Another technical scheme of the present invention is:
The application of described medical gradient composites aspect artificial joint, spinal fusion material and bone support repair materials.
Compare with existing bone implant material, the present invention has the following advantages:
1, there is good mechanical property, bone transmission and bone inducing properties;
2, significantly reduce preparation cost;
3, excellent performance, rational in infrastructure, can meet the requirement of most of bone fillings, bone reparation, bone graft application.
Accompanying drawing explanation
Fig. 1 is structural representation of the present invention.
Fig. 2 is the schematic diagram of the gradient porous structure of inside of the present invention.
Fig. 3 is preparation process schematic diagram of the present invention.
Fig. 4 is exterior appearance schematic diagram of the present invention.
The specific embodiment
The present invention is a kind of medical gradient composites, as shown in Figure 1 and Figure 4, its matrix is by the POROUS TITANIUM of tinsel machinery coiling, porous tantalum, porous zirconium, the medical materials such as porous stainless steel, composition can be that the metal wire knitted of single kind forms, also can multiple different types of metal wire combined braiding form, the preparation of matrix porous material can be controlled its pore radiuses and distribution and porosity size by controlling tinsel string diameter or knitting skill, its structure can be the three-dimensional even loose structure connecting, also can be the three-dimensional loose structure changing in gradient connecting, as shown in Figure 2.Hardening constituent material is magnesium or magnesium alloy, zinc or kirsite, titanium or titanium alloy, zirconium or the low-melting medical metal material of zircaloy geometric ratio parent metal silk, by pressure, cast ooze, pressure-free impregnation or inhale the processes such as casting and hardening constituent metal is penetrated in the loose structure of matrix, obtain a kind of composite construction, then by chemical mordant, carry out selective corrosion (corrosion hardening constituent as required, but do not corrode parent metal silk), part is removed hardening constituent, thereby form the medical gradient composites of outside porous, internal entity gradient-structure, as shown in Figure 3.Chemical mordant can be according to matrix material different selection of chemical characteristic from hardening constituent material, in addition according to whether volume is removed and removed to the hardening constituent that need to determine of gradient composites performance, the removal volume of hardening constituent can be realized by controlling the chemical attack time, to regulate the relative volume mark of internal entity structure and outside loose structure, i.e. volume proportion separately, thereby the performance such as structure, mechanics, physics that regulates and controls this medical gradient composites, meets the instructions for use under different situations.
The wire diameter of described matrix is between 0.005mm-3mm, and the porosity of matrix is adjustable within the scope of 10%-90%, and the volume fraction of hardening constituent can be adjustable at 0%-90%.The porosity of described gradient composites can regulate and control arbitrarily in 0% to 90% scope, and comprcssive strength scope is at 5.0MPa-300MPa, and modulus of elasticity in comperssion scope is at 100MPa-120GPa.
Described gradient composites can add the sterilizations such as Ag, Ca, Sr or be beneficial to the beneficial element of skeletonization in preparation process, and preparation can be carried out the surface treatments such as differential arc oxidation, anodic oxidation later, to improve its bone transmission and bone inducing properties.
Described medical gradient porous composite can meet the needs that great majority are transplanted the higher bone filling of requirement of strength, bone reparation, bone, such as all kinds of artificial jointes (hip joint, knee joint etc.), spinal fusion material, bone support the application of the aspects such as repair materials.
Be below embodiments of the invention.
Example 1
The titanium silk that the diameter that adopts medical grade is 0.4mm, makes the POROUS TITANIUM matrix of setting shape and setting porosity with mechanical winding, its porosity is 50%; The hole that medical high-purity Mg is injected to POROUS TITANIUM matrix by pressure-free impregnation technology is inner, form composite, the hcl corrosion that is 10% by volumetric concentration again, etching time is 10 minutes, the gradient porous titanium magnesium base composite material that formation porosity is 30%, the comprcssive strength of this gradient composites is 120MPa, and elastic modelling quantity reaches 6GPa, and the bone that is applicable to bone to have relatively high expectations is repaired occasion.
Example 2
The tantalum wire that the diameter that adopts medical grade is 0.1mm, with mechanical winding, make the porous tantalum matrix of setting shape and setting porosity, its porosity is 90%, by inhaling casting technology, the hole that medical titanium alloy is injected to porous tantalum matrix is inner, form composite, the sulphuric acid chemical attack that is 40% by volumetric concentration again, etching time is 30 minutes, the gradient porous tantalum titanium composite material that formation porosity is 70%, the comprcssive strength of this gradient composites is 220MPa, and its elastic modelling quantity is 40GPa, and the bone that is applicable to bone to have relatively high expectations is repaired occasion.
Example 3
Adopt the zirconium silk of medical grade, its inner zirconium filament diameter is 0.05mm, outside zirconium filament diameter is 1mm, with mechanical winding, make inner aperture little, the large gradient porous titanio body in outside aperture, by pressure-free impregnation technology, medical Mg-RE alloy is injected to the hole of POROUS TITANIUM matrix, form gradient composites, the rare nitric acid chemical that is 20% by volumetric concentration again corrodes, etching time is 5 minutes, the gradient porous titanium magnesium alloy composite that formation porosity is 10%, the comprcssive strength of this gradient composites is 160MPa, its elastic modelling quantity is 15GPa, the bone that is applicable to bone to have relatively high expectations is repaired occasion.
Example 4
The tantalum wire that the diameter that adopts medical grade is 3mm, makes the porous tantalum of setting shape and setting porosity with mechanical winding, its porosity is 40%; By inhaling casting technology, the hole that medical zircaloy is injected to porous tantalum matrix is inner, form composite, the sulphuric acid that is 80% by volumetric concentration again carries out chemical attack, etching time is 15 minutes, the gradient porous tantalum zirconium composite material that formation porosity is 20%, and the comprcssive strength of this gradient composites is 300MPa, its elastic modelling quantity is 120GPa, and the bone that is applicable to bone to have relatively high expectations is repaired occasion.
Example 5
The 316L stainless steel silk that the diameter that adopts medical grade is 1.8mm, with mechanical winding, make the porous stainless steel of setting shape and setting porosity, its porosity is 10%, by pressure, cast the technology of oozing and kirsite is injected to the hole inside of porous stainless steel base, form composite, by volumetric concentration, be 10% dilute sulfuric acid chemical attack again, etching time is 3 minutes, gradient porous rustless steel-zinc composite that formation porosity is 5%, the comprcssive strength of this gradient composites is 60MPa, elastic modelling quantity is 3GPa, and the bone that is applicable to bone to have relatively high expectations is repaired occasion.
Example 6
Portion aperture is little intentionally for the zirconium silk mixed weaving that the titanium silk that the diameter that adopts medical grade is 0.005mm and diameter are 3mm, the large gradient porous titanium zirconio body in outside aperture, its porosity is 90%, by pressure-free impregnation technology, kirsite is infiltrated in the hole of this POROUS TITANIUM zirconio body, gradient titanium zirconium-zinc alloy composites that formation porosity is 0%, the comprcssive strength of this gradient composites is 140MPa, and elastic modelling quantity is 33GPa, and the bone that is applicable to bone to have relatively high expectations is repaired occasion.
Example 7
The titanium silk that the diameter that adopts medical grade is 0.01mm, the zirconium silk of 0.08mm, it is titanium from inside to outside successively that the tantalum wire of 0.5mm and the stainless steel silk of 1.5mm are woven into, zirconium, tantalum, stainless gradient porous structure matrix, the porosity of each layer of porous material is respectively 40%, 60%, 70% and 90%, whole porosity is 68%, the method that magnesium calcium alloy is cast by suction is infiltrated in this matrix loose structure, form the composite of structure-component gradient, by volumetric concentration, be that 7% hydrochloric acid corrodes again, etching time is 20 minutes, obtain porosity and be 40% gradient composites, its comprcssive strength is 245MPa, elastic modelling quantity is 100GPa, the bone that is applicable to bone to have relatively high expectations is repaired occasion.
Example 8
The titanium silk that the diameter that adopts medical grade is 0.006mm is woven into the gradient porous material that interior porosity is 10%, external pores rate is 90%, its whole porosity is 70%, magnesium-zinc alloy is injected to this matrix porous material, form composite, by volumetric concentration, be that 15% dilute sulfuric acid corrodes again, etching time is 45 minutes, obtain porosity and be gradient porous titanium-magnesium-zinc alloy composite of 50%, its comprcssive strength is 5MPa, elastic modelling quantity is 100MPa, and the bone that is applicable to bone to have relatively high expectations is repaired occasion.
Claims (10)
1. a medical gradient composites, it is characterized in that: described gradient composites comprises the matrix of the loose structure that has uniform loose structure or change in gradient and infiltrates the hardening constituent of this matrix, described matrix is formed by medical metal wire knitted, described hardening constituent is that fusing point is than this low-melting metal wiry, its by pressure, cast ooze, pressure-free impregnation or inhale casting process and infiltrate in the loose structure of described matrix, then with chemical mordant, carry out selective corrosion and partly remove this hardening constituent, form internal entity and the medical gradient composites of outside porous.
2. medical gradient composites according to claim 1, is characterized in that: by changing described string diameter wiry or weaving method, control aperture and the porosity of described matrix, the porosity of this matrix is adjustable within the scope of 10%-90%.
3. medical gradient composites according to claim 1 and 2, is characterized in that: described tinsel is medical titanium silk, tantalum wire, zirconium silk or stainless steel silk, and diameter is 0.005mm-3mm.
4. medical gradient composites according to claim 1, is characterized in that: described hardening constituent is magnesium, magnesium alloy, titanium, titanium alloy, zirconium, zircaloy, zinc or kirsite.
5. medical gradient composites according to claim 1, it is characterized in that: the removal volume that regulates hardening constituent by controlling etching time, regulate and control the volume fraction of described matrix and hardening constituent, to regulate and control structure and the mechanical property of described medical gradient composites, meet the instructions for use under different situations.
6. medical gradient composites according to claim 5, is characterized in that: described etching time is 3-45 minute, and the volume fraction of described hardening constituent is adjustable within the scope of 0%-90%.
7. medical gradient composites according to claim 1, is characterized in that: described chemical mordant is hydrochloric acid, sulphuric acid, dilute sulfuric acid or rare nitric acid.
8. medical gradient composites according to claim 1, is characterized in that: the porosity ranges of described gradient composites is 0% to 90%, and comprcssive strength scope is 5.0MPa-300MPa, and modulus of elasticity in comperssion scope is 100MPa-120GPa.
9. medical gradient composites according to claim 1, is characterized in that: described gradient composites adds Ag, Ca or Sr element in preparation process, carries out differential arc oxidation or anodized surface and process after having prepared.
10. the application of medical gradient composites aspect artificial joint, spinal fusion material and bone support repair materials described in a claim 1.
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| CN104911515A (en) * | 2015-05-25 | 2015-09-16 | 上海交通大学 | Preparation method of fiber reinforced porous magnesium |
| CN106109064A (en) * | 2016-06-15 | 2016-11-16 | 东北大学 | A kind of spinal fusion device |
| CN106267361A (en) * | 2016-08-29 | 2017-01-04 | 上海交通大学 | A kind of medical gradient porous composite of medicine-carried metal-polymer |
| CN107638235A (en) * | 2017-06-22 | 2018-01-30 | 宁波创导三维医疗科技有限公司 | Finger joint prosthesis |
| CN108568511A (en) * | 2018-05-16 | 2018-09-25 | 广东鸿特精密技术肇庆有限公司 | A kind of Metal screen cloth reinforced phase and its application in infiltration by squeeze casting casting |
| CN111250703A (en) * | 2020-05-06 | 2020-06-09 | 季华实验室 | Magnesium-based composite material taking titanium or titanium alloy as framework reinforcement and preparation method thereof |
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| CN103589888A (en) * | 2013-11-05 | 2014-02-19 | 上海交通大学 | Preparation method of structure-controllable magnesium-based three-dimensional porous material |
| CN103599560A (en) * | 2013-11-05 | 2014-02-26 | 上海交通大学 | Medical titanium/magnesium composite material and preparation method thereof |
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Cited By (8)
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| CN104911515A (en) * | 2015-05-25 | 2015-09-16 | 上海交通大学 | Preparation method of fiber reinforced porous magnesium |
| CN104911515B (en) * | 2015-05-25 | 2017-01-25 | 上海交通大学 | Preparation method of fiber reinforced porous magnesium |
| CN106109064A (en) * | 2016-06-15 | 2016-11-16 | 东北大学 | A kind of spinal fusion device |
| CN106267361A (en) * | 2016-08-29 | 2017-01-04 | 上海交通大学 | A kind of medical gradient porous composite of medicine-carried metal-polymer |
| CN107638235A (en) * | 2017-06-22 | 2018-01-30 | 宁波创导三维医疗科技有限公司 | Finger joint prosthesis |
| CN108568511A (en) * | 2018-05-16 | 2018-09-25 | 广东鸿特精密技术肇庆有限公司 | A kind of Metal screen cloth reinforced phase and its application in infiltration by squeeze casting casting |
| CN108568511B (en) * | 2018-05-16 | 2020-02-28 | 广东鸿特精密技术肇庆有限公司 | Metal mesh cloth reinforcing phase and application thereof in extrusion infiltration casting |
| CN111250703A (en) * | 2020-05-06 | 2020-06-09 | 季华实验室 | Magnesium-based composite material taking titanium or titanium alloy as framework reinforcement and preparation method thereof |
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Effective date of registration: 20200119 Address after: 201203 room 105g, No.199, GuoShouJing Road, Shanghai pilot Free Trade Zone, Pudong New Area, Shanghai (biological and pharmaceutical innovation building) Co-patentee after: He Guo Patentee after: Shanghai Jiaotong University Intellectual Property Management Co., Ltd. Address before: 200240 Dongchuan Road, Shanghai, No. 800, No. Patentee before: Shanghai Jiaotong University |
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Effective date of registration: 20220111 Address after: 200240 No. 800, Dongchuan Road, Shanghai, Minhang District Patentee after: SHANGHAI JIAO TONG University Address before: Room 105g, biology and medicine innovation building, 199 GuoShouJing Road, Shanghai pilot Free Trade Zone, Pudong New Area, Shanghai, 201203 Patentee before: Shanghai Jiaotong University Intellectual Property Management Co.,Ltd. Patentee before: He Guo |
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