CN102205145A - Bionic cartilage material and preparation process thereof - Google Patents
Bionic cartilage material and preparation process thereof Download PDFInfo
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- CN102205145A CN102205145A CN2011101303258A CN201110130325A CN102205145A CN 102205145 A CN102205145 A CN 102205145A CN 2011101303258 A CN2011101303258 A CN 2011101303258A CN 201110130325 A CN201110130325 A CN 201110130325A CN 102205145 A CN102205145 A CN 102205145A
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Abstract
The invention discloses a bionic cartilage material and a preparation process thereof. A mixed material of polyvinyl alcohol, nano hydroxyapatite, silk and deionized water is adopted. The preparation process comprises the following steps of: weighing the polyvinyl alcohol, the nano hydroxyapatite, the silk and the deionized water in percentage by mass, putting the mixed material into a container, and stirring and mixing the mixed material uniformly; placing the container for a certain time at the temperature of 18 DEG C so that the polyvinyl alcohol in the mixture is fully swollen; putting the container in a thermostatic water bath of 95 DEG C, and heating and stirring till the polyvinyl alcohol is fully dissolved; taking the container out of the thermostatic water bath, and stirring and mixing uniformly to obtain polyvinyl alcohol mixture hydrogel; and pouring the obtained polyvinyl alcohol mixture hydrogel into a die, freezing the die in a low-temperature freezer of 20 DEG C below zero, taking out the frozen hydrogel, unfreezing the frozen hydrogel, freezing the unfrozen hydrogel in the low-temperature freezer, unfreezing the frozen hydrogel, and repeating the process for multiple times to obtain the bionic cartilage material. The process is simple; and the material has good bonding property and good mechanical property similar to that of natural cartilage.
Description
Technical field
The present invention relates to a kind of bionical cartilage material and preparation technology thereof, belong to bio-medical material or Biocomposite material technical field, especially a kind of high buffered bionical cartilage implant material of low friction and preparation technology thereof of being applicable to.
Background technology
The joint is the biological friction pair of human body bearing load maximum, and cartilage is the soft tissue between bone and bone.Cartilage under the physiological stress is a kind of good stress-buffering material, and evenly transfer charge enlarges the joint loading surface, reduces contact stress, the buffering concussion, and slick cartilage surface can be reduced to Min. to friction and wear when the articular surface relative motion.Articular cartilage is the hyperhydrated biological tissue that covers the first end of ossa articularia, mainly is made up of extracellular matrix and chondrocyte, does not contain blood vessel, lymph and nervous tissue in it.In most of synovial jointss, the biomechanics function of articular cartilage generally can be kept 70 years or the longer time.The joint of daily life high frequency makes the loss of articular cartilage and the common phenomenon that pathological changes becomes clinical orthopaedics.Because body intrinsic articulation cartilage self repair ability is extremely limited, in case cause damage or pathological changes, seldom can spontaneous recovery.Cartilage wearing and tearing in the joint can cause arthritis.According to investigations, China osteoarthritis patient has 3600～4,000 ten thousand, has 100～1,500,000 to need to implement prosthetic replacement's operation among them.Therefore, researching and developing the artificial cartilage material with excellent biomechanical property and alternative cartilage is the demand that satisfies the articular cartilage treatment.
Articular cartilage repair materials commonly used at present mainly contains silicone rubber, polyurethane, polyvinyl alcohol hydrogel etc., though yet these cartilage prostheses can play the effect that substitutes cartilage to a certain extent, but also there are loosening, deficiencies such as boundary lubrication is poor, shortage biological activity easy to wear, especially in composition and structural unicity, be difficult to the real cartilage function of realizing replacing.For example, the polymer gel is made of crosslinked elasticity macromolecule network, and network is filled with liquid in the gap, and these liquid can not free-flow owing to being fettered by internetwork interaction force.Gel it seems it is solid in appearance, in fact but is a kind of material between solid and liquid.The network structure of gel makes it have porous, liquid can be extruded and is sucked under the effect of external force.Structure that these of gel are special and natural joint cartilage are quite similar.Partial gel has and similar bio-mechanical property of human articular cartilage and excellent biological compatibility, can alleviate wearing and tearing, part substitutes articular cartilage, and delay or stop the arthritic generation of traumatic bone, be a kind of very promising clinically articular cartilage substitution material.But polyvinyl alcohol (PVA) hydrogel surface is smooth, there is not biological activity, during as cartilage prosthese implantation joint position and the binding ability of substrate poor, influenced the fixing and repair function of cartilage, adopt polyvinyl alcohol and have that bioactive hydroxyapatite is compound can be addressed this is that.Have when how to give the high biomechanical property of cartilage implant material to make it have excellent surface lubrication and biological activity connectivity, this remains a problem.
Summary of the invention
Technical problem: the present invention seeks to overcome the weak point in the prior art, a kind of excellent bonding performance, the high buffered bionical cartilage material of low friction and preparation technology thereof are provided.
Technical scheme: bionical cartilage material of the present invention: polyvinyl alcohol 11～17%, nanometer hydroxyapatite 0.1～4.0%, silkworm silk 0.1～1.0%, deionized water 78～88.8%, mix homogeneously by mass percentage.
The preparation technology of bionical cartilage material of the present invention comprises the steps:
A. silkworm silk is shredded to the length less than 2mm, be loaded in the sealing bag standby;
B. weighing polyvinyl alcohol 11～17%, the silkworm silk 0.1～1.0% that shreds, nanometer hydroxyapatite 0.1～4.0% and deionized water 78～88.8% by mass percentage place container, mix;
C. on container, mark the initial liquid level of mixture liquid level, then container is placed under 18 ℃ the temperature and place 12h, make the abundant swelling of polyvinyl alcohol in the mixture;
D. container being placed temperature is 95 ℃ thermostat water bath, and heated and stirred is dissolved fully until polyvinyl alcohol;
E. container is taken out from thermostat water bath, replenish deionized water to liquid level and reach initial liquid level in container, mix, sonic oscillation 2h discharges the bubble in the mixed liquor, promptly obtains polyvinyl alcohol mixture hydrogel;
F. polyvinyl alcohol mixture hydrogel is poured into mould, put into temperature and be-20 ℃ low temperature storage box after freezing 10 hours, take out and at room temperature thawed 3 hours, put into again afterwards the low temperature storage box carry out freezing, thaw, so circulation is 7～11 times, makes bionical cartilage material;
The bionical cartilage material that g will prepare is put into the sealing bag that fills deionized water and is preserved.
Beneficial effect: owing to adopt technique scheme, the bionical cartilage of making has more the feature near microstructure of human body cartilage and mechanical property.The bionical cartilage material of this kind is a kind of liquid, solid biphase porous media material, and the water content height has preferably and the similar mechanical characteristic of natural cartilage, and the surface easily produces strain, and contact area increases, and cushioning effect is effective; Be a kind of permeable material simultaneously, its permeability makes it under the load effect, and the synovial fluid between friction pair can infiltrate or extrude, and the liquid of extruding has played lubrication, has reduced friction and wear.The present invention has solved bionical cartilage mechanical property and greasy property collision problem to a certain extent, has improved the combination property of bionical cartilage material.
The specific embodiment
Bionical cartilage material of the present invention is: polyvinyl alcohol 11～17%, nanometer hydroxyapatite 0.1～4.0%, silkworm silk 0.1～1.0%, deionized water 78～88.8%, mix homogeneously by mass percentage.
Preparation technology's example of bionical cartilage material is as follows:
Embodiment one, silkworm silk is shredded to the length less than 2mm, be loaded in the sealing bag standby; Claim polyvinyl alcohol 11% by mass percentage, shred to silkworm silk 0.1%, nanometer hydroxyapatite 4% and deionized water 84.9% less than 2mm length, place container to mix, after treating that the interior mixed liquor of container is static, on container, mark the initial liquid level of mixture, then container is placed on 12h under 18 ℃ the temperature, makes the abundant swelling of polyvinyl alcohol in the mixture; Afterwards container being placed temperature is 95 ℃ thermostat water bath, heats while stirring and dissolves fully until polyvinyl alcohol; Container is taken out from thermostat water bath, because a part of water in the evaporation process of temperature in the container is volatilized, in container, replenish the height that deionized water to liquid level reaches initial liquid level this moment, and stir, make its mix homogeneously, the reuse ultrasonator to discharge the bubble in the mixed liquor, promptly obtains polyvinyl alcohol mixture hydrogel to mixed liquor sonic oscillation 2h; The polyvinyl alcohol mixing liquid hydrogel that obtains is poured into mould, put into temperature and be-20 ℃ low temperature storage box after freezing 10 hours, take out and at room temperature thawed 3 hours, putting into the low temperature storage box afterwards again carries out freezing, the same time of thawing, so circulation is 11 times, makes bionical cartilage material; The bionical cartilage material that will prepare is at last put into the sealing bag that fills deionized water and is preserved.Resulting bionical cartilage material moisture content is 81.21%, and the water content of natural cartilage is about 75%; Its mechanical property is good, and elastic modelling quantity is 2.73MPa, and the elastic modelling quantity of natural cartilage is between 1.9～14.4MPa; Total deformation 1.55mm, permanent deformation 0.03mm; Its buffer capacity is strong, and stress relaxation rate is 76.76%.
Embodiment two, silkworm silk is shredded to the length less than 2mm, be loaded in the sealing bag standby; Silkworm silk 0.6% that claim polyvinyl alcohol 17% by mass percentage, shreds and nanometer hydroxyapatite 0.1% and deionized water 82.3% place container to mix; After treating that the interior mixed liquor of container is static, on container, mark the initial liquid level of mixture, then container is placed 12h under 18 ℃ temperature, make the abundant swelling of polyvinyl alcohol in the mixture; It is 95 ℃ thermostat water bath that container is placed temperature, and heated and stirred is dissolved fully until polyvinyl alcohol; Container is taken out from thermostat water bath, replenish deionized water to liquid level and reach initial liquid level in container, mix, sonic oscillation 2h discharges the bubble in the mixed liquor, can obtain polyvinyl alcohol mixture hydrogel; Polyvinyl alcohol mixture hydrogel is poured into mould, put into temperature and be-20 ℃ low temperature storage box after freezing 10 hours, take out and at room temperature thawed 3 hours, putting into the low temperature storage box afterwards again carries out freezing, the same time of thawing, so circulation is 7 times, makes bionical cartilage material; The bionical cartilage material for preparing is put into the sealing bag that fills deionized water to be preserved.Resulting bionical cartilage material moisture content is 82%, and the water content of natural cartilage is about 75%; Its mechanical property is good, and elastic modelling quantity is 2.6MPa, and the elastic modelling quantity of natural cartilage is between 1.9～14.4MPa; Total deformation 1.37mm, permanent deformation 0.11mm; Its buffer capacity is strong, and stress relaxation rate is 63.94%.
Embodiment three, silkworm silk is shredded to the length less than 2mm, be loaded in the sealing bag standby; Silkworm silk 1% that claim polyvinyl alcohol 15.0% by mass percentage, shreds and nanometer hydroxyapatite 2% and deionized water 82% place container to mix; After treating that the interior mixed liquor of container is static, on container, mark the initial liquid level of mixture, then container is placed 12h under 18 ℃ temperature, make the abundant swelling of polyvinyl alcohol in the mixture; It is 95 ℃ thermostat water bath that container is placed temperature, and heated and stirred is dissolved fully until polyvinyl alcohol; Container is taken out from thermostat water bath, replenish deionization to liquid level and reach initial liquid level in container, mix, sonic oscillation 2h discharges the bubble in the mixed liquor, can obtain polyvinyl alcohol mixture hydrogel; Polyvinyl alcohol mixture hydrogel is poured into mould, put into temperature and be-20 ℃ low temperature storage box after freezing 10 hours, take out and at room temperature thawed 3 hours, putting into the low temperature storage box afterwards again carries out freezing, the same time of thawing, so circulation is 9 times, obtains bionical cartilage material; The bionical cartilage material for preparing is put into the sealing bag that fills deionized water to be preserved.Resulting bionical cartilage material moisture content is 78.5%, and swelling ratio is 2.78 in deionized water; Degree of crystallinity is 48.02%; Its mechanical property is good, and elastic modelling quantity is 3.65MPa; Total deformation 1.83mm, permanent deformation 0.04mm; Its buffer capacity is strong, and stress relaxation rate is 75.1%; Its coefficient of starting friction is 0.082; Average friction coefficient is 0.095 in the wear process, and the maximum friction deforming depth is 0.52mm after back and forth wearing and tearing in 1 hour, and recovering two hours after strain degree of depth is 0.30mm, and recovery rate is 42.3%.
Be illustrated in figure 1 as the electron scanning micrograph that bionical cartilage material section of the present invention amplifies 200 times, bionical cartilage material of the present invention as can be seen presents tangible network structure, and a large amount of micropores is arranged; Silkworm silk is not reunited, and is scattered in more uniformly in the polyvinyl alcohol hydrogel matrix; Also can be observed simultaneously the distribution of nano-hydroapatite particles, most of silkworm silk and polyvinyl alcohol hydrogel matrix bond are fine.
Claims (2)
1. a bionical cartilage material is characterized in that: polyvinyl alcohol 11～17%, nanometer hydroxyapatite 0.1～4.0%, silkworm silk 0.1～1.0%, deionized water 78～88.8%, mix homogeneously by mass percentage.
2. the preparation technology as bionical cartilage material as described in the claim is characterized in that comprising the steps:
A. silkworm silk is shredded to the length less than 2mm, be loaded in the sealing bag standby;
B. weighing polyvinyl alcohol 11～17%, the silkworm silk 0.1～1.0% that shreds, nanometer hydroxyapatite 0.1～4.0% and deionized water 78～88.8% by mass percentage place container, mix;
C. on container, mark the initial liquid level of mixture liquid level, then container is placed under 18 ℃ the temperature and place 12h, make the abundant swelling of polyvinyl alcohol in the mixture;
D. container being placed temperature is 95 ℃ thermostat water bath, and heated and stirred is dissolved fully until polyvinyl alcohol;
E. container is taken out from thermostat water bath, replenish deionized water to liquid level and reach initial liquid level in container, mix, sonic oscillation 2h discharges the bubble in the mixed liquor, promptly obtains polyvinyl alcohol mixture hydrogel;
F. polyvinyl alcohol mixture hydrogel is poured into mould, put into temperature and be-20 ℃ low temperature storage box after freezing 10 hours, take out and at room temperature thawed 3 hours, put into again afterwards the low temperature storage box carry out freezing, thaw, so circulation is 7～11 times, makes bionical cartilage material;
The bionical cartilage material that g. will prepare is put into the sealing bag that fills deionized water and is preserved.
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| CN2011101303258A CN102205145A (en) | 2011-05-19 | 2011-05-19 | Bionic cartilage material and preparation process thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103301509A (en) * | 2013-06-13 | 2013-09-18 | 中国矿业大学 | Process for preparing glenoid fossa with bionic cartilage layer |
| CN103834130A (en) * | 2014-02-19 | 2014-06-04 | 上海应用技术学院 | Gamma-polyglutamic acid/polyvinyl alcohol/silk composite hydrogel and preparation method thereof |
| CN107126583A (en) * | 2017-05-03 | 2017-09-05 | 中国矿业大学 | The preparation technology of multilayer heterogeneous bionic joint cartilage material |
Citations (2)
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|---|---|---|---|---|
| WO2004092264A1 (en) * | 2003-04-15 | 2004-10-28 | Innogel Ag | Polyvinyl alcohol gels |
| CN101108261A (en) * | 2007-06-15 | 2008-01-23 | 金大地 | Pectin/polyvinyl alcohol hydrogel material and method of preparing the same |
-
2011
- 2011-05-19 CN CN2011101303258A patent/CN102205145A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004092264A1 (en) * | 2003-04-15 | 2004-10-28 | Innogel Ag | Polyvinyl alcohol gels |
| CN101108261A (en) * | 2007-06-15 | 2008-01-23 | 金大地 | Pectin/polyvinyl alcohol hydrogel material and method of preparing the same |
Non-Patent Citations (2)
| Title |
|---|
| 张德坤等: "聚乙烯醇/羟基磷灰石复合水凝胶的摩擦磨损机理研究", 《中国科学 E辑：技术科学》, vol. 39, no. 4, 20 April 2009 (2009-04-20), pages 714 * |
| 程慧茹等: "PVA-Silk复合水凝胶的摩擦磨损性能研究", 《润滑与密封》, vol. 35, no. 3, 15 March 2010 (2010-03-15), pages 15 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103301509A (en) * | 2013-06-13 | 2013-09-18 | 中国矿业大学 | Process for preparing glenoid fossa with bionic cartilage layer |
| CN103301509B (en) * | 2013-06-13 | 2015-09-23 | 中国矿业大学 | A kind of glenoid fossa preparation technology with bionical cartilage layers |
| CN103834130A (en) * | 2014-02-19 | 2014-06-04 | 上海应用技术学院 | Gamma-polyglutamic acid/polyvinyl alcohol/silk composite hydrogel and preparation method thereof |
| CN107126583A (en) * | 2017-05-03 | 2017-09-05 | 中国矿业大学 | The preparation technology of multilayer heterogeneous bionic joint cartilage material |
| CN107126583B (en) * | 2017-05-03 | 2019-06-28 | 中国矿业大学 | The preparation process of multilayer heterogeneous bionic joint cartilage material |
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Application publication date: 20111005 |