CN102569749A - 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 material and preparation method thereof, be meant the method for hydrothermal preparation Graphene/hydroxyapatite nano composite material that a kind of amino acid is auxiliary especially, 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 dried bone tissue; Apatite in people's natural bone mainly is distributed in the collagenous network along an orientation with the form of nanoscale acicular crystal, thereby has improved the implantation effect of compound bone material; Because it has good biologically active and biocompatibility, stable chemical characteristic and various structure, makes it in fields such as artificial bone, medicament slow release, gas sensing device, catalyst, photoelectric material, Chemical Engineering and environmental engineerings achievement arranged more.
Up to the present; People have developed the multiple method for preparing hydroxyapatite; Like 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 also is not quite similar, and bar-shaped, whisker shape, sheet-shaped hydroxyapatite can be applicable to biomedical functional material and polymer matrix composite field; The 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 influence its performance, and therefore, it is significant to the influence of product pattern and draw ratio to explore preparation method and corresponding synthesis condition.
The literature survey discovery, as
ElliotDeng [
Nature, 1967,214,904] and said, the viscosity of solution descends under the hydrothermal condition, causes the aggravation of ion migration, and nucleus growth speed is higher than other system, and this is high for preparation degree of crystallinity, the different product of crystal structure has been created condition; Therefore, hydro thermal method has significant advantage in synthesizing of nanometer hydroxyapatite, and the product degree of crystallinity of acquisition is high, does not generally need follow-up high-temperature process, and it is few to reunite, and purity is high, form, controllable size; Lin [
Mater. Res. Soc. Sym.Proc., 1994,346,237] and with Ca (OH)
2Na
3PO
412H
2O is a predecessor, in agitated reactor, has synthesized the hydroxyapatite nano-powder that particle diameter is about 50 nm, 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
4Be Ca source and P source, adopt 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, through changing the AB type podolite that heat preserving mode has prepared needle-like, sheet, hexagonal prism shape and platelet-like; The two is respectively to explore the control influence to the hydroxyapatite structure pattern of different pH and heat-treat condition; But its concrete mechanism is still waiting further research, and the pattern of product and particle size distribution receive the initial configuration of raw material and even mix the influence of degree very big; In order to overcome forefathers' shortcoming, Yang Qing etc. [
Beijing University of Chemical Technology's journal, 2010,37 (6); 93 97] attempting adopting chemical precipitation method to combine the process route of hydro thermal method to prepare hydroxyapatite, the key of implementing this process route is that Y type micro passage reaction evenly mixes the microcosmic of reaction mass, and the corynebacterium hydroxyapatite particle diameter that makes reaches 85 nm; The structure favorable reproducibility, but its equipment requirements is high, complex process; Chemical b ` strong between high specific area and particle can cause the nucleus coalescence, is unfavorable for uniform particlesization.
For the structure and morphology that can improve hydroxyapatite simultaneously prepares difficulty with reducing; Reach a kind of situation of doulbe-sides' victory; Many researchers have turned one's attention in the modification and compound research of hydroxyapatite, adopt the mode that adds modifier and composite interstitial substance to prepare the hydroxyapatite nano composite material of modification; As Damia etc.
Mater.Lett., 2006,60; 3,192 3196 ］ utilize silane coupling A-1130 and A-187 to the hydroxyapatite surface modification; Utilize silane group and intermetallic effect then, make hydroxyapatite be wrapped in the metal surface, this method can better be controlled its crystallinity and porosity; Since Graphene comes to light, because it has very high intensity (130 GPa) and high stretch modulus (1.01 TPa), light weight, big (2600 m of specific area
2/ g), and have excellent biological compatibility and less cytotoxicity, the ideal that is considered to the composite material wild phase is selected; Amino acid is as good bioactivator; Also can carry out effective structure regulating and modification to hydroxyapatite material under certain condition, adopt graphene oxide not appear in the newspapers as structure regulating agent Hydrothermal Preparation Graphene/hydroxyapatite nano composite material at present as presoma, amino acid.
Summary of the invention
The objective of the invention is to develop a kind of with low cost, preparation and simply have surface topography, big specific area, an in-situ synthetic method of evengranular bar-shaped Graphene/hydroxyapatite nano composite material preferably, for application low-cost, high-performance hydroxyapatite nano composite material provides technical support.
Realize that the technical solution that the object of the invention adopted is: a kind of Graphene/hydroxyapatite nano composite material; It is characterized in that the nano composite material that is obtained is composited by Graphene and hydroxyapatite; Both evenly distribute and effective compound dispersion in composite material, and preparation method's step is:
1) graphene oxide is scattered in deionized water for ultrasonic 3-5 hour and obtains the graphene oxide dispersion liquid, graphene oxide concentration is 1 ~ 10 mg/mL in the dispersion liquid; In above-mentioned graphene oxide dispersion liquid, add anhydrous calcium chloride, stir, obtain mixed solution A, Ca in the mixed solution A
2+Ion concentration is 1.5 mol/L;
2) SPA is dissolved in the 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, amino acid whose concentration is 3 mol/L among the mixed solution B;
3) pH that under stirring condition, regulates mixed solution B with dilute hydrochloric acid solution stirs to 7.5-8.5;
4) mixed solution A is dropwise joined among the mixed solution B, after stirring mixed liquor is changed in the polytetrafluoroethylene agitated reactor inner bag, after reaction mass will be housed the agitated reactor inner bag place stainless steel outer sleeve; Sealing is incubated 12-24 hour down at 160-200 ℃ and carries out hydrothermal treatment consists, lets agitated reactor naturally cool to room temperature then; After unloading still; Centrifugal, with absolute ethyl alcohol and deionized water cyclic washing product, filter vacuumize..
The present invention compared with prior art has following advantage:
A) Graphene that makes/hydroxyapatite nano composite material has surface topography preferably, big specific area, size uniformly, has excellent biological compatibility and performances such as excellent mechanics and tribology concurrently;
B) the process route simple possible that is adopted, with low cost, raw material is easy to get.
Description of drawings
Fig. 1 is the scanning electron microscope diagram of Graphene/hydroxyapatite nano composite material;
Fig. 2 is the transmission electron microscope figure of Graphene/hydroxyapatite nano composite material;
Fig. 3 is Graphene/hydroxyapatite nano composite material X-ray diffractogram.
Embodiment
To combine specific embodiment further to illustrate content of the present invention below, but these embodiment do not limit protection scope of the present invention.
Embodiment 1
20 mg graphene oxides are scattered in 20 ml deionized water for ultrasonic obtained graphene oxide solution in 3 hours, add 3.33 g anhydrous calcium chlorides in the graphene oxide solution after ultrasonic, stirred 10 minutes, obtain mixed solution A; Measure 1.4 ml, 98% concentrated phosphoric acid and be dissolved in the 20 ml deionized waters and form dilute phosphoric acid solution, and dispose the dilute hydrochloric acid solution of 3 mol/L; Take by weighing 4.5 g glycine and join in the dilute phosphoric acid solution, stirred 10 minutes, obtain mixed solution B; PH=7.5 with dilute hydrochloric acid solution adjusting mixed solution B continues to stir 10 minutes; Mixed solution A is dropwise joined among the mixed solution B, stirred 15 minutes, then mixed solution is transferred in the 100 ml agitated reactor inner bags; Place stainless steel outer sleeve, sealing is incubated 24 hours down at 160 ℃ and carries out hydrothermal treatment consists; Let agitated reactor naturally cool to room temperature then, unload still after, centrifugal; With absolute ethyl alcohol and deionized water cyclic washing product, filter vacuumize.
50 mg graphene oxides are scattered in 20 ml deionized water for ultrasonic obtained graphene oxide solution in 5 hours, add 3.33 g anhydrous calcium chlorides in the graphene oxide solution after ultrasonic, stirred 10 minutes, obtain mixed solution A; Measure 1.4 ml, 98% concentrated phosphoric acid and be dissolved in the 20 ml deionized waters and form dilute phosphoric acid solution, and dispose the dilute hydrochloric acid solution of 3 mol/L; Take by weighing 4.5 g glycine and join in the dilute phosphoric acid solution, stirred 10 minutes, obtain mixed solution B; PH=8 with dilute hydrochloric acid solution adjusting mixed solution B continues to stir 10 minutes; Mixed solution A is dropwise joined among the mixed solution B, stirred 15 minutes, then mixed solution is transferred in the 100 ml agitated reactor inner bags; Place stainless steel outer sleeve, sealing is incubated 18 hours down at 180 ℃ and carries out hydrothermal treatment consists; Let agitated reactor naturally cool to room temperature then, unload still after, centrifugal; With absolute ethyl alcohol and deionized water cyclic washing product, filter vacuumize.
The scanning electron microscope diagram of Graphene/hydroxyapatite nano composite material that Fig. 1 goes out for this embodiment is prepared; We can find out that a large amount of rod-like nano hydroxyapatites are deposited on the Graphene lamella from figure, obtain the Graphene/hydroxyapatite nano composite material of even composite compact; The low multiple transmission electron microscope figure of Graphene/hydroxyapatite nano composite material that Fig. 2 goes out for this embodiment is prepared; Visible bar-shaped nanometer hydroxyapatite is covered by the Graphene lamella of tulle shape among the figure; Nanometer hydroxyapatite is dispersed on the Graphene more uniformly, and the sharpness of border of Graphene lamella is visible; The X-ray diffracting spectrum of Graphene/hydroxyapatite nano composite material that Fig. 3 goes out for this embodiment is prepared; Among the figure all diffraction maximum all with the thing of hydroxyapatite mutually (JCPDS9-432) coincide; But because the addition of graphene oxide seldom; For the diffraction maximum of hydroxyapatite, the diffraction peak intensity of the Graphene that is generated very a little less than, therefore can't observe in the drawings.
Embodiment 3
100 mg graphene oxides are scattered in 20 ml deionized water for ultrasonic obtained graphene oxide solution in 4 hours, add 3.33 g anhydrous calcium chlorides in the graphene oxide solution after ultrasonic, stirred 10 minutes, obtain mixed solution A; Measure 1.4 ml, 98% concentrated phosphoric acid and be dissolved in the 20 ml deionized waters and form dilute phosphoric acid solution, and dispose the dilute hydrochloric acid solution of 3 mol/L; Take by weighing 4.5 g glycine and join in the dilute phosphoric acid solution, stirred 10 minutes, obtain mixed solution B; PH=8.5 with dilute hydrochloric acid solution adjusting mixed solution B continues to stir 10 minutes; Mixed solution A is dropwise joined among the mixed solution B, stirred 15 minutes, then mixed solution is transferred in the 100 ml agitated reactor inner bags; Place stainless steel outer sleeve, sealing is incubated 12 hours down at 200 ℃ and carries out hydrothermal treatment consists; Let agitated reactor naturally cool to room temperature then, unload still after, centrifugal; With absolute ethyl alcohol and deionized water cyclic washing product, filter vacuumize.
Embodiment 4
50 mg graphene oxides are scattered in 20 ml deionized water for ultrasonic obtained graphene oxide solution in 3-5 hour, add 3.33 g anhydrous calcium chlorides in the graphene oxide solution after ultrasonic, stirred 10 minutes, obtain solution A; Measure 1.4 ml, 98% concentrated phosphoric acid and be dissolved in the 20 ml deionized waters and form dilute phosphoric acid solution, and dispose the dilute hydrochloric acid solution of 3 mol/L; Take by weighing 10.96 g L-lysines and join in the dilute phosphoric acid solution, stirred 10 minutes, obtain mixed solution B; PH=8 with dilute hydrochloric acid solution adjusting mixed solution B continues to stir 10 minutes; Mixed solution A is dropwise joined among the mixed solution B, stirred 15 minutes, then mixed solution is transferred in the 100 ml agitated reactor inner bags; Place stainless steel outer sleeve, sealing is incubated 18 hours down at 180 ℃ and carries out hydrothermal treatment consists; Let agitated reactor naturally cool to room temperature then, unload still after, centrifugal; With absolute ethyl alcohol and deionized water cyclic washing product, filter vacuumize.
Embodiment 5
100 mg graphene oxides are scattered in 20 ml deionized water for ultrasonic obtained graphene oxide solution in 3-5 hour, add 3.33 g anhydrous calcium chlorides in the graphene oxide solution after ultrasonic, stirred 10 minutes, obtain solution A; Measure 1.4 ml, 98% concentrated phosphoric acid and be dissolved in the 20 ml deionized waters and form dilute phosphoric acid solution, and dispose the dilute hydrochloric acid solution of 3 mol/L; Take by weighing 10.96 g L-lysines and join in the dilute phosphoric acid solution, stirred 10 minutes, obtain mixed solution B; Regulate the pH=8 of mixed solution B with the dilute hydrochloric acid solution of 3 mol/L, continue to stir 10 minutes; Mixed solution A is dropwise joined among the mixed solution B, stirred 15 minutes, then mixed solution is transferred in the 100 ml agitated reactor inner bags; Place stainless steel outer sleeve, sealing is incubated 18 hours down at 180 ℃ and carries out hydrothermal treatment consists; Let agitated reactor naturally cool to room temperature then, unload still after, centrifugal; With absolute ethyl alcohol and deionized water cyclic washing product, filter vacuumize.
Embodiment 6
200 mg graphene oxides are scattered in 20 ml deionized water for ultrasonic obtained graphene oxide solution in 3-5 hour, add 3.33 g anhydrous calcium chlorides in the graphene oxide solution after ultrasonic, stirred 10 minutes, obtain solution A; Measure 1.4 ml, 98% concentrated phosphoric acid and be dissolved in the 20 ml deionized waters and form dilute phosphoric acid solution, and dispose the dilute hydrochloric acid solution of 3 mol/L; Take by weighing 10.96 g L-lysines and join in the dilute phosphoric acid solution, stirred 10 minutes, obtain mixed solution B; PH=8 with dilute hydrochloric acid solution adjusting mixed solution B continues to stir 10 minutes; Mixed solution A is dropwise joined among the mixed solution B, stirred 15 minutes, then mixed solution is transferred in the 100 ml agitated reactor inner bags; Place stainless steel outer sleeve, sealing is incubated 12 hours down at 200 ℃ and carries out hydrothermal treatment consists; Let agitated reactor naturally cool to room temperature then, unload still after, centrifugal; With absolute ethyl alcohol and deionized water cyclic washing product, filter vacuumize.
Embodiment 7
100 mg graphene oxides are scattered in 20 ml deionized water for ultrasonic obtained graphene oxide solution in 3-5 hour, add 3.33 g anhydrous calcium chlorides in the graphene oxide solution after ultrasonic, stirred 10 minutes, obtain solution A; Measure 1.4 ml, 98% concentrated phosphoric acid and be dissolved in the 20 ml deionized waters and form dilute phosphoric acid solution, and dispose the dilute hydrochloric acid solution of 3 mol/L; Take by weighing 10.45 g L-arginine and join in the dilute phosphoric acid solution, stirred 10 minutes, obtain mixed solution B; PH=8 with dilute hydrochloric acid solution adjusting mixed solution B continues to stir 10 minutes; Mixed solution A is dropwise joined among the mixed solution B, stirred 15 minutes, then mixed solution is transferred in the 100 ml agitated reactor inner bags; Place stainless steel outer sleeve, sealing is incubated 18 hours down at 180 ℃ and carries out hydrothermal treatment consists; Let agitated reactor naturally cool to room temperature then, unload still after, centrifugal; With absolute ethyl alcohol and deionized water cyclic washing product, filter vacuumize.
Embodiment 8
200 mg graphene oxides are scattered in 20 ml deionized water for ultrasonic obtained graphene oxide solution in 3-5 hour, add 3.33 g anhydrous calcium chlorides in the graphene oxide solution after ultrasonic, stirred 10 minutes, obtain solution A; Measure 1.4 ml, 98% concentrated phosphoric acid and be dissolved in the 20 ml deionized waters and form dilute phosphoric acid solution, and dispose the dilute hydrochloric acid solution of 3 mol/L; Take by weighing 10.45 g L-arginine and join in the dilute phosphoric acid solution, stirred 10 minutes, obtain mixed solution B; Regulate the pH=8 of mixed solution B with the dilute hydrochloric acid solution of 3 mol/L, continue to stir 10 minutes; Mixed solution A is dropwise joined among the mixed solution B, stirred 15 minutes, then mixed solution is transferred in the 100 ml agitated reactor inner bags; Place stainless steel outer sleeve, sealing is incubated 12 hours down at 200 ℃ and carries out hydrothermal treatment consists; Let agitated reactor naturally cool to room temperature then, unload still after, centrifugal; With absolute ethyl alcohol and deionized water cyclic washing product, filter vacuumize.
Claims (2)
1. Graphene/hydroxyapatite nano composite material; It is characterized in that: composite material is made up of hydroxyapatite and Graphene, and hydroxyapatite has nanorod structure, the pattern rule; Size is even; Diameter is between 15-30nm, and length is between 50-200nm, and hydroxyapatite material evenly distributes on the Graphene lamella structure.
2. the preparation method of a kind of Graphene as claimed in claim 1/hydroxyapatite nano composite material is characterized in that: may further comprise the steps:
1) graphene oxide is scattered in deionized water for ultrasonic 3-5 hour and obtains the graphene oxide dispersion liquid, graphene oxide concentration is 1 ~ 10 mg/mL in the dispersion liquid; In above-mentioned graphene oxide dispersion liquid, add anhydrous calcium chloride, stir, obtain mixed solution A, Ca in the mixed solution A
2+Ion concentration is 1.5 mol/L;
2) SPA is dissolved in the 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, amino acid whose concentration is 3 mol/L among the mixed solution B;
3) pH that under stirring condition, regulates mixed solution B with dilute hydrochloric acid solution stirs to 7.5-8.5;
4) mixed solution A is dropwise joined among the mixed solution B, after stirring mixed liquor is changed in the polytetrafluoroethylene agitated reactor inner bag, after reaction mass will be housed the agitated reactor inner bag place stainless steel outer sleeve; Sealing is incubated 12-24 hour down at 160-200 ℃ and carries out hydrothermal treatment consists, lets agitated reactor naturally cool to room temperature then; After unloading still; Centrifugal, with absolute ethyl alcohol and deionized water cyclic washing product, filter vacuumize.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102757218A (en) * | 2012-07-31 | 2012-10-31 | 山东大学 | Graphene/dual-phase calcium phosphate composite material and preparation method thereof |
| CN103420364A (en) * | 2013-07-13 | 2013-12-04 | 西南交通大学 | Preparation method of grapheme/hydroxyapatite composite material |
| CN103656752A (en) * | 2012-09-25 | 2014-03-26 | 中南大学 | Method for strengthening and toughening biological ceramic material by use of graphene and preparing artificial bone prepared from material |
| CN103751850A (en) * | 2013-12-23 | 2014-04-30 | 西南交通大学 | Three-dimensional graphene/hydroxyapatite hydrogel material |
| CN103845757A (en) * | 2013-12-13 | 2014-06-11 | 天津大学 | Artificial articular cartilage material and preparation method thereof |
| CN104117367A (en) * | 2014-08-12 | 2014-10-29 | 福州大学 | BiOBr/RGO composite aerogel, preparation method and application of BiOBr/RGO composite aerogel |
| 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 |
| CN107254076A (en) * | 2017-06-27 | 2017-10-17 | 过春明 | A kind of composite reinforced rubber and preparation method thereof |
| CN107440913A (en) * | 2017-07-27 | 2017-12-08 | 武汉大学 | A kind of preparation method of coloured hydroxyapatite available for the detection of dentistry bleaching agent effectiveness |
| CN107462617A (en) * | 2017-06-30 | 2017-12-12 | 浙江理工大学 | A kind of Uricase biosensor based on calcium monohydrogen phosphate reduced graphene/nanogold particle and preparation method thereof |
| CN107847640A (en) * | 2015-07-29 | 2018-03-27 | 卓英医疗有限责任公司 | The Biocomposite material of the graphene oxide of biomineralization and its purposes for bone tissue engineer |
| CN108421085A (en) * | 2018-05-18 | 2018-08-21 | 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 |
| CN114889175A (en) * | 2022-05-25 | 2022-08-12 | 福州大学 | Preparation and application of modified graphene oxide/hydroxyapatite nanowire composite paper |
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| CN103656752A (en) * | 2012-09-25 | 2014-03-26 | 中南大学 | Method for strengthening and toughening biological ceramic material by use of graphene and preparing artificial bone prepared from material |
| CN103420364A (en) * | 2013-07-13 | 2013-12-04 | 西南交通大学 | Preparation method of grapheme/hydroxyapatite composite material |
| CN103420364B (en) * | 2013-07-13 | 2016-02-03 | 西南交通大学 | A kind of preparation method of grapheme/hydroxyapatcomposite composite material |
| CN103845757A (en) * | 2013-12-13 | 2014-06-11 | 天津大学 | Artificial articular cartilage material and preparation method thereof |
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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 |
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| CN107254076A (en) * | 2017-06-27 | 2017-10-17 | 过春明 | A kind of composite reinforced rubber and preparation method thereof |
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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 |
| CN107440913A (en) * | 2017-07-27 | 2017-12-08 | 武汉大学 | A kind of preparation method of coloured hydroxyapatite available for the detection of dentistry bleaching agent effectiveness |
| CN107440913B (en) * | 2017-07-27 | 2020-02-14 | 武汉大学 | Application of colored hydroxyapatite in dental bleaching agent effect detection |
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| 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 |
| CN114889175A (en) * | 2022-05-25 | 2022-08-12 | 福州大学 | Preparation and application of modified graphene oxide/hydroxyapatite nanowire composite paper |
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