CN105669084B - It is a kind of for biomimetic material of shoulder joint and its preparation method and application - Google Patents
It is a kind of for biomimetic material of shoulder joint and its preparation method and application Download PDFInfo
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- CN105669084B CN105669084B CN201610024994.XA CN201610024994A CN105669084B CN 105669084 B CN105669084 B CN 105669084B CN 201610024994 A CN201610024994 A CN 201610024994A CN 105669084 B CN105669084 B CN 105669084B
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B26/00—Compositions of mortars, concrete or artificial stone, containing only organic binders, e.g. polymer or resin concrete
- C04B26/02—Macromolecular compounds
- C04B26/04—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS 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
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/02—Inorganic materials
- A61L27/025—Other specific inorganic materials not covered by A61L27/04 - A61L27/12
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS 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
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/02—Inorganic materials
- A61L27/08—Carbon ; Graphite
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS 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
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/14—Macromolecular materials
- A61L27/16—Macromolecular materials obtained by reactions only involving carbon-to-carbon unsaturated bonds
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS 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
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/14—Macromolecular materials
- A61L27/20—Polysaccharides
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS 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
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/36—Materials for grafts or prostheses or for coating grafts or prostheses containing ingredients of undetermined constitution or reaction products thereof, e.g. transplant tissue, natural bone, extracellular matrix
- A61L27/3637—Materials for grafts or prostheses or for coating grafts or prostheses containing ingredients of undetermined constitution or reaction products thereof, e.g. transplant tissue, natural bone, extracellular matrix characterised by the origin of the biological material other than human or animal, e.g. plant extracts, algae
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS 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
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS 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
- A61L2430/00—Materials or treatment for tissue regeneration
- A61L2430/02—Materials or treatment for tissue regeneration for reconstruction of bones; weight-bearing implants
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- Health & Medical Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Veterinary Medicine (AREA)
- Medicinal Chemistry (AREA)
- Oral & Maxillofacial Surgery (AREA)
- Transplantation (AREA)
- Epidemiology (AREA)
- Dermatology (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Biomedical Technology (AREA)
- Botany (AREA)
- Ceramic Engineering (AREA)
- Inorganic Chemistry (AREA)
- Biotechnology (AREA)
- Molecular Biology (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Meat, Egg Or Seafood Products (AREA)
- Prostheses (AREA)
- Materials For Medical Uses (AREA)
- Dental Preparations (AREA)
Abstract
The invention discloses a kind of for biomimetic material of shoulder joint and its preparation method and application, the biomimetic material is made up of the raw material below according to parts by weight：2 28 parts of montmorillonite 2,45 58 parts of polyvinyl alcohol, 10 16 parts of poplar, 37 parts of graphite, 150 170 parts of ethanol, 110 125 parts of ammoniacal liquor, 8 15 parts of carragheen.Montmorillonite, polyvinyl alcohol, poplar, graphite are crushed standby；Montmorillonite pretreatment liquid is made with Ethanol Treatment in montmorillonite powder；The processing of montmorillonite pretreatment liquid will be added after polyvinyl alcohol powder AMMONIA TREATMENT mixture A is made；White poplar wood powder, graphite powder are mixed with remaining ethanol, mixture B is made in microwave treatment.By the stirring of mixture A, mixture B and carragheen, ultrasonically treated, drying.Biomimetic material produced by the present invention has high tensile strength, high impact flexibility, fabulous antifouling property, and without abrasion between material when using, boundary lubrication is good.Preparation method of the present invention is simple, suitable for industrialized production.
Description
Technical field
It is specifically a kind of for biomimetic material of shoulder joint and preparation method thereof the present invention relates to medical material technical field
And application.
Background technology
The material that biomimetic material refers to the various features or characteristic of mimic biology and developed.Generally copying life system
The operational mode of system and the structure law of biomaterial and the artificial material referred to as biomimetic material manufactured and designed.Joint is that human body is held
Maximum biological friction pair loaded, cartilage is the soft tissue being located between bone and bone.The joint of daily life high frequency makes
Turn into the common phenomenon of clinical orthopaedicses with the loss and lesion for making articular cartilage.Although conventional joint biomimetic material is one at present
Determine to play a part of in degree to substitute cartilage, but also exist it is easy to wear loosen, boundary lubrication is poor, shortage bioactivity not
It is sufficient, the defect such as initial mechanical properties are low, poor toughness, it is difficult to which real realize replaces cartilage function.
The content of the invention
There is high impact flexibility, fabulous antifouling property, the use without abrasion it is an object of the invention to provide a kind of
In biomimetic material of shoulder joint and its preparation method and application, to solve the problems mentioned in the above background technology.
To achieve the above object, the present invention provides following technical scheme：
A kind of biomimetic material for shoulder joint, is made up of the raw material below according to parts by weight：It is 2-28 parts of montmorillonite 2, poly-
45-58 parts of vinyl alcohol, 10-16 parts of poplar, 3-7 parts of graphite, 150-170 parts of ethanol, 110-125 parts of ammoniacal liquor, carragheen 8-15
Part.
It is used as further scheme of the invention：The biomimetic material for shoulder joint, by below according to the original of parts by weight
Material composition：4-26 parts of montmorillonite 2,49-53 parts of polyvinyl alcohol, 12-14 parts of poplar, 4-6 parts of graphite, 155-165 parts of ethanol, ammonia
115-120 parts of water, 10-13 parts of carragheen.
It is used as further scheme of the invention：The biomimetic material for shoulder joint, by below according to the original of parts by weight
Material composition：5 parts of montmorillonite 2,51 parts of polyvinyl alcohol, 13 parts of poplar, 5 parts of graphite, 160 parts of ethanol, 118 parts of ammoniacal liquor, carragheen
11 parts.
The preparation method of the biomimetic material for shoulder joint, is comprised the steps of：
1) montmorillonite, polyvinyl alcohol, poplar, graphite are cleaned, dried, pulverized, crossed 100 mesh sieves, then distinguish
Insert in micronizer and be crushed to 350 mesh, montmorillonite powder, polyvinyl alcohol powder, white poplar wood powder, graphite powder is made standby；
2) montmorillonite powder is inserted in the ethanol of 3-3.2 times of its quality, the sealing immersion 1.8-2h at 50-52 DEG C, then
Ultrasonically treated 1-1.5h is carried out, ultrasonic power is 900-1000W, montmorillonite pretreatment liquid is made；
3) polyvinyl alcohol powder is inserted in ammoniacal liquor, the sealing preserve 18-20h at a temperature of 45-48 DEG C adds montmorillonite
Pretreatment fluid, sealing stirring 1-1.3h, is then made mixture A at 55-60 DEG C；
4) white poplar wood powder, graphite powder are mixed with remaining ethanol, 2-2.5h is soaked at a temperature of 60-65 DEG C, is then put
In microwave reaction intracavitary；At ambient pressure, nitrogen is passed through to microwave reaction intracavitary, in control temperature to guarantor under the conditions of 180-200 DEG C
Warm 45-50min, is made mixture B；
5) mixture A is warming up to 65-68 DEG C, adds mixture B and carragheen sealing stirring 2-3h, then carry out ultrasound
1-1.5h is handled, ultrasonic power is 900-1000W, then stirring and drying is handy under nitrogen protection, under conditions of 90-100 DEG C
In the biomimetic material of shoulder joint.
Application of the biomimetic material in shoulder joint biomimetic material is prepared.
Compared with prior art, the beneficial effects of the invention are as follows：
The present invention has high stretching strong using biomimetic material made from the above method under the collective effect of each raw material
Degree and high impact flexibility, while biomimetic material produced by the present invention has fabulous antifouling property, it is imitative applied to shoulder joint
Green material, without abrasion between material when using, boundary lubrication is good.Preparation method of the present invention is simple, not using toxic thing
Matter, the material polluted to environment is not produced yet, suitable for industrialized production in process of production.
Embodiment
Below in conjunction with the embodiment of the present invention, the technical scheme in the embodiment of the present invention is clearly and completely described,
Obviously, described embodiment is only a part of embodiment of the invention, rather than whole embodiments.Based in the present invention
Embodiment, the every other embodiment that those of ordinary skill in the art are obtained under the premise of creative work is not made, all
Belong to the scope of protection of the invention.
Embodiment 1
In the embodiment of the present invention, a kind of biomimetic material for shoulder joint is made up of the raw material below according to parts by weight：Cover
De- 22 parts of stone, 45 parts of polyvinyl alcohol, 10 parts of poplar, 3 parts of graphite, 150 parts of ethanol, 110 parts of ammoniacal liquor, 8 parts of carragheen.
Montmorillonite, polyvinyl alcohol, poplar, graphite are cleaned, dried, is pulverized, 100 mesh sieves is crossed, then puts respectively
Enter and 350 mesh are crushed in micronizer, montmorillonite powder, polyvinyl alcohol powder, white poplar wood powder, graphite powder is made standby.It is de- by covering
Stone flour is inserted in the ethanol of 3 times of its quality, and sealing immersion 1.8h, then carries out ultrasonically treated 1h, ultrasonic power is at 50 DEG C
900W, is made montmorillonite pretreatment liquid.Polyvinyl alcohol powder is inserted in ammoniacal liquor, the sealing preserve 18h at a temperature of 45 DEG C, then added
Enter montmorillonite pretreatment liquid, sealing stirring 1h, is then made mixture A at 55 DEG C.By white poplar wood powder, graphite powder with it is remaining
Ethanol is mixed, and is soaked 2h at a temperature of 60 DEG C, is subsequently placed in microwave reaction intracavitary；At ambient pressure, it is passed through to microwave reaction intracavitary
Nitrogen, in control temperature to 45min is incubated under the conditions of 180 DEG C, is made mixture B.Mixture A is warming up to 65 DEG C, added mixed
Compound B and carragheen sealing stirring 2h, then carry out ultrasonically treated 1h, ultrasonic power is 900W, then under nitrogen protection, 90 DEG C
Under conditions of stirring and drying produce biomimetic material for shoulder joint.
Embodiment 2
In the embodiment of the present invention, a kind of biomimetic material for shoulder joint is made up of the raw material below according to parts by weight：Cover
De- 28 parts of stone, 58 parts of polyvinyl alcohol, 16 parts of poplar, 7 parts of graphite, 170 parts of ethanol, 125 parts of ammoniacal liquor, 15 parts of carragheen.
Montmorillonite, polyvinyl alcohol, poplar, graphite are cleaned, dried, is pulverized, 100 mesh sieves is crossed, then puts respectively
Enter and 350 mesh are crushed in micronizer, montmorillonite powder, polyvinyl alcohol powder, white poplar wood powder, graphite powder is made standby.It is de- by covering
Stone flour is inserted in the ethanol of 3.2 times of its quality, and sealing immersion 2h, then carries out ultrasonically treated 1.5h, ultrasonic power at 52 DEG C
For 1000W, montmorillonite pretreatment liquid is made.Polyvinyl alcohol powder is inserted in ammoniacal liquor, the sealing preserve 20h at a temperature of 48 DEG C,
Montmorillonite pretreatment liquid is added, sealing stirring 1.3h, is then made mixture A at 60 DEG C.By white poplar wood powder, graphite powder with
Remaining ethanol mixing, soaks 2.5h at a temperature of 65 DEG C, is subsequently placed in microwave reaction intracavitary；At ambient pressure, to microwave reaction
Intracavitary is passed through nitrogen, and in control temperature to 50min is incubated under the conditions of 200 DEG C, mixture B is made.Mixture A is warming up to 68
DEG C, mixture B and carragheen sealing stirring 3h are added, ultrasonically treated 1.5h is then carried out, ultrasonic power is 1000W, then in nitrogen
Stirring and drying produces the biomimetic material for shoulder joint under gas shielded, under conditions of 100 DEG C.
Embodiment 3
In the embodiment of the present invention, a kind of biomimetic material for shoulder joint is made up of the raw material below according to parts by weight：Cover
De- 24 parts of stone, 49 parts of polyvinyl alcohol, 12 parts of poplar, 4 parts of graphite, 155 parts of ethanol, 115 parts of ammoniacal liquor, 10 parts of carragheen.
Montmorillonite, polyvinyl alcohol, poplar, graphite are cleaned, dried, is pulverized, 100 mesh sieves is crossed, then puts respectively
Enter and 350 mesh are crushed in micronizer, montmorillonite powder, polyvinyl alcohol powder, white poplar wood powder, graphite powder is made standby.It is de- by covering
Stone flour is inserted in the ethanol of 3.1 times of its quality, and sealing immersion 1.9h, then carries out ultrasonically treated 1.2h, ultrasonic work(at 51 DEG C
Rate is 1000W, and montmorillonite pretreatment liquid is made.Polyvinyl alcohol powder is inserted in ammoniacal liquor, the sealing preserve at a temperature of 47 DEG C
19h, adds montmorillonite pretreatment liquid, and sealing stirring 1.2h, is then made mixture A at 57 DEG C.By white poplar wood powder, graphite
Powder is mixed with remaining ethanol, and 2.2h is soaked at a temperature of 62 DEG C, is subsequently placed in microwave reaction intracavitary；At ambient pressure, to microwave
Nitrogen is passed through in reaction chamber, in control temperature to 48min is incubated under the conditions of 190 DEG C, mixture B is made.Mixture A is warming up to
67 DEG C, mixture B and carragheen sealing stirring 2.5h are added, ultrasonically treated 1.2h is then carried out, ultrasonic power is 1000W, then
Under nitrogen protection, stirring and drying produces the biomimetic material for shoulder joint under conditions of 95 DEG C.
Embodiment 4
In the embodiment of the present invention, a kind of biomimetic material for shoulder joint is made up of the raw material below according to parts by weight：Cover
De- 26 parts of stone, 53 parts of polyvinyl alcohol, 14 parts of poplar, 6 parts of graphite, 165 parts of ethanol, 120 parts of ammoniacal liquor, 13 parts of carragheen.
Preparation process is consistent with embodiment 3.
Embodiment 5
In the embodiment of the present invention, a kind of biomimetic material for shoulder joint is made up of the raw material below according to parts by weight：Cover
De- 25 parts of stone, 51 parts of polyvinyl alcohol, 13 parts of poplar, 5 parts of graphite, 160 parts of ethanol, 118 parts of ammoniacal liquor, 11 parts of carragheen.
Preparation process is consistent with embodiment 3.
Comparative example 1
In addition to poplar is not contained, remaining process is consistent with embodiment 5.
Comparative example 2
In addition to ammoniacal liquor is not contained, remaining process is consistent with embodiment 5.
Above-described embodiment 1-5 and comparative example 1-2 material normal temperature condition is placed naturally carries out performance test after 36h, as a result
As shown in table 1.
Table 1
| Group | Tensile strength (MPa) | Elongation at break (%) | Impact flexibility (kJ/m2) |
| Embodiment 1 | 219 | 83 | 15.3 |
| Embodiment 2 | 232 | 88 | 15.8 |
| Embodiment 3 | 264 | 105 | 17.5 |
| Embodiment 4 | 281 | 116 | 18.2 |
| Embodiment 5 | 345 | 143 | 19.6 |
| Comparative example 1 | 74 | 30 | 10.2 |
| Comparative example 2 | 45 | 18 | 7.5 |
From table 1 it follows that material made from 1-5 of the embodiment of the present invention is substantially better than comparative example 1-2, illustrate at ammoniacal liquor
Reason polyvinyl alcohol after and addition poplar made from biomimetic material there is high tensile strength and high toughness, this hair
It is bright to play a role under the collective effect of each raw material.
Material made from embodiment 1-5 is inserted and placed 6 months in simulation inside of human body environment, the life of material surface inanimate object
It is long, also noresidue.Also simulation shoulder joint is rotated simultaneously, it is found that biomimetic material is without abrasion, interface at the shoulder joint of connection
Lubricity is good.
It is obvious to a person skilled in the art that the invention is not restricted to the details of above-mentioned one exemplary embodiment, Er Qie
In the case of without departing substantially from spirit or essential attributes of the invention, the present invention can be realized in other specific forms.Therefore, no matter
From the point of view of which point, embodiment all should be regarded as exemplary, and be nonrestrictive, the scope of the present invention is by appended power
Profit is required rather than described above is limited, it is intended that all in the implication and scope of the equivalency of claim by falling
Change is included in the present invention.
Moreover, it will be appreciated that although the present specification is described in terms of embodiments, not each embodiment is only wrapped
Containing an independent technical scheme, this narrating mode of specification is only that for clarity, those skilled in the art should
Using specification as an entirety, the technical solutions in the various embodiments may also be suitably combined, forms those skilled in the art
It may be appreciated other embodiment.
Claims (4)
1. a kind of biomimetic material for shoulder joint, it is characterised in that be made up of the raw material below according to parts by weight：Montmorillonite
22-28 parts, 45-58 parts of polyvinyl alcohol, 10-16 parts of poplar, 3-7 parts of graphite, 150-170 parts of ethanol, 110-125 parts of ammoniacal liquor,
8-15 parts of carragheen；
Its preparation method, is comprised the steps of：
1) montmorillonite, polyvinyl alcohol, poplar, graphite are cleaned, dried, pulverized, crossed 100 mesh sieves, be then respectively implanted
350 mesh are crushed in micronizer, montmorillonite powder, polyvinyl alcohol powder, white poplar wood powder, graphite powder are made standby；
2) montmorillonite powder is inserted in the ethanol of 3-3.2 times of its quality, sealing immersion 1.8-2h, is then carried out at 50-52 DEG C
Ultrasonically treated 1-1.5h, ultrasonic power is 900-1000W, and montmorillonite pretreatment liquid is made；
3) polyvinyl alcohol powder is inserted in ammoniacal liquor, the sealing preserve 18-20h at a temperature of 45-48 DEG C adds montmorillonite and located in advance
Liquid is managed, sealing stirring 1-1.3h, is then made mixture A at 55-60 DEG C；
4) white poplar wood powder, graphite powder are mixed with remaining ethanol, 2-2.5h is soaked at a temperature of 60-65 DEG C, be subsequently placed in micro-
In ripple reaction chamber；At ambient pressure, nitrogen is passed through to microwave reaction intracavitary, in control temperature to being incubated 45- under the conditions of 180-200 DEG C
50min, is made mixture B；
5) mixture A is warming up to 65-68 DEG C, adds mixture B and carragheen sealing stirring 2-3h, then carry out ultrasonically treated
1-1.5h, ultrasonic power is 900-1000W, then stirring and drying is produced for shoulder under nitrogen protection, under conditions of 90-100 DEG C
The biomimetic material in joint.
2. the biomimetic material according to claim 1 for shoulder joint, it is characterised in that by below according to the original of parts by weight
Material composition：4-26 parts of montmorillonite 2,49-53 parts of polyvinyl alcohol, 12-14 parts of poplar, 4-6 parts of graphite, 155-165 parts of ethanol, ammonia
115-120 parts of water, 10-13 parts of carragheen.
3. the biomimetic material according to claim 2 for shoulder joint, it is characterised in that by below according to the original of parts by weight
Material composition：5 parts of montmorillonite 2,51 parts of polyvinyl alcohol, 13 parts of poplar, 5 parts of graphite, 160 parts of ethanol, 118 parts of ammoniacal liquor, carragheen
11 parts.
4. according to application of any biomimetic materials of claim 1-3 in shoulder joint biomimetic material is prepared.
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| CN201610024994.XA CN105669084B (en) | 2016-01-14 | 2016-01-14 | It is a kind of for biomimetic material of shoulder joint and its preparation method and application |
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| EP0677297B1 (en) * | 1993-09-24 | 2000-12-13 | Takiron Co. Ltd. | Implantation material |
| JP4280775B2 (en) * | 2003-04-15 | 2009-06-17 | インノゲル アクチエンゲゼルシャフト | Polyvinyl alcohol gel |
| CN1279104C (en) * | 2003-10-31 | 2006-10-11 | 四川大学 | Preparation method of nano-hydroxy apatitel poly vinyl alcohol composite hydrogel |
| CN100418587C (en) * | 2006-12-08 | 2008-09-17 | 北京科技大学 | Method for preparing bionic laminar articular cartilage/bone compound implant |
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