CN110670040B - Water-resistant and hydrogen-resistant Al/Al on surface of uranium metal2O3Composite coating and preparation method thereof - Google Patents

Water-resistant and hydrogen-resistant Al/Al on surface of uranium metal2O3Composite coating and preparation method thereof Download PDF

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CN110670040B
CN110670040B CN201911147407.6A CN201911147407A CN110670040B CN 110670040 B CN110670040 B CN 110670040B CN 201911147407 A CN201911147407 A CN 201911147407A CN 110670040 B CN110670040 B CN 110670040B
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coating
uranium
layer
hydrogen
composite
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CN110670040A (en
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王庆富
刘柯钊
江帆
鲜晓斌
法涛
汪小琳
丁晶晶
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Institute of Materials of CAEP
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34—Sputtering
    • C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/0021—Reactive sputtering or evaporation
    • C23C14/0036—Reactive sputtering
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/08—Oxides
    • C23C14/081—Oxides of aluminium, magnesium or beryllium
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/14—Metallic material, boron or silicon
    • C23C14/16—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon
    • C23C14/165—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon by cathodic sputtering
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/14—Metallic material, boron or silicon
    • C23C14/18—Metallic material, boron or silicon on other inorganic substrates
    • C23C14/185—Metallic material, boron or silicon on other inorganic substrates by cathodic sputtering

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  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Physical Vapour Deposition (AREA)

Abstract

The invention discloses a water-resistant and hydrogen-resistant Al/Al alloy on the surface of uranium2O3The composite coating and the preparation method thereof aim at developing a corrosion-resistant coating with high compactness, particularly capable of effectively blocking water and hydrogen permeation so as to solve the problem of surface corrosion of a uranium metal material. The composite coating takes uranium as a matrix and consists of an Al coating and Al2O3The plating layers are alternately deposited. In the application, the alumina coating has a sealing effect on the pores of the aluminum coating and has the following effects: on one hand, the introduction of the aluminum oxide coating blocks the continuous growth of columnar grains of the aluminum coating, greatly reduces the penetration holes and defects in the coating, improves the compactness of the coating, and obviously reduces the permeation channels of corrosive media such as water, hydrogen and the like; on the other hand, the aluminum oxide has compact structure, stable performance and low hydrogen permeability, can more effectively block the permeation of small atom size corrosive media such as hydrogen and the like, and improves the protective performance of the coating on a matrix. Through the survey, the composite coating of this application can effectively block the infiltration of environmental atmospheres such as water and hydrogen to uranium.

Description

Water-resistant and hydrogen-resistant Al/Al on surface of uranium metal2O3Composite coating and preparation method thereof
Technical Field
The invention relates to the field of metal protection, in particular to the technical field of active metal surface corrosion prevention, and specifically relates to a water-blocking and hydrogen-blocking Al/Al alloy on a uranium metal surface2O3A composite plating layer and a preparation method thereof. More specifically, the application provides a metallic uranium surface water and hydrogen resistant protective layer and a preparation method thereof.
Background
Metal uranium has wide applications in both the nuclear industry and military fields due to its unique physical properties. However, the chemical property of uranium is active, and uranium is very easy to react with environmental media (water and hydrogen) to corrode in the using and storing processes, so that the performance of uranium is influenced. Aiming at corrosion protection of uranium materials, the most widely applied technology is physical or chemical coating technology, namely a layer of compact film is prepared on the surface of a metal uranium matrix to prevent a corrosion medium from contacting with the matrix, so that the matrix is protected from corrosion.
The aluminum coating is one of ideal protective coatings of metallic uranium, and has the following two advantages: on one hand, the corrosion resistance of the aluminum plating layer is excellent; on the other hand, the aluminum plating layer has good compatibility with uranium, not only does not influence the nuclear performance of the uranium, but also is easy to form UAl on an interface with the uranium2And UAl3Thereby enhancing membrane-based binding (ref: C.M. Egert, Aluminum Ion plate for corosion Protection of Uranium, Oak Ridge Y-12 plate, 1985.). In a paper' influence of ion bombardment plating on the structure and the corrosion resistance of an aluminum coating on uranium, the influence of bias plating, circulating argon ion bombardment plating and intermittent plating on the structure and the corrosion resistance of the aluminum coating on uranium is researched in a study of the influence of ion bombardment plating on the structure and the corrosion resistance of the aluminum coating on uranium published by China Proc of engineering and physics research institute of China, Luzhong and the like (volume 23, page 5 and 299 of 2003), and the research shows that the ion bombardment mode has certain influence on the structure of the aluminum coating and the compactness of the structure is closely related to the corrosion resistance of the aluminum coating.
Disclosure of Invention
Research shows that when a single aluminum coating is sputtered on uranium, the single magnetron sputtering coating is generally in a typical columnar structure and has a loose structure, the gaps and microscopic pores among crystal grains are channels for corrosive media to pass through the coating to reach a substrate, and the barrier to the channels is the key for further improving the overall compactness of the coating and inhibiting the corrosion of the uranium. In addition, in the presence of hydrogen, uranium is highly reactive with hydrogen and UH is formed3Such hydrides can lead to degradation of the metallic properties, and in severe cases can lead to failure of the component properties. In addition, UH3Such hydridesSpontaneous combustion is easy to occur, and great hidden danger is caused to the safety of human beings [ reference: albrecht W M, Mallettt M W.reaction of hydrogen with uranium [ J ]]．J Electrochem Soc，1956，103：404～409．]。
Therefore, the development of the corrosion-resistant coating which can improve the compactness of the coating and particularly effectively prevent the permeation of water, hydrogen and other environmental atmospheres has important significance for expanding the service time of uranium and enabling the service environment.
The invention provides a water-resistant and hydrogen-resistant Al/Al alloy on the surface of uranium2O3The composite coating and the preparation method thereof aim at developing a corrosion-resistant coating with high compactness, particularly capable of effectively blocking water and hydrogen permeation so as to solve the problem of surface corrosion of a uranium metal material. The application discloses composite coating uses uranium as the base member, and composite coating is by Al cladding material and Al2O3The plating layers are alternately deposited. In the application, the alumina coating has a sealing effect on the pores of the aluminum coating and has the following effects: on one hand, the introduction of the aluminum oxide coating blocks the continuous growth of columnar grains of the aluminum coating, greatly reduces the penetration holes and defects in the coating, improves the compactness of the coating, and obviously reduces the permeation channels of corrosive media such as water, hydrogen and the like; on the other hand, the aluminum oxide has compact structure, stable performance and low hydrogen permeability, can more effectively block the permeation of small atom size corrosive media such as hydrogen and the like, and improves the protective performance of the coating on a matrix. Through the survey, the metal uranium surface of this application hinders water and hinders hydrogen Al/Al2O3The composite coating is a corrosion-resistant coating with good compactness, can effectively prevent the permeation of water, hydrogen and other environmental atmospheres to uranium, and has high application value.
In order to achieve the purpose, the invention adopts the following technical scheme:
water-resistant and hydrogen-resistant Al/Al on surface of uranium metal2O3The composite coating takes metal uranium as a matrix, and consists of an Al coating and Al2O3The plating layers are alternately deposited;
the bottom layer of the composite coating is an Al coating, the composite coating is connected with the substrate into a whole through the Al coating on the bottom layer, and the top layer of the composite coating is the Al coating.
The number of the Al coating layers is more than that of the Al2O3The number of the coating layers is one more.
The thickness of the single-layer Al coating is 1-5 mu m, and the single-layer Al coating2O3The thickness of the plating layer is 10-25 nm, and the thickness of the composite plating layer is 3-15 mu m.
The number of Al layers and Al2O3The sum of the number of the layers of the plating layers is odd and is more than or equal to 3.
The Al coating is prepared by taking metal aluminum as a magnetron sputtering target and adopting pulse bias magnetron sputtering ion aluminizing; the Al is2O3The coating layer takes aluminum as a magnetron sputtering target and is filled with reaction gas O2The material is prepared by adopting intermediate frequency reactive sputtering.
The metal uranium surface water-resistant and hydrogen-resistant Al/Al2O3The preparation method of the composite coating comprises the following steps:
(1) substrate pretreatment
Removing the surface oxide layer of the uranium metal, and cleaning the uranium metal for later use;
(2) preparation of Al coating
Depositing a single-layer Al coating with the thickness of 1-5 mu m on the surface of the metal uranium substrate pretreated in the step 1 by adopting a pulse bias magnetron sputtering method; wherein the magnetron sputtering bias is-100 to-200V, and the air pressure is 0.3 to 0.6 Pa;
(3) preparation of Al2O3Coating layer
After the step (2) is finished, depositing a single layer of Al with the thickness of 10-25 nm on the surface of the Al coating by adopting a medium-frequency reactive sputtering method2O3Plating; wherein, magnetron sputtering bias is-100 to-200V, air pressure is 0.3 to 0.6Pa, sputtering time is 10 to 20min, and reactive sputtering voltage control point is 20 to 40 percent;
(4) alternate deposition
After the step (3) is finished, the steps (2) and (3) are repeated in sequence to enable the Al coating and the Al to be coated2O3And (3) alternately depositing the plating layers to form a composite plating layer, wherein the Al plating layer formed in the step (2) is a final deposition step of the composite plating layer.
In the step 1, removing a surface oxidation layer of the uranium metal by adopting a mechanical grinding and polishing mode, then respectively cleaning the surface of the uranium metal without the oxidation layer by using trichloroethylene, absolute ethyl alcohol and acetone, and drying the uranium metal by using dry inert gas; putting the cleaned metal uranium into a vacuum chamber, and vacuumizing the vacuum chamber to 1 x 10-3Baking and degassing the vacuum chamber below Pa, wherein the baking temperature is 60-120 ℃, and the baking time is 30-60 min; then, pulse bias glow discharge cleaning is carried out to finish the pretreatment of the substrate for standby.
In the step 1, the inert gas is one or more of nitrogen or argon.
In the step 1, the background vacuum degree of the vacuum chamber is 3 multiplied by 10-4The baking temperature is below 80 +/-10 ℃ and the baking time is 30-50 min.
In the step 1, a magnetic suspension molecular pump with the pumping speed of more than 2000L/s and a low-temperature pump with the pumping speed of more than 6000L/s are adopted to work simultaneously, and the vacuum chamber is vacuumized to 1 x 10-3Pa or less. Preferably, a magnetic suspension molecular pump with the pumping speed of 2200L/s and a cryogenic pump with the pumping speed of 7500L/s work simultaneously, and the background vacuum degree of the vacuum chamber is pumped to 3 x 10-4Pa or less.
In the step 1, when pulse bias glow discharge cleaning is carried out, argon is introduced into the vacuum chamber, pulse bias is applied to enable the vacuum chamber to carry out glow discharge, plasma is generated, and cleaning of the metal uranium of the matrix is realized through the action of the plasma and the matrix.
In the step 2, the bias voltage of magnetron sputtering is-200V, the air pressure is 0.5Pa, and the target power is 1.5 kW.
In the step 3, the magnetron sputtering bias is-200V, the air pressure is 0.5Pa, the target power is 0.8kW, the sputtering time is 10min, and the voltage control point is 25-35%.
In the step 4, the thickness of the composite coating is 3-15 mu m.
To the problem, the application provides a metal uranium surface blocks water and hinders hydrogen Al/Al2O3A composite plating layer and a preparation method thereof. The substrate of the composite coating is uranium, and the composite coating is composed of an Al coating and Al2O3Coating intersectionThe bottom layer and the top layer of the composite coating are respectively Al coatings (namely the quantity of the Al coatings is more than that of the Al coatings)2O3The number of the plating layers is one more, so that the Al plating layers are divided into an upper end and a lower end which are positioned on the composite plating layers), and the Al plating layer at the bottommost layer of the composite plating layers is deposited on the base metal uranium. As shown in FIG. 1, the bottom is a base metal uranium, an Al coating is firstly formed on the surface of the uranium, and then Al is formed on the Al coating2O3Coating on Al2O3And (4) arranging an Al coating on the coating, and repeating the steps until the top layer is the Al coating. In the application, the thickness of the single-layer Al coating is 1-5 mu m, and the single-layer Al coating2O3The thickness of the coating is 10-25 nm, the thickness of the composite coating is 3-15 mu m, and the number of layers of the Al coating and the Al2O3The sum of the number of the coating layers is more than or equal to 3. In the application, the Al coating takes metal aluminum as a magnetron sputtering target, and adopts pulse bias magnetron sputtering ion aluminum plating; al (Al)2O3The coating layer takes aluminum as a magnetron sputtering target and is filled with reaction gas O2The material is prepared by adopting a medium-frequency reactive sputtering method.
Further, another object of the present application is to provide a method for preparing the aforementioned composite plating layer, which comprises the following steps:
(1) matrix pretreatment: firstly, removing an oxide layer on the surface of the uranium by adopting a mechanical grinding and polishing mode, carrying out surface cleaning on the uranium with the oxide layer removed by trichloroethylene, absolute ethyl alcohol and acetone, and drying by dry nitrogen or dry argon; putting the cleaned metal uranium into a vacuum chamber, and vacuumizing the vacuum chamber to 1 x 10-3Baking and degassing the vacuum chamber below Pa, wherein the baking temperature is 60-120 ℃, and the baking time is 30-60 min; followed by a pulsed bias glow discharge clean. Preferably, the background vacuum degree of the vacuum chamber is 3X 10-4The baking temperature is below 80 +/-10 ℃ and the baking time is 30-50 min.
(2) Depositing an aluminum coating: depositing a single-layer Al coating with the thickness of 1-5 mu m on the surface of the matrix by adopting a pulse bias magnetron sputtering method; wherein the magnetron sputtering bias is-100 to-200V, the air pressure is 0.3 to 0.6Pa, and the target power is 1 to 2 kW. Preferably, the magnetron sputtering bias is-200V, the gas pressure is 0.5Pa, and the target power is 1.5 kW.
(3) Deposition of Al2O3Plating: depositing a single layer of Al with the thickness of 10-25 nm on the surface of the Al coating by adopting a medium-frequency reactive sputtering method2O3And the coating, wherein the magnetron sputtering bias is-100 to-200V, the air pressure is 0.3 to 0.6Pa, the sputtering time is 10 to 20min, the voltage control point is 30 to 40 percent, and the target power is 0.5 to 1.0 kW. Preferably, the magnetron sputtering bias is-200V, the air pressure is 0.5Pa, the target power is 0.8kW, the sputtering time is 10min, and the voltage control point is 25-35%.
(4) Repeating the steps (2) and (3) in sequence to enable the Al coating and the Al2O3Al/Al is formed by alternate deposition of plating layers2O3Composite coating, and step (2) is the final step of coating deposition, i.e. Al2O3The plating layer is the outermost layer of the formed composite plating layer. The thickness of the composite coating is 3-15 mu m, the total thickness of the Al coating is 5-10 mu m, and Al2O3The total thickness of the plating layer is 20-80 nm. Preferably, the thickness of the Al coating is 10 mu m, and Al is2O3The thickness of the plating layer was 50 nm.
In step 1, a magnetic suspension molecular pump with the pumping speed of more than 2000L/s and a low-temperature pump with the pumping speed of more than 6000L/s are adopted to work simultaneously, and a vacuum chamber is vacuumized to 1 x 10-3Pa or less. Further, a magnetic suspension molecular pump with the pumping speed of 2200L/s and a low-temperature pump with the pumping speed of 7500L/s work simultaneously, and the background vacuum degree of the vacuum chamber is pumped to 3 multiplied by 10-4Pa or less.
In the step 1, the pulse bias glow discharge cleaning is to introduce argon into the vacuum chamber, apply a certain pulse bias to make the vacuum chamber glow discharge to generate plasma, and generate cleaning effect through the action of the plasma and the substrate. Wherein the Ar partial pressure is 1.5 to 2.5Pa, the pulse bias is-600 to-900V, and the cleaning time is 20 to 60 min. Preferably, the Ar partial pressure is 2.0Pa, the pulse bias is-800V, and the cleaning time is 30-50 min.
This application uses metal uranium as the base member, adopts Al and Al2O3The two coatings are compounded to form a multi-layer coating which can block water and hydrogen on the surface of uranium. In the invention, on the basis of the aluminum plating layer, A is usedl2O3The introduction of the coating can effectively block the continuous growth of aluminum coating grains, reduce the penetrating holes and defects in the coating and improve the compactness of the coating, thereby reducing the permeation channels of corrosive media such as water, hydrogen and the like; at the same time, Al2O3The structure is compact, the hydrogen permeability is very low, the permeation of small atom size corrosive media such as hydrogen and the like can be more effectively blocked, and the corrosion resistance of the coating is improved. By the design and preparation of the composite coating, the invention provides a practical and effective thought and a new protective structure for solving the problem of corrosion of uranium, and has obvious progressive significance.
FIG. 1 shows a schematic diagram of the design principle of the composite coating of the present invention. In FIG. 1, U is a substrate, a metal Al coating is deposited on the U substrate by a magnetron sputtering method, and Al is deposited on the Al coating by a reactive sputtering method2O3Coating with Al followed by Al coating2O3And alternately depositing the coatings to form the composite coatings. The invention adopts a magnetron sputtering method, and has the advantages of low preparation temperature, simple preparation process, good controllability, low cost and the like. The invention forms Al/Al on the surface of metallic uranium2O3The composite coating has low impurity content, high chemical stability, close combination with a substrate, controllable thickness and excellent water and hydrogen resistance, and can provide more effective protection for the uranium substrate.
In summary, due to the adoption of the technical scheme, the invention has the beneficial effects that:
(1) the water-and hydrogen-resistant composite coating consists of an Al coating and Al2O3Coating layers deposited alternately, Al2O3The introduction of the coating can effectively interrupt the growth of columnar crystals of the aluminum coating, greatly reduce the through holes and defects in the coating, improve the compactness of the coating, reduce the permeation channels of corrosive media such as water, oxygen, hydrogen and the like, and improve the protective performance of the composite coating on a matrix;
(2) al used in the present application2O3The structure is compact, the hydrogen permeation resistance is strong, the permeation of small atom size corrosive media such as hydrogen and the like can be effectively blocked, and the protection of the coating is improved;
(3) the comparison experiment result shows that the composite coating has better water and hydrogen resistance, and has important significance for expanding the service time of uranium and enabling the service environment.
Drawings
The invention will now be described, by way of example, with reference to the accompanying drawings, in which:
FIG. 1 shows a metallic uranium surface water and hydrogen resistant Al/Al2O3The design schematic diagram of the composite coating.
FIG. 2 shows Al/Al in example 12O3The preparation flow and the process parameter chart of the composite coating.
FIG. 3 shows Al/Al prepared in example 12O3Surface topography of the composite coating.
FIG. 4 shows Al/Al prepared in example 12O3And (4) a sectional profile of the plating layer.
FIG. 5 shows Al/Al prepared in example 12O3The distribution diagram of the U/Al interface elements in the coating.
FIG. 6 is a diagram showing the process flow and process parameters for preparing the Al plating layer in comparative example 1.
Fig. 7 is a surface topography of the Al plating layer prepared in comparative example 1.
Fig. 8 is a sectional view of the Al plating layer prepared in comparative example 1.
Detailed Description
All of the features disclosed in this specification, or all of the steps in any method or process so disclosed, may be combined in any combination, except combinations of features and/or steps that are mutually exclusive.
Any feature disclosed in this specification may be replaced by alternative features serving equivalent or similar purposes, unless expressly stated otherwise. That is, unless expressly stated otherwise, each feature is only an example of a generic series of equivalent or similar features.
Example 1
In the embodiment, 10 mu m Al/Al is prepared on the surface of uranium metal2O3The preparation flow and the technological parameters of the composite coating are shown in figure 2, and the preparation process is as follows.
1) Substrate pretreatment
Removing an oxide layer on the surface of the uranium by adopting a mechanical grinding and polishing mode, and then respectively cleaning the surface of the uranium with the oxide layer removed by using absolute ethyl alcohol, acetone and dry nitrogen. Putting the cleaned metal uranium into a vacuum chamber, adopting two magnetic suspension molecular pumps with the pumping speed of 2200L/s as main pumps and a low-temperature pump with the pumping speed of 7500L/s to work simultaneously, and vacuumizing the vacuum chamber to 3 x 10-4Pa, and baking and degassing the vacuum chamber at the baking temperature of 80 ℃ for 30 min. Then, filling high-purity argon into the vacuum chamber after baking to 2.0Pa, and applying pulse bias voltage of-800V to make it glow discharge and generate plasma Ar+By Ar+The ions bombard the surface of the substrate to generate a cleaning effect on the substrate, and the cleaning time is 30 min.
2) Depositing an aluminum coating
Depositing a single-layer-3 mu m thick Al coating on the surface of the matrix by a magnetron sputtering method, which comprises the following steps: after glow cleaning is carried out on the surface of a uranium matrix, argon is adjusted to maintain the vacuum at 0.5Pa, pulse bias voltage of-200V with the duty ratio of 20% is applied to the matrix, a target sputtering power supply is started, the target power is 1.5kW, and the sputtering time is 30 min.
3) Deposition of Al2O3Coating layer
Adopting a medium-frequency reactive sputtering method to deposit a single layer of 25nm Al on the surface of the Al coating2O3Plating; wherein the air pressure is 0.5Pa, the magnetron sputtering bias is-200V, the target power is 0.8kW, the sputtering time is 10min, and the voltage control point is 30%.
Repeating the steps (2) and (3) (wherein the step (2) is repeated three times and the step (3) is repeated two times) to form Al coating and Al2O3The thickness of the composite plating layer formed by alternate deposition of the plating layer is about 10 mu m, wherein the thickness of the Al plating layer is about 10 mu m, and the thickness of the Al plating layer is about 10 mu m2O3The thickness of the plating layer is about 50 nm.
Al/Al is obtained on the surface of metallic uranium through the parameters2O3And compounding a plating layer, and characterizing the appearance, the structure, the moisture permeability coefficient and the hydrogen permeability coefficient of a sample.
Wherein FIG. 3 showsAl/Al2O3Surface topography of the composite coating, Al/Al2O3The surface appearance of the composite plating layer seen by magnifying 20000 gamma rays is still compact, and the surface is in a flowing corrugated structure.
In order to obtain a cross-sectional structure, a monocrystalline silicon substrate is particularly selected as a substrate. And (4) directly brittle-breaking after the plating layer is prepared. The cross-sectional morphology of the coating obtained by scanning electron microscopy is shown in FIG. 4, and Al/Al can be seen2O3The section of the composite plating layer is of a compact lath-shaped layered structure.
After glow discharge cleaning for 30min under argon partial pressure of 2.0Pa and pulse bias of-800V, Al coating preparation was performed, and interface element distribution was subjected to depth analysis by Auger Electron Spectrometer (AES), and the results are shown in FIG. 5. According to the distribution diagram of the elements of the interface between the aluminum film and the uranium matrix, the O content of the interface between the obtained film and the matrix is low by adopting determined glow discharge cleaning parameters, the oxide layer of the matrix is thin, and aluminum atoms migrate into the matrix under the action of ion bombardment, so that the effective combination between aluminum and metal uranium is facilitated.
The moisture permeability coefficient of the plating layer is visual reflection of the compactness of the plating layer, the more compact the plating layer is, the less water vapor is easy to permeate through the plating layer, and the lower the moisture permeability coefficient is. According to the GB1037-70 plastic moisture permeability test method, for self-sustaining Al/Al2O3And (4) measuring the moisture permeability coefficient of the composite plating layer. For Al/Al prepared in this example2O3The moisture permeability coefficient of the composite plating layer is measured, and reaches 3.1 multiplied by 10-9 g cm/(cm2 h mmHg)。
The hydrogen permeability coefficient of the coating and the diffusion coefficient of hydrogen in the coating at room temperature are measured by adopting a gas-phase hydrogen permeation method, and experimental test results show that Al/Al2O3The hydrogen permeability coefficient of the coating was 9.06X 10-9 mol[H]/m∙s∙Pa1/2。
Comparative example 1
In this embodiment, a 10 μm Al plating layer is prepared on the surface of uranium metal, the preparation process and the process parameters are shown in fig. 6, and the preparation process is as follows.
1) Substrate pretreatment
By mechanical beatingRemoving an oxide layer on the surface of the uranium by a grinding and polishing mode, and then respectively cleaning the surface of the uranium with the oxide layer removed by absolute ethyl alcohol, acetone and dry nitrogen. Putting the cleaned metal uranium into a vacuum chamber, adopting two magnetic suspension molecular pumps with the pumping speed of 2200L/s as main pumps and a low-temperature pump with the pumping speed of 7500L/s to work simultaneously, and vacuumizing the vacuum chamber to 3 x 10-4Pa, and baking and degassing the vacuum chamber at the baking temperature of 80 ℃ for 30 min. Then, filling high-purity argon into the vacuum chamber after baking to 2.0Pa, and applying pulse bias voltage of-800V to make it glow discharge and generate plasma Ar+By Ar+The ions bombard the surface of the substrate to generate a cleaning effect on the substrate, and the cleaning time is 30 min.
2) Depositing an aluminum coating
After glow cleaning is carried out on the surface of a uranium matrix, argon is adjusted to maintain the vacuum at 0.5Pa, pulse bias voltage of-200V with the duty ratio of 20% is applied to the matrix, a target sputtering power supply is started, the target power is 1.5kW, the sputtering time is 90min, and a layer of Al coating with the thickness of 10 mu m is deposited on the surface of the matrix by a magnetron sputtering method.
The Al coating is obtained on the surface of the uranium metal through the parameters, and the appearance, the structure, the moisture permeability coefficient and the hydrogen permeability coefficient of the sample are characterized.
FIG. 7 shows the surface morphology of the Al coating, and the single Al coating is magnified 1000 times, so that the granular texture of the coating can be seen, and the coating is relatively loose.
Fig. 8 shows the cross-sectional morphology of the aluminum plating layer, wherein the single aluminum plating layer has a typical columnar structure, and the crystal grains have the characteristic of columnar continuous growth.
The moisture permeability coefficient of the aluminum plating layer is 6 multiplied by 10 measured by the humidity coefficient of the sample prepared in comparative example 1-9 g cm/(cm2h mmHg) compared to Al/Al of example 12O3The composite coating is increased by about one time. The results show that, compared to example 1, under the same conditions, water vapor more easily permeates through the aluminum plating layer of comparative example 1, causing corrosion of the substrate.
The hydrogen permeability of the aluminum plating layer was 3.56X 10 as measured by the diffusion coefficient of the sample prepared in comparative example 1-7 mol[H]/m∙s∙Pa1/2Comparison of Al to Al2O3The composite coating is increased by 2 orders of magnitude. The results show that hydrogen gas permeates more easily through the aluminum plating layer of comparative example 1 and corrodes the substrate under the same conditions as in example 1.
The invention is not limited to the foregoing embodiments. The invention extends to any novel feature or any novel combination of features disclosed in this specification and any novel method or process steps or any novel combination of features disclosed.

Claims (7)

1. Water-resistant and hydrogen-resistant Al/Al on surface of uranium metal2O3The preparation method of the composite coating is characterized in that the composite coating takes metal uranium as a matrix, and the composite coating consists of an Al coating and Al2O3The plating layers are alternately deposited;
the bottom layer of the composite coating is an Al coating, the composite coating is connected with the substrate into a whole through the Al coating on the bottom layer, and the top layer of the composite coating is the Al coating;
the method comprises the following steps:
(1) substrate pretreatment
Removing the surface oxide layer of the uranium metal, and cleaning the uranium metal for later use;
(2) preparation of Al coating
Depositing a single-layer Al coating with the thickness of 1-5 mu m on the surface of the metal uranium substrate pretreated in the step 1 by adopting a pulse bias magnetron sputtering method; wherein the magnetron sputtering bias is-100 to-200V, and the air pressure is 0.3 to 0.6 Pa;
(3) preparation of Al2O3Coating layer
After the step (2) is finished, depositing a single layer of Al with the thickness of 10-25 nm on the surface of the Al coating by adopting a medium-frequency reactive sputtering method2O3Plating; wherein, magnetron sputtering bias is-100 to-200V, air pressure is 0.3 to 0.6Pa, sputtering time is 10 to 20min, and reactive sputtering voltage control point is 20 to 40 percent;
(4) alternate deposition
After the step (3) is finished, the steps (2) and (3) are repeated in sequence to enable the Al coating and the Al to be coated2O3Alternately depositing the plating layers to form a composite plating layer, wherein the Al plating layer formed in the step (2) is a final deposition step of the composite plating layer;
the Al coating is prepared by taking metal aluminum as a magnetron sputtering target and adopting pulse bias magnetron sputtering ion aluminizing; the Al is2O3The coating layer takes aluminum as a magnetron sputtering target and is filled with reaction gas O2The material is prepared by adopting intermediate frequency reactive sputtering;
the thickness of the single-layer Al coating is 1-5 mu m, and the single-layer Al coating2O3The thickness of the plating layer is 10-25 nm, and the thickness of the composite plating layer is 3-15 mu m;
in the step (1), when the substrate is cleaned by adopting pulse bias glow discharge, argon is introduced into the vacuum chamber, and pulse bias is applied to cause the vacuum chamber to glow discharge to generate plasma, and the cleaning of the substrate metal uranium is realized through the action of the plasma and the substrate;
the Ar partial pressure is 1.5 to 2.5Pa, the pulse bias is-600 to-900V, and the cleaning time is 20 to 60 min.
2. The method according to claim 1, wherein the Al plating layer has a number of layers smaller than that of Al2O3The number of the coating layers is one more.
3. The preparation method according to claim 1, wherein in the step (1), a mechanical grinding and polishing mode is adopted to remove the surface oxidation layer of the uranium, and then trichloroethylene, absolute ethyl alcohol and acetone are respectively used for carrying out surface cleaning on the uranium with the oxidation layer removed, and dry inert gas is used for blow drying; putting the cleaned metal uranium into a vacuum chamber, and vacuumizing the vacuum chamber to 1 x 10-3Baking and degassing the vacuum chamber below Pa, wherein the baking temperature is 60-120 ℃, and the baking time is 30-60 min; then, pulse bias glow discharge cleaning is carried out to finish the pretreatment of the substrate for standby.
4. The production method according to claim 3, wherein in the step (1), a vacuum chamberBackground vacuum degree of 3X 10-4The baking temperature is below 70-90 ℃ and the baking time is 30-50 min.
5. The production method according to claim 1, wherein in the step (2), the magnetron sputtering bias is-200V, the gas pressure is 0.5Pa, and the target power is 1.5 kW.
6. The production method according to claim 1, wherein in the step (3), magnetron sputtering bias is-200V, gas pressure is 0.5Pa, target power is 0.8kW, sputtering time is 10min, and voltage control point is 25-35%.
7. A coating produced by the production method according to any one of claims 1 to 6.
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