CN103253932B - Silicon calcium phosphate biomaterial, preparation method and uses thereof - Google Patents
Silicon calcium phosphate biomaterial, preparation method and uses thereof Download PDFInfo
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Abstract
The invention relates to a silicon calcium phosphate biomaterial, a preparation method and uses thereof, wherein a soluble silicon source, a soluble phosphorus source and a soluble calcium source are adopted as raw materials, water is adopted as a solvent, a sol-gel method is adopted to synthesize pure phase silicon calcium phosphate (Ca5(PO4)2SiO4) powder, the silicon calcium phosphate powder is subjected to pressing forming and sintering to obtain silicon calcium phosphate (Ca5(PO4)2SiO4) ceramic blocks, the silicon calcium phosphate (Ca5(PO4)2SiO4) ceramic blocks are soaked in a simulated body fluid (SBF) for 1 day, a bone-like apatite layer is deposited on the surface of the ceramic, and a apatite layer thickness can be increased along with soaking time prolonging. The prepared silicon calcium phosphate (Ca5(PO4)2SiO4) material has good biology performances, is a potential biological and medical material, and can be used as a material for bone tissue repair and filling, and dental repair.
Description
Technical field
The present invention relates to silicon calcium phosphate biomaterial and its production and use, particularly a kind of chemical formula is Ca
5(PO
4)
2siO
4silicon calcium phosphate biomaterial, belong to technical field of biological material.
Background technology
For biomaterial, synthos are owing to having and vertebrate sclerous tissues, and as similar mineral composition and structures such as skeleton, teeth, this class material, no matter with what form application, is all proved to be and has good biocompatibility, has no side effect.But have certain deficiency, for example hydroxyapatite good stability in vivo, be difficult for being degraded and absorbed, and biological activity is not high yet.Although calcium phosphate ceramics has good biodegradable absorbent properties for another example, also has the problem that biological activity is not high.
For these problems, research worker be take the phosphate of synthetic and is basis, adopts ion exchange method or organic-inorganic material doping, the method such as compound, has prepared the phosphate that silicon doping or silicon replace, and has improved the biology performance of material.
Silicon calcium phosphate (Ca
5(PO
4)
2siO
4) multiphase ceramics material in report in the past, be generally used for reparation, filling and the gear division reparation of osseous tissue, the biomaterial of therefore studying this Ca of being rich in, P, Si has certain meaning.
But up to the present, pure phase silicon calcium phosphate (Ca
5(PO
4)
2siO
4) ceramic material and preparation method thereof, especially pure phase silicon calcium phosphate (Ca
5(PO
4)
2siO
4) ceramic material has no report as biomaterial.
Summary of the invention
Report and substantive innovation and creation of the present invention in view of above-mentioned conventional art, one of object of the present invention is to propose a kind of silicon calcium phosphate biomaterial, two of object of the present invention is to propose a kind of preparation method of silicon calcium phosphate biomaterial, and three of object of the present invention is to propose a kind of silicon calcium phosphate material in the purposes of biological and medical field.
The silicon calcium phosphate biomaterial that the first object of the present invention proposes, is characterized in that chemical formula is Ca
5(PO
4)
2siO
4.
The preparation method of the silicon calcium phosphate biomaterial that the second object of the present invention proposes, its first technical scheme is, adopting soluble silicon source, soluble sources and solubility calcium source is raw material, take water as solvent, the proportioning that is 5: 2: 1 by the mol ratio of Ca: P: Si, is used the synthetic powder body for preparing of sol-gel process.
In the first technical scheme, described sol-gel process synthetic method comprises the steps:
(1) soluble silicon source, soluble sources and solubility calcium source are added to the water successively to stirring, ageing, dry;
The Ca in described soluble silicon source, soluble sources and solubility calcium source: the mol ratio of P: Si is 5: 2: 1, gained
The nitric acid that preferably adds 1～2 mol/L in described step (1), the volume ratio in the addition of described nitric acid and soluble silicon source is 1: (6～8).
In described step (1), after soluble silicon source, soluble sources and solubility calcium source are added to the water successively, preferably add ethanol, preferably adding the amount of ethanol and the mol ratio in soluble silicon source is 1: 1.
(2) step (1) products therefrom is ground to form to powder body, calcining at 1380 ℃～1450 ℃, temperature retention time is 2 hours～7 hours.
Described mixing time is preferably 1 hour～and 10 hours, more preferably 2 hours～6 hours.
Described Aging Temperature is preferably 30 ℃～80 ℃, and more preferably 50 ℃～80 ℃, described digestion time is preferably 24 hours～and 96 hours, preferably 48 hours～72 hours.
Described baking temperature is preferably 80 ℃～200 ℃, and more preferably 100 ℃～200 ℃, more more preferably 100 ℃～150 ℃.
The preparation method of the silicon calcium phosphate biomaterial that the second object of the present invention proposes, its second technical scheme is, adopting soluble silicon source, soluble sources and solubility calcium source is raw material, take water as solvent, the proportioning that is 5: 2: 1 by the mol ratio of Ca: P: Si, is used the synthetic powder body for preparing of sol-gel process; In powder body, add dry-pressing and/or cold isostatic compaction after binding agent, make biscuit pressureless sintering and obtain block.
In the second technical scheme, described sol-gel process synthetic method comprises the steps:
(1) soluble silicon source, soluble sources and solubility calcium source are added to the water successively to stirring, ageing, dry;
The Ca in described soluble silicon source, soluble sources and solubility calcium source: the mol ratio of P: Si is 5: 2: 1, gained
The nitric acid that preferably adds 1～2 mol/L in described step (1), the volume ratio in the addition of described nitric acid and soluble silicon source is 1: (6～8).
In described step (1), after soluble silicon source, soluble sources and solubility calcium source are added to the water successively, preferably add ethanol, preferably adding the amount of ethanol and the mol ratio in soluble silicon source is 1: 1.
(2) step (1) products therefrom is ground to form to powder body, calcining at 1380 ℃～1450 ℃, temperature retention time is 2 hours～7 hours.
Described mixing time is preferably 1 hour～and 10 hours, more preferably 2 hours～6 hours.
Described Aging Temperature is preferably 30 ℃～80 ℃, and more preferably 50 ℃～80 ℃, described digestion time is preferably 24 hours～and 96 hours, preferably 48 hours～72 hours.
Described baking temperature is preferably 80 ℃～200 ℃, and more preferably 100 ℃～200 ℃, more more preferably 100 ℃～150 ℃.
In the second technical scheme, described pressureless sintering condition is that calcining heat is calcining at 1380 ℃～1450 ℃, and calcination time is 1 hour～6 hours.
In the second technical scheme, the preferred water-soluble binder of described binding agent, further preferably polyethylene alcohol-water solution; Polyvinyl alcohol water solution concentration is 5～10wt% preferably, and the addition of polyvinyl alcohol water solution is preferably 1/10 of powder quality.
In the second technical scheme, the pressure of described dry-pressing is 2～20MPa, preferably 4～10MPa.
In the second technical scheme, the pressure of described isostatic cool pressing is 150MPa～250MPa, pressurize 5 minutes～10 minutes.
The preparation method of the silicon calcium phosphate biomaterial that the second object of the present invention proposes, its the 3rd technical scheme is, adopting soluble silicon source, soluble sources and solubility calcium source is raw material, take water as solvent, the proportioning that is 5: 2: 1 by the mol ratio of Ca: P: Si, is used the synthetic powder body for preparing of sol-gel process; Powder body hot pressed sintering obtains block.
In the 3rd technical scheme, described sol-gel process synthetic method comprises the steps:
(1) soluble silicon source, soluble sources and solubility calcium source are added to the water successively to stirring, ageing, dry;
The Ca in described soluble silicon source, soluble sources and solubility calcium source: the mol ratio of P: Si is 5: 2: 1, gained
The nitric acid that preferably adds 1～2 mol/L in described step (1), the volume ratio in the addition of described nitric acid and soluble silicon source is 1: (6～8).
In described step (1), after soluble silicon source, soluble sources and solubility calcium source are added to the water successively, preferably add ethanol, preferably adding the amount of ethanol and the mol ratio in soluble silicon source is 1: 1.
(2) step (1) products therefrom is ground to form to powder body, calcining at 1380 ℃～1450 ℃, temperature retention time is 2 hours～7 hours.
Described mixing time is preferably 1 hour～and 10 hours, more preferably 2 hours～6 hours.
Described Aging Temperature is preferably 30 ℃～80 ℃, and more preferably 50 ℃～80 ℃, described digestion time is preferably 24 hours～and 96 hours, preferably 48 hours～72 hours.
Described baking temperature is preferably 80 ℃～200 ℃, and more preferably 100 ℃～200 ℃, more more preferably 100 ℃～150 ℃.
In the 3rd technical scheme, the condition of described hot pressed sintering is that pressure is 20MPa～40MPa, with 10 ℃/min～20 ℃/min, is warming up to calcining at 1380 ℃～1450 ℃, temperature retention time 0.5 hour～1 hour; The condition of described hot pressed sintering further preferably adopts argon shield.
Silicon calcium phosphate (Ca
5(PO
4)
2siO
4) ceramic evaluated biological activity.
The silicon calcium phosphate ceramic block preparing is carried out to simulated body fluid and soak 1 day～7 days, observe the variation of soaking a period of time rear surface pattern, judge that whether silicon calcium phosphate ceramic surface has bone like apatite layer to form, and evaluates its biological activity.Ratio between the surface area of the addition of simulated body fluid and silicon calcium phosphate ceramic sheet is 10 milliliters/1 square centimeter.The silicon calcium phosphate ceramic that has soaked different time sections is taken out from simulated body fluid, by deionized water clean surface gently, then at 60 ℃ dry 6 hours, with SEM, observe the variation of surface topography.Simulated body fluid contains the ion close with human plasma and ion cluster concentration.It consists of:
Before soaking, silicon calcium phosphate ceramic surface distributed a large amount of holes, and EDS measures its Ca: P: Si=5: 2: 1, and with Ca
5(PO
4)
2siO
4the stoichiometric proportion of pottery is identical, and Ca/P is 2.50.After immersion simulated body fluid 1 day, the vermiform apatite that a large amount of hole in silicon calcium phosphate ceramic surface is newly deposited is filled, and obvious hole has been can't see on surface, but still out-of-flatness of surface, surface-element analysis shows that Ca/P is the content reduction of 2.28, Si element.Soak simulated body fluid after 3 days, silicon calcium phosphate ceramic surface is covered by nano level apatite completely, and crackle appears in surface layer, illustrates that deposited apatite layer is thicker, and Ca/P further reduces, and reaches 1.71, approaches the Ca/P of hydroxyapatite.Work as Ca
5(PO
4)
2siO
4after ceramic immersion 7 days, apatite layer thickness further increases.Silicon calcium phosphate ceramic (Ca is described
5(PO
4)
2siO
4) there is good biological activity, can be used as bone renovating material, engineering material of bone tissue and dental material.
Silicon calcium phosphate (Ca
5(PO
4)
2siO
4) ceramic Evaluating Mechanical Properties
By silicon calcium phosphate ceramic (Ca
5(PO
4)
2siO
4) block materials is according to GB/T6569-2006/ISO14704: 2000 standards are made proof force and are learned test sample, test its mechanical property, span 30mm, three-point bending method test, sample size is 5.The bending strength of the silicon calcium phosphate of scheme one preparation is 36.4MPa, and elastic modelling quantity is 17.8GPa; The bending strength of the silicon calcium phosphate of scheme two preparations is 60.4MPa, and elastic modelling quantity is 77.5GPa.The mechanical property of contrast human body cortical bone, through the Ca of hot pressed sintering
5(PO
4)
2siO
4its bending strength of pottery approaches human body cortical bone, can use as the repair materials of non-bearing bony site.
The 3rd object of the present invention proposes a kind of purposes of silicon calcium phosphate material, due to the result of above-mentioned material performance, and the silicon calcium phosphate (Ca obtaining prepared by the present invention
5(PO
4)
2siO
4) can, for biology and medical field, especially can be used as the application of bone renovating material, engineering material of bone tissue or dental material.
The invention has the advantages that:
(1) sol-gel method craft is simple, with low cost and be convenient to promote;
(2) adopt the synthetic pure phase silicon calcium phosphate (Ca of sol-gel process preparation
5(PO
4)
2siO
4), material composition is even, and thing is mutually pure;
(3) silicon calcium phosphate (Ca
5(PO
4)
2siO
4) ceramic material has good biological activity, bending strength is close with human body cortical bone, can use as the repair materials of non-bearing bony site; Also can be used as bone tissue engineer, biological coating material and dental material uses.
Accompanying drawing explanation
Fig. 1 is the XRD figure spectrum of the synthetic silicon calcium phosphate powder body of sol-gel process.As we know from the figure, no matter the position of diffraction maximum or intensity are equal and Ca
5(PO
4)
2siO
4standard card (PDF No.40-0393) matches, and illustrates that the powder body crystalline phase of synthesized is very pure, free from foreign meter.
Fig. 2 is the XRD figure spectrum of silicon calcium phosphate ceramic block after hot pressed sintering.As can be seen from the figure, diffraction maximum position and intensity and the Ca of pottery after hot pressed sintering
5(PO
4)
2siO
4standard card (PDF No.40-0393) matches, and illustrates that the ceramic block material thing after hot pressed sintering is mutually pure, does not conform to dephasign.
Fig. 3 is the surface topography photo of (A figure) and 1 day (B figure), 3 days (C figure) of immersion simulated body fluid before silicon calcium phosphate ceramic block immersion simulated body fluid, 7 days (D figure).
Fig. 4 is that the surface of (A figure) and 1 day (B figure), 3 days (C figure) of immersion simulated body fluid before silicon calcium phosphate ceramic block immersion simulated body fluid, 7 days (D figure) can spectrogram.
Table 1 is the quantitative component analysis result of the X-fluorescence of powder body.Can find out CaO, P
2o
5, SiO
2the content of each component and Ca
5(PO
4)
2siO
4stoichiometric proportion very approaching, the powder body that synthesized is described is pure phase Ca
5(PO
4)
2siO
4.
Table 1
Table 2 is the silicon calcium phosphate ceramic Ca of pressureless sintering and hot pressed sintering
5(PO
4)
2siO
4mechanical property.The bending strength of silicon calcium phosphate prepared by pressureless sintering method is 36.4MPa, and elastic modelling quantity is 17.8GPa; The bending strength of silicon calcium phosphate prepared by hot-pressing sintering method is 60.4MPa, and elastic modelling quantity is 77.5GPa.The mechanical property of contrast human body cortical bone, through the Ca of hot pressed sintering
5(PO
4)
2siO
4its bending strength of pottery approaches human body cortical bone, can use as the repair materials of non-bearing bony site.
Table 2
The specific embodiment
Below in conjunction with embodiment, the present invention is further detailed, but is not limited only to embodiment.
Embodiment 1
(1) by 22.4 milliliters of ethyl orthosilicates and concentration, be that 4 milliliters, the nitric acid of 2 mol/L mixes, and add 9.6 ml deionized water and 5.8 milliliters of dehydrated alcohol, at room temperature stir 2 hours, then add 34.2 milliliters of triethyl phosphates, continue to stir 2 hours, then add 118.1 grams of calcium nitrate tetrahydrates, stir 4 hours, obtain silicon Calcium phosphate gel; By colloidal sol ageing 48 hours at 60 ℃, obtain gel; Gel is dried to 120 hours at 120 ℃, obtains xerogel;
(2) xerogel is ground to form to powder body, calcining at 1400 ℃, programming rate is 2 ℃/min, the temperature retention time at 1400 ℃ is 6 hours, obtains silicon calcium phosphate (Ca
5(PO
4)
2siO
4) powder body.
The powder body of preparation is carried out to XRD test, the diffraction maximum of powder body and Ca
5(PO
4)
2siO
4standard card (PDF No.40-0393) matches (as Fig. 1), illustrates that the powder body crystalline phase of synthesized is very pure, free from foreign meter.
Embodiment 2
(1) by 44.8 milliliters of ethyl orthosilicates and concentration, be that 8 milliliters, the nitric acid of 2 mol/L mixes, and add 19.2 ml deionized water and 11.6 milliliters of dehydrated alcohol, at room temperature stir 3 hours, then add 68.4 milliliters of triethyl phosphates, continue to stir 4 hours, then add 236.2 grams of calcium nitrate tetrahydrates, stir 6 hours, obtain silicon Calcium phosphate gel; By colloidal sol ageing 72 hours at 60 ℃, obtain gel; Gel is dried to 168 hours at 120 ℃, obtains xerogel;
(2) xerogel is ground to form to powder body, calcining at 1400 ℃, programming rate is 2 ℃/min, the temperature retention time at 1400 ℃ is 6 hours, obtains silicon calcium phosphate (Ca
5(PO
4)
2siO
4) powder body;
(3) silicon calcium phosphate powder body is ground, sieved, then take 0.2 gram of powder, dry-pressing formed under 8MPa, make the biscuit of ceramics of 1 millimeter of 10 millimeters of thickness of diameter; Silicon calcium phosphate ceramic biscuit is calcined 2 hours at 1400 ℃, and programming rate is 5 ℃/min, is prepared into silicon calcium phosphate ceramic disk;
(3) the silicon calcium phosphate ceramic disk preparing is carried out to simulated body fluid and soak 1 day, 3 days and 7 days, observe the variation of soaking a period of time rear surface pattern, judge that whether silicon calcium phosphate ceramic surface has bone like apatite layer to form, and evaluates its biological activity.Ratio between the surface area of the addition of simulated body fluid and silicon calcium phosphate ceramic disk is 10 milliliters/1 square centimeter.The silicon calcium phosphate ceramic that has soaked different time sections is taken out from simulated body fluid, by deionized water clean surface gently, then at 60 ℃ dry 6 hours, with SEM, observe the variation of surface topography.Soak (Fig. 3 B) after simulated body fluid 1 day, the vermiform apatite that a large amount of hole of silicon calcium phosphate ceramic disk surfaces is newly deposited is filled, and surface-element analysis shows that Ca/P is 2.28.Soak simulated body fluid after 3 days (Fig. 3 C), silicon calcium phosphate ceramic surface is covered by nano level apatite completely, and crackle appears in surface layer, illustrate that deposited apatite layer is thicker, Ca/P further reduces, and reaches 1.71, approaches the Ca/P of hydroxyapatite.Work as Ca
5(PO
4)
2siO
4ceramic immersion is (Fig. 3 D) after 7 days, and apatite layer thickness further increases.Silicon calcium phosphate ceramic (Ca is described
5(PO
4)
2siO
4) there is good biological activity.
Embodiment 3
(1) by 44.8 milliliters of ethyl orthosilicates and concentration, be that 8 milliliters, the nitric acid of 2 mol/L mixes, and add 19.2 ml deionized water and 11.6 milliliters of dehydrated alcohol, at room temperature stir 3 hours, then add 68.4 milliliters of triethyl phosphates, continue to stir 4 hours, then add 236.2 grams of calcium nitrate tetrahydrates, stir 6 hours, obtain silicon Calcium phosphate gel; By colloidal sol ageing 72 hours at 60 ℃, obtain gel; Gel is dried to 168 hours at 120 ℃, obtains xerogel;
(2) xerogel is ground to form to powder body, calcining at 1400 ℃, programming rate is 2 ℃/min, the temperature retention time at 1400 ℃ is 6 hours, obtains silicon calcium phosphate (Ca
5(PO
4)
2siO
4) powder body;
(3) silicon calcium phosphate powder body is ground, sieved, and in the powder body sieving, to add concentration be the polyvinyl alcohol water solution of 6wt%, the quality that adds of polyvinyl alcohol water solution is 1/10 of silicon calcium phosphate powder quality, carry out pelletize, then take 1.5 grams of powders, dry-pressing formed under 8MPa, then through isostatic cool pressing, process, isostatic cool pressing pressure is 200MPa, and pressurize 5 minutes, makes biscuit of ceramics; Silicon calcium phosphate ceramic biscuit is carried out to pressureless sintering, 1400 ℃ of sintering temperatures, temperature retention time 2 hours, programming rate is 5 ℃/min, is prepared into silicon calcium phosphate ceramic block;
(5) by silicon calcium phosphate ceramic block according to GB/T6569-2006/ISO14704: 2000 standards are made proof force and are learned test sample, test its mechanical property.The test of employing three-point bending method, span 30mm, sample size is 5.The bending strength of silicon calcium phosphate ceramic block prepared by pressureless sintering method is 36.4MPa, and elastic modelling quantity is 17.8GPa (table 2).
Embodiment 4
(1) by 44.8 milliliters of ethyl orthosilicates and concentration, be that 8 milliliters, the nitric acid of 2 mol/L mixes, and add 19.2 ml deionized water and 11.6 milliliters of dehydrated alcohol, at room temperature stir 3 hours, then add 68.4 milliliters of triethyl phosphates, continue to stir 4 hours, then add 236.2 grams of calcium nitrate tetrahydrates, stir 6 hours, obtain silicon Calcium phosphate gel; By colloidal sol ageing 72 hours at 60 ℃, obtain gel; Gel is dried to 168 hours at 120 ℃, obtains xerogel;
(2) xerogel is ground to form to powder body, calcining at 1400 ℃, programming rate is 2 ℃/min, the temperature retention time at 1400 ℃ is 6 hours, obtains silicon calcium phosphate (Ca
5(PO
4)
2siO
4) powder body;
(3) silicon calcium phosphate powder body is taken to 20g hot pressed sintering in graphite furnace, the pressure in sintering process is 20MPa, and programming rate is 10 ℃/min, argon shield, and sintering temperature is 1400 ℃, temperature retention time is 0.5 hour;
(4) block materials sintering being obtained is according to GB/T6569-2006/ISO14704: 2000 standards are made proof force and learned test sample, test its mechanical property.The test of employing three-point bending method, span 30mm, sample size is 5.The bending strength of silicon calcium phosphate ceramic block prepared by hot pressing sintering method is 60.4MPa, and elastic modelling quantity is 77.5GPa (table 2).The mechanical property of contrast human body cortical bone, through the Ca of hot pressed sintering
5(PO
4)
2siO
4its bending strength of pottery approaches human body cortical bone, can use as the repair materials of non-bearing bony site.
Claims (2)
1. a chemical formula is Ca
5(PO
4)
2siO
4the purposes of silicon calcium phosphate biomaterial in bone renovating material or dental material,
It is raw material that described silicon calcium phosphate biomaterial adopts soluble silicon source, soluble sources and solubility calcium source, take water as solvent, and the proportioning that is 5: 2: 1 by the mol ratio of Ca: P: Si, is used the synthetic powder body for preparing of sol-gel process, powder body hot pressed sintering obtains block
Described sol-gel process comprises the steps:
(1) soluble silicon source, soluble sources and solubility calcium source are added to the water successively, stirring, ageing, dry,
The nitric acid that adds 1～2 mol/L in described step (1), the volume ratio in the addition of described nitric acid and soluble silicon source is 1: (6～8),
In described step (1), after soluble silicon source, soluble sources and solubility calcium source are added to the water successively, add ethanol, wherein adding the amount of ethanol and the mol ratio in soluble silicon source is 1: 1;
(2) step (1) products therefrom is ground to form to powder body, calcining at 1380 ℃～1450 ℃, temperature retention time is 2 hours～7 hours;
Described mixing time is 2 hours～6 hours, and described Aging Temperature is 50 ℃～80 ℃, and described digestion time is 24 hours～96 hours, and described baking temperature is 100 ℃～150 ℃,
The pressure of described hot pressed sintering is 20MPa～40MPa, with 10 ℃/min～20 ℃/min, is warming up to calcining at 1380 ℃～1450 ℃, temperature retention time 0.5 hour～1 hour.
2. by a kind of chemical formula claimed in claim 1, be Ca
5(PO
4)
2siO
4the purposes of silicon calcium phosphate biomaterial in bone renovating material or dental material, wherein the condition of hot pressed sintering comprises employing argon shield.
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