CN101700414B - Calcium silicate nanowire/hydroxylapatite nanoparticle composite powder and preparation method thereof - Google Patents
Calcium silicate nanowire/hydroxylapatite nanoparticle composite powder and preparation method thereof Download PDFInfo
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- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 title claims abstract description 67
- 229910052588 hydroxylapatite Inorganic materials 0.000 title claims abstract description 54
- 239000002131 composite material Substances 0.000 title claims abstract description 50
- 239000000843 powder Substances 0.000 title claims abstract description 40
- 239000000378 calcium silicate Substances 0.000 title claims abstract description 30
- 229910052918 calcium silicate Inorganic materials 0.000 title claims abstract description 30
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 239000002070 nanowire Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- 238000010335 hydrothermal treatment Methods 0.000 claims abstract description 11
- 238000001354 calcination Methods 0.000 claims abstract description 9
- 239000002994 raw material Substances 0.000 claims abstract description 9
- 238000001914 filtration Methods 0.000 claims abstract description 4
- 235000012241 calcium silicate Nutrition 0.000 claims description 59
- 238000000034 method Methods 0.000 claims description 37
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 32
- 239000011575 calcium Substances 0.000 claims description 25
- 239000000243 solution Substances 0.000 claims description 21
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 16
- 229910021529 ammonia Inorganic materials 0.000 claims description 16
- 230000008569 process Effects 0.000 claims description 14
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 13
- 229910052791 calcium Inorganic materials 0.000 claims description 13
- 229910052698 phosphorus Inorganic materials 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 6
- -1 silicate ion Chemical class 0.000 claims description 5
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 4
- CUXQLKLUPGTTKL-UHFFFAOYSA-M microcosmic salt Chemical compound [NH4+].[Na+].OP([O-])([O-])=O CUXQLKLUPGTTKL-UHFFFAOYSA-M 0.000 claims description 4
- 239000001038 titanium pigment Substances 0.000 claims description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 239000011574 phosphorus Substances 0.000 claims description 3
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims description 2
- 230000032683 aging Effects 0.000 claims description 2
- 239000012670 alkaline solution Substances 0.000 claims description 2
- 229910001424 calcium ion Inorganic materials 0.000 claims description 2
- 159000000007 calcium salts Chemical class 0.000 claims description 2
- MWKXCSMICWVRGW-UHFFFAOYSA-N calcium;phosphane Chemical compound P.[Ca] MWKXCSMICWVRGW-UHFFFAOYSA-N 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 24
- 239000011858 nanopowder Substances 0.000 abstract description 15
- 239000000725 suspension Substances 0.000 abstract description 10
- 238000005406 washing Methods 0.000 abstract description 6
- 238000009388 chemical precipitation Methods 0.000 abstract description 5
- 230000008901 benefit Effects 0.000 abstract description 2
- 230000001105 regulatory effect Effects 0.000 abstract description 2
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 abstract 4
- 239000005696 Diammonium phosphate Substances 0.000 abstract 1
- 239000004115 Sodium Silicate Substances 0.000 abstract 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 abstract 1
- 229910000388 diammonium phosphate Inorganic materials 0.000 abstract 1
- 235000019838 diammonium phosphate Nutrition 0.000 abstract 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 abstract 1
- 229910052911 sodium silicate Inorganic materials 0.000 abstract 1
- 230000004071 biological effect Effects 0.000 description 17
- 239000008367 deionised water Substances 0.000 description 16
- 229910021641 deionized water Inorganic materials 0.000 description 16
- 150000001875 compounds Chemical class 0.000 description 14
- 239000007864 aqueous solution Substances 0.000 description 13
- 239000012620 biological material Substances 0.000 description 13
- 239000000919 ceramic Substances 0.000 description 13
- 239000000203 mixture Substances 0.000 description 13
- 239000008187 granular material Substances 0.000 description 12
- 229910010293 ceramic material Inorganic materials 0.000 description 11
- 239000000126 substance Substances 0.000 description 11
- 210000000988 bone and bone Anatomy 0.000 description 9
- 229910004298 SiO 2 Inorganic materials 0.000 description 8
- 238000000498 ball milling Methods 0.000 description 8
- 238000012423 maintenance Methods 0.000 description 8
- 230000000694 effects Effects 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 238000001027 hydrothermal synthesis Methods 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 238000005245 sintering Methods 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000003462 bioceramic Substances 0.000 description 4
- 239000002114 nanocomposite Substances 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000000956 alloy Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000006121 base glass Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 230000008439 repair process Effects 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000012890 simulated body fluid Substances 0.000 description 2
- 238000005728 strengthening Methods 0.000 description 2
- 235000019738 Limestone Nutrition 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000004069 differentiation Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000014509 gene expression Effects 0.000 description 1
- 239000002241 glass-ceramic Substances 0.000 description 1
- 238000010237 hybrid technique Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 210000004409 osteocyte Anatomy 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 210000001519 tissue Anatomy 0.000 description 1
- 208000037816 tissue injury Diseases 0.000 description 1
- 230000017423 tissue regeneration Effects 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
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- Materials For Medical Uses (AREA)
Abstract
The invention relates to calcium silicate nanowire/hydroxylapatite nanoparticle composite powder and a preparation method thereof, belonging to the field of biomedical materials. The calcium silicate nanowire/hydroxylapatite nanoparticle composite powder is prepared by compositing calcium silicate nanowires and hydroxylapatite nanoparticles by the following steps: firstly, preparing hydroxylapatite nanopowder by using diammonium phosphate and calcium nitrate as raw materials through chemical precipitation; dispersing the prepared hydroxylapatite nanopowder into a water solution dissolved with calcium nitrate, and regulating the pH value to obtain a suspension; dripping a water solution of sodium silicate into the suspension for carrying out secondary chemical precipitation reaction, and transferring the reaction system into an airtight high-pressure reaction kettle for hydro-thermal treatment at 160-250 DEG C for 12-36 hours; and after the hydro-thermal treatment, filtering, washing and calcining at 800-1000 DEG C. The invention has the advantages of easy regulation and control of composite proportion of the powder, simple and easy preparation processes, low cost, convenient popularization, and the like.
Description
Technical field
The method that two-step chemical precipitation combines with hydro-thermal prepares calcium silicates/hydroxyapatite nano composite granule method, belongs to biomedical materials field.
Background technology
The medical hard tissue repair of lithotroph and alternate material aspect mainly contain calcium-phosphorio biomaterial and calcium-silica-based biomaterial.Wherein calcium-phosphorio biomaterial research has had very long history.The research in past finds that hydroxyapatite has preferably biological activity in calcium-phosphorio material, but degradability is poor; In addition, mechanical strength is also lower, has limited the clinical scope of application.Calcium-silica-based biomaterial such as bioactivity glass and calcium silicates class material are then because its good biological activity and degradability and more and more come into one's own in recent years.Except the composition of material, the structure of material, the microstructure of composite, complex method and compound uniformity also affect intensity, the biological activity of material to a great extent, thereby directly have influence on the clinical practice of material.
The eighties in 20th century Japan the people such as Kokubo (J.Mater.Sci., 1986, the A-W glass that 21:536) works out be a kind of in glassy phase the glass ceramics of precipitation of phosphorus lime stone and two kinds of crystalline phases of calcium silicates.This material has preferably mechanical mechanics property and biological activity but can not degrade.The people's such as Kokubo research also confirms, CaO-SiO in simulated body fluid
2The base glass surface can form class bone hydroxyapatite layer, and CaO-P
2O
5The base glass surface does not have class bone hydroxyapatite to form.The people such as Punnama (J.Biomed.Mater.Res., 2000,52:30) prepared first fine and close calcium silicates bioceramic, the formation speed of concurrent present simulated body fluid mesosilicic acid calcium ceramic surface class bone hydroxyapatite is very fast, has extraordinary biological activity.Present inventor's previous research shows that also the calcium silicates biomaterial has good biological activity, degradability and mechanical strength, and can make the porous calcium silicate bioceramic (China Patent No.: ZL02137248.9) that is suitable for tissue injury's reparation usefulness.Being formed with of class bone hydroxyapatite is beneficial to bone conduction and the osteanagenesis that promotes biomaterial, and promotes that material forms closely chemical bonding effect with soft/sclerous tissues.In addition, the silicon ion that the calcium silicates component discharges in degradation process can also active cell and is stimulated the gene expression effect of osteocyte propagation and differentiation (Biomaterials 2004,25:2941).Therefore, adopt calcium silicates as compound phase, will regulate the degradability of hydroxyl apatite bioceramic material.In addition, calcium silicate material, especially fibrous calcium silicate powder extensively are used as the mechanics wild phase of pottery and macromolecular material.Therefore, calcium silicate nanowire also will be expected to be used for as the mechanics wild phase mechanical property of enhancing hydroxyl apatite bioceramic because of its good mechanical property except having good biological activity and degradability.
At present, a kind of preparation method of the routine of composite ceramic material is: the ceramic powder of preparing first various single compositions; Afterwards, by design proportion batch mixing is carried out in different powder body mixing and the method for application machine ball milling, thereby prepare composite ceramic material.Although the method technique of this mechanical ball milling batch mixing is simple, fatal shortcoming is: at first, prepare different single ceramic powders, the preparation process of every kind of single ceramic powder all needs the techniques such as complexity, loaded down with trivial details washing, filtration, drying, calcining; Secondly application machine ball mill mixing method must be introduced ball-milling medium, common ball-milling medium is the materials such as aluminium oxide or zirconium oxide, therefore very easily be introduced as the impurity of ball-milling medium in the ball mill mixing process, and technical field of biological material is very high to the purity requirement of material, so, the ball milling hybrid technique is a kind of Technology of nonideal preparation biomaterial, and the Compound Degree of the composite granule that obtains of ball-milling method is not very even usually.So, the reasons such as phase transformation inhomogeneous owing to the Compound Degree of powder body, that sintering activity is bad, excess Temperature causes in the sintering process, cause the mechanical strength of the composite ceramics for preparing bad, affected widely clinical practice, the shortcoming such as particularly under the higher occasion of mechanics load bearing requirements, be restricted.
Crystal grain is tiny, specific surface area is large owing to having for composite nano-powder, and its sintering activity is more much better than the composite granule of conventional micron and submicron-scale, obtains easily ceramic material fine and close and that crystal grain is tiny.Studies show that high-intensity ceramic material basic demand is high density and fine grain.Therefore the applying nano powder body might obtain the ceramic material of better mechanical strength as the initial powder body of sintered body.As seen, develop a kind of Technology simple, with low cost, be uniformly dispersed and method that sintering activity is good prepares calcium silicates/hydroxyapatite nano composite granule, and pattern and the dispersibility of control composite granule mesosilicic acid calcium nano wire, thereby and easily the compositely proportional of controlled material improve the sintering behavior of powder body and the Technology of mechanical property has very important significance.Thereby visualize purpose of the present invention, to overcome the shortcoming of the general mechanical ball milling method for mixing of routine recited above.
Summary of the invention
The first purpose of the present invention is to provide a kind of new good mechanical property, biological activity and degradability and the controlled calcium silicate nanowire/hydroxylapatite nanoparticle composite powder of mechanical strength, biological activity and degradability by Optimization Technology.
The second purpose of the present invention is to provide the preparation method of calcium silicate nanowire/hydroxylapatite nanoparticle composite powder.
A first aspect of the present invention provides a kind of calcium silicate nanowire/hydroxylapatite nanoparticle composite powder, and this composite granule mesosilicic acid calcium accounts for the 5wt-95wt% of calcium silicates and hydroxyapatite total amount, preferred 10-90wt%.
The diameter of calcium silicate nanowire is the 10-100 nanometer, and length is 50 nanometers-10 micron; Hydroxyapatite nanoparticle is of a size of the 10-200 nanometer;
Adopt method provided by the invention to prepare calcium silicates/hydroxyapatite nano composite granule, because nano-material has excellent mechanical property, in field of compound material as mechanics wild phase and flexibilizer be widely used [J.Alloys Compounds, 472:395-399; 2009; Composite Science andTechnology, 66:1002-1111; 2006].Therefore, the composite granule that adopts the present invention to prepare is that raw material prepares calcium silicates/hydroxylapatite composite biological ceramic material, its calcium silicate nanowire will be used for strengthening as the mechanics wild phase mechanical property of composite ceramic material, thereby prepare the composite biological material of good mechanical properties.In addition, the component of calcium silicates has good biological activity and degradability [J.Mater.Res., 14:529-536; 1999.; Biomaterials, 29:2588-2596; 2008.].Therefore, adopt calcium silicate nanowire as compound phase, except meeting improves the mechanical property of material, can also improve the biological activity of hydroxylapatite ceramic and improve the degradability (usually, hydroxylapatite ceramic is considered to substantially not degrade) of hydroxylapatite ceramic.Simultaneously, compositely proportional by controlled material mesosilicic acid calcium and hydroxyapatite, mechanical property, biological activity and the degradability of the calcium silicates that can also Effective Regulation prepares/hydroxyapatite composite ceramics are repaired ceramic material for clinical bone defect repair field provides the new type bone of different performance.
A second aspect of the present invention provides a kind of preparation method of calcium silicate nanowire/hydroxylapatite nanoparticle composite powder, comprises the steps:
(1) take soluble calcium salt as raw material, preparation solubility calcium saline solution, the pH of regulator solution is 9-11.5; Take the solubility microcosmic salt as raw material, preparation titanium pigment saline solution, the pH of regulator solution is 8-10.5; Take soluble silicate as raw material, preparation mensuration dissolubility silicic saline solution, the pH of regulator solution is 9-12;
(2) ratio take calcium phosphorus mol ratio as 1.60-1.70 adds the titanium pigment saline solution in the solubility calcium saline solution, and keeping reaction solution pH in the adition process is 9-12, then with product ageing, filtration;
(3) step (2) gained powder body is added to the water formation dirty solution accounts for the proportioning of calcium silicates and hydroxyapatite total amount 5wt%-95wt% by calcium silicates, adds the mensuration dissolubility silicic saline solution in above-mentioned dirty solution;
(4) will be that the pH of adition process regulator solution is 9-12, continues to stir after adding in solubility calcium saline solution adding step (3) products therefrom of 0.8-1.2 with the silicate ion mol ratio;
(5) place the enclosed high pressure still in 160-250 ℃ of hydrothermal treatment consists 12-36 hour step (4) products therefrom, filter after the hydrothermal treatment consists, wash, and 800-1000 ℃ of calcining.
In the above-mentioned steps, the calcium ion concentration of preferred solubility calcium saline solution is 0.05-2mol/L; The phosphorus acid ion concentration of preferred solubility microcosmic salt is 0.05-2mol/L; The silicate ion concentration of preferred soluble silicate is 0.05-2mol/L.
In the above-mentioned steps, the pH of regulator solution is for adopting alkaline solution to regulate, and preferred employing adds ammonia to be regulated, and the concentration of preferred ammonia is 0.05-2mol/L.
The characteristics of the method are that the two-step chemical precipitation method is combined with hydro-thermal aid in treatment method.Namely adopt first chemical precipitation method to prepare hydroxyapatite nano-powder, afterwards the hydroxy apatite powder that obtains is scattered in the aqueous solution, under agitation precipitation calcium silicate powder for the second time precipitates hydrothermal treatment consists in the complete rear hydrothermal reaction kettle.
The selection of this calcinating system is according to being: if temperature is lower than 800 ℃, can not obtain the calcium silicates phase, but the afwillite phase; If temperature is higher than 1000 ℃, the calcium silicate nanowire of acquisition will seriously reunite and cause diameter sharply to increase to (Asia) micro-meter scale.
Table 1 is the chemical composition (quality percentage composition) of the composite nano-powder of the calcium silicates/hydroxyapatite of the different composite ratio (mass ratio) using the inventive method and prepare.The chemical composition of the powder body that as seen, prepares is coincide finely with theoretical value.Illustrate, use the composite nano-powder that method provided by the invention can design and synthesize the calcium silicates/hydroxyapatite that obtains preset ratio well.
Table 1
* the data in the bracket are theoretical value.
The calcium silicates that is composited by calcium silicate nanowire and hydroxyapatite nanoparticle that adopts that method provided by the invention prepares/hydroxyapatite nano composite granule has following advantage: because nano-material has excellent mechanical property, in field of compound material as mechanics wild phase and flexibilizer be widely used [J.Alloys Compounds, 472:395-399; 2009; Composite Science and Technology, 66:1002-1111; 2006].Therefore, the composite granule that adopts the present invention to prepare is that raw material prepares calcium silicates/hydroxylapatite composite biological ceramic material, its calcium silicate nanowire will be used for strengthening as the mechanics wild phase mechanical property of composite ceramic material, thereby prepare the composite biological material of good mechanical properties.In addition, the component of calcium silicates has good biological activity and degradability [J.Mater.Res., 14:529-536; 1999.; Biomaterials, 29:2588-2596; 2008.].Therefore, adopt calcium silicate nanowire as compound phase, except meeting improves the mechanical property of material, can also improve the biological activity of hydroxylapatite ceramic and improve the degradability (usually, hydroxylapatite ceramic is considered to substantially not degrade) of hydroxylapatite ceramic.Simultaneously, compositely proportional by controlled material mesosilicic acid calcium and hydroxyapatite, mechanical property, biological activity and the degradability of the calcium silicates that can also Effective Regulation prepares/hydroxyapatite composite ceramics are repaired ceramic material for clinical bone defect repair field provides the new type bone of different performance.
Description of drawings
Fig. 1 is the X-ray diffracting spectrum of composite nano-powder of the calcium silicates/hydroxyapatite of the different composite ratio for preparing of the present invention: 30wt.%CS (A), 50wt.%CS (B), 70wt.%CS (C) and 90wt.%CS (D).As seen the powder body of different composite ratio forms by calcium silicates and two kinds of phases of hydroxyapatite.
Fig. 2 is the transmission photo of calcium silicates/hydroxyapatite of adopting the inventive method and preparing: 30wt.%CS (A), 50wt.%CS (B), 70wt.%CS (C) and 90wt.%CS (D).As seen from the figure, about 50 nanometers-10 of diameter 10-100 nanometer, length of fibrous phase micron in the composite granule for preparing; The about 10-100 nanometer of the particle diameter of graininess powder body.In addition, two kinds of powder body distribute evenly and favorable dispersibility.Nano wire in the composite granule will play the mechanical property effect that strengthens sintered body, simultaneously biological activity and the degradability of all right Effective Raise material of the performance of its biological activity and degradability.
Fig. 3 is the electronogram of choosing that adopts nano-particle (3A) that the inventive method prepares and nano wire (3B).Choose the electronic diffraction results verification nano-particle be that hydroxyapatite phase, nano wire are the calcium silicates phases.
The specific embodiment
Below in conjunction with specific embodiment, further illustrate the present invention.Should be understood that these embodiment only to be used for explanation the present invention and be not used in and limit the scope of the invention.The experimental technique of unreceipted actual conditions in the following example usually according to normal condition, for example is the condition in the workshop manual, or the condition of advising according to manufacturer.Ratio and percentage ratio are based on molar ratio (or being called atomic ratio), unless stated otherwise.
Unless otherwise defined or explanation, same meanings of being familiar with of all specialties used herein and scientific words and those skilled in the art.Any method similar or impartial to described content and material all can be applicable in the inventive method in addition.
Embodiment 1:
Get the Ca (NO of 11.76 grams
3)
2Be dissolved in the 100mL deionized water, and be adjusted to pH=11 with 1: 1 ammonia, with (the NH of 3.95g gram
4)
2HPO
4Be dissolved in and get (NH in the 100mL deionized water
4)
2HPO
4Aqueous solution.With above-mentioned (NH
4)
2HPO
4Aqueous solution is added drop-wise to Ca (NO
3)
2In the solution, reinforced process is 11 with the pH value of 1: 1 ammonia spirit maintenance reaction system, finishes and continues to stir 24 hours, filters and obtains hydroxyapatite nano-powder, hydroxyapatite nano-powder is scattered in the 800mL deionized water, and dissolves 91.61 gram Ca (NO
3)
2, acquisition is dispersed with the white suspension of hydroxyapatite nano-powder; With pH be 11.0 800mL and be dissolved with 110.25 the gram Na
2SiO
3Aqueous solution dropwise adds in the above-mentioned suspension, and reinforced process is 11 with the pH value of 1: 1 ammonia spirit maintenance reaction system, transfers to after finishing in the hydro-thermal reaction under high pressure, airtight and in 200 ℃ of hydrothermal treatment consists 24 hours.Afterwards, filter, with deionized water and absolute ethanol washing, be filtered dry, dry in 80 ℃ and obtained the dry powder body in 12 hours, the dry powder body 950 ℃ of calcinings 2 hours, is obtained mass percent and is 10: 90 even compound hydroxyapatite/calcium silicates composite nano-powder.The pattern of the composite nano-powder for preparing shown in Fig. 2 D, the about 10-30 nanometer of hydroapatite particles size wherein, the diameter 20-50 nanometer of calcium silicate nanowire, about 200 nanometers-10 of length micron.Phase as shown in Figure 1; Chemical composition (mass percent) is: CaO 48.09%, SiO
246.56%, P
2O
54.44%, and theoretical value is respectively CaO 49.03%, SiO
246.55%, P
2O
54.24%.The chemical composition of the powder body that as seen, prepares is coincide finely with theoretical value.
Embodiment 2:
Get the Ca (NO of 58.80 grams
3)
2Be dissolved in the 500mL deionized water, and be adjusted to pH=11 with 1: 1 ammonia, with (the NH of 19.73 grams
4)
2HPO
4Be dissolved in and get (NH in the 500mL deionized water
4)
2HPO
4Aqueous solution.With above-mentioned (NH
4)
2HPO
4Aqueous solution is added drop-wise to Ca (NO
3)
2In the solution, reinforced process is 11 with the pH value of 1: 1 ammonia spirit maintenance reaction system, finishes and continues to stir 24 hours, filters and obtains hydroxyapatite nano-powder, hydroxyapatite nano-powder is scattered in the 500mL deionized water, and dissolves 50.89 gram Ca (NO
3)
2, acquisition is dispersed with the white suspension of hydroxyapatite nano-powder; With pH be 11.0 500mL and be dissolved with 61.25 the gram Na
2SiO
3Aqueous solution dropwise adds in the above-mentioned suspension, and reinforced process is 11 with the pH value of 1: 1 ammonia spirit maintenance reaction system, transfers to after finishing in the hydro-thermal reaction under high pressure, airtight and in 200 ℃ of hydrothermal treatment consists 24 hours.Afterwards, filter, with deionized water and absolute ethanol washing, be filtered dry, dry in 80 ℃ and obtained the dry powder body in 12 hours, the dry powder body 950 ℃ of calcinings 2 hours, is obtained mass percent and is 50: 50 even compound hydroxyapatite/calcium silicates composite nano-powder.The pattern of the composite nano-powder for preparing shown in Fig. 2 B, about 30 nanometers of hydroapatite particles size wherein, the diameter 30-50 nanometer of calcium silicate nanowire, about 300 nanometers-10 of length micron.Phase as shown in Figure 1; Chemical composition (mass percent) is: CaO 51.03%, SiO
225.58%, P
2O
521.59%, and theoretical value is respectively CaO 52.03%, SiO
225.86%, P
2O
521.22%.The chemical composition of the powder body that as seen, prepares is coincide finely with theoretical value.
Embodiment 3:
Get the Ca (NO of 82.32 grams
3)
2Be dissolved in the 700mL deionized water, and be adjusted to pH=11 with 1: 1 ammonia, with (the NH of 26.62 grams
4)
2HPO
4Be dissolved in and get (NH in the 700mL deionized water
4)
2HPO
4Aqueous solution.With above-mentioned (NH
4)
2HPO
4Aqueous solution is added drop-wise to Ca (NO
3)
2In the solution, reinforced process is 11 with the pH value of 1: 1 ammonia spirit maintenance reaction system, finishes and continues to stir 24 hours, filters and obtains hydroxyapatite nano-powder, hydroxyapatite nano-powder is scattered in the 300mL deionized water, and dissolves 30.54 gram Ca (NO
3)
2, acquisition is dispersed with the white suspension of hydroxyapatite nano-powder; With pH be 11.0 300mL and be dissolved with 36.75 the gram Na
2SiO
3Aqueous solution dropwise adds in the above-mentioned suspension, and reinforced process is 11 with the pH value of 1: 1 ammonia spirit maintenance reaction system, transfers to after finishing in the hydro-thermal reaction under high pressure, airtight and in 200 ℃ of hydrothermal treatment consists 24 hours.Afterwards, filter, with deionized water and absolute ethanol washing, be filtered dry, dry in 80 ℃ and obtained the dry powder body in 12 hours, the dry powder body 950 ℃ of calcinings 2 hours, is obtained mass percent and is 70: 30 even compound hydroxyapatite/calcium silicates composite nano-powder.The pattern of the composite nano-powder for preparing shown in Fig. 2 A, about 20 nanometers of hydroapatite particles size wherein, calcium silicate nanowire diameter 20 nanometers, about 500 nanometers-10 of length micron.Phase as shown in Figure 1; Chemical composition (mass percent) is: CaO 52.79%, SiO
215.54%, P
2O
530.21%, and theoretical value is respectively CaO 53.53%, SiO
215.22%, P
2O
529.70%.The chemical composition of the powder body that as seen, prepares is coincide finely with theoretical value.
Embodiment 4
Get the Ca (NO of 35.28 grams
3)
2Be dissolved in the 400mL deionized water, and be adjusted to pH=11 with 1: 1 ammonia, with (the NH of 11.84 grams
4)
2HPO
4Be dissolved in and get (NH in the 350mL deionized water
4)
2HPO
4Aqueous solution.With above-mentioned (NH
4)
2HPO
4Aqueous solution is added drop-wise to Ca (NO
3)
2In the solution, reinforced process is 11 with the pH value of 1: 1 ammonia spirit maintenance reaction system, finishes and continues to stir 24 hours, filters and obtains hydroxyapatite nano-powder, hydroxyapatite nano-powder is scattered in the 700mL deionized water, and dissolves 71.25 gram Ca (NO
3)
2, acquisition is dispersed with the white suspension of hydroxyapatite nano-powder; With pH be 11.0 700mL and be dissolved with 85.75 the gram Na
2SiO
3Aqueous solution dropwise adds in the above-mentioned suspension, and reinforced process is 11 with the pH value of 1: 1 ammonia spirit maintenance reaction system, transfers to after finishing in the hydro-thermal reaction under high pressure, airtight and in 200 ℃ of hydrothermal treatment consists 24 hours.Afterwards, filter, with deionized water and absolute ethanol washing, be filtered dry, dry in 80 ℃ and obtained the dry powder body in 12 hours, the dry powder body 950 ℃ of calcinings 2 hours, is obtained mass percent and is 30: 70 even compound hydroxyapatite/calcium silicates composite nano-powder.The pattern of the composite nano-powder for preparing shown in Fig. 2 C, about 20 nanometers of hydroapatite particles size wherein, calcium silicate nanowire diameter 10-80 nanometer, about 500 nanometers-10 of length micron.Phase as shown in Figure 1; Chemical composition (mass percent) is: CaO 49.32%, SiO
236.89%, P
2O
512.98%, and theoretical value is respectively CaO 50.53%, SiO
236.21%, P
2O
512.73%.The chemical composition of the powder body that as seen, prepares is coincide finely with theoretical value.
All quote in this application as a reference at all documents that the present invention mentions, just as each piece document is quoted separately as a reference.Should be understood that in addition those skilled in the art can make various changes or modifications the present invention after having read above-mentioned teachings of the present invention, these equivalent form of values fall within the application's appended claims limited range equally.
Claims (4)
1. the preparation method of calcium silicate nanowire/hydroxylapatite nanoparticle composite powder, the mass percentage content of calcium silicates accounts for the 5-95% of total amount, and wherein, the diameter of calcium silicate nanowire is the 10-100 nanometer, and length is 50 nanometers-10 micron; Hydroxyapatite nanoparticle is of a size of the 10-200 nanometer, comprises the steps:
(1) take soluble calcium salt as raw material, preparation solubility calcium saline solution, the pH of regulator solution is 9-11.5; Take the solubility microcosmic salt as raw material, preparation titanium pigment saline solution, the pH of regulator solution is 8-10.5; Take soluble silicate as raw material, preparation mensuration dissolubility silicic saline solution, the pH of regulator solution is 9-12;
(2) ratio take calcium phosphorus mol ratio as 1.60-1.70 adds the titanium pigment saline solution in the solubility calcium saline solution, and keeping reaction solution pH in the adition process is 9-12, then with product ageing, filtration;
(3) step (2) gained powder body is added to the water formation dirty solution accounts for the proportioning of calcium silicates and hydroxyapatite total amount 5wt%-95wt% by calcium silicates, adds the mensuration dissolubility silicic saline solution in above-mentioned dirty solution;
(4) will be that the pH of adition process regulator solution is 9-12, continues to stir after adding in solubility calcium saline solution adding step (3) products therefrom of 0.8-1.2 with the silicate ion mol ratio;
(5) place the enclosed high pressure still in 160-250 ℃ of hydrothermal treatment consists 12-36 hour step (4) products therefrom, filter after the hydrothermal treatment consists, wash, and 800-1000 ℃ of calcining.
2. by the preparation method of calcium silicate nanowire/hydroxylapatite nanoparticle composite powder claimed in claim 1, it is characterized in that the calcium ion concentration of described solubility calcium saline solution is 0.05-2mol/L; The phosphorus acid ion concentration of described solubility microcosmic salt is 0.05-2mol/L; The silicate ion concentration of described soluble silicate is 0.05-2mol/L.
3. by the preparation method of calcium silicate nanowire/hydroxylapatite nanoparticle composite powder claimed in claim 1, it is characterized in that the pH of described regulator solution adopts alkaline solution to regulate.
4. by the preparation method of calcium silicate nanowire/hydroxylapatite nanoparticle composite powder claimed in claim 3, it is characterized in that the pH of described preferred regulator solution adopts and adds the ammonia adjusting, the concentration of preferred ammonia is 0.05-2mol/L.
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| 林开利."纳米磷酸钙、硅酸钙及其复合生物与环境材料的制备和性能研究".《中国博士学位论文全文数据库,工程科技I辑》.2008,(第11期), * |
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