CN104383602B - A kind of Medical implant - Google Patents

A kind of Medical implant Download PDF

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Publication number
CN104383602B
CN104383602B CN201410707693.8A CN201410707693A CN104383602B CN 104383602 B CN104383602 B CN 104383602B CN 201410707693 A CN201410707693 A CN 201410707693A CN 104383602 B CN104383602 B CN 104383602B
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medical
porous
embedded material
medical embedded
biodegradable
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CN104383602A (en
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叶雷
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Chongqing Runze Pharmaceutical Co Ltd
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蔡淑芬
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    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/40Composite materials, i.e. containing one material dispersed in a matrix of the same or different material
    • A61L27/42Composite materials, i.e. containing one material dispersed in a matrix of the same or different material having an inorganic matrix
    • A61L27/427Composite materials, i.e. containing one material dispersed in a matrix of the same or different material having an inorganic matrix of other specific inorganic materials not covered by A61L27/422 or A61L27/425
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/50Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/50Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • A61L27/56Porous materials, e.g. foams or sponges
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/50Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • A61L27/58Materials at least partially resorbable by the body
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2430/00Materials or treatment for tissue regeneration
    • A61L2430/02Materials or treatment for tissue regeneration for reconstruction of bones; weight-bearing implants

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  • Health & Medical Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Veterinary Medicine (AREA)
  • Public Health (AREA)
  • Dermatology (AREA)
  • Medicinal Chemistry (AREA)
  • Oral & Maxillofacial Surgery (AREA)
  • Transplantation (AREA)
  • Epidemiology (AREA)
  • General Health & Medical Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Composite Materials (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Dispersion Chemistry (AREA)
  • Materials For Medical Uses (AREA)
  • Prostheses (AREA)

Abstract

The invention provides a kind of Medical implant with composite construction, be made up of two kinds of medical embedded material compounds, it is characterized in that: the biodegradation rate of two kinds of medical embedded materials is different; Two kinds of medical embedded materials are chimeric each other and composite construction in intertexture shape forms DB; Wherein arbitrary medical embedded material still keeps its biology performance alone and physical and mechanical properties, and is a continuous structure body separately.The present invention of this construction features provides multi-level healing space can to the reparation of implant site, to the growth time that normal structure is longer, be actually the implantation space progressively reserved with medical embedded material biodegradation and exchange the longer growth time of normal structure for, be more conducive to be suitable for mutually with the normal healing process of impaired host's implant site.

Description

A kind of Medical implant
The present patent application is application number 2011104403934,2011 applyings date December 26 days, the divisional application of denomination of invention " a kind of Medical implant ".
Technical field
The present invention relates to a kind of medical embedded material, particularly a kind of Medical implant with composite construction.
Background technology
Medical embedded material refers to plantation, bury, be fixed on the impaired or diseased region of host, support, repair, substitute the special medical disposable materials of a class of its function, that a class has property and function, reproduce for artificial organ, surgical repair, physiotherapy and rehabilitation, medical diagnosis on disease and treatment, to the material that tissue, blood have no adverse effects.
Medical embedded material can be classified by materials application position, and as hard tissue materials such as bone, cartilage, teeth, the hard tissue material wherein for orthopaedics is a very important class medical embedded material.
Medical embedded material can also be classified by the biodegradability of material, as biodegradable medical embedded material and not biodegradable medical embedded material; And different biodegradable medical embedded materials, they implant host in biodegradation rate be also different usually, faster or slower.
Medical embedded material roughly can be divided into several classes such as metal, pottery and polymer by the classification of material own.As the replacing material of the bearing type sclerous tissueses such as knee joint, marrow joint, fracture fixation and artificial bone, metal, pottery and polymer respectively have its advantages and disadvantages; Up to now, for the consideration of intensity and safety, the skeleton derivants of bioceramic and humans and animals etc. generally give the certain biocompatibility of metal and biological activity as coating or second-phase, and there is the high mechanical properties and excellent fatigue behaviour that other materials can not compare due to metal material, be now still the biomaterial of most widely used load clinically.
Along with develop rapidly that is scientific and technological and medical science, at present, metal medical embedded material is made porous metals medical embedded material and comes true, this kind of material has the important and special purposes such as treatment osseous tissue wound and bone formation necrosis.As porous metals rustless steel, porous metals titanium, porous metals tantalum, porous metals niobium, porous magnesium zinc etc., the porous embedded material that they use as osseous tissue wound and bone formation necrosis therapeutic, its porosity should reach 30 ~ 80%, hole is all communicated with and is uniformly distributed, make it namely consistent with body bone tissue growth phase, and the weight of lightening material of should trying one's best itself, implant with applicable human body and use.At present, can by refractory metals tantalum, niobium is made has the higher physical and mechanical properties being uniformly distributed interconnected pore and adapting with human body, become gradually and ensure that the important of freshman bone tissue's normal growth connects and composes material pieces.
Emphasize as front, as the hard tissue implanting material of orthopaedics, except possessing certain biocompatibility and biological activity, it also needs the physical and mechanical properties adapted with human body, connects bearing strength accordingly to reach in implant into body to have; The more important thing is that its needs to have and higher be uniformly distributed interconnected pore, to ensure that there are normal growing space and repair time in freshman bone tissue.As medical implant, these demands are conflicting, and for providing more normal growth space to freshman bone tissue, embedded material just should have more interconnected pore; And along with the porosity of embedded material constantly increase time, the physical and mechanical propertiess such as its bearing strength usually do not reach again human body implant needed for other correlated performances.And the implantation space of human body damaged part is very limited usually, implantation piece will meet the porosity of physical and mechanical properties and Geng Gao simultaneously, and the normal growth space that this porous medical embedded material provides to freshman bone tissue in limited implantation space is determined by the porosity of embedded material substantially.
Also have in prior art and adopt a kind of biological and medicinal implant material to solve support strength as basal layer, the another kind of biological and medicinal implant material of coated gives certain biocompatibility and biological activity thereon again, their binding sites are each other only that a kind of face combines, the Medical implant of this composite construction still can not match with the normal healing process of impaired host well, is unfavorable for the reparation of the impaired or diseased region of host.
Summary of the invention
The object of the present invention is to provide a kind of have to be applicable to repairing support and the Medical implant that matches of normal healing process.
The object of the present invention is achieved like this: a kind of Medical implant, and it is made up of two or more medical embedded material compounds, it is characterized in that: the biodegradation rate of various medical embedded material is different; Various medical embedded material is chimeric each other and composite construction in intertexture shape forms DB; Wherein arbitrary medical embedded material still keeps its biology performance alone and physical and mechanical properties, and is a continuous structure body separately.
Why the present invention of this construction features selects the medical embedded material that biodegradation rate is different, to provide multi-level healing space to the reparation of implant site, to the growth time that normal structure is longer, be actually the implantation space progressively reserved with medical embedded material biodegradation and exchange the longer growth time of normal structure for, be more conducive to be suitable for mutually with the normal healing process of impaired host's implant site.
Preferred embodiments of the present invention are that the medical embedded material that employing two kinds of biodegradation rates are different forms corresponding DB, namely described DB interweaves chimeric with matched molds structure each other by two kinds of medical embedded materials, and the maximum space that often kind of medical embedded material limits to the external boundary that its stereo directional extends continuously is identical with the maximum space that the DB external boundary be made up of them limits or substantially suitable.Here the matched molds structure mentioned can be interpreted as that these two kinds have the medical embedded material of continuous structure body of one's own each other a kind of " chiral structure " visually, and they are not simply in the matched molds structure that one side combines, but the intertexture chimeric surface that comparatively intricately is crisscross, the DB of the supporter of the other side each other, the present invention one of this construction features is easily obtained, two is requirements that the DB formed from two kinds of medical embedded materials for continuum also more easily reaches the support strength of implant site, and two can be provided to cure space due to the implantation space not coexisting identical of degradation speed again, more be conducive to the reparation of impaired host.
So-called biodegradation rate refers to medical embedded material biodegradable speed in the host implanted; The medical embedded material that biodegradation rate is different, the biodegradation rate faster or slower in the host implanted of the medical embedded material of employing can be referred to, but also can be a kind of extreme case, wherein one is not biodegradable medical embedded material, and another kind is biodegradable medical embedded material.The preferred two kinds of medical embedded materials of the present invention are exactly a kind of is not biodegradable porous medical embedded material, and another kind is biodegradable medical embedded material; Be easy to get in not biodegradable porous medical embedded material prior art like this, on this material, equally distributed hole through continuously adopts the conventional means of prior art also easily to be filled by biodegradable medical embedded material the composite construction forming DB completely simultaneously.Obviously, these two kinds of medical embedded materials all keep its biology performance alone and physical and mechanical properties, are also a continuous structure body separately; Clearly, the hole of porous medical embedded material is filled by another kind of medical embedded material, and the space that the another kind in DB is continuous structure body medical embedded material to be reserved equally fill by the porous medical embedded material of continuous structure body, namely both holes are filled continuously by the other side mutually, thus the maximum space that often kind of medical embedded material is limited to the external boundary that its stereo directional extends continuously is identical with the maximum space that the DB external boundary that they are formed limits or substantially quite also become easy realization.
The further preferred scheme of the present invention is described not biodegradable porous medical embedded material is porous medical metal implanted material or porous medical ceramic embedded material; Described biodegradable medical embedded material is biodegradable medical macromolecular materials or methylol inorganic salt materials.
Wherein the preferred scheme of porous medical metal implanted material adopts as porous tantalum, porous niobium, POROUS TITANIUM or porous stainless steel etc.Biodegradable medical macromolecular materials are polyester, poe, condensing model, polyamide, poly-alpha-cyanoacrylate or poly phosphazene.
Medical implant provided by the invention, can also be fitted together to completely by three kinds of medical embedded materials that biodegradation rate is different and formed DB in intertexture shape composite construction, it is chimeric that three kinds of medical embedded materials in described DB are that complementary structure interweaves, and the maximum space that the maximum space that limits to the external boundary that its stereo directional extends continuously of often kind of medical embedded material and the complementary DB external boundary formed of three limit is identical or substantially suitable.
The DB that three kinds of medical embedded material compounds are formed, is preferably made up of the not biodegradable porous medical embedded material of one and other two kinds of biodegradable medical embedded materials; The hole through continuously wherein porous medical embedded material distributed is adopted depositional mode or/and plating mode is filled respectively by other Biodegradable material, until form DB.Certainly, when " the porous body support " of a kind of porous medical embedded material as Medical implant, on it, the hole through continuously of distribution can also adopt and first deposit or electroplate a kind of biodegradable medical embedded material layer, grouting solidification is adopted to fill another kind of biodegradable medical embedded material layer again, until form DB.The gradation no matter this section is mentioned deposits different medical embedded material layers; Or different medical embedded material layers is electroplated in gradation; Or first deposit re-plating; Or first electroplate and deposit again; Or first deposit solidification of being in the milk again; Or first electroplate solidification of being in the milk again, it is all to form a kind of DB, more importantly to meet in described DB maximum space that often kind of medical embedded material limits to the external boundary that its stereo directional extends continuously identical or substantially suitable with the maximum space that the DB external boundary that three's complementation is formed limits.Can learn, after these three kinds of medical embedded materials form DBs, they separately continuous structure body must become " the porous body support " of other medical embedded materials.
Similarly, about three kinds of medical embedded materials, wherein a kind of to be preferably not biodegradable porous medical embedded material be porous medical metal implanted material or porous medical ceramic embedded material; Described biodegradable medical embedded material is biodegradable medical macromolecular materials or methylol inorganic salt materials.
The preferred scheme of porous medical metal implanted material adopts as porous tantalum, porous niobium, POROUS TITANIUM or porous stainless steel etc.Biodegradable medical macromolecular materials are polyester, poe, condensing model, polyamide, poly-alpha-cyanoacrylate or poly phosphazene.
In the market or the not biodegradable porous metals medical embedded material that document is reported or porous medical ceramic material can be the selection of Medical implant of the present invention, these porous medical embedded materials have continuously the implantation requirement that through hole meets human body, by biodegradable medical macromolecular materials by prior art make molten carry out perfusion fill again sintering make; Or become feasible by the depositional mode of prior art or/and described implantation piece is made in plating mode filling.
In sum, beneficial effect of the present invention is as follows:
Due to not biodegradable porous medical embedded material selected in above-mentioned Medical implant and another or multiple biodegradable medical embedded material, they all keep self biology performance and physical and mechanical properties, all meet as the medical embedded related request of human body.Because they are fitted together to the DB in the composite construction formed with interweaving each other, its mechanical strength is higher than the intensity of simple porous medical embedded material; When mechanical strength is identical, the porosity of porous medical embedded material can be improved once again again, the intensity caused due to the increase of porosity reduces, can by the other biodegradable medical embedded material reinforcement be filled in wherein or raising.Such Medical implant, in identical implantation space, the growing space of the larger freshman bone tissue of host can be supplied to than the embedded material of prior art, along with the biodegradation of biodegradable medical embedded material, the growing space expanded gradually is provided to the normal growth of freshman bone tissue, the freshman bone tissue constantly grown then substitutes biodegradable medical embedded material and occupies in the hole of not biodegradable porous medical embedded material, with the support strength of supplementary Medical implant, to meet the normal instructions for use of host's damaged part.
Medical implant of the present invention, compared with the composite implantation material formed, is supplied to the time and space that host repairs longer larger with existing coating for metal surfaces or two kinds of that simple composite of medical embedded material in identical implantation space.If adopt the composite construction being fitted together to or superposing two or more medical embedded materials simply, the implantation volume that their mutual independence determines this implantation piece is the volume sum that external world's end that various medical embedded material extends limits, although this implantation piece is due to their biodegradation rate difference, also provide the headspace that two place's normal structures grow into host, but, it but needs larger implantation space, could provide the repair time identical with described product of the present invention to normal structure.
Accompanying drawing explanation
Below in conjunction with drawings and Examples, the invention will be further described
Fig. 1 is the structural representation of the embodiment of the present invention 1;
Fig. 2 is the structural representation of the embodiment of the present invention 2;
Fig. 3 is A portion enlarged drawing in Fig. 2.
Detailed description of the invention
Embodiment 1: see Fig. 1, a kind of Medical implant, is made up of two kinds of medical embedded material compounds, and the biodegradation rate of these two kinds of medical embedded materials is different, and their chimeric each other and in intertexture shape composite constructions form a DB; Wherein arbitrary medical embedded material still keeps its biology performance alone and physical and mechanical properties, and is a continuous structure body separately.
With further reference to Fig. 1, medical embedded material 1 and medical embedded material 2 interweave with matched molds structure each other and are chimericly formed DB, and the maximum space that often kind of medical embedded material limits to the external boundary that its stereo directional extends continuously is identical with the maximum space that the DB external boundary that they are formed limits.
Two kinds of medical embedded materials of this example are respectively not biodegradable porous medical embedded material (as porous medical metal implanted material, porous medical ceramic embedded material) and biodegradable medical macromolecular materials (polyester, poe, condensing model, polyamide, poly-alpha-cyanoacrylate or poly phosphazene); Wherein medical embedded material 1 is porous medical embedded material, medical embedded material 2 is biodegradable medical macromolecular materials, and the hole through continuously that porous medical embedded material distributes is filled the composite construction forming described DB completely by biodegradable medical macromolecular materials.
Porous medical metal implanted material of the present invention can be porous tantalum well known in the prior art, porous niobium, POROUS TITANIUM or porous stainless steel etc.During using porous medical metal implanted material as " the porous body support " of Medical implant of the present invention, molten made by biodegradable medical macromolecular materials in addition, adopts the grouting of prior art solidification to fill.
Embodiment 2: see Fig. 2, a kind of Medical implant, it is by the completely chimeric DB in intertexture shape formed of three kinds of medical embedded materials that biodegradation rate is different; Wherein arbitrary medical embedded material still keeps its biology performance alone and physical and mechanical properties, and is a continuous structure body certainly.
Medical embedded material 1 in described DB interweaves chimeric with medical embedded material 2 and medical embedded material 3 complementary structure, and the maximum space that often kind of medical embedded material limits to the external boundary that its stereo directional extends continuously is identical with the maximum space that the DB external boundary that three's complementation is formed limits.
Wherein medical embedded material 1 is not biodegradable porous medical embedded material, medical embedded material 2 and medical embedded material 3 are biodegradable medical embedded material, biodegradable medical embedded material in this example is biodegradable medical macromolecular materials, and these three kinds of medical embedded materials form Medical implant of the present invention; Wherein on porous medical embedded material 1, the hole through continuously of distribution is adopted depositional mode or/and plating mode is filled respectively by other biodegradable medical macromolecular materials, until form DB.
Certainly, when " the porous body support " of a kind of porous medical embedded material as Medical implant, on it, the hole through continuously of distribution can also adopt and first deposit or electroplate a kind of biodegradable medical embedded material layer, grouting solidification is adopted to fill another kind of biodegradable medical embedded material layer again, until form DB.
Porous medical embedded material is porous medical metal implanted material or porous medical ceramic embedded material; Described biodegradable medical embedded material is biodegradable medical macromolecular materials or methylol inorganic salt materials.
Wherein the preferred scheme of porous medical metal implanted material adopts as porous tantalum, porous niobium, POROUS TITANIUM or porous stainless steel etc.Biodegradable medical macromolecular materials are polyester, poe, condensing model, polyamide, poly-alpha-cyanoacrylate or poly phosphazene.

Claims (4)

1. a Medical implant, is made up of two kinds of medical embedded material compounds, it is characterized in that: the biodegradation rate of these two kinds of medical embedded materials is different, and their chimeric each other and in intertexture shape composite constructions form a DB; Wherein arbitrary medical embedded material still keeps its biology performance alone and physical and mechanical properties, and is a continuous structure body separately; Described medical embedded material and medical embedded material interweave with matched molds structure each other and are chimericly formed DB, and the maximum space that often kind of medical embedded material limits to the external boundary that its stereo directional extends continuously is identical with the maximum space that the DB external boundary that they are formed limits; Two kinds of described medical embedded materials are respectively not biodegradable porous medical embedded material and biodegradable medical macromolecular materials, and described not biodegradable porous medical embedded material is porous medical metal implanted material; The hole through continuously wherein porous medical embedded material distributed is filled the composite construction forming described DB completely by biodegradable medical macromolecular materials; Using the porous body support of described porous medical metal implanted material as Medical implant, molten made by described biodegradable medical macromolecular materials, adopts grouting solidification to fill described porous medical metal implanted material.
2. Medical implant as claimed in claim 1, is characterized in that: described porous medical metal implanted material is porous tantalum, porous niobium, POROUS TITANIUM or porous stainless steel.
3. Medical implant as claimed in claim 1 or 2, is characterized in that: described biodegradable medical macromolecular materials are polyester, condensing model, polyamide, poly-alpha-cyanoacrylate or poly phosphazene.
4. Medical implant as claimed in claim 1, it is characterized in that: described porous medical metal implanted material is porous tantalum, described biodegradable medical macromolecular materials are polyester.
CN201410707693.8A 2011-12-26 2011-12-26 A kind of Medical implant Active CN104383602B (en)

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CN201410707693.8A CN104383602B (en) 2011-12-26 2011-12-26 A kind of Medical implant
CN201110440393.4A CN103170013B (en) 2011-12-26 2011-12-26 Medical implant

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US20160176107A1 (en) * 2014-12-18 2016-06-23 Cardiac Pacemakers, Inc. Fibrous joinery interface between structures
CN107198600A (en) * 2016-03-18 2017-09-26 重庆润泽医药有限公司 A kind of interbody spinal implant
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
CN109893304B (en) * 2019-04-16 2021-03-23 南京医科大学附属逸夫医院 3D of specific form and structure prints tissue engineering support

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DE29822563U1 (en) * 1998-12-18 1999-02-18 Aesculap Ag & Co Kg Implant
CN1302820C (en) * 2005-09-16 2007-03-07 哈尔滨工程大学 Bone tissue rack of TiO2 reinforced polyhydroxyethyl methacrylate and its prepn process
WO2008017170A1 (en) * 2006-08-10 2008-02-14 Ao Technology Ag Biomedical polymer material for tissue repair and engineering
CN100546661C (en) * 2006-12-01 2009-10-07 华南理工大学 A kind of preparation method of in situ pore-forming self-setting calcium phosphate composite tissue engineering scaffold
KR101289122B1 (en) * 2008-03-18 2013-07-23 한국보건산업진흥원 COMPLEX IMPLANTS INFILTERATED WITH BIODEGRADABLE Mg(ALLOYS) INSIDE POROUS STRUCTURAL MATERIALS AND METHOD FOR MANUFACTURING THE SAME
CN101474428B (en) * 2009-01-16 2012-09-05 浙江普洛家园生物医学材料有限公司 Polyester reinforced degradable porous gastrosil compound stent material, preparation and use
CN101906549B (en) * 2010-08-17 2012-11-21 南京航空航天大学 Porous foam metal based embedded type solid self-lubricating composite material and preparation method thereof
CN101983728B (en) * 2010-11-09 2013-12-04 厦门大学 Shell porous hydroxyapatite basal bone repair material and preparation method thereof

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CN103170013B (en) 2014-12-24
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WO2013097383A1 (en) 2013-07-04

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