CN108379589B - Preparation method of hydroxyapatite/graphene oxide composite material - Google Patents
Preparation method of hydroxyapatite/graphene oxide composite material Download PDFInfo
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- CN108379589B CN108379589B CN201810210074.6A CN201810210074A CN108379589B CN 108379589 B CN108379589 B CN 108379589B CN 201810210074 A CN201810210074 A CN 201810210074A CN 108379589 B CN108379589 B CN 108379589B
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Abstract
The invention discloses a preparation method of a hydroxyapatite/graphene oxide composite material, which comprises the following steps: dissolving hydroxyapatite in an acid environment, adding a complexing agent for regulation and control reaction, regulating the pH value, performing centrifugal filtration, washing a filter cake obtained by centrifugal filtration, and freeze-drying to obtain a flaky self-assembled hydroxyapatite microsphere crystal; and secondly, mixing the prepared flaky self-assembled hydroxyapatite microsphere crystal with a dispersed graphene oxide solution under the action of ultrasonic waves, washing, putting into a freeze drying box, and freeze drying for 24-48 hours to obtain the hydroxyapatite/graphene oxide composite material. The invention simplifies the preparation process, does not need to specially add a cross-linking agent, and is suitable for biological medicine carrying application.
Description
Technical Field
The invention relates to the field of preparation of inorganic biomedical materials, in particular to a preparation method of a hydroxyapatite/graphene oxide composite material.
Background
The molecular formula of Hydroxyapatite (HA) is Ca10(PO4)6(OH)2Density of 3.16g/cm2. Slightly soluble in water, weakly alkaline, easily soluble in acid and hardly soluble in alkali. Hydroxyapatite is the most stable calcium phosphate salt between normal temperature and pH 4-12. Hydroxyapatite, which is a main inorganic component in calcified hard tissues (e.g., bones and teeth) of vertebrates, accounts for about 75% or more of human bone tissues, and is widely used in bone tissue engineering techniques and the like because of its excellent biocompatibility, osteoconductivity, fluidity, and adsorbability. In recent years, in order to meet different application requirements, researchers have prepared hydroxyapatite materials in various forms such as spheres, rods, sheets, whiskers and the like. Among these forms, spherical hydroxyapatite has been receiving great attention because it has advantages such as good fluidity, high specific surface area, good affinity, high filling degree, and minimal tumor induction rate. However, the poor tensile strength and poor fracture toughness of pure hydroxyapatite crystals limit its practical application.
Graphene oxide (abbreviated as GO) is a single-layer carbon atom as a graphene oxide derivative, and has a plurality of aromatic rings with different sizes on the surface of a hexagonal sheet layer consisting of carbon atoms, and a certain amount of hydroxyl, epoxy and carboxyl exist on the aromatic rings, wherein the carboxyl and the hydroxyl are mostly located at the edge of the graphite oxide sheet, and the carbonyl and the epoxy are located on the graphite oxide layer or between the layers. The active oxygen-containing functional groups on the graphene oxide sheet layer can enable the graphene oxide sheet layer to be stably dispersed in an aqueous medium, the binding force among components is enhanced, and the stress transfer among composite materials can be promoted. Therefore, the graphene oxide is expected to become a nano-scale reinforcing filler in the field of biological composite materials. Despite the above mentioned advantages, graphene oxide does not show any osteoconductivity, and hydroxyapatite is superior to graphene oxide in this respect. Unfortunately, the inherent brittleness of hydroxyapatite makes it impossible to use it alone as a structural member, and the reinforcing effect of hydroxyapatite is not as good as graphene oxide. Therefore, when the hydroxyapatite and the graphene oxide are simultaneously used as the reinforcing agent, the composite of the hydroxyapatite and the graphene oxide can fully combine the advantages of the hydroxyapatite and the graphene oxide, and the composite material has expected good mechanical properties and favorable cellular reaction and is expected to be applied to the field of inorganic biomedical materials.
At present, the method for synthesizing the hydroxyapatite/graphene oxide composite material comprises a hydrothermal synthesis method, an in-situ synthesis method, a biomimetic mineralization process, electrophoretic deposition, a discharge plasma sintering technology (SPS) and the like. Among them, the hydrothermal synthesis method is a relatively effective method for preparing high-quality inorganic crystals, and can also be used for preparing graphene-based composites. The closed reaction kettle can provide high pressure for reaction at high temperature, so that substances which are difficult to dissolve at normal pressure are well dissolved, products are well dissolved, and the solution can form crystals with good crystallinity in a supersaturated state. The hydrothermal synthesis method can be used for preparing a target sample in one step, and graphene oxide is reduced in the reaction. However, the particles obtained by the method have wide particle size distribution and irregular morphology, and have strict requirements on parameters such as stoichiometric ratio, pH value, temperature, time and the like of raw materials in the whole preparation process, so that the method is difficult to be used in large-scale industrial production; the sol-gel process for in-situ preparation of the graphene-based composite has the advantages that a large number of hydroxyl groups on the surface of graphene oxide can be used as nucleation points for hydrolysis, so that metal oxides can be directly connected to the surface by chemical bonds, and the sol-gel process has the disadvantages that organic solvents with low surface tension are required, influence factors are more, such as hydrolysis time, solution pH value, heat treatment temperature and the like, the shape of a product cannot be effectively controlled, and spherical hydroxyapatite is usually difficult to obtain; the template method is one of biomimetic mineralization processes, and is a soft template method taking flexible organic molecules with large structure variability as templates and a hard template method taking substances with rigid structures as templates to synthesize and prepare particles with required structures and shapes through ion exchange reaction. The hydroxyapatite particles prepared by the method have the problem that the surface oil phase, the surfactant and the template are difficult to completely remove; electrophoretic deposition is a special colloid treatment technology, is widely applied to coatings on various metal surfaces of bioactive ceramics or composite materials, well controls the thickness and the crystallinity of the coatings, and even obtains coatings with good uniformity on substrates with complex shapes, but the complexity and inconvenience of the process limit the popularization and the application.
In order to solve the problems in the prior art, a preparation method of a hydroxyapatite/graphene oxide composite material needs to be designed.
Disclosure of Invention
In order to overcome the defects in the prior art, a preparation method of a hydroxyapatite/graphene oxide composite material is provided.
The invention is realized by the following scheme:
a preparation method of a hydroxyapatite/graphene oxide composite material comprises the following steps:
dissolving hydroxyapatite in an acid environment, adding a complexing agent for regulation and control reaction, regulating the pH value, performing centrifugal filtration, washing a filter cake obtained by centrifugal filtration, and freeze-drying to obtain a flaky self-assembled hydroxyapatite microsphere crystal;
and secondly, mixing the prepared flaky self-assembled hydroxyapatite microsphere crystal with a dispersed graphene oxide solution under the action of ultrasonic waves, washing, putting into a freeze drying box, and freeze drying for 24-48 hours to obtain the hydroxyapatite/graphene oxide composite material.
The acid environment is a strong acid solution with the concentration of 0.001-0.01 mol/L, and the strong acid is one or two of nitric acid and hydrochloric acid.
The complexing agent is Na2One or more of EDTA, sodium citrate and potassium sodium tartrate, wherein the molar ratio of the complexing agent to the hydroxyapatite is 0.1-10.
The hydroxyapatite is dissolved in an acid environment and added with a complexing agent for regulation and control reaction, and the mixture is stirred at normal temperature.
And the pH value is adjusted by adding ammonia water, and after the ammonia water is added, the diffusion and reaction process lasts for 0.5-2 d.
The mass ratio of the hydroxyapatite to the graphene oxide is 0.8-1.5: 1.
the mixing is carried out at room temperature under the action of ultrasonic waves, and the reaction time is 0.5-5 h.
The washing in the first step is washing alternately by deionized water and absolute ethyl alcohol for multiple times.
And the washing in the second step is to alternately wash with deionized water and absolute ethyl alcohol for multiple times.
The invention has the beneficial effects that:
the preparation method of the hydroxyapatite/graphene oxide composite material simplifies the preparation process, does not need to specially add a cross-linking agent, and avoids pollution of the cross-linking agent residue on a final sample; meanwhile, the hydroxyapatite/graphene oxide composite material prepared by the method has a high specific surface area and is suitable for biological drug-loaded application.
Drawings
FIG. 1 is a field emission scanning electron microscope image of a hydroxyapatite/graphene oxide composite material prepared by the preparation method of the present invention; wherein (a) is a macroscopic scanning electron micrograph; (b) is a high-power scanning electron microscope picture;
fig. 2 is a fourier infrared spectrum of the hydroxyapatite microspheres prepared by the preparation method of the present invention.
Detailed Description
The invention is further illustrated by the following specific examples:
the technical scheme of the invention is as follows: a preparation method of a hydroxyapatite/graphene oxide composite material comprises the following steps:
dissolving hydroxyapatite in an acid environment, adding a complexing agent for regulation and control reaction, regulating the pH value, performing centrifugal filtration, washing a filter cake obtained by centrifugal filtration, and freeze-drying to obtain a flaky self-assembled hydroxyapatite microsphere crystal; by the preparation method, the complexing agent with proper dosage effectively regulates and controls the crystallization and growth of the hydroxyapatite, and the hydroxyapatite forms the flaky self-assembled compact microspheres under the condition of ammonia water diffusion; ultrasonic treatment is carried out to obtain a dispersion liquid of hydroxyapatite and graphene oxide, so that the whole reaction process can be carried out at normal temperature, large-scale industrial production is facilitated, and other technical schemes cannot be realized.
The hydroxyapatite can be purchased from the market or prepared by self, and the invention provides the following technical scheme for preparing the hydroxyapatite raw material with controllable morphology: the prepared hydroxyapatite and graphene oxide are used as raw materials, added into water to be uniformly dispersed, and subjected to ultrasonic treatment to obtain the hydroxyapatite/graphene oxide composite material. The dosage of the hydroxyapatite and the complexing agent can be adjusted according to the requirement, and the molar ratio of the hydroxyapatite and the complexing agent is just generated into the flaky self-assembled hydroxyapatite microspheres under the optimal condition; in order to facilitate feeding in production, the mass ratio of hydroxyapatite to graphene oxide in preparation of the composite material is generally 0.8-1.5: 1, the reaction can be carried out efficiently.
And secondly, mixing the prepared flaky self-assembled hydroxyapatite microsphere crystal with a dispersed graphene oxide solution under the action of ultrasonic waves, washing, putting into a freeze drying box, and freeze drying for 24-48 hours to obtain the hydroxyapatite/graphene oxide composite material.
The acid environment is a strong acid solution with the concentration of 0.001-0.01 mol/L, and the strong acid is one or two of nitric acid and hydrochloric acid.
The complexing agent is Na2EDTA, sodium citrate and tartaric acidOne or more of potassium and sodium, wherein the molar ratio of the complexing agent to the hydroxyapatite is 0.1-10.
The hydroxyapatite is dissolved in an acid environment and added with a complexing agent for regulation and control reaction, and the mixture is stirred at normal temperature.
And the pH value is adjusted by adding ammonia water, and after the ammonia water is added, the diffusion and reaction process lasts for 0.5-2 d.
The mass ratio of the hydroxyapatite to the graphene oxide is 0.8-1.5: 1.
the mixing is carried out at room temperature under the action of ultrasonic waves, and the reaction time is 0.5-5 h.
The washing in the first step is washing alternately by deionized water and absolute ethyl alcohol for multiple times.
And the washing in the second step is to alternately wash with deionized water and absolute ethyl alcohol for multiple times.
The present invention will be described in detail with reference to specific examples.
Example 1:
(1) dissolving 0.502g of nano hydroxyapatite in 100mL of deionized water, uniformly stirring, and slowly dropwise adding 1mol/L hydrochloric acid while stirring until the hydroxyapatite is completely dissolved;
(2) the hydroxyapatite solution was added with 0.7446g of Na complexing agent2EDTA is slowly added while stirring, and the mixture is stirred for 10 to 30min at normal temperature;
(3) placing the obtained solution and ammonia water in a closed reactor for reaction, wherein the reaction time is 0.5-2 d;
(4) centrifugally filtering the solution obtained in the step (3), and washing the solution with deionized water and absolute ethyl alcohol for more than 3 times respectively;
(5) putting the filter cake washed cleanly in the step (4) into a freeze drying box, and freeze drying for 24-48 hours to obtain the flaky self-assembled hydroxyapatite microsphere crystal;
(6) and mixing the prepared hydroxyapatite crystal with a dispersed graphene oxide solution with the concentration of 1mg/mL, performing ultrasonic action, washing with deionized water and absolute ethyl alcohol for more than 3 times respectively, putting into a freeze drying oven, and freeze drying for 24-48 h to obtain the hydroxyapatite/graphene oxide composite material.
Through detection: example 1 prepared are flake-like self-assembled hydroxyapatite microspheres, hydroxyapatite/graphene oxide composites, and these nanoparticles are coated and interwoven with graphene oxide (see fig. 1(a, b)).
Example 2
(1) Dissolving 0.502g of nano hydroxyapatite in 100mL of deionized water, uniformly stirring, and slowly dropwise adding 1mol/L hydrochloric acid while stirring until the hydroxyapatite is completely dissolved;
(2) adding 0.5645g of citric acid serving as a complexing agent into the hydroxyapatite solution, slowly adding the citric acid while stirring, and stirring for 10-30 min at normal temperature;
(3) placing the obtained solution and ammonia water in a closed reactor for reaction, wherein the reaction time is 0.5-2 d;
(4) centrifugally filtering the solution obtained in the step (3), and washing the solution with deionized water and absolute ethyl alcohol for more than 3 times respectively;
(5) putting the filter cake washed cleanly in the step (4) into a freeze drying box, and freeze drying for 24-48 hours to obtain the flaky self-assembled hydroxyapatite microsphere crystal;
(6) and mixing the prepared hydroxyapatite crystal with a dispersed graphene oxide solution with the concentration of 1mg/mL, performing ultrasonic action, washing with deionized water and absolute ethyl alcohol for more than 3 times respectively, putting into a freeze drying oven, and freeze drying for 24-48 h to obtain the hydroxyapatite/graphene oxide composite material.
Through detection: example 2 also prepared is a hydroxyapatite/graphene oxide composite. FTIR analysis performed knows that: the-OH peak appears at 3434cm-1The peak of the stretching vibration of the saturated C-H bond appears at 2923cm-1The carboxylic acid negative ion antisymmetric telescopic vibration absorption peak appears at 1630cm-1The absorption peak of the carboxylic acid anion symmetric stretching vibration appears at 1400cm-1The P-O asymmetric stretching vibration absorption peak appears at 1046cm-1The peak of O-P-O bending vibration appears at 603cm-1The material can be determined to be a hydroxyapatite/graphene oxide composite materialMaterial (as shown in figure 2).
Example 3
(1) Dissolving 0.502g of nano hydroxyapatite in 100mL of deionized water, uniformly stirring, and slowly dropwise adding 1mol/L hydrochloric acid while stirring until the hydroxyapatite is completely dissolved;
(2) adding 0.4203g of sodium potassium tartrate serving as a complexing agent into the hydroxyapatite solution, slowly adding the sodium potassium tartrate while stirring, and stirring for 10-30 min at normal temperature;
(3) placing the obtained solution and ammonia water in a closed reactor for reaction, wherein the reaction time is 0.5-2 d;
(4) centrifugally filtering the solution obtained in the step (3), and washing the solution with deionized water and absolute ethyl alcohol for more than 3 times respectively;
(5) putting the filter cake washed cleanly in the step (4) into a freeze drying box, and freeze drying for 24-48 hours to obtain the flaky self-assembled hydroxyapatite microsphere crystal;
(6) and mixing the prepared hydroxyapatite crystal with a dispersed graphene oxide solution with the concentration of 1mg/mL, performing ultrasonic action, washing with deionized water and absolute ethyl alcohol for more than 3 times respectively, putting into a freeze drying oven, and freeze drying for 24-48 h to obtain the hydroxyapatite/graphene oxide composite material.
Through detection: raman analysis of the material prepared in example 3 was also a hydroxyapatite/graphene oxide composite.
Aiming at the defects of the prior art, the invention creatively places a complexing agent in an acid solution environment dissolved with hydroxyapatite, changes the pH value of the solution through the diffusion of ammonia water to prepare a hydroxyapatite crystal with controllable morphology and compactness, and mixes the hydroxyapatite crystal with a graphene oxide dispersion liquid to prepare the hydroxyapatite/graphene oxide composite material. The method realizes that the forming process of the composite material can be carried out at room temperature, thereby effectively reducing the production difficulty and cost; meanwhile, the method can completely separate the preparation process of the hydroxyapatite from the forming process of the composite material, thereby maximally avoiding the influence of the raw materials in the early stage on the purity and yield of the final product and improving the production efficiency.
Although the invention has been described and illustrated in some detail, it should be understood that various modifications may be made to the described embodiments or equivalents may be substituted, as will be apparent to those skilled in the art, without departing from the spirit of the invention.
Claims (1)
1. A preparation method of a hydroxyapatite/graphene oxide composite material is characterized by comprising the following steps:
dissolving hydroxyapatite in an acid environment, adding a complexing agent for regulation and control reaction, regulating the pH value, performing centrifugal filtration, washing a filter cake obtained by centrifugal filtration, and freeze-drying to obtain a flaky self-assembled hydroxyapatite microsphere crystal;
secondly, mixing the prepared flaky self-assembled hydroxyapatite microsphere crystal with a dispersed graphene oxide solution under the action of ultrasonic waves, washing the mixture, putting the mixture into a freeze drying box, and freeze drying the mixture for 24-48 hours to obtain a hydroxyapatite/graphene oxide composite material;
the acid environment is a strong acid solution with the concentration of 0.001-0.01 mol/L, and the strong acid is one or two of nitric acid and hydrochloric acid; the complexing agent is Na2One or more of EDTA, sodium citrate and potassium sodium tartrate, wherein the molar ratio of the complexing agent to the hydroxyapatite is 0.1-10; dissolving the hydroxyapatite in an acidic environment, adding a complexing agent, and carrying out regulation and control reaction, wherein the hydroxyapatite is obtained by stirring at normal temperature; the pH value is adjusted by adding ammonia water, and after the ammonia water is added, the diffusion and reaction process lasts for 0.5-2 d; the mass ratio of the hydroxyapatite to the graphene oxide is 0.8-1.5: 1; the mixing is carried out at room temperature under the action of ultrasonic waves, and the reaction time is 0.5-5 h; the washing in the first step is washing alternately by deionized water and absolute ethyl alcohol for multiple times; and the washing in the second step is to alternately wash with deionized water and absolute ethyl alcohol for multiple times.
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| 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 |
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