CN1200043C - Inorganic/organic nano-composite bioactivity porous material and its preparation method - Google Patents
Inorganic/organic nano-composite bioactivity porous material and its preparation method Download PDFInfo
- Publication number
- CN1200043C CN1200043C CN 03135261 CN03135261A CN1200043C CN 1200043 C CN1200043 C CN 1200043C CN 03135261 CN03135261 CN 03135261 CN 03135261 A CN03135261 A CN 03135261A CN 1200043 C CN1200043 C CN 1200043C
- Authority
- CN
- China
- Prior art keywords
- water
- soluble salt
- medical
- porous material
- inorganic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Images
Abstract
The present invention relates to a porous inorganic/organic nano-composite bioactivity material and a preparation method thereof. The material is prepared from the composite materials of hydroxyapatite and medical polyamide 66 with the proportion by weight of (0.25 to 1.5)/1. The material contains pores whose pore diameter is from 1 to 300 micrometers, and the pores are mutually penetrated; the total volume of the pores accounts for 30% to 70% of the total volume of the material. A compound mixed by the nanometer hydroxyapatite and the medical polyamide 66 according to the scheduled proportion is uniformly mixed with medical water-soluble salt particles whose particle diameter and proportion in the total voltage are respectively corresponding to the wished pore diameter and the pore rate in the prepared material during preparation. The mixture is put in water and is fully dissolved for removing water-soluble salt ingredients existing in the solidified material after being formed by solidified under the pressure condition of 3 to 8MPa and the temperature condition of 260 DEG C to 290 DEG C, and then, the porous bioactivity material with the wished pore diameter and pore rate is obtained. The material can have favorable biological functions and porosity and can satisfy mechanical strength required by mechanical performance.
Description
Technical field
What the present invention relates to is a kind of inorganic-organic nanocomposite composite bio-active porous material and preparation method thereof.
Background technology
Bone renovating material and tissue engineering material are new crossing domains of Materials science and life science, for the damaged and bone tumor of bone, and intractable fracture repair a kind of extremely promising novel method is provided, wherein porous material is one of gordian technique of bone recovery project.
Calcium-phosphate material has natural affinity owing to be the main component that constitutes the human body hard tissue inanimate matter with tissue, can and human body is soft, sclerous tissues forms firm biological bonding, have excellent biological compatibility and biological activity.Because the inanimate matter of natural bone mainly is to be made of nanometer hydroxyapatite, nanometer hydroxyapatite accounts for about 65% of weight in natural bone.Therefore, be self-evident with nanometer hydroxyapatite as the principle and advantage of bone substitute.Understand at present, the exchange of substance between osteon is that process is undertaken by the volkmann canal that passes across spatium interosseum, and it makes blood can flow to the darkest osteon place, to keep the physiologically active of bone.Therefore will design a kind of planting body with osteoconductive, it should similar matrix or interstitial bone in logic.Because the diameter of osteon is about 190～230 microns, and be to carry out exchange of substance, have mutual perforation, channel system that diameter is very little so the ideal bone graft substitute should be simulated cortex bone by volkmann canal.
The purpose of porous material is for the cell that makes up tissue provides a three-dimensional rack, for the cell growth provides suitable environment.Porous material is the basic framework and the metabolism place of cell attachment, for cambium provides support, and keeps certain hour to have self biomechanics characteristic until cambium.Porous material not only plays a supportive role in bone reparation and tissue engineering material, keeps former shape in a organized way, but also plays template action, for cell provides the place of the boarding of relying, growth, differentiation and propagation, thereby guides the regeneration of damaged tissue.Bone reparation and tissue engineering material require material should have good biological function, satisfy the requirement of mechanical property again, and material also requires to have porousness and high strength simultaneously.
The present employed calcium-phosphorus bioactive ceramics equivalent material that contains the hydroxyapatite composition, the fragility of its bulk product is big, difficult processing, easy fracture; And the particulate ceramic product has the shortcoming of migration, displacement, and the mechanical property of these calcium phosphate bioactive materials and unsatisfactory.And the natural bone of the inorganic-organic composite material form that for example is made of hydroxyapatite and macromolecule glue protofibril then has excellent mechanical property.Based on bionical notion, people wish can be by the composition form and the structure of natural biologic materials such as natural bone, prepare materials similar and microtexture with it, make it to have the performance that can wait the biocompatibility aspect as good bone conduction and osteoinductive, excellent mechanical intensity and toughness are arranged again, aspect Young's modulus, also approach natural bone, the biological active materials that can have excellent comprehensive performances.This all has crucial meaning in theory with in the clinical practice, and the heat that has become Recent study more.
Summary of the invention
In view of the above, the application at first will provide a kind of can simulate the nature bone moiety, by
NanometerThe bioactivity, porous material of the inorganic-organic composite material form that hydroxyapatite composition and macromolecular material constitute, provide the three-dimensional rack of a suitable cell growing environment for making up histocyte, make it as have as bone conduction and osteoinductive can wait aspect the biocompatibility, physical strength and toughness and all approach natural bone at aspects such as Young's modulus, thereby can have the biological active materials of excellent comprehensive performances.On this basis, the present invention further will provide a kind of preparation method to this biological active materials.
The said inorganic-organic nanocomposite composite bio-active of the present invention porous material, by weight ratio is that the nano-grade hydroxy apatite of (0.25～1.5)/l and the matrix material of medical polyamide 66 are formed, wherein contain the hole that the aperture is the mutual perforation of 1-300 micron, the cumulative volume of hole accounts for the 30%-70% of material cumulative volume.
As above-mentioned, because the inanimate matter of natural bone mainly is to be made of nanometer hydroxyapatite, therefore in the above-mentioned bioactivity, porous material of the present invention, said hydroxyapatite composition is good to adopt nano-grade hydroxy apatite also.
Simultaneously, because the weight of nanometer hydroxyapatite accounts for about 65% in natural bone, therefore based on bionical notion, the calcium in the hydroxyapatite composition in above-mentioned materials/phosphorus mol ratio also is advisable to be adopted as 1.60-1.67.
In bioactivity, porous material of the present invention, for further near and the simulation cortex bone have mutual perforation, pore passage structure system that diameter is very little, the organization bracket structure of the boarding of relying, growth, differentiation and propagation is provided for cell, so that the macropore of 100-300 micron and the hole of the different pore sizes such as micropore of 1-50 micron are arranged in the contained hole, and micropore wherein should be distributed on the hole wall of macropore in material.The aperture is between macropore and micropore, and then to belong to be the hole of transition state.
The above-mentioned bioactivity, porous preparation methods of the present invention; can adopt will be in the nanometer hydroxyapatite and the medical polyamide 66 blended mixture of said ratio; mix with the medical water soluble salt particle that desirable hole aperture and porosity in making material adapt respectively with particle diameter and the proportional that in cumulative volume, accounts for; behind curing molding under the pressure of 3～8Mpa and 260 ℃～290 ℃ temperature condition; place water fully to dissolve again and remove the said water-soluble salt constituents that is present in solidify material, the bioactivity, porous material that obtains having desirable aperture and porosity.Said under pressurization and heating condition, be cured the operation of moulding herein, both can have adopted and will pressurize and heat the mode of carrying out and finishing simultaneously, also can adopt first press molding after, the mode of finalizing the design is carried out being heating and curing.
In above-mentioned preparation method, said nanometer hydroxyapatite powder, medical polyamide 66 fine powder with and mixed mixture, can adopt method commercial or existing report at present to prepare respectively.
Said medical water soluble salt, its basic demand should comprise: can have certain crystal or particle grain size size, water-soluble being the bigger the better, nontoxicity and can not with the component generation chemical reaction in the matrix material, under the Heating temperature of processing and preparing process, do not decompose, do not have releasable gas yet and produce.Generally can select in the medicine water-soluble salt compounds as alkali metal chloride forms such as Repone K, sodium-chlor commonly used for use, wherein sodium-chlor preferably.
Because said medical water soluble salt particle is in the early stage of above-mentioned preparation process, be to be present in the material intermediate after the solidifying and setting with hybrid mode, handle by the material intermediate after the solidifying and setting being carried out water dissolution again, make these salt particles dissolved removing and stay its corresponding occupy-place hole in situ from material intermediate, thereby when feeding intake the ratio of these salt constituents shared cumulative volume in material, dissolved to remove back left porosity in material bodies be consistent with it.Therefore by in the preparation to the granular size of used medical water soluble salt and/or the selection and the adjustment of consumption, just can realize easily hole aperture in the prepared material and/or porosity are controlled in the scope of desired or needs.For example, experimental result shows as the porosity in the porous material of water-soluble salt constituents feed intake volume ratio and gained in the preparation following relation can be arranged with sodium-chlor:
During sodium-chlor/matrix material=1/2 (volume), the porosity in the gained porous material is 33.3%;
During sodium-chlor/matrix material=1/1 (volume), the porosity in the gained porous material is 50%;
During sodium-chlor/matrix material=1/0.5 (volume), the porosity in the gained porous material is 66.7%.
In order to guarantee to interconnect between water-soluble salt constituents particle, to form the hole of mutual perforation form.The shared volume of water-soluble salt constituents consumption should maintain enough vast scales, preferably makes its consumption volume energy account for more than 40% of material cumulative volume, promptly so that the porosity of porous material is good greater than 40%.
In order to form the porous material that macropore and aperture link up mutually, can be when using oarse-grained water-soluble salt constituents, add a part of short grained composition simultaneously, as particle diameter is the short grained salt constituents of 1-50 μ m, so just, can form on the hole wall that makes aperture or micropore be present in macropore, and the porous material that macropore and aperture or micropore are linked up mutually.Experimental result shows, is realizing that this result is, the ratio of different-grain diameter size particles generally can be controlled in interior the getting final product of scope of small-particle/macrobead=1/3.
In the concrete preparation method who carries out in a manner described; after can adopting above-mentioned mixture with said nanometer hydroxyapatite and medical polyamide 66 fine powder and medical water soluble salt particle mixing; with shaped device under the normal temperature after keeping static pressure compression moulding in 10～30 minutes under the said pressure condition; be incubated 10～60 minutes solidifying and setting down in said temperature condition again; the hot water that places room temperature～80 ℃ then fully dissolving is removed the water miscible salt constituents such as sodium-chlor of section bar, promptly makes desirable (nanometer) hydroxyapatite/polymeric amide composite bio-active porous material.
In addition; also can adopt mixture with said nanometer hydroxyapatite and medical polyamide 66 fine powder to mix with medical water soluble salt particle and cold-press moulding after, with the aluminum tissue paper parcel or directly the building mortion that sample is housed is together put into silicone oil and heat.Heat-up time, length can size per sample determine, generally can handle by the mode of 30～60 minutes/10 grammes per square metres; Also the sample behind the cold-press moulding can be placed in the vacuum drying oven and heat 1 hour.Add in the middle of the material bodies after the heat setting type and polish off upper layer on the available fine sandpaper of product, immersion eliminates salt particulate component in the material bodies in the water of room temperature to 80 ℃ again, promptly obtains the bioactivity, porous material of desired composite materials after the oven dry.
Experimental result shows, according to the size of institute's material volume and/or used salt constituents particulate size, and the difference of the factors such as water temperature of dissolving usefulness, said herein place water fully the dissolving scope in treatment time of removing the water-soluble salt constituents of material generally can be 1-5 days.
Understood easily by foregoing, adopt the molten eliminating method of the above-mentioned particle of the present invention to prepare bioactivity, porous material, porosity and pore size in the porous material are controlled easily, and the connectivity of hole might as well be controlled, and the equipment of preparation is simple, and is easy to operate.Because the formation of material mesoporosity is to realize by the particle of removing the water-soluble salt constituents with water-soluble processing mode, therefore this method is suitable for preparing the less porous material of thickness especially, for example can prepare porous film material, but the also good complex three-dimensional porous material of processability.
Based on foregoing, under the prerequisite that does not break away from basic fundamental thought of the present invention,, modification, replacement or the change of various ways can also be arranged to its content according to the ordinary skill knowledge and the customary means of this area.
The embodiment of form is described in further detail foregoing of the present invention again by the following examples.But this should be interpreted as that following each example is the restriction to the related scope of the above-mentioned theme of the present invention.All technology that realizes based on foregoing of the present invention all belong to scope of the present invention.
Description of drawings
Fig. 1 is that the porosity with the inventive method preparation is the electron scanning micrograph of 65% the bioactivity, porous material microstructure of matrix material
Fig. 2 is that the porosity with the inventive method preparation is the electron scanning micrograph of 40% the bioactivity, porous material microstructure of matrix material
Embodiment
The preparation of nano-apatite crystals
With 20 gram analytical pure Ca (NO
3)
2.H
2O joins in the 30 gram analytical pure N,N-DIMETHYLACETAMIDEs (or dimethyl formamide) wiring solution-forming A under whipped state.12 gram analytical pure Na
3PO
410H
2O is dissolved in the 1000ml deionized water, wiring solution-forming B.Ca (NO
3)
2.H
2O and Na
3PO
410H
2The amount ranges of O is that the calcium/phosphorus mol ratio that makes the hydroxyapatite that is generated is 1.60～1.67.B to 60 ℃ of heated solution under the state that constantly stirs, slowly splashes into solution A in the solution B, after titration is intact, continue to stir 2 hours, temperature is controlled at 60 ℃, then, and room temperature ageing 24 hours, centrifugal, abandon supernatant liquor, use washed with de-ionized water 3 times, get the sedimental slurries of phosphatic rock.The sedimental slurries of content 10% (weight ratio) left and right sides phosphatic rock heated 2-4 hour under boiling state.Can replenish in this process because the water yield that evaporation is reducing.Reaction is finished postcooling and is obtained nano-apatite crystals to room temperature.
The preparation of nanometer hydroxyapatite/polyamide 66 mixture
750ml, concentration 10% (weight ratio) nano-apatite slurries are joined 3000ml and have in the three-necked bottle of division box, whipping appts and condensing works, add 1000ml dimethylacetamide solution and 15 gram calcium chloride then.Temperature progressively rises to 120 ℃, draining (passing through division box), in this process, fall amount and in bottle, add N,N-DIMETHYLACETAMIDE 750ml with the time according to the venting of water, fallen by complete venting up to water, temperature progressively rises to 140 ℃, add 50 gram polyamide 66s (molecular weight is 25000, and Asahi Chemical Industry company provides), and kept 4 hours at 140 ℃.All dissolve up to polyamide 66, be cooled under 100 ℃, mixture is constantly being splashed in the container that deionized water is housed under the whipped state lentamente, product deionized water wash 6 times, with washing with alcohol once, centrifugal overanxious, use alcohol immersion 24 hours, centrifugal overanxious, with the product that obtains 80-100 ℃ of drying 24 hours, levigate, cross 200 mesh sieves, obtain nanometer hydroxyapatite/polyamide 66 (n-HA/66) composite powder.
The preparation of bioactivity, porous material
The sodium-chlor of selecting pharmaceutical grade for use is as the drilling particulate, and adjusts the size of used sodium chloride particle and the volume that sodium-chlor adds according to pore size scope in the porous material of required preparation and the porosity in the material.
The full and uniform mixing of sodium-chlor powder with above-mentioned n-HA/66 composite powder and selected particle size range and volumetric usage ratio in the impouring shaped device, under the condition that does not heat, is forced into 5Mpa (can adjust as required) in 3～8Mpa scope.After keeping static pressure 15min, temperature is risen to 270 ℃ (can adjust as required) in 260 ℃～290 ℃ scopes, insulation 10min.After taking out formed material, put into water 48h (according to the size and/or the consumption of material volume size and used sodium chloride particle particle diameter, can adjust) in 1～5 day scope, dissolving eliminates the sodium-chlor composition in the material bodies.The porous, shaped material of gained 100 ℃ of oven dry down, is made the bioactivity, porous material of n-HA/66.
Except that above-mentioned aforesaid method, also can adopt and to wrap up with aluminum tissue paper behind the cold-press moulding earlier, be put in the silicone oil and heat for some time (length of size decision time per sample), the sample heating half an hour of general 10 gram different shapes, or directly the shaped device that sample is housed is put into silicone oil and heat; Perhaps the sample behind the cold-press moulding is placed in the vacuum drying oven and heated 1 hour.All modes grind off the surface through the sample that heating is shaped on fine sandpaper, be placed in the water of room temperature to 80 ℃ to soak more than 2 days, take out the back and dry in the baking oven below 80 ℃, promptly obtain bioactivity, porous material.
Respectively with sodium-chlor: matrix material volume ratio is that the amount of 1: 0.54 and 2: 3 feeds intake, operate in a manner described resulting bioactivity, porous material in porosity be respectively 65% and 40%, to showing the electron scanning micrograph of its microtexture, respectively as depicted in figs. 1 and 2.
Hole pore diameter range in Fig. 1 display material is 200-300 μ m, and hole interpenetrates, and its porosity is 65%.According to data, in porous material, connect bore dia at 15-40 μ m, the fibrous tissue material internal of can growing into; And the aperture allows the osteoid tissue of non-mineralising to grow into when being 40-100 μ m; Can grow into for bone the ideal place is provided when 150 μ m in the aperture.Therefore, for make in the n-HA/66 bioactive composite material, can provide be suitable for the growth of bone forming and cell in connect the hole, its aperture should be not less than 100 μ m.Therefore this porous material has bone forming and the cell required aperture size of growing into.Hole aperture in the biological active materials that Fig. 2 shows can reach 200 μ m, links up between the hole, and porosity is 40%.
Be that the mechanical properties such as ultimate compression strength of n-HA/66 biological active materials of the different porosities of the 50wt% test result of carrying out is as shown in table 1 to phosphatic rock content.
Table 1 shows that the ultimate compression strength of porous material reduces with the porosity increase.When porosity reached 65%, the composite porous ultimate compression strength of n-HA/66 reached 3MPa, (was generally less than 10 far above the intensity of other pure superpolymer composition timbering material
4Pa).This is because the n-HA crystal has played enhancement mutually to superpolymer.Current, cultivating bone and its cells in ambient stress is one of advanced subject of bone tissue engineer, but general pure superpolymer support can not carry the stress that is applied.The composite porous mechanical property of n-HA/66 is improved largely by comparison, can be used as the timbering material that cell is grown in ambient stress.The significant application of another of porous n-HA/66 matrix material is to utilize its hole and other materials, as further compound with bioactive macromolecule, the bone renovating material that has new function with preparation, as prepare the complex body of porous bio-ceramic and bone morphogenetic protein (BMP), to reach the purpose of accelerated bone tissue growth.This bioactivity, porous material also can be mutually compound with some drugs, makes a kind of slow releasing carrier of medication that spreads medicine in human body gradually.
Table 1 makes the mechanical property of porous material with the molten division of particle
Porosity ultimate compression strength flexural strength tensile strength
(％) (MPa) (MPa) (MPa)
25 12 9 13
40 8 5 7
65 3 2 2.5
Claims (8)
1. inorganic-organic nanocomposite composite bio-active porous material, it is characterized in that forming for the nanometer hydroxyapatite and the medical polyamide 66 of (0.25～1.5)/1 by weight ratio, wherein contain the hole that the aperture is the mutual perforation of 1-300 micron, the cumulative volume of hole accounts for the 30%-70% of material cumulative volume.
2. inorganic-organic nanocomposite composite bio-active porous material as claimed in claim 1 is characterized in that the calcium/phosphorus mol ratio in the hydroxyapatite composition in the said material composition is 1.60-1.67.
3. inorganic-organic nanocomposite composite bio-active porous material as claimed in claim 1 or 2 is characterized in that having in the said hole macropore of 100-300 micron and the micropore of 1-50 micron, and micropore wherein is distributed on the hole wall of macropore.
4. the method for preparing the described inorganic-organic nanocomposite composite bio-active of claim 1 porous material; it is characterized in that will be in the nanometer hydroxyapatite and the medical polyamide 66 blended mixture of said ratio; mix with the medical water-soluble salt particle that hole aperture in making material and porosity adapt respectively with particle diameter and the proportional that in cumulative volume, accounts for; behind curing molding under the pressure of 3～8Mpa and 260 ℃～290 ℃ temperature condition; place water fully to dissolve again and remove the said water-soluble salt composition that is present in solidify material, the bioactivity, porous material that obtains having desirable aperture and porosity.
5. method as claimed in claim 4; after it is characterized in that the mixture that will constitute by nanometer hydroxyapatite and medical polyamide 66 and medical water-soluble salt particle mixing; with shaped device under the normal temperature after keeping static pressure compression moulding in 10～30 minutes under the said pressure condition; again in following 10～60 minutes solidifying and setting of insulation of said temperature condition, the hot water that places room temperature to 80 ℃ then fully dissolving is removed the water-soluble salt composition of section bar.
6. method as claimed in claim 5 is characterized in that the said treatment time that places water fully to dissolve the water-soluble salt composition of removing formed material is 1-5 days.
7. method as claimed in claim 4; it is characterized in that mixing with medical water-soluble salt particle by the mixture that nanometer hydroxyapatite and medical polyamide 66 constitute and compression moulding after, together place silicone oil by the typing that is heating and curing of time of 30～60 minutes/10 grammes per square metres with building mortion.
8. as the described method of one of claim 4 to 7, it is characterized in that said medical water-soluble salt is a sodium-chlor.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03135261 CN1200043C (en) | 2003-06-20 | 2003-06-20 | Inorganic/organic nano-composite bioactivity porous material and its preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03135261 CN1200043C (en) | 2003-06-20 | 2003-06-20 | Inorganic/organic nano-composite bioactivity porous material and its preparation method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1493615A CN1493615A (en) | 2004-05-05 |
| CN1200043C true CN1200043C (en) | 2005-05-04 |
Family
ID=34240007
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 03135261 Expired - Fee Related CN1200043C (en) | 2003-06-20 | 2003-06-20 | Inorganic/organic nano-composite bioactivity porous material and its preparation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1200043C (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100427152C (en) * | 2006-12-26 | 2008-10-22 | 四川国纳科技有限公司 | Method for preparing porous osteolith/polyamide compound material |
| CN103796688B (en) * | 2010-12-14 | 2016-06-29 | 泰克里斯公司 | Biomaterial and its implementation |
| CN102604146A (en) * | 2012-03-20 | 2012-07-25 | 中国科学院力学研究所 | Inorganic bioactive material and method for preparing polymer porous composite material |
| CN104027849B (en) * | 2014-06-30 | 2016-02-10 | 四川大学 | Carry Biocomposite material porous support and the preparation of soybean isoflavone |
| CN106674830B (en) * | 2015-11-11 | 2021-01-26 | 重庆润泽医药有限公司 | Porous non-metallic material |
| CN105903082B (en) * | 2016-06-17 | 2019-01-18 | 三峡大学 | A kind of biodegradable medical nano composite porous material, preparation method and applications |
| CN107837425B (en) * | 2016-09-18 | 2021-08-06 | 浙江蓝怡医药有限公司 | Novel porous biological ceramic bone material and preparation method thereof |
| CN107837419A (en) * | 2016-09-20 | 2018-03-27 | 重庆润泽医药有限公司 | A kind of porous hydroxyapatite |
| CN111154256B (en) * | 2020-01-13 | 2022-07-15 | 四川国纳科技有限公司 | Preparation method of nano hydroxyapatite/polyamide composite material |
-
2003
- 2003-06-20 CN CN 03135261 patent/CN1200043C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN1493615A (en) | 2004-05-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105194728B (en) | A kind of degradable biological porous ceramic film material, preparation method and applications | |
| CN1209170C (en) | Porous synthetic bone graft and method of manufacture thereof | |
| RU2662326C2 (en) | Biomimetic collagen-hydroxyapatite composite material | |
| KR101357673B1 (en) | The scaffold composition for regeneration of hard tissue having magnesium phosphate, scaffold for regeneration of hard tissue comprising the same and preparation methods thereof | |
| CN101041087A (en) | Degradable biphase ceramics bone frame with high-strength and phosphate cement containing strontium and the preparing method | |
| CN114452439B (en) | Hydroxyapatite/whitlockite bioactive ceramic scaffold consisting of bionic natural bone minerals and preparation method thereof | |
| Kusmanto et al. | Development of composite tissue scaffolds containing naturally sourced mircoporous hydroxyapatite | |
| Zhang et al. | Biodegradable elastic sponge from nanofibrous biphasic calcium phosphate ceramic as an advanced material for regenerative medicine | |
| CN1200043C (en) | Inorganic/organic nano-composite bioactivity porous material and its preparation method | |
| CN113101410B (en) | Tricalcium phosphate support with uniform mesopore and three-dimensional communicated hierarchical pore structure as well as preparation method and application of tricalcium phosphate support | |
| KR20090112760A (en) | Method for preparing a composite material, resulting material and use thereof | |
| KR101562556B1 (en) | The scaffold composition for regeneration of hard tissue having magnesium phosphate, scaffold for regeneration of hard tissue comprising the same and preparation methods thereof | |
| Zhang et al. | Microstructural, mechanical properties and strengthening mechanism of DLP produced β-tricalcium phosphate scaffolds by incorporation of MgO/ZnO/58S bioglass | |
| WO2000030998A1 (en) | Porous ceramic composites | |
| CN1460526A (en) | Porous bone prosthesis containing hydroxy apatite component and its preparation method | |
| CN100591365C (en) | Inorganic resorbable bone substitute material | |
| KR100941374B1 (en) | Bio-degradable triple pore ceramic-polymer scaffold and preparation method thereof | |
| JP2002501785A (en) | Synthetic biomaterial compounds | |
| CN114129771A (en) | Flexible biological ceramic scaffold imitating spongy spicule microstructure and preparation method and application thereof | |
| CN114028620A (en) | Mineralized artificial periosteum and preparation method and application thereof | |
| CN104744022A (en) | Laser preparation method for strengthening and toughening ceramic bone scaffold with silicon carbide fibers | |
| TW202112404A (en) | Collagen matrix or granulate blend of bone substitute material | |
| Stojkovska et al. | Novel composite scaffolds based on alginate and Mg‐doped calcium phosphate fillers: Enhanced hydroxyapatite formation under biomimetic conditions | |
| Chernobrovchenko et al. | Influence of technological manufacturing conditions on the porosity of calcium-phosphate scaffolds | |
| CN108079369B (en) | Portland bone cement scaffold with surface nano structure and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20050504 Termination date: 20130620 |