CN111518315A - Microstructure-order-based high-gas-barrier-property composite material and preparation method thereof - Google Patents
Microstructure-order-based high-gas-barrier-property composite material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a microstructure-ordered high-gas-barrier composite material and a preparation method thereof, wherein a shearing force is utilized to destroy an interlayer acting force between three-dimensional block nanosheets, and the three-dimensional block nanosheets are stripped into two-dimensional nanosheets; in an alkaline aqueous solution, hydrochloric acid dopamine is subjected to self-polymerization on the surfaces of the nano sheets, strong pi-pi interaction is formed between the generated polydopamine and the nano sheets, so that the pi-pi conjugate modification of the polydopamine on the surfaces of the nano sheets is realized, meanwhile, hydroxyl and amino on the surfaces of the two-dimensional nano sheets modified by the polydopamine can form a large number of hydrogen bonds with hydroxyl on a polyvinyl alcohol molecular chain, the dispersity and the interface binding force of the nano sheets in a matrix are effectively improved, the directional arrangement of the nano sheets on the matrix can be effectively realized by means of the gravity effect generated by vacuum-assisted suction filtration, the effect on the aspect can effectively prolong the diffusion path of gas, and the gas barrier property of the composite material is remarkably improved.
Description
Technical Field
The invention belongs to the field of nano composite materials, and particularly relates to a high-gas-barrier-property composite material with an ordered microstructure and a preparation method thereof.
Background
Since the birth of composite material pressure vessels, the composite material pressure vessels are widely used in the fields of national defense, traffic, petrochemical industry and the like. In recent years, with the development of advanced technologies and equipment such as advanced engine systems and new energy vehicles, in order to meet the severe requirements of high airtightness, low weight, multifunction and the like, researchers have gained more and more favor of a novel ultra-light linerless polymer composite pressure vessel. Generally, the inner liner of the composite pressure vessel accounts for more than 30% of the total weight of the vessel, and therefore, the non-liner design can greatly improve the structural efficiency and realize effective weight reduction. However, the gas tightness of the composite pressure vessel is seriously reduced by adopting a linerless design, so that the composite pressure vessel cannot meet the strict gas tightness requirement under the action of high-pressure load, and therefore, a high-gas-barrier polymer material is urgently needed. In addition, due to the advantages of light weight, easy processing, and being not easy to break, the demand of high-barrier polymer materials in the fields of packaging, agriculture, industry, medical treatment, etc. is increasing. For this reason, the development of polymer materials with high gas barrier properties has been one of the hot spots of research.
At present, various methods for improving the barrier property of materials have been reported, such as a filling modification method, a blending method, a multilayer compounding method, a surface treatment method, and the like. The filling method is to fill inorganic nanoparticles serving as a filler into a polymer matrix by a certain method to prepare the nanocomposite with excellent barrier property, and is an internationally recognized effective means for improving the gas barrier property of the material at present. Researchers focused on the filling modification method two points: firstly, selecting and processing nano filler; secondly, the dispersity and orientation of the filler in the matrix are controlled. The two-dimensional layered nano material can form the largest contact area with a matrix due to the larger length-diameter ratio of the two-dimensional layered nano material, and can effectively prolong the diffusion path of gas molecules, so that the two-dimensional layered nano material becomes the most ideal nano filler of the gas barrier composite material. Sheet-like nano-graphite, graphene, layered silicate and boron nitride nanosheets have been widely used to prepare gas barrier polymer composites. However, the prior art has the following problems: (1) the nano filler has poor dispersibility and is easy to agglomerate seriously, so that the barrier property of the obtained composite material is far lower than a theoretical value; (2) the nano-fillers are arranged in disorder in the matrix, so that the effect of prolonging the gas diffusion path is limited. Therefore, how to effectively improve the dispersibility of the nano filler in the resin matrix so as to realize the highly ordered and oriented arrangement of the nano filler in the resin matrix is a research hotspot in the field of high-gas-barrier nano composite materials.
Disclosure of Invention
The invention aims to provide a simple and effective high-gas-barrier composite material based on microstructure order and a preparation method thereof.
The purpose of the invention is realized by the following technical scheme.
A two-dimensional nanosheet with a surface modified with polydopamine is prepared by the following steps:
(1) dispersing the flaky three-dimensional nano particles in absolute ethyl alcohol and continuously stirring, then adding a trihydroxymethyl aminomethane hydrochloride buffer solution, and continuously stirring to obtain a mixed solution;
(2) adding dopamine hydrochloride into the mixed solution prepared in the step (1), and uniformly stirring and mixing;
(3) placing the mixed solution prepared in the step (2) in a high-speed shearing emulsifying instrument, and shearing at a high speed for a plurality of hours to obtain a sheared dispersion liquid;
(4) and (4) carrying out centrifugal separation on the dispersion liquid prepared in the step (3), and then taking supernatant liquid to carry out filtration, washing and drying to obtain the surface modified polydopamine two-dimensional nanosheet.
Preferably, in the step (1), the flaky three-dimensional nanoparticles are any one of hexagonal boron nitride powder and natural graphite.
Preferably, in the step (1), the dosage ratio of the flaky three-dimensional nanoparticles to the absolute ethyl alcohol is 10-50 mg: 1 ml.
Preferably, in step (1), the concentration of the tris hydrochloride buffer is 0.01-0.04 mol/l, and the pH is 8.5-10.
Preferably, in the step (1), the dosage ratio of the flaky three-dimensional nanoparticles to the tris hydrochloride buffer solution is 6-20 mg: 1 ml.
Preferably, in the step (2), the mass ratio of the flaky three-dimensional nanoparticles to the dopamine hydrochloride is 2-6: 1.
preferably, in the step (3), the high-speed shearing is carried out at a high-speed shearing speed of 6000 to 8000rpm for 3 to 6 hours.
Preferably, in the step (4), the centrifugal speed is 2000-5000 rpm, and the centrifugal time is 10-30 min.
A high-gas barrier composite material based on microstructure order and a preparation method thereof specifically comprise the following steps:
(a) dispersing the two-dimensional nano sheet modified by the polydopamine in distilled water, performing ultrasonic dispersion for 20-50 min at room temperature, then adding a certain amount of polyvinyl alcohol (PVA), and continuing to perform ultrasonic dispersion for 30-60 min to obtain a uniform aqueous solution;
(b) and (b) carrying out vacuum filtration on the aqueous solution prepared in the step (a), and drying the obtained filter membrane in a vacuum oven for several hours to obtain the high-gas-barrier-property composite material with ordered microstructure.
Preferably, in the step (a), the concentration of the polydopamine-modified two-dimensional nanosheet in distilled water is 2-4 mg/1ml, and the mass ratio of the polydopamine-modified two-dimensional nanosheet to polyvinyl alcohol is 1-4: 20.
preferably, in step (b), the concentration is 50 to 70oAnd C, drying in a vacuum oven for 24 hours.
Compared with the prior art, the invention has the following beneficial effects:
(1) the invention realizes the stripping and surface modification of the two-dimensional nanosheet at the same time, and has the advantages of simple and easy process, room-temperature operation, low cost and high production efficiency.
(2) The poly-dopamine pi-pi conjugated modified two-dimensional nanosheet can effectively maintain inherent high gas barrier property of the nanosheet, can form hydrogen bonds with a polymer matrix, solves the problems of poor dispersibility and low interface binding force of the nanosheet in the resin matrix, and promotes the application of the nanosheet in the field of high-barrier composite materials.
(3) The directional arrangement of the nano particles in the resin matrix can be realized by simple vacuum filtration, the diffusion path of gas molecules can be prolonged to the maximum extent, and the gas barrier property of the composite material is obviously improved.
Drawings
FIG. 1 is a transmission electron micrograph of BNNSs-PDA prepared in example 1.
FIG. 2 is a graph of the thermogravimetric curves of the original h-BN and the BNNSs-PDA made in example 1.
FIG. 3 is a graph of the thermogravimetric curves of the original h-BN and the BNNSs-PDA made in example 2.
FIG. 4 is a graph of the thermogravimetric curves of the original h-BN and the BNNSs-PDA made in example 3.
Fig. 5 is a transmission electron microscope of the surface-modified poly-dopamine graphene prepared in example 4.
Fig. 6 is a thermogravimetric plot of natural graphite and graphene-PDA prepared in example 4.
FIG. 7 is a transmission electron micrograph of the product prepared in comparative example 1.
FIG. 8 is a graph of the thermal weight loss of virgin h-BN and BNNSs made in comparative example 1.
FIG. 9 is a thermogravimetric plot of the product made from virgin h-BN and comparative example 2.
FIG. 10 is a scanning electron micrograph of the product obtained in comparative example 2.
Detailed Description
The principle of the invention is as follows: in the preparation process of the two-dimensional nanosheet with the surface modified with polydopamine, on one hand, interlaminar acting force among the three-dimensional block nanosheets is destroyed by utilizing shearing force, and the three-dimensional block nanosheets are stripped into the two-dimensional nanosheets; on the other hand, dopamine hydrochloride in an alkaline aqueous solution can undergo self-polymerization on the surfaces of the nano sheets, and the generated polydopamine and the nano sheets have strong pi-pi interaction, so that the pi-pi conjugated modification of the polydopamine on the surfaces of the nano sheets is realized at the same time. In the preparation process of the composite material, on one hand, hydroxyl and amido on the surface of the two-dimensional nano sheet modified by polydopamine can form a large number of hydrogen bonds with hydroxyl on a polyvinyl alcohol molecular chain, so that the dispersibility and the interface binding force of the nano sheet in a matrix are effectively improved; on the other hand, the oriented arrangement of the nano-sheets on the matrix can be effectively realized by means of the gravity effect generated by vacuum-assisted suction filtration. The effect of the aspect can effectively prolong the diffusion path of the gas, thereby obviously improving the gas barrier property of the composite material.
Example 1
2g of bulk hexagonal boron nitride (h-BN) powder were dispersed in 150ml of absolute ethanol with constant stirring, and then 400ml of tris hydrochloride buffer, having a concentration of 0.03mol/l and a pH of 8.5, were added. After stirring well, 0.5g dopamine hydrochloride was added and the dispersion was placed in a high shear emulsifier and high shear sheared at 7000rpm for 5 h. The mixture after shearing was centrifuged at 4000rpm for 20min to remove the large un-peeled pieces. Filtering the supernatant, and washing with distilled water until the filtrate is neutral. The product is placed at 80oAnd C, drying for 8 hours in a vacuum oven to obtain the boron nitride nanosheet (BNNSs-PDA) with the surface modified with polydopamine.
FIG. 1 is a transmission electron microscope image of the prepared BNNSs-PDA, which shows that it is highly transparent to electron beams, indicating that h-BN is effectively stripped, and ultrathin nanosheets are obtained. FIG. 2 is a graph of the thermal weight loss curves for raw h-BN and the BNNSs-PDA produced, showing that the PDA content on the surface of BNNSs is about 3.72%.
Example 2
2g h-BN powder was dispersed in 150ml of absolute ethanol with stirring, and then 400ml of tris hydrochloride buffer solution was added, wherein the buffer solution had a concentration of 0.03mol/l and a pH of 8.5. After stirring uniformly, 1g of dopamine hydrochloride was added, and the dispersion was placed in a high-speed shear emulsifier and subjected to high-speed shearing at 7000rpm for 5 hours. The mixture after shearing was centrifuged at 4000rpm for 20min to remove the large un-peeled pieces. Filtering the supernatant, and washing with distilled water until the filtrate is neutral. The product is placed at 80oAnd C, drying for 8 hours in a vacuum oven to obtain BNNSs-PDA. From FIG. 3, which is the thermogravimetric curves of the original h-BN and the BNNSs-PDA produced, it can be seen that the PDA content in the BNNSs-PDA produced is about 3.08%.
Example 3
2g h-BN powder was dispersed in 150ml of absolute ethanol with stirring, and then 400ml of tris hydrochloride buffer solution was added, wherein the buffer solution had a concentration of 0.03mol/l and a pH of 8.5. After stirring well, 0.35g of dopamine hydrochloride was added and the dispersion was placed in a high shear emulsifier and high shear sheared at 7000rpm for 5 h. The mixture after shearing was centrifuged at 4000rpm for 20min to remove the large un-peeled pieces. Filtering the supernatant, and washing with distilled water until the filtrate is neutral. The product is placed at 80oAnd C, drying for 8 hours in a vacuum oven to obtain BNNSs-PDA. From FIG. 4, which is the thermogravimetric curves of the original h-BN and the BNNSs-PDA produced, it can be seen that the PDA content in the BNNSs-PDA produced is about 2.39%.
Example 4
2g of natural graphite was dispersed in 150ml of absolute ethanol with stirring, and then 400ml of tris hydrochloride buffer solution was added, wherein the buffer solution had a concentration of 0.03mol/l and a pH of 8.5. After stirring well, 0.5g dopamine hydrochloride was added and the dispersion was placed in a high shear emulsifier and high shear sheared at 7000rpm for 5 h. The mixture after shearing was centrifuged at 4000rpm for 20min to remove the large un-peeled pieces. Taking the supernatant to filter,washing the filtrate with distilled water until the filtrate is neutral. The product is placed at 80oAnd C, drying for 8 hours in a vacuum oven to obtain the graphene with the surface modified with the polydopamine. Fig. 5 is a transmission electron microscope of the prepared graphene with the surface modified with polydopamine, which shows that the graphene is highly transparent to electron beams, and shows that natural graphite is effectively stripped to obtain ultrathin nanosheets. Fig. 6 is a thermogravimetric curve of natural graphite and prepared graphene-PDA, and it can be seen that the content of PDA on the surface of graphene is about 4.06%.
Example 5
0.104g of BNNSs-PDA prepared in example 1 was dispersed in 200ml of distilled water and ultrasonically dispersed at room temperature for 30 min. 1.9g of PVA were then added and the ultrasonic dispersion was continued for 45 min. The obtained uniform aqueous dispersion was subjected to vacuum filtration at a vacuum degree of-0.1 MPa, and the filtration membrane was an organic membrane having a pore size of 0.22 μm. After suction filtration, the polymer film on the filter membrane was removed and placed at 60 deg.CoAnd C, drying for 24 hours in a vacuum oven to obtain the composite material film with ordered microstructure, wherein the BNNSs accounts for 5% of the composite material by mass. The gas barrier properties of the composite are listed in table 1.
Example 6
0.103g of BNNSs-PDA prepared in example 2 was dispersed in 200ml of distilled water and ultrasonically dispersed at room temperature for 30 min. 1.9g of PVA were then added and the ultrasonic dispersion was continued for 45 min. The obtained uniform aqueous dispersion was subjected to vacuum filtration at a vacuum degree of-0.1 MPa, and the filtration membrane was an organic membrane having a pore size of 0.22 μm. After suction filtration, the polymer film on the filter membrane was removed and placed at 60 deg.CoAnd C, drying for 24 hours in a vacuum oven to obtain the composite material film with ordered microstructure, wherein the BNNSs accounts for 5% of the composite material by mass. The gas barrier properties of the composite are listed in table 1.
Example 7
0.102g of BNNSs-PDA prepared in example 3 was dispersed in 200ml of distilled water and ultrasonically dispersed at room temperature for 30 min. 1.9g of PVA were then added and the ultrasonic dispersion was continued for 45 min. The obtained uniform aqueous dispersion was subjected to vacuum filtration at a vacuum degree of-0.1 MPa, and the filtration membrane was an organic membrane having a pore size of 0.22 μm. After suction filtration, the polymer film on the filter membrane was removed and placed at 60 deg.CoAnd C, drying for 24 hours in a vacuum oven to obtain the composite material film with ordered microstructure, wherein the BNNSs accounts for 5% of the composite material by mass. The gas barrier properties are listed in table 1. Comparing the results of the gas barrier performance tests of examples 5, 6 and 7, it is known that the increase of the content of PDA on the surface of BNNSs is beneficial to the improvement of the barrier performance of the composite material under the condition of the same BNNSs content.
Example 8
0.208g of BNNSs-PDA prepared in example 1 was dispersed in 200ml of distilled water and ultrasonically dispersed at room temperature for 30 min. 1.8g of PVA were then added and the ultrasonic dispersion was continued for 45 min. The obtained uniform aqueous dispersion was subjected to vacuum filtration at a vacuum degree of-0.1 MPa, and the filtration membrane was an organic membrane having a pore size of 0.22 μm. After suction filtration, the polymer film on the filter membrane was removed and placed at 60 deg.CoAnd C, drying in a vacuum oven for 24 hours to obtain the composite material film with ordered microstructure, wherein the BNNSs accounts for 10% of the composite material by mass. The gas barrier properties are listed in table 1.
Example 9
0.312g of BNNSs-PDA prepared in example 1 was dispersed in 200ml of distilled water and ultrasonically dispersed at room temperature for 30 min. 1.7g of PVA were then added and the ultrasonic dispersion was continued for 45 min. The obtained uniform aqueous dispersion was subjected to vacuum filtration at a vacuum degree of-0.1 MPa, and the filtration membrane was an organic membrane having a pore size of 0.22 μm. After suction filtration, the polymer film on the filter membrane was removed and placed at 60 deg.CoAnd C, drying for 24 hours in a vacuum oven to obtain the composite material film with ordered microstructure, wherein the BNNSs accounts for 15% of the composite material by mass. The gas barrier properties are listed in table 1. Comparing the results of the gas barrier property tests of example 5, example 8 and example 9, it can be seen that the gas barrier property of the composite material increases with the increase of the BNNSs-PDA content.
Example 10
0.104g of the polydopamine modified graphene prepared in example 4 was dispersed in 200ml of distilled water and subjected to ultrasonic dispersion at room temperature for 30 min. 1.9g of PVA were then added and the ultrasonic dispersion was continued for 45 min. Vacuum filtering the obtained uniform aqueous dispersion under-0.1 MPa, with filter membrane having pore diameter0.22 μm organic film. After suction filtration, the polymer film on the filter membrane was removed and placed at 60 deg.CoAnd C, drying for 24 hours in a vacuum oven to obtain the composite material film with an ordered microstructure, wherein the mass fraction of the graphene in the composite material is 5%. The gas barrier properties of the composite are listed in table 1.
Comparative example 1
The preparation process of the two-dimensional nanosheet material was the same as in example 1, but dopamine hydrochloride was not added during the experiment. Fig. 7 is a transmission electron micrograph of the product prepared in comparative example 1, and it can be seen that ultra-thin BNNSs were successfully worth obtaining by comparative example 1, but from fig. 8, the surface of the BNNSs prepared in comparative example 1 did not have polydopamine molecules.
Comparative example 2
The preparation process of the two-dimensional nanosheet material is the same as that of example 1, but the high-speed shearing treatment is not adopted in the experimental process, and the reaction is carried out for 5 hours at room temperature under the magnetic stirring of 500 rpm. FIG. 9 is a thermogravimetric plot of the reaction product and the original h-BN, showing that about 2.78% of PDA molecules are grafted on the surface of the product. However, as can be seen from FIG. 10 (scanning electron micrograph of product), no effective exfoliation of h-BN occurred without high shear treatment, i.e., the h-BN-PDA was obtained in comparative example 2.
Comparative example 3
Unmodified BNNSs prepared in comparative example 1 were compounded with PVA in the same manner as in example 5 to prepare a microstructure-ordered composite having the gas barrier properties listed in table 1. Comparing the gas barrier properties of comparative example 23 and example 5, it can be seen that the gas barrier property of the composite material prepared in example 5 is improved by 43.8% over the barrier property of comparative example 3 due to the effective modification of PDA.
Comparative example 4
0.104g of BNNSs-PDA prepared in example 1 was dispersed in 200ml of distilled water and ultrasonically dispersed at room temperature for 30 min. 1.9g of PVA were then added and the ultrasonic dispersion was continued for 45 min. The resulting homogeneous aqueous dispersion was transferred to 60oC, stirring at 600rpm to evaporate the aqueous solution, and stirring until a relatively viscous liquid is obtained. Pouring the obtained viscous liquid into a mold, and placing at 60 deg.CoC vacuum dryingAnd drying for 24 hours in a box to obtain the composite material film with disordered microstructure, wherein the BNNSs accounts for 5 percent of the mass of the composite material. The gas barrier properties of the composite are listed in table 1. Comparing the gas barrier properties of comparative example 4 and example 5, it can be seen that the gas barrier property of the composite material prepared in example 5 is improved by 58.1% over the barrier property of comparative example 4 due to the ordered arrangement of the nanosheets.
Comparative example 5
The h-BN-PDA prepared in comparative example 2 was compounded with PVA in the same manner as in example 5 to prepare a composite material having an ordered microstructure, the gas barrier properties of which are shown in Table 1. Comparing the gas barrier performance of comparative example 5 with that of example 5, it can be seen that a larger contact area can be formed with the matrix due to the effective stripping of h-BN, the diffusion path of the gas molecules can be more effectively prolonged, and the gas barrier performance of the composite material prepared in example 5 is improved by 41.9% compared with that of comparative example 5.
TABLE 1 helium leak rate of composites made in examples and comparative examples
Note: the composites prepared in the examples and comparative examples were tested for helium barrier properties using volumetric flow measurements. The helium gas barrier property is reflected by a helium leakage rate value, the smaller the helium leakage rate value is, the better the barrier property of the material is, and conversely, the larger the helium leakage rate value is, the worse the barrier property is.
According to the invention, the stripping of three-dimensional flaky nano particles and the surface poly-dopamine pi-pi conjugated modification are simultaneously realized through one-step in-situ high-speed shearing, so that the dispersibility and the interface binding force of the nano sheets in a resin matrix are improved; and then, realizing the sequential directional arrangement of the nanosheets in the resin matrix by means of vacuum-assisted filtration, thereby remarkably improving the gas barrier property of the composite material.
Claims (10)
1. A preparation method of a two-dimensional nanosheet with a surface modified with polydopamine is characterized by comprising the following steps:
(1) dispersing the flaky three-dimensional nano particles in absolute ethyl alcohol and continuously stirring, then adding a trihydroxymethyl aminomethane hydrochloride buffer solution, and continuously stirring to obtain a mixed solution;
(2) adding dopamine hydrochloride into the mixed solution prepared in the step (1), and uniformly stirring and mixing;
(3) placing the mixed solution prepared in the step (2) in a high-speed shearing emulsifying instrument, and shearing at a high speed for a plurality of hours to obtain a sheared dispersion liquid;
(4) and (4) carrying out centrifugal separation on the dispersion liquid prepared in the step (3), and then taking supernatant liquid to carry out filtration, washing and drying to obtain the surface modified polydopamine two-dimensional nanosheet.
2. A method for preparing two-dimensional nanoplatelets according to claim 1 wherein in step (1) the platelet-shaped three-dimensional nanoparticles are any one of hexagonal boron nitride powder and natural graphite.
3. A preparation method of two-dimensional nanosheets as claimed in claim 1, wherein in step (1), the ratio of the amount of the flaky three-dimensional nanoparticles to the amount of absolute ethanol is 10-50 mg: 1 ml.
4. A method for preparing two-dimensional nano-sheets according to claim 1, wherein in step (1), the concentration of tris hydrochloride buffer is 0.01-0.04 mol/l, and the pH is 8.5-10.
5. A preparation method of two-dimensional nano-sheets as claimed in claim 1, wherein in the step (1), the dosage ratio of the flaky three-dimensional nano-particles to the tris hydrochloride buffer solution is 6-20 mg: 1 ml.
6. A preparation method of two-dimensional nano-sheets according to claim 1, wherein in the step (2), the mass ratio of the flaky three-dimensional nano-particles to dopamine hydrochloride is 2-6: 1.
7. a method of preparing two-dimensional nanoplatelets according to claim 1 wherein in step (3) the high shear is carried out at a high shear rate of 6000 to 8000rpm for 3 to 6 hours.
8. A preparation method of two-dimensional nano-sheet according to claim 1, wherein in the step (4), the centrifugal rotation speed is 2000-5000 rpm, and the centrifugal time is 10-30 min.
9. Two-dimensional nanoplatelets of surface-modified polydopamine prepared according to the process of any of claims 1 to 8.
10. A preparation method of a microstructure-ordered high-gas-barrier-property composite material specifically comprises the following steps:
(a) dispersing the two-dimensional nano-sheets of the surface-modified polydopamine prepared by the method according to any one of claims 1 to 8 in distilled water, performing ultrasonic dispersion for 20-50 min at room temperature, adding a certain amount of polyvinyl alcohol resin, and continuing the ultrasonic dispersion for 30-60 min to obtain a uniform aqueous solution;
(b) and (b) carrying out vacuum filtration on the aqueous solution prepared in the step (a), and drying the obtained filter membrane in a vacuum oven for several hours to obtain the high-gas-barrier-property composite material with ordered microstructure.
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| CN114427086A (en) * | 2022-01-08 | 2022-05-03 | 华中科技大学 | Al (aluminum)2O3Nanosheet-reinforced ZrO2Tritium-resistant coating and preparation method thereof |
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