CN102569749B - Graphene/hydroxyapatite nano composite and preparation method thereof - Google Patents
Graphene/hydroxyapatite nano composite and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a graphene/hydroxyapatite nano composite and the preparation method thereof, particularly relates to a hydrothermal method for preparing graphene/hydroxyapatite nano composite through the assistance of amino acid, and belongs to the field of nano composite and biological material. According to the invention, graphene oxide is placed in deionized water for ultrasonic dispersion, and calcium chloride anhydrous is added for stirring, so as to form mixed solution A; amino acid is added into dilute phosphoric acid for stirring so as to form solution b, the dilute hydrochloric acid solution is used for adjusting the solution to enable the PH value to be 7.5 to 8.5, finally the mixed solution A and the mixed solution B are mixed to transfer into a polytetrafluoroethylene reaction kettle for hydro-thermal reaction, and after the reaction is finished, the composite can be obtained through centrifugating, cleaning and vacuum drying the product. The invention has the advantages that the operating process is relatively simple, the structure is controllable, the surface appearance is better, the specific surface area is larger, the dimension is even, and the like.
Description
Technical field
The present invention relates to a kind of graphene/hydroxyapatite nano composite and preparation method thereof, refer to that especially the auxiliary hydro-thermal of a kind of amino acid prepares the method for graphene/hydroxyapatite nano composite, belong to nano composite material and technical field of biological material.
Background technology
Bioceramic hydroxyapatite (Hydroxyapatite, HA) be the main inorganic composition of human body and animal skeleton, tooth, account for 45% of dry bone tissue, apatite in people's natural bone mainly with the form of nanoscale acicular crystal along certain azimuth distribution in collagenous network, thereby improved the implantation effect of compound bone material; Because it has good biologically active and biocompatibility, stable chemical characteristic and various structure, make it in fields such as artificial bone, medicament slow release, gas sensor, catalyst, photoelectric material, Chemical Engineering and environmental engineerings, have achievement more.
Up to the present, people have developed the multiple method of preparing hydroxyapatite, as dry method, mechanochemical reaction, liquid-phase precipitation method, solid reaction process, auto-combustion method, hydro thermal method, sol-gel process, microemulsion method etc., adopt certain method, can obtain the hydroxyapatite of different structure; Structure and morphology is different, and application is also not quite similar, and bar-shaped, crystal whisker-shaped, sheet-shaped hydroxyapatite can be applicable to Biomedical function material and polymer matrix composite field; Cellular hydroxyapatite can be applicable to separation, the green material field of catalysis, catalytic carrier, protein or enzyme; Granular, bar-shaped, sheet-shaped hydroxyapatite can be applicable to intelligent sensitive material field; The particle size of hydroxyapatite, anisotropy, pattern, microstructure etc. will directly affect its performance, and therefore, exploration preparation method and corresponding synthesis condition are significant on the impact of product pattern and draw ratio.
Literature survey discovery, as
elliotdeng [
nature, 1967,214,904] described in, under hydrothermal condition, the viscosity of solution declines, and causes the aggravation of ion migration, and nucleus growth speed is higher compared with other system, and this has created condition for preparing degree of crystallinity product high, that crystal structure is different; Therefore, hydro thermal method has significant advantage on nanometer hydroxyapatite synthetic, and the product degree of crystallinity of acquisition is high, does not generally need follow-up high-temperature process, reunites few, and purity is high, and form, size are controlled; Lin [
mater. Res. Soc. Sym.Proc., 1994,346,237] and with Ca (OH)
2na
3pO
412H
2o is predecessor, has synthesized the hydroxyapatite nano-powder that particle diameter is about 50 nm in reactor, and material reaches the spotlight that nano-grade size is it; Zhang etc. [
crystal Growth & Design,2009,9 (6), 2,725 2733] respectively with Ca (NO
3)
24H
2o and (NH
4)
2hPO
4for Ca source and P source, adopt the hydro thermal method under different pH values, prepared the hydroxyapatite of nano bar-shape, bur shape, flower-shaped and sheet; NEIRA etc. [
crystal Growth & Design, 2009,9 (1), 466 474] and adopt hydro thermal method, by changing heat preserving mode, prepared the AB type podolite of needle-like, sheet, hexagonal prism shape and platelet-like; The two is respectively to explore different pH and the control effect of heat-treat condition to hydroxyapatite structure pattern, but its concrete mechanism need further research, and the pattern of product and particle size distribution be subject to the initial configuration of raw material so that the impact of mixing uniformity very large; In order to overcome forefathers' shortcoming, Yang Qing etc. [
beijing University of Chemical Technology's journal2010,37 (6), 93 97] attempting adopting chemical precipitation method to prepare hydroxyapatite in conjunction with the process route of hydro thermal method, the key of implementing this process route is that Y type micro passage reaction evenly mixes the microcosmic of reaction mass, the corynebacterium hydroxyapatite particle diameter making reaches 85 nm, structure favorable reproducibility, but its equipment requirement is high, complex process, chemical bond strong between high specific area and particle can cause nucleus coalescence, is unfavorable for uniform particles.
In order to improve the structure and morphology of hydroxyapatite and to reduce preparation difficulty simultaneously, reach a kind of situation of doulbe-sides' victory, many researchers have turned one's attention in the modification and compound research of hydroxyapatite, and employing adds the mode of modifier and composite interstitial substance to prepare the Hydroxyapatite Nanocomposites of modification; As Damia etc.
mater.Lett., 2006,60,3192 3196 ］ utilize silane coupling A-1130 and A-187 to hydroxyapatite surface modification, then utilize silane group and intermetallic effect, make hydroxyapatite be wrapped in metal surface, this method can better be controlled its crystallinity and porosity; Since Graphene is found, because it has very high intensity (130 GPa) and high stretch modulus (1.01 TPa), quality is light, large (2600 m of specific area
2/ g), and there is good biocompatibility and less cytotoxicity, be considered to the ideal chose of composite material wild phase; Amino acid is as good bioactivator, also can to hydroxyapatite material, carry out effective structure regulating and modification under certain condition, adopt at present graphene oxide as structure regulating agent hydro thermal method, to prepare graphene/hydroxyapatite nano composite as presoma, amino acid and have no report.
Summary of the invention
The object of the invention is to develop a kind of with low cost, preparation and simply there is good surface topography, large specific area, the in-situ synthetic method of evengranular bar-shaped graphene/hydroxyapatite nano composite, for application low-cost, high-performance Hydroxyapatite Nanocomposites provides technical support.
Realizing the technical solution that the object of the invention adopts is: a kind of graphene/hydroxyapatite nano composite, it is characterized in that obtained nano composite material is composited by Graphene and hydroxyapatite, both are uniformly distributed and effective compound dispersion in composite material, and preparation method's step is:
1) graphene oxide is scattered in to deionized water for ultrasonic 3-5 hour and obtains graphene oxide dispersion liquid, in dispersion liquid, graphene oxide concentration is 1 ~ 10 mg/mL; In above-mentioned graphene oxide dispersion liquid, add anhydrous calcium chloride, stir, obtain mixed solution A, Ca in mixed solution A
2+ion concentration is 1.5 mol/L;
2) SPA is dissolved in deionized water, obtains the phosphoric acid solution of 1 mol/L.In above-mentioned dilute phosphoric acid solution, add amino acid, stir, obtain mixed solution B, in mixed solution B, amino acid whose concentration is 3 mol/L;
3) under stirring condition, with dilute hydrochloric acid solution, regulate the pH of mixed solution B to 7.5-8.5, stir;
4) mixed solution A is dropwise joined in mixed solution B, after stirring, mixed liquor is proceeded in polytetrafluoroethylene reactor inner bag, after the reactor inner bag that reaction mass is housed is placed in to stainless steel outer sleeve, sealing is incubated 12-24 hour and carries out hydrothermal treatment consists at 160-200 ℃, then allows reactor naturally cool to room temperature, unload after still, centrifugal, by absolute ethyl alcohol and deionized water cyclic washing product, filter vacuumize..
Compared with prior art, tool has the following advantages in the present invention:
A) graphene/hydroxyapatite nano composite making has good surface topography, large specific area, size uniformly, has the performances such as good biocompatibility and excellent mechanics and tribology concurrently;
B) the process route simple possible adopting, with low cost, raw material is easy to get.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscope diagram of graphene/hydroxyapatite nano composite;
Fig. 2 is the transmission electron microscope figure of graphene/hydroxyapatite nano composite;
Fig. 3 is graphene/hydroxyapatite nano composite X-ray diffractogram.
Embodiment
Below in conjunction with specific embodiment, further illustrate content of the present invention, but these embodiment do not limit the scope of the invention.
embodiment 1
20 mg graphene oxides are scattered in to 20 ml deionized water for ultrasonic and within 3 hours, obtain graphene oxide solution, in the graphene oxide solution after ultrasonic, add 3.33 g anhydrous calcium chlorides, stir 10 minutes, obtain mixed solution A; Measure 1.4 ml 98% concentrated phosphoric acids and be dissolved in 20 ml deionized waters and form dilute phosphoric acid solution, and configure the dilute hydrochloric acid solution of 3 mol/L; Take 4.5 g glycine and join in dilute phosphoric acid solution, stir 10 minutes, obtain mixed solution B; With dilute hydrochloric acid solution, regulate the pH=7.5 of mixed solution B, continue to stir 10 minutes; Mixed solution A is dropwise joined in mixed solution B, stir 15 minutes, then mixed solution is transferred in 100 ml reactor inner bags, is placed in stainless steel outer sleeve, sealing, at 160 ℃, be incubated 24 hours and carry out hydrothermal treatment consists, then allow reactor naturally cool to room temperature, unload after still, centrifugal, by absolute ethyl alcohol and deionized water cyclic washing product, filter vacuumize.
embodiment 2
50 mg graphene oxides are scattered in to 20 ml deionized water for ultrasonic and within 5 hours, obtain graphene oxide solution, in the graphene oxide solution after ultrasonic, add 3.33 g anhydrous calcium chlorides, stir 10 minutes, obtain mixed solution A; Measure 1.4 ml 98% concentrated phosphoric acids and be dissolved in 20 ml deionized waters and form dilute phosphoric acid solution, and configure the dilute hydrochloric acid solution of 3 mol/L; Take 4.5 g glycine and join in dilute phosphoric acid solution, stir 10 minutes, obtain mixed solution B; With dilute hydrochloric acid solution, regulate the pH=8 of mixed solution B, continue to stir 10 minutes; Mixed solution A is dropwise joined in mixed solution B, stir 15 minutes, then mixed solution is transferred in 100 ml reactor inner bags, is placed in stainless steel outer sleeve, sealing, at 180 ℃, be incubated 18 hours and carry out hydrothermal treatment consists, then allow reactor naturally cool to room temperature, unload after still, centrifugal, by absolute ethyl alcohol and deionized water cyclic washing product, filter vacuumize.
Fig. 1 is the scanning electron microscope diagram of the prepared graphene/hydroxyapatite nano composite of this embodiment, from figure, we can find out that a large amount of rod-like nano hydroxyapatite depositions, on graphene sheet layer, obtain the graphene/hydroxyapatite nano composite of even composite compact; Fig. 2 is the low multiple transmission electron microscope figure of the prepared graphene/hydroxyapatite nano composite of this embodiment, in figure, visible bar-shaped nanometer hydroxyapatite is covered by the graphene sheet layer of tulle shape, nanometer hydroxyapatite is dispersed on Graphene more uniformly, and the sharpness of border of graphene sheet layer is visible; Fig. 3 is the X-ray diffracting spectrum for the prepared graphene/hydroxyapatite nano composite of this embodiment, diffraction maximums all in figure are all coincide with the thing phase (JCPDS9-432) of hydroxyapatite, but due to the addition of graphene oxide seldom, for the diffraction maximum of hydroxyapatite, the diffraction peak intensity of the Graphene generating is very weak, therefore cannot observe in the drawings.
embodiment 3
100 mg graphene oxides are scattered in to 20 ml deionized water for ultrasonic and within 4 hours, obtain graphene oxide solution, in the graphene oxide solution after ultrasonic, add 3.33 g anhydrous calcium chlorides, stir 10 minutes, obtain mixed solution A; Measure 1.4 ml 98% concentrated phosphoric acids and be dissolved in 20 ml deionized waters and form dilute phosphoric acid solution, and configure the dilute hydrochloric acid solution of 3 mol/L; Take 4.5 g glycine and join in dilute phosphoric acid solution, stir 10 minutes, obtain mixed solution B; With dilute hydrochloric acid solution, regulate the pH=8.5 of mixed solution B, continue to stir 10 minutes; Mixed solution A is dropwise joined in mixed solution B, stir 15 minutes, then mixed solution is transferred in 100 ml reactor inner bags, is placed in stainless steel outer sleeve, sealing, at 200 ℃, be incubated 12 hours and carry out hydrothermal treatment consists, then allow reactor naturally cool to room temperature, unload after still, centrifugal, by absolute ethyl alcohol and deionized water cyclic washing product, filter vacuumize.
embodiment 4
50 mg graphene oxides are scattered in to 20 ml deionized water for ultrasonic and within 3-5 hour, obtain graphene oxide solution, in the graphene oxide solution after ultrasonic, add 3.33 g anhydrous calcium chlorides, stir 10 minutes, obtain solution A; Measure 1.4 ml 98% concentrated phosphoric acids and be dissolved in 20 ml deionized waters and form dilute phosphoric acid solution, and configure the dilute hydrochloric acid solution of 3 mol/L; Take 10.96 g 1Bs and join in dilute phosphoric acid solution, stir 10 minutes, obtain mixed solution B; With dilute hydrochloric acid solution, regulate the pH=8 of mixed solution B, continue to stir 10 minutes; Mixed solution A is dropwise joined in mixed solution B, stir 15 minutes, then mixed solution is transferred in 100 ml reactor inner bags, is placed in stainless steel outer sleeve, sealing, at 180 ℃, be incubated 18 hours and carry out hydrothermal treatment consists, then allow reactor naturally cool to room temperature, unload after still, centrifugal, by absolute ethyl alcohol and deionized water cyclic washing product, filter vacuumize.
embodiment 5
100 mg graphene oxides are scattered in to 20 ml deionized water for ultrasonic and within 3-5 hour, obtain graphene oxide solution, in the graphene oxide solution after ultrasonic, add 3.33 g anhydrous calcium chlorides, stir 10 minutes, obtain solution A; Measure 1.4 ml 98% concentrated phosphoric acids and be dissolved in 20 ml deionized waters and form dilute phosphoric acid solution, and configure the dilute hydrochloric acid solution of 3 mol/L; Take 10.96 g 1Bs and join in dilute phosphoric acid solution, stir 10 minutes, obtain mixed solution B; With the dilute hydrochloric acid solution of 3 mol/L, regulate the pH=8 of mixed solution B, continue to stir 10 minutes; Mixed solution A is dropwise joined in mixed solution B, stir 15 minutes, then mixed solution is transferred in 100 ml reactor inner bags, is placed in stainless steel outer sleeve, sealing, at 180 ℃, be incubated 18 hours and carry out hydrothermal treatment consists, then allow reactor naturally cool to room temperature, unload after still, centrifugal, by absolute ethyl alcohol and deionized water cyclic washing product, filter vacuumize.
embodiment 6
200 mg graphene oxides are scattered in to 20 ml deionized water for ultrasonic and within 3-5 hour, obtain graphene oxide solution, in the graphene oxide solution after ultrasonic, add 3.33 g anhydrous calcium chlorides, stir 10 minutes, obtain solution A; Measure 1.4 ml 98% concentrated phosphoric acids and be dissolved in 20 ml deionized waters and form dilute phosphoric acid solution, and configure the dilute hydrochloric acid solution of 3 mol/L; Take 10.96 g 1Bs and join in dilute phosphoric acid solution, stir 10 minutes, obtain mixed solution B; With dilute hydrochloric acid solution, regulate the pH=8 of mixed solution B, continue to stir 10 minutes; Mixed solution A is dropwise joined in mixed solution B, stir 15 minutes, then mixed solution is transferred in 100 ml reactor inner bags, is placed in stainless steel outer sleeve, sealing, at 200 ℃, be incubated 12 hours and carry out hydrothermal treatment consists, then allow reactor naturally cool to room temperature, unload after still, centrifugal, by absolute ethyl alcohol and deionized water cyclic washing product, filter vacuumize.
embodiment 7
100 mg graphene oxides are scattered in to 20 ml deionized water for ultrasonic and within 3-5 hour, obtain graphene oxide solution, in the graphene oxide solution after ultrasonic, add 3.33 g anhydrous calcium chlorides, stir 10 minutes, obtain solution A; Measure 1.4 ml 98% concentrated phosphoric acids and be dissolved in 20 ml deionized waters and form dilute phosphoric acid solution, and configure the dilute hydrochloric acid solution of 3 mol/L; Take 10.45 g L-arginines and join in dilute phosphoric acid solution, stir 10 minutes, obtain mixed solution B; With dilute hydrochloric acid solution, regulate the pH=8 of mixed solution B, continue to stir 10 minutes; Mixed solution A is dropwise joined in mixed solution B, stir 15 minutes, then mixed solution is transferred in 100 ml reactor inner bags, is placed in stainless steel outer sleeve, sealing, at 180 ℃, be incubated 18 hours and carry out hydrothermal treatment consists, then allow reactor naturally cool to room temperature, unload after still, centrifugal, by absolute ethyl alcohol and deionized water cyclic washing product, filter vacuumize.
embodiment 8
200 mg graphene oxides are scattered in to 20 ml deionized water for ultrasonic and within 3-5 hour, obtain graphene oxide solution, in the graphene oxide solution after ultrasonic, add 3.33 g anhydrous calcium chlorides, stir 10 minutes, obtain solution A; Measure 1.4 ml 98% concentrated phosphoric acids and be dissolved in 20 ml deionized waters and form dilute phosphoric acid solution, and configure the dilute hydrochloric acid solution of 3 mol/L; Take 10.45 g L-arginines and join in dilute phosphoric acid solution, stir 10 minutes, obtain mixed solution B; With the dilute hydrochloric acid solution of 3 mol/L, regulate the pH=8 of mixed solution B, continue to stir 10 minutes; Mixed solution A is dropwise joined in mixed solution B, stir 15 minutes, then mixed solution is transferred in 100 ml reactor inner bags, is placed in stainless steel outer sleeve, sealing, at 200 ℃, be incubated 12 hours and carry out hydrothermal treatment consists, then allow reactor naturally cool to room temperature, unload after still, centrifugal, by absolute ethyl alcohol and deionized water cyclic washing product, filter vacuumize.
Claims (1)
1. the preparation method of a graphene/hydroxyapatite nano composite, composite material is comprised of hydroxyapatite and Graphene, hydroxyapatite has nanorod structure, pattern rule, size uniform, diameter is between 15-30nm, and length is between 50-200nm, hydroxyapatite material is uniformly distributed in graphene sheet layer structure, it is characterized in that: comprise the following steps:
1) graphene oxide is scattered in to deionized water for ultrasonic 3-5 hour and obtains graphene oxide dispersion liquid, in dispersion liquid, graphene oxide concentration is 1 ~ 10 mg/mL; In above-mentioned graphene oxide dispersion liquid, add anhydrous calcium chloride, stir, obtain mixed solution A, Ca in mixed solution A
2+ion concentration is 1.5 mol/L;
2) SPA is dissolved in deionized water, obtains the phosphoric acid solution of 1 mol/L; In above-mentioned phosphoric acid solution, add amino acid, stir, obtain mixed solution B, in mixed solution B, amino acid whose concentration is 3 mol/L;
3) under stirring condition, with dilute hydrochloric acid solution, regulate the pH of mixed solution B to 7.5-8.5, stir;
4) mixed solution A is dropwise joined in mixed solution B, after stirring, mixed liquor is proceeded in polytetrafluoroethylene reactor inner bag, after the reactor inner bag that reaction mass is housed is placed in to stainless steel outer sleeve, sealing is incubated 12-24 hour and carries out hydrothermal treatment consists at 160-200 ℃, then allows reactor naturally cool to room temperature, unload after still, centrifugal, by absolute ethyl alcohol and deionized water cyclic washing product, filter vacuumize.
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| CN105126160A (en) * | 2015-07-21 | 2015-12-09 | 常州大学 | Hydroxyapatite scaffold material with graphene-modified surface and preparation method of hydroxyapatite scaffold material |
| ITUB20152595A1 (en) * | 2015-07-29 | 2017-01-29 | Jointherapeutics S R L | BIOCOMPOSITOR OF BIOMINERALIZED GRAPHENE OXIDE AND ITS USE IN BONE FABRIC ENGINEERING |
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| CN107462617B (en) * | 2017-06-30 | 2020-02-21 | 浙江理工大学 | Uricase biosensor based on calcium hydrophosphate-reduced graphene/nano gold particles and preparation method thereof |
| CN107440913B (en) * | 2017-07-27 | 2020-02-14 | 武汉大学 | Application of colored hydroxyapatite in dental bleaching agent effect detection |
| CN108421085B (en) * | 2018-05-18 | 2022-06-03 | 青岛大学附属医院 | Graphene and hydroxyapatite composite bionic bone material and preparation method thereof |
| CN109437138A (en) * | 2018-10-31 | 2019-03-08 | 昆明理工大学 | A kind of preparation method of Dental Erosion modifted-nano-hydroxyapatite composite material |
| CN109498467A (en) * | 2018-10-31 | 2019-03-22 | 昆明理工大学 | A kind of preparation method of Dental Erosion modifted-nano-hydroxyapatite composite material |
| CN114889175B (en) * | 2022-05-25 | 2023-07-18 | 福州大学 | Preparation and application of modified graphene oxide/hydroxyapatite nanowire composite paper |
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