CN114180984B - Hydroxyapatite/silicon oxide composite aerogel and preparation method thereof - Google Patents
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Abstract
The invention discloses a preparation method of hydroxyapatite/silicon oxide composite aerogel, which relates to the technical field of aerogel, wherein hydroxyapatite is taken as a reinforcing phase, the hydroxyapatite and silicon oxide are compounded in situ through a sol-gel process, and finally, a composite aerogel material is obtained through normal-pressure drying; the density of the composite aerogel is 0.086g/cm 3 Reducing the temperature to 0.57-0.66 g/cm 3 The Young modulus is improved to 3.7-9.0 KPa from 1.4KPa, and the porosity, specific surface area, thermal conductivity and average pore diameter are not changed greatly. Compared with the prior art, the silica aerogel heat insulation structure effectively enhances the mechanical strength of the silica aerogel and reduces the density while maintaining the heat insulation effect of the silica aerogel.
Description
The technical field is as follows:
the invention relates to the technical field of aerogel, in particular to hydroxyapatite/silicon oxide composite aerogel and a preparation method thereof.
Background art:
compared with the traditional heat insulation materials, the aerogel has extremely low heat conductivity and density under the same size, so that the aerogel has unusual advantages in the field of heat insulation. Silica aerogel, one of them, has many advantages such as high porosity, low thermal conductivity, low dielectric constant, high specific surface area, and good biocompatibility, but silica aerogel has many disadvantages such as: poor mechanical properties, easy crushing and difficult processing; the high-temperature heat conductivity is high; in an air atmosphere, the residual unreacted-OH functional groups on the surface of the gel can make the aerogel hygroscopic, and can automatically adsorb moisture in the air to collapse the aerogel structure and lose the heat insulation effect.
In order to improve the strength of the aerogel, a common method is to reinforce the aerogel, and the method can be classified into a chemical reinforcement method and a physical reinforcement method according to the difference of the reinforcing phase. The chemical strengthening method generally uses organic components such as epoxy resin, isocyanate, and isophthalaldehyde as a strengthening phase, and the organic components are crosslinked with silica gel particles to strengthen the mechanical properties of the silica aerogel. However, this method is likely to have adverse effects on flame retardancy, and introduces flammable components, which may generate toxic gases.
The physical reinforcement method usually takes fiber as a reinforcing phase, and the mechanical property of the prepared aerogel is better improved. The Chinese patent publication No. CN104556965 discloses a hydrophobic silica aerogel heat-insulating composite material, which is prepared by using rock wool fibers, alumina fibers, zirconia fibers and other inorganic fibers as reinforcing phases, wherein the porosity of the prepared aerogel is only 50-70%, and is obviously reduced compared with the conventional non-reinforced aerogel which is more than 90%. 1-7[2021-07-30] discloses the effect of glass fiber on the structure and performance of aerogel composite material, which takes glass fiber as reinforcement, the density of the prepared silica aerogel is linearly related to the fiber content, when the performance of the aerogel (the fiber content is 1.5 wt%) is optimal, the specific surface area of the aerogel is reduced by 12.6%, and the density is increased by 14.2%.
This is because the diameter of common inorganic fibers is usually in the micrometer range, such as glass fiber with a diameter of 3-80 um, alumina fiber with a diameter of 3-7 um, zirconia fiber with a diameter of 3-6 um; the pore diameter of the silica aerogel is in the nanometer level, and the fiber diameter is too large, so that silica particles are adsorbed on the surface of the fiber to form a relatively compact structure, and the original porous structure of the silica aerogel is influenced, so that the traditional inorganic fiber can enhance the mechanical property and the thermal property of the silica aerogel, but cannot keep the original characteristics of light weight and high porosity.
In the text of the performance research of the carbon nanotube reinforced aerogel heat insulation composite material, the Wu Hui Jun, guangzhou university disperses the carbon nanotubes into the silica aerogel, the strength of the aerogel is improved along with the increase of the content of the carbon nanotubes, and the density of the aerogel is increased.
The invention content is as follows:
the invention aims to solve the technical problem of providing a preparation method of hydroxyapatite/silicon oxide composite aerogel. The method can improve the strength of the aerogel and simultaneously reduce the density, so that the aerogel has the advantages of high strength, light weight and high porosity.
The technical problem to be solved by the invention is realized by adopting the following technical scheme:
the invention aims to provide a hydroxyapatite/silicon oxide composite aerogel, wherein the diameter of the hydroxyapatite and the pore diameter of the aerogel are both nano-scale, and the length-diameter ratio of the hydroxyapatite is more than 2000.
The content of hydroxyapatite in the aerogel is 1-10 wt% of the content of silicon oxide.
Preferably, the content of hydroxyapatite in the aerogel is 6 to 8wt% of the content of silica.
The invention also aims to provide a normal pressure preparation method of the hydroxyapatite/silicon oxide composite aerogel, which comprises the following steps:
(1) Dispersing hydroxyapatite into a solvent, and simultaneously dripping a silicon source and a first catalyst into hydroxyapatite dispersion liquid to obtain a precursor solution;
(2) Adding a second catalyst into the precursor solution, uniformly stirring and standing for gelation to obtain hydroxyapatite/silicon oxide in-situ composite wet gel;
(3) And (3) aging the wet gel, replacing the solvent, and drying at normal pressure to obtain the white hydroxyapatite/silicon oxide composite aerogel.
The silicon source includes but is not limited to one of tetraethyl silicate, tetramethyl silicate, organosilane and water glass.
The solvent includes but is not limited to at least one of methanol, ethanol, acetone, dimethyl sulfoxide, and ethylene glycol.
Preferably, the organosilane includes but is not limited to at least one of methyltrimethoxysilane, methyltriethoxysilane, and derivatives thereof, and the solvent is methanol.
The molar ratio of the solvent to the first catalyst to the silicon source is (5-40) to (1-8) to 1.
Preferably, the molar ratio of the solvent, the first catalyst and the silicon source is 32.
The first catalyst is an acid catalyst, and comprises at least one of hydrochloric acid, nitric acid, acetic acid and oxalic acid solution, and the concentration of the first catalyst is 0.001-1 mol/L.
Preferably, the acid catalyst is oxalic acid solution with the concentration of 0.01 mol/L.
The molar ratio of the second catalyst to the silicon source is (1-8) to 1.
Preferably, the molar ratio of the second catalyst to the silicon source is 4.
The second catalyst is an alkaline catalyst, including but not limited to at least one of sodium hydroxide, potassium hydroxide and ammonia water solution, and the concentration is 4-12 mol/L.
Preferably, the alkaline catalyst is 10mol/L ammonia water solution.
The solvent used for solvent replacement is the same as the solvent used in the step (1), the aging temperature is 50 ℃, the aging time is 24h, and the solvent replacement condition is that the temperature is kept constant at 50 ℃ for 24h for 3 times.
The invention has the beneficial effects that:
(1) According to the invention, hydroxyapatite is used as a reinforcing phase, the hydroxyapatite and silicon oxide are compounded in situ through a sol-gel process, and finally, the composite aerogel material is obtained through normal pressure drying; the density of the composite aerogel is 0.086g/cm 3 Reducing the temperature to 0.57-0.66 g/cm 3 The Young modulus is improved from 1.4KPa to 3.7-9.0 KPa, and the porosity, the specific surface area, the thermal conductivity and the average pore diameter are not greatly changed.
(2) Compared with the prior art, the silica aerogel heat insulation structure effectively enhances the mechanical strength of the silica aerogel and reduces the density while maintaining the heat insulation effect of the silica aerogel.
Description of the drawings:
FIG. 1 is an SEM image of hydroxyapatite fibers used in an example;
FIG. 2 is the nitrogen adsorption desorption isotherm of example 4;
FIG. 3 is a plot of the pore size distribution of example 4;
FIG. 4 is a nitrogen adsorption-desorption isotherm of comparative example 1;
fig. 5 is a pore size distribution curve of comparative example 1.
The specific implementation mode is as follows:
in order to make the technical means, the original characteristics, the achieved purposes and the effects of the invention easy to understand, the invention is further explained by combining the specific embodiments and the drawings.
The hydroxyapatite used in examples 1 to 6 below had a fiber diameter of 18nm and an aspect ratio of 2200.
Example 1
Weighing 0.0135g of hydroxyapatite fiber, ultrasonically dispersing into 26mL of methanol solution, then adding 2.87mL of methyltrimethoxysilane (MTMS) and 1.44mL of 0.01mol/L of oxalic acid solution into the dispersion while stirring, standing at a constant temperature of 50 ℃ for 24h after uniformly stirring, hydrolyzing to obtain a precursor solution, adding 1.44mL of 10mol/L of ammonia water solution into the precursor solution, uniformly stirring, standing at a temperature of 50 ℃ for gelation to obtain hydroxyapatite/silicon oxide composite wet gel, aging the wet gel, replacing the solvent, and drying at a temperature of 25-200 ℃ under normal pressure to obtain the hydroxyapatite/silicon oxide composite aerogel.
Example 2
Weighing 0.0405g of hydroxyapatite fiber, ultrasonically dispersing the hydroxyapatite fiber in 26mL of methanol solution, then adding 2.87mL of methyltrimethoxysilane and 1.44mL of 0.01mol/L of oxalic acid solution into the dispersion while stirring, standing at a constant temperature of 50 ℃ for 24h after uniform stirring, hydrolyzing to obtain a precursor solution, adding 1.44mL of 10mol/L ammonia water solution into the precursor solution, stirring uniformly, standing at a temperature of 50 ℃ for gelation to obtain hydroxyapatite/silicon oxide composite wet gel, aging the wet gel, replacing the solvent, and drying at a temperature of 25-200 ℃ under normal pressure to obtain the hydroxyapatite/silicon oxide composite aerogel.
Example 3
Weighing 0.0675g of hydroxyapatite fiber, ultrasonically dispersing into 26mL of methanol solution, then adding 2.87mL of methyltrimethoxysilane and 1.44mL of 0.01mol/L of oxalic acid solution into the dispersion while stirring, standing at a constant temperature of 50 ℃ for 24h after uniform stirring for hydrolysis to obtain precursor solution, adding 1.44mL of 10mol/L ammonia water solution into the precursor solution, stirring uniformly, standing at a temperature of 50 ℃ for gelation to obtain hydroxyapatite/silicon oxide composite wet gel, aging the wet gel, replacing the solvent, and drying at a temperature of 25-200 ℃ under normal pressure to obtain the hydroxyapatite/silicon oxide composite aerogel.
Example 4
Weighing 0.0945g of hydroxyapatite fiber, ultrasonically dispersing into 26mL of methanol solution, then adding 2.87mL of methyltrimethoxysilane and 1.44mL of 0.01mol/L of oxalic acid solution into the dispersion liquid while stirring, standing at a constant temperature of 50 ℃ for 24h for hydrolysis to obtain precursor solution after uniform stirring, adding 1.44mL of 10mol/L of ammonia solution into the precursor solution, standing at a temperature of 50 ℃ for gelation to obtain hydroxyapatite/silicon oxide composite wet gel after uniform stirring, aging the wet gel, replacing the solvent, and drying at a temperature of 25-200 ℃ under normal pressure to obtain the hydroxyapatite/silicon oxide composite aerogel.
Example 5
Weighing 0.135g of hydroxyapatite fiber, ultrasonically dispersing into 26mL of methanol solution, then adding 2.87mL of methyltrimethoxysilane and 1.44mL of 0.01mol/L of oxalic acid solution into the dispersion while stirring, standing at a constant temperature of 50 ℃ for 24h after uniform stirring for hydrolysis to obtain precursor solution, adding 1.44mL of 10mol/L ammonia water solution into the precursor solution, stirring uniformly, standing at 50 ℃ for gelation to obtain hydroxyapatite/silicon oxide composite wet gel, aging the wet gel, replacing the solvent, and drying at a normal pressure of 25-200 ℃ to obtain the hydroxyapatite/silicon oxide composite aerogel.
Example 6
Weighing 0.0414g of hydroxyapatite fiber, ultrasonically dispersing into 20mL of ethanol solution, then dropwise adding 2.2mL of tetraethyl silicate (TEOS) into the dispersion while stirring, dropwise adding 0.4mL of 10mol/L ammonia water solution after uniformly stirring, standing at room temperature after stirring for 2min to obtain hydroxyapatite/silicon oxide composite wet gel, aging the wet gel, replacing the solvent, and drying at the temperature of 25-200 ℃ under normal pressure to obtain the hydroxyapatite/silicon oxide composite aerogel.
Comparative example 1
Measuring 26mL of methanol solution, dropwise adding 2.87mL of methyltrimethoxysilane and 1.44mL of 0.01mol/L oxalic acid solution while stirring, standing at a constant temperature of 50 ℃ for 24h after uniform stirring for hydrolysis to obtain a precursor solution, dropwise adding 1.44mL of 10mol/L ammonia water solution into the precursor solution, standing at a temperature of 50 ℃ for gelation after uniform stirring to obtain silica wet gel, aging the wet gel, replacing the solvent, and drying at a temperature of 25-200 ℃ under normal pressure to obtain the silica aerogel.
Comparative example 2
Weighing 0.0945g of attapulgite fiber, dispersing the attapulgite fiber in 26mL of methanol solution by ultrasonic, wherein the diameter of the attapulgite fiber is about 20nm, the length of the attapulgite fiber is about 0.7um, the length-diameter ratio of the attapulgite fiber is 35, then adding 2.87mL of methyltrimethoxysilane and 1.44mL of 0.01mol/L of oxalic acid solution dropwise while stirring the dispersion solution, standing the dispersion solution at a constant temperature of 50 ℃ for 24h after stirring the dispersion solution uniformly, hydrolyzing the dispersion solution to obtain a precursor solution, adding 1.44mL of 10mol/L of ammonia water solution dropwise into the precursor solution after stirring the dispersion solution uniformly, standing the dispersion solution at a temperature of 50 ℃ for gelation to obtain the attapulgite/silicon oxide composite wet gel, aging the wet gel, replacing the solvent, and drying the wet gel at a temperature of 25-200 ℃ under normal pressure to obtain the attapulgite/silicon oxide composite aerogel.
Comparative example 3
Weighing 0.0945g of hydroxyapatite fiber with a low length-diameter ratio, ultrasonically dispersing the hydroxyapatite fiber into 26mL of methanol solution, wherein the diameter of the hydroxyapatite fiber in the comparative example is 18nm, the length of the hydroxyapatite fiber is about 10um, and the length-diameter ratio of the hydroxyapatite fiber is 555, then dropwise adding 2.87mL of methyltrimethoxysilane and 1.44mL of 0.01mol/L of oxalic acid solution into the dispersion while stirring, standing at 50 ℃ for 24h for hydrolysis after uniform stirring to obtain a precursor solution, dropwise adding 1.44mL of 10mol/L of ammonia water solution into the precursor solution, stirring uniformly, standing at 50 ℃ for gelation to obtain a hydroxyapatite/silicon oxide composite wet gel, aging the wet gel, performing solvent replacement, and drying at 25-200 ℃ under normal pressure to obtain the hydroxyapatite/silicon oxide composite aerogel.
Comparative example 4
Uniformly mixing 10mL of ethanol and 3.2mL of deionized water, then dropwise adding 2.2mL of tetraethyl silicate into the mixed solution while stirring, continuing stirring for 5min after the dropwise addition is finished, then dropwise adding 0.4mL of 10mol/L ammonia water solution, stirring for 2min, standing at room temperature to obtain wet silica gel, aging the wet gel, replacing the solvent, and drying at the normal pressure of 25-200 ℃ to obtain the pure silica aerogel taking tetraethyl silicate as a silicon source.
The density and porosity of the aerogel are measured by an Archimedes drainage method; compressing the aerogel block body at room temperature by using a dynamic thermomechanical analyzer to obtain a stress-strain curve of the aerogel block body, and analyzing to obtain the Young modulus of the aerogel; transient thermal conductivity of the aerogel material is tested by a thermal constant analyzer of the HotDisk, the specific surface area and the average pore diameter of the aerogel are obtained by a nitrogen adsorption and desorption method of a full-automatic specific surface area pore analyzer, and performance test results are shown in Table 1.
TABLE 1 results of performance test of examples and comparative examples
As can be seen from comparison of comparative examples and examples, when methyltrimethoxysilane (MTMS) is used as a silicon source, the addition of the hydroxyapatite fibers with high aspect ratio improves the advantages of light weight and porosity of the aerogel while enhancing the mechanical properties of the aerogel, wherein when the fiber content is low (less than 7 wt%), the mechanical properties of the aerogel are gradually enhanced along with the increase of the fiber content, the composite aerogel can better resist the volume shrinkage caused by capillary force during the normal pressure drying process, therefore, the porosity of the aerogel is increased along with the increase of the fiber content, and when the components are similar, the density and the thermal conductivity of the aerogel are also reduced along with the increase of the porosity. However, when the content of the fibers exceeds a critical value, the fibers are easy to agglomerate in the gelling process, the obtained composite aerogel structure has defects to cause stress concentration, the mechanical property is reduced, the porosity is reduced, and the density and the thermal conductivity of the aerogel are increased. Therefore, the optimum doping amount of the hydroxyapatite fiber is 7wt%. In addition, when the doping amount of other nanoscale inorganic fibers such as attapulgite and hydroxyapatite fiber with low length-diameter ratio is 7wt%, the mechanical properties are enhanced, but the porosity is reduced to different degrees, and the light weight, the porosity and the mechanical enhancement cannot be simultaneously achieved. When tetraethyl silicate (TEOS) is used as a silicon source, hydroxyapatite fibers are added to change the aerogel from particles into blocks, so that the mechanical property of the aerogel is improved, the density is reduced, the porosity is increased, and the hydroxyapatite fibers with high length-diameter ratio have the same effect in other silicon sources.
The specific surface area of the samples of examples and comparative examples was further measured to obtain the performance parameters shown in table 2:
TABLE 2 specific surface areas of examples and comparative examples
As can be seen from Table 2, the specific surface area of the aerogel is slightly reduced but still high after the hydroxyapatite fibers are added, because the diameter of the hydroxyapatite fibers is larger than the average pore diameter of the aerogel, the fibers can block part of the pores of the aerogel, and further reduce the specific surface area of the aerogel, but the influence on the specific surface area is not great.
The result shows that the hydroxyapatite/silicon oxide composite aerogel has lower density, better heat insulation effect, higher porosity and mechanical strength than pure silicon oxide aerogel, and is an aerogel material with excellent performance prepared by normal pressure drying.
The foregoing shows and describes the general principles and broad features of the present invention and advantages thereof. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are given by way of illustration of the principles of the present invention, but that various changes and modifications may be made without departing from the spirit and scope of the invention, and such changes and modifications are within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (9)
1. A hydroxyapatite/silicon oxide composite aerogel is characterized in that: the diameter of the hydroxyapatite and the pore diameter of the aerogel are both nano-scale, and the length-diameter ratio of the hydroxyapatite is larger than 2000;
the content of hydroxyapatite in the aerogel is 1 to 7 weight percent of the content of silicon oxide;
through the sol-gel process, the hydroxyapatite and the silicon oxide are compounded in situ.
2. The atmospheric pressure preparation method of hydroxyapatite/silica composite aerogel described in claim 1, characterized by comprising the following steps:
(1) Dispersing hydroxyapatite into a solvent, and simultaneously dripping a silicon source and a first catalyst into hydroxyapatite dispersion liquid to obtain a precursor solution;
(2) Adding a second catalyst into the precursor solution, uniformly stirring and standing for gelation to obtain hydroxyapatite/silicon oxide in-situ composite wet gel;
(3) And (3) aging the wet gel, replacing the solvent, and drying at normal pressure to obtain the white hydroxyapatite/silicon oxide composite aerogel.
3. The atmospheric-pressure preparation method of hydroxyapatite/silica composite aerogel according to claim 2, characterized in that: the silicon source includes but is not limited to one of tetraethyl silicate, tetramethyl silicate, organosilane and water glass.
4. The atmospheric-pressure preparation method of hydroxyapatite/silica composite aerogel according to claim 2, characterized in that: the solvent includes, but is not limited to, at least one of methanol, ethanol, acetone, dimethyl sulfoxide, and ethylene glycol.
5. The atmospheric-pressure preparation method of hydroxyapatite/silica composite aerogel according to claim 2, characterized in that: the molar ratio of the solvent to the first catalyst to the silicon source is (5-40) to (1-8) to 1.
6. The atmospheric pressure preparation method of hydroxyapatite/silica composite aerogel according to claim 2, characterized in that: the first catalyst is an acid catalyst, and comprises at least one of hydrochloric acid, nitric acid, acetic acid and oxalic acid solution, and the concentration of the first catalyst is 0.001-1 mol/L.
7. The atmospheric pressure preparation method of hydroxyapatite/silica composite aerogel according to claim 2, characterized in that: the molar ratio of the second catalyst to the silicon source is (1-8): 1.
8. The atmospheric pressure preparation method of hydroxyapatite/silica composite aerogel according to claim 2, characterized in that: the second catalyst is an alkaline catalyst, including but not limited to at least one of sodium hydroxide, potassium hydroxide and ammonia water solution, and the concentration is 4-12 mol/L.
9. The atmospheric-pressure preparation method of hydroxyapatite/silica composite aerogel according to claim 2, characterized in that: the solvent used for solvent replacement is the same as the solvent used in the step (1), the aging temperature is 50 ℃, the aging time is 24 hours, and the solvent replacement condition is that the temperature is kept constant at 50 ℃ and 24 hours for replacement for 3 times.
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