CN113716954A - Preparation method of tetragonal barium titanate ceramic powder with antibacterial performance - Google Patents
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Abstract
The invention discloses a preparation method of tetragonal barium titanate ceramic powder with antibacterial performance, belonging to the technical field of ferroelectric and piezoelectric ceramic materials. The method completes the atomic scale mixing of a barium source and a titanium source in a liquid phase state by means of a liquid phase chemical process; thirdly, fixing the precursor in a liquid precursor form through a rotary evaporation reaction; finally, the washed and dried precursor is subjected to a certain heat treatment process, so that the tetragonal barium titanate ceramic powder with good antibacterial performance can be controllably synthesized. The synthesis process mainly takes common inorganic salt and simple reagents as main materials, and has the advantages of low cost, simplicity, easy operation and good repeatability. The synthesized tetragonal barium titanate ceramic powder has stable components, narrow size and particle size distribution, high crystal face index and good antibacterial performance, is suitable for large-scale batch production, and provides a certain theoretical basis for antibacterial research of ferroelectric materials.
Description
Technical Field
The invention relates to the technical field of ferroelectric and piezoelectric ceramic materials, in particular to a preparation method of tetragonal barium titanate ceramic powder with antibacterial performance.
Background
With the continuous development of social economy, the global environmental pollution is becoming more serious, and pathogenic bacteria, mold and harmful microorganisms which are found everywhere in life affect the health of people. Therefore, the use and research of antibacterial materials have become an important means for the research and development of the current urgent and for maintaining human health. The antibacterial material is a novel functional material which can inhibit the growth and reproduction of microorganisms such as bacteria and the like or inactivate the bacteria, can be obtained by adding an antibacterial agent into the material or introducing an antibacterial group into a carrier material in other ways, and has the main function of the antibacterial material. Antibacterial agents that have been developed and used at present are mainly classified into natural antibacterial agents, organic antibacterial agents and inorganic antibacterial agents.
The natural antibacterial agents extracted from animals, plants, bacteria, fungi, algae and the like have the advantages of good safety, biocompatibility, function diversification and the like, but almost every natural antibacterial agent has other unique properties besides antibacterial property, is difficult to control by people, has higher preparation cost, is easy to deteriorate under the influence of the environment such as temperature, illumination, evaporation and the like, and is greatly limited in the use process. The organic antibacterial agents such as quaternary ammonium salts, halogen amines, chitosan polymers and the like have strong initial bactericidal power and good antibacterial broad spectrum, but have the problems of short antibacterial time, poor chemical stability, easy thermal decomposition, complex components, difficult degradation, secondary pollution of different degrees and the like. The inorganic antibacterial agent has good stability, high and durable antibacterial effect, small side effect and low cost, and is widely applied to the antibacterial fields of environmental remediation, pollution treatment and the like in actual production.
Perovskite type oxide barium titanate (BaTiO) with micro-nano structure3) As a typical N-type semiconductor functional material, the material has high dielectric constant, low dielectric loss and excellent piezoelectric propertyThe important basic material of modern electronic ceramic industry is known as the pillar of electronic ceramic industry. Non-centrosymmetric tetragonal phase BaTiO3The ferroelectric material has excellent ferroelectricity, positive and negative charge centers in crystal lattices are not overlapped, and electric dipole moment can be generated without an external electric field to generate spontaneous polarization; when it is polarized in external electric field, the electric domain is oriented toward external electric field direction, and when the external electric field is removed, the electric domain can retain a certain directional arrangement to form residual polarization, so that the ferroelectric tetragonal phase BaTiO can be obtained3Has antibacterial activity. The prior methods for preparing tetragonal barium titanate powder mainly comprise a solid phase method and a liquid phase method. The solid phase method is to prepare BaTiO3According to a conventional synthesis method, BaTiO synthesized by the method3Although the powder has higher tetragonal phase content, the prepared powder has larger particle size, serious agglomeration, poor dispersibility and poor use effect, and is difficult to meet the performance requirement of industrial application; the liquid phase production method mainly comprises a hydrothermal method, a sol-gel method, a chemical precipitation method and the like, and is widely used for synthesizing nanometer and micrometer-scale superfine tetragonal phase barium titanate powder with high purity and uniform size in recent years, however, the tetragonal phase BaTiO prepared by the methods3The powder yield is limited, and large-scale industrial production is difficult.
Disclosure of Invention
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides a preparation method of tetragonal barium titanate ceramic powder with antibacterial performance. Firstly, completing atomic scale mixing of a barium source and a titanium source in a liquid phase state by means of a liquid phase chemical process; thirdly, fixing the precursor in a liquid precursor form through a rotary evaporation reaction; finally, the washed and dried precursor is subjected to a certain heat treatment process, so that the tetragonal barium titanate ceramic powder with good antibacterial performance can be controllably synthesized.
(II) technical scheme
In order to achieve the purpose, the invention provides the following technical scheme: a preparation method of tetragonal barium titanate ceramic powder with antibacterial performance comprises the following steps:
step 1, preparing a barium salt solution: with barium chloride BaCl2·2H2O is a barium source, ethanolamine C6H8O7Weighing barium chloride BaCl as a reaction chelating agent2·2H2Adding deionized water into the beaker, and stirring until the deionized water is completely dissolved to obtain a colorless transparent solution; taking ethanolamine C6H8O7Adding the solution into the colorless transparent solution, and uniformly stirring to obtain a barium salt solution;
step 2, preparing a titanium salt solution: with butyl titanate C16H36O4Ti is taken as a titanium source, and butyl titanate C is weighed16H36O4Adding Ti into a beaker, adding absolute ethyl alcohol, and fully mixing to obtain a titanium salt solution;
step 3, preparing an alkaline solution: weighing NaOH powder, dissolving the NaOH powder into deionized water successively, and stirring uniformly to obtain an alkaline solution;
step 4, mixing to prepare BaTiO3Precursor solution: mixing the barium salt solution obtained in the step 1 with the titanium salt solution obtained in the step 2, uniformly stirring, adding the NaOH solution obtained in the step 3, reacting under a high-concentration alkaline condition to obtain an upper-layer clear and lower-layer white turbid solution, wherein the lower-layer white turbid solution is BaTiO3A precursor solution;
step 5, preparing BaTiO by rotary evaporation3Precursor powder: the BaTiO obtained in the step 43Transferring the precursor solution into a eggplant-shaped bottle, performing rotary evaporation reaction, centrifugally washing, and drying in an oven to obtain BaTiO3Precursor powder;
step 6, synthesizing tetragonal barium titanate ceramic powder with good antibacterial performance by heat treatment: the BaTiO obtained in the step 5 is treated3And placing the precursor powder in a muffle furnace, and calcining at high temperature in the air to obtain the tetragonal barium titanate ceramic powder with good antibacterial performance.
Preferably, ethanolamine C in said step 16H8O7With barium chloride BaCl2·2H2The molar ratio of O is 1: 1, adding deionized water and barium chloride BaCl2·2H2The mass ratio of O is 3-5: 1.
preferably, theButyl titanate C in the above step 216H36O4Ti and barium chloride BaCl2·2H2The molar ratio of O is 1: 1, Anhydrous ethanol with butyl titanate C16H36O4The mass ratio of Ti is 2-4: 1.
preferably, NaOH and barium chloride BaCl are adopted in the step 32·2H2The molar ratio of O is 3-15: 1, the mass ratio of the added deionized water to NaOH is 3-5: 1, adding NaOH powder into deionized water for 5-20 times.
Preferably, the conditions of rotary evaporation in step 5 are as follows: performing rotary evaporation at 142mbar and 55 deg.C for 60-90min, and performing rotary evaporation at 72mbar and 60 deg.C for 120-150 min; during centrifugal washing, firstly washing with ultrapure water for 3 times, and then washing with absolute ethyl alcohol for 3 times; the drying conditions are as follows: drying at 60 deg.C for 36-48 h.
Preferably, the temperature of the high-temperature calcination in step 6 is selected from one of 650 ℃ and 800 ℃, and the time of the high-temperature calcination is 120 min.
(III) advantageous effects
The invention provides a preparation method of tetragonal barium titanate ceramic powder with antibacterial performance. The method has the following beneficial effects:
the synthesis process mainly takes common inorganic salt and simple reagents as main materials, and has the advantages of low cost, simplicity, easy operation and good repeatability. The synthesized tetragonal barium titanate ceramic powder has stable components, narrow size and particle size distribution, high crystal face index and good antibacterial performance, is suitable for large-scale batch production, and provides a certain theoretical basis for antibacterial research of ferroelectric materials. The method has the further significance of establishing the important requirements of the country on clean energy application and environmental management, not only widening the preparation method of the perovskite material, but also promoting the scientific intersection of the material and the environment, laying a theoretical foundation for the research and application of related perovskite antibacterial devices, and having important scientific significance.
Drawings
FIG. 1 is a flow chart of a method for preparing tetragonal barium titanate ceramic powder with antibacterial property according to the present invention;
FIG. 2 is an X-ray diffraction pattern of the tetragonal barium titanate ceramic powder with good antibacterial property prepared in examples 1-6 of the present invention;
FIG. 3 is a scanning electron microscope image of tetragonal barium titanate ceramic powder with good antibacterial property prepared in examples 1-6 of the present invention;
FIG. 4 is a scanning electron microscope image of the tetragonal barium titanate ceramic powder having good antibacterial properties prepared in examples 1 to 6 of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a technical scheme that: a preparation method of tetragonal barium titanate ceramic powder with antibacterial property is shown in a process flow chart of figure 1, and comprises the following specific operation steps:
step 1, preparing a barium salt solution system: with BaCl2·2H2O is barium source, C6H8O7Weighing appropriate amount of BaCl for reaction of chelating agent2·2H2Adding a proper amount of deionized water into the beaker, and stirring until the deionized water is completely dissolved to obtain a colorless transparent solution; in addition, balance right amount of C6H8O7Adding the barium salt solution into the solution, and uniformly stirring to obtain a barium salt solution system; wherein C is6H8O7With BaCl2·2H2The molar ratio of O is 1: 1, adding deionized water and BaCl2·2H2The mass ratio of O is 3-5: 1.
step 2, preparing a titanium salt solution system: with C16H36O4Ti is taken as a titanium source, and an appropriate amount of C is weighed16H36O4Adding a proper amount of absolute ethyl alcohol into Ti in a beaker, and fully mixing to obtain a titanium salt solution system; wherein C is16H36O4Ti and BaCl2·2H2The molar ratio of O is 1: 1, anhydrous ethanol withC16H36O4The mass ratio of Ti is 2-4: 1.
step 3, preparing an alkaline solution: weighing a proper amount of NaOH powder, gradually dissolving the NaOH powder into deionized water, and uniformly stirring to obtain an alkaline solution; wherein NaOH and BaCl2·2H2The molar ratio of O is 3-15: 1, adding deionized water and NaOH according to the mass ratio of 3-5: 1, adding NaOH powder into deionized water for 5-20 times.
Step 4, mixing to obtain BaTiO3Precursor solution: mixing the barium salt solution obtained in the step 1 with the titanium salt solution obtained in the step 2, uniformly stirring, adding the NaOH solution obtained in the step 3, and reacting under a high-concentration alkaline condition to obtain a white turbid liquid system with a clear upper layer and a white turbid lower layer, namely BaTiO3A precursor solution.
Step 5, preparing BaTiO by rotary evaporation3Precursor powder: the BaTiO obtained in the step 43Transferring the precursor solution into an eggplant-shaped bottle, performing rotary evaporation reaction under certain parameters, centrifugally washing, and drying in an oven to obtain BaTiO3Precursor powder; wherein the conditions of rotary evaporation are as follows: performing rotary evaporation at 142mbar and 55 deg.C for 60-90min, and performing rotary evaporation at 72mbar and 60 deg.C for 120-150 min; during centrifugal washing, firstly washing with ultrapure water for 3 times, and then washing with absolute ethyl alcohol for 3 times; the drying conditions are as follows: drying at 60 deg.C for 36-48 h.
Step 6, synthesizing tetragonal barium titanate ceramic powder with good antibacterial performance by heat treatment: the BaTiO obtained in the step 5 is treated3Putting the precursor powder into a muffle furnace, and calcining at high temperature in the air to obtain tetragonal barium titanate ceramic powder with good antibacterial performance; wherein the high-temperature calcination temperature is 650 ℃ or 800 ℃, and the high-temperature calcination time is 120 min.
Example 1:
step 1, preparing a barium salt solution system: with BaCl2·2H2O is barium source, C6H8O7To react the chelating agent, 0.05mol (12g) of BaCl was weighed out2·2H2Adding 50mL of deionized water into a beaker, and stirring until the deionized water is completely dissolved to obtain a colorless transparent solution; 0.05mol (3g) of C6H8O7Adding the barium salt solution into the solution, and uniformly stirring to obtain a barium salt solution system;
step 2, preparing a titanium salt solution system: with C16H36O4Ti is used as a titanium source, and 0.05mol (17mL) of C is weighed16H36O4Adding Ti into a beaker, adding 30mL of absolute ethyl alcohol, and fully mixing to obtain a titanium salt solution system;
step 3, preparing an alkaline solution: weighing 0.15mol (6.25g) of NaOH powder, gradually dissolving the NaOH powder into 30mL of deionized water for 5 times, and uniformly stirring to obtain an alkaline solution;
step 4, mixing to obtain BaTiO3Precursor solution: mixing the barium salt solution obtained in the step 1 with the titanium salt solution obtained in the step 2, uniformly stirring, adding the NaOH solution obtained in the step 3, and reacting under a high-concentration alkaline condition to obtain a white turbid liquid system with a clear upper layer and a white turbid lower layer, namely BaTiO3A precursor solution;
step 5, preparing BaTiO by rotary evaporation3Precursor powder: the BaTiO obtained in the step 43Transferring the precursor solution into an eggplant-shaped bottle, performing rotary evaporation reaction under certain parameters, centrifugally washing, and drying in an oven to obtain BaTiO3Precursor powder; wherein the conditions of rotary evaporation are as follows: rotary steaming at 142mbar and 55 deg.C for 90min, and further rotary steaming at 72mbar and 60 deg.C for 150 min; during centrifugal washing, firstly washing with ultrapure water for 3 times, and then washing with absolute ethyl alcohol for 3 times; the drying conditions are as follows: drying at 60 deg.C for 48 h.
Step 6, synthesizing tetragonal barium titanate ceramic powder with good antibacterial performance by heat treatment: the BaTiO obtained in the step 5 is treated3Putting the precursor powder into a muffle furnace, and calcining at high temperature in the air to obtain tetragonal barium titanate ceramic powder with good antibacterial performance; wherein the high-temperature calcination temperature is 650 ℃, and the high-temperature calcination time is 120 min.
Example 2:
step 1, preparing a barium salt solution system: with BaCl2·2H2O is barium source, C6H8O7To react the chelating agent, 0.05mol (12g) of BaCl was weighed out2·2H2O in a beaker and add50mL of deionized water is stirred until the deionized water is completely dissolved to obtain a colorless transparent solution; 0.05mol (3g) of C6H8O7Adding the barium salt solution into the solution, and uniformly stirring to obtain a barium salt solution system;
step 2, preparing a titanium salt solution system: with C16H36O4Ti is used as a titanium source, and 0.05mol (17mL) of C is weighed16H36O4Adding Ti into a beaker, adding 30mL of absolute ethyl alcohol, and fully mixing to obtain a titanium salt solution system;
step 3, preparing an alkaline solution: weighing 0.3mol (12.50g) of NaOH powder, dissolving the NaOH powder into 50mL of deionized water successively by 10 times, and uniformly stirring to obtain an alkaline solution;
step 4, mixing to obtain BaTiO3Precursor solution: mixing the barium salt solution obtained in the step 1 with the titanium salt solution obtained in the step 2, uniformly stirring, adding the NaOH solution obtained in the step 3, and reacting under a high-concentration alkaline condition to obtain a white turbid liquid system with a clear upper layer and a white turbid lower layer, namely BaTiO3A precursor solution;
step 5, preparing BaTiO by rotary evaporation3Precursor powder: the BaTiO obtained in the step 43Transferring the precursor solution into an eggplant-shaped bottle, performing rotary evaporation reaction under certain parameters, centrifugally washing, and drying in an oven to obtain BaTiO3Precursor powder; wherein the conditions of rotary evaporation are as follows: performing rotary evaporation at 142mbar and 55 deg.C for 80min, and performing rotary evaporation at 72mbar and 60 deg.C for 140 min; during centrifugal washing, firstly washing with ultrapure water for 3 times, and then washing with absolute ethyl alcohol for 3 times; the drying conditions are as follows: drying at 60 deg.C for 48 h.
Step 6, synthesizing tetragonal barium titanate ceramic powder with good antibacterial performance by heat treatment: the BaTiO obtained in the step 5 is treated3Putting the precursor powder into a muffle furnace, and calcining at high temperature in the air to obtain tetragonal barium titanate ceramic powder with good antibacterial performance; wherein the high-temperature calcination temperature is 650 ℃, and the high-temperature calcination time is 120 min.
Example 3:
step 1, preparing a barium salt solution system: with BaCl2·2H2O is barium source, C6H8O7Is reversedChelating agent, 0.05mol (12g) of BaCl is weighed out2·2H2Adding 50mL of deionized water into a beaker, and stirring until the deionized water is completely dissolved to obtain a colorless transparent solution; 0.05mol (3g) of C6H8O7Adding the barium salt solution into the solution, and uniformly stirring to obtain a barium salt solution system;
step 2, preparing a titanium salt solution system: with C16H36O4Ti is used as a titanium source, and 0.05mol (17mL) of C is weighed16H36O4Adding Ti into a beaker, adding 30mL of absolute ethyl alcohol, and fully mixing to obtain a titanium salt solution system;
step 3, preparing an alkaline solution: weighing 0.5mol (20.83g) of NaOH powder, gradually dissolving the NaOH powder in 70mL of deionized water for 15 times, and uniformly stirring to obtain an alkaline solution;
step 4, mixing to obtain BaTiO3Precursor solution: mixing the barium salt solution obtained in the step 1 with the titanium salt solution obtained in the step 2, uniformly stirring, adding the NaOH solution obtained in the step 3, and reacting under a high-concentration alkaline condition to obtain a white turbid liquid system with a clear upper layer and a white turbid lower layer, namely BaTiO3A precursor solution;
step 5, preparing BaTiO by rotary evaporation3Precursor powder: the BaTiO obtained in the step 43Transferring the precursor solution into an eggplant-shaped bottle, performing rotary evaporation reaction under certain parameters, centrifugally washing, and drying in an oven to obtain BaTiO3Precursor powder; wherein the conditions of rotary evaporation are as follows: rotary steaming at 142mbar and 55 deg.C for 70min, and further rotary steaming at 72mbar and 60 deg.C for 130 min; during centrifugal washing, firstly washing with ultrapure water for 3 times, and then washing with absolute ethyl alcohol for 3 times; the drying conditions are as follows: drying at 60 deg.C for 36 h.
Step 6, synthesizing tetragonal barium titanate ceramic powder with good antibacterial performance by heat treatment: the BaTiO obtained in the step 5 is treated3Putting the precursor powder into a muffle furnace, and calcining at high temperature in the air to obtain tetragonal barium titanate ceramic powder with good antibacterial performance; wherein the high-temperature calcination temperature is 650 ℃, and the high-temperature calcination time is 120 min.
Example 4:
step 1, preparing a barium salt solution system: with BaCl2·2H2O is barium source, C6H8O7To react the chelating agent, 0.05mol (12g) of BaCl was weighed out2·2H2Adding 50mL of deionized water into a beaker, and stirring until the deionized water is completely dissolved to obtain a colorless transparent solution; 0.05mol (3g) of C6H8O7Adding the barium salt solution into the solution, and uniformly stirring to obtain a barium salt solution system;
step 2, preparing a titanium salt solution system: with C16H36O4Ti is used as a titanium source, and 0.05mol (17mL) of C is weighed16H36O4Adding Ti into a beaker, adding 30mL of absolute ethyl alcohol, and fully mixing to obtain a titanium salt solution system;
step 3, preparing an alkaline solution: weighing 0.7mol (29.17g) of NaOH powder, gradually dissolving the NaOH powder into 100mL of deionized water for 20 times, and uniformly stirring to obtain an alkaline solution;
step 4, mixing to obtain BaTiO3Precursor solution: mixing the barium salt solution obtained in the step 1 with the titanium salt solution obtained in the step 2, uniformly stirring, adding the NaOH solution obtained in the step 3, and reacting under a high-concentration alkaline condition to obtain a white turbid liquid system with a clear upper layer and a white turbid lower layer, namely BaTiO3A precursor solution;
step 5, preparing BaTiO by rotary evaporation3Precursor powder: the BaTiO obtained in the step 43Transferring the precursor solution into an eggplant-shaped bottle, performing rotary evaporation reaction under certain parameters, centrifugally washing, and drying in an oven to obtain BaTiO3Precursor powder; wherein the conditions of rotary evaporation are as follows: performing rotary evaporation at 142mbar and 55 deg.C for 60min, and performing rotary evaporation at 72mbar and 60 deg.C for 120 min; during centrifugal washing, firstly washing with ultrapure water for 3 times, and then washing with absolute ethyl alcohol for 3 times; the drying conditions are as follows: drying at 60 deg.C for 36 h.
Step 6, synthesizing tetragonal barium titanate ceramic powder with good antibacterial performance by heat treatment: the BaTiO obtained in the step 5 is treated3Putting the precursor powder into a muffle furnace, and calcining at high temperature in the air to obtain tetragonal barium titanate ceramic powder with good antibacterial performance; wherein the high-temperature calcination temperature is 650 ℃, and the high-temperature calcination time is 120 min.
Example 5:
step 1, preparing a barium salt solution system: with BaCl2·2H2O is barium source, C6H8O7To react the chelating agent, 0.05mol (12g) of BaCl was weighed out2·2H2Adding 50mL of deionized water into a beaker, and stirring until the deionized water is completely dissolved to obtain a colorless transparent solution; 0.05mol (3g) of C6H8O7Adding the barium salt solution into the solution, and uniformly stirring to obtain a barium salt solution system;
step 2, preparing a titanium salt solution system: with C16H36O4Ti is used as a titanium source, and 0.05mol (17mL) of C is weighed16H36O4Adding Ti into a beaker, adding 30mL of absolute ethyl alcohol, and fully mixing to obtain a titanium salt solution system;
step 3, preparing an alkaline solution: weighing 0.3mol (12.50g) of NaOH powder, dissolving the NaOH powder into 50mL of deionized water successively by 10 times, and uniformly stirring to obtain an alkaline solution;
step 4, mixing to obtain BaTiO3Precursor solution: mixing the barium salt solution obtained in the step 1 with the titanium salt solution obtained in the step 2, uniformly stirring, adding the NaOH solution obtained in the step 3, and reacting under a high-concentration alkaline condition to obtain a white turbid liquid system with a clear upper layer and a white turbid lower layer, namely BaTiO3A precursor solution;
step 5, preparing BaTiO by rotary evaporation3Precursor powder: the BaTiO obtained in the step 43Transferring the precursor solution into an eggplant-shaped bottle, performing rotary evaporation reaction under certain parameters, centrifugally washing, and drying in an oven to obtain BaTiO3Precursor powder; wherein the conditions of rotary evaporation are as follows: performing rotary evaporation at 142mbar and 55 deg.C for 80min, and performing rotary evaporation at 72mbar and 60 deg.C for 140 min; during centrifugal washing, firstly washing with ultrapure water for 3 times, and then washing with absolute ethyl alcohol for 3 times; the drying conditions are as follows: drying at 60 deg.C for 48 h.
Step 6, synthesizing tetragonal barium titanate ceramic powder with good antibacterial performance by heat treatment: the BaTiO obtained in the step 5 is treated3Putting the precursor powder into a muffle furnace, and calcining at high temperature in the air to obtain tetragonal barium titanate ceramic powder with good antibacterial performance; wherein the temperature of the high-temperature calcinationThe temperature is 800 ℃, and the high-temperature calcination time is 120 min.
Example 6:
step 1, preparing a barium salt solution system: with BaCl2·2H2O is barium source, C6H8O7To react the chelating agent, 0.05mol (12g) of BaCl was weighed out2·2H2Adding 50mL of deionized water into a beaker, and stirring until the deionized water is completely dissolved to obtain a colorless transparent solution; 0.05mol (3g) of C6H8O7Adding the barium salt solution into the solution, and uniformly stirring to obtain a barium salt solution system;
step 2, preparing a titanium salt solution system: with C16H36O4Ti is used as a titanium source, and 0.05mol (17mL) of C is weighed16H36O4Adding Ti into a beaker, adding 30mL of absolute ethyl alcohol, and fully mixing to obtain a titanium salt solution system;
step 3, preparing an alkaline solution: weighing 0.5mol (20.83g) of NaOH powder, gradually dissolving the NaOH powder in 70mL of deionized water for 15 times, and uniformly stirring to obtain an alkaline solution;
step 4, mixing to obtain BaTiO3Precursor solution: mixing the barium salt solution obtained in the step 1 with the titanium salt solution obtained in the step 2, uniformly stirring, adding the NaOH solution obtained in the step 3, and reacting under a high-concentration alkaline condition to obtain a white turbid liquid system with a clear upper layer and a white turbid lower layer, namely BaTiO3A precursor solution;
step 5, preparing BaTiO by rotary evaporation3Precursor powder: the BaTiO obtained in the step 43Transferring the precursor solution into an eggplant-shaped bottle, performing rotary evaporation reaction under certain parameters, centrifugally washing, and drying in an oven to obtain BaTiO3Precursor powder; wherein the conditions of rotary evaporation are as follows: rotary steaming at 142mbar and 55 deg.C for 70min, and further rotary steaming at 72mbar and 60 deg.C for 130 min; during centrifugal washing, firstly washing with ultrapure water for 3 times, and then washing with absolute ethyl alcohol for 3 times; the drying conditions are as follows: drying at 60 deg.C for 36 h.
Step 6, synthesizing tetragonal barium titanate ceramic powder with good antibacterial performance by heat treatment: the BaTiO obtained in the step 5 is treated3Putting the precursor powder into a muffle furnace, and calcining at high temperature in air to obtain the catalystObtaining tetragonal barium titanate ceramic powder with good antibacterial performance; wherein the high-temperature calcination temperature is 800 ℃, and the high-temperature calcination time is 120 min.
X-ray diffraction analysis (XRD) was performed on the tetragonal barium titanate ceramic powders having good antibacterial properties prepared in examples 1 to 6 of the present invention (as shown in fig. 2), and it can be seen that the peak intensity increased as the content of NaOH increased. Typical Bragg reflection peaks of 2 theta to 45 DEG can be seen in the inset, the sample corresponding to tetragonal BaTiO3The standard characteristic peak (JCPDS NO.05-0626) of (5) shows a tetragonal phase of BaTiO3The prepared composite material has good crystallinity and basically has no impurity phase. It can be concluded that tetragonal BaTiO can be successfully prepared by the process of the present invention3And (4) concluding.
The morphology of the tetragonal barium titanate ceramic powder having good antibacterial properties prepared in examples 1-6 of the present invention was analyzed by Scanning Electron Microscopy (SEM) (as shown in fig. 3). It can be seen that tetragonal phase BaTiO3The nanoparticles exhibited a surface morphology similar to strawberries, with a relatively smooth surface embedded with a number of discrete spherical particles, similar to seeds embedded in the surface of pulp. The morphology and particle size of the particles show a tendency to increase and then decrease with increasing sodium hydroxide content and a tendency to increase with increasing heat treatment temperature. BaTiO at different sodium hydroxide contents and heat treatment temperatures3The strawberry-like morphology of the nanoparticles remained unchanged throughout. Therefore, the method of the invention can complete the batch production of the tetragonal barium titanate ceramic powder with good antibacterial performance under the temperature setting of safety, high efficiency and energy saving.
The bacterial inhibition zones of the tetragonal barium titanate ceramic powder with good antibacterial performance prepared in the embodiments 2 and 3 of the invention are observed by an agar diffusion method, and an intuitive evidence is provided for the antibacterial activity of the tetragonal barium titanate ceramic powder. FIG. 4 shows the antibacterial performance of tetragonal barium titanate ceramic powder before and after polarization in example 2 (FIG. 4(a)) and example 3 (FIG. 4(b)) of the present invention against E.coli, respectively, (a1) and (b1) are unpolarized samples, and (a2) and (b2) are polarized samples, respectively. The result shows that the sample of the invention has better antibacterial property to escherichia coli, and the polarized sample has better antibacterial activity than an unpolarized sample. Therefore, the tetragonal barium titanate ceramic powder with good antibacterial performance can be successfully prepared by the method.
It is noted that, herein, relational terms such as first and second, and the like may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising an … …" does not exclude the presence of other identical elements in a process, method, article, or apparatus that comprises the element.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (6)
1. A preparation method of tetragonal barium titanate ceramic powder with antibacterial performance is characterized by comprising the following steps:
step 1, preparing a barium salt solution: with barium chloride BaCl2·2H2O is a barium source, ethanolamine C6H8O7Weighing barium chloride BaCl as a reaction chelating agent2·2H2Adding deionized water into the beaker, and stirring until the deionized water is completely dissolved to obtain a colorless transparent solution; taking ethanolamine C6H8O7Adding the solution into the colorless transparent solution, and uniformly stirring to obtain a barium salt solution;
step 2, preparing titanium salt solutionLiquid: with butyl titanate C16H36O4Ti is taken as a titanium source, and butyl titanate C is weighed16H36O4Adding Ti into a beaker, adding absolute ethyl alcohol, and fully mixing to obtain a titanium salt solution;
step 3, preparing an alkaline solution: weighing NaOH powder, dissolving the NaOH powder into deionized water successively, and stirring uniformly to obtain an alkaline solution;
step 4, mixing to prepare BaTiO3Precursor solution: mixing the barium salt solution obtained in the step 1 with the titanium salt solution obtained in the step 2, uniformly stirring, adding the NaOH solution obtained in the step 3, reacting under a high-concentration alkaline condition to obtain an upper-layer clear and lower-layer white turbid solution, wherein the lower-layer white turbid solution is BaTiO3A precursor solution;
step 5, preparing BaTiO by rotary evaporation3Precursor powder: the BaTiO obtained in the step 43Transferring the precursor solution into a eggplant-shaped bottle, performing rotary evaporation reaction, centrifugally washing, and drying in an oven to obtain BaTiO3Precursor powder;
step 6, synthesizing tetragonal barium titanate ceramic powder with good antibacterial performance by heat treatment: the BaTiO obtained in the step 5 is treated3And placing the precursor powder in a muffle furnace, and calcining at high temperature in the air to obtain the tetragonal barium titanate ceramic powder with good antibacterial performance.
2. The method for preparing tetragonal barium titanate ceramic powder with antibacterial property as claimed in claim 1, wherein ethanolamine C is added in step 16H8O7With barium chloride BaCl2·2H2The molar ratio of O is 1: 1, adding deionized water and barium chloride BaCl2·2H2The mass ratio of O is 3-5: 1.
3. the method for preparing tetragonal barium titanate ceramic powder with antibacterial property as claimed in claim 1, wherein butyl titanate C in step 216H36O4Ti and barium chloride BaCl2·2H2The molar ratio of O is 1: 1, anhydrous ethanol with titanic acidButyl ester C16H36O4The mass ratio of Ti is 2-4: 1.
4. the method for preparing tetragonal barium titanate ceramic powder with antibacterial property as claimed in claim 1, wherein NaOH and barium chloride BaCl are added in step 32·2H2The molar ratio of O is 3-15: 1, the mass ratio of the added deionized water to NaOH is 3-5: 1, adding NaOH powder into deionized water for 5-20 times.
5. The method for preparing tetragonal barium titanate ceramic powder with antibacterial property according to claim 1, wherein the conditions of rotary evaporation in step 5 are as follows: performing rotary evaporation at 142mbar and 55 deg.C for 60-90min, and performing rotary evaporation at 72mbar and 60 deg.C for 120-150 min; during centrifugal washing, firstly washing with ultrapure water for 3 times, and then washing with absolute ethyl alcohol for 3 times; the drying conditions are as follows: drying at 60 deg.C for 36-48 h.
6. The method for preparing tetragonal barium titanate ceramic powder with antibacterial property according to claim 1, wherein the high-temperature calcination temperature in step 6 is selected from one of 650 ℃ and 800 ℃, and the high-temperature calcination time is 120 min.
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| CN114315349A (en) * | 2021-12-17 | 2022-04-12 | 西安理工大学 | Method for preparing mesoporous barium zirconate titanate ceramic nanoparticles |
| CN117945754A (en) * | 2024-01-31 | 2024-04-30 | 江南大学 | Method for preparing ceramic false tooth based on photocuring additive manufacturing and microwave sintering technology |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111233463A (en) * | 2020-01-20 | 2020-06-05 | 西安理工大学 | Method for preparing tetragonal phase barium titanate powder |
| CN111333105A (en) * | 2020-03-05 | 2020-06-26 | 西安理工大学 | Method for preparing cubic tetragonal barium titanate by using hydrothermal method |
| CN112679216A (en) * | 2020-12-25 | 2021-04-20 | 西安理工大学 | Method for preparing tetragonal phase BaTiO by liquid phase rotary evaporation method3Method for preparing/HA composite nano-particles |
| CN113372131A (en) * | 2021-04-26 | 2021-09-10 | 西安理工大学 | Micro-nano pore channel structure tetragonal phase BaTiO3Preparation method of/HA hollow microspheres |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111233463A (en) * | 2020-01-20 | 2020-06-05 | 西安理工大学 | Method for preparing tetragonal phase barium titanate powder |
| CN111333105A (en) * | 2020-03-05 | 2020-06-26 | 西安理工大学 | Method for preparing cubic tetragonal barium titanate by using hydrothermal method |
| CN112679216A (en) * | 2020-12-25 | 2021-04-20 | 西安理工大学 | Method for preparing tetragonal phase BaTiO by liquid phase rotary evaporation method3Method for preparing/HA composite nano-particles |
| CN113372131A (en) * | 2021-04-26 | 2021-09-10 | 西安理工大学 | Micro-nano pore channel structure tetragonal phase BaTiO3Preparation method of/HA hollow microspheres |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114315349A (en) * | 2021-12-17 | 2022-04-12 | 西安理工大学 | Method for preparing mesoporous barium zirconate titanate ceramic nanoparticles |
| CN114315349B (en) * | 2021-12-17 | 2023-01-24 | 西安理工大学 | Method for preparing mesoporous barium zirconate titanate ceramic nanoparticles |
| CN117945754A (en) * | 2024-01-31 | 2024-04-30 | 江南大学 | Method for preparing ceramic false tooth based on photocuring additive manufacturing and microwave sintering technology |
| CN117945754B (en) * | 2024-01-31 | 2024-09-06 | 江南大学 | Method for preparing ceramic false tooth based on photocuring additive manufacturing and microwave sintering technology |
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