CN101041087A - Degradable biphase ceramics bone frame with high-strength and phosphate cement containing strontium and the preparing method - Google Patents
Degradable biphase ceramics bone frame with high-strength and phosphate cement containing strontium and the preparing method Download PDFInfo
- Publication number
- CN101041087A CN101041087A CN 200710017754 CN200710017754A CN101041087A CN 101041087 A CN101041087 A CN 101041087A CN 200710017754 CN200710017754 CN 200710017754 CN 200710017754 A CN200710017754 A CN 200710017754A CN 101041087 A CN101041087 A CN 101041087A
- Authority
- CN
- China
- Prior art keywords
- bone
- negative norm
- phosphate
- saamite
- strontium
- 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.)
- Pending
Links
Landscapes
- Materials For Medical Uses (AREA)
Abstract
The invention discloses a high-strength degradable strontium phosphate dual-phase ceramic bone skeleton and relative preparation, wherein the initial material is calciprivia fermorite bone cement, whose solid phase powder is the mixture of Ca4(PO4)2O, SrHPO4, CaHPO4, and the liquid phase is 0.1mol/L-1mol/L H3PO4 water solution. The invention uses skeleton structure to controllably quickly print and shape RP optical sensitive resin as concave mold, to irrigate slurry, solidify, and thermally remove mold and following sinter to obtain the strontium phosphate dual-phase ceramic bone support with adjustable phases. The total porous rate of skeleton is 42.5-75%, the size of macro hole is 300mum-600mum, the volume of macro hole is 0-50%, the size of micro hole is 2-10mum, and the compression strength is 3.15MPa-21.53MPa, with wide application.
Description
Technical field
The invention belongs to biomedical materials field, the preparation method that relates to a kind of high-strength degradable phosphate cement containing strontium biphase ceramics bone frame, the preparation method that is suitable for the phosphate cement containing strontium biphase ceramics bone frame that human body bearing position bone tissue engineer uses that relates in particular to that a kind of degradation rate is controlled, pore structure is adjustable.
Background technology
Bone tissue engineer provides new thinking for realizing the permanent reparation of defect of human body bone.Yet developing a kind of bone tissue engineering stent material with good combination property is that its final clinical repair operation of decision is able to one of key factor of success.Studies show that bone tissue engineering stent material must possess following condition: (1) excellent biological compatibility; (2) Shi Du biological degradability, degradation speed need to be complementary with osteanagenesis speed; (3) good structural compatibility and bone conductibility comprises suitable bore hole size and connective, porosity and material surface micro structure and chemical property; (4) enough intensity and formability; (5) with the compatibility of signaling molecule; (6) easy sterilization property.In the bone tissue engineering stent material that people set about studying, the most general at present with the research of degradable high polymer material and porous hydroxyapatite.Though the former has good biodegradability properties, and easily realize the pore space structure controllability with connective, its intensity is often lower, and biocompatibility is relatively poor relatively.Though the latter has excellent biological compatibility, biological activity, but the degradability of hydroxyapatite is extremely slow, the pore space structure controllability is relatively poor relatively, and the intensity of existing high porosity hydroxyl apatite bone support is very low, generally be no more than 5MPa (Kim HW, et al.PorousZrO2 bone scaffold coated with hydroxyapatite with fluorapatite intermediate layer.Biomaterials, 2003; 24:3277-3284), be unsuitable for the mechanics requirement of human body bearing position bone tissue engineer.Developing a kind of novel bone tissue engineering stent material system and being aided with suitable hole building method is the important topic that solution is badly in need of in present bone tissue engineer field.
Biphasic calcium phosphate BCP pottery is beginning of the eighties in last century American scholar Lynch, Nery and the LeGeros important calcium phosphate composite ceramics of being made up of by a certain percentage hydroxyapatite HA, tricalcium phosphate β-TCP of making joint efforts and putting forward down.This material combines HA higher-strength, high bioactivity, and the quick advantage such as degraded of β-TCP, is subjected to technical field of biological material scholars' great attention always, has obtained application widely at present in fields such as dentistry, plastic surgery.In recent years, Chinese scholars begins traditional bone renovating material of this excellence of BCP has been carried out bone tissue engineer research, in the hope of obtaining a kind of bone tissue engineering stent material with good combination property.Yet studies show that, though the degradability of the BCP bone support of exploitation than the hydroxyl apatite bone support be improved significantly, its mechanical strength is still lower, this be because: on the one hand, high porosity and grand hole be weakening mechanical strength key factor; On the other hand, in the BCP compound system, HA is as the main contribution phase of intensity, and not only itself intensity is limited, and its extremely slowly degradation rate limited its content in BCP.For example, when overall porosity up to 73%, interior intercommunicating pore diameter is 30 μ m, when grand hole percentage composition is 18%, the comprcssive strength of BCP bone holder material only is 1.5MPa (Bignon A, et al.Effect of micro-andmacroporosity of bone substitues on their mechanical properties and celluarresponse.J Mater Sci:Mater Med, 2003; 14:1089-1097).In order further to improve the mechanical strength of BCP bone tissue engineer support, Chinese scholars has proposed some and has improved one's methods, for example improve sintering technology (season gold is careless etc. the research of microwave plasma sintering porous HA/b-TCP two-phase biological ceramic. Journal of Inorganic Materials, 2004; 19 (4): 845-850), add the bio-vitric phase (Zhao Junliang etc. the foam impregnation legal system is equipped with the porous hydroxyapatite complex phase ceramic. Chinese pottery, 2003; 39 (1): 4-7) etc., though improved the intensity of BCP bone support to a certain extent, intensity amplification is obvious inadequately, and the excessive biological activity that can reduce timbering material of the glassy phase that adds.Recently, the thinking of utilizations such as American scholar Ramay HRR " nanofiber enhancing ", replace HA powder body among the conventional BCP with the HA nanofiber, obtained HA nanofiber enhancement mode BCP bone holder material, its intensity has obtained improving comparatively significantly (RamayHRR, et al.Biphasic calcium phosphate nanocomposite porous scaffolds forload-bearing bone tissue engineering.Biomaterials.2004; 25:5171-5180).But insufficient is that they fail when using the template modulation technique framing structure of organic foam template is effectively regulated and control, so the final bone support that obtains lacks adjustability on pore space structure.Therefore, adopt conventional improving one's methods, be difficult to make the BCP ceramics bone frame between desirable pore structure and higher mechanical strength, to reach ideal taking into account.
There are some researches show, mix saamite Sr-HA and have than conventional H A better mechanical strength, vivo degradation speed and biological activity.If start with from the angle of composition modification or element doping, adopt the strontium ion doping techniques, construct the novel strontium biphasic calcium phosphate pottery Sr-BCP system that contains, and be aided with suitable hole constructing technology and sintering process, then might obtain all to be better than the New type of S r-BCP bone holder material of traditional B CP at aspects such as mechanical strength, degradation property, biological activitys.With this thinking, we once adopted calcium deficiency to mix the saamite bone cement is raw material, use foam template dipping principle, obtained the degradable foam-like strontium-doped calcium phosphate biphase ceramics bone frame by sintering method, and intensity (Guo Dagang etc., the preparation technology of degradable foam-like strontium-doped calcium phosphate ceramic bone holder material, the Chinese invention patent of this bone support have obviously been improved by the improvement technology of " defect repair and double sintering ", CN1762897A), but insufficient be that intensity still is no more than 5MPa.And it is generally acknowledged, bone support comprcssive strength is higher than bone tissue engineer application (Ramay HRR, the et al.Biphasiccalcium phosphate nanocomposite porous scaffolds for load-bearing bone tissueengineering.Biomaterials.2004 that might be applicable to just more than the 5MPa that human body bearing position bone is damaged; 25:5171-5180).
Summary of the invention
The object of the present invention is to provide a kind of high-strength degradable phosphate cement containing strontium biphase ceramics bone frame and preparation method thereof, this bone holder material has high compression strength, good controlled degradation rate, suitable pore structure and excellent biological compatibility, bone conductibility, biological activity.Framing structure controllability, the calcium deficiency that this preparation method has merged printing speed photosensitive resin negative norm mixed the pyrolytic of saamite bone cement and contained the good biological activity of saamite, high strength and controlled degradation rate, contain strontium tricalcium phosphate multiple advantage such as degraded fast.
Technical scheme of the present invention is to solve like this:
High-strength degradable phosphate cement containing strontium biphase ceramics bone frame, its final bone support that obtains consist of the mixture that contains the strontium tricalcium phosphate and contain saamite, the quality percentage composition that wherein contains the strontium tricalcium phosphate is 0.5%～80%, and the quality percentage composition that contains saamite is 20%～99.5%; The overall porosity of bone support is 42.5%～75%, and grand hole dimension is 300 μ m～600 μ m, and grand pore volume is 0%～50%, and pore size is 2 μ m～10 μ m, and micro pore volume is 21.38%～44.70%.
The preparation method of high-strength degradable phosphate cement containing strontium biphase ceramics bone frame, carry out as follows:
1) calcium deficiency is mixed the preparation of saamite bone cement SrCPC slurry:
Mean particle size range is respectively the tetracalcium phosphate Ca of 10.0 μ m～50.0 μ m, 0.7 μ m～10.0 μ m, 0.7 μ m～10.0 μ m
4(PO
4)
2O, strontium monophosphate SrHPO
4, calcium hydrogen phosphate CaHPO
4Powder is according to mol ratio 2: x: (2-x) mixed, obtain the solid phase powder of SrCPC, wherein x=0.1～1; Compound concentration is the phosphoric acid H of 0.1mol/L～1mol/L
3PO
4Aqueous solution is as the liquid phase of SrCPC; With solid phase powder and liquid phase mediation 30s～60s, obtain the SrCPC cement slurry, solid phase powder and liquid phase mass ratio are 1.5～3.0 when wherein being in harmonious proportion;
2) slurry cast and curing:
The calcium deficiency of above-mentioned preparation is mixed saamite bone cement SrCPC slurry injection printing speed become the type photosensitive resin negative norm, wherein the negative norm profile is cylindrical shape, height is 15mm～17mm, external diameter is Φ 10mm～Φ 11mm, wall thickness 0.5mm～1.0mm, the inner skeleton diameter is 200 μ m～800 μ m, and the aperture is 400 μ m～1000 μ m, and porosity is 50%～100%; During the slurry cast, constantly vibrate the RP negative norm,, make the bone cement slurry fully tamp the RP negative norm to eliminate the bubble that the bone cement slurry is sneaked in casting process; After wipeing the unnecessary bone cement slurry in RP negative norm surface off, the RP negative norm that fills up cement slurry is inserted 37 ℃, the following 24h～96h of curing of 100% humidity air ambient, obtain calcium deficiency and mix saamite bone cement/RP negative norm complex;
3) RP negative norm heat treatment is removed and the follow-up sintering method:
Calcium deficiency after solidifying mixed in the baking oven that saamite bone cement/RP negative norm complex is placed at 100 ℃～120 ℃ toast 5h～10h, put into the controllable silicon sintering furnace then and slowly be heated to 400 ℃～600 ℃ insulation 2h～10h down with 0.5 ℃/min of the rate of heat addition～1.5 ℃/min, with abundant removal RP negative norm, obtain porous phosphate cement containing strontium porous blocks; This porous blocks is further continued to be heated to 1000 ℃～1200 ℃ insulation 1h～10h down with the rate of heat addition of 2 ℃/min～10 ℃/min, cool to room temperature then with the furnace, obtain the phosphate cement containing strontium biphase ceramics bone frame.
The phosphate cement containing strontium biphase ceramics bone frame that adopts preparation technology of the present invention to make, its final comprcssive strength is 3.15MPa～21.53MPa, overall porosity is 42.5%～75%, grand hole dimension is 300 μ m～600 μ m, grand pore volume is 0%～50%, pore size is 2 μ m～10 μ m, and micro pore volume is 21.38%～44.70%; Its good pore space structure not only satisfies the requirement that osseous tissue and cell are grown into, and satisfies the essential condition that the calcium phosphate pottery has osteoinductive.
The phosphate cement containing strontium biphase ceramics bone frame that adopts preparation technology of the present invention to make, its comprcssive strength is apparently higher than the respective horizontal of existing phosphate bone support, near human body spongy bone upper limit comprcssive strength 2MPa～12MPa, the bone tissue engineer that is suitable for the human body bearing position is used.
The phosphate cement containing strontium biphase ceramics bone frame that adopts preparation technology of the present invention to make, not only have intensity height, pore structure is controlled, degradation rate is adjustable, phase composition is variable characteristics, and discharging strontium ion gradually after being on active service in the material bodies, the performance strontium ion is to the beneficial effect of new bone tissue growth with mineralization process.
The phosphate cement containing strontium biphase ceramics bone frame 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 phosphate cement containing strontium biphase ceramics bone frame has good bone conductibility, biological activity and vivo degradation performance.
The specific embodiment
Embodiment 1:
Particle mean size is respectively the Ca of 13.0 μ m, 6.7 μ m, 1.0 μ m
4(PO
4)
2O, SrHPO
4, CaHPO
4Powder mixes according to mol ratio at 2: 1.5: 0.5, makes phosphate cement containing strontium bone cement solid phase powder.With this powder of 50ml small beaker weighing 1.379g, be that the phosphoric acid,diluted consolidation liquid of 0.75mol/L mixes with 0.7ml concentration then, and be in harmonious proportion 30s to form the phosphate cement containing strontium bone cement slurry of uniformity with spoon.Adopting printing speed molding RP technology, is the negative norm material with the photosensitive resin, according to printing principle, prepares the high 17mm that is, external diameter is Φ 11mm, the interior empty drum type negative norm of wall thickness 0.5mm.Phosphate cement containing strontium bone cement slurry is injected this negative norm, and constantly vibrate negative norm,, make the bone cement slurry fully tamp negative norm to eliminate the bubble that the bone cement slurry is sneaked in casting process.After wipeing the unnecessary bone cement slurry in RP negative norm surface off, the RP negative norm that fills up cement slurry is inserted 37 ℃, the following 48h of curing of 100% humidity air ambient, obtain calcium deficiency and mix saamite bone cement/RP negative norm complex.Calcium deficiency after solidifying mixed in the baking oven that saamite bone cement/RP negative norm complex is placed at 110 ℃ toast 8h, put into the controllable silicon sintering furnace then and slowly be heated to 500 ℃ of insulation 4h down with 0.5 ℃/min of the rate of heat addition, fully remove the RP negative norm, and then continue to be heated to 1200 ℃ of insulation 2h down with the rate of heat addition of 5 ℃/min, cool to room temperature at last with the furnace, obtain the phosphate cement containing strontium biphase ceramics bone frame.
The phase composition of gained bone support is the mixture that contains saamite and contain the strontium tricalcium phosphate, and quality percentage composition ratio is 30%: 70%, and final comprcssive strength is 13.22MPa, overall porosity is 44.06%, grand pore volume is 0%, and pore size is 2 μ m～5 μ m, and micro pore volume is 44.06%.
Embodiment 2:
Particle mean size is respectively the Ca of 13.0 μ m, 6.7 μ m, 1.0 μ m
4(PO
4)
2O, SrHPO
4, CaHPO
4Powder mixes according to mol ratio at 2: 1.5: 0.5, makes phosphate cement containing strontium bone cement solid phase powder.With this powder of 50ml small beaker weighing 1.379g, be that the phosphoric acid,diluted consolidation liquid of 0.75mol/L mixes with 0.7ml concentration then, and be in harmonious proportion 30s to form the phosphate cement containing strontium bone cement slurry of uniformity with spoon.Adopting printing speed molding RP technology, is the negative norm material with the photosensitive resin, according to printing principle, prepares the high 17mm that is, external diameter is Φ 11mm, and wall thickness 0.5mm, inner skeleton diameter are 600 μ m, and the aperture is 800 μ m, and porosity is 30% porous negative norm.Phosphate cement containing strontium bone cement slurry is injected this negative norm, and constantly vibrate negative norm,, make the bone cement slurry fully tamp negative norm to eliminate the bubble that the bone cement slurry is sneaked in casting process.After wipeing the unnecessary bone cement slurry in RP negative norm surface off, the RP negative norm that fills up cement slurry is inserted 37 ℃, the following 48h of curing of 100% humidity air ambient, obtain calcium deficiency and mix saamite bone cement/RP negative norm complex.Calcium deficiency after solidifying mixed in the baking oven that saamite bone cement/RP negative norm complex is placed at 110 ℃ toast 8h, put into the controllable silicon sintering furnace then and slowly be heated to 500 ℃ of insulation 4h down with 0.5 ℃/min of the rate of heat addition, fully remove the RP negative norm, and then continue to be heated to 1200 ℃ of insulation 2h down with the rate of heat addition of 5 ℃/min, cool to room temperature at last with the furnace, obtain the phosphate cement containing strontium biphase ceramics bone frame.
The phase composition of gained bone support is the mixture that contains saamite and contain the strontium tricalcium phosphate, quality percentage composition ratio is 30%: 70%, final comprcssive strength is 3.32MPa, overall porosity is 62.01%, grand hole dimension is 600 μ m, grand pore volume is 30%, and pore size is 2 μ m～5 μ m, and micro pore volume is 32.01%.
Embodiment 3:
Particle mean size is respectively the Ca of 13.0 μ m, 6.7 μ m, 1.0 μ m
4(PO
4)
2O, SrHPO
4, CaHPO
4Powder mixes according to mol ratio at 2: 1.5: 0.5, makes phosphate cement containing strontium bone cement solid phase powder.With this powder of 50ml small beaker weighing 1.5486g, be that the phosphoric acid,diluted consolidation liquid of 0.40mol/L mixes with 0.6ml concentration then, and be in harmonious proportion 30s to form the phosphate cement containing strontium bone cement slurry of uniformity with spoon.Adopting printing speed molding RP technology, is the negative norm material with the photosensitive resin, according to printing principle, prepares the high 17mm that is, external diameter is Φ 11mm, the interior empty drum type negative norm of wall thickness 0.5mm.Phosphate cement containing strontium bone cement slurry is injected this negative norm, and constantly vibrate negative norm,, make the bone cement slurry fully tamp negative norm to eliminate the bubble that the bone cement slurry is sneaked in casting process.After wipeing the unnecessary bone cement slurry in RP negative norm surface off, the RP negative norm that fills up cement slurry is inserted 37 ℃, the following 48h of curing of 100% humidity air ambient, obtain calcium deficiency and mix saamite bone cement/RP negative norm complex.Calcium deficiency after solidifying mixed in the baking oven that saamite bone cement/RP negative norm complex is placed at 110 ℃ toast 8h, put into the controllable silicon sintering furnace then and slowly be heated to 500 ℃ of insulation 4h down with 0.5 ℃/min of the rate of heat addition, fully remove the RP negative norm, and then continue to be heated to 1200 ℃ of insulation 2h down with the rate of heat addition of 5 ℃/min, cool to room temperature at last with the furnace, obtain the phosphate cement containing strontium biphase ceramics bone frame.
The phase composition of gained bone support is the mixture that contains saamite and contain the strontium tricalcium phosphate, and quality percentage composition ratio is 78%: 22%, and final comprcssive strength is 21.53MPa, overall porosity is 44.21%, grand pore volume is 0%, and pore size is 2 μ m～5 μ m, and micro pore volume is 44.21%.
Embodiment 4:
Particle mean size is respectively the Ca of 13.0 μ m, 6.7 μ m, 1.0 μ m
4(PO
4)
2O, SrHPO
4, CaHPO
4Powder mixes according to mol ratio at 2: 1.5: 0.5, makes phosphate cement containing strontium bone cement solid phase powder.With this powder of 50ml small beaker weighing 1.5486g, be that the phosphoric acid,diluted consolidation liquid of 0.40mol/L mixes with 0.6ml concentration then, and be in harmonious proportion 30s to form the phosphate cement containing strontium bone cement slurry of uniformity with spoon.Adopting printing speed molding RP technology, is the negative norm material with the photosensitive resin, according to printing principle, prepares the high 17mm that is, external diameter is Φ 11mm, and wall thickness 0.5mm, inner skeleton diameter are 600 μ m, and the aperture is 800 μ m, and porosity is 30% porous negative norm.Phosphate cement containing strontium bone cement slurry is injected this negative norm, and constantly vibrate negative norm,, make the bone cement slurry fully tamp negative norm to eliminate the bubble that the bone cement slurry is sneaked in casting process.After wipeing the unnecessary bone cement slurry in RP negative norm surface off, the RP negative norm that fills up cement slurry is inserted 37 ℃, the following 48h of curing of 100% humidity air ambient, obtain calcium deficiency and mix saamite bone cement/RP negative norm complex.Calcium deficiency after solidifying mixed in the baking oven that saamite bone cement/RP negative norm complex is placed at 110 ℃ toast 8h, put into the controllable silicon sintering furnace then and slowly be heated to 500 ℃ of insulation 4h down with 0.5 ℃/min of the rate of heat addition, fully remove the RP negative norm, and then continue to be heated to 1200 ℃ of insulation 2h down with the rate of heat addition of 5 ℃/min, cool to room temperature at last with the furnace, obtain the phosphate cement containing strontium biphase ceramics bone frame.
The phase composition of gained bone support is the mixture that contains saamite and contain the strontium tricalcium phosphate, quality percentage composition ratio is 78%: 22%, final comprcssive strength is 9.20MPa, overall porosity is 63.01%, grand hole dimension is 600 μ m, grand pore volume is 30%, and pore size is 2 μ m～5 μ m, and micro pore volume is 33.01%.
Embodiment 5:
Particle mean size is respectively the Ca of 13.0 μ m, 6.7 μ m, 1.0 μ m
4(PO
4)
2O, SrHPO
4, CaHPO
4Powder mixes according to mol ratio at 2: 1.5: 0.5, makes phosphate cement containing strontium bone cement solid phase powder.With this powder of 50ml small beaker weighing 1.130g, be that the phosphoric acid,diluted consolidation liquid of 0.25mol mol/L mixes with 0.2ml concentration then, and be in harmonious proportion 30s to form the phosphate cement containing strontium bone cement slurry of uniformity with spoon.Adopting printing speed molding RP technology, is the negative norm material with the photosensitive resin, according to printing principle, prepares the high 17mm that is, external diameter is Φ 11mm, and wall thickness 0.5mm, inner skeleton diameter are 600 μ m, and the aperture is 800 μ m, and porosity is 30% porous negative norm.Phosphate cement containing strontium bone cement slurry is injected this negative norm, and constantly vibrate negative norm,, make the bone cement slurry fully tamp negative norm to eliminate the bubble that the bone cement slurry is sneaked in casting process.After wipeing the unnecessary bone cement slurry in RP negative norm surface off, the RP negative norm that fills up cement slurry is inserted 37 ℃, the following 48h of curing of 100% humidity air ambient, obtain calcium deficiency and mix saamite bone cement/RP negative norm complex.Calcium deficiency after solidifying mixed in the baking oven that saamite bone cement/RP negative norm complex is placed at 110 ℃ toast 8h, put into the controllable silicon sintering furnace then and slowly be heated to 500 ℃ of insulation 4h down with 0.5 ℃/min of the rate of heat addition, fully remove the RP negative norm, and then continue to be heated to 1200 ℃ of insulation 2h down with the rate of heat addition of 5 ℃/min, cool to room temperature at last with the furnace, obtain the phosphate cement containing strontium biphase ceramics bone frame.
The phase composition of gained bone support is the mixture that contains saamite and contain the strontium tricalcium phosphate, quality percentage composition ratio is 99.5%: 0.5%, final comprcssive strength is 3.44MPa, overall porosity is 61.85%, grand hole dimension is 600 μ m, grand pore volume is 30%, and pore size is 2 μ m～5 μ m, and micro pore volume is 31.85%.
Embodiment 6:
Particle mean size is respectively the Ca of 13.0 μ m, 6.7 μ m, 1.0 μ m
4(PO
4)
2O, SrHPO
4, CaHPO
4Powder mixes according to mol ratio at 2: 1.5: 0.5, makes phosphate cement containing strontium bone cement solid phase powder.With this powder of 50ml small beaker weighing 1.5486g, be that the phosphoric acid,diluted consolidation liquid of 0.40mol/L mixes with 0.6ml concentration then, and be in harmonious proportion 30s to form the phosphate cement containing strontium bone cement slurry of uniformity with spoon.Adopting printing speed molding RP technology, is the negative norm material with the photosensitive resin, according to printing principle, prepares the high 17mm that is, external diameter is Φ 11mm, and wall thickness 0.5mm, inner skeleton diameter are 600 μ m, and the aperture is 800 μ m, and porosity is 50% porous negative norm.Phosphate cement containing strontium bone cement slurry is injected this negative norm, and constantly vibrate negative norm,, make the bone cement slurry fully tamp negative norm to eliminate the bubble that the bone cement slurry is sneaked in casting process.After wipeing the unnecessary bone cement slurry in RP negative norm surface off, the RP negative norm that fills up cement slurry is inserted 37 ℃, the following 48h of curing of 100% humidity air ambient, obtain calcium deficiency and mix saamite bone cement/RP negative norm complex.Calcium deficiency after solidifying mixed in the baking oven that saamite bone cement/RP negative norm complex is placed at 110 ℃ toast 8h, put into the controllable silicon sintering furnace then and slowly be heated to 500 ℃ of insulation 4h down with 0.5 ℃/min of the rate of heat addition, fully remove the RP negative norm, and then continue to be heated to 1200 ℃ of insulation 2h down with the rate of heat addition of 5 ℃/min, cool to room temperature at last with the furnace, obtain the phosphate cement containing strontium biphase ceramics bone frame.
The phase composition of gained bone support is the mixture that contains saamite and contain the strontium tricalcium phosphate, quality percentage composition ratio is 78%: 22%, final comprcssive strength is 7.65MPa, overall porosity is 74.80%, grand hole dimension is 600 μ m, grand pore volume is 50%, and pore size is 2 μ m～5 μ m, and micro pore volume is 34.80%.
Claims (2)
1, high-strength degradable phosphate cement containing strontium biphase ceramics bone frame, it is characterized in that, its final bone support that obtains consist of the mixture that contains the strontium tricalcium phosphate and contain saamite, the quality percentage composition that wherein contains the strontium tricalcium phosphate is 0.5%～80%, and the quality percentage composition that contains saamite is 20%～99.5%; The overall porosity of bone support is 42.5%～75%, and grand hole dimension is 300 μ m～600 μ m, and grand pore volume is 0～50%, and pore size is 2 μ m～10 μ m, and micro pore volume is 21.38%～44.70%.
2, a kind of preparation method of high-strength degradable phosphate cement containing strontium biphase ceramics bone frame as claimed in claim 1 is characterized in that, carries out as follows:
1) calcium deficiency is mixed the preparation of saamite bone cement SrCPC slurry:
Mean particle size range is respectively the tetracalcium phosphate Ca of 10.0 μ m～50.0 μ m, 0.7 μ m～10.0 μ m, 0.7 μ m～10.0 μ m
4(PO
4)
2O, strontium monophosphate SrHPO
4, calcium hydrogen phosphate CaHPO
4Powder is according to mol ratio 2: x: (2-x) mixed, obtain the solid phase powder of SrCPC, wherein x=0.1～1; Compound concentration is the phosphoric acid H of 0.1mol/L～1mol/L
3PO
4Aqueous solution is as the liquid phase of SrCPC; With solid phase powder and liquid phase mediation 30s～60s, obtain the SrCPC cement slurry, solid phase powder and liquid phase mass ratio are 1.5～3.0 when wherein being in harmonious proportion;
2) slurry cast and curing:
The calcium deficiency of above-mentioned preparation is mixed saamite bone cement slurry injection printing speed become the type photosensitive resin negative norm, wherein the negative norm profile is cylindrical shape, height is 15mm～17mm, external diameter is Φ 10mm～Φ 11mm, wall thickness 0.5mm～1.0mm, the inner skeleton diameter is 200 μ m～800 μ m, and the aperture is 400 μ m～1000 μ m, and porosity is 50%～100%; During the slurry cast, constantly vibrate the RP negative norm,, make the bone cement slurry fully tamp the RP negative norm to eliminate the bubble that the bone cement slurry is sneaked in casting process; After wipeing the unnecessary bone cement slurry in RP negative norm surface off, the RP negative norm that fills up cement slurry is inserted 37 ℃, the following 24h～96h of curing of 100% humidity air ambient, obtain calcium deficiency and mix saamite bone cement/RP negative norm complex;
3) RP negative norm heat treatment is removed and the follow-up sintering method:
Calcium deficiency after solidifying mixed in the baking oven that saamite bone cement/RP negative norm complex is placed at 100 ℃～120 ℃ toast 5h～10h, put into the controllable silicon sintering furnace then and slowly be heated to 400 ℃～600 ℃ insulation 2h～10h down with 0.5 ℃/min of the rate of heat addition～1.5 ℃/min, with abundant removal RP negative norm, obtain porous phosphate cement containing strontium porous blocks; This porous blocks is further continued to be heated to 1000 ℃～1200 ℃ insulation 1h～10h down with the rate of heat addition of 2 ℃/min～10 ℃/min, cool to room temperature then with the furnace, obtain the phosphate cement containing strontium biphase ceramics bone frame.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200710017754 CN101041087A (en) | 2007-04-27 | 2007-04-27 | Degradable biphase ceramics bone frame with high-strength and phosphate cement containing strontium and the preparing method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200710017754 CN101041087A (en) | 2007-04-27 | 2007-04-27 | Degradable biphase ceramics bone frame with high-strength and phosphate cement containing strontium and the preparing method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101041087A true CN101041087A (en) | 2007-09-26 |
Family
ID=38807016
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200710017754 Pending CN101041087A (en) | 2007-04-27 | 2007-04-27 | Degradable biphase ceramics bone frame with high-strength and phosphate cement containing strontium and the preparing method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101041087A (en) |
Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102249728A (en) * | 2011-05-13 | 2011-11-23 | 天津大学 | Biological porous bone cement prepared by compositing Sr-doped calcium-phosphorus bioglass and alpha-tricalcium phosphate and preparation method thereof |
| CN101444639B (en) * | 2008-12-30 | 2013-03-13 | 西安交通大学 | Process for preparing strontium-doped calcium polyphosphate biological active bone cement |
| CN101444638B (en) * | 2008-12-30 | 2013-04-17 | 西安交通大学 | Process for preparing degradable strontium-doped biphasic calcium phosphate bioactive bone cement |
| CN104783929A (en) * | 2015-04-23 | 2015-07-22 | 西安交通大学 | Personally-customized tantalum implantation material manufacturing method |
| CN104799932A (en) * | 2015-04-14 | 2015-07-29 | 西安交通大学 | Porous structure bone cement screw design and manufacturing method thereof |
| CN105712735A (en) * | 2016-01-29 | 2016-06-29 | 云南省第一人民医院 | Preparation method for porous hydroxyapatite material for bone repairing |
| CN105712737A (en) * | 2016-01-29 | 2016-06-29 | 云南省第一人民医院 | Preparation method for porous strontium-doped hydroxyapatite material for bone repairing |
| CN107721408A (en) * | 2017-11-01 | 2018-02-23 | 江苏师范大学 | A kind of method that 3D printing prepares β tricalcium phosphate porous bio-ceramics |
| CN107952109A (en) * | 2017-11-27 | 2018-04-24 | 山东明德生物医学工程有限公司 | A kind of injected bone packing material and preparation method |
| CN108478879A (en) * | 2018-03-30 | 2018-09-04 | 华南理工大学 | A kind of porous calcium phosphate/natural polymer compound rest and the preparation method and application thereof |
| CN109260523A (en) * | 2018-09-14 | 2019-01-25 | 广州润虹医药科技股份有限公司 | A kind of calcium phosphate bone cement complex microsphere and its preparation method and application |
| CN109381744A (en) * | 2018-09-14 | 2019-02-26 | 广州润虹医药科技股份有限公司 | A kind of calcium orthophosphate base bone repairing support and preparation method thereof |
| WO2020008555A1 (en) * | 2018-07-04 | 2020-01-09 | オリンパス株式会社 | Bone substitute and method for producing bone substitute |
| WO2020008558A1 (en) * | 2018-07-04 | 2020-01-09 | オリンパス株式会社 | Bone substitute and method for producing bone substitute |
| CN111151220A (en) * | 2020-01-09 | 2020-05-15 | 中山大学惠州研究院 | Preparation method of cement-based polyconnected honeycomb catalyst/adsorbent |
| CN111848150A (en) * | 2020-07-09 | 2020-10-30 | 上海交通大学医学院附属第九人民医院 | SrCuSi4O10－Ca3(PO4)2Composite bioceramic, bone scaffold and application thereof |
| CN112223485A (en) * | 2019-07-15 | 2021-01-15 | 张志国 | Preparation method of three-dimensional network ceramic framework |
| CN113233887A (en) * | 2021-05-27 | 2021-08-10 | 四川大学 | Controllable porous calcium phosphate scaffold and preparation method thereof |
-
2007
- 2007-04-27 CN CN 200710017754 patent/CN101041087A/en active Pending
Cited By (22)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101444639B (en) * | 2008-12-30 | 2013-03-13 | 西安交通大学 | Process for preparing strontium-doped calcium polyphosphate biological active bone cement |
| CN101444638B (en) * | 2008-12-30 | 2013-04-17 | 西安交通大学 | Process for preparing degradable strontium-doped biphasic calcium phosphate bioactive bone cement |
| CN102249728B (en) * | 2011-05-13 | 2012-11-21 | 天津大学 | Biological porous bone cement prepared by compositing Sr-doped calcium-phosphorus bioglass and alpha-tricalcium phosphate and preparation method thereof |
| CN102249728A (en) * | 2011-05-13 | 2011-11-23 | 天津大学 | Biological porous bone cement prepared by compositing Sr-doped calcium-phosphorus bioglass and alpha-tricalcium phosphate and preparation method thereof |
| CN104799932A (en) * | 2015-04-14 | 2015-07-29 | 西安交通大学 | Porous structure bone cement screw design and manufacturing method thereof |
| CN104799932B (en) * | 2015-04-14 | 2017-04-26 | 西安交通大学 | Porous structure bone cement screw design and manufacturing method thereof |
| CN104783929A (en) * | 2015-04-23 | 2015-07-22 | 西安交通大学 | Personally-customized tantalum implantation material manufacturing method |
| CN105712735A (en) * | 2016-01-29 | 2016-06-29 | 云南省第一人民医院 | Preparation method for porous hydroxyapatite material for bone repairing |
| CN105712737A (en) * | 2016-01-29 | 2016-06-29 | 云南省第一人民医院 | Preparation method for porous strontium-doped hydroxyapatite material for bone repairing |
| CN107721408B (en) * | 2017-11-01 | 2021-03-16 | 江苏卓燃高新科技有限公司 | Method for preparing beta-tricalcium phosphate porous bioceramic through 3D printing |
| CN107721408A (en) * | 2017-11-01 | 2018-02-23 | 江苏师范大学 | A kind of method that 3D printing prepares β tricalcium phosphate porous bio-ceramics |
| CN107952109A (en) * | 2017-11-27 | 2018-04-24 | 山东明德生物医学工程有限公司 | A kind of injected bone packing material and preparation method |
| CN108478879A (en) * | 2018-03-30 | 2018-09-04 | 华南理工大学 | A kind of porous calcium phosphate/natural polymer compound rest and the preparation method and application thereof |
| WO2020008555A1 (en) * | 2018-07-04 | 2020-01-09 | オリンパス株式会社 | Bone substitute and method for producing bone substitute |
| WO2020008558A1 (en) * | 2018-07-04 | 2020-01-09 | オリンパス株式会社 | Bone substitute and method for producing bone substitute |
| CN109260523A (en) * | 2018-09-14 | 2019-01-25 | 广州润虹医药科技股份有限公司 | A kind of calcium phosphate bone cement complex microsphere and its preparation method and application |
| CN109381744A (en) * | 2018-09-14 | 2019-02-26 | 广州润虹医药科技股份有限公司 | A kind of calcium orthophosphate base bone repairing support and preparation method thereof |
| CN112223485A (en) * | 2019-07-15 | 2021-01-15 | 张志国 | Preparation method of three-dimensional network ceramic framework |
| CN111151220A (en) * | 2020-01-09 | 2020-05-15 | 中山大学惠州研究院 | Preparation method of cement-based polyconnected honeycomb catalyst/adsorbent |
| CN111848150A (en) * | 2020-07-09 | 2020-10-30 | 上海交通大学医学院附属第九人民医院 | SrCuSi4O10－Ca3(PO4)2Composite bioceramic, bone scaffold and application thereof |
| CN111848150B (en) * | 2020-07-09 | 2022-05-24 | 上海交通大学医学院附属第九人民医院 | SrCuSi4O10－Ca3(PO4)2Composite bioceramic, bone scaffold and application thereof |
| CN113233887A (en) * | 2021-05-27 | 2021-08-10 | 四川大学 | Controllable porous calcium phosphate scaffold and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101041087A (en) | Degradable biphase ceramics bone frame with high-strength and phosphate cement containing strontium and the preparing method | |
| Xu et al. | Injectable and macroporous calcium phosphate cement scaffold | |
| Miao et al. | Porous calcium phosphate ceramics modified with PLGA–bioactive glass | |
| Kim et al. | Gas foaming fabrication of porous biphasic calcium phosphate for bone regeneration | |
| Barralet et al. | High‐strength apatitic cement by modification with α‐hydroxy acid salts | |
| Qi et al. | Improved injectability and in vitro degradation of a calcium phosphate cement containing poly (lactide-co-glycolide) microspheres | |
| Qi et al. | Alginate/poly (lactic‐co‐glycolic acid)/calcium phosphate cement scaffold with oriented pore structure for bone tissue engineering | |
| Zhao et al. | Improving mechanical and biological properties of macroporous HA scaffolds through composite coatings | |
| CN103585677B (en) | A kind of HA micro-nano whisker reinforcement calcium phosphate ceramic material and its preparation method and application | |
| CN1736928A (en) | Preparation method of calcium orthophosphate bone cement degradable to pore in human body | |
| Sethuraman et al. | Development and characterization of biodegradable nanocomposite injectables for orthopaedic applications based on polyphosphazenes | |
| Lett et al. | Porous hydroxyapatite scaffolds for orthopedic and dental applications-the role of binders | |
| Wang et al. | Digital light processing (DLP) of nano biphasic calcium phosphate bioceramic for making bone tissue engineering scaffolds | |
| FU et al. | Zirconia incorporation in 3D printed β-Ca2SiO4 scaffolds on their physicochemical and biological property | |
| Sayed et al. | Developing porous diopside/hydroxyapatite bio-composite scaffolds via a combination of freeze-drying and coating process | |
| Jadidi et al. | Mechanical strength and biocompatibility of bredigite (Ca7MgSi4O16) tissue-engineering scaffolds modified by aliphatic polyester coatings | |
| Tsuru et al. | Mechanical behavior and cell response of PCL coated α-TCP foam for cancellous-type bone replacement | |
| CN103893828A (en) | Method for improving toughness of calcium phosphate bone cement | |
| KR20180062132A (en) | Composition for three-dimensional ceramic scaffold having dual-pore | |
| JP2012016517A (en) | Bone regeneration material and method for manufacturing the same | |
| CN104744022A (en) | Laser preparation method for strengthening and toughening ceramic bone scaffold with silicon carbide fibers | |
| CN106693063B (en) | A kind of anti-collapsibility calcium silicon substrate composite bone cement and its preparation method and application | |
| Hesaraki | Feasibility of alumina and alumina-silica nanoparticles to fabricate strengthened betatricalcium phosphate scaffold with improved biological responses | |
| CN104708736A (en) | Modified polyvinyl alcohol hydrogel material, special die, preparation method and application | |
| CN1278744C (en) | Macroporous brushite bone cement with latent hole forming agent and preparation process 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 | ||
| C12 | Rejection of a patent application after its publication | ||
| RJ01 | Rejection of invention patent application after publication |
Open date: 20070926 |