CN108553684A - A kind of composite aerogel microballoon and preparation method thereof - Google Patents
A kind of composite aerogel microballoon and preparation method thereof Download PDFInfo
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Abstract
A kind of composite aerogel microballoon and preparation method thereof, removes the graphite oxide ultrasound of preparation to obtain graphene oxide solution, adds Ca first2+、PO4 3‑And Zn2+Solution, Ca2+With PO4 3‑Molar ratio 1.17~2.17, hydroxyapatite and graphene oxide mass ratio are 1:0.1~1:10, add ammonium hydroxide, stirring form composite dispersion liquid, finally by spraying, cooling bath receive, sieving, freeze-drying and obtain composite aerogel microballoon.This method non-environmental-pollution, cost of material is low, and production efficiency is high；The hydroxyapatite of preparation/graphite oxide aerogel microballoon pattern rule, size is adjustable, with porous network structure, light weight, density are small, porosity is high, large specific surface area, with excellent biocompatibility, antibiotic property, cell Proliferation is can effectively promote, it can be directly as biologic applications materials'use.
Description
Technical field
The present invention relates to a kind of composite aerogel microballoons and preparation method thereof, belong to nanocomposite and biomaterial skill
Art field.
Background technology
Graphene is a kind of New Two Dimensional material of carbon atom regular arrangement form in a manner of cellular.With superior power
Performance, electric property, optical property, thermal property are learned, therefore receives the extensive concern of each field personage.By two-dimensional graphite
Alkene is configured to three-dimensional graphene macroscopic material, under conditions of ensureing that the excellent properties of graphene are not destroyed, makes graphite
Alkene can be really applied in industrial production, an important method and approach with practical use.Graphene oxide (GO)
It is the high oxidation form of chemical modification graphene, there is carboxylic acid, a large amount of oxygen-containing group such as epoxides and hydroxyl in plane
Group, also includes the Free Surface pi-electron in the unmodified region from graphene.Therefore, GO is a kind of amphiphilic sheet molecule, can be used
Make surfactant with the hydrophobic molecule [ACS Nano, 5 (2011), pp.8019-8025] in stablizing solution.The oxygen of reduction
Graphite alkene (rGO) [Nano Lett., 9 (2009), pp.1593-1597] is with hydrazine or other reducing agents or by heat, change
It learns and processing GO acquisitions under the reducing conditions such as UV.Functionalized graphite's alkene is modified by polymer, small molecule, nano particle etc.
Any graphene family member, to enhance or change the performance needed for specific application.The unique structure of graphene, makes it have out
The machinery of color, physical chemistry, calorifics, electronics, optics and biomedical properties.
The graphene aerogel represented as three-dimensional grapheme macroscopic material can not only retain the huge specific surface of graphene
Product and excellent properties, moreover it is possible to while there is the unique porosity of aeroge, ultralow density, the property such as low-k
Can, therefore, graphene aerogel cause researcher greatly pay attention to and start to be widely applied to energy conversion with
Storage, High-performance catalyst carrier, environmental protection and purification, biomaterial and biotechnology field.
Hydroxyapatite (Hydroxyapatite, HA) is a kind of typical biomaterial, is body bone tissue and tooth
Main inorganic composition, have good biocompatibility and osteogenic activity, be in Bone Defect Repari replacement field generally acknowledge it is good
Bone replaces biomaterial.The research of nano-HAP is proceeded by since the later stage eighties, and people synthesize column and acicular nanometer
Grade HAP powders and crystallite, these nano-HAP powders not only provide excellent performance in terms of preparing HAP ceramics, but also in work(
Energy aspect shows some specific performances.But the brittleness of hydroxyapatite is larger, toughness is relatively low.Currently, improving hydroxy-apatite
The main method of stone mechanical property is that hydroxyapatite and other materials progress is compound, improves its mechanical property.
Aerogel microball has a series of superior properties compared to aerogel block body, such as：As catalyst carrier
Specific surface area with bigger can provide more active reaction centers；As packing material there is good fluidity to be easy to uniform
Dispersion, is not easy to cause stress concentration etc..Therefore it can largely improve the service efficiency of aeroge and widen aeroge
Application field.Aerogel microball common at present has SiO2Aerogel microball, carbon aerogels microballoon and macromolecule aerogel-like are micro-
Ball, it is micro- that 105195067 B of CN 106185908 A and CN is prepared for graphene aerogel with emulsion method and electrostatic spraying processes respectively
Ball.
Some researches show that graphene oxide/nano hydroxyapatite composite material has excellent with biological in-vivo tissue
Biocompatibility, preferable bone tissue binding ability and good bone cell proliferation.GO/HAP composite material surfaces contain
Oxygen functional group is conducive to interface and is combined and homogeneous scattering problem.Aerogel microball has higher porosity, is conducive to cell
Attachment and growth.Currently, the patent document of the aerogel microball compound about hydroxyapatite/graphene oxide and non-not yet
The report of patent document.Therefore by hydroxyapatite with graphene oxide is compound prepares HA/GO composite aerogel microballoons, simultaneously
With excellent biocompatibility, antibiotic property, cell Proliferation is can effectively promote, before there are very high biomedical applications
Scape.
Invention content
The object of the present invention is to provide a kind of composite aerogel microballoon and preparation method thereof, this method non-environmental-pollution is former
Expect at low cost, production efficiency height；The hydroxyapatite of preparation/graphite oxide aerogel microballoon pattern rule, size is adjustable, tool
Have porous network structure, light weight, density are small, porosity is high, large specific surface area, have excellent biocompatibility, antibiotic property,
Cell Proliferation is can effectively promote, it can be directly as biologic applications materials'use.
In order to achieve the above object, the technical solution adopted by the present invention is that：
A kind of composite aerogel microballoon, including mass ratio is 1:0.1~1:10 hydroxyapatite and graphene oxide, institute
Hydroxyapatite is stated by Ca (NO3)2·4H2O and (NH4)2HPO4It is constituted according to 1.17~2.17 molar ratio.
A kind of preparation method of composite aerogel microballoon, the dosage of each component is mass fraction in this method, including with
Lower step：
(1) preparation of graphite oxide
Natural graphite is prepared into graphite oxide through chemical oxidization method, wherein chemical oxidization method is Brodie oxidizing process,
Staudemaier oxidizing process, any one of Hummer methods or improved Hummer methods；
(2) preparation of graphene oxide aqueous dispersions
After evenly mixing by 100 parts of deionized water, 0.05-5 parts of graphite oxide, 20- is removed through 200-400W ultrasounds
60min is prepared into the graphene oxide aqueous dispersions of a concentration of 0.1-20mg/mL；
(3) preparation of hydroxyapatite/graphene oxide mixed dispersion liquid
A, by Ca (NO3)2·4H2O、(NH4)2HPO4With Zn (NO3)2·6H2O is as Ca2+、PO4 3-And Zn2+Presoma,
It is dissolved in the Ca (NO that 0.1~5mol/L is configured in distilled water respectively3)2·4H2(the NH of O solution, 0.1~5mol/L4)2HPO4It is molten
Zn (the NO of liquid and 0.1~5mol/L3)2·6H2O solution；
B, the Ca (NO are added in the graphene oxide dispersion of step (2)3)2·4H2O solution, 100~
It is stirred evenly under the speed of 1000rpm；
C, (the NH is added in the gains of step b4)2HPO4Solution so that Ca2+With PO4 3-Molar ratio keep
1.17~2.17, and the mass ratio of hydroxyapatite and graphene oxide is 1 in solution:0.1~1:10；It is added again in solution
Ammonium hydroxide so that pH >=11, and at 40 DEG C stirring 1~form uniform hydroxyapatite/graphene oxide composite diffusion afterwards for 24 hours
Liquid system；
(4) the composite diffusion liquid system obtained by step (3) is atomized by hydroxyapatite/graphene oxide as spray-on process
Drop microballoon, and the compound ice microballoon of hydroxyapatite/graphene oxide is formed in cooling bath receiving liquid, wherein spray-on process is
Press atomization, any one of ullrasonic spraying or electrostatic spray；
(5) the compound ice microballoon obtained by the screen filtration step (4) with 100~300 mesh will tail over the freeze-drying of ice microballoon
Hydroxyapatite/graphene oxide composite aerogel microballoon is obtained afterwards.
Further, moreover it is possible to Zn (NO be added in step (3) b3)2·6H2O solution, and then obtain the hydroxyl phosphorus of zinc doping
Lime stone/graphene oxide composite aerogel microballoon, wherein Ca2+With Zn2+Molar ratio be 1:1~100:1.
Further, moreover it is possible to the zinc be replaced with into the either element in silver, fluorine, magnesium, carbon, strontium, silicon, iron, titanium, and then obtained
Obtain corresponding doped hydroxyapatite/graphene oxide composite aerogel microballoon.
Further, the present invention also provides a kind of compound gas of hydroxyapatite/graphene oxide by obtained by step (5)
Gel micro-ball obtains hydroxyapatite/redox graphene composite aerogel microballoon by thermal reduction or chemical reduction method
Method,
The thermal reduction is：Under inert gas protection, using in Muffle furnace Program heating thermal reduction or microwave spoke
According to thermal reduction, wherein Muffle furnace Program heating thermal reduction method be to be warming up to 800 with the heating speed of 5-10 DEG C/min
DEG C, and 2-5h is kept at 800 DEG C, and microwave irradiation thermal reduction is to keep 1-10min under the power of 600-800W；
The chemical reduction method is hydroiodic acid reduction method or hydrazine steam reduction method：The hydroiodic acid reduction method is to use matter
Measure the hydriodic acid aqueous solution and hydroxyapatite/graphene oxide composite aerogel microballoon room temperature in closed environment of concentration 55%
React 12h；The hydrazine steam reduction is that hydrazine hydrate solution and composite aerogel microballoon are placed in closed environment, at 90 DEG C
Restore 8-12h.
Beneficial effects of the present invention：
1) present invention combines the method for spray-on process and freeze-drying to prepare the compound gas of hydroxyapatite/graphene oxide for the first time
Gel micro-ball, easy to operate, production efficiency is high, and production process is safe and reliable, solvent recoverable；
2) method by being atomized and cooling bath receives is easy to adjust jet velocity, voltage, spraying distance, receives bath temperature
The parameters such as degree, to which composite aerogel microballoon regular shape, the size of acquisition are uniform, multi-pore channel network with center divergent shape
Structure, and the size of microballoon can arbitrarily control in 10-1000 μ ms；In addition to this, the composite aerogel microballoon energy of preparation
Enough promote cell Proliferation, improves mechanical strength, and the surface active groups of microballoon increase, thus with higher chemistry and life
Object activity；
3) present invention is by further restoring hydroxyapatite/graphene oxide composite aerogel microballoon so that hydroxyl phosphorus
After lime stone and redox graphene are compound, there is superior antibiotic property and adsorptivity, can be used for nanocomposite and life
Object material technology；
4) it is micro- to obtain doped hydroxyapatite/graphene oxide composite aerogel also by adulterating other elements by the present invention
Ball is further changed the performance of hydroxyapatite/graphene oxide composite aerogel microballoon using the performance of doped chemical
It is good, so that it is more widely applied.
Description of the drawings
Fig. 1 is the scanning electron microscope (SEM) photograph of the hydroxyapatite aerogel microball of embodiment 1；
Fig. 2 is the scanning electron microscope (SEM) photograph of hydroxyapatite/graphene oxide composite aerogel microballoon of embodiment 2；
Fig. 3 is the scanning electron microscope (SEM) photograph for mixing zinc hydroxyapatite/graphene oxide composite aerogel microballoon of embodiment 3.
Specific implementation mode
The present invention is specifically described below by embodiment.
Embodiment 1
(1) hydroxyapatite is prepared：By the Ca (NO of 3mol/L3)2·4H2(the NH of O aqueous solutions and 3.5mol/L4)2HPO4
Aqueous solution is according to 2:1 volume ratio uniformly mixes so that Ca/P molar ratios are maintained at 1.67 ± 0.5.PH value is adjusted with ammonium hydroxide
Solution is to alkalinity (pH>11), magnetic agitation is uniform at 40 DEG C, waits for that electrostatic spray is spare.
(2) ethyl acetate is placed in the good open Dewar bottle of heat preservation, a large amount of liquid nitrogen is added while stirring, until being formed
Slush shape liquid nitrogen/ethyl acetate cooling bath.Beaker equipped with toluene and n-hexane is put into cold in liquid nitrogen/ethyl acetate cooling bath
But it is used as receiving liquid, meanwhile, prepared hydroxyapatite solution is fitted into the syringe on electrostatic atomizer, note is adjusted
Injector spray tip height is allowed to after being separated by suitable distance with receiving liquid, and adjusting voltage is 15Kv, starts spraying and in receiving liquid
It is quickly cooled down drop microballoon.
(3) white hydroxyapatite ice microballoon is obtained with 200 mesh sieve fast filtering ethyl acetate receiving liquids, is transferred to freezing
In drying machine, under the conditions of 1~5Pa of vacuum degree, -50 DEG C of temperature, drying obtains white hydroxyapatite aerogel microball for 24 hours.
Embodiment 2
(1) graphite oxide is prepared：The improved Hummer methods of natural graphite are prepared as graphite oxide.
(2) graphene oxide aqueous dispersions are prepared：At room temperature, by the 0.5g graphite oxides of preparation and 100ml deionized waters
Mixing, is placed in ultrasonic washing instrument, is sufficiently stirred after 400W ultrasonic disperses 1h, obtain being uniformly dispersed in dark-brown 5mg/mL
Graphene oxide dispersion.
(3) hydroxyapatite/graphene oxide dispersion is prepared：By Ca (NO3)2·4H2O and (NH4)2HPO4It is dissolved in distillation
The solution of a concentration of 3mol/L and 3.5mol/L are configured in water.The graphene oxide dispersion of 5mg/mL is added to Ca2+It is molten
It in liquid, stirs evenly so that the mass ratio of hydroxyapatite and graphene oxide is 1 in mixed solution:0.02.Certain body is added
Long-pending PO4 3-Solution (3.5mol/L) so that the molar ratio of Ca/P is maintained at 1.67.With ammonium hydroxide by pH value be adjusted to alkalinity (pH >=
11), at 40 DEG C stirring 1~formed afterwards for 24 hours uniform hydroxyapatite/graphene oxide mixing dispersion liquid system, wait for electrostatic
It sprays spare.
(4) ethyl acetate is placed in the good open Dewar bottle of heat preservation, a large amount of liquid nitrogen is added while stirring, until being formed
Slush shape liquid nitrogen/ethyl acetate cooling bath.Beaker equipped with n-hexane is put into liquid nitrogen/ethyl acetate cooling bath cooling conduct
Receiving liquid.Meanwhile prepared hydroxyapatite/graphene oxide dispersion is packed into the syringe on ultrasonic spray apparatus
In, it adjusts syringe nozzle height and is allowed to after being separated by suitable distance with receiving liquid, adjusting supersonic frequency is 150kHz, starts to spray
Mist is simultaneously quickly cooled down drop microballoon in receiving liquid.
(5) to obtain brown hydroxyapatite/graphene oxide ice with 300 mesh sieve fast filtering ethyl acetate receiving liquids micro-
Ball is transferred in freeze drier, under the conditions of 1~5Pa of vacuum degree, -50 DEG C of temperature, it is dry obtain for 24 hours brown hydroxyapatite/
Graphene oxide composite aerogel microballoon.
Embodiment 3
(1) graphite oxide is prepared：The improved Hummer methods of natural graphite are prepared as graphite oxide.
(2) graphene oxide dispersion is prepared：At room temperature, 0.5g graphite oxides and 100ml deionized waters are mixed, is placed in
It in ultrasonic washing instrument, is sufficiently stirred after 400W ultrasonic disperses 1h, obtains the oxidation stone being uniformly dispersed in dark-brown 5mg/ml
Black dispersion liquid.
(3) it prepares and mixes zinc hydroxyapatite/graphene oxide dispersion：By 3mol/L Ca (NO3)2·4H2O、
Zn (the NO of 2.76mol/L3)2·6H2O is with 17.5:1 volume ratio uniformly mixes, and the 5mg/mL graphite oxides of certain volume are added
Alkene dispersion liquid is to Ca2+/Zn2+It in solution, stirs evenly (100~1000rpm) so that hydroxyapatite and oxygen in mixed solution
The mass ratio of graphite alkene is 1:0.02.In the proper ratio, the PO of 3.5mol/L is added4 3-Solution so that [Ca+Zn]/P's
Molar ratio is maintained at 1.67.PH value is adjusted to alkaline (pH >=11) with ammonium hydroxide, stir 1 at 40 DEG C~formed afterwards for 24 hours it is uniform
Mix the dispersion liquid system of zinc hydroxyapatite/graphene oxide mixing.
(4) ethyl acetate is placed in the good open Dewar bottle of heat preservation, a large amount of liquid nitrogen is added while stirring, until being formed
Slush shape liquid nitrogen/ethyl acetate cooling bath.Beaker equipped with n-hexane is put into liquid nitrogen/ethyl acetate cooling bath cooling conduct
Receiving liquid.Meanwhile by the prepared injection mixed zinc hydroxyapatite/graphene oxide dispersion and be packed on ultrasonic spray apparatus
In device, adjusts syringe nozzle height and be allowed to after being separated by suitable distance with receiving liquid, adjusting supersonic frequency is 150kHz, is started
It sprays and is quickly cooled down drop microballoon in receiving liquid.
(5) it obtains mixing zinc hydroxyapatite/graphene oxide ice with 300 mesh sieve fast filtering ethyl acetate receiving liquids micro-
Ball is transferred in freeze drier, and under the conditions of 1~5Pa of vacuum degree, -50 DEG C of temperature, drying obtains brown and mixes zinc hydroxyl phosphorus for 24 hours
Lime stone/graphene oxide composite aerogel microballoon.
Embodiment 4
(1) it prepares and mixes zinc nanometer hydroxyapatite solution：By the Ca (NO of 3mol/L3)2·4H2The Zn of O and 2.76mol/L
(NO3)2·6H2O is with 17.5:1 volume ratio uniformly mixes, and (the NH of the 3.5mol/L of certain volume is then added4)2HPO4It is water-soluble
Liquid so that [Ca+Zn]/P molar ratios are 1.67 in mixed solution.PH value is adjusted into solution to alkaline (pH >=11) with ammonium hydroxide,
At 40 DEG C stirring 1~for 24 hours afterwards formed uniformly mix zinc hydroxyapatite system, wait for that electrostatic spray is spare.
(2) ethyl acetate is placed in the good open Dewar bottle of heat preservation, a large amount of liquid nitrogen is added while stirring, until being formed
Slush shape liquid nitrogen/ethyl acetate cooling bath.Beaker equipped with toluene and n-hexane is put into cold in liquid nitrogen/ethyl acetate cooling bath
But it is used as receiving liquid.Meanwhile being mixed prepared in the syringe that zinc hydroxyapatite aqueous solution is fitted on electrostatic atomizer,
It adjusts syringe nozzle height to be allowed to after being separated by suitable distance with receiving liquid, adjusting voltage is 15Kv, starts to spray and connecing
It receives in liquid and is quickly cooled down drop microballoon.
(3) it obtains white with 300 mesh sieve fast filtering ethyl acetate receiving liquids and mixes zinc hydroxyapatite ice microballoon, be transferred to
In freeze drier, under the conditions of 1~5Pa of vacuum degree, -50 DEG C of temperature, drying obtains white and mixes zinc hydroxyapatite airsetting for 24 hours
Glue microballoon.
Embodiment 5
(1) graphite oxide is prepared：The improved Hummer methods of natural graphite are prepared as graphite oxide.
(2) graphene oxide aqueous dispersions are prepared：At room temperature, the graphite oxide prepared by the improved Hummer methods of 0.25g
It is mixed with 100ml deionized waters, is placed in ultrasonic washing instrument, is sufficiently stirred, is uniformly dispersed after 400W ultrasonic disperses 1h
In the graphene oxide dispersion of dark-brown 2.5mg/ml.
(3) hydroxyapatite/graphene oxide dispersion is prepared：By Ca (NO3)2·4H2O and (NH4)2HPO4It is dissolved in distillation
The solution of a concentration of 3mol/L and 3.5mol/L are configured in water.The graphene oxide dispersion of 2.5mg/mL is added to Ca2+
It in solution, stirs evenly so that the mass ratio of hydroxyapatite and graphene oxide is 1 in mixed solution:0.01, it is added certain
The PO of volume4 3-Solution so that the molar ratio of Ca/P is maintained at 1.67.PH value is adjusted to alkaline (pH >=11) with ammonium hydroxide, 40
The dispersion liquid system of DEG C stirring 1~formed afterwards for 24 hours uniform hydroxyapatite/graphene oxide mixing, waits for that electrostatic spray is spare.
(4) ethyl acetate is placed in the good open Dewar bottle of heat preservation, a large amount of liquid nitrogen is added while stirring, until being formed
Slush shape liquid nitrogen/ethyl acetate cooling bath.Beaker equipped with n-hexane is put into liquid nitrogen/ethyl acetate cooling bath cooling conduct
Receiving liquid.Meanwhile prepared hydroxyapatite/graphene oxide mixed solution is packed into the syringe on ultrasonic spray apparatus
In, it adjusts syringe nozzle height and is allowed to after being separated by suitable distance with receiving liquid, adjusting supersonic frequency is 150kHz, starts to spray
Mist is simultaneously quickly cooled down drop microballoon in receiving liquid.
(5) to obtain brown hydroxyapatite/graphene oxide ice with 300 mesh sieve fast filtering ethyl acetate receiving liquids micro-
Ball is transferred in freeze drier, under the conditions of 1~5Pa of vacuum degree, -50 DEG C of temperature, it is dry obtain for 24 hours brown hydroxyapatite/
Graphene oxide composite aerogel microballoon.
Embodiment 6
(1) graphite oxide is prepared：The improved Hummer methods of natural graphite are prepared as graphite oxide.
(2) graphene oxide dispersion is prepared：At room temperature, the graphite oxide that prepared by the improved Hummer methods of 0.25g and
100ml deionized waters mix, and are placed in ultrasonic washing instrument, are sufficiently stirred after 400W ultrasonic disperses 1h, obtaining being uniformly dispersed is in
The graphite oxide dispersion of dark-brown 5mg/ml.
(3) it prepares and mixes zinc hydroxyapatite/graphene oxide dispersion:Prepare 3mol/L Ca (NO3)2·4H2O、
Zn (the NO of 2.76mol/L3)2·6H2O, 3.5mol/L (NH4)2HPO4Aqueous solution.By Ca (NO3)2·4H2O and Zn (NO3)2·
6H2O is with 17.5:1 volume ratio uniformly mixes, and the 2.5mg/mL graphene oxide dispersions of certain volume are added to Ca2+/Zn2+
It in solution, stirs evenly (100~1000rpm) so that the mass ratio of hydroxyapatite and graphene oxide is in mixed solution
1:0.01.In the proper ratio, the PO of 3.5mol/L is added4 3-Solution so that the molar ratio of [Ca+Zn]/P is maintained at 1.67.With
PH value is adjusted to alkaline (pH >=11) by ammonium hydroxide, stir 1 at 40 DEG C~it is formed afterwards uniformly mix zinc hydroxyapatite/oxidation for 24 hours
The dispersion liquid system of graphene mixing, waits for that electrostatic spray is spare.
(4) ethyl acetate is placed in the good open Dewar bottle of heat preservation, a large amount of liquid nitrogen is added while stirring, until being formed
Slush shape liquid nitrogen/ethyl acetate cooling bath.Beaker equipped with n-hexane is put into liquid nitrogen/ethyl acetate cooling bath cooling conduct
Receiving liquid.Meanwhile by the prepared injection mixed zinc hydroxyapatite/graphene oxide dispersion and be packed on ultrasonic spray apparatus
In device, adjusts syringe nozzle height and be allowed to after being separated by suitable distance with receiving liquid, adjusting supersonic frequency is 150kHz, is started
It sprays and is quickly cooled down drop microballoon in receiving liquid.
(5) it obtains mixing zinc hydroxyapatite/graphene oxide ice with 300 mesh sieve fast filtering ethyl acetate receiving liquids micro-
Ball is transferred in freeze drier, and under the conditions of 1~5Pa of vacuum degree, -50 DEG C of temperature, drying obtains brown and mixes zinc hydroxyl phosphorus for 24 hours
Lime stone/graphene oxide composite aerogel microballoon.
Embodiment 7
(1) graphite oxide is prepared：The improved Hummer methods of natural graphite are prepared as graphite oxide.
(2) graphene oxide aqueous dispersions are prepared：At room temperature, the graphite oxide prepared by the improved Hummer methods of 0.25g
It is mixed with 100ml deionized waters, is placed in ultrasonic washing instrument, is sufficiently stirred, is uniformly dispersed after 400W ultrasonic disperses 1h
In the graphene oxide dispersion of dark-brown 2.5mg/ml.
(3) hydroxyapatite/graphene oxide dispersion is prepared：By Ca (NO3)2·4H2O and (NH4)2HPO4It is dissolved in distillation
The solution of a concentration of 3mol/L and 3.5mol/L are configured in water.The graphene oxide dispersion of 2.5mg/mL is added to Ca2+
It in solution, stirs evenly so that the mass ratio of hydroxyapatite and graphene oxide is 1 in mixed solution:0.01, it is added certain
The PO of volume4 3-Solution so that the molar ratio of Ca/P is maintained at 1.67.PH value is adjusted to alkaline (pH >=11) with ammonium hydroxide, 40
The dispersion liquid system of DEG C stirring 1~formed afterwards for 24 hours uniform hydroxyapatite/graphene oxide mixing, waits for that electrostatic spray is spare.
(4) ethyl acetate is placed in the good open Dewar bottle of heat preservation, a large amount of liquid nitrogen is added while stirring, until being formed
Slush shape liquid nitrogen/ethyl acetate cooling bath.Beaker equipped with n-hexane is put into liquid nitrogen/ethyl acetate cooling bath cooling conduct
Receiving liquid.Meanwhile prepared hydroxyapatite/graphene oxide mixed solution is packed into the syringe on ultrasonic spray apparatus
In, it adjusts syringe nozzle height and is allowed to after being separated by suitable distance with receiving liquid, adjusting supersonic frequency is 150kHz, starts to spray
Mist is simultaneously quickly cooled down drop microballoon in receiving liquid.
(5) to obtain brown hydroxyapatite/graphene oxide ice with 300 mesh sieve fast filtering ethyl acetate receiving liquids micro-
Ball is transferred in freeze drier, under the conditions of 1~5Pa of vacuum degree, -50 DEG C of temperature, it is dry obtain for 24 hours brown hydroxyapatite/
Graphene oxide composite aerogel microballoon.
(6) under nitrogen protection, by the composite aerogel microballoon of step (5) in Muffle furnace according to the heating of 10 DEG C/min
Speed is warming up to 800 DEG C, and keeps 5h at 800 DEG C, and it is micro- to obtain hydroxyapatite/redox graphene composite aerogel
Ball.
Structural characterization and performance test：
The hydroxyapatite aerogel microball of embodiment 1, the hydroxy-apatite of embodiment 2 are observed using scanning electron microscope
Stone/graphene oxide composite aerogel microballoon, embodiment 3 mix zinc hydroxyapatite/graphene oxide composite aerogel microballoon
Appearance structure, SEM figures are the results detailed in shown in Fig. 1-Fig. 3, the results showed that：The hydroxyapatite prepared for the first time with electrostatic spraying processes
Aerogel microball, hydroxyapatite/graphene oxide composite aerogel microballoon, to mix zinc hydroxyapatite/graphene oxide compound
Aerogel microball good sphericity has porous reticular structure, is established for the biologic applications in next step as biological stephanoporate bracket
Good basis.Further comparison is it is found that the hydroxyapatite composite aerogel microballoon containing graphene oxide, reticular structure more it is thick more
Securely, thus mechanical strength higher, chondritic is more stablized.
Claims (5)
1. a kind of composite aerogel microballoon, which is characterized in that comprising mass ratio be 1:0.1~1:10 hydroxyapatite and oxidation
Graphene, the hydroxyapatite is by Ca (NO3)2·4H2O and (NH4)2HPO4It is constituted according to 1.17~2.17 molar ratio.
2. a kind of preparation method of composite aerogel microballoon, the dosage of each component is mass fraction in this method, and feature exists
In including the following steps：
(1) preparation of graphite oxide
Natural graphite is prepared into graphite oxide through chemical oxidization method, wherein chemical oxidization method is Brodie oxidizing process,
Staudemaier oxidizing process, any one of Hummer methods or improved Hummer methods；
(2) preparation of graphene oxide aqueous dispersions
After evenly mixing by 100 parts of deionized water, 0.05-5 parts of graphite oxide, 20-60min, system are removed through 200-400W ultrasounds
The standby graphene oxide aqueous dispersions at a concentration of 0.1-20mg/mL；
(3) preparation of hydroxyapatite/graphene oxide mixed dispersion liquid
A, by Ca (NO3)2·4H2O、(NH4)2HPO4With Zn (NO3)2·6H2O is as Ca2+、PO4 3-And Zn2+Presoma, respectively
It is dissolved in the Ca (NO that 0.1~5mol/L is configured in distilled water3)2·4H2(the NH of O solution, 0.1~5mol/L4)2HPO4Solution and
Zn (the NO of 0.1~5mol/L3)2·6H2O solution；
B, the Ca (NO are added in the graphene oxide dispersion of step (2)3)2·4H2O solution, in 100~1000rpm
Speed under stir evenly；
C, (the NH is added in the gains of step b4)2HPO4Solution so that Ca2+With PO4 3-Molar ratio be maintained at
1.17~2.17, and the mass ratio of hydroxyapatite and graphene oxide is 1 in solution:0.1~1:10；Ammonia is added in solution again
Water so that pH >=11, and at 40 DEG C stirring 1~form uniform hydroxyapatite/graphene oxide composite dispersion liquid afterwards for 24 hours
System；
(4) hydroxyapatite obtained by step (3)/graphene oxide composite diffusion liquid system is atomized by hydroxyl as spray-on process
Apatite/graphene oxide drop microballoon, and the formation compound ice of hydroxyapatite/graphene oxide is micro- in cooling bath receiving liquid
Ball, wherein spray-on process is press atomization, any one of ullrasonic spraying or electrostatic spray；
(5) the compound ice microballoon obtained by the screen filtration step (4) with 100~300 mesh obtains after tailing over the freeze-drying of ice microballoon
Obtain hydroxyapatite/graphene oxide composite aerogel microballoon.
3. a kind of preparation method of composite aerogel microballoon as claimed in claim 2, which is characterized in that can also be in step (3) b
Middle addition Zn (NO3)2·6H2O solution, and then hydroxyapatite/graphene oxide composite aerogel microballoon of zinc doping is obtained,
Wherein Ca2+With Zn2+Molar ratio be 1:1~100:1.
4. a kind of preparation method of composite aerogel microballoon as claimed in claim 3, which is characterized in that the zinc can also be replaced
The either element being changed in silver, fluorine, magnesium, carbon, strontium, silicon, iron, titanium, and then obtain corresponding doped hydroxyapatite/graphite oxide
Alkene composite aerogel microballoon.
5. a kind of preparation method of composite aerogel microballoon as claimed in claim 2, which is characterized in that can also be by step (5)
The hydroxyapatite of gained/graphene oxide composite aerogel microballoon obtains hydroxyl phosphorus by thermal reduction or chemical reduction method
The method of lime stone/redox graphene composite aerogel microballoon；
The thermal reduction is：Under inert gas protection, using in Muffle furnace Program heating thermal reduction or microwave irradiation heat
Reduction, wherein Muffle furnace Program heating thermal reduction method be to be warming up to 800 DEG C with the heating speed of 5-10 DEG C/min,
And 2-5h is kept at 800 DEG C, and microwave irradiation thermal reduction is to keep 1-10min under the power of 600-800W；
The chemical reduction method is hydroiodic acid reduction method or hydrazine steam reduction method：The hydroiodic acid reduction method is dense using quality
The hydriodic acid aqueous solution of degree 55% and hydroxyapatite/graphene oxide composite aerogel microballoon normal-temperature reaction in closed environment
12h；The hydrazine steam reduction method is that hydrazine hydrate solution and composite aerogel microballoon are placed in closed environment, at 90 DEG C also
Original reaction 8-12h.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110745811A (en) * | 2019-11-26 | 2020-02-04 | 中国船舶重工集团公司第七二五研究所 | Hydroxyapatite/graphene aerogel anode and preparation method thereof |
| CN111760553A (en) * | 2020-07-28 | 2020-10-13 | 苏州市职业大学 | Preparation method and application of graphene oxide-Brillouin stone compound |
| CN113881399A (en) * | 2021-09-27 | 2022-01-04 | 宁波金榜新能源有限公司 | Brake pad friction material for new energy automobile and preparation method thereof |
| CN114180984A (en) * | 2021-11-10 | 2022-03-15 | 安徽壹石通材料科学研究院有限公司 | Hydroxyapatite/silicon oxide composite aerogel and preparation method thereof |
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| CN105498649A (en) * | 2015-12-24 | 2016-04-20 | 四川大学 | Graphene nano particle compound aerogel microspheres 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 |
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| 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 |
| CN105498649A (en) * | 2015-12-24 | 2016-04-20 | 四川大学 | Graphene nano particle compound aerogel microspheres and preparation method thereof |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110745811A (en) * | 2019-11-26 | 2020-02-04 | 中国船舶重工集团公司第七二五研究所 | Hydroxyapatite/graphene aerogel anode and preparation method thereof |
| CN110745811B (en) * | 2019-11-26 | 2022-08-16 | 中国船舶重工集团公司第七二五研究所 | Hydroxyapatite/graphene aerogel anode and preparation method thereof |
| CN111760553A (en) * | 2020-07-28 | 2020-10-13 | 苏州市职业大学 | Preparation method and application of graphene oxide-Brillouin stone compound |
| CN113881399A (en) * | 2021-09-27 | 2022-01-04 | 宁波金榜新能源有限公司 | Brake pad friction material for new energy automobile and preparation method thereof |
| CN114180984A (en) * | 2021-11-10 | 2022-03-15 | 安徽壹石通材料科学研究院有限公司 | Hydroxyapatite/silicon oxide composite aerogel and preparation method thereof |
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