CN101199870B - Hydroxyl apatite/nylon nanometer artificial bone preparing method - Google Patents
Hydroxyl apatite/nylon nanometer artificial bone preparing method Download PDFInfo
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- CN101199870B CN101199870B CN200610147383A CN200610147383A CN101199870B CN 101199870 B CN101199870 B CN 101199870B CN 200610147383 A CN200610147383 A CN 200610147383A CN 200610147383 A CN200610147383 A CN 200610147383A CN 101199870 B CN101199870 B CN 101199870B
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Abstract
The invention provides a hydroxyapatite/nylon manometer artificial bone, including hydroxyapatite which accounts for 50-66% of the total weight of the artificial bone; nylon which accounts for 34-50% of the total weight of the artificial bone; the hydroxyapatite disperses in the nylon under the dispersed phase with the average length between 60-80nm; the molecular weight of the nylon is between 9000-13000; in addition, the artificial bone is free of organic solvent. The invention can achieve high filling amount, no use of organic solvent, high product purity and can reach the standard set for the medical material.
Description
Technical field
The present invention relates to a kind of polymer composite and preparation method thereof, relate to a kind of hydroxyl apatite/nylon nanometer artificial bone and preparation method thereof particularly.
Background technology
The main inorganic composition of natural bone mainly is a nanometer hydroxyapatite, is about 60～67% of osseous tissue, and organic principle mainly is an ossein, accounts for 33～40%.Utilize the nanometer needle-like hydroxyapatite and the compound preparation nano artificial of the polymer bone composite material of synthetic, not only have hydroxyapatite excellent biological compatibility and bone guided characteristic, and combine macromolecular material good mechanical performance and biodegradable, be a kind of up-and-coming artificial bone composite.
Nylon (nylon 66) is a kind of polyamide, is the good engineering plastics of a kind of combination property, good mechanical properties not only, and have good biocompatibility and biological degradability to a certain degree.Owing to contain amide group on its strand, this has to a certain degree similar with the molecular structure of ossein, therefore utilizes the artificial bone of nylon 66 and the compound preparation of hydroxyapatite can satisfy the needs of aspects such as biocompatibility and mechanical compatibility.
The method for preparing at present nylon 66/ nanometer hydroxyapatite mainly contains two kinds: blending method and solution coprecipitation.Blending method is exactly that nylon 66 and nano hydroxyapatite powder are carried out melt blending by equipment such as screw extruders, Zhi Bei composite is difficult to realize the high filler loading capacity of hydroxyapatite in this way, and the hydroxyapatite particle reunites in composite seriously, disperses inhomogeneous.The solution coprecipitation is exactly that nylon 66 is dissolved in the solvent that contains nanometer hydroxyapatite, precipitate then composite, though this method can make the hydroxyapatite particle be in nanoscale and be uniformly dispersed, good product performance, but in preparation process, used a large amount of high boiling solvents, not only increased cost greatly, and product has contained the solvent that is difficult to remove, material purity is lower, is difficult to satisfy the requirement of medical material.
Therefore, this area presses for and a kind ofly solves the nanoscale scattering problem of hydroxyapatite and can realize high filler loading capacity, do not contain with an organic solvent, the product purity height, reach the artificial bone and preparation method thereof of the standard of medical material.
Summary of the invention
The objective of the invention is to obtain a kind ofly solve the nanoscale scattering problem of hydroxyapatite and can realize high filler loading capacity, do not contain with an organic solvent, the product purity height, reach the artificial bone of the standard of medical material.
Another object of the present invention is to obtain a kind ofly solve the nanoscale scattering problem of hydroxyapatite and can realize high filler loading capacity, do not contain with an organic solvent, the product purity height, reach the preparation method of artificial bone of the standard of medical material.
The medical product that a further object of the invention is to obtain a kind ofly can to realize high filler loading capacity, does not contain with an organic solvent, product purity is high.
Of the present invention have a purpose to be to obtain the purposes of artificial bone of the present invention again.
In a first aspect of the present invention, a kind of hydroxyl apatite/nylon nanometer artificial bone is provided, it comprises: the nanometer hydroxyapatite of 50～66 weight %, in the artificial bone gross weight; The nylon of 34～50 weight % is in the artificial bone gross weight; Described nanometer hydroxyapatite is dispersed in the nylon with the decentralized photo of average length size between 60～80nm; The molecular weight of described nylon is between 9000～13000; And the organic solvent that described artificial bone contains is not higher than 1%, in the gross weight of described artificial bone.
Preferably, the organic solvent that described artificial bone contains be not higher than described artificial bone gross weight 0.1%, preferably, described artificial bone does not contain organic solvent substantially, does not more preferably contain organic solvent.
Preferably, described artificial bone does not have obvious agglomeration through 20000 times of tests of scanning electron microscope.
Preferably, described nylon is obtained by nylon salt, lactams monomer or its mixture polycondensation, the preferred nylon salt of described nylon salt, NYLON610 salt; The preferred caprolactam of described lactams monomer, lauric lactam or its combination.
In a preferred embodiment of the present invention, the average length of the nanometer hydroxyapatite in the described decentralized photo is of a size of 60～80nm, average diameter size 10～20nm, and draw ratio is 4～8.
In a preferred embodiment of the present invention, the hot strength that described artificial bone records by ASTM D638 standard is 50～82MPa, and bending strength is 50～90MPa, and bending modulus is 5.0～6.5Gpa.
In a preferred embodiment of the present invention, described artificial bone is made by the method that may further comprise the steps: the aqueous dispersion that hydroxyapatite and nylon salt (a) are provided; The part by weight of wherein said hydroxyapatite and nylon salt is (50～66): (34～50); The total content of hydroxyapatite and nylon salt is 60～80 weight %, with total dispersion weight; (b) dispersion of described step (a) is carried out home position polymerization reaction and is obtained described artificial bone under 200～290 ℃.
In a preferred embodiment of the present invention, the dispersion of described step (a) is obtained by the method that comprises the steps: (i) mol ratio is 1: the phosphoric acid of (1.5～1.8) and calcium hydroxide reacted 20～60 hours down in 60～100 ℃ in water, obtained the aqueous solution of nanometer hydroxyapatite; (ii) the aqueous solution of described nanometer hydroxyapatite mixes with nylon salt, and the part by weight of wherein said hydroxyapatite and nylon salt is (50～66): (34～50); And/or the home position polymerization reaction in the described step (b) comprises pre-polymerization stage, the stage of dewatering, polymerization stage, and the described pre-polymerization stage carries out under 200～240 ℃, 1.60～2.60MPa; Described polymerization stage carries out under 270～290 ℃, 10～50KPa.
Preferably, the response time in described pre-polymerization stage is 2～4 hours.
Preferably, the response time of described polymerization stage is 0.5～1.5 hour.
Preferably, preferred 1～2 hour of the described time that dewaters.
Further aspect of the present invention provides a kind of preparation method of hydroxyl apatite/nylon nanometer artificial bone, comprises the steps: that (A) provides the aqueous dispersion of hydroxyapatite and nylon salt; The part by weight of wherein said hydroxyapatite and nylon salt is (50～66): (34～50); The total content of hydroxyapatite and nylon salt is 60～80 weight %, with total dispersion weight; (B) dispersion of described step (a) is carried out home position polymerization reaction and is obtained described artificial bone.
In a preferred embodiment of the present invention, the hydroxyapatite in the step (A) is made by the acid-base neutralization method; And/or the polycondensation reaction in the step (C) comprises pre-polymerization stage, the stage of dewatering and polymerization stage, and the described pre-polymerization stage carries out under 200～240 ℃, 1.60～2.60MPa; Described polymerization stage carries out under 270～290 ℃, 10～50KPa.
Preferably, the response time in described pre-polymerization stage is 2～4 hours.
Preferably, the response time of described polymerization stage is 0.5～1.5 hour.
More preferably, between pre-polymerization stage and polymerization stage, dewater preferred 1～2 hour of the described time that dewaters.
In a preferred embodiment of the present invention, the acid-base neutralization method of described step (A) comprises the steps: that (I) mol ratio is 1: the calcium hydroxide of (1.5～1.8) and phosphoric acid reacted 20～60 hours down in 60～100 ℃ in water, obtained the aqueous solution of nanometer hydroxyapatite; (II) aqueous solution of described nanometer hydroxyapatite mixes with nylon salt, and the part by weight of wherein said hydroxyapatite and nylon salt is (50～66): (34～50).
The medical product that a further aspect of the invention provides hydroxyl apatite/nylon nanometer artificial bone of the present invention to prepare.
The present invention has an aspect that a kind of purposes of hydroxyl apatite/nylon nanometer artificial bone is provided again, and it is as hard bone grafting material or repair materials.
The specific embodiment
The inventor by improving preparation technology, has not only realized the nanoscale scattering problem of hydroxyapatite through extensive and deep research, and can realize high filler loading capacity, the more important thing is in preparation process that not with an organic solvent the product purity height reaches the standard of medical material easily.Finished the present invention on this basis.
In a specific embodiment of the present invention, dissolve in the nylon salt of high concentration in the nanometer hydroxyapatite aqueous solution that utilizes the acid-base neutralization method to prepare, then the muddy mixture is carried out the polycondensation reaction of nylon salt in autoclave, can be up to 50～66% thereby prepare hydroxyapatite content, good biocompatibility (after in simulated body fluid, soaking for 3 weeks, confirming have new hydroxyapatite to form), have the nylon 66/ hydroxyapatite nano artificial bone composite of good mechanical compatibility with natural bone at material surface through X-ray diffraction.
The definition of " in-situ polymerization " of the present invention is: directly utilize monomeric polymerization to obtain composite under the situation that hydroxyapatite exists.
The definition of " nylon salt " of the present invention is: carried out in conjunction with the salt that forms according to mol ratio (particularly for example to) by adipic acid and hexamethylene diamine.
" hydroxyl apatite/nylon nanometer artificial bone " of the present invention is meant and contains hydroxyapatite and nylon in the described artificial bone.
Below product of the present invention is described.
Artificial bone
Artificial bone of the present invention contains the nanometer hydroxyapatite of 50～66 weight %; The nylon of 33～50 weight % is in the artificial bone gross weight.
Preferably, contain 50～66% nanometer hydroxyapatite.
Wherein nanometer hydroxyapatite is dispersed in the nylon with the decentralized photo of average-size between 60～80nm.Described artificial bone is through 20000 times of sem tests, no agglomeration.
Artificial bone of the present invention does not contain organic solvent.Described organic solvent is meant the various high boiling solvents that are difficult to remove and make the decline of artificial bone purity, as N,N-dimethylacetamide, N, and dinethylformamide, dimethyl sulfoxine etc.
The hot strength of artificial bone of the present invention is 50～82MPa, and bending strength is 50～90MPa, and bending modulus is 5.0～6.5Gpa.
Artificial bone of the present invention soaked for 3 weeks in simulated body fluid after, confirm have new hydroxyapatite to form at material surface through X-ray diffraction.
Nanometer hydroxyapatite
Nanometer hydroxyapatite of the present invention is dispersed in the nylon with the decentralized photo of average-size between 60～80nm.
Preferably, nanometer hydroxyapatite length dimension of the present invention is 60～80nm, 65～75nm more preferably, and diameter dimension 10～20nm, 10～14nm more preferably, draw ratio is 4～8, more preferably 6～7.
Nylon
The molecular weight of nylon of the present invention is between 9000～13000.
Preferably, described nylon is obtained by nylon salt, lactams monomer or its mixture polycondensation, the preferred nylon salt of described nylon salt, NYLON610 salt; The preferred caprolactam of described lactams monomer, lauric lactam or its combination.
Medical material
Preferably, described medical material is to can be used for the composite that the hard bone is transplanted or repaired.
Below preparation method of the present invention is described:
Preparation method
Preparation method of the present invention comprises the steps:
(A) provide the aqueous dispersion of hydroxyapatite and nylon salt;
The part by weight of wherein said hydroxyapatite and nylon salt is (50～66): (34～50); The total content of hydroxyapatite and nylon salt is 60～80 weight %, with total dispersion weight;
(B) dispersion of described step (a) is carried out home position polymerization reaction and is obtained described artificial bone.
For example be particularly: at first utilize the acid-base neutralization legal system to be equipped with nanometer hydroxyapatite, nylon salt is dissolved in the aqueous solution of nanometer hydroxyapatite after, steam moisture by boiling and concentrate, in autoclave, carry out the condensation polymerization of nylon salt then.
The acid-base neutralization method
Preferably, described hydroxyapatite is made by the acid-base neutralization method.For example; specifically be to utilize acid-base neutralization prepared in reaction nanometer hydroxyapatite; then monomer is dissolved in the aqueous solution of nanometer hydroxyapatite; concentrate by explosive evaporation; then the gained concentrated solution is carried out polycondensation in polymeric kettle under nitrogen protection, thereby make hydroxyl apatite/nylon nanometer artificial bone.Preferably, the polymerization single polymerization monomer that synthetic nylon is selected for use is a nylon salt, and nylon salt is directly mixed in aqueous solution with synthetic nanometer hydroxyapatite, concentrates then.
In a preferred embodiment of the present invention, described acid-base neutralization method comprises the steps:
(I) mol ratio is 1: the calcium hydroxide of (1.5～1.8) and phosphoric acid reacted 20～60 hours down in 60～100 ℃ in water, obtained the aqueous solution of nanometer hydroxyapatite;
(II) aqueous solution of described nanometer hydroxyapatite mixes with nylon salt, and the part by weight of wherein said hydroxyapatite and nylon salt is (50～66): (34～50).
Concrete example in this way nanometer hydroxyapatite by calcium hydroxide and phosphoric acid by in aqueous solution, carrying out the acid-base neutralization prepared in reaction, the mol ratio of calcium hydroxide and phosphoric acid is 1.67, reaction temperature is 60～100 ℃, carries out under normal pressure.
The initiation material that the present invention prepares the hydroxyapatite employing is highly purified calcium hydroxide and phosphoric acid.At first the calcium hydroxide powder is joined in the deionized water, stir, the back of waiting to be uniformly dispersed drips phosphate aqueous solution, and the mol ratio of calcium hydroxide and phosphoric acid is 1.5～1.8.Reaction is carried out according to following chemical equation.
10Ca(OH)2+6H
3PO
4→Ca
10(PO
4)
6(OH)
2+18H2O
Be reflected under the normal pressure and carry out, temperature is controlled at 60～100 ℃, after question response carries out 20～60 hours, obtains the solution of nanometer hydroxyapatite.
Second step: add nylon salt in ebullient nanometer hydroxyapatite aqueous solution, usage ratio can be calculated according to the requirement of composite.By boiling steam behind the part water the muddy mixture, wherein the total content of hydroxyapatite and nylon salt is 60～80%.
Home position polymerization reaction
Described home position polymerization reaction generally includes the High Temperature High Pressure precondensation, dewaters, three Main Stage of high temperature evacuation aftercondensated.The described pre-polymerization stage (also being precondensation) carries out under 200～240 ℃, 1.60～2.60MPa; Described polymerization stage carries out under 270～290 ℃, 10～50KPa.
The time of described polyreaction is not particularly limited, only otherwise goal of the invention of the present invention is produced restriction to get final product.Preferably, the response time in described pre-polymerization stage is 2～4 hours.Preferably, the response time of described polymerization stage is 0.5～1.5 hour.Preferably, preferred 1～2 hour of the described time that dewaters.
For example, the aqueous solution that contains nanometer hydroxyapatite and nylon salt that will prepare specifically carried out precondensation 2～15 hours under 200～240 ℃ and 16～26 atmospheric pressure, evacuation dewaters then, at last carries out high-temperature polycondensation 0.5～4 hour under the condition of 250～300 ℃ and 6000～60000Pa.
In autoclave, carry out the discontinuous polycondensation reaction of nylon salt.
Prepared slurry is joined in the polymeric kettle; material is heated to 200～240 ℃; under the condition of nitrogen protection, 1.60～2.60MPa, stop dehydration prepolymerization in 2～4 hours; release dewatered 1～2 hour then; carry out evacuation at last; after under 270～290 ℃, the condition of 10～50KPa, reacting 0.5～1.5 hour, utilize the high pressure nitrogen discharging.Material obtains the hydroxyl apatite/nylon nanometer composite after pelletizing and dried.
Advantage of the present invention is:
(1) the artificial bone composite with this method preparation contains the nanometer hydroxyapatite of 50～66w% and the nylon of 33～50w%, described hydroxyapatite is a nanoscale acicular crystal, its degree of crystallinity is lower, have with human body natural's bone in close size and the degree of crystallinity of hydroxyapatite, and hydroxyapatite nano particle is uniformly dispersed in composite.
(2) the artificial bone composite with this method preparation has excellent biological compatibility and mechanical compatibility.Wherein hydroxyapatite content can be up to 50～66%.After in simulated body fluid, soaking for 3 weeks, confirm have new hydroxyapatite to form (explanation good biocompatibility) at material surface through X-ray diffraction.And has good mechanical compatibility with natural bone.
(3) this preparation method not with an organic solvent with therefore any deleterious additive, the easier standard that reaches medical artificial bone of artificial bone of preparation.
(4) according to what of contained nanometer hydroxyapatite consumption, its hot strength is 50～82MPa, and bending strength is 50～90MPa, and bending modulus is 5.0～6.5GPa, the mechanical property of this and human body cortical bone is complementary, and with human body natural's bone the good mechanical compatibility is arranged.
Below in conjunction with specific embodiment, further illustrate the present invention.Should be understood that these embodiment only to be used to the present invention is described and be not used in and limit the scope of the invention.The experimental technique of unreceipted actual conditions in the following example usually according to normal condition, for example is " condition in the smooth organic chemistry handbook of Bel Si (Chemical Industry Press, 1996), or the condition of advising according to manufacturer.Ratio and percentage ratio are based on weight, unless stated otherwise.
Embodiment 1:
Calcium hydroxide and phosphoric acid in 70 ℃ of reactions 48 hours, add nylon salt according to mol ratio 1.67 batching then in deionized water, consumption is identical with hydroxyapatite, and the simmer down to that dewaters of seething with excitement contains the slurry of total material 70%.Slurry is joined reactor, be warming up to 235 ℃ gradually, pressure is controlled at 17.5MPa, reacting after 3 hours decompression and dewatering 1～1.5 hour, treat that pressure is reduced to normal pressure after, be warming up to 280～290 ℃, under the condition of 1～6KPa, reacted discharging then 40～60 minutes.Material can pass through compression molding or injection moulding.
The size of hydroxyapatite is as follows in the composite:
| Profile | Needle-like |
| Average length | 80nm |
| Average diameter | 14nm |
| Draw ratio | 5.7 |
Performance of composites is as follows: wherein hot strength is according to ASTM D638 standard testing, and bending strength and bending modulus are according to ASTM D638 standard testing.
Performance of composites is as follows:
| Nanometer hydroxyapatite content | 57％ |
| Hot strength | 68MPa |
| Bending strength | 42MPa |
| Bending modulus | 6.0GPa |
Embodiment 2:
Implementation process is with example 1, and the charge ratio that changes hydroxyapatite and nylon salt is 1.2/1.
The size of hydroxyapatite is with embodiment 1 in the composite.
Performance of composites is as follows: wherein hot strength is according to ASTM D638 standard testing, and bending strength and bending modulus are according to ASTM D638 standard testing.
| Nanometer hydroxyapatite content | 62％ |
| Hot strength | 76MPa |
| Bending strength | 48MPa |
| Bending modulus | 6.5GPa |
Other physical property test
The composite that obtains is through transmissioning electric mirror test, and hydroxyapatite is a needle-like, and length is less than 100nm, and diameter is uniformly dispersed in composite in 10～20 nanometers, does not have tangible agglomeration.
Confirm by photoelectron spectroscopy: the Ca binding energy is 351.8 and 347.3 electron-volts in the pure ha, the binding energy of P is 134.5 electron-volts, and in composite, the binding energy of Ca is brought up to 352.0 and 348.5 electron-volts, and the binding energy of P is brought up to 135.6 electron-volts.The raising of the binding energy of Ca and P has confirmed to interact in the composite median surface good.
The composite that obtains soaked for 3 weeks in simulated body fluid after, confirm have new hydroxyapatite to form at material surface through X-ray diffraction
All quote in this application as a reference at all documents that the present invention mentions, just quoted as a reference separately as each piece document.Should be understood that in addition those skilled in the art can make various changes or modifications the present invention after having read above-mentioned teachings of the present invention, these equivalent form of values fall within the application's appended claims institute restricted portion equally.
Claims (5)
1. hydroxyl apatite/nylon nanometer artificial bone is characterized in that it comprises:
The nanometer hydroxyapatite of 50～66 weight % is in the artificial bone gross weight;
The nylon of 34～50 weight % is in the artificial bone gross weight;
Described nanometer hydroxyapatite is dispersed in the nylon with the decentralized photo of average length size between 60～80nm;
The molecular weight of described nylon is between 9000～13000;
And the organic solvent that described artificial bone contains be not higher than described artificial bone gross weight 1%;
It is made by the method that may further comprise the steps:
(a) provide the aqueous dispersion of hydroxyapatite and nylon salt;
The part by weight of wherein said hydroxyapatite and nylon salt is (50～66): (34～50); The total content of hydroxyapatite and nylon salt is 60～80 weight %, with total dispersion weight;
(b) dispersion of described step (a) is carried out home position polymerization reaction and is obtained described artificial bone under 200～290 ℃.
2. artificial bone as claimed in claim 1 is characterized in that,
The dispersion of described step (a) is obtained by the method that comprises the steps:
(i) mol ratio is 1: the phosphoric acid of (1.5～1.8) and calcium hydroxide reacted 20～60 hours down in 60～100 ℃ in water, obtained the aqueous solution of nanometer hydroxyapatite;
(ii) the aqueous solution of described nanometer hydroxyapatite mixes with nylon salt, and the part by weight of wherein said hydroxyapatite and nylon salt is (50～66): (34～50);
And/or
Home position polymerization reaction in the described step (b) comprises pre-polymerization stage, the stage of dewatering, polymerization stage,
The described pre-polymerization stage carries out under 200～240 ℃, 1.60～2.60MPa;
Described polymerization stage carries out under 270～290 ℃, 10～50KPa.
3. the preparation method of a hydroxyl apatite/nylon nanometer artificial bone is characterized in that, comprises the steps:
(A) provide the aqueous dispersion of hydroxyapatite and nylon salt;
The part by weight of wherein said hydroxyapatite and nylon salt is (50～66): (34～50); The total content of hydroxyapatite and nylon salt is 60～80 weight %, with total dispersion weight;
(B) dispersion of described step (A) is carried out home position polymerization reaction and is obtained described artificial bone.
4. method as claimed in claim 3 is characterized in that, the hydroxyapatite in the step (A) is made by the acid-base neutralization method; Or
Polycondensation reaction in the step (C) comprises pre-polymerization stage, the stage of dewatering and polymerization stage,
The described pre-polymerization stage carries out under 200～240 ℃, 1.60～2.60MPa;
Described polymerization stage carries out under 270～290 ℃, 10～50KPa.
5. method as claimed in claim 4 is characterized in that, the acid-base neutralization method of described step (A) comprises the steps:
(I) mol ratio is 1: the calcium hydroxide of (1.5～1.8) and phosphoric acid reacted 20～60 hours down in 60～100 ℃ in water, obtained the aqueous solution of nanometer hydroxyapatite;
(II) aqueous solution of described nanometer hydroxyapatite mixes with nylon salt, and the part by weight of wherein said hydroxyapatite and nylon salt is (50～66): (34～50).
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| CN103785062A (en) * | 2014-02-07 | 2014-05-14 | 许自霖 | Bone repair material of coating hydroxyapatite and preparation method of bone repair material |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6013104A (en) * | 1992-03-12 | 2000-01-11 | Kampner; Stanley L. | Implant with reinforced resorbable stem |
| JP3217454B2 (en) * | 1992-06-17 | 2001-10-09 | 株式会社アマダ | Fault diagnosis system for thermal cutting machine |
| CN1460526A (en) * | 2003-06-13 | 2003-12-10 | 四川大学 | Porous bone prosthesis containing hydroxy apatite component and its preparation method |
| CN1544099A (en) * | 2003-11-27 | 2004-11-10 | 四川大学 | Method for making biologic composite materials of nanometer hydroxyapatite/polyamide series for medical use |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6013104A (en) * | 1992-03-12 | 2000-01-11 | Kampner; Stanley L. | Implant with reinforced resorbable stem |
| JP3217454B2 (en) * | 1992-06-17 | 2001-10-09 | 株式会社アマダ | Fault diagnosis system for thermal cutting machine |
| CN1460526A (en) * | 2003-06-13 | 2003-12-10 | 四川大学 | Porous bone prosthesis containing hydroxy apatite component and its preparation method |
| CN1544099A (en) * | 2003-11-27 | 2004-11-10 | 四川大学 | Method for making biologic composite materials of nanometer hydroxyapatite/polyamide series for medical use |
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