CN105154878B - A kind of α-Al2O3The preparation method of hydrogen infiltration-resistant erosion resisting insulation layer - Google Patents

Abstract

The invention discloses a preparation method of an α-Al ₂ O ₃ hydrogen permeation resistance and corrosion-resistant insulating layer, comprising the following steps: (1) forming a chromium-aluminum alloy layer on the surface of a base material; Perform in-situ thermal oxidation at 500‑800 ^o C in the atmosphere, followed by thermal annealing to obtain a dense α‑Al ₂ O ₃ hydrogen permeation barrier layer. During the whole process, the surface temperature of the substrate was controlled below 800 ^o C to avoid the phase transition of the substrate caused by the high temperature during the preparation of the hydrogen barrier layer and thus affect its mechanical properties. After the formed oxide layer is stabilized, further oxidation will be carried out. There will be remaining chromium-aluminum alloys between the oxide layer and the substrate as an intermediate transition layer to enhance the bonding force between the oxide layer and the substrate, and at the same time improve the thermal expansion coefficient between the substrate and the oxide layer. Mismatch.

Description

A kind of α-Al2O3The preparation method of hydrogen infiltration-resistant erosion resisting insulation layer

Technical field

The present invention relates to resistance hydrogen Material Fields, are exactly a kind of α-Al₂O₃The preparation of hydrogen infiltration-resistant erosion resisting insulation layer Method.

Background technique

Due to the radioactivity and expensive cost of hydrogen isotope tritium, infiltration of the tritium in fusion reactor material and delay behavior are direct It is related to the economy and safety of the following fusion stack operation.Currently, fusion reactor blanket structural material is with the steel of Thief zone, vanadium Alloy is main candidate material, and the exploitation and application for hindering hydrogen material will directly influence tritium increment efficiency.It is a kind of at present feasible Scheme is to form the low ceramic tritium-permeation barrier layer of permeability in cladding structure material surface, can both guarantee material in this way Structural behaviour, while tritium-permeation can be inhibited again.With the development that fusion is studied, the international and country has developed a series of painting Layer material has excellent hydrogen infiltration-resistant for fusion reactor blanket structural material surface and storage tritium vessel wall surface, aluminium oxide Can, it is the research hotspot of hydrogen resistance coating all the time.However, compactness is best, the optimal α-Al of Tritium Resistivity₂O₃Formation temperature Degree is generally 1150^oPhase transition temperature (the low activation iron element of C or more, significantly larger than matrix (low activation ferrito-martensite steel etc.) Body steel phase transition temperature is about 850^oC), in patent No. CN 103160828, it is compound to disclose a kind of base steel aluminium oxide hydrogen infiltration-resistant The preparation process of coating, the aluminum oxide coating layer which uses the techniques such as magnetron sputtering, plasma spray coating to obtain is amorphous state Or γ phase alumina, resistance tritium effect are much worse than α-Al₂O₃.In view of possible application of the hydrogen permeation barrier in liquid blanket, It is required that coating has electrical insulating property and resistance to liquid metal corrosion ability.Simultaneously, it is contemplated that during coating will receive under fusion reactor environment The irradiation of son, and may be subjected to the corrosion of liquid tritium multiplication agent and liquid coolant, when resistance tritium effect will be with work Between growth and acutely reduce, therefore coating is preferably provided with self-healing properties.

Summary of the invention

The purpose of the present invention is to provide a kind of α-Al₂O₃The preparation method of hydrogen infiltration-resistant erosion resisting insulation layer.

Above-mentioned purpose is realized by following scheme:

A kind of α-Al₂O₃The preparation method of hydrogen infiltration-resistant erosion resisting insulation layer, it is characterised in that: the following steps are included:

(1) Cr-Al alloy layer is formed in substrate material surface；

(2) 500-800 is carried out in atmosphere or other oxygen enriched atmosphere again^oC in-situ thermal oxidation, insulation annealing can be obtained One layer of densification α-Al₂O₃Hydrogen permeation barrier.

A kind of α-Al₂O₃The preparation method of hydrogen infiltration-resistant erosion resisting insulation layer, it is characterised in that: in basis material The method of surface formation Cr-Al alloy layer are as follows: with magnetron sputtering or chemical vapor deposition or the method for spraying in basis material table One layer of chromium and one layer of aluminium are successively plated in face, after carry out heat treatment obtain Cr-Al alloy layer.

A kind of α-Al₂O₃The preparation method of hydrogen infiltration-resistant erosion resisting insulation layer, it is characterised in that: in basis material The method of surface formation Cr-Al alloy layer are as follows: directly obtain chromium by directly sputtering Cr-Al alloy target or spraying Cr-Al alloy powder Aluminium alloy layer.

A kind of α-Al₂O₃The preparation method of hydrogen infiltration-resistant erosion resisting insulation layer, it is characterised in that: the chromium aluminium Alloy is Al₇Cr, Al₁₁Cr₂ , Al₄Cr , Al₁₁Cr₄ , Al₉Cr₄ ,Al₈Cr₅ , AlCr , AlCr₂One of or Several mixing.

It with magnetron sputtering, chemical vapor deposition or is sprayed on substrate material surface and successively plates one layer of chromium and one layer of aluminium, then Heat treatment is carried out to obtain Cr-Al alloy layer or directly obtain by directly sputtering Cr-Al alloy target or spraying Cr-Al alloy powder Cr-Al alloy layer, Cr-Al alloy chemical component are Al₇Cr, Al₁₁Cr₂ , Al₄Cr , Al₁₁Cr₄ , Al₉Cr₄ ,Al₈Cr₅ , AlCr , AlCr₂.Then.500-800 is carried out in atmosphere or other oxygen enriched atmosphere^oC in-situ thermal oxidation, insulation annealing then may be used Obtain one layer of densification α-Al₂O₃Hydrogen permeation barrier.

The invention has the benefit that meet the basic demand of fusion hydrogen infiltration-resistant material, the present invention is by cladding structure Material in situ low temperature obtains α-Al₂O₃Hydrogen permeation barrier concept is introduced into the research and development field of hydrogen permeation preventing coating, utilizes magnetron sputtering Or spraying (vacuum plasma spray, supersonic flame spraying, aerodynamic force spraying etc.) is micro- in matrix surface preparation 10-100 Then the Cr-Al alloy layer of rice carries out in-situ oxidation and obtains the thick densification of about 100nm and the α-with fabulous hydrogen infiltration-resistant effect Al₂O₃Oxide layer.In whole process, matrix surface temperature is controlled 800^oC is hereinafter, avoid in resistance hydrogen layer preparation process high temperature Caused matrix phase transformation influences its mechanical property in turn.The oxide layer of formation is further aoxidized after stablizing, oxide layer and Remaining Cr-Al alloy is had between matrix enhances the binding force of oxide layer and matrix as intermediate layer, while improving base Coefficient of thermal expansion between body and oxide layer mismatches.Meanwhile in α-Al₂O₃Oxide layer is because by the irradiation of neutron and possible After corrosion impact causes hydrogen infiltration-resistant efficiency to decline, oxide layer can be carried out by way of in-situ oxidation again repairing weight It is new to restore efficiently resistance hydrogen function, i.e. realization selfreparing.

Specific embodiment

Below with reference to specific example, the present invention is described in further detail.α-Al of the invention₂O₃Hydrogen infiltration-resistant corrosion resistant Erosion insulating layer preparation method is not limited to specific raw material or technique, two as described below be only presently preferred embodiments of the present invention and , it is not intended to limit the invention, any modifications, equivalent replacements, and improvements done within the spirit and principles of the present invention Deng should all be included in the protection scope of the present invention.

Embodiment 1:

Basis material is low activation ferrito-martensite steel, and by taking F82H as an example, chemical component (weight percent) is main For Cr:7.46, C:0.09, Mn:0.21, W:1.96, Ta:0.023, Si:0.24, V:0.19.Matrix is cut into sheet, removes Rust oil removing sandblasting, and matrix is preheated using torch flame tail portion.Spraying powder is to utilize ball milling-mist projection granulating-sintering Cr-Al alloy (the Al of law technology preparation₉Cr₅) spherical powder, powder mean particle sizes are about 30 μm.It is spray coated in order to further prevent Matrix temperature rise is excessive in journey, by sample be fixed on copper it is heat sink on, and water flowing is cooling.Using propane as combustion adjuvant, oxygen is combustion adjuvant, Nitrogen is to carry powder gas, control matrix surface and spraying direction degree in a vertical angle, Cr-Al alloy layer needed for can get.Utilize penetrating fluid Body weighing method obtains, and the porosity of alloy-layer is about 8%.

To alloy-layer coated sample 750 under atmospheric environment^oC keeps the temperature 10h, then anneals.It can be obtained in alloyed layer Obtain the α-Al of the fine and close flawless of one layer of 110nm thickness₂O₃.The bond strength of oxide layer is 13Mpa.By 350^oC-550^oC temperature 10-10 in range⁵Pa deuterium mutually drives penetration testing, and deuterium permeability/diffusion coefficient has under about 10000 times compared to base material Drop.

Embodiment 2:

Basis material is V-4Cr-4Ti, and chemical component (weight percent) is mainly Cr:4.02%, Ti:3.98%, O: 0.0148%, H:0.029%, C:0.0067%, N:0.0122%, surplus V.

Matrix is cut into sheet, and mechanical grinding is polished to mirror surface, then successively carries out ultrasound clearly with acetone, alcohol, deionized water It washes.Magnetron sputtering Chamber vacuum degree is controlled 1.0 × 10^-4Pa, and 99.99% pure chromium, aluminium direct current target are selected, every time before sputtering Target surface adsorbed gas and oxide layer are removed by pre-sputtering 20min.Double target co-sputtering, and the sputtering power of each target is controlled, it obtains 10 μm of sputtered alloy layers, vacuum annealing after sample takes out, annealing temperature 700^oC, annealing time 4h.The hole of alloy-layer Rate is about 12%

To alloy-layer coated sample 750 under atmospheric environment^oC keeps the temperature 10h, then anneals.It can be obtained in alloyed layer Obtain the α-Al of the fine and close flawless of one layer of 100nm thickness₂O₃.The bond strength of oxide layer is 11.5Mpa.By 350^oC-550^oC temperature Spend 10-10 in range⁵Pa deuterium mutually drives penetration testing, and deuterium permeability/diffusion coefficient has under about 20000 times compared to base material Drop.

Claims (1)

1. a kind of α-Al ₂ O ₃ the preparation method of hydrogen resistance permeation corrosion-resistant insulating layer, it is characterized in that: comprise the following steps: (1) A chromium-aluminum alloy layer is formed on the surface of the base material; (2) In-situ thermal oxidation at 500-800 ^o C in the atmosphere or other oxygen-rich atmosphere, and thermal annealing, a dense α-Al ₂ O ₃ hydrogen permeation barrier layer can be obtained; The method of forming a chromium-aluminum alloy layer on the surface of the base material is as follows: using magnetron sputtering, chemical vapor deposition, or spraying to sequentially coat a layer of chromium and a layer of aluminum on the surface of the base material, and then heat treatment to obtain a chromium-aluminum alloy layer ; Or, directly obtain the chrome-aluminum alloy layer by sputtering the chrome-aluminum alloy target directly or spraying the chrome-aluminum alloy powder; The chromium-aluminum alloy is one or a mixture of Al ₇ Cr, Al ₁₁ Cr ₂ , Al ₄ Cr , Al ₁₁ Cr ₄ , Al ₉ Cr ₄ , Al ₈ Cr ₅ , AlCr and AlCr ₂ .