CN108379589A - A kind of preparation method of hydroxyapatite/graphene oxide composite material - Google Patents
A kind of preparation method of hydroxyapatite/graphene oxide composite material Download PDFInfo
- Publication number
- CN108379589A CN108379589A CN201810210074.6A CN201810210074A CN108379589A CN 108379589 A CN108379589 A CN 108379589A CN 201810210074 A CN201810210074 A CN 201810210074A CN 108379589 A CN108379589 A CN 108379589A
- Authority
- CN
- China
- Prior art keywords
- hydroxyapatite
- graphene oxide
- composite material
- preparation
- oxide composite
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K47/00—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
- A61K47/02—Inorganic compounds
Abstract
The invention discloses a kind of preparation methods of hydroxyapatite/graphene oxide composite material, and this approach includes the following steps：The first step dissolves hydroxyapatite in acidic environment, and complexing agent is added and carries out regulation and control reaction, carries out centrifugal filtration after adjusting pH value, the filter cake that centrifugal filtration obtains is rinsed well, up to sheet self assembly hydroxyapatite micro-sphere crystal after freeze-drying；Second step, by above-mentioned made sheet self assembly hydroxyapatite micro-sphere crystal, it is mixed under ul-trasonic irradiation with scattered graphene oxide solution, it is put into freeze drying box after rinsing well, is freeze-dried 24~48h, obtains hydroxyapatite/graphene oxide composite material.This invention simplifies preparation process to be suitable for biology and carry medicine application without being intentionally added crosslinking agent.
Description
Technical field
The present invention relates to lithotroph medical material preparation field more particularly to a kind of hydroxyapatite/graphene oxides
The preparation method of composite material.
Background technology
The molecular formula of hydroxyapatite (hydroxyapatite, abbreviation HA) is Ca10(PO4)6(OH)2, density 3.16g/
cm2.It is slightly soluble in water, is in alkalescent, is soluble in acid, is insoluble in alkali.Hydroxyapatite is between normal temperature and pH value 4~12
Most stable of synthos.Hydroxyapatite is as the main nothing in the calcification sclerous tissues (for example, bone and tooth) of vertebrate
Machine component, accounts for about 75% of body bone tissue or more, due to its with good biocompatibility, osteoconductive, mobility and
Adsorptivity is widely used in bone tissue engineer technology etc..In recent years, it is the application demand for meeting different, researchers' system
It is standby gone out the hydroxyapatite material of the variforms such as spherical, rodlike, sheet, crystal whisker-shaped.In these forms, spherical hydroxyl phosphorus
Lime stone have many advantages, such as the tumor promotion rate that good fluidity, specific surface area are high, compatibility is good, compactedness is high, minimum and by pole
Big concern.However, pure ha crystal poor tensile strength and the weak practical application for limiting it of fracture toughness.
The derivative that graphene oxide (abbreviation GO) is aoxidized as graphene is single layer of carbon atom, in carbon atom composition
Six square piece layer surfaces have many various sizes of aromatic rings, and also a certain amount of hydroxyl, epoxy group and carboxyl are present in fragrance
On ring, wherein carboxyl and hydroxyl are located at the edge of oxidized graphite flake mostly, and carbonyl and epoxy group are located at graphite oxide level
Upper or interlayer.Active oxygen-containing functional group in graphene oxide layer can make its stable dispersion in an aqueous medium, increase
Binding force between strong component, and the stress transfer between composite material can also be promoted.This makes graphene oxide is expected to become to receive
Meter level reinforcing filler is in Biocomposite material field.In spite of above-mentioned the advantages of referring to, graphene oxide is again without showing
Any osteoconductive, in this respect, hydroxyapatite more has superiority than graphene oxide.Unfortunately, hydroxyapatite is solid
Some brittleness makes it that can not possibly be used alone as structural member, and the enhancing effect of hydroxyapatite does not have graphene oxide good.Cause
This, when hydroxyapatite and graphene oxide are simultaneously used as reinforcing agent, hydroxyapatite and graphene oxide it is compound
By the abundant advantage for combining the two, and composite material possesses desired excellent mechanical performances and advantageous cell effect, has
Prestige is applied in lithotroph field of medical materials.
Currently, the method for synthesizing hydroxylapatite/graphene oxide composite material includes hydrothermal synthesis method, fabricated in situ side
Method, biomimetic mineralization process, electrophoretic deposition, discharge plasma sintering technology (SPS) etc..Wherein, hydrothermal synthesis method is for making
The relatively effective method of standby high quality mineral crystal, equally can also be used to prepare graphene-based compound.It is closed under high temperature
Reaction kettle can give reaction to provide high pressure so that very insoluble substance dissolves well under normal pressure, and it is more preferable to be also conducive to product
Dissolving, solution can form the extraordinary crystal of crystallinity under hypersaturated state.It often may be implemented using hydrothermal synthesis method
Target sample is made in one step, and at the same time graphene oxide is restored in the reaction.But particle diameter obtained by this method
Distributed more widely, pattern is not regular enough, and to the stoichiometric ratio of raw material, pH value, temperature, time etc. in whole preparation process
Parameter has strict demand, it is difficult to be used for big industrial production；The advantages of graphene-based compound is prepared in situ in sol-gel method craft
Be that surface of graphene oxide possess great amount of hydroxy group can as hydrolysis nucleating point so that metal oxide can be with chemistry
Key is directly connected to be disadvantageous in that the organic solvent that it is needed using low surface tension on the surface, and influence factor is relatively more,
Such as hydrolysis time, solution ph, heat treatment temperature can not effectively control the shape of product, be typically difficult to obtain ball shaped hydroxy
Apatite；Template is one kind during biomimetic mineralization, using the flexible organic molecule of structural variability greatly as the soft of template
Template, using the substance with rigid structure as the hard template method of template, by ion-exchange reactions to be synthetically prepared out
Need the particle of structure and pattern.There are surface oil phase, surfactant and templates to be difficult to for hydroapatite particles made from this method
The problem of thoroughly removing；Electrophoretic deposition is a kind of special colloid treatment technology, is widely used in bioactive ceramics or compound
Coating on the various metal surfaces of material well controls coating layer thickness, crystallinity, even obtains in complicated shape substrate
The good coating of even property, but process complicated and be inconvenient to limit and promote the use of.
In order to solve the problems in the existing technology, it needs to design a kind of hydroxyapatite/graphene oxide composite wood
The preparation method of material.
Invention content
In order to overcome the defects of the prior art, a kind of preparation of hydroxyapatite/graphene oxide composite material is provided
Method.
The present invention is realized by following proposal：
A kind of preparation method of hydroxyapatite/graphene oxide composite material, this approach includes the following steps：
The first step dissolves hydroxyapatite in acidic environment, and complexing agent is added and carries out regulation and control reaction, after adjusting pH value
Centrifugal filtration is carried out, the filter cake that centrifugal filtration obtains is rinsed well, up to sheet self assembly hydroxyapatite after freeze-drying
Microballoon crystal；
Second step, by above-mentioned made sheet self assembly hydroxyapatite micro-sphere crystal, it is molten with scattered graphene oxide
Liquid mixes under ul-trasonic irradiation, is put into freeze drying box after rinsing well, is freeze-dried 24~48h, obtains hydroxy-apatite
Stone/graphene oxide composite material.
The acidic environment is the strong acid solution of a concentration of 0.001~0.01mol/L, and the strong acid is in nitric acid, hydrochloric acid
It is one or two kinds of.
The complexing agent is Na2One or more, the complexing agent and the hydroxyl of EDTA, sodium citrate and sodium potassium tartrate tetrahydrate
The molar ratio of apatite is 0.1~10.
The hydroxyapatite, which dissolves in acidic environment and be added complexing agent, to carry out regulating and controlling to react stirring at normal temperatures
.
The adjusting pH value is to be spread after ammonium hydroxide is added by the way of ammonium hydroxide is added and reaction process continues 0.5~2d.
The mass ratio of the hydroxyapatite and graphene oxide is 0.8~1.5：1.
Mixing is to carry out at room temperature under the ul-trasonic irradiation, and the reaction time is 0.5~5h.
Flushing in the first step is that deionized water, absolute ethyl alcohol is employed many times alternately to rinse.
Flushing in the second step is that deionized water, absolute ethyl alcohol is employed many times alternately to rinse.
Beneficial effects of the present invention are：
A kind of preparation method of hydroxyapatite/graphene oxide composite material of the present invention simplifies preparation process, is not necessarily to
It is intentionally added crosslinking agent, also avoids pollution of the crosslinking agent residual to final sample；Meanwhile the hydroxyl prepared by the above method
Apatite/graphene oxide composite material has high specific surface area, is suitable for biology and carries medicine application.
Description of the drawings
Fig. 1 is the Flied emission scanning electricity of hydroxyapatite/graphene oxide composite material prepared by preparation method of the present invention
Mirror figure；Wherein (a) is low power scanning electron microscope (SEM) photograph；(b) it is high power scanning electron microscope (SEM) photograph；
Fig. 2 is the FTIR spectrum figure of hydroxyapatite micro-sphere prepared by preparation method of the present invention.
Specific implementation mode
With reference to specific embodiment, the present invention is further described：
The technical scheme is that：A kind of preparation method of hydroxyapatite/graphene oxide composite material, this method
Include the following steps：
The first step dissolves hydroxyapatite in acidic environment, and complexing agent is added and carries out regulation and control reaction, after adjusting pH value
Centrifugal filtration is carried out, the filter cake that centrifugal filtration obtains is rinsed well, up to sheet self assembly hydroxyapatite after freeze-drying
Microballoon crystal；By above-mentioned preparation method, the crystallization and growth of the complexing agent Effective Regulation hydroxyapatite of appropriate dosage, and
So that hydroxyapatite forms sheet self assembly densification microballoon under ammonium hydroxide diffusion conditions；Supersound process obtains hydroxyapatite, oxygen
The dispersion liquid of graphite alkene so that entire reaction process can carry out at normal temperatures, be convenient for large-scale industrial production, this is
What other technical solutions cannot achieve.
Hydroxyapatite used is commercially available also can voluntarily to be prepared, and the present invention provides following patterns that prepare can
Control the technical solution of hydroxyapatite raw material：Using made hydroxyapatite and graphene oxide as raw material, it is added to the water point
It dissipates and uniformly is ultrasonically treated to obtain hydroxyapatite/graphene oxide composite material.Wherein, hydroxyapatite used and complexing
The dosage of agent can be adjusted as needed, and optimally the molar ratio of the two generates sheet self assembly hydroxyl just
Apatite microballoon；For the ease of the charging in production, usual hydroxyapatite, both graphene oxides when preparing composite material
Mass ratio meet 0.8~1.5：1 can guarantee that reaction efficiently carries out.
Second step, by above-mentioned made sheet self assembly hydroxyapatite micro-sphere crystal, it is molten with scattered graphene oxide
Liquid mixes under ul-trasonic irradiation, is put into freeze drying box after rinsing well, is freeze-dried 24~48h, obtains hydroxy-apatite
Stone/graphene oxide composite material.
The acidic environment is the strong acid solution of a concentration of 0.001~0.01mol/L, and the strong acid is in nitric acid, hydrochloric acid
It is one or two kinds of.
The complexing agent is Na2One or more, the complexing agent and the hydroxyl of EDTA, sodium citrate and sodium potassium tartrate tetrahydrate
The molar ratio of apatite is 0.1~10.
The hydroxyapatite, which dissolves in acidic environment and be added complexing agent, to carry out regulating and controlling to react stirring at normal temperatures
.
The adjusting pH value is to be spread after ammonium hydroxide is added by the way of ammonium hydroxide is added and reaction process continues 0.5~2d.
The mass ratio of the hydroxyapatite and graphene oxide is 0.8~1.5：1.
Mixing is to carry out at room temperature under the ul-trasonic irradiation, and the reaction time is 0.5~5h.
Flushing in the first step is that deionized water, absolute ethyl alcohol is employed many times alternately to rinse.
Flushing in the second step is that deionized water, absolute ethyl alcohol is employed many times alternately to rinse.
Below in conjunction with specific embodiment, the present invention is described in detail.
Embodiment 1：
(1) 0.502g nanometer hydroxyapatites are dissolved in 100mL deionized waters, are stirred evenly, slowly dripped while stirring
Add the hydrochloric acid of a concentration of 1mol/L, until hydroxyapatite is completely dissolved；
(2) complexing agent 0.7446g Na are added into above-mentioned hydroxyapatite solution2EDTA is slowly added to while stirring,
10~30min is stirred under room temperature；
(3) solution of gained and ammonium hydroxide are placed in closed reactor and are reacted, the reaction time is 0.5~2d；
(4) by the solution centrifugal filtration obtained by step (3), deionized water, absolute ethyl alcohol is used in combination to rinse each 3 times or more；
(5) filter cake rinsed well in step (4) is put into freeze drying box, is freeze-dried 24~48h, gained is just
It is sheet self assembly hydroxyapatite micro-sphere crystal；
(6) it by above-mentioned made hydroxyapatite crystal, is mixed with scattered a concentration of 1mg/mL graphene oxide solutions,
Ultrasonication is used in combination deionized water, absolute ethyl alcohol to rinse each for 3 times or more, is put into freeze drying box, is freeze-dried 24~48h,
Obtain hydroxyapatite/graphene oxide composite material.
After testing：Prepared by embodiment 1 is sheet self assembly hydroxyapatite micro-sphere, hydroxyapatite/graphite oxide
Alkene composite material, these nano-particles are by graphene oxide cladding weave in (such as Fig. 1 (a, b)).
Embodiment 2
(1) 0.502g nanometer hydroxyapatites are dissolved in 100mL deionized waters, are stirred evenly, slowly dripped while stirring
Add the hydrochloric acid of a concentration of 1mol/L, until hydroxyapatite is completely dissolved；
(2) complexing agent 0.5645g citric acids are added into above-mentioned hydroxyapatite solution, are slowly added to while stirring, often
Temperature is lower to stir 10~30min；
(3) solution of gained and ammonium hydroxide are placed in closed reactor and are reacted, the reaction time is 0.5~2d；
(4) by the solution centrifugal filtration obtained by step (3), deionized water, absolute ethyl alcohol is used in combination to rinse each 3 times or more；
(5) filter cake rinsed well in step (4) is put into freeze drying box, is freeze-dried 24~48h, gained is just
It is sheet self assembly hydroxyapatite micro-sphere crystal；
(6) it by above-mentioned made hydroxyapatite crystal, is mixed with scattered a concentration of 1mg/mL graphene oxide solutions,
Ultrasonication is used in combination deionized water, absolute ethyl alcohol to rinse each for 3 times or more, is put into freeze drying box, is freeze-dried 24~48h,
Obtain hydroxyapatite/graphene oxide composite material.
After testing：Prepared by embodiment 2 is also hydroxyapatite/graphene oxide composite material.The FTIR of progress points
Analysis is known：The peaks-OH appear in 3434cm-1, it is saturated c h bond stretching vibration peak and appears in 2923cm-1, carboxylic acid anion antisymmetry
Stretching vibration absworption peak appears in 1630cm-1, carboxylic acid anion symmetrical stretching vibration absorption peak appears in 1400cm-1, P-O is non-
Symmetry stretching vibration absworption peak appears in 1046cm-1, O-P-O flexural vibrations peaks appear in 603cm-1, it may be determined that this substance
For hydroxyapatite/graphene oxide composite material (as shown in Figure 2).
Embodiment 3
(1) 0.502g nanometer hydroxyapatites are dissolved in 100mL deionized waters, are stirred evenly, slowly dripped while stirring
Add the hydrochloric acid of a concentration of 1mol/L, until hydroxyapatite is completely dissolved；
(2) complexing agent 0.4203g sodium potassium tartrate tetrahydrates are added into above-mentioned hydroxyapatite solution, slowly add while stirring
Enter, 10~30min is stirred under room temperature；
(3) solution of gained and ammonium hydroxide are placed in closed reactor and are reacted, the reaction time is 0.5~2d；
(4) by the solution centrifugal filtration obtained by step (3), deionized water, absolute ethyl alcohol is used in combination to rinse each 3 times or more；
(5) filter cake rinsed well in step (4) is put into freeze drying box, is freeze-dried 24~48h, gained is just
It is sheet self assembly hydroxyapatite micro-sphere crystal；
(6) it by above-mentioned made hydroxyapatite crystal, is mixed with scattered a concentration of 1mg/mL graphene oxide solutions,
Ultrasonication is used in combination deionized water, absolute ethyl alcohol to rinse each for 3 times or more, is put into freeze drying box, is freeze-dried 24~48h,
Obtain hydroxyapatite/graphene oxide composite material.
After testing：It is also that hydroxyapatite/graphene oxide is compound that material prepared by embodiment 3, which carries out Raman analyses,
Material.
In view of the deficiencies of the prior art, acidity complexing agent being placed in dissolved with hydroxyapatite of the invention is molten
In pendular ring border, change the pH value of solution by the diffusion of ammonium hydroxide, morphology controllable and the hydroxyapatite crystal of densification is made, with oxygen
Graphite alkene dispersion liquid carries out being mixed with hydroxyapatite/graphene oxide composite material.The method achieve composite materials
Forming process can carry out at room temperature, effectively reduce production difficulty and cost；Meanwhile method of the invention can be by hydroxyl
The preparation process of base apatite is completely detached with the forming process of composite material, and raw material early period is avoided to final to maximize
The influence of product purity and yield, improves production efficiency.
Although having done more detailed elaboration to technical scheme of the present invention and having enumerated, it should be understood that for ability
For field technique personnel, modification is made to above-described embodiment or uses equivalent alternative solution, this is to those skilled in the art
It is it is clear that these modifications or improvements without departing from theon the basis of the spirit of the present invention, belong to the present invention for member
Claimed range.
Claims (9)
1. a kind of preparation method of hydroxyapatite/graphene oxide composite material, which is characterized in that this method includes following step
Suddenly：
The first step dissolves hydroxyapatite in acidic environment, and complexing agent is added and carries out regulation and control reaction, is carried out after adjusting pH value
The filter cake that centrifugal filtration obtains is rinsed in centrifugal filtration well, up to sheet self assembly hydroxyapatite micro-sphere after freeze-drying
Crystal；
Second step, by above-mentioned made sheet self assembly hydroxyapatite micro-sphere crystal, exist with scattered graphene oxide solution
It mixes under ul-trasonic irradiation, is put into freeze drying box after rinsing well, be freeze-dried 24~48h, obtain hydroxyapatite/oxygen
Graphite alkene composite material.
2. a kind of preparation method of hydroxyapatite/graphene oxide composite material according to claim 1, feature exist
In：The acidic environment is the strong acid solution of a concentration of 0.001~0.01mol/L, and the strong acid is one kind in nitric acid, hydrochloric acid
Or two kinds.
3. a kind of preparation method of hydroxyapatite/graphene oxide composite material according to claim 1, feature exist
In：The complexing agent is Na2One or more, the complexing agent and the hydroxy-apatite of EDTA, sodium citrate and sodium potassium tartrate tetrahydrate
The molar ratio of stone is 0.1~10.
4. a kind of preparation method of hydroxyapatite/graphene oxide composite material according to claim 1, feature exist
In：The hydroxyapatite dissolves and is added in acidic environment complexing agent and carries out regulation and control reaction stirring at normal temperatures.
5. a kind of preparation method of hydroxyapatite/graphene oxide composite material according to claim 1, feature exist
In：The adjusting pH value is to be spread after ammonium hydroxide is added by the way of ammonium hydroxide is added and reaction process continues 0.5~2d.
6. a kind of preparation method of hydroxyapatite/graphene oxide composite material according to claim 1, feature exist
In：The mass ratio of the hydroxyapatite and graphene oxide is 0.8~1.5：1.
7. a kind of preparation method of hydroxyapatite/graphene oxide composite material according to claim 1, feature exist
In：Mixing is to carry out at room temperature under the ul-trasonic irradiation, and the reaction time is 0.5~5h.
8. a kind of preparation method of hydroxyapatite/graphene oxide composite material according to claim 1, feature exist
In：Flushing in the first step is that deionized water, absolute ethyl alcohol is employed many times alternately to rinse.
9. a kind of preparation method of hydroxyapatite/graphene oxide composite material according to claim 1, feature exist
In：Flushing in the second step is that deionized water, absolute ethyl alcohol is employed many times alternately to rinse.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810210074.6A CN108379589B (en) | 2018-03-14 | 2018-03-14 | Preparation method of hydroxyapatite/graphene oxide composite material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810210074.6A CN108379589B (en) | 2018-03-14 | 2018-03-14 | Preparation method of hydroxyapatite/graphene oxide composite material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108379589A true CN108379589A (en) | 2018-08-10 |
| CN108379589B CN108379589B (en) | 2021-03-09 |
Family
ID=63067324
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810210074.6A Active CN108379589B (en) | 2018-03-14 | 2018-03-14 | Preparation method of hydroxyapatite/graphene oxide composite material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108379589B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110935063A (en) * | 2019-12-06 | 2020-03-31 | 锦州医科大学 | Apatite sponge material and preparation method and application thereof |
| CN111054404A (en) * | 2020-01-08 | 2020-04-24 | 沈阳师范大学 | Preparation method of flaky hydroxyapatite carrier and supported nano-silver catalyst |
| CN112022727A (en) * | 2020-10-20 | 2020-12-04 | 哈工宁伯医疗科技泰州有限公司 | Light-cured ceramic material for oral dental restoration and application thereof |
| CN113599535A (en) * | 2021-07-21 | 2021-11-05 | 深圳大学 | nHA/GO/CS composite microspheres and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102716514A (en) * | 2012-05-29 | 2012-10-10 | 苏州大学 | Nano composite biological coating and preparation method thereof |
| CN104944399A (en) * | 2015-06-16 | 2015-09-30 | 西南科技大学 | Preparation method for hydroxyapatite microspheres |
| 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 |
| CN105536050A (en) * | 2016-02-05 | 2016-05-04 | 山东明德生物医学工程有限公司 | Graphene oxide modified bone cement as well as preparation method and application thereof |
-
2018
- 2018-03-14 CN CN201810210074.6A patent/CN108379589B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102716514A (en) * | 2012-05-29 | 2012-10-10 | 苏州大学 | Nano composite biological coating and preparation method thereof |
| CN104944399A (en) * | 2015-06-16 | 2015-09-30 | 西南科技大学 | Preparation method for hydroxyapatite microspheres |
| 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 |
| CN105536050A (en) * | 2016-02-05 | 2016-05-04 | 山东明德生物医学工程有限公司 | Graphene oxide modified bone cement as well as preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| 齐永成: "羟基磷灰石晶体生长的调控研究", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑（月刊）》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110935063A (en) * | 2019-12-06 | 2020-03-31 | 锦州医科大学 | Apatite sponge material and preparation method and application thereof |
| CN111054404A (en) * | 2020-01-08 | 2020-04-24 | 沈阳师范大学 | Preparation method of flaky hydroxyapatite carrier and supported nano-silver catalyst |
| CN111054404B (en) * | 2020-01-08 | 2022-12-23 | 沈阳师范大学 | Preparation method of flaky hydroxyapatite carrier and supported nano-silver catalyst |
| CN112022727A (en) * | 2020-10-20 | 2020-12-04 | 哈工宁伯医疗科技泰州有限公司 | Light-cured ceramic material for oral dental restoration and application thereof |
| CN113599535A (en) * | 2021-07-21 | 2021-11-05 | 深圳大学 | nHA/GO/CS composite microspheres and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108379589B (en) | 2021-03-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108379589A (en) | A kind of preparation method of hydroxyapatite/graphene oxide composite material | |
| CN106565974B (en) | Alginate/hydroxyapatite overlong nanowire composite hydrogel | |
| CN102616762B (en) | Method for hydro-thermal preparation of hydroxyapatite powder by calcium silicate precursor | |
| CN107161969A (en) | A kind of preparation method of nanometer hydroxyapatite/graphene oxide composite material | |
| CN104415399B (en) | A kind of hydroxyapatite/graphene nano composite powder preparation method and products thereof | |
| CN101891175B (en) | Enamel-shaped hydroxyapatite and preparation method and application thereof | |
| CN101623514A (en) | Preparation method for nano hydroxylapatite doped with metal ions | |
| CN101297978A (en) | Preparation method of hydroxyapatite nano pole | |
| CN108404203B (en) | Preparation method of reduced graphene oxide/biological glass nanofiber scaffold | |
| CN101474429A (en) | Method for preparing hydroxylapatite-silk fibroin compound stent material using two-step method | |
| CN101401964A (en) | Organic-inorganic compound bone restoration bioactive material | |
| CN112830464B (en) | Strontium-doped hydroxyapatite nanotube and preparation method thereof | |
| CN101401950A (en) | Nano-calcium phosphate biological active ceramic material containing silicon dioxide and preparation method thereof | |
| Essien et al. | Microwave energy-assisted formation of bioactive CaO–MgO–SiO 2 ternary glass from bio-wastes | |
| CN104998301B (en) | Preparation method of carbon nano tube reinforced mesoporous hydroxyapatite composite material | |
| Baskaran et al. | Synthesis methods of doped hydroxyapatite: a brief review | |
| CN101716370A (en) | Method for preparing nano doped hydroxylapatite powder | |
| Prasad et al. | Surfactant-assisted synthesis of hydroxyapatite particles: A comprehensive review | |
| CN104944399B (en) | The preparation method of hydroxyapatite micro-sphere | |
| Sha et al. | A modified calcium silicate composite bone cement prepared from polyethylene glycol and graphene oxide for biomaterials | |
| CN101949046B (en) | Preparation method of carbonate hydroxyapatite/carbon nano tube composite coating material | |
| JP2011011971A (en) | Tubular calcium phosphate and method for production thereof | |
| CN100560505C (en) | The in-situ preparation method of nano zircite and hydroxyapatite composite powder | |
| CN101401951A (en) | Calcium phosphate biological active ceramic material containing silicon dioxide and preparation method thereof | |
| CN102328922A (en) | Preparation method of nano hydroxyapatite |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |