CN111961383B - Gamma-ray irradiation resistant high hydrogen storage composite protective film layer and preparation method thereof - Google Patents
Gamma-ray irradiation resistant high hydrogen storage composite protective film layer and preparation method thereof Download PDFInfo
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- G21F—PROTECTION AGAINST X-RADIATION, GAMMA RADIATION, CORPUSCULAR RADIATION OR PARTICLE BOMBARDMENT; TREATING RADIOACTIVELY CONTAMINATED MATERIAL; DECONTAMINATION ARRANGEMENTS THEREFOR
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Abstract
The invention discloses a gamma-ray irradiation resistant high hydrogen storage composite protective film and a preparation method thereof, belonging to the field of space radiation resistance. The invention aims to solve the technical problem of poor radiation protection performance of a spacecraft structure functional material. According to the invention, an atomic layer deposition technology is adopted to deposit a ZnO film on the surface of a cobalt-sulfur metal compound, a high-energy ball milling technology is utilized to design and prepare a high-hydrogen storage metal compound, and the performance of the compound is improved through graphene modification, so that a composite film layer structure is constructed. Abundant defects and surface functional groups in the graphene can provide binding sites for cobalt-sulfur metal compound nanoparticles, and free radicals generated by radiation are captured and quenched by the graphene with large specific surface area, strong electron transfer capacity and surface addition reaction, so that radiation aging degradation is weakened, the stability of the crosslinking degree is kept, the space radiation-resistant reinforcement of a satellite structure unit is realized, and technical support is provided for material selection and design of a long-life and high-reliability spacecraft.
Description
Technical Field
The invention belongs to the field of space radiation resistance; in particular to a gamma-ray irradiation resistant high hydrogen storage composite protective film layer and a preparation method thereof.
Background
During the working period of the space aircraft, space electronic components are necessarily exposed to space irradiation, and space high-energy charged particles can penetrate through the surface and enter the space aircraft, so that radiation damage to the electronic components and biological substances is caused, and the abnormality and even failure of the space aircraft are caused. In order to reduce the harm caused by space irradiation, certain irradiation protection measures need to be adopted to ensure the normal work of the device. Gamma rays are high-energy and uncharged photon streams generated by decay reactions of radioactive nuclei, and the high-energy rays have extremely short wavelength and extremely high penetrating power and are very harmful to biological substances, so that research on protective film layers irradiated by the gamma rays is an important research subject.
At present, the basic method of spatial radiation protection is to control the radiation dose by shielding through a physical method. Therefore, a special material having both excellent radiation stability and corrosion protection capability is required for shielding metal surfaces. Although the surface film layer traditionally used for the spacecraft has excellent corrosion resistance, a large amount of free radicals are generated by molecular chain fracture and degradation under the irradiation action of gamma rays for a long time, so that the free radicals are rapidly reacted with residual oxygen molecules in the film layer to generate peroxy radicals, macroscopically represented by wrinkling, chapping and aging of the film layer, finally the bonding force between the film layer and a substrate is sharply reduced, and the service life of the film layer is greatly influenced.
Disclosure of Invention
The invention aims to provide a high hydrogen storage composite protective film layer for gamma ray irradiation and a preparation method thereof, and aims to solve the technical problem of poor radiation resistance of a spacecraft structure functional material. According to the invention, an atomic layer deposition technology is adopted to deposit a ZnO film on the surface of a cobalt-sulfur metal compound, a high-energy ball-milling technology is utilized to design and prepare a high-hydrogen-storage metal compound, the performance of the compound is improved through graphene modification, a novel composite film structure is constructed, the space radiation resistance reinforcement of a satellite structure unit is realized, and technical support is provided for material selection and design of a long-life high-reliability spacecraft.
In order to solve the technical problem, the high hydrogen storage composite protective film layer resisting gamma ray irradiation is a ZnO film deposited on the surface of cobalt-sulfur metal compound nano particles; then adding the graphene into graphene, carrying out high-energy ball milling under the protection of protective gas, taking out, adding an adhesive, uniformly mixing, coating the mixture on the surface of a substrate to form a film, drying and carrying out hydrotreating to obtain the graphene-based composite material; the preparation method is realized by the following steps:
step one, depositing a ZnO film on the surface of cobalt-sulfur metal compound nano particles to obtain a ZnO-cobalt-sulfur metal compound;
step two, adding the graphene into the graphene, carrying out high-energy ball milling under the protection of protective gas, and taking out;
step three, adding an adhesive, uniformly mixing, coating the mixture on the surface of a base material to form a film, and drying;
and step four, carrying out hydrogenation treatment to obtain the gamma-ray irradiation resistant high hydrogen storage composite protective film layer.
Further defined, the cobalt-sulfur metal compound nanoparticles of step one are Co9S8Nano-particlesGranulating; the particle size is 100 to 500 nm.
Further, the ZnO film is deposited on the surface of the cobalt-sulfur metal compound nano-particles by using an atomic layer deposition method in the step one, and the method is specifically completed by the following operations:
placing cobalt-sulfur metal compound nanoparticles in a deposition chamber, and vacuumizing to a vacuum degree of 4 × 10-3Torr～6×10-3And (3) Torr, introducing high-purity nitrogen until the pressure in the deposition chamber is 0.1-0.2 Torr, keeping the temperature of the chamber at 100-200 ℃, and repeatedly executing 100-300 growth deposition cycles.
Further defined, the process of each growth deposition cycle is:
(1) the zinc source is injected into the primary sedimentation cavity in a pulse mode, and the pulse time t1Is 0.01s to 0.03 s;
(2) the reaction is carried out by cutting off the air inlet valve and the exhaust valve, and the reaction time t2Is 1s to 5 s;
(3) opening an air inlet valve and an air outlet valve, purging by using high-purity nitrogen, and purging for time t3Is 30s to 60 s;
(4) injecting an oxygen source into the reaction cavity in a pulse mode, wherein the temperature of the oxygen source is room temperature, and the pulse time t4Is 0.01s to 0.03 s;
(5) the reaction is carried out by cutting off the air inlet valve and the exhaust valve, and the reaction time t5Is 1 s-5 s, and ZnO is formed;
(6) opening an air inlet valve and an air outlet valve, purging by using high-purity nitrogen, and purging for time t630-60 s, completing a deposition growth period.
Further limiting, in the second step, the mass ratio of the cobalt-sulfur metal compound to the graphene is (4-10): 1.
further limiting, in the second step, the protective gas is high-purity argon, the ball milling time is 4 hours, the rotating speed of the ball mill is 400 rpm-800 rpm, and the mass ratio of ball materials is 10: 1, the grinding ball is ZrO with the diameter of 1 mm-3 mm2And (5) grinding balls.
Further, the substrate in step three is an aluminum substrate, a lead substrate, a titanium substrate, a tantalum substrate or a polyimide substrate.
Further limit, the adhesive in the third step is epoxy resin, and the dosage of the adhesive is Co9S8And 50% -100% of the total mass of graphene; the thickness of the film layer is 50 to 100 μm.
Depositing a ZnO film on the surface of cobalt-sulfur metal compound nanoparticles by adopting an atomic layer deposition technology, preparing a high-hydrogen-storage cobalt-sulfur metal compound by adopting a high-energy ball milling technology, and improving the performance of the compound by modifying graphene to construct a composite film layer structure.
The zinc oxide modified cobalt-sulfur metal compound has the following functions: part of nano particles of the zinc oxide are positioned at the edge of a graphene sheet layer or are intercalated between the graphene layers, so that the loss of the high specific surface area of the graphene can be reduced or even avoided. The graphene sheet layer is large, Van der Waals force is utilized for combination between layers, and electrolyte particles can easily penetrate through the surface of the graphene, so that the electrochemical utilization rate of the nano zinc oxide can be remarkably improved. After the zinc oxide is doped, the sheet layers of the graphene are opened, the interlayer spacing is increased, and the overlapping between the layers is reduced, so that the specific surface area is increased, and the zinc oxide is used as a transition metal oxide and has a certain catalytic action on hydrogen storage, thereby having larger hydrogen storage capacity.
The core-shell structure formed by the cobalt-sulfur metal compound nanoparticles, the zinc oxide and the graphene is as follows: abundant defects and surface functional groups in the graphene can provide sites for combining with the cobalt-sulfur metal compound nanoparticles, so that hydrogen atoms can be activated, diffused, migrated and diffused to the surface of the graphene far away from an activation center through the surface of the cobalt-sulfur metal compound nanoparticles, and the hydrogen storage capacity of the composite material is improved by the action of more hydrogen storage sites; and the graphene has a huge specific surface area, a strong electron transfer capacity and a surface addition reaction, and free radicals generated by radiation are captured and quenched, so that the radiation aging degradation is weakened, the stability of the crosslinking degree is maintained, and the space radiation resistance reinforcement is realized. The hydrogen storage capacity of the material reaches 3.69 wt%, and the radiation protection capability of the high-hydrogen storage composite protective film layer material with the same surface density is improved by 30% compared with that of a film-free substrate under the irradiation of gamma rays with the simulated dose of 250-300 kGy.
Drawings
FIG. 1 shows Co as described in example 19S8SEM images of nanoparticles, a)5810 ×, b)7800 ×;
FIG. 2 shows the preparation of Co in different proportions9S8SEM image of graphene material, (a) Co9S8: the mass ratio of the graphene is 4: 1, (b) Co9S8: the mass ratio of the graphene is 6: 1, (c) Co9S8: the mass ratio of the graphene is 8: 1, (d) Co9S8: the mass ratio of the graphene is 10: 1
Detailed Description
Example 1: the preparation method of the gamma-ray irradiation resistant high hydrogen storage composite protective film layer in the embodiment is realized by the following steps:
step one, Co with the average grain diameter of 500nm9S8Depositing a ZnO film on the surface of the nano-particles to obtain ZnO-Co9S8The method specifically comprises the following steps:
mixing Co9S8Placing the nanoparticles in a deposition chamber, and vacuumizing to a vacuum degree of 5 × 10-3Torr, then introducing high-purity nitrogen with the mass concentration of 99.99% until the pressure in the deposition chamber is 0.15Torr, keeping the temperature of the chamber at 150 ℃, and repeatedly executing 230 growth deposition cycles;
in the first step, the atomic layer deposition method is utilized to deposit Co9S8Depositing a ZnO film on the surface of the nano-particles, and specifically, completing the following operations:
mixing Co9S8Placing the nanoparticles in a deposition chamber, and vacuumizing to a vacuum degree of 5 × 10-3Torr, then introducing high-purity nitrogen with the mass concentration of 99.99% until the pressure in the deposition chamber is 0.15Torr, keeping the temperature of the chamber at 150 ℃, and repeatedly executing 230 growth deposition cycles;
wherein, the process of each growth and deposition cycle comprises the following steps:
(1) the diethyl zinc (zinc source) is injected into the primary sedimentation cavity in a pulse mode, and the pulse time t1Is 0.03 s;
(2) the reaction is carried out by cutting off the air inlet valve and the exhaust valve, and the reaction time t2Is 5 s;
(3) opening an air inlet valve and an air outlet valve, and purging by using high-purity nitrogen with the mass concentration of 99.99 percent for purging time t3Is 4 s;
(4) injecting deionized water into the reaction cavity in a pulse mode, wherein the temperature of the deionized water is room temperature, and the pulse time t4Is 0.02 s;
(5) the reaction is carried out by cutting off the air inlet valve and the exhaust valve, and the reaction time t55s, forming ZnO;
(6) opening an air inlet valve and an air outlet valve, and purging by using high-purity nitrogen with the mass concentration of 99.99 percent for purging time t6For 40s, one deposition growth cycle was completed.
Step two, then pressing Co9S8The mass ratio of graphene to graphene is 4: 1 the ratio of ZnO to Co obtained in the step one9S8To graphene, together with ZrO2ZrO is put together with the grinding balls2In the ball milling tank with the inner lining, after the cover is covered, high-purity argon with the mass concentration of 99.99 percent is filled for 10min by using two air filling holes reserved on the tank cover through proper air flow so as to completely exhaust air, finally, the ball milling tank is fixed in a ball mill, and the ball mill is operated to start ball milling after parameters are set. And opening the pot periodically during the ball milling process for inspection, when the material is stuck or agglomerated, crushing the agglomerated material, stripping the pot body, refilling carrier gas, continuing ball milling, cooling the ball milling pot to room temperature after the ball milling is finished, and taking out the sample.
In the ball milling process, the protective gas is high-purity argon, the ball milling time is 4h, the rotating speed of the ball mill is 800rpm, and the mass ratio of ball materials is 10: 1, the grinding ball is ZrO with a diameter of 3mm2The amount of the grinding balls is 0.1 g.
The sample and the adhesive are uniformly mixed, and the mixture is coated on the surface of the substrate with the same surface density for multiple times by adopting a high-speed glue homogenizing method to form a composite film layer structure with controllable film thickness, so that the effect of radiation resistance and reinforcement is realized.
Thirdly, adding adhesive epoxy resin, wherein the dosage of the adhesive is ZnO-Co9S8And 100 percent of the total mass of the graphene, uniformly mixing, and coating the mixture on the surface of an aluminum substrate to form a film, wherein the thickness of the film is 15 mu m.
And step four, carrying out hydrotreating by adopting high-pressure hydrogen equipment to obtain the gamma-ray irradiation resistant high-hydrogen storage composite protective film layer.
This embodiment forms hydrogen and a metal compound into a hydride, which is advantageous for stable storage.
The temperature in the space environment is between plus or minus 100 ℃ and is far less than the hydrogen desorption temperature threshold (more than 200 ℃) of the hydrogen storage material.
The graphene and the hydrogen storage material are effectively compounded, so that the binding capacity between the composite film layer and the substrate can be enhanced, and hydrogen can be more effectively fixed.
Example 2: this example is different from example 1 in that Co is used9S8The mass ratio of graphene to graphene is 6: 1 the ratio of ZnO to Co obtained in the step one9S8The other steps and parameters were the same as in example 1.
Example 3: this example is different from example 1 in that Co is used9S8The mass ratio of graphene to graphene is 8: 1 the ratio of ZnO to Co obtained in the step one9S8The other steps and parameters were the same as in example 1.
Example 4: this example is different from example 1 in that Co is used9S8The mass ratio of graphene to graphene is 8: 1 the ratio of ZnO to Co obtained in the step one9S8The other steps and parameters were the same as in example 1.
Example 5: this example is different from example 1 in that Co is used9S8The mass ratio of graphene to graphene is 10: 1 the ratio of ZnO to Co obtained in the step one9S8The other steps and parameters were the same as in example 1.
Table 1: hydrogen storage capacity and radiation protection capacity table for obtaining composite coating under different conditions
| The hydrogen storage capacity wt% | The radiation protection capability is improved by | |
| Blank (substrate without film layer) | 3.000 | 0 |
| Comparative example 1 (no ZnO modification) | 3.525 | 19 |
| Comparative example 2 (no graphene modification) | 3.400 | 15 |
| Example 1 | 3.690 | 30 |
| Example 2 | 3.651 | 28 |
| Example 3 | 3.633 | 25 |
| Example 4 | 3.627 | 21 |
| Example 5 | 3.600 | 20 |
As can be seen from table 1, the coating of the present invention exhibits good radiation resistance.
Claims (9)
1. The gamma-ray irradiation resistant high hydrogen storage composite protective film is characterized in that the composite protective film is made of Co9S8Depositing a ZnO film on the surface of the metal compound; then adding the graphene into graphene, carrying out high-energy ball milling under the protection of protective gas, taking out, adding an adhesive, uniformly mixing, coating the mixture on the surface of a substrate to form a film, drying and carrying out hydrotreating to obtain the graphene-based composite material; the preparation method is realized by the following steps:
step one, depositing a ZnO film on the surface of cobalt-sulfur metal compound nano particles to obtain a ZnO-cobalt-sulfur metal compound;
step two, adding the graphene into the graphene, carrying out high-energy ball milling under the protection of protective gas, and taking out;
step three, adding an adhesive, uniformly mixing, coating the mixture on the surface of a base material to form a film, and drying;
step four, then carrying out hydrogenation treatment to obtain a high hydrogen storage composite protective film layer with gamma-ray irradiation resistance;
in the first step, an atomic layer deposition method is used for depositing a ZnO film on the surface of cobalt-sulfur metal compound nanoparticles, and the method is specifically completed by the following operations:
placing cobalt-sulfur metal compound nanoparticles in a deposition chamber, and vacuumizing to a vacuum degree of 4 × 10-3 Torr～6×10-3 Torr, then introducing high-purity nitrogen until the pressure in the deposition chamber is 0.1 Torr-0.2 Torr, keeping the temperature of the chamber at 100-200 ℃, and repeatedly executing 100-300 growth deposition cycles;
the process of each growth and deposition cycle is as follows:
(1) the zinc source is injected into the primary sedimentation cavity in a pulse mode, and the pulse time t1Is 0.01s to 0.03 s;
(2) reaction by cutting off the inlet valve and the exhaust valveReaction time t2Is 1 s-5 s;
(3) opening an air inlet valve and an air outlet valve, purging by using high-purity nitrogen, and purging for time t3Is 30 s-60 s;
(4) injecting an oxygen source into the reaction cavity in a pulse mode, wherein the temperature of the oxygen source is room temperature, and the pulse time t4Is 0.01 s-0.03 s;
(5) the reaction is carried out by cutting off the air inlet valve and the exhaust valve, and the reaction time t5Forming ZnO within 1 s-5 s;
opening an air inlet valve and an air outlet valve, purging by using high-purity nitrogen, and purging for time t6And finishing a deposition growth cycle within 30-60 s.
2. A preparation method of a high hydrogen storage composite protective film layer with gamma ray irradiation resistance is characterized by comprising the following steps:
step one, depositing a ZnO film on the surface of cobalt-sulfur metal compound nano particles to obtain a ZnO-cobalt-sulfur metal compound;
step two, adding the graphene into the graphene, carrying out high-energy ball milling under the protection of protective gas, and taking out;
step three, adding an adhesive, uniformly mixing, coating the mixture on the surface of a base material to form a film, and drying;
and step four, carrying out hydrogenation treatment to obtain the gamma-ray irradiation resistant high hydrogen storage composite protective film layer.
3. The preparation method according to claim 2, wherein the step one is to deposit a ZnO film on the surface of the cobalt-sulfur metal compound nanoparticles by using an atomic layer deposition method, and is specifically performed by:
placing cobalt-sulfur metal compound nanoparticles in a deposition chamber, and vacuumizing to a vacuum degree of 4 × 10-3 Torr～6×10-3 And (3) Torr, introducing high-purity nitrogen until the pressure in the deposition chamber is 0.1-0.2 Torr, keeping the temperature of the chamber at 100-200 ℃, and repeatedly executing 100-300 growth deposition cycles.
4. The method of claim 3, wherein each growth-deposition cycle is performed by:
(1) the zinc source is injected into the primary sedimentation cavity in a pulse mode, and the pulse time t1Is 0.01s to 0.03 s;
(2) the reaction is carried out by cutting off the air inlet valve and the exhaust valve, and the reaction time t2Is 1 s-5 s;
(3) opening an air inlet valve and an air outlet valve, purging by using high-purity nitrogen, and purging for time t3Is 30 s-60 s;
(4) injecting an oxygen source into the reaction cavity in a pulse mode, wherein the temperature of the oxygen source is room temperature, and the pulse time t4Is 0.01 s-0.03 s;
(5) the reaction is carried out by cutting off the air inlet valve and the exhaust valve, and the reaction time t5Forming ZnO within 1 s-5 s;
(6) opening an air inlet valve and an air outlet valve, purging by using high-purity nitrogen, and purging for time t6And finishing a deposition growth cycle within 30-60 s.
5. The production method according to claim 4, characterized in that the zinc source in step (1) is diethyl zinc; and (4) the oxygen source is deionized water.
6. The method according to claim 2, wherein the cobalt-sulfur metal compound nanoparticles of step one are Co9S8And (2) nanoparticles with the particle size of 100-500 nm, wherein in the second step, the mass ratio of the cobalt-sulfur metal compound to the graphene is (4-10): 1, adding the ZnO-cobalt-sulfur metal compound obtained in the step one to graphene.
7. The preparation method according to claim 2, wherein the protective gas in the second step is high-purity argon, the ball milling time is 4-20 h, the rotation speed of the ball mill is 400-800 rpm, and the mass ratio of the ball material is 10: 1, the grinding ball is ZrO with the diameter of 1 mm-3 mm2And (5) grinding balls.
8. The method according to claim 2, wherein the substrate in the third step is an aluminum substrate, a lead substrate, a titanium substrate, a tantalum substrate, or a polyimide substrate.
9. The preparation method according to claim 2, characterized in that the adhesive in the third step is epoxy resin, and the amount of the adhesive is 50% -100% of the total mass of the ZnO-Co-S metal compound and the graphene; the film has a thickness of 50 to 100 μm.
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