CN102249728B - Biological porous bone cement prepared by compositing Sr-doped calcium-phosphorus bioglass and alpha-tricalcium phosphate and preparation method thereof - Google Patents
Biological porous bone cement prepared by compositing Sr-doped calcium-phosphorus bioglass and alpha-tricalcium phosphate and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/34—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing cold phosphate binders
- C04B28/344—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing cold phosphate binders the phosphate binder being present in the starting composition solely as one or more phosphates
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B14/00—Use of inorganic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of inorganic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
- C04B14/02—Granular materials, e.g. microballoons
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/447—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on phosphates, e.g. hydroxyapatite
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- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
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- C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
- C04B38/0051—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof characterised by the pore size, pore shape or kind of porosity
- C04B38/0054—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof characterised by the pore size, pore shape or kind of porosity the pores being microsized or nanosized
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Abstract
The invention relates to a biological porous bone cement prepared by compositing Sr-doped calcium-phosphorus bioglass and alpha-tricalcium phosphate and a preparation method thereof. The bone cement provided by the invention is characterized in that the porousness of the bone cement is 39-57%, and the size of a micropore is between 0.5 um and 4 um; and the compression strength is 23.6-38.5 Mpa. In the invention, through compositing the Sr-doped calcium-phosphorus bioglass and alpha-tricalcium phosphate, the porous-structured bone cement is formed. In the invention, the solidification time andmicrostructure of the bone cement can be adjusted through the rapid dissolving of the Sr-doped calcium-phosphorus glass so as to form a porous structure with a high porousness, and the degradation property of a hydrated product (hydroxyapatite) can be improved; and in addition, by virtue of Sr ions introduced by biodegradable calcium-phosphorus glass, the compression strength of the bone cement is improved, thereby achieving the properties such as high strength and good degradability of the bone cement better.
Description
Technical field
The present invention relates to mix Sr calcium phosphorus bio-vitric compound type alpha tricalcium phosphate biological stephanoporate bone cement and preparation method, belong to the bio-medical material preparing technical field.
Background technology
(Calcium Phosphate Cement is a kind of novel artificial bone CPC) to calcium phosphate bone cement, can be used for bone tissue restoration.Carry out in-situ solidifying owing to can slurry form during its good biocompatibility and orthopaedic surgical operations are performed the operation directly inject the bone defect; Solve the difficult problem of other inorganic bio profile flexibility, therefore in orthopaedics, dentistry and plastic sugery, obtained widespread use.CPC also can be used as microbiotic, antitumor drug and the good slow-released carrier of various growth factor simultaneously.Wherein set time and product structure are to weigh two important factor in order that can bone cement satisfy clinical requirement.For satisfying the operation technique requirement, bone cement generally should be controlled at about 10～30min hardening time; And the penetration type loose structure helps the infiltration of tissue fluid, makes tissue fluid can enter into material internal, and not only is confined to the interface contact, thereby improves the degradation rate of material, impels micropore to enlarge and microvascular growing into.As the reparation of load bone, the ultimate compression strength of CPC there is higher requirement.Pass through at present the design of bone cement composition and the optimization of aquation condition; Can realize the CPC control of set time to a certain extent; But because the crystallization degree of hydrated product Win 40350 (HAp) is high, Stability Analysis of Structures; Bone cement is difficult to degraded in vivo, is unfavorable for repairing the recovery of position bone function.Also there is the insufficient shortcoming of mechanical property in CPC in addition, it is applied in to a certain extent is restricted.The present invention set forth, and to mix the compound type alpha tricalcium phosphate biological stephanoporate of Sr calcium phosphorus bio-vitric bone cement be exactly a kind of study on the modification on this basis.
Sr is one of trace element of needed by human, and the content in bone accounts for 0.01% of bone mass.Sr and other micro-the same normal functions that plays a part in vivo to keep, its existence is considered to the effect of preventing decayed tooth and enhance bone intensity.In the CPC bone cement, mix the strontium-incorporated hydroxyapatite (SrCPC) that Sr can form displaced type, change the structural stability of bone cement, promote degraded.There are some researches show that SrCPC has higher biological degradability than CPC, behind the SrCPC implantable bone tissue, biological degradation can take place in its surface quickly, and the skeletonization amount is than the CPC showed increased, and has prolonged new osteogenetic total time and peak period.On the one hand, Sr mixes among the CPC can not prolong set time, and can play the effect that improves CPC intensity.Like Chinese patent CN1559888A with tetracalcium phosphate Ca
4(PO
4)
2O, strontium monophosphate SrHPO
4, secondary calcium phosphate CaHPO
4Be solid phase, with phosphoric acid H
3PO
4The aqueous solution is that solid solution is the nano-calcium phosphate biological active bone cement of daisy_petal part or the bent bar-shaped Sr of containing with suitable solid-liquid than having prepared microscopic pattern; The presetting period of bone cement is 4～11min; Final setting time is 10～17min; Compressive strength is 40～60MPa, and more traditional CPC intensity is enhanced.Chinese patent CN101444638A has also introduced the preparation of the degradable biphasic calcium phosphate biological bone cement of strontium doping: with Ca
4(PO
4)
2O and β-Sr
xCa
(3-X)(PO
4) be solid phase, be liquid phase with the water-reducible phosphoric acid of de-ionized, the biphasic calcium phosphate biological bone cement that contains Sr of preparation, its presetting period is 2.5～10min, and final setting time is 8～25min, and compressive strength is 15～50MPa.Realized under the suitable situation in set time the HS of bone cement, being difficult to obtain the ideal vesicular structure though this type of mixes the Sr bone cement, thereby failed fundamentally to improve the degradation property of bone cement because the porosity of gained bone cement is lower.Similarly patent also has USP 7,758, and 693, US20090239787A1 and international monopoly WO2010055483 etc.On the other hand, can in mixing the Sr bone cement, form vesicular structure though utilize organism to form foraminous die plate or add pore former, realize high porosity, improve the degradation property of bone cement, ultimate compression strength obviously reduces.Like Chinese patent CN101041078A with tetracalcium phosphate Ca
4(PO
4)
2O, strontium monophosphate SrHPO
4, secondary calcium phosphate CaHPO
4Be solid phase, with phosphoric acid H
3PO
4The aqueous solution is solid solution, and adopting photosensitive resin to prepare porosity is 30% foraminous die plate, has finally prepared degradable phosphate cement containing strontium two-phase cement bracket.The overall porosity of bone support is 42.5%～75%, and macro-size is 300～600 μ m, and grand pore volume is 0～50%, and pore size is 2～10 μ m, and micro pore volume is 21.38%～44.70%, and ultimate compression strength is 3.15MPa～21.53MPa.In addition; It is raw material with polyphosphoric acid strontium and calcium polyphosphate that Chinese patent CN101716371A has also introduced a kind of; Preparation can owing to added 30%～50% pore former, obtain the bone support of high porosity from the strontium calcium polyphosphate bone support of vascularization promoting; Biodegradability is good, but can't solve the insufficient problem of ultimate compression strength equally.Similarly patent also has USP 6,593, and 394, US20080317807A1 etc.
Can know from existing disclosed related patent U.S. Patent No. report; Do not adding pore former or do not using under the situation of organic formwork; Can be on the basis that guarantees suitable set time through in calcium phosphate bone cement, adding the inorganic salt that contain Sr; Improve the ultimate compression strength of bone cement, but gained bone cement porosity is merely about 40%.The degradation property of bone cement is not improved at all, therefore is difficult to form the ideal vesicular structure, is unfavorable for that blood vessel is grown into and body fluid circulates.Though the use of pore former or organic formwork can obtain the cement bracket of high voidage, form vesicular structure, the ultimate compression strength of bone cement is lower, can't satisfy the requirement of bone tissue restoration to bone cement intensity.
Summary of the invention
The object of the present invention is to provide a kind of Sr of mixing calcium phosphorus bio-vitric compound type alpha tricalcium phosphate biological stephanoporate bone cement and preparation method; This bone cement is to carry out bio-vitric that contains Sr and type alpha tricalcium phosphate compound; Utilize the rapid degraded of bio-vitric, obtained the bone cement of high porosity; Simultaneously through Sr to the granule-morphology of bone cement hydrated product, the control of particle diameter, realized the HS of bone cement, finally prepared help blood vessel grow into the degradable high-strength bone cement of body fluid round-robin.The molar percentage of Sr can be regulated set time and porosity in massfraction through regulating calcium phosphorus bio-vitric in the bone cement and the glass, improves the ultimate compression strength of bone cement.
A kind of compound type alpha tricalcium phosphate biological stephanoporate of Sr calcium phosphorus bio-vitric bone cement of mixing of the present invention, the porosity of bone cement is 39%～57%, pore size is between 0.5～4um; Ultimate compression strength is 23.6～38.5Mpa.
A kind of preparation method who mixes the compound type alpha tricalcium phosphate biological stephanoporate of Sr calcium phosphorus bio-vitric bone cement of the present invention, step is following:
1) mix the preparation of Sr calcium phosphorus bio-vitric:
With four water-calcium nitrate, Vanadium Pentoxide in FLAKES, strontium nitrate, SODIUMNITRATE is raw material, wherein the corresponding oxide compound CaO of each material: P in the raw material
2O
5: SrO: Na
2The molar percentage of O is (50～42): 40: (3～11): 7; Take by weighing P
2O
5, adding in the absolute ethyl alcohol, controlled temperature is no more than 38.0 ℃ in the adition process, stirs to become clear solution until solution, makes phosphorus base precursor solution, leaves standstill behind the 24h subsequent use; Take by weighing four water-calcium nitrate, strontium nitrate, SODIUMNITRATE and join successively in the deionized water, mix and stir, be mixed with the Ca that concentration is 0.3～0.9mol/L
2+, Sr
2+, Na
+The clear solution of ion component; To contain Ca then
2+, Sr
2+And Na
+Clear solution dropwise join in the phosphorus base precursor solution, evenly stir, obtain even colloidal sol; In colloidal sol, dropwise splash into ammoniacal liquor, regulate pH to 8～9, obtain evenly colloidal sol of white, form uniform and stable gel after leaving standstill 24h; This gel as for 60 ℃ of oven dry down, is pulverized the back and in retort furnace, slowly is warming up to 300 ℃, and insulation 2～5h rises to 450 ℃～550 ℃ again, and insulation 1～3h forms calcium phosphorus bio-vitric;
2) preparation of type alpha tricalcium phosphate compound bio bone cement:
Choose consisting of of alpha-calcium phosphate bone cement: type alpha tricalcium phosphate, Ca (H
2PO
4)
2H
2O, CaCO
3And Win 40350, wherein the mass ratio of each component is α-TCP: Ca (H
2PO
4)
2H
2O: CaCO
3: HAp is 86: 5: 5: 4.
3) mix the preparation of the compound type alpha tricalcium phosphate biological stephanoporate of Sr calcium phosphorus bio-vitric bone cement:
With the prepared bio-vitric of step 1 set by step in 1%～10% admixture bone cement of the two type alpha tricalcium phosphate bone cement quality that make, be that 0.4ml/g modulates according to the ratio of distiller liquor and bone cement powder, distiller liquor is the Na of 0.8wt%
2HPO
4Solution injects punching block with slurry after being in harmonious proportion evenly, at room temperature is in harmonious proportion 60～90s, takes out the back and in 37 ℃ of constant temperature, relative humidity be under 100% the condition to solidify, and obtains composite bone cement.
The novelty of this patent is the calcium phosphorus bio-vitric of mixing strontium and type alpha tricalcium phosphate are carried out compound, has formed the bone cement of vesicular structure.Can regulate the set time and the microtexture of bone cement through mixing the quick dissolving of Sr calcium phosphorus glass, form the higher vesicular structure of porosity, can improve again the hydrated product Win 40350 degradation property; In addition, the Sr ion through degradable calcium phosphorus glass is introduced has improved the ultimate compression strength of bone cement, thereby has realized the characteristic of bone cement HS and good degradation property preferably.When the bio-vitric that in bone cement, adds mass percent 1%～10%; Wherein the molecular fraction of Sr is 3%～11%; Be 11min～22min the set time of gained bone cement; The porosity of aquation bone cement after 7 days is 39%～57%, and its ultimate compression strength is 23.6MPa～38.5MPa, satisfies the clinical requirement that bone is repaired.
This patent relates to mixes the compound type alpha tricalcium phosphate biological stephanoporate of Sr calcium phosphorus bio-vitric bone cement under set time suitable situation; Realized the characteristic of bone cement high porosity, HS and good degradation property preferably, had good application prospects in clinical medicine bone tissue restoration field.
The advantage of mixing the compound type alpha tricalcium phosphate biological stephanoporate of Sr calcium phosphorus bio-vitric bone cement of the present invention's preparation is: calcium phosphorus bio-vitric is dissolution rate faster; Changed the microtexture of bone cement; Formed the ideal vesicular structure, be convenient to body fluid circulation and blood vessel and grow into; The Sr that introduces through the calcium phosphorus glass simultaneously exerts an influence to the crystalline form of hydrated product Win 40350, structure etc., has realized bone cement HS and degradable characteristic preferably.Though, can also not influence the enforcement of operation with controlling 11min～22min set time through regulating its content along with the add-on increase of calcium phosphorus glass slightly prolongs its set time.
Description of drawings
The X diffracting spectrum of the compound type alpha tricalcium phosphate biological stephanoporate of calcium phosphorus bio-vitric bone cement aquation after 7 days that Fig. 1 makes for the embodiment of the invention 1;
The sem photograph of the compound type alpha tricalcium phosphate biological stephanoporate of calcium phosphorus bio-vitric bone cement aquation after 7 days that Fig. 2 makes for the embodiment of the invention 3;
The sem photograph of the compound type alpha tricalcium phosphate biological stephanoporate of calcium phosphorus bio-vitric bone cement aquation after 7 days that Fig. 3 makes for the embodiment of the invention 5;
Relation between the molar content of Sr in the quality percentage composition of glass and the glass in ultimate compression strength and the bone cement of the compound type alpha tricalcium phosphate biological stephanoporate of the calcium phosphorus bio-vitric bone cement aquation that Fig. 4 makes for the present invention after 7 days.
Embodiment
Embodiment 1
Step 1: the preparation of mixing Sr calcium phosphorus bio-vitric
With four water-calcium nitrate, Vanadium Pentoxide in FLAKES, strontium nitrate, SODIUMNITRATE is raw material, takes by weighing respective substance in molar ratio, makes each material is corresponding in the raw material oxide compound according to CaO: P
2O
5: SrO: Na
2The molar percentage of O 50: 40: 3: 7 preparation calcium phosphorus bio-vitrics.With 8.517g P
2O
5Be dissolved in the 40ml absolute ethyl alcohol, controlled temperature is no more than 38.0 ℃ in the adition process, stirs the phosphorus base precursor solution that becomes clear until solution, with subsequent use behind this solution left standstill 24h.Take by weighing 0.952gSr (NO respectively
3)
2, 17.711g Ca (NO
3)
24H
2O, 1.785g NaNO
3, be dissolved in successively in the 45ml zero(ppm) water in this order, be configured to transparent settled solution.Gained solution is dropwise added in the above-mentioned phosphorus base precursor solution, obtain uniform sol, again ammoniacal liquor is dropwise added in the colloidal sol, regulate pH to 8～9, form uniform and stable gel after leaving standstill 24h.This gel as for 60 ℃ of oven dry down, is pulverized, in retort furnace, slowly be warming up to 300 ℃, insulation 4h rises to 550 ℃ again, and insulation 2h forms calcium phosphorus bio-vitric.
Step 2: the preparation of type alpha tricalcium phosphate biological bone cement
Synthetic and the composition of alpha-calcium phosphate bone cement (CPC) powder, patent CN101843920A and the preparation of CN1338425A disclosed method of adopting us to apply for.Consisting of of alpha-calcium phosphate bone cement: type alpha tricalcium phosphate (α-TCP), Ca (H
2PO
4)
2H
2O, CaCO
3, Win 40350 (HAp), wherein the mass ratio of each component is α-TCP: Ca (H
2PO
4)
2H
2O: CaCO
3: HAp is 86: 5: 5: 4.
Step 3: the preparation of mixing Sr biological calcium phosphorus glass type alpha tricalcium phosphate compound bio porous bone cement
With the prepared bio-vitric of step 1 7% being spiked in the bone cement of the two type alpha tricalcium phosphate bone cement quality that make set by step, uniform mixing is that 0.4ml/g modulates according to the ratio of distiller liquor and bone cement powder, and distiller liquor is the Na of 0.8wt%
2HPO
4Solution injects punching block with slurry after being in harmonious proportion evenly, at room temperature is in harmonious proportion 60～90s, takes out the back and in 37 ℃ of constant temperature, relative humidity be under 100% the condition to solidify.Be 15min the set time of gained composite bone cement, and the bone cement aquation is transformed into Win 40350 fully after 7 days, and its ultimate compression strength is (23.6+1.2) MPa, and porosity is 51%.Its XRD diffractogram is as shown in Figure 1, and the halfwidth of diffraction peak is little, and peak shape is sharp-pointed, shows that the bone cement crystal habit after the aquation is good, has higher percent crystallinity.
Embodiment 2
Step 1: the preparation of mixing Sr calcium phosphorus bio-vitric
In bio-vitric four water-calcium nitrate different with the molar percentage of strontium nitrate, other the operation with embodiment 1 in step 1 identical.With four water-calcium nitrate, Vanadium Pentoxide in FLAKES, strontium nitrate, SODIUMNITRATE is raw material, takes by weighing respective substance in molar ratio, makes each material is corresponding in the raw material oxide compound according to CaO: P
2O
5: SrO: Na
2The molar percentage of O 44: 40: 9: 7 preparation calcium phosphorus bio-vitrics.With 8.517g P
2O
5Be dissolved in the 40ml absolute ethyl alcohol, controlled temperature is no more than 38.0 ℃ in the adition process, stirs the phosphorus base precursor solution that becomes clear until solution, with subsequent use behind this solution left standstill 24h.Take by weighing 2.857gSr (NO respectively
3)
2, 15.586g Ca (NO
3)
24H
2O, 1.785gNaNO
3, be dissolved in successively in the 45ml zero(ppm) water in this order, be configured to transparent settled solution.Gained solution is dropwise added in the above-mentioned phosphorus base precursor solution, obtain uniform sol, again ammoniacal liquor is dropwise added in the colloidal sol, regulate pH to 8～9, form uniform and stable gel after leaving standstill 24h.This gel as for 60 ℃ of oven dry down, is pulverized, in retort furnace, slowly be warming up to 300 ℃, insulation 4h rises to 500 ℃ again, and insulation 2h forms calcium phosphorus bio-vitric.
Step 2 is identical with embodiment 1 with step 3.
Be 16min the set time of gained composite bone cement, and the bone cement aquation is transformed into Win 40350 fully after 7 days, and its ultimate compression strength is (38.5+1.4) MPa, and porosity is 52%.The relation of Sr content is as shown in Figure 4 in the ultimate compression strength of bone cement and the addition of bio-vitric and the glass; The glass addition is 7wt% in bone cement; And when Sr content was 9mol% in the glass, bone cement ultimate compression strength when obtaining comparatively ideal vesicular structure reached peak 38.5MPa.
Embodiment 3
Step 1: the preparation of mixing Sr calcium phosphorus bio-vitric
In bio-vitric four water-calcium nitrate different with the molar percentage of strontium nitrate, other the operation with embodiment 1 in step 1 identical.With four water-calcium nitrate, Vanadium Pentoxide in FLAKES, strontium nitrate, SODIUMNITRATE is raw material, takes by weighing respective substance in molar ratio, makes each material is corresponding in the raw material oxide compound according to CaO: P
2O
5: SrO: Na
2The molar percentage of O is 42: 40: 11: 7 preparation calcium phosphorus bio-vitrics.With 8.517gP
2O
5Be dissolved in the 40ml absolute ethyl alcohol, controlled temperature is no more than 38.0 ℃ in the adition process, stirs the phosphorus base precursor solution that becomes clear until solution, with subsequent use behind this solution left standstill 24h.Take by weighing 3.492g Sr (NO respectively
3)
2, 15.586g Ca (NO
3)
24H
2O, 1.785gNaNO
3, be dissolved in successively in the 45ml zero(ppm) water in this order, be configured to the water white transparency settled solution.This solution is dropwise added above-mentioned P
2O
5In the ethanolic soln, until obtaining an achromaticity and clarification uniform sol.Dropwise splash into ammoniacal liquor to above-mentioned gained colloidal sol, regulate pH to 8～9, gained white evenly colloidal sol forms uniform and stable gel after leaving standstill 24h.As for 60 ℃ of oven dry down, the gained dry gel powder slowly is warming up to 300 ℃ in retort furnace with this gel, and insulation 4h rises to 480 ℃ again, and insulation 3h forms calcium phosphorus bio-vitric.
Step 2 is identical with embodiment one with step 3
Be 16min the set time of gained composite bone cement, and the bone cement aquation is transformed into Win 40350 fully after 7 days, and its microstructure is as shown in Figure 2.Because the degraded of bio-vitric obtains comparatively ideal vesicular structure, pore size is between 0.5～1um, and crosslinked micropore showed increased, its porosity are 52%; Being cross-linked with each other of hydrated product rod-shpaed particle makes bone cement its ultimate compression strength when obtaining comparatively ideal vesicular structure still maintain higher level, is (31.5+1.6) MPa, aspect clinical operation, has good prospect.
Embodiment 4
Is raw material according to embodiment 2 with four water-calcium nitrate, Vanadium Pentoxide in FLAKES, strontium nitrate, SODIUMNITRATE, takes by weighing respective substance in molar ratio, makes each material is corresponding in the raw material oxide compound according to CaO: P
2O
5: SrO: Na
2The molar percentage of O is 44: 40: 9: 7 preparation calcium phosphorus bio-vitrics.Other concrete operations of step 1 and step 2 are identical with embodiment two.
Step 3: the preparation of mixing Sr biological calcium phosphorus glass type alpha tricalcium phosphate compound bio porous bone cement
In bone cement, add the massfraction difference of bio-vitric, other operations are identical with step 3 among the embodiment 2.With the prepared bio-vitric of step 1 1% being spiked in the bone cement of the two type alpha tricalcium phosphate bone cement quality that make set by step, uniform mixing is that 0.4ml/g modulates according to the ratio of distiller liquor and bone cement powder, and distiller liquor is the Na of 0.8wt%
2HPO
4Solution injects punching block with slurry after being in harmonious proportion evenly, at room temperature is in harmonious proportion 60～90s, takes out the back and in 37 ℃ of constant temperature, relative humidity be under 100% the condition to solidify.Be 11min the set time of gained composite bone cement; The bone cement aquation is transformed into Win 40350 fully after 7 days; Because the bio-vitric amount that adds is merely 1% of bone cement quality; Fail to realize the high porosity of bone cement, the porosity of gained bone cement is merely 39%, compares the voidage basically identical with other the Sr bone cement of mixing; And its ultimate compression strength is (25.2+1.3) MPa, still satisfies the requirement of strength that body bone tissue is repaired.
Is raw material according to embodiment 2 with four water-calcium nitrate, Vanadium Pentoxide in FLAKES, strontium nitrate, SODIUMNITRATE, takes by weighing respective substance in molar ratio, makes each material is corresponding in the raw material oxide compound according to CaO: P
2O
5: SrO: Na
2The molar percentage of O 44: 40: 9: 7 preparation calcium phosphorus bio-vitrics.Other concrete operations of step 1 and step 2 are identical with embodiment two.
Step 3: the preparation of mixing Sr biological calcium phosphorus glass type alpha tricalcium phosphate compound bio porous bone cement
In bone cement, add the massfraction difference of bio-vitric, other operations are identical with step 3 among the embodiment 2.With the prepared bio-vitric of step 1 10% being spiked in the bone cement of the two type alpha tricalcium phosphate bone cement quality that make set by step, be that 0.4ml/g modulates according to the ratio of distiller liquor and bone cement powder, distiller liquor is the Na of 0.8wt%
2HPO
4Solution injects punching block with slurry after being in harmonious proportion evenly, at room temperature is in harmonious proportion 60～90s, takes out the back and in 37 ℃ of constant temperature, relative humidity be under 100% the condition to solidify.Be 22min the set time of gained composite bone cement, and the bone cement aquation is transformed into Win 40350 fully after 7 days.Its microstructure is as shown in Figure 3, because the degraded of bio-vitric has obtained the ideal vesicular structure, pore size is between 1～4um, and micropore is evenly distributed and connects each other, and its porosity is 57%.Because the glass add-on increases, bone cement ultimate compression strength slightly descends, but still satisfies the clinical operation requirement, is (29.8+1.7) MPa.
Claims (2)
1. mix the compound type alpha tricalcium phosphate biological stephanoporate of Sr calcium phosphorus bio-vitric bone cement for one kind, the porosity that it is characterized in that bone cement is 39%～57%, and pore size is between 0.5～4 μ m; Ultimate compression strength is 23.6～38.5MPa.
2. preparation method who mixes the compound type alpha tricalcium phosphate biological stephanoporate of Sr calcium phosphorus bio-vitric bone cement is characterized in that step is following:
1) mix the preparation of Sr calcium phosphorus bio-vitric:
With four water-calcium nitrate, Vanadium Pentoxide in FLAKES, strontium nitrate, SODIUMNITRATE is raw material, wherein the corresponding oxide compound CaO:P of each material in the raw material
2O
5: SrO:Na
2The molar percentage of O is (50～42): 40: (3～11): 7; Take by weighing P
2O
5, adding in the absolute ethyl alcohol, controlled temperature is no more than 38.0 ℃ in the adition process, stirs to become clear solution until solution, makes phosphorus base precursor solution, leaves standstill behind the 24h subsequent use; Take by weighing four water-calcium nitrate, strontium nitrate, SODIUMNITRATE and join successively in the deionized water, mix and stir, be mixed with the Ca that concentration is 0.3～0.9mol/L
2+, Sr
2+, Na
+The clear solution of ion component; To contain Ca then
2+, Sr
2+And Na
+Clear solution dropwise join in the phosphorus base precursor solution, evenly stir, obtain even colloidal sol; In colloidal sol, dropwise splash into ammoniacal liquor, regulate pH to 8～9, obtain evenly colloidal sol of white, form uniform and stable gel after leaving standstill 24h; This gel is placed 60 ℃ of oven dry down, pulverize the back and in retort furnace, slowly be warming up to 300 ℃, insulation 2～5h rises to 450 ℃～550 ℃ again, and insulation 1～3h forms calcium phosphorus bio-vitric;
2) preparation of type alpha tricalcium phosphate compound bio bone cement:
Choose consisting of of alpha-calcium phosphate bone cement: type alpha tricalcium phosphate, Ca (H
2PO
4)
2H
2O, CaCO
3And Win 40350, wherein the mass ratio of each component is α-TCP:Ca (H
2PO
4)
2H
2O:CaCO
3: HAP is 86:5:5:4;
3) mix the preparation of the compound type alpha tricalcium phosphate biological stephanoporate of Sr calcium phosphorus bio-vitric bone cement:
With the prepared bio-vitric of step 1 set by step in 1%～10% admixture bone cement of the two type alpha tricalcium phosphate bone cement quality that make, be that 0.4ml/g modulates according to the ratio of distiller liquor and bone cement powder, distiller liquor is the Na of 0.8wt%
2HPO
4Solution injects punching block with slurry after being in harmonious proportion evenly, at room temperature is in harmonious proportion 60～90s, takes out the back and in 37 ℃ of constant temperature, relative humidity be under 100% the condition to solidify, and obtains composite bone cement.
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| CN102249728B true CN102249728B (en) | 2012-11-21 |
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| CN109133972A (en) * | 2018-10-09 | 2019-01-04 | 广州润虹医药科技股份有限公司 | A kind of porous bioceramic scaffold and preparation method thereof |
| CN112316208A (en) * | 2020-09-29 | 2021-02-05 | 山东明德生物医学工程有限公司 | Strontium bioglass artificial bone and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1657483A (en) * | 2005-02-07 | 2005-08-24 | 武汉理工大学 | Preparation method of calcium phosphate composite bone cement |
| CN1762897A (en) * | 2005-08-30 | 2006-04-26 | 西安交通大学 | Preparation process of degradable foam-like strontium-doped calcium phosphate ceramic bone holder material |
| CN101041087A (en) * | 2007-04-27 | 2007-09-26 | 西安交通大学 | Degradable biphase ceramics bone frame with high-strength and phosphate cement containing strontium and the preparing method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1657483A (en) * | 2005-02-07 | 2005-08-24 | 武汉理工大学 | Preparation method of calcium phosphate composite bone cement |
| CN1762897A (en) * | 2005-08-30 | 2006-04-26 | 西安交通大学 | Preparation process of degradable foam-like strontium-doped calcium phosphate ceramic bone holder material |
| CN101041087A (en) * | 2007-04-27 | 2007-09-26 | 西安交通大学 | Degradable biphase ceramics bone frame with high-strength and phosphate cement containing strontium and the preparing method |
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