CN115029677B - Preparation process of high-hydrogen-permeability isotope and high-temperature-resistant TaVNbZr/(TaVNbZrM) Nx composite gradient barrier layer - Google Patents
Preparation process of high-hydrogen-permeability isotope and high-temperature-resistant TaVNbZr/(TaVNbZrM) Nx composite gradient barrier layer Download PDFInfo
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- CN115029677B CN115029677B CN202210734160.3A CN202210734160A CN115029677B CN 115029677 B CN115029677 B CN 115029677B CN 202210734160 A CN202210734160 A CN 202210734160A CN 115029677 B CN115029677 B CN 115029677B
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- 239000002131 composite material Substances 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title abstract description 10
- 230000004888 barrier function Effects 0.000 title description 8
- 238000000576 coating method Methods 0.000 claims abstract description 95
- 239000011248 coating agent Substances 0.000 claims abstract description 92
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 49
- 239000001257 hydrogen Substances 0.000 claims abstract description 49
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 45
- 238000000151 deposition Methods 0.000 claims abstract description 45
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 41
- 150000004767 nitrides Chemical class 0.000 claims abstract description 23
- 239000000758 substrate Substances 0.000 claims abstract description 23
- 229910052715 tantalum Inorganic materials 0.000 claims abstract description 19
- 230000007704 transition Effects 0.000 claims abstract description 18
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 7
- 238000004544 sputter deposition Methods 0.000 claims description 122
- 229910052763 palladium Inorganic materials 0.000 claims description 73
- 230000008021 deposition Effects 0.000 claims description 32
- 239000007789 gas Substances 0.000 claims description 27
- 238000004140 cleaning Methods 0.000 claims description 26
- 229910052751 metal Inorganic materials 0.000 claims description 24
- 239000002184 metal Substances 0.000 claims description 24
- 239000012528 membrane Substances 0.000 claims description 23
- 229910052697 platinum Inorganic materials 0.000 claims description 20
- 229910052758 niobium Inorganic materials 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 17
- 238000000746 purification Methods 0.000 claims description 16
- 238000005516 engineering process Methods 0.000 claims description 15
- 230000008569 process Effects 0.000 claims description 14
- 239000012535 impurity Substances 0.000 claims description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 238000005238 degreasing Methods 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 244000137852 Petrea volubilis Species 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 238000005086 pumping Methods 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 238000005137 deposition process Methods 0.000 claims description 4
- 239000011159 matrix material Substances 0.000 claims description 3
- 238000005477 sputtering target Methods 0.000 claims description 3
- 239000013077 target material Substances 0.000 claims description 3
- 229910052722 tritium Inorganic materials 0.000 abstract description 19
- YZCKVEUIGOORGS-NJFSPNSNSA-N Tritium Chemical compound [3H] YZCKVEUIGOORGS-NJFSPNSNSA-N 0.000 abstract description 15
- 230000032683 aging Effects 0.000 abstract description 9
- 230000008859 change Effects 0.000 abstract description 8
- 230000035882 stress Effects 0.000 abstract description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 147
- 239000010955 niobium Substances 0.000 description 44
- 239000010410 layer Substances 0.000 description 23
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 22
- 229910045601 alloy Inorganic materials 0.000 description 11
- 239000000956 alloy Substances 0.000 description 11
- 230000004927 fusion Effects 0.000 description 11
- 238000009792 diffusion process Methods 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 8
- 229910000510 noble metal Inorganic materials 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 5
- 229910004298 SiO 2 Inorganic materials 0.000 description 5
- 230000004907 flux Effects 0.000 description 5
- 230000035699 permeability Effects 0.000 description 5
- 230000002285 radioactive effect Effects 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 238000005336 cracking Methods 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 229910052805 deuterium Inorganic materials 0.000 description 4
- 239000010948 rhodium Substances 0.000 description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000012876 carrier material Substances 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 239000002912 waste gas Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000000137 annealing Methods 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000033228 biological regulation Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- -1 hydrogen compound Chemical class 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 150000002736 metal compounds Chemical class 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- 230000035939 shock Effects 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 description 1
- 241001082241 Lythrum hyssopifolia Species 0.000 description 1
- 229910001252 Pd alloy Inorganic materials 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000005524 ceramic coating Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 238000001493 electron microscopy Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 230000000155 isotopic effect Effects 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 229910052754 neon Inorganic materials 0.000 description 1
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- 150000002830 nitrogen compounds Chemical class 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000003904 radioactive pollution Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000004901 spalling Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
- 230000010512 thermal transition Effects 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
Classifications
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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
- C23C14/352—Sputtering by application of a magnetic field, e.g. magnetron sputtering using more than one target
-
- 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
- C23C14/0084—Producing gradient compositions
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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
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/0641—Nitrides
-
- 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
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/3492—Variation of parameters during sputtering
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E30/00—Energy generation of nuclear origin
- Y02E30/10—Nuclear fusion reactors
Abstract
A preparation process of a high-hydrogen-permeability isotope and high-temperature-resistant TaVNbZr/(TaVNbZrM) Nx composite gradient coating comprises the following steps: preparing a TaVNbZr transition layer, and depositing a TaVNbZr gradient coating on the Ta substrate for 10min when depositing the transition layer; then N is introduced into 2 The flow rate was increased from 0sccm to 12sccm and a (TaVNbZrM) Nx multinitride coating was prepared under vacuum. In the deposited TaVNbZr transition layer, the atomic percentage content of Ta element is changed in a gradient manner from 100at% to 25at% along the thickness direction, and the atomic percentage content of V, nb and Zr element is changed in a gradient manner from 0at% to 25at% along the thickness direction; the atomic percentage of Ta, V, nb, zr elements in the deposited (TaVNbZrM) Nx multi-element nitride coating is 10at% to 25at%, the atomic percentage of M elements is 2at% to 5at%, and the atomic percentage of N elements is 5 to 20at%. The coating is in a gradient change microstructure, and has the characteristics of relieving residual stress in the composite gradient coating, along with good binding force, high hydrogen permeation isotope, tritium aging resistance, high temperature resistance, excellent mechanical property and the like.
Description
Technical Field
The application belongs to the technical field of preparation of hydrogen isotope purification membrane systems in fusion reactor plasma ash discharge gas treatment systems, and particularly relates to a process for preparing TaVNbZr/(TaVNbZrM) Nx composite gradient coating with high-temperature interdiffusion prevention, high hydrogen permeation isotope resistance, tritium aging resistance and excellent mechanical properties between Pd/Ta/Pd (or Pd/Nb/Pd or Pd/V/Pd) selective hydrogen isotope purification membrane systems by adopting a multi-target co-sputtering technology.
Background
The energy collection and transformation is an inexhaustible clean energy source, and has remarkable advantages in the aspects of solving the future energy crisis, protecting the environment and the like. Fusion reactions are carried out by feeding deuterium (D) and tritium (T), two isotopes of hydrogen, into a fusion reactor in a prescribed ratio to maintain the nuclear fusion reaction. However, the deuterium-tritium burning rate of the fusion reactor is very low (0.3-5%), and a large amount of deuterium-tritium gas is discharged along with the ash gas discharged by the plasma. In order to avoid radioactive pollution of radioactive T gas to the environment, the price of T is extremely high (8-13 ten thousand dollars/gram), and D and T in the radioactive T gas can be recovered through a plasma ash gas treatment (Tokamak Exhaust Processing, TEP) system, so that the radioactive T gas can realize safe control of radioactive fuel and has extremely high economic value [ W, jason, B, james, et al, fusion Sci, technology 75 (8) (2019) 794-801 ].
Because the fusion reactor plasma waste gas is a rather complex mixture, the fusion reactor plasma waste gas comprises helium (He) ash generated by deuterium-tritium fusion reaction, toroidal exhaust during plasma operation, glow discharge cleaning and other non-deuterium-tritium gases (such as argon (Ar), neon (Ne) and hydrogen (H) 2 ) He, nitrogen (N) 2 ) Substances from chemical reactions (e.g. hydrogen isotopic compounds with carbon (C), oxygen (O) and N) and substances from nuclear reactions (e.g. 40 Ar+ 1 n→ 41 Ar). The exhaust gas contains free hydrogen isotopes (Q 2 Q=h, D or T), tritium containing impurities (e.g., NQ 3 , CQ 4 And Q 2 O), and tritium-free impurities (e.g., he, ne, and Ar). According to two core key objectives of current TEP systems: (1) front end processing: a large amount of plasma waste gas is pumped into a palladium (Pd) -silver (Ag) alloy permeator after passing through an air inlet buffer from a low-temperature pump, most of free hydrogen isotopes are separated to the permeation side of a Pd-Ag film at the temperature of 450 ℃, and DT buffer is pumped through the permeation pump; (2) impurity treatment: impurity molecules of some hydrogen-containing isotopes (e.g., NQ 3 , CQ 4 And Q 2 O) cannot be separated directly from the exhaust gas by means of a front-end permeate apparatus, for example tritiated methane is difficult to decompose, and the direct thermal decomposition requires temperatures up to 1200 ℃ 5,7]. Thus, experimental studies have found that noble metals such as platinum (Pt), rhodium (Rh), palladium (Pd), etc. catalysts and porous aluminum oxide (Al) 2 O 3 ) Or silicon dioxide (SiO) 2 ) The carrier material is formed of Pt/Al 2 O 3 、Pd/Al 2 O 3 、Rh/Al 2 O 3 Or Pt/SiO 2 、Pd/SiO 2 And Ru/SiO 2 The noble metal film tube can effectively crack impurity molecules of hydrogen-containing isotopes at the temperature of 500 ℃ or above. These alloy film tubes made from typical noble metal (e.g., pt, rh, pd, etc.) catalysts and porous support materials, while having potential for commercial application, require coating of a thicker noble metal film of Pt, rh, pd on porous Al 2 O 3 Or SiO 2 The surface of the carrier material is subjected to hole sealing, so that the cost is too high, meanwhile, the thicker noble metal films of Pt, rh and Pd also greatly reduce the hydrogen isotope permeation rate, and the urgent requirement (140 standard liters per minute on average) of maintaining the fusion fuel circulation by recovering tritium fuel in the commercial fusion reactor is difficult to meet]。
Recently, pd/(vanadium (V), niobium (Nb), tantalum (Ta) and their alloys) composite films or composite film tubes as a high purity hydrogen purification and for various hydrogen compound reforming or cracking reactions [ c.h. Lee, et al, j. Membrane. Sci. 595 (2020) 117506:1-10.]Is of interest, and Pd is relatively inexpensive and has a relatively abundant storage amount among three noble metals of Pt, rh, and Pd. Pd and Pd alloys are the most widely studied and commercially used H at present 2 Separating the membrane material. By analogy, if a V, nb and Ta metal film of a certain thickness is used instead of porous Al 2 O 3 Or SiO 2 The carrier material not only has equivalent mechanical strength and high permeability of hydrogen isotopes, but also can greatly reduce the thickness of noble metal (such as Pt, rh, pd and the like) catalysts, remarkably improve the permeability of the hydrogen isotopes and reduce the manufacturing cost of a hydrogen isotope treatment module of a TEP system, so that the Pd/(Ta, V, nb and alloys thereof) composite membrane tube is expected to be widely applied to a TEP tritium purification system. But the key to the problem is that for impurity molecules containing hydrogen isotopes (e.g., NQ 3 , CQ 4 And Q 2 O, q=h, D or T) at a cracking temperature above 500 ℃, V, nb and Ta metal membrane elements readily diffuse into the Pd membrane body at high temperatures and form various metal compounds resulting in degradation of the hydrogen permeation properties of the Pd/V/Pd, pd/Nb/Pd and Pd/Ta/Pd systems. Edlund et al found that the hydrogen flux dropped dramatically when the Pd/V/Pd composite membrane was operated at 700℃due to diffusion between Pd and V and formation of metal compounds [ D.J. Edlund, J. McCarthy, J. Member. Sci.107 (1-2) (1995) 147-153.]. A similar trend is in Pd/Nb/Pd membranes [ V.N. Alimov, et al, int.J. Hydrogen Energy 36 (13) (2011) 7737-7746.]And Pd/Ta/Pd membrane systems [ Yongha Park, yeonsu Kwak, saerom Yu et al Journal of Alloys and Compounds 854 (2021) 157196.]Both microstructure analysis and in situ electron microscopy analysis of (c) demonstrated that interdiffusion of the Pd/Nb/Pd and Pd/Ta/Pd membrane systems resulted in a dramatic decrease in hydrogen permeation performance. In order to improve the thermal stability of Pd/Ta, V, nb and their alloy composite metal films, researchers have attempted to embed a metal atom diffusion barrier layer between Pd/V, pd/Nb and Pd/Ta metal films, which is required to have not only good ability to migrate H atoms but also to hinder diffusion and reaction between Pd and Ta, V, nb and their alloy elements at high temperatures. To date, researchers have found that designing a 50 nm HfN barrier layer at the Pd/Ta film interface is significantly effective in improving the Hydrogen permeability weakening of Pd/Ta film systems at high temperatures, but have also found that the Hydrogen permeability of Pd/HfN/Ta film systems containing HfN barrier layers is reduced by about an order of magnitude compared to the original Pd/Ta film systems [ T. Nozaki, Y. Hatano, J. Hydrogen Energy 38 (2 01 3) 11 9 8 3-1 19 8 7.]The root cause is that a dense HfN barrier layer with a certain thickness is opposite to H 2 Diffusion hysteresis. In addition, the thermal expansion coefficients and the crystal structures of the Pd/HfN/Ta film system layer and the interface are greatly different, and the thermal stress and the residual stress at high temperature are easy to cause the interface cracking, even delamination failure and the like of the Pd/HfN/Ta film system. The Pd/V/Pd, pd/Nb/Pd and Pd/Ta/Pd selective hydrogen isotope purification membrane systems facing TEP systems not only require high temperature resistance, interfacial structural integrity and stability, high hydrogen isotope permeability, but also must consider radioactive tritium reflective decay radiation damage and decay products 3 He (i.e., tritium aging) causes He clusters to accumulate into helium bubbles, which leads to interlayer interface cracking and spalling failure, and seriously affects the service reliability of the hydrogen isotope purification membrane system. Thus, TEP systems face serious challenges with selective hydrogen isotope purification membrane systems Pd/V/Pd, pd/Nb/Pd and Pd/Ta/Pd surface/interface modification techniques.
The metal or ceramic coating can be coated on the surface/interface of the material as an important means for improving the irradiation resistance, high-temperature oxidation resistance and mechanical properties of the surface/interface of the material such as metal. Metal coatings (FeCrAl), carbides (SiC, zrC, etc.), nitrides (TiN), where nitrides such as TiN, tiAlN, zrN, etc. have higher hardness, melting point and high thermal conductivity. The nitride coatings studied have gradually evolved from mono-to di-to poly-e.g. poly (AlCrNbSiTi) N films exhibiting excellent oxidation resistance at 900℃, see literature [ M.H. Hsieh, M.H. Tsai, W.H. Shen, et al Surf Coat Technol,2013; 221:118 ]. Firstov et al have performed a high temperature annealing treatment on a poly (TiVZrNbHf) N film, and found that the film hardness can reach 66 GPa when annealed at 1000 ℃ for 1 h, and after annealed at 1100 ℃ for 10 h, the film hardness can still maintain a high hardness of 44 GPa, and exhibits excellent toughness and high temperature stability, see literature [ s.a. Firstov, v.f. gorman, n.i. Danilenko, powder Metall Metal Ceram,2014, 52:560 ]. And the latest researches find that the fiber also has irradiation resistance [ A.D. Pogrebnjak, O.V. Bondar, S.O. Borba, et al, nuclear Inst & Methods in Physics Research B, 2016, 385:74-83 ]. The surface/interface of Pd/V/Pd (or Pd/Nb/Pd or Pd/Ta/Pd) of the selective hydrogen isotope purification membrane system for a TEP system has various performance requirements of high-temperature oxidation resistance, high-temperature stability, irradiation resistance and the like, and faces serious challenges. It was found that some multi-component high entropy alloy nitride coatings maintain stable single phase structure and good high temperature stability even at 1000 c [ p.k. Huang, j.w. Yeh, scr mate, 2010,62 (2): 105]. The reason for this is that the increase of elements increases the structural entropy, which leads to serious distortion of the crystal lattice of the high-entropy alloy nitride coating, reduces the energy of the crystal grain boundary, and further leads the multi-element high-entropy nitride coating to show good high-temperature stability.
Disclosure of Invention
The application aims to improve high-temperature interdiffusion, tritium aging resistance and high hydrogen permeation isotope performance of the surface/interface of a selective hydrogen isotope purification membrane system Pd/V/Pd (or Pd/Nb/Pd or Pd/Ta/Pd) for a TEP system, and provides a process for preparing TaVNbZr/(TaVNbZrM) Nx composite gradient coating between Pd/V/Pd, pd/Nb/Pd and Pd/Ta/Pd layers.
The technical scheme provided by the application is as follows: the process for preparing the high-permeability hydrogen isotope and high-temperature resistant TaVNbZr/(TaVNbZrM) Nx composite gradient coating between Pd/V/Pd (or Pd/Nb/Pd or Pd/Ta/Pd) layers of a hydrogen isotope purification membrane system is characterized by comprising the following steps:
a. cleaning a base material:
sequentially adopting water sand paper with different roughness to grind and polish a Ta (or Nb or V) substrate; then degreasing, degreasing and cleaning are carried out in an ultrasonic instrument by using acetone and ethanol as solvents; then cleaning with deionized water, drying, and vacuum-pumping to vacuum degree less than 5.0X10 -4 Pa；
b. Treatment of the substrate prior to deposition:
maintaining the vacuum of the vacuum chamber to be less than 5.0X10 -4 Under the Pa condition, adopting bias reverse sputtering cleaning for 15 min, and aiming at carrying out reverse sputtering cleaning on a Ta (or Nb or V) substrate; the reverse sputtering bias voltage is-450V to-550V; the reverse sputtering gas is Ar; the reverse sputtering air pressure in the vacuum chamber is 3.5-3.8 Pa;
c. pre-sputtering:
maintaining the vacuum of the vacuum chamber to be less than 5.0X10 -4 Under the Pa condition, each target is cleaned for 15 min by adopting pre-sputtering, and the aim is to remove impurities on the surface of the target; the pre-sputtering power is 120-150W; the pre-sputtering bias voltage is-120V to 150V; the pre-sputtering gas is Ar; the pre-sputtering air pressure in the vacuum chamber is 0.30-0.35 Pa;
d. sputtering deposition TaVNbZr/(TaVNbZrM) Nx composite gradient coating:
and (3) introducing Ar gas into a vacuum chamber by adopting an ultra-high vacuum multi-target co-sputtering technology, depositing a TaVNbZr coating on a Ta (or Nb or V) substrate, wherein the Ar flow is 50 sccm, the bias operating voltage is-80V to-150V, starting the Ta target, the V target, the Nb target and the Zr target to start co-sputtering deposition of the TaVNbZr coating, and the sputtering operating pressure is 0.30 Pa to 0.50 Pa. The sputtering power of Ta is always kept to be 150W in the process of depositing the transition layer, the sputtering power of a V target is gradually increased from 0W to 150W at the speed of 15W/min, the sputtering power of a Nb target is gradually increased from 0W to 150W at the speed of 15W/min, the sputtering power of a Zr target is gradually increased from 0W to 150W at the speed of 15W/min, and the deposition time is 10min; under the condition of uninterrupted vacuum, N is introduced 2 The flow rate was increased from 0sccm to 12sccm at a flow rate increase of 2 sccm/min, while maintaining N 2 The flow was 12sccm, followed by deposition (TaVNbZrM) Nx multi-element nitride coating, and simultaneously starting another M target, namely, pt, rh and Pd, wherein one target is a direct current target, sputtering current and sputtering voltage are respectively 0.5A and 160V-180V, and deposition time is 20 min.
The purity of each target of Ta, V, nb, zr and M is higher than 99.99%, and the purity of nitrogen is 99.99%.
In the deposition process, the rotation speed of the sample stage is 20-30 rpm; the target base distance in the sputtering deposition process of the coating is 4.5-5.5 cm.
Compared with the prior art, the application has the following beneficial effects:
1. in the preparation process of TaVNbZr/(TaVNbZrM) Nx transitional coating by adopting a multi-target co-sputtering technology, the power of a Ta, V, nb, zr target is regulated and controlled in the initial stage, the TaVNbZr coating is subjected to gradient transition, and N is introduced into a vacuum cavity at a flow rate of 2 sccm/min after the TaVNbZr coating is deposited 2 The flow rate was increased from 0sccm to 12sccm, which gradually transitioned the coating to a (TaVNbZrM) Nx coating. The coating is designed to be in a gradient change microstructure, so that internal stress caused by thermal mismatch between a substrate and the coating can be effectively reduced, and meanwhile, the interface binding force between the coating and a Ta (or Nb or V) substrate is improved by regulating and controlling the composite coating with element components in gradient change;
2. the TaVNbZr/(TaVNbZrM) Nx composite gradient coating prepared by the method is of a nano composite structure, so that the coating has high strength and hardness; meanwhile, the element components in the coating are of a gradient change structure, and the gradient component change is beneficial to improving the self-repairing capability of the composite coating, so that the coating has more excellent toughness and thermal shock resistance;
3. according to the prepared TaVNbZr/(TaVNbZrM) Nx composite gradient coating, the atomic percentage content of Ta element in a deposited TaVNbZr transition layer is changed in a gradient manner from 100at% to 25% at% along the thickness direction, and the atomic percentage content of V, nb and Zr element is changed in a gradient manner from 0at% to 25at% along the thickness direction; the atomic percentage of Ta, V, nb, zr elements in the deposited (TaVNbZrM) Nx multi-element nitride coating is 10at% -25 at%, the atomic percentage content of M (any one metal of M=Pt, rh and Pd) elements is 2at% -5 at%, and the atomic percentage content of N elements is 5% -20 at%, so that a stable phase structure is obtained. The prepared TaVNbZr/(TaVNbZrM) Nx composite gradient coating is applied to the improvement of high-temperature diffusion barrier, high-hydrogen permeation isotope and tritium aging resistance of hydrogen isotope purification membrane systems Pd/V/Pd, pd/Nb/Pd and Pd/Ta/Pd;
4. the preparation method adopts the ultra-high vacuum multi-target co-sputtering technology, can realize the preparation of TaVNbZr/(TaVNbZrM) Nx composite gradient coating under the room temperature condition, and has the characteristics of high deposition efficiency, low cost and strong process stability.
Drawings
FIG. 1 is an XRD pattern of a Ta/TaVNbZr/(TaVNbZrM) Nx/Pd composite gradient coating in as-deposited and 600 ℃ annealed states.
FIG. 2 shows TaVNbZr/(TaVNbZrM) Nx composite gradient coating at an energy of 60 keV He + The dosage is 5×10 16 cm -2 And (5) irradiating the electronic scanning electron microscope image.
FIG. 3 is 5X 10 16 cm -2 Dose He + And (3) carrying out high-resolution transmission images on the cross section of the Ta/TaVNbZr/(TaVNbZrM) Nx/Pd composite gradient coating in an annealed state at 600 ℃ after irradiation.
Detailed Description
The application is described in detail below with reference to the drawings and examples, but is not meant to limit the scope of the application in any way.
The application adopts the composite gradient coating with gradient change of element components, which not only can effectively reduce internal stress caused by mismatch of thermal expansion coefficients between Pd/V/Pd (or Pd/Nb/Pd or Pd/Ta/Pd) surfaces/interfaces, but also can improve interfacial bonding force of Pd/V/Pd (or Pd/Nb/Pd or Pd/Ta/Pd) surfaces/interfaces, and meanwhile, the gradient structure coating always shows more excellent toughness, high-temperature thermal stability resistance and thermal shock resistance. In addition, the outer layer of the composite gradient nitride coating is a multi-component high-entropy alloy nitride coating. Compared with the traditional surface treatment technology, the multi-target co-sputtering technology is adopted as a plasma preparation method with the excellent characteristics of high deposition efficiency, low cost, no pollution to the environment and the like, and the multi-target co-sputtering technology is adopted to prepare the TaVNbZr/(TaVNbZrM) Nx composite gradient coating with high-temperature diffusion resistance, high hydrogen permeation isotopes, tritium aging resistance and excellent mechanical properties between Pd/V/Pd (or Pd/Nb/Pd or Pd/Ta/Pd) selective hydrogen isotope purification membrane systems, so that the preparation method has wide application prospect.
According to the embodiment of the application, an ultra-high vacuum multi-target co-sputtering technology is adopted, ar gas is introduced into a vacuum chamber, a TaVNbZr coating is deposited on a Ta (or Nb or V) substrate, the Ar flow is 50 sccm, the bias operating voltage is-80V to-150V, the Ta target, the V target, the Nb target and the Zr target are started to start co-sputtering to deposit the TaVNbZr coating, and the sputtering operating air pressure is 0.30 Pa to 0.50 Pa. The sputtering power of Ta is always kept to be 150W in the process of depositing the transition layer, the sputtering power of a V target is gradually increased from 0W to 150W at the speed of 15W/min, the sputtering power of a Nb target is gradually increased from 0W to 150W at the speed of 15W/min, the sputtering power of a Zr target is gradually increased from 0W to 150W at the speed of 15W/min, and the deposition time is 10min; under the condition of uninterrupted vacuum, N is introduced 2 The flow rate was increased from 0sccm to 12sccm at a flow rate increase of 2 sccm/min, while maintaining N 2 The flux is 12sccm, then a (TaVNbZrM) Nx polynary nitride coating is deposited, and meanwhile, another M target, namely Pt, rh and Pd, is started, one target is a direct current target, sputtering current and sputtering voltage are respectively 0.5A and 160V-180V, and the deposition time is 20 min.
Example 1
a. Cleaning a base material:
sequentially adopting water sand paper with different roughness to grind and polish a Ta (or Nb or V) substrate; then degreasing, degreasing and cleaning are carried out in an ultrasonic instrument by using acetone and ethanol as solvents; then cleaning with deionized water, drying, and vacuum-pumping to vacuum degree less than 5.0X10 -4 Pa；
b. Treatment of the substrate prior to deposition:
maintaining the vacuum of the vacuum chamber to be less than 5.0X10 -4 Under the Pa condition, adopting bias reverse sputtering cleaning for 15 min, and aiming at carrying out reverse sputtering cleaning on a Ta (or Nb or V) substrate; the reverse sputtering bias voltage is-450V; the reverse sputtering gas is Ar; the reverse sputtering air pressure in the vacuum chamber is 3.5 Pa;
c. pre-sputtering:
maintaining the vacuum of the vacuum chamber to be less than 5.0X10 -4 Under the Pa condition, each target is cleaned for 15 min by adopting pre-sputtering, and the aim is to remove impurities on the surface of the target; the pre-sputtering power is 120W-150W; the pre-sputter bias is-120V; the pre-sputtering gas is Ar; the pre-sputtering air pressure in the vacuum chamber is 0.30 Pa;
d. sputtering deposition TaVNbZr/(TaVNbZrM) Nx composite gradient coating:
and introducing Ar gas into a vacuum chamber by adopting an ultrahigh vacuum multi-target co-sputtering technology, depositing a TaVNbZr coating on a Ta (or Nb or V) substrate, wherein the Ar flow is 50 sccm, the bias operating voltage is-80 VV, starting the Ta target, the V target, the Nb target and the Zr target to start co-sputtering deposition of the TaVNbZr coating, and the sputtering operating pressure is 0.30 Pa. The sputtering power of Ta is always kept to be 150W in the process of depositing the transition layer, the sputtering power of a V target is gradually increased from 0W to 150W at the speed of 15W/min, the sputtering power of a Nb target is gradually increased from 0W to 150W at the speed of 15W/min, the sputtering power of a Zr target is gradually increased from 0W to 150W at the speed of 15W/min, and the deposition time is 10min; under the condition of uninterrupted vacuum, N is introduced 2 The flow rate was increased from 0sccm to 12sccm at a flow rate increase of 2 sccm/min, while maintaining N 2 The flux is 12sccm, then a (TaVNbZrM) Nx polynary nitride coating is deposited, and meanwhile, another M target, namely Pt, rh and Pd, is started, one target is a direct current target, sputtering current and sputtering voltage are respectively 0.5A and 160V-180V, and the deposition time is 20 min.
e. Ta/TaVNbZr/(TaVNbZrM) Nx laminated surface sputtering deposition Pd metal layer:
closing all sputtering targets under the uninterrupted vacuum condition, and starting Pd target sputtering, wherein the bias voltage working voltage of the Pd target is-50V; the Pd target sputtering power was 150W and the deposition time was 20 min.
The structure of the Ta/TaVNbZr/(TaVNbZrM) Nx/Pd film system sample described in example 1 was subjected to high temperature heat preservation at 600℃for 24 hours for annealing, and then was tested by X-ray diffraction (XRD). Meanwhile, the atomic percentage content of Ta element in the deposited TaVNbZr transition layer is detected to be changed from 100at% -25 at% in a gradient manner along the thickness direction, and the atomic percentage content of V, nb and Zr elementGradient change is carried out from 0at% to 25% at% along the thickness direction; the atomic percentage of Ta, V, nb, zr elements in the deposited (TaVNbZrM) Nx multi-element nitride coating is 10at% -35 at%, the atomic percentage of M (any one metal of M=Pt, rh and Pd) elements is 2at% -4 at%, and the atomic percentage of N elements is 5% -20 at%. FIG. 1 shows that after the Ta/TaVNbZr/(TaVNbZrM) Nx/Pd film system sample is annealed at 600 ℃ for 24 hours, no compound phase structural peak formed by Ta/Pd interdiffusion is found, and Pd (111) peaks are clearly visible, which indicates that the Ta/TaVNbZr/(TaVNbZrM) Nx/Pd film system film is still stable in structure after being annealed at 600 ℃ for 24 hours. From TaVNbZr/(TaVNbZrM) Nx film at an energy of 60 keV He + The dosage is 5×10 16 cm -2 The result of the electron scanning electron microscope image (shown in figure 2) after irradiation shows that the TaVNbZr/(TaVNbZrM) Nx composite film system has excellent tritium aging resistance, and no surface foaming and peeling phenomenon occurs. 5X 10 16 cm -2 Dose He + The high-resolution transmission image (shown in figure 3) of the cross section of the annealed Ta/TaVNbZr/(TaVNbZrM) Nx/Pd composite gradient coating at 600 ℃ after irradiation further proves that the thickness of a compact and uniform TaVNbZr/(TaVNbZrM) Nx composite gradient alloy barrier layer is about 80 nm, each interface of the Ta/TaVNbZr/(TaVNbZrM) Nx/Pd film system is clear, interlayer interdiffusion is not seen, the prepared (TaVNbZrM) Nx composite gradient coating is mainly of a face-centered cubic nitride (TaN, zrN, tiN, nbN) (FCC) solid solution structure, and M (M=any metal of Pt, rh and Pd is difficult to be distributed with nitrogen compounds along the nitride crystal boundary, so that a rapid channel is provided for tritium permeation.
Example 2
a. Cleaning a base material:
sequentially adopting water sand paper with different roughness to grind and polish a Ta (or Nb or V) substrate; then degreasing, degreasing and cleaning are carried out in an ultrasonic instrument by using acetone and ethanol as solvents; then cleaning with deionized water, drying, and vacuum-pumping to vacuum degree less than 5.0X10 -4 Pa；
b. Treatment of the substrate prior to deposition:
maintaining the vacuum of the vacuum chamber to be less than 5.0X10 -4 Pa conditionPerforming bias reverse sputtering cleaning for 15 min, wherein the purpose is to perform reverse sputtering cleaning on a Ta (or Nb or V) substrate; the reverse sputtering bias voltage is-500V; the reverse sputtering gas is Ar; the reverse sputtering air pressure in the vacuum chamber is 3.7 Pa;
c. pre-sputtering:
maintaining the vacuum of the vacuum chamber to be less than 5.0X10 -4 Under the Pa condition, each target is cleaned for 15 min by adopting pre-sputtering, and the aim is to remove impurities on the surface of the target; the pre-sputtering power was 130W; the pre-sputter bias is-130V; the pre-sputtering gas is Ar; the pre-sputtering air pressure in the vacuum chamber is 0.32 Pa;
d. sputtering deposition TaVNbZr/(TaVNbZrM) Nx composite gradient coating:
and introducing Ar gas into a vacuum chamber by adopting an ultrahigh vacuum multi-target co-sputtering technology, depositing a TaVNbZr coating on a Ta (or Nb or V) substrate, wherein the Ar flow is 50 sccm, the bias operating voltage is-100V, starting the Ta target, the V target, the Nb target and the Zr target to start co-sputtering deposition of the TaVNbZr coating, and the sputtering operating pressure is 0.4 Pa. During the deposition of the transition layer, the sputtering power of Ta is always kept to be 150W, the sputtering power of a V target is gradually increased from 0W to 150W at a rate of 15W/min, the sputtering power of a Nb target is gradually increased from 0W to 150W at a rate of 15W/min, the sputtering power of a Zr target is gradually increased from 0W to 150W at a rate of 15W/min, and the deposition time is 10min; under the condition of uninterrupted vacuum, N is introduced 2 The flow rate was increased from 0sccm to 12sccm at a flow rate increase of 2 sccm/min, while maintaining N 2 The flux was 12sccm, then a (TaVNbZrM) Nx polynary nitride coating was deposited, and at the same time, another M target, namely, pt, rh, pd was turned on, optionally using a metal target, wherein one target was a DC target, the sputtering current and voltage were 0.5A and 170V, respectively, for a deposition time of 20 minutes.
In the TaVNbZr transition layer deposited under the process condition, the atomic percentage content of Ta element is changed in a gradient manner from 100at% to 25% at% along the thickness direction, and the atomic percentage content of V, nb and Zr element is changed in a gradient manner from 0at% to 25% at% along the thickness direction; the atomic percentage of Ta, V, nb, zr elements in the deposited (TaVNbZrM) Nx multi-element nitride coating is 10at% -35 at%, the atomic percentage content of M (any metal of M=Pt, rh and Pd) is 2at% -4 at%, the atomic percentage content of N elements is 5% -20 at%, and the structure and performance regulation of the prepared TaVNbZr/(TaVNbZrM) Nx composite gradient coating are realized by changing the type of target materials so as to meet the use requirements of product application.
Example 3
a. Cleaning a base material:
sequentially adopting water sand paper with different roughness to grind and polish a Ta (or Nb or V) substrate; then degreasing, degreasing and cleaning are carried out in an ultrasonic instrument by using acetone and ethanol as solvents; then cleaning with deionized water, drying, and vacuum-pumping to vacuum degree less than 5.0X10 -4 Pa；
b. Treatment of the substrate prior to deposition:
maintaining the vacuum of the vacuum chamber to be less than 5.0X10 -4 Under the Pa condition, adopting bias reverse sputtering cleaning for 15 min, and aiming at carrying out reverse sputtering cleaning on a Ta (or Nb or V) substrate; the reverse sputtering bias voltage is-550V; the reverse sputtering gas is Ar; the reverse sputtering air pressure in the vacuum chamber is 3.6 Pa;
c. pre-sputtering:
maintaining the vacuum of the vacuum chamber to be less than 5.0X10 -4 Under the Pa condition, each target is cleaned for 15 min by adopting pre-sputtering, and the aim is to remove impurities on the surface of the target; the pre-sputtering power was 150W; the pre-sputter bias is 150V; the pre-sputtering gas is Ar; the pre-sputtering air pressure in the vacuum chamber is 0.30-0.35 Pa;
d. sputtering deposition TaVNbZr/(TaVNbZrM) Nx composite gradient coating:
and introducing Ar gas into a vacuum chamber by adopting an ultrahigh vacuum multi-target co-sputtering technology, depositing a TaVNbZr coating on a Ta (or Nb or V) substrate, wherein the Ar flow is 50 sccm, the bias operating voltage is-150V, starting the Ta target, the V target, the Nb target and the Zr target to start co-sputtering deposition of the TaVNbZr coating, and the sputtering operating pressure is 0.30 Pa-0.50 Pa. The sputtering power of Ta is always kept to be 150W in the process of depositing the transition layer, the sputtering power of a V target is gradually increased from 0W to 150W at the speed of 15W/min, the sputtering power of a Nb target is gradually increased from 0W to 150W at the speed of 15W/min, the sputtering power of a Zr target is gradually increased from 0W to 150W at the speed of 15W/min, and the deposition time is 10min; under the condition of uninterrupted vacuum, N is introduced 2 The flow rate was increased from 0sccm to 12sccm at a flow rate increase of 2 sccm/min, while maintaining N 2 The flux was 12sccm, then a (TaVNbZrM) Nx polynary nitride coating was deposited, and at the same time, another M target, namely, pt, rh, pd was turned on, optionally using a metal target, wherein one target was a DC target, the sputtering current and voltage were 0.5A and 180V, respectively, and the deposition time was 20 min.
In the TaVNbZr transition layer deposited under the process condition, the atomic percentage content of Ta element is changed in a gradient manner from 100at% to 25% at% along the thickness direction, and the atomic percentage content of V, nb and Zr element is changed in a gradient manner from 0at% to 25% at% along the thickness direction; the atomic percentage of Ta, V, nb, zr elements in the deposited (TaVNbZrM) Nx multi-element nitride coating is 10at% -35 at%, the atomic percentage content of M (any metal of M=Pt, rh and Pd) is 2at% -4 at%, the atomic percentage content of N elements is 5% -20 at%, and the structure and performance regulation of the prepared TaVNbZr/(TaVNbZrM) Nx composite gradient coating are realized by changing the type of target material so as to meet the use requirements of product application.
The gradient composite coating adopted by the embodiment of the application has the following advantages in improving the high temperature stability resistance: first, the process of the application is simple to operate, and the process is transited from TaVNbZr coating to (TaVNbZrM) Nx coating in the initial stage of the process. On one hand, the transition composite coating can effectively play a role in thermal transition, can relieve the reduction of binding force between the coating and the matrix caused by mismatch of thermal expansion coefficients, and on the other hand, the component gradient change of the transition layer can improve the mechanical property of the composite coating. The second point is that the preparation of the composite gradient coating by adopting the multi-target co-sputtering technology can be realized under the room temperature condition, which is beneficial to keeping the stability of Pd/V/Pd (or Pd/Nb/Pd or Pd/Ta/Pd) matrix structure. Thirdly, when the TaVNbZr/(TaVNbZrM) Nx composite gradient coating is in a high temperature condition, nitrogen elements dissolved in the composite coating can effectively inhibit the generation of oxides, and solid solution phase structures in the composite coating can keep stable, so that mutual diffusion between Pd/V/Pd (or Pd/Nb/Pd or Pd/Ta/Pd) layers can be effectively prevented; meanwhile, the content of a trace amount of M element (any metal of M=Pt, rh and Pd) in the composite gradient coating is regulated, and because any metal of Pt, rh and Pd has high reaction enthalpy with N, any metal of Pt, rh and Pd is slightly doped in the multi-target co-sputtering process, so that the trace amount of any metal of Pt, rh and Pd does not react with N atoms, but is separated out along the nanocrystalline grain boundary of the (TaVNbZrM) Nx coating, and Pt or Rh or Pd distributed at the nanocrystalline grain boundary serves as a hydrogen isotope selective permeation diffusion path, so that the hydrogen isotope permeation performance of the TaVNbZr/(TaVNbZrM) Nx composite gradient coating is further improved.
According to the embodiment of the application, a multi-target co-sputtering technology is adopted, and in the deposited TaVNbZr transition layer, the atomic percentage content of Ta element is changed in a gradient manner from 100at% to 30 at% along the thickness direction, and the atomic percentage content of V, nb and Zr element is changed in a gradient manner from 0at% to 35 at% along the thickness direction; the atomic percentage of Ta, V, nb, zr elements in the deposited (TaVNbZrM) Nx multi-element nitride coating is 10at% -35 at%, the atomic percentage content of N elements is 5at% -20 at%, and the atomic percentage content of M (TaVNbZr/(TaVNbZrM) Nx) elements is 2at% -5 at%. The prepared composite coating has simple phase structure, good crystallinity and compact and uniform surface by optimizing the technological parameters of depositing the composite coating and selecting the doping amount of M element (any one metal of M=Pt, rh and Pd). The performance test of the composite coating shows that the composite coating has high binding force, high strength, high hydrogen permeation isotope, high temperature diffusion resistance, tritium aging radiation resistance and other excellent performances, and provides a new technical approach for improving the high temperature diffusion resistance, high hydrogen permeation isotope, tritium aging resistance and mechanical properties of selective hydrogen isotope purification membrane systems Pd/V/Pd (or Pd/Nb/Pd or Pd/Ta/Pd) for TEP systems.
Claims (3)
1. A process for preparing a high-permeability hydrogen isotope and high-temperature resistant TaVNbZr/(TaVNbZrM) Nx composite gradient coating between Pd/Ta/Pd or Pd/Nb/Pd or Pd/V/Pd layers of a hydrogen isotope purification membrane system is characterized by comprising the following steps:
a. cleaning a base material:
sequentially adopting water sand paper with different roughness to grind and polish the Ta or Nb or V matrix; then degreasing, degreasing and cleaning are carried out in an ultrasonic instrument by using acetone and ethanol as solvents; then cleaning with deionized water, drying, and vacuum-pumping to vacuum degree less than 5.0X10 -4 Pa；
b. Treatment of the substrate prior to deposition:
maintaining the vacuum of the vacuum chamber to be less than 5.0X10 -4 Under the Pa condition, adopting bias reverse sputtering cleaning for 15 min, and performing reverse sputtering cleaning on a Ta or Nb or V substrate; the reverse sputtering bias voltage is-450V to-550V; the reverse sputtering gas is Ar; the reverse sputtering air pressure in the vacuum chamber is 3.5-3.8 Pa;
c. pre-sputtering:
maintaining the vacuum of the vacuum chamber to be less than 5.0X10 -4 Under the Pa condition, each target is cleaned for 15 min by adopting pre-sputtering, and the aim is to remove impurities on the surface of the target; the pre-sputtering power is 120-150W; the pre-sputtering bias voltage is-120V to 150V; the pre-sputtering gas is Ar; the pre-sputtering air pressure in the vacuum chamber is 0.30-0.35 Pa;
d. sputtering deposition TaVNbZr/(TaVNbZrM) Nx composite gradient coating:
introducing Ar gas into a vacuum chamber by adopting an ultra-high vacuum multi-target co-sputtering technology, depositing TaVNbZr coating on Ta, nb or V substrate, wherein Ar flow is 50 sccm, bias operating voltage is-80V to-150V, starting Ta target, V target, nb target and Zr target to start co-sputtering to deposit TaVNbZr coating, and sputtering operating pressure is 0.30 Pa to 0.50 Pa; the sputtering power of Ta is always kept to be 150W in the process of depositing the transition layer, the sputtering power of a V target is gradually increased from 0W to 150W at the speed of 15W/min, the sputtering power of a Nb target is gradually increased from 0W to 150W at the speed of 15W/min, the sputtering power of a Zr target is gradually increased from 0W to 150W at the speed of 15W/min, and the deposition time is 10min; under the condition of uninterrupted vacuum, N is introduced 2 The flow rate was increased from 0sccm to 12sccm at a flow rate increase of 2 sccm/min, while maintaining N 2 The flow is 12sccm, then a (TaVNbZrM) Nx polynary nitride coating is deposited, and meanwhile, another M target is started, wherein the M target is a metal target selected from Pt, rh and Pd, one target position is a direct current target, the sputtering current and the sputtering voltage are respectively 0.5A and 160V-180V, and the deposition time is 20 min;
in the deposited TaVNbZr transition layer, the atomic percentage content of Ta element is changed in a gradient manner from 100at% to 25at% along the thickness direction, and the atomic percentage content of V, nb and Zr element is changed in a gradient manner from 0at% to 25at% along the thickness direction; the atomic percentage of Ta, V, nb, zr elements in the deposited (TaVNbZrM) Nx multi-element nitride coating is 10at% -25 at%, the atomic percentage content of M elements is 2at% -5 at%, the atomic percentage content of N elements is 5% -20 at%, and the M elements are any one metal of Pt, rh and Pd.
2. The process for preparing a high hydrogen permeation isotope and high temperature resistant TaVNbZr/(TaVNbZrM) Nx composite gradient coating between hydrogen isotope purification membrane systems Pd/Ta/Pd or Pd/Nb/Pd or Pd/V/Pd layers according to claim 1, wherein the process is characterized in that: the purity of each target material of Ta, V, nb, zr and M is higher than 99.99 percent, N 2 The purity of the gas was 99.99%.
3. The process for preparing a high hydrogen permeation isotope and high temperature resistant TaVNbZr/(TaVNbZrM) Nx composite gradient coating between hydrogen isotope purification membrane systems Pd/Ta/Pd or Pd/Nb/Pd or Pd/V/Pd layers according to claim 1, wherein the process is characterized in that: in the deposition process, the rotation speed of the sample stage is kept at 20-30 rpm; the target base distance in the sputtering deposition process of the coating is 4.5-5.5 cm; one of the target positions is a direct current sputtering target and is positioned under the sample table, the other four target positions are magnetic control sputtering targets, and the four magnetic control target positions form an included angle of 40 degrees with the central axis direction of the vacuum chamber.
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