CN101053673A - High strength and tenacity degradable strontium calcium superphosphate composite bone cement and its preparation method - Google Patents
High strength and tenacity degradable strontium calcium superphosphate composite bone cement and its preparation method Download PDFInfo
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- CN101053673A CN101053673A CN 200710017716 CN200710017716A CN101053673A CN 101053673 A CN101053673 A CN 101053673A CN 200710017716 CN200710017716 CN 200710017716 CN 200710017716 A CN200710017716 A CN 200710017716A CN 101053673 A CN101053673 A CN 101053673A
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Abstract
The invention discloses a high tensile degradable strontium phosphate calcium composite bone cement for repairing or intensifying fixation of human body holding bone defect and preparation method thereof. The solid material of bone cement is mixed powder of Ca4(PO4)2O ceramic with high crystallinity, SrHPO4, CaHPO4, curing liquid is thin phosphoric acid water solution, additive plasticizing unit is biocompatibility degradable macomolecule fiber with high tensile strength, selecting from lactic acid - hydroxyacetic acid copolymer fibre, polylatic acid fiber or polyglycolic acid fiber or other absorbable surgical suture, the enhancing unit is Ca4(PO4)2O residual ceramic particles after curing reaction. The preparation method coalesces kinds of techniques of ceramic particles in-situ reinforcing, initial plasticizing and later stage degradation of degradable fiber, Sr modification to get a novel high tensile degradable strontium phosphate calcium composite bone cement in like physiologic environment. The material has good biocompatibility, bioactivity, bone conductivity and degradation property.
Description
Technical field
The invention belongs to biomedical materials field, relate to a kind of suitable human body bearing position bone defect repair or strengthen fixed high strength and tenacity degradable strontium calcium superphosphate composite bone cement and preparation method thereof, the original position that this preparation method has merged high crystalline tetracalcium phosphate ceramic particle strengthens, the degradable macromolecule fiber initial stage is toughness reinforcing and multiple technologies advantages such as later stage degradation pore-creating, strontium ion modification.
Background technology
In synthetic material, calcium phosphate bone cement has special advantages: on the one hand, cured product is a hydroxyapatite, and is consistent with human body bone inorganic mineral composition, has excellent biological compatibility, biological activity and bone conductibility; On the other hand, as biological cement, have advantages such as self-curing, syringeability, easy plasticity, carried medicine sustained-release again.Can be adaptive when especially the latter makes this material application with the damaged anatomical shape of complicated bone, needn't carry out second operation, thereby reduce patient's misery, be subjected to clinician and patient's welcome.At present, this material is fixed as medical screw at non-heavy burden position bone damaged (as skull, lid marrow etc.) and other, is shown good effect in the fields such as fractures, slow release medicine carrying.Yet, mainly there is the deficiency of two aspects in existing calcium phosphate bone cement product: first, intensity is generally on the low side, and (comprcssive strength is generally 30~55MPa), and (the horizontal comprcssive strength of human body long bone is 106~133MPa) reparations still can not to be used for bearing position bone defect; The second, vivo degradation is poor, be difficult to freshman bone tissue faster the speed of growth be complementary, and undegradable cement residue may become the potential source of infection in the body; The 3rd, fragility is big, and fatiguability lost efficacy when being on active service in the body.Therefore, on existing research basis,, then not only further expand the clinical application range of this material, and might solve the reparation difficult problem that the bearing position bone is damaged clinically if can work in coordination with intensity, fragility and the vivo degradation performance of capturing calcium phosphate bone cement.
In recent years, done big quantity research aspect calcium phosphate bone cement mechanical property and the degradability improving both at home and abroad.For example, add carbon fiber, glass fibre and SiC whisker, Si
3N
4Can improve the comprcssive strength of bone cement behind the whisker etc. greatly.But these fibers and whisker can not be degraded after implanting with bone cement, are difficult to realize permanent reparation.Adopt biodegradable Ployglactin910 fiber to replace these not degradation of fibers, though the curing initial stage has been improved the work to break of complex cement, but its comprcssive strength reduces (XuHHK, Janet B.Quinn.Calcium phosphate cement containing resorbable fibers forshort-term reinforcement and macroporosity.Biomaterials, 2002,23:193-202).Domestic scholars is by adding crystal seed and selecting consolidation liquid, the intensity of bone cement is increased to 76.1MPa, and developed bone cement product with independent intellectual property right, but this cement intensity level is lower than the respective horizontal of human body long bone, still can not satisfy the application requirements of bearing position bone defect repair, and the fragility and the degradation property of its initial stage material that implants are not solved (Shao Huifang at all, Liu Changsheng etc. the morphology control of hydroxyapatite crystal seed and the original position of calcium phosphate bone cement strengthened research. Journal of Inorganic Materials, 2001; 16 (5): 933-938).In addition, improving aspect the degradability, nineteen ninety-five, Constanz etc. have reported that on internal authority magazine Science the carbonating hydroxyapatite bone cement has the degradation rate more superior than conventional bone cement, and obtained good clinical repair effect, but regrettably not enough 50Mpa (Constanz BR, Ison JC of its comprcssive strength, Fulmer MT et al.Skeletal repair by in situformation of the mineral phase of bone.Science, 1995; 257:1796-1799.).Through nearly 5 years research, present inventor and person seminar of institute have obtained certain progress in the collaborative improvement of calcium phosphate bone cement mechanics, degradation property.On the one hand, invented with " Ca
4(PO
4)
2O-CaHPO
4-SrHPO
4" to contain the strontium mixture of powders be solid phase; with the phosphoric acid,diluted be liquid phase the saamite bone cement system of mixing (Guo Dagang; Xu Kewei etc. contain the preparation technology of strontium nano-calcium phosphate biological active bone cement. national inventing patent; the patent No.: ZL200410025920.5); discover; the relative pure ha bone cement of this cement material vivo degradation speed improved~73.9%, firming body comprcssive strength on average can reach 66.6MPa, mean level (the Guo Dagang that is higher than existing calcium phosphate bone cement product, .Development of astrontium-containing hydroxyapatite bone cement.Biomaterials such as Xu Kewei, 2005; 26 (19): 4073-4083), show that the strontium ion modification is the collaborative effective ways that improve calcium phosphate bone cement degraded and mechanical property, but insufficient be that its mechanical property is compared with human body load bone defect repair clinical requirement and still had certain gap.On the other hand, utilize the enhanced method of product tetracalcium phosphate remainder particulate original position to prepare a kind of high early strength hydroxyapatite bone cement, mean compressive strength when solidifying 3 days reaches 103.9MPa, peak is 115MPa, elastic modelling quantity is 2~10GPa, this material on comprcssive strength and elastic modelling quantity near the respective horizontal of human body long bone, yet its fragility, slow etc. the still needing of degraded are further improved.In sum, though Chinese scholars is done a lot of work improving the mechanical property of calcium phosphate bone cement, vivo degradation and toughness, and on one-sided performance, obtained certain improvement, but still do not have a kind of product and both had higher intensity and toughness, take into account good vivo degradation performance again.Based on this, the present invention with the original position of high crystalline tetracalcium phosphate pottery strengthen, the degradable macromolecule fiber initial stage is toughness reinforcing and multiple advantage technologies such as later stage degradation pore-creating, strontium ion modification combine, and has proposed a kind of strontium calcium superphosphate composite bone cement and technology of preparing thereof for preparing the tough controlled degradation of novel high-strength.So far, the technology of preparing and the performance thereof of the toughness reinforcing degradable strontium calcium superphosphate biological activity composite bone cement of this type of ceramic original position fortifying fibre are not appeared in the newspapers.
Summary of the invention
The object of the present invention is to provide a kind of high strength and tenacity degradable strontium calcium superphosphate composite bone cement and preparation method thereof, this material has excellent biological compatibility, biological activity, bone conductibility and degradation property.This preparation method has merged the enhancing of ceramic particle original position, the biodegradable fiber initial stage is toughness reinforcing and multiple technologies such as later stage degradation, strontium modification.
Technical scheme of the present invention is to solve like this:
High strength and tenacity degradable strontium calcium superphosphate composite bone cement, its end product is by high crystalline tetracalcium phosphate Ca
4(PO
4)
2The block materials that O ceramic particle, biocompatibility degradable macromolecule fiber and nanometer strontium-doped apatite crystal grain are formed, wherein the quality percentage composition of tetracalcium phosphate is 1%~10%, biocompatibility degradable macromolecule fiber quality percentage composition is 0.1%~10%, and the quality percentage composition of nanometer strontium-doped apatite crystal grain is respectively 80%~98.9%.
A kind of preparation method of high strength and tenacity degradable strontium calcium superphosphate composite bone cement, carry out according to the following steps:
1) preparation of composite bone cement solid phase powder:
With calcium phosphate dibasic anhydrous CaHPO
4With calcium carbonate CaCO
3Carrying out wet ball grinding in 1: 1 in molar ratio mixed 20~60 hours, ball-milling medium is a dehydrated alcohol, heating rate with 4.0~5.0 ℃/min is heated under 1450~1500 ℃ then, be incubated 20~40 hours, cooldown rate with 150~300 ℃/min is cooled to room temperature at last, thereby obtain high crystalline tetracalcium phosphate block, behind fragmentation, hand lapping, ball milling, obtain being of a size of the high crystalline tetracalcium phosphate granule of 10.0~50.0 μ m; With this high crystalline tetracalcium phosphate granule and strontium monophosphate SrHPO
4, calcium phosphate dibasic anhydrous CaHPO
4The powder three is (2+x): y in molar ratio: (2-y) fully mixes, obtains the composite bone cement solid phase powder, and x=0~0.2 wherein, y=0~2.0, three's mean particle size range is respectively 10.0~50.0 μ m, 0.7~10.0 μ m, 0.7~10.0 μ m;
2) composite bone cement solid phase powder and fiber mixing:
To have biocompatibility, high-tensile degradable macromolecule fiber or can absorb operation suture thread and add in the above-mentioned composite bone cement solid phase powder, fibre diameter 10~50 μ m wherein, fibre length is 1~20mm; The composite bone cement solid phase powder is 0.1%~15% with degradable macromolecule fiber quality ratio.
3) preparation of composite bone cement consolidation liquid:
Phosphoric acid H by 0.01~0.75mol/L of phosphoric acid and deionized water preparation
3PO
4Aqueous solution;
4) mediation of composite bone cement, curing and final formation:
Mixed system and phosphoric acid H with above-mentioned composite bone cement solid phase powder that obtains and fiber
3PO
4Aqueous solution fully is in harmonious proportion, both mass ratios are (1.0~3.0) during mediation: 1, form the cement of uniformity after being in harmonious proportion, inserting temperature with slurry or forming blocks form is that 37 ℃, relative humidity are that 100% class physiological environment solidifies 24 hours down to 2 weeks, and the gained material is the toughness reinforcing degradable strontium calcium superphosphate composite bone cement of ceramic original position fortifying fibre.
The high strength and tenacity degradable strontium calcium superphosphate biological activity composite bone cement that adopts preparation technology of the present invention to make, soak 24 hours to 2 weeks through 37 ℃ of simulated body fluids, its end product is the saamite of mixing that residue tetracalcium phosphate ceramic particle strengthens, macromolecular fibre is toughness reinforcing.
The high strength and tenacity degradable strontium calcium superphosphate biological activity composite bone cement that adopts preparation technology of the present invention to make, in 37 ℃ of simulated body fluids soak for 3~October, partially or completely degraded takes place in macromolecular fibre, and its cured product is mixed saamite for the enhanced porous of residue tetracalcium phosphate ceramic particle.
The high strength and tenacity degradable strontium calcium superphosphate biological activity composite bone cement that adopts preparation technology of the present invention to make, after mould molding, 37 ℃ of simulated body fluids soaked 24 hours, comprcssive strength was 76~104Mpa, work to break is 860~2500Jm
-2And its comprcssive strength increases with residue tetracalcium phosphate ceramic particle content and obviously increases, its work to break enlarges markedly with the increase of macromolecular fibre content, and its excellent comprehensive performances makes this complex cement be fit to the damaged reparation of human body bearing position bone or strengthens fixing.
The high strength and tenacity degradable strontium calcium superphosphate biological activity composite bone cement that adopts preparation technology of the present invention to make, has the effect of slow release strontium ion, thereby prolong the pharmacological treatment effect of strontium ion, and the displacement of strontium and part calcium helps improving the degradability of this bone cement to implant site.
The strontium calcium superphosphate biological activity composite bone cement that adopts preparation technology of the present invention to make, through acute toxicity test, pyrogen testing, hemolytic test test, the result is qualified, and vitro cytotoxicity is 0~1 grade, has excellent biological compatibility; Show that by tame rabbit muscle and skeleton heeling-in experiment this high strength and tenacity degradable strontium calcium superphosphate biological activity composite bone cement has good bone conductibility, biological activity and vivo degradation performance.
The specific embodiment
Below in conjunction with embodiment content of the present invention is described in further detail:
Embodiment 1: with calcium phosphate dibasic anhydrous CaHPO
4With calcium carbonate CaCO
3Carrying out wet ball grinding in 1: 1 in molar ratio mixed 20~60 hours, ball-milling medium is a dehydrated alcohol, heating rate with 4.0~5.0 ℃/min is heated under 1450~1500 ℃ then, be incubated 20~40 hours, cooldown rate with 150~300 ℃/min is cooled to room temperature at last, thereby obtain high crystalline tetracalcium phosphate block, behind fragmentation, hand lapping, ball milling, obtain being of a size of the high crystalline tetracalcium phosphate granule of 10.0~50.0 μ m.Quality is respectively the Ca of 0.7686g, 0.0184g, 0.2584g
4(PO
4)
2O, SrHPO
4, CaHPO
4Powder fully mixes, and adds 0.0523g poly lactic coglycolic acid PLGA fiber (diameter is 14 μ m, length 1.5mm), and with 0.5227g concentration be the H of 0.5mol/L
3PO
4Aqueous solution (x=0.1 wherein, y=0.1, Sr/ (Sr+Ca)=1%; W
1: W
2: W
3=2: 0.1: 1.0) mediation 30s, form the cement slurry of uniformity, insert diameter and be 6mm, high in the rustless steel cylinder mold of 12mm and apply the pressure compacting of 0.7MPa, the cylinder sample of making is filled in the glass tubing of diameter 6.5mm, high 13mm, seal with adhesive tape at two ends, insert temperature then and be 37 ℃, relative humidity and be solidify 30min in 100% the environment after, sample taken out and immerse among the SBF (simulated body fluid) rapidly.The end product composition that forms firming body after 3 days is that tetracalcium phosphate ceramic particle original position strengthens, poly lactic coglycolic acid PLGA is fiber reinforced contains the saamite composite bone cement.Average compressive strength is 91.5MPa, and work to break is 1008.7Jm
-2, final setting time is 12min.Cell toxicity test result is 1 grade.The static immersing experimental result shows in normal saline, prolongs with soak time, and fiber is degraded (June, fiber was degraded fully) gradually, and tetracalcium phosphate content reduces gradually, and strontium ion concentration slowly increases in the solution.
Embodiment 2: with calcium phosphate dibasic anhydrous CaHPO
4With calcium carbonate CaCO
3Carrying out wet ball grinding in 1: 1 in molar ratio mixed 20~60 hours, ball-milling medium is a dehydrated alcohol, heating rate with 4.0~5.0 ℃/min is heated under 1450~1500 ℃ then, be incubated 20~40 hours, cooldown rate with 150~300 ℃/min is cooled to room temperature at last, thereby obtain high crystalline tetracalcium phosphate block, behind fragmentation, hand lapping, ball milling, obtain being of a size of the high crystalline tetracalcium phosphate granule of 10.0~50.0 μ m.Quality is respectively the Ca of 0.7686g, 0.0184g, 0.2584g
4(PO
4)
2O, SrHPO
4, CaHPO
4Powder fully mixes, and adds 0.1046g poly lactic coglycolic acid PLGA fiber (diameter is 14 μ m, length 1.5mm), and with 0.5227g concentration be the H of 0.5mol/L
3PO
4Aqueous solution (x=0.1 wherein, y=0.1, Sr/ (Sr+Ca)=1%; W
1: W
2: W
3=2: 0.2: 1.0) mediation 30s, form the cement slurry of uniformity, insert diameter and be 6mm, high in the rustless steel cylinder mold of 12mm and apply the pressure compacting of 0.7MPa, the cylinder sample of making is filled in the glass tubing of diameter 6.5mm, high 13mm, seal with adhesive tape at two ends, insert temperature then and be 37 ℃, relative humidity and be solidify 30min in 100% the environment after, sample taken out and immerse among the SBF (simulated body fluid) rapidly.The end product composition that forms firming body after 3 days is that tetracalcium phosphate ceramic particle original position strengthens, poly lactic coglycolic acid PLGA is fiber reinforced contains the saamite composite bone cement.Average compressive strength is 82.6MPa, and work to break is 1620.5Jm
-2, final setting time is 10min.Cell toxicity test result is 1 grade.The static immersing experimental result shows in normal saline, prolongs with soak time, and fiber is degraded (June, fiber was degraded fully) gradually, and tetracalcium phosphate content reduces gradually, and strontium ion concentration slowly increases in the solution.
Embodiment 3: with calcium phosphate dibasic anhydrous CaHPO
4With calcium carbonate CaCO
3Carrying out wet ball grinding in 1: 1 in molar ratio mixed 20~60 hours, ball-milling medium is a dehydrated alcohol, heating rate with 4.0~5.0 ℃/min is heated under 1450~1500 ℃ then, be incubated 20~40 hours, cooldown rate with 150~300 ℃/min is cooled to room temperature at last, thereby obtain high crystalline tetracalcium phosphate block, behind fragmentation, hand lapping, ball milling, obtain being of a size of the high crystalline tetracalcium phosphate granule of 10.0~50.0 μ m.Quality is respectively the Ca of 0.7503g, 0.0918g, 0.2040g
4(PO
4)
2O, SrHPO
4, CaHPO
4Powder fully mixes, and adds 0.0523g polyglycolic acid fiber (diameter is 14 μ m, length 1.5mm), and with 0.5231g concentration be the H of 0.5mol/L
3PO
4Aqueous solution (x=0.05 wherein, y=0.5, Sr/ (Sr+Ca)=5%; W
1: W
2: W
3=2: 0.1: 1.0) mediation 30s, form the cement slurry of uniformity, insert diameter and be 6mm, high in the rustless steel cylinder mold of 12mm and apply the pressure compacting of 0.7MPa, the cylinder sample of making is filled in the glass tubing of diameter 6.5mm, high 13mm, seal with adhesive tape at two ends, insert temperature then and be 37 ℃, relative humidity and be solidify 30min in 100% the environment after, sample taken out and immerse among the SBF (simulated body fluid) rapidly.The end product composition that forms firming body after 3 days is that tetracalcium phosphate ceramic particle original position strengthens, polyglycolic acid is fiber reinforced contains the saamite composite bone cement.Average compressive strength is 88.7MPa, and work to break is 1020.5Jm
-2, final setting time is 11.5min.Cell toxicity test result is 1 grade.The static immersing experimental result shows in normal saline, prolongs with soak time, and fiber is degraded (June, fiber was degraded fully) gradually, and tetracalcium phosphate content reduces gradually, and strontium ion concentration slowly increases in the solution.
Embodiment 4: with calcium phosphate dibasic anhydrous CaHPO
4With calcium carbonate CaCO
3Carrying out wet ball grinding in 1: 1 in molar ratio mixed 20~60 hours, ball-milling medium is a dehydrated alcohol, heating rate with 4.0~5.0 ℃/min is heated under 1450~1500 ℃ then, be incubated 20~40 hours, cooldown rate with 150~300 ℃/min is cooled to room temperature at last, thereby obtain high crystalline tetracalcium phosphate block, behind fragmentation, hand lapping, ball milling, obtain being of a size of the high crystalline tetracalcium phosphate granule of 10.0~50.0 μ m.Quality is respectively the Ca of 0.7503g, 0.0918g, 0.2040g
4(PO
4)
2O, SrHPO
4, CaHPO
4Powder fully mixes, and adds 0.1046g acid fiber by polylactic (diameter is 14 μ m, length 1.5mm), and with 0.5231g concentration be the H of 0.5mol/L
3PO
4Aqueous solution (x=0.05 wherein, y=0.5, Sr/ (Sr+Ca)=5%; W
1: W
2: W
3=2: 0.2: 1.0) mediation 30s, form the cement slurry of uniformity, insert diameter and be 6mm, high in the rustless steel cylinder mold of 12mm and apply the pressure compacting of 0.7MPa, the cylinder sample of making is filled in the glass tubing of diameter 6.5mm, high 13mm, seal with adhesive tape at two ends, insert temperature then and be 37 ℃, relative humidity and be solidify 30min in 100% the environment after, sample taken out and immerse among the SBF (simulated body fluid) rapidly.The end product composition that forms firming body after 3 days is that tetracalcium phosphate ceramic particle original position strengthens, acid fiber by polylactic is toughness reinforcing contains the saamite composite bone cement.Average compressive strength is 76.2MPa, and work to break is 1560.2Jm
-2, final setting time is 13.5min.Cell toxicity test result is 1 grade.The static immersing experimental result shows in normal saline, prolongs with soak time, and fiber is degraded (June, fiber was degraded fully) gradually, and tetracalcium phosphate content reduces gradually, and strontium ion concentration slowly increases in the solution.
Embodiment 5: with calcium phosphate dibasic anhydrous CaHPO
4With calcium carbonate CaCO
3Carrying out wet ball grinding in 1: 1 in molar ratio mixed 20~60 hours, ball-milling medium is a dehydrated alcohol, heating rate with 4.0~5.0 ℃/min is heated under 1450~1500 ℃ then, be incubated 20~40 hours, cooldown rate with 150~300 ℃/min is cooled to room temperature at last, thereby obtain high crystalline tetracalcium phosphate block, behind fragmentation, hand lapping, ball milling, obtain being of a size of the high crystalline tetracalcium phosphate granule of 10.0~50.0 μ m.Quality is respectively the Ca of 0.8052g, 0.1836g, 0.1360g
4(PO
4)
2O, SrHPO
4, CaHPO
4Powder fully mixes, and adds 0.0562g poly lactic coglycolic acid fiber PLGA (diameter is 14 μ m, length 1.5mm), and with 0.5624g concentration be the H of 0.5mol/L
3PO
4Aqueous solution (x=0.05 wherein, y=1.0, Sr/ (Sr+Ca)=10%; W
1: W
2: W
3=2: 0.1: 1.0) mediation 30s, form the cement slurry of uniformity, insert diameter and be 6mm, high in the rustless steel cylinder mold of 12mm and apply the pressure compacting of 0.7MPa, the cylinder sample of making is filled in the glass tubing of diameter 6.5mm, high 13mm, seal with adhesive tape at two ends, insert temperature then and be 37 ℃, relative humidity and be solidify 30min in 100% the environment after, sample taken out and immerse among the SBF (simulated body fluid) rapidly.The end product composition that forms firming body after 3 days is that tetracalcium phosphate ceramic particle original position strengthens, poly lactic coglycolic acid PLGA is fiber reinforced contains the saamite composite bone cement.Average compressive strength is 103.7MPa, and work to break is 1020.5Jm
-2, final setting time is 10.5min.Cell toxicity test result is 1 grade.The static immersing experimental result shows in normal saline, prolongs with soak time, and fiber is degraded (June, fiber was degraded fully) gradually, and tetracalcium phosphate content reduces gradually, and strontium ion concentration slowly increases in the solution.
Embodiment 6: with calcium phosphate dibasic anhydrous CaHPO
4With calcium carbonate CaCO
3Carrying out wet ball grinding in 1: 1 in molar ratio mixed 20~60 hours, ball-milling medium is a dehydrated alcohol, heating rate with 4.0~5.0 ℃/min is heated under 1450~1500 ℃ then, be incubated 20~40 hours, cooldown rate with 150~300 ℃/min is cooled to room temperature at last, thereby obtain high crystalline tetracalcium phosphate block, behind fragmentation, hand lapping, ball milling, obtain being of a size of the high crystalline tetracalcium phosphate granule of 10.0~50.0 μ m.Quality is respectively the Ca of 0.8052g, 0.1836g, 0.1360g
4(PO
4)
2O, SrHPO
4, CaHPO
4Powder fully mixes, and adds 0.1124g polyglycolic acid fiber (diameter is 14 μ m, length 1.5mm), and with 0.5624g concentration be the H of 0.5mol/L
3PO
4Aqueous solution (x=0.05 wherein, y=1.0, Sr/ (Sr+Ca)=10%; W
1: W
2: W
3=2: 0.2: 1.0) mediation 30s, form the cement slurry of uniformity, insert diameter and be 6mm, high in the rustless steel cylinder mold of 12mm and apply the pressure compacting of 0.7MPa, the cylinder sample of making is filled in the glass tubing of diameter 6.5mm, high 13mm, seal with adhesive tape at two ends, insert temperature then and be 37 ℃, relative humidity and be solidify 30min in 100% the environment after, sample taken out and immerse among the SBF (simulated body fluid) rapidly.The end product composition that forms firming body after 3 days is that tetracalcium phosphate ceramic particle original position strengthens, polyglycolic acid is fiber reinforced contains the saamite composite bone cement.Average compressive strength is 85.6MPa, and work to break is 1820.5Jm
-2, final setting time is 14min.Cell toxicity test result is 1 grade.The static immersing experimental result shows in normal saline, prolongs with soak time, and fiber is degraded (June, fiber was degraded fully) gradually, and tetracalcium phosphate content reduces gradually, and strontium ion concentration slowly increases in the solution.
Claims (3)
1, high strength and tenacity degradable strontium calcium superphosphate composite bone cement is characterized in that, end product is by high crystalline tetracalcium phosphate Ca
4(PO
4)
2The block materials that O ceramic particle, high-tensile biocompatibility degradable macromolecule fiber and nanometer strontium-doped apatite crystal grain are formed, wherein the quality percentage composition of tetracalcium phosphate is 1%~10%, high-tensile biocompatibility degradable macromolecule fiber quality percentage composition is 0.1%~10%, and the quality percentage composition of nanometer strontium-doped apatite crystal grain is respectively 80%~98.9%.
2, high strength and tenacity degradable strontium calcium superphosphate composite bone cement according to claim 1, it is characterized in that, high-tensile biocompatibility degradable macromolecule fiber is selected from poly lactic coglycolic acid PLGA fiber, acid fiber by polylactic or polyglycolic acid fiber or can absorbs operation suture thread, fibre diameter 10~50 μ m wherein, fibre length is 1~20mm.
3, a kind of preparation method of high strength and tenacity degradable strontium calcium superphosphate composite bone cement as claimed in claim 1 is characterized in that: carry out as follows:
1) preparation of composite bone cement solid phase powder:
With calcium phosphate dibasic anhydrous CaHPO
4With calcium carbonate CaCO
3Carrying out wet ball grinding in 1: 1 in molar ratio mixed 20~60 hours, ball-milling medium is a dehydrated alcohol, heating rate with 4.0~5.0 ℃/min is heated under 1450~1500 ℃ then, be incubated 20~40 hours, cooldown rate with 150~300 ℃/min is cooled to room temperature at last, thereby obtain high crystalline tetracalcium phosphate block, behind fragmentation, hand lapping, ball milling, obtain being of a size of the high crystalline tetracalcium phosphate granule of 10.0~50.0 μ m; With this high crystalline tetracalcium phosphate granule and strontium monophosphate SrHPO
4, calcium phosphate dibasic anhydrous CaHPO
4The powder three is (2+x): y in molar ratio: (2-y) fully mixes, obtains the composite bone cement solid phase powder, and x=0~0.2 wherein, y=0~2, three's mean particle size range is respectively 10.0~50.0 μ m, 0.7~10.0 μ m, 0.7~10.0 μ m;
2) composite bone cement solid phase powder and fiber mixing:
To have biocompatibility, high-tensile degradable macromolecule fiber or can absorb operation suture thread and add in the above-mentioned composite bone cement solid phase powder, fibre diameter 10~50 μ m wherein, fibre length is 1~20mm; The composite bone cement solid phase powder is 0.1%~15% with degradable macromolecule fiber quality ratio.
3) preparation of composite bone cement consolidation liquid:
Phosphoric acid H by 0.01~0.75mol/L of phosphoric acid and deionized water preparation
3PO
4Aqueous solution;
4) mediation of composite bone cement, curing and final formation:
Mixed system and phosphoric acid H with above-mentioned composite bone cement solid phase powder that obtains and fiber
3PO
4Aqueous solution fully is in harmonious proportion, both mass ratios are (1.0~3.0) during mediation: 1, form the cement of uniformity after being in harmonious proportion, inserting temperature with slurry or forming blocks form is that 37 ℃, relative humidity are that 100% class physiological environment solidifies 24 hours down to 2 weeks, and gained material end product is by high crystalline tetracalcium phosphate Ca
4(PO
4)
2The block materials that O ceramic particle, high-tensile biocompatibility degradable macromolecule fiber and nanometer strontium-doped apatite crystal grain are formed, wherein the quality percentage composition of tetracalcium phosphate is 1%~10%, biocompatibility degradable macromolecule fiber quality percentage composition is 0.1%~10%, and the quality percentage composition of nanometer strontium-doped apatite crystal grain is respectively 80%~98.9%.
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