CN101700414A - 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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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
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.Past discover that hydroxyapatite has biological activity preferably 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 superior bioactive 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 influence 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 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.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.People such as Punnama (J.Biomed.Mater.Res., 2000,52:30) prepared fine and close calcium silicates bioceramic first, 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 chemical bonding effect closely 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, will regulate the degradability of hydroxyl apatite bioceramic material as compound phase.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 to strengthen as the mechanics wild phase mechanical property of hydroxyl apatite bioceramic because of its excellent 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 various single compositions earlier; Afterwards, by design proportion batch mixing is carried out in the different powder body mixing and the method for application machine ball milling, thereby prepare composite ceramic material.Though the method technology 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 technologies 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 materials such as aluminium oxide or zirconium oxide, therefore very easily introduce impurity in the ball mill mixing process as ball-milling medium, 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, inhomogeneous owing to the compound degree of powder body, sintering activity is bad, the too high reasons such as phase transformation that cause of temperature in the sintering process, cause the mechanical strength of the composite ceramics for preparing bad, influenced wider clinical application, shortcoming such as particularly under the higher occasion of mechanics load bearing requirements, be restricted.
Crystal grain is tiny, specific surface area is big 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 fine and close easily and ceramic material 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 the 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
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 optimizing technology.
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 feedstock production calcium silicates/hydroxylapatite composite biological ceramic material, its calcium silicate nanowire will be used to strengthen the mechanical property of composite ceramic material as the mechanics wild phase, 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 not degrade substantially) 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 effectively regulate and control to prepare/hydroxyapatite composite ceramics are repaired ceramic material for clinical bone defect repair field provides the novel 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) with the soluble calcium salt be raw material, preparation solubility calcium saline solution, the pH of regulator solution is 9-11.5; With the solubility microcosmic salt is raw material, preparation titanium pigment saline solution, and the pH of regulator solution is 8-10.5; With the soluble silicate is raw material, preparation mensuration dissolubility silicic saline solution, and the pH of regulator solution is 9-12;
(2) be the ratio of 1.60-1.70 with calcium phosphorus mol ratio, the titanium pigment saline solution added in the solubility calcium saline solution that 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 forms muddy liquid, account for the proportioning of calcium silicates and hydroxyapatite total amount 5wt%-95wt%, in above-mentioned muddy liquid, add the mensuration dissolubility silicic saline solution by calcium silicates;
(4) will be that the pH of adition process regulator solution is 9-12, adds the back and continues to stir in solubility calcium saline solution adding step (3) products therefrom of 0.8-1.2 with the silicate ion mol ratio;
(5) place airtight autoclave in 160-250 ℃ of hydrothermal treatment consists 12-36 hour step (4) products therefrom, hydrothermal treatment consists after-filtration, washing, 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 regulates for adopting alkaline solution, and preferred employing adds ammonia to be regulated, and the concentration of preferred ammonia is 0.05-2mol/L.
The characteristics of this method are that the two-step chemical precipitation method is combined with hydro-thermal aid in treatment method.Promptly adopt chemical precipitation method to prepare hydroxyapatite nano-powder earlier, the hydroxy apatite powder with acquisition is scattered in the aqueous solution afterwards, under agitation precipitates the preparation calcium silicate powder for the second time, hydrothermal treatment consists in the hydrothermal reaction kettle after precipitation finishes.
The selection of this calcinating system is according to being: if temperature is lower than 800 ℃, can not obtain calcium silicates thing phase, but afwillite thing 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.
Calcium silicates/hydroxyapatite nano the composite granule that is composited by calcium silicate nanowire and hydroxyapatite nanoparticle that adopts method provided by the invention to prepare 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 feedstock production calcium silicates/hydroxylapatite composite biological ceramic material, its calcium silicate nanowire will be used to strengthen the mechanical property of composite ceramic material as the mechanics wild phase, 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 not degrade substantially) 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 effectively regulate and control to prepare/hydroxyapatite composite ceramics are repaired ceramic material for clinical bone defect repair field provides the novel bone of different performance.
Description of drawings
The X-ray diffracting spectrum of the composite nano-powder of the calcium silicates/hydroxyapatite of the different composite ratio that Fig. 1 prepares for 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 is by calcium silicates and two kinds of thing phase compositions 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).The about 10-100 nanometer of the diameter of the middle fibrous material phase of the composite granule for preparing as seen from the figure,, about 50 nanometers-10 of length micron; 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, and the performance of its biological activity and degradability can also effectively improve the biological activity and the degradability of material simultaneously.
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 thing phase, nano wire are calcium silicates thing 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 to the present invention is described 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 in addition method similar or impartial to described content and material all can be applicable in the inventive method.
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 (the NH of 3.95g gram with 1: 1 ammonia
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 is 11.0 800mL and the Na that is dissolved with 110.25 grams
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, do, obtained the dry powder body in 12 hours in 80 ℃ of oven dry with deionized water and absolute ethanol washing, filter, the dry powder body 950 ℃ of calcinings 2 hours, is obtained mass percent and is even compound hydroxyapatite/calcium silicates composite nano-powder of 10: 90.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 about 20-50 nanometer of the diameter of calcium silicate nanowire, about 200 nanometers-10 of length micron.Thing mutually 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 (the NH of 19.73 grams with 1: 1 ammonia
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 is 11.0 500mL and the Na that is dissolved with 61.25 grams
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, do, obtained the dry powder body in 12 hours in 80 ℃ of oven dry with deionized water and absolute ethanol washing, filter, the dry powder body 950 ℃ of calcinings 2 hours, is obtained mass percent and is even compound hydroxyapatite/calcium silicates composite nano-powder of 50: 50.The pattern of the composite nano-powder for preparing shown in Fig. 2 B, about 30 nanometers of hydroapatite particles size wherein, the about 30-50 nanometer of the diameter of calcium silicate nanowire, about 300 nanometers-10 of length micron.Thing mutually 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 (the NH of 26.62 grams with 1: 1 ammonia
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 is 11.0 300mL and the Na that is dissolved with 36.75 grams
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, do, obtained the dry powder body in 12 hours in 80 ℃ of oven dry with deionized water and absolute ethanol washing, filter, the dry powder body 950 ℃ of calcinings 2 hours, is obtained mass percent and is even compound hydroxyapatite/calcium silicates composite nano-powder of 70: 30.The pattern of the composite nano-powder for preparing shown in Fig. 2 A, about 20 nanometers of hydroapatite particles size wherein, about 20 nanometers of calcium silicate nanowire diameter, about 500 nanometers-10 of length micron.Thing mutually 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 (the NH of 11.84 grams with 1: 1 ammonia
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 is 11.0 700mL and the Na that is dissolved with 85.75 grams
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, do, obtained the dry powder body in 12 hours in 80 ℃ of oven dry with deionized water and absolute ethanol washing, filter, the dry powder body 950 ℃ of calcinings 2 hours, is obtained mass percent and is even compound hydroxyapatite/calcium silicates composite nano-powder of 30: 70.The pattern of the composite nano-powder for preparing shown in Fig. 2 C, about 20 nanometers of hydroapatite particles size wherein, the about 10-80 nanometer of calcium silicate nanowire diameter, about 500 nanometers-10 of length micron.Thing mutually 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 quoted as a reference separately as each piece document.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 institute restricted portion equally.
Claims (6)
1. calcium silicate nanowire/hydroxylapatite nanoparticle composite powder is characterized in that, wherein 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;
2. by the described calcium silicate nanowire/hydroxylapatite nanoparticle composite powder of claim 1, it is characterized in that wherein the mass percentage content of calcium silicates accounts for 10～90% of total amount.
3. the preparation method of calcium silicate nanowire/hydroxylapatite nanoparticle composite powder comprises the steps:
(1) with the soluble calcium salt be raw material, preparation solubility calcium saline solution, the pH of regulator solution is 9-11.5; With the solubility microcosmic salt is raw material, preparation titanium pigment saline solution, and the pH of regulator solution is 8-10.5; With the soluble silicate is raw material, preparation mensuration dissolubility silicic saline solution, and the pH of regulator solution is 9-12;
(2) be the ratio of 1.60-1.70 with calcium phosphorus mol ratio, the titanium pigment saline solution added in the solubility calcium saline solution that 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 forms muddy liquid, account for the proportioning of calcium silicates and hydroxyapatite total amount 5wt%-95wt%, in above-mentioned muddy liquid, add the mensuration dissolubility silicic saline solution by calcium silicates;
(4) will be that the pH of adition process regulator solution is 9-12, adds the back and continues to stir in solubility calcium saline solution adding step (3) products therefrom of 0.8-1.2 with the silicate ion mol ratio;
(5) place airtight autoclave in 160-250 ℃ of hydrothermal treatment consists 12-36 hour step (4) products therefrom, hydrothermal treatment consists after-filtration, washing, and 800-1000 ℃ of calcining.
4. by the preparation method of the described calcium silicate nanowire/hydroxylapatite nanoparticle composite powder of claim 3, 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.
5. by the preparation method of the described calcium silicate nanowire/hydroxylapatite nanoparticle composite powder of claim 3, it is characterized in that the pH of described regulator solution adopts alkaline solution to regulate.
6. by the preparation method of the described calcium silicate nanowire/hydroxylapatite nanoparticle composite powder of claim 5, 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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| CN101927989A (en) * | 2010-06-04 | 2010-12-29 | 山东轻工业学院 | Method for preparing ordered nest-shaped porous hydroxylapatite material |
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| CN1569736A (en) * | 2002-09-28 | 2005-01-26 | 中国科学院上海硅酸盐研究所 | Preparation method of degradable porous calcium-silicate ceramic bioactive materials |
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| CN101927989B (en) * | 2010-06-04 | 2012-03-21 | 山东轻工业学院 | Method for preparing ordered nest-shaped porous hydroxylapatite material |
| CN101914329A (en) * | 2010-09-08 | 2010-12-15 | 安徽工业大学 | Nano multifunctional outer wall heat preservation coating |
| CN101914329B (en) * | 2010-09-08 | 2013-01-09 | 安徽工业大学 | Nano multifunctional outer wall heat preservation coating |
| CN110373199A (en) * | 2019-06-21 | 2019-10-25 | 湖南大学 | A kind of composite soil renovation agent and preparation method thereof and restorative procedure |
| CN110373199B (en) * | 2019-06-21 | 2021-10-01 | 湖南大学 | Composite soil repairing agent and preparation method and repairing method thereof |
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| CN114886782A (en) * | 2022-05-07 | 2022-08-12 | 深圳市博威凯特科技有限公司 | Active calcium compound based on nano hydroxyapatite and preparation method and application thereof |
| WO2023216349A1 (en) * | 2022-05-07 | 2023-11-16 | 深圳市博威凯特科技有限公司 | Nano-hydroxyapatite-based active calcium complex, preparation method therefor and use thereof |
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